JP5450114B2 - Pattern forming method, chemically amplified resist composition, and resist film - Google Patents

Description

  The present invention relates to a pattern forming method applicable to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes, and a chemical amplification type used in the pattern forming method. The present invention relates to a resist composition and a resist film. In particular, a pattern formation method suitable for exposure in an ArF exposure apparatus, an ArF immersion projection exposure apparatus, and an EUV exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a chemical amplification type used in the pattern formation method The present invention relates to a resist composition and a resist film.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. An example of a positive-type chemical amplification image forming method will be described. By exposure with an excimer laser, an electron beam, extreme ultraviolet light, or the like, an acid generator in an exposed area is decomposed to generate an acid, and a post-exposure baking (PEB) : Post Exposure Bake) using an acid generated as a reaction catalyst to change an alkali-insoluble group to an alkali-soluble group and removing an exposed portion with an alkali developer.
In the above method, various alkali developers have been proposed, but an aqueous alkali developer of 2.38% by mass TMAH (tetramethylammonium hydroxide aqueous solution) is generally used.

  Also, for the miniaturization of semiconductor elements, the wavelength of the exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). Yes. Further, as a technique for further increasing the resolving power, a so-called immersion method in which a liquid with a high refractive index (hereinafter also referred to as “immersion liquid”) is conventionally filled between the projection lens and the sample, or a shorter wavelength (13 EUV lithography that performs exposure with ultraviolet light of .5 nm) has been proposed.

  However, in reality, it is extremely difficult to find an appropriate combination of a resist composition, a developing solution, a rinsing solution, and the like necessary for forming a pattern with a comprehensively good performance. It has been demanded. In particular, as the resolution line width of the resist becomes finer, improvements in line edge roughness performance of line patterns and in-plane uniformity of pattern dimensions are required.

On the other hand, not only the currently mainstream positive type, but also development of negative chemically amplified resist compositions in pattern formation by alkali development (see, for example, Patent Documents 1 to 4). This is because, in the manufacture of semiconductor elements and the like, there is a demand for forming patterns having various shapes such as lines, trenches, holes, and the like, but there are patterns that are difficult to form with current positive resists.
However, in pattern formation by alkali development using a conventional negative resist, swelling during development is presumed to be the main factor, line width variation (LWR), focus margin (DOF), and other various performances There is a need for improvement.

  Further, Patent Document 5 describes a double development technique as a double patterning technique for further increasing the resolution. By utilizing the fact that the polarity of the resin in the resist composition by exposure becomes high polarity in regions with high light intensity and low polarity in regions with low light intensity, By dissolving in a high-polarity developer and dissolving the low exposure area in a developer containing an organic solvent, the intermediate exposure area remains undissolved by development and has a line-and-half with an exposure mask half pitch. A space pattern is formed.

JP 2006-317803 A JP 2006-259582 A JP 2006-195050 A JP 2000-206694 A JP 2008-292975 A

  The present invention solves the above-described problems, and provides a pattern forming method, a chemical method capable of forming a pattern with a wide focus margin (DOF), small line width variation (LWR), excellent pattern shape, and further reduced bridge defects. An object of the present invention is to provide an amplified resist composition (chemically amplified negative resist composition) and a resist film.

  The present invention has the following configuration, which solves the above-described problems of the present invention.

<1>
(A) forming a film with a chemically amplified resist composition;
(A) a step of exposing the film, and (c) a step of developing using a developer containing an organic solvent,
A pattern forming method including:
The resist composition is
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) A pattern forming method comprising a compound having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid.

<2>
The pattern forming method as described in <1>, wherein the compound (G) is a nitrogen-containing compound.

<3>
The molecular weight of the said compound (G) is 500 or less, The pattern formation method as described in <1> or <2> characterized by the above-mentioned.

<4>
The pattern forming method according to <2> or <3>, wherein the compound (G) is a compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.

<5>
The method for forming a pattern according to <1> or <2>, wherein the compound (G) is a resin.

<6>
The compound (G) is a resin having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a basic group or a group whose basicity is increased by the action of an acid. The pattern formation method as described in <5>.

<7>
The pattern forming method according to any one of <1> to <6>, wherein the resist composition further contains a crosslinking agent (C).

<8>
<1> to <7>, wherein the developer contains at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. The pattern formation method in any one.

<9>
Furthermore, (d) The pattern formation method in any one of <1>-<8> characterized by including the process of rinsing using a rinse liquid.

<10>
<9> characterized in that the rinse liquid is at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. The pattern formation method as described.

<11>
The pattern forming method according to <1> to <10>, wherein the exposure in the step of exposing the film is immersion exposure.

一般式（１）において、
Ｒａ、Ｒｂ_１、Ｒｂ_２及びＲｂ_３は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。Ｒｂ_１〜Ｒｂ_３の内の２つは、互いに結合して、環を形成してもよい。但し、Ｒｂ_１〜Ｒｂ_３の全てが同時に水素原子となることはない。
Ｒｃは、単結合又は２価の連結基を示す。
Ｒｆは、有機基を表す。
ｘは０又は１を、ｙは１又は２を、ｚは１又は２をそれぞれ表し、ｘ＋ｙ＋ｚ＝３である。
ｘ＝ｚ＝１のとき、ＲａとＲｃは相互に結合して含窒素複素環を形成してもよい。
ｚ＝１のとき、Ｒｆとしての有機基は、フッ素原子又は珪素原子を含む。
ｚ＝２のとき、２つのＲｆの少なくとも一方は、フッ素原子又は珪素原子を含む。
ｚ＝２のとき、２つのＲｃ及び２つのＲｆは、それぞれ同じでも異なっていてもよく、２つのＲｃは相互に結合して環を形成してもよい。
ｙ＝２のとき、２つのＲ_ｂ１、２つのＲ_ｂ２及び２つのＲ_ｂ３は、それぞれ同じでも異なっていてもよい。
＜１３’＞
（Ａ）酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂、
（Ｂ）活性光線又は放射線の照射により酸を発生する化合物、
（Ｄ）溶剤、
（Ｇ）フッ素原子及び珪素原子の少なくとも一方を有するとともに、塩基性を有する又は酸の作用により塩基性が増大する化合物、及び、
前記化合物（Ｇ）には相当しない、フッ素原子を有する疎水性樹脂
を含有する化学増幅型レジスト組成物。
＜１４’＞
前記化合物（Ｇ）の分子量が５００以下であることを特徴とする＜１２’＞又は＜１３’＞に記載の化学増幅型レジスト組成物。
＜１５’＞
（Ａ）酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂、
（Ｂ）活性光線又は放射線の照射により酸を発生する化合物、
（Ｄ）溶剤、及び、
（Ｇ−２）フッ素原子及び珪素原子の少なくとも一方を有するとともに、酸の作用により塩基性が増大する化合物、
を含有する化学増幅型レジスト組成物であって、
前記化合物（Ｇ−２）が樹脂であることを特徴とする化学増幅型レジスト組成物。
＜１６’＞
前記化合物（Ｇ−２）が、フッ素原子及び珪素原子の少なくとも一方を有する繰り返し単位と、酸の作用により塩基性が増大する基を有する繰り返し単位とを有する樹脂であることを特徴とする＜１５’＞に記載の化学増幅型レジスト組成物。
＜１７’＞
更に、上記成分（Ｇ）又は（Ｇ−２）には相当しない、フッ素原子及び珪素原子の少なくともいずれかを有する疎水性樹脂を含有することを特徴とする、＜１２’＞、＜１５’＞及び＜１６’＞のいずれかに記載の化学増幅型レジスト組成物。
＜１８’＞
更に、架橋剤（Ｃ）を含有することを特徴とする＜１２’＞〜＜１７’＞のいずれかに記載の化学増幅型レジスト組成物。
＜１９’＞
＜１２’＞〜＜１８’＞のいずれかに記載の化学増幅型レジスト組成物により形成されたレジスト膜。
本発明は、上記＜１＞〜＜１１＞及び＜１２’＞〜＜１９’＞に係る発明であるが、以下、参考のため、他の事項も含めて記載している。
＜１２＞
（Ａ）酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂、
（Ｂ）活性光線又は放射線の照射により酸を発生する化合物、
（Ｄ）溶剤、及び、
（Ｇ）フッ素原子及び珪素原子の少なくとも一方を有するとともに、塩基性を有する又は酸の作用により塩基性が増大する化合物、を含む化学増幅型レジスト組成物。 <12 '>
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) a compound having at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid,
A chemically amplified resist composition comprising:
The chemical amplification resist composition, wherein the compound (G) is a compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.
<13 '>
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) solvent,
(G) a compound having at least one of a fluorine atom and a silicon atom, having basicity or increasing basicity by the action of an acid, and
A chemically amplified resist composition containing a hydrophobic resin having a fluorine atom, which does not correspond to the compound (G).
<14 '>
The chemical amplification resist composition as described in <12 ′> or <13 ′>, wherein the molecular weight of the compound (G) is 500 or less.
<15 '>
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G- 2 ) a compound having at least one of a fluorine atom and a silicon atom and having increased basicity by the action of an acid ,
A chemically amplified resist composition comprising:
The chemical amplification resist composition, wherein the compound (G- 2 ) is a resin .
<16 '>
The compound (G −2 ) is a resin having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a group whose basicity is increased by the action of an acid <15 Chemically amplified resist composition as described in '>.
< 17 '>
Furthermore, it contains a hydrophobic resin having at least one of a fluorine atom and a silicon atom, which does not correspond to the component (G) or (G-2) , <12 ′>, <15 ′> And the chemically amplified resist composition according to any one of < 16 ′>.
< 18 '>
The chemical amplification resist composition according to any one of <12 ′> to < 17 ′>, further comprising a crosslinking agent (C).
< 19 '>
<12 '>-< 18 '> The resist film formed with the chemically amplified resist composition in any one of.
The present invention relates to the above <1> to <11> and <12 ′> to < 19 ′>, and is described below including other matters for reference.
<12>
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) A chemically amplified resist composition comprising a compound having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid.

<13>
The chemical amplification resist composition according to <12>, wherein the compound (G) is a nitrogen-containing compound.

<14>
The chemical amplification resist composition according to <12> or <13>, wherein the molecular weight of the compound (G) is 500 or less.

<15>
The chemical amplification resist composition according to <13> or <14>, wherein the compound (G) is a compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.

<16>
The chemical amplification resist composition as described in <12> or <13>, wherein the compound (G) is a resin.

<17>
The compound (G) is a resin having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a basic group or a group whose basicity is increased by the action of an acid. The chemically amplified resist composition according to <16>.

<18>
Furthermore, a crosslinking agent (C) is contained, The pattern formation method in any one of <12>-<17> characterized by the above-mentioned.

<19>
A resist film formed from the chemically amplified resist composition according to any one of <12> to <18>.

<20>
A compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.

<21>
Resin (G) which has at least one of a fluorine atom and a silicon atom, has basicity or increases basicity by the action of an acid.

  According to the present invention, there is provided a pattern forming method and a chemically amplified negative resist composition capable of forming a pattern with a wide focus margin (DOF), small line width variation (LWR), excellent pattern shape, and reduced bridge defects. Can be provided.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

A pattern forming process necessary for carrying out the present invention includes the following steps.
(A) a step of forming a film of a chemically amplified resist composition;
(A) a step of exposing the film;
(C) developing with a developer containing an organic solvent;
A pattern forming method comprising:

  In the pattern forming method of the present invention, the organic solvent contained in the developer is at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Preferably there is.

  It is preferable that the pattern forming method of the present invention further includes a step of rinsing with (d) a rinsing solution.

  The rinsing liquid is preferably a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

  The pattern forming method of the present invention preferably includes (e) a heating step after (b) the exposure step.

  The pattern forming method of the present invention may further include (f) a step of developing using an aqueous alkaline developer.

To carry out the present invention,
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) a chemically amplified resist composition containing a compound having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid,
In addition, a developer containing an organic solvent is required.
In order to carry out the present invention, it is preferable to use a rinse solution containing an organic solvent.

The film formed in the present invention is
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) A film formed by applying a chemically amplified resist composition containing a compound having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid. .
Hereinafter, the resist composition of the present invention will be described.

[1] Resin (A)
The chemically amplified resist composition of the present invention forms a negative pattern by the pattern forming method of the present invention.
That is, in the resist film obtained from the chemically amplified resist composition of the present invention, the exposed portion is insoluble or hardly soluble due to the decrease in solubility in a developer containing an organic solvent by the action of an acid, and the unexposed portion is A negative pattern is formed by being soluble in a developer containing an organic solvent.

The resin (A) is preferably substantially insoluble in alkali.
Substantially insoluble in alkali means a coating film (film) obtained by dissolving only the resin (A) in a solvent such as butyl acetate and applying a composition having a solid content of 3.5% by mass on a silicon wafer. The film was formed on a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at room temperature (25 ° C.) measured using a QCM (quartz crystal microbalance) sensor or the like. It shows that the average dissolution rate (thickness reduction rate) when immersed for 1000 seconds is 1 nm / s or less, preferably 0.1 nm / s or less, whereby the organic solvent of the resist film in the unexposed area Solubility in a developer containing

The resin (A) may or may not contain a repeating unit having an acid group as long as it is substantially insoluble in alkali, but it is preferably not contained.
Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol substituted with an electron withdrawing group at the α-position (for example, hexafluoroisopropanol group, —C (CF ₃ ). ₂ OH).
When the resin (A) contains an acid group, the content of the repeating unit having an acid group in the resin (A) is preferably 10 mol% or less, and more preferably 5 mol% or less. When the resin (A) has a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.
Here, the electron withdrawing group is a substituent having a tendency to attract an electron, for example, a substituent having a tendency to attract an electron from an atom at a position close to the group in the molecule.
Specific examples of the electron withdrawing group include the same groups as those described for Z _ka1 in formula (KA-1) described later.

  The resin may not necessarily be soluble in the developer by itself if the film dissolves in a developer containing an organic solvent when a film is formed using a resist composition. For example, depending on the properties and contents of other components contained in the resist composition, a film formed using the resist composition may be dissolved in the developer.

  The resin (A) is generally synthesized by polymerizing a monomer having a partial structure to be polymerized by radical polymerization or the like, and has a repeating unit derived from the monomer having a partial structure to be polymerized. Examples of the partial structure to be polymerized include an ethylenically polymerizable partial structure.

  Hereinafter, each repeating unit that the resin (A) may have will be described in detail.

(A1) Repeating unit having acid-decomposable group Resin (A) is a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid, and the main chain or side chain of the resin, or the main chain and side Both chains have a repeating unit having a group that decomposes by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”). When a polar group is generated, the affinity with a developer containing an organic solvent is lowered, and insolubilization or poor solubility (negative conversion) proceeds.

The acid-decomposable group preferably has a structure in which a polar group is protected with a group that decomposes and leaves by the action of an acid.
The polar group is not particularly limited as long as it is a group that is insolubilized in a developer containing an organic solvent, but is preferably an acidic group such as a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonic acid group ( And a group that can be dissociated in an aqueous 2.38 mass% tetramethylammonium hydroxide solution, which has been conventionally used as a resist developer.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The repeating unit having an acid-decomposable group that can be contained in the resin (A) is preferably a repeating unit represented by the following general formula (AI).

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. An alkyl group, more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, more preferably a hydrogen atom, a methyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
Rx ₂ and Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, or a group formed by combining two or more of these, and has a total carbon number of 1 to 12. Are preferred. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.
Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 15 carbon atoms), a halogen atom, a hydroxyl group, and an alkoxy group. (C1-C4), a carboxyl group, an alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

Although the preferable specific example of the repeating unit which has an acid-decomposable group is shown below, this invention is not limited to this.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of R ₁₀ in formula (2-1) described later.

  The resin (A) is a resin having at least one of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) as the repeating unit represented by the general formula (AI). More preferably.

In general formulas (1) and (2),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₉ are the same as those described for R ₉ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent.
The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.
The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

Examples of the repeating unit represented by the general formula (1) include a repeating unit represented by the following general formula (1-a). In the formula, _{R 1} and _{R 2} have the same meanings as those in formula (1).

  The repeating unit represented by the general formula (2) is preferably a repeating unit represented by the following general formula (2-1).

In formula (2-1),
R < ₃ > -R < ₅ > is synonymous with the thing in General formula (2), respectively.
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group itself, or a linear or branched alkyl group or cycloalkyl group having at least one of them. An alkyl group having a hydroxyl group is preferable. More preferably, it is a branched alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.
The resin (A) may contain a plurality of repeating units having an acid-decomposable group.
The resin (A) is more preferably a resin having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) as the repeating unit represented by the general formula (AI). preferable. Moreover, in another form, it is more preferable that it is resin which has at least 2 types of repeating units represented by General formula (1) as a repeating unit represented by general formula (AI).
Moreover, the resist composition of this invention contains multiple types of resin (A), and the repeating unit which has the acid-decomposable group which this multiple resin (A) contains may mutually differ. For example, you may use together resin (A) which has a repeating unit represented by General formula (1), and resin (A) which has a repeating unit represented by General formula (2).
As a preferable combination when the resin (A) contains a plurality of repeating units containing an acid-decomposable group and when the plurality of resins (A) have repeating units containing a different acid-decomposable group, for example, The following can be mentioned. In the following formula, each R independently represents a hydrogen atom or a methyl group.

(A2) Repeating unit having alcoholic hydroxyl group The resin (A) may have a repeating unit (a2) having an alcoholic hydroxyl group in at least one of the main chain and the side chain. By containing such a unit, improvement in substrate adhesion can be expected. Moreover, when the resist composition of this invention contains the crosslinking agent mentioned later, it is preferable that resin (A) has a repeating unit (a2) which has an alcoholic hydroxyl group. Since the alcoholic hydroxyl group functions as a crosslinkable group, the hydroxyl group reacts with the crosslinking agent by the action of an acid, so that insolubility or poor solubility of the resist film in the developer containing the organic solvent is further promoted, and line width roughness ( This is because the effect of further improving the (LWR) performance occurs.
The alcoholic hydroxyl group in the present invention is a hydroxyl group bonded to a hydrocarbon group and is not limited as long as it is other than a hydroxyl group bonded directly on an aromatic ring (phenolic hydroxyl group). Those other than the hydroxyl group in the aliphatic alcohol in which the α-position is substituted with an electron-withdrawing group are preferable. In order to improve the reaction efficiency with the crosslinking agent (C), the hydroxyl group is substituted with a primary alcoholic hydroxyl group (a group in which the hydroxyl group has two hydrogen atoms apart from the hydroxyl group) or a hydroxyl group is substituted. It is preferably a secondary alcoholic hydroxyl group in which no other electron-withdrawing group is bonded to the carbon atom.
It is preferable to have 1-3 alcoholic hydroxyl groups per repeating unit (a2), and more preferably to have one or two.
Examples of such a repeating unit include a repeating unit represented by the general formula (2) or the general formula (3).

In the general formula (2), at least one of R _X and R represents a structure having an alcoholic hydroxyl group.
In the general formula (3), at least one of two R _X and R represents a structure having an alcoholic hydroxyl group. Two R _X may be the same or different.
Examples of the structure having an alcoholic hydroxyl group include a hydroxyalkyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms), a hydroxycycloalkyl group (preferably having 4 to 14 carbon atoms), and a hydroxyalkyl group. A substituted cycloalkyl group (preferably having a total carbon number of 5 to 20), an alkyl group substituted with a hydroxyalkoxy group (preferably a total of 3 to 15 carbon atoms), a cycloalkyl group substituted with a hydroxyalkoxy group (preferably total number 5-20) such as carbon and the like, preferably residues of primary alcohols as described _{above, - (CH 2) n-} OH (n is an integer of 1 or more, preferably an integer of 2 to 4) The structure represented is more preferred.
R _X is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent (preferably having 1 to 4 carbon atoms) or a cycloalkyl group which has a substituent (having 5 to 12 carbon atoms). Preferred). The alkyl group and cycloalkyl group are preferred substituents that have the R _X, a hydroxyl group and a halogen atom. Examples of the halogen atom of R _X, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. R _X is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a hydroxyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
R represents a hydrocarbon group which may have a hydroxyl group. The hydrocarbon group for R is preferably a saturated hydrocarbon, an alkyl group (preferably having 1 to 8 carbon atoms, more preferably 2 to 4 carbon atoms) or a monocyclic or polycyclic cyclic hydrocarbon group (preferably having 3 carbon atoms). To 20, for example, an alicyclic group described later). n ′ represents an integer of 0 to 2.

The repeating unit (a2) is preferably a repeating unit derived from an ester of acrylic acid that may be substituted at the α-position of the main chain (for example, Rx in the formula (2)), and corresponds to the formula (2). More preferably, it is derived from a monomer having the structure Moreover, it is preferable to have an alicyclic group in a unit. The alicyclic group may be a monocyclic or polycyclic structure, but a polycyclic structure is preferred from the viewpoint of etching resistance.
Specifically, as the alicyclic group, the monocyclic structure includes cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the polycyclic structure includes norbornyl, isobornyl, tricyclodecanyl, tetracyclododecanyl, Examples include hexacycloheptadecanyl, adamantyl, diamantyl, spirodecanyl, spiroundecanyl and the like. Of these, adamantyl, diamantyl and norbornyl structures are preferred.

Although the repeating unit (a2) is illustrated below, this invention is not limited to these. In specific examples, R ^X represents a hydrogen atom or a methyl group.

The repeating unit (a2) may have a structure in which at least one of the above-mentioned repeating unit (a1) and the following repeating units (a3) and (a4) has an alcoholic hydroxyl group. For example, the above-mentioned (a1) repeating unit having an acid-decomposable group may have an alcoholic hydroxyl group in the portion released by the action of an acid. It is presumed that the crosslinking efficiency can be optimized by containing such a repeating unit. Specifically, as such a structure, in the above-described general formula (AI), when the moiety of the atomic group -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) has a hydroxyl group, more specifically, In the repeating unit represented by the general formula (2-1), when R ₁₀ is a hydroxyl group, a linear or branched alkyl group having a hydroxyl group, or a cycloalkyl group having a hydroxyl group.

(A3) Repeating unit having nonpolar group The resin (A) preferably further has a repeating unit (a3) having a nonpolar group. Thus, elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. The repeating unit (a3) having a nonpolar group is preferably a repeating unit that does not contain a polar group (for example, the acid group, hydroxyl group, cyano group, etc.) in the repeating unit. A repeating unit having no lactone structure is preferred. Examples of such a repeating unit include a repeating unit represented by the general formula (4) or the general formula (5).

In the above general formula,
R ₅ represents a hydrocarbon group having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, a hydroxyl group, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms) independently of each other when a plurality of Ra are present. The alkyl group of Ra may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom. Examples of the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, particularly preferably a hydrogen atom or a methyl group.
n represents an integer of 0 to 2.

R ₅ preferably has at least one cyclic structure.
Examples of the hydrocarbon group for R ₅ include chain and branched hydrocarbon groups, monocyclic hydrocarbon groups, and polycyclic hydrocarbon groups. From the viewpoint of dry etching resistance, R ₅ preferably contains a monocyclic hydrocarbon group and a polycyclic hydrocarbon group, and more preferably contains a polycyclic hydrocarbon group.
R ₅ is preferably _-L 4 _-A 4 _- represents a group represented by (R _{4) n4.} L ₄ represents a single bond or a divalent hydrocarbon group, preferably a single bond, an alkylene group (preferably having 1 to 3 carbon atoms) or a cycloalkylene group (preferably having 5 to 7 carbon atoms), more preferably. It is a single bond. A ₄ represents an (n4 + 1) -valent hydrocarbon group (preferably having 3 to 30 carbon atoms, more preferably 3 to 14 carbon atoms, still more preferably 6 to 12 carbon atoms), and preferably a monocyclic or polycyclic aliphatic group. Represents a cyclic hydrocarbon group. n4 represents an integer of 0 to 5, preferably an integer of 0 to 3. R ₄ represents a hydrocarbon group, preferably an alkyl group (preferably having 1 to 3 carbon atoms) or a cycloalkyl group (preferably having 5 to 7 carbon atoms).

  Examples of chain and branched hydrocarbon groups include alkyl groups having 3 to 12 carbon atoms. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, and a phenyl group. A preferred monocyclic hydrocarbon group is a monocyclic saturated hydrocarbon group having 3 to 7 carbon atoms.

  The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group (for example, a bicyclohexyl group) and a bridged cyclic hydrocarbon group. Examples of the bridged cyclic hydrocarbon group include a bicyclic hydrocarbon group, a tricyclic hydrocarbon group, and a tetracyclic hydrocarbon group. The bridged cyclic hydrocarbon group also includes a condensed cyclic hydrocarbon group (for example, a group in which a plurality of 5- to 8-membered cycloalkane rings are condensed). Preferred examples of the bridged cyclic hydrocarbon group include a norbornyl group and an adamantyl group.

  These groups may further have a substituent, and preferred examples of the substituent include a halogen atom and an alkyl group. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and examples of the substituent that may further have a halogen atom and an alkyl group.

  Although the specific example of the repeating unit which has a nonpolar group is given below, this invention is not limited to these. In the formula, Ra represents a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Preferable substituents that the alkyl group of Ra may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

(A4) Repeating unit having a lactone structure The resin (A) may contain a repeating unit having a lactone structure.

  Any lactone structure can be used, but it is preferably a 5- to 7-membered ring lactone structure, and other ring structures are condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. Is preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17). By using this lactone structure, LWR and development defects are improved.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  The repeating unit having a lactone structure is preferably a repeating unit represented by the following general formula (AII ′).

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms). Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

  V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

  Specific examples of the repeating unit having a lactone structure are given below, but the present invention is not limited thereto.

  Particularly preferred repeating units having a lactone structure include the following repeating units. By selecting an optimal lactone structure, the pattern profile and the density dependency are improved.

  The repeating unit having a lactone structure preferably contains a unit represented by the following general formula (III).

In formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
When there are a plurality of Zs, each independently represents an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ₈ represents a monovalent organic group having a lactone structure.
n is the repeating number of the structure represented by —R ₀ —Z—, represents an integer of 1 to 5, and is preferably 1.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, Examples thereof include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acyloxy groups such as acetyloxy group and propionyloxy group.
R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Preferable chain alkylene group in R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and is represented by general formulas (LC1-1) to (LC1-17) as specific examples. Among them, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-17) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) as is more preferable.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (III) are shown below, but the present invention is not limited thereto.
In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetyloxymethyl group.

  The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (III-1).

In general formula (III-1),
R ₇ , A, R ₀ , Z, and n are as defined in the general formula (III).
R ₉ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group when there are a plurality of R _{9 s, and} when there are a plurality of R _{9 s} , May be formed.

X represents an alkylene group, an oxygen atom, or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 0 or 1.

The alkyl group for R ₉ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxyl group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

  Examples of the alkylene group for X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

When m is 1 or more, at least one R ₉ is preferably substituted at the α-position or β-position of the lactone carbonyl group, particularly preferably at the α-position.

  Specific examples of the repeating unit having a group having a lactone structure represented by formula (III-1) are shown below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetyloxymethyl group.

  In order to enhance the effect of the present invention, two or more lactone repeating units can be used in combination. When using together, it is also preferable to select and use 2 or more types from the lactone repeating unit in which n is 1 in general formula (III).

Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.
Resin (A) may be a resin formed by mixing two or more kinds of resins, and has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required characteristic of resist. For the purpose of adjusting heat resistance, sensitivity, etc., for example, a resin in which a resin containing a repeating unit (a2) and a resin containing a repeating unit (a3) are mixed can be used.
Moreover, it is also preferable to mix and use resin containing a repeating unit (a1) and resin which does not contain a repeating unit (a1).
When the composition of the present invention is for ArF exposure, the resin (A) used in the composition of the present invention has substantially no aromatic group from the viewpoint of transparency to ArF light (specifically, The ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In addition, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

In the present invention, the content of each repeating unit is as follows. Each repeating unit may contain a plurality of types, and the following contents are total amounts when a plurality of types are included.
As for content of the repeating unit (a1) which has an acid-decomposable group, 20-70 mol% is preferable with respect to all the repeating units which comprise resin (A), More preferably, it is 30-60 mol%.
When the resin (A) contains the repeating unit (a2) having an alcoholic hydroxyl group, the content thereof is generally 10 to 80 mol%, preferably 10 with respect to all the repeating units constituting the resin (A). ~ 60 mol%.
When the repeating unit (a3) having a nonpolar group is contained, the content thereof is generally 20 to 80 mol%, preferably 30 to 60 mol%, based on all repeating units constituting the resin (A). .
When the repeating unit (a4) having a lactone is contained, the content thereof is preferably 15 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 30 to 50 mol%, based on all repeating units in the resin. is there.

  In addition, in the resin (A), the content molar ratio of each repeating unit is the resist dry etching resistance, the developer suitability, the substrate adhesion, the resist profile, and the general required performance of the resist, resolving power, heat resistance, It can be set as appropriate to adjust the sensitivity and the like.

  Resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. For the detailed synthesis method and purification method, the method described in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd. can be used.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15 in terms of polystyrene by GPC method. 1,000, particularly preferably 3,000 to 10,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased and film forming property is deteriorated. Can be prevented.
The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 1.7. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.

In the resist composition of the present invention, the blending amount of the resin (A) in the whole composition is preferably 65 to 97% by mass, more preferably 75 to 95% by mass in the total solid content.
In the present invention, the resin (A) may be used alone or in combination.

[2] Compound (B) that generates an acid upon irradiation with an actinic ray or radiation
The resist composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro resist Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20. Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group). Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, and preferably includes an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. it can.

  The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), ant Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-C15) can further be mentioned as a substituent.

  As the aromatic sulfonate anion, an anion that generates an aryl sulfonic acid represented by the following formula (BI) is also preferable.

In formula (BI),
Ar represents an aromatic ring and may further have a substituent in addition to the sulfonic acid group and the A group.
p represents an integer of 0 or more.
A represents a group having a hydrocarbon group.
When p is 2 or more, the plurality of A groups may be the same or different.

General formula (BI) will be described in more detail.
As the aromatic ring represented by Ar, an aromatic ring having 6 to 30 carbon atoms is preferable.
Specifically, benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, Triphenylene ring, indene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthri Down ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, and the like, a benzene ring, a naphthalene ring, an anthracene ring are preferred, a benzene ring is more preferable.

  Examples of the substituent that the aromatic ring may have other than the sulfonic acid group and the A group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl group, cyano group, nitro group, carboxyl group, and the like. Can be mentioned. Moreover, when it has two or more substituents, at least two substituents may be bonded to each other to form a ring.

Examples of the group having a hydrocarbon group represented by A include an alkoxy group such as a methoxy group, an ethoxy group, and a tert-butoxy group, an aryloxy group such as a phenoxy group and a p-tolyloxy group, a methylthioxy group, and an ethylthioxy group. , Alkylthioxy groups such as tert-butylthioxy group, arylthioxy groups such as phenylthioxy group, p-tolylthioxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, methyl group, Straight chain alkyl groups such as ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, 2-ethylhexyl group and branched alkyl groups, alkenyl groups such as vinyl group, propenyl group, hexenyl group, acetylene group, propynyl Group, hexynyl group, etc. Group, aryl groups such as phenyl and tolyl groups, a benzoyl group, an acetyl group, and the like acyl groups such as tolyl group.
Examples of the hydrocarbon group in the group having a hydrocarbon group represented by A include an acyclic hydrocarbon group or a cyclic aliphatic group, and the hydrocarbon group has 3 or more carbon atoms. preferable.
As the A group, the carbon atom adjacent to Ar is preferably a tertiary or quaternary carbon atom.
As the acyclic hydrocarbon group in the A group, isopropyl group, t-butyl group, t-pentyl group, neopentyl group, s-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group, 2-ethylhexyl group Groups and the like. The upper limit of the number of carbon atoms of the acyclic hydrocarbon group is preferably 12 or less, more preferably 10 or less.

  Examples of the cycloaliphatic group in the A group include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, Examples thereof include a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group, which may have a substituent. The upper limit of the carbon number of the cycloaliphatic group is preferably 15 or less, more preferably 12 or less.

When the acyclic hydrocarbon group or the cyclic aliphatic group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a methoxy group, and an ethoxy group. Group, alkoxy group such as tert-butoxy group, aryloxy group such as phenoxy group, p-tolyloxy group, alkylthioxy group such as methylthioxy group, ethylthioxy group, tert-butylthioxy group, phenylthioxy group, p-tolyloxy group Arylthiooxy group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, etc., acetoxy group, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, 2- Linear alkyl groups such as ethylhexyl group, branched alkyl groups, A cyclic alkyl group such as a rohexyl group, an alkenyl group such as a vinyl group, a propenyl group and a hexenyl group, an alkynyl group such as an acetylene group, a propynyl group and a hexynyl group, an aryl group such as a phenyl group and a tolyl group, a hydroxy group, a carboxy group, Examples include a sulfonic acid group, a carbonyl group, and a cyano group.
Specific examples of the group having a cyclic aliphatic group or an acyclic hydrocarbon group as A include the following.

  Among the above, the following structures are more preferable from the viewpoint of suppressing acid diffusion.

  p represents an integer of 0 or more, and the upper limit is not particularly limited as long as it is a chemically possible number. From the viewpoint of suppressing acid diffusion, p is usually 0 to 5, preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

From the viewpoint of suppressing acid diffusion, the A group preferably substitutes at least one o-position of the sulfonic acid group, and more preferably has a structure in which two o-positions are substituted.
In one embodiment, the acid generator (B) of the present invention is a compound that generates an acid represented by the following general formula (BII).

In the formula, A is the same as A in the general formula (BI), and two A may be the same or different. R _{1 to} R ₃ each independently represents a hydrogen atom, a group having a hydrocarbon group, a halogen atom, a hydroxyl group, a cyano group, or a nitro group. Specific examples of the group having a hydrocarbon group include the same groups as those exemplified above.

  Moreover, the anion which produces the acid represented with the following general formula (I) as a preferable sulfonate anion can also be mentioned.

In the formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represents a group selected from a hydrogen atom, a fluorine atom and an alkyl group, and when there are a plurality of R ¹ and R ² , they may be the same or different. L represents a divalent linking group, and when there are a plurality of L, L may be the same or different. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (I) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2 CF} 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, CH ₂ CH ₂ C ₄ F ₉ is mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specific examples of the alkyl group having a substituent for R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C ₇ F _{15. , C 8 F 17, CH 2} CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ can be mentioned, among which CF ₃ is preferable.
R ¹ and R ² are preferably a fluorine atom or CF ₃ .

y is preferably 0 to 4, and more preferably 0. x is preferably from 1 to 8, and preferably from 1 to 4. z is preferably 0 to 8, particularly preferably 0 to 4. The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred. Among these, —COO—, —OCO—, —CO—, —O—, and —SO ₂ — are preferable, and —COO—, —OCO—, and —SO ₂ — are more preferable.

  The cyclic organic group of A is not particularly limited, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only those having an aromatic attribute but also those having no aromatic attribute).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in the PEB (post-exposure heating) step. It is preferable from the viewpoint of improving MEEF (mask error enhancement factor) because diffusibility in the film can be suppressed.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

  Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, and a piperidine ring. Of these, those derived from a furan ring, a thiophene ring, a pyridine ring and a piperidine ring are preferred.

  In addition, examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) even if the resin (A) described above has. Lactone structure.

  The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear or branched and preferably have 1 to 12 carbon atoms), a cycloalkyl group. (A monocyclic ring, a polycyclic ring or a spiro ring may be used, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane Group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom as in the aromatic sulfonate anion, Examples thereof include an alkyl group, a cycloalkyl group, an alkoxy group, and an alkylthio group.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.
The two alkyl groups in the bis (alkylsulfonyl) imide anion may be the same or different. Similarly, the plurality of alkyl groups in the tris (alkylsulfonyl) methide anion may be the same or different.
In particular, examples of the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion include anions represented by the following general formula (A3) or (A4).

In general formulas (A3) and (A4),
Y is an alkylene group substituted with at least one fluorine atom, preferably an alkylene group having 2 to 4 carbon atoms. An oxygen atom may be contained in the alkylene chain. A perfluoroalkylene group having 2 to 4 carbon atoms is more preferable, and a tetrafluoroethylene group, a hexafluoropropylene group, and an octafluorobutylene group are most preferable.
R in the formula (A4) represents an alkyl group or a cycloalkyl group. In addition, the alkylene chain in the alkyl group or cycloalkyl group may contain an oxygen atom.
Specific examples of the compound having an anion represented by the general formula (A3) or (A4) include those described in JP-A-2005-221721.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) include corresponding groups in the compounds (ZI-1) to (ZI-4) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by (ZI), the structures attached to at least one of _R 201 _{to R 203} of another compound represented by formula (ZI) It may be a compound.

  More preferred (ZI) components include compounds (ZI-1) to (ZI-4) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

Preferred examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms.

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In General Formula (ZI-3), R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, a phenylthio group, or a halogen atom. R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom , An ester bond and an amide bond may be included.
Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

Zc ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 8 carbon atoms.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. And a cyclic alkoxy group having 3 to 8 carbon atoms. The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
When R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene Group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of carbon numbers of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as those in R _{1c to} R _7c, such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, An alkoxycarbonylmethyl group is more preferred.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylalkyl group include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms, preferably 1 to 1 carbon atom. 5 linear alkyl groups (for example, a methyl group and an ethyl group) can be exemplified.
The allyl group is not particularly limited, but is preferably an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group.
Although there is no restriction | limiting in particular as a vinyl group, It is preferable that it is a vinyl group substituted by the unsubstituted or monocyclic or polycyclic cycloalkyl group.
As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

  The compound (ZI-4) is a compound represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 10.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.
Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include monocyclic or polycyclic cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms), and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclodecanyl, tetracyclodecanyl, adamantyl and the like, particularly cyclopropyl, cyclopentyl, cyclohexyl, cyclo Heptyl and cyclooctyl are preferred.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.

The alkoxycarbonyl group for R ₁₃ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an i-propoxycarbonyl group. N-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyl Examples thereof include an oxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). Examples thereof include a polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
The monocyclic or polycyclic cycloalkyloxy group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, and a monocyclic ring It is preferable to have a cycloalkyl group. Monocyclic cycloalkyloxy group having 7 or more carbon atoms in total is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t -Alkyl group such as butyl group, iso-amyl group, hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, methoxy group, ethoxy group, hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, butoxy group, methoxy Monocyclic cycloalkyloxy groups having substituents such as carbonyl groups, alkoxycarbonyl groups such as ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, acyloxy groups such as acetoxy groups and butyryloxy groups, and carboxy groups And the total number of carbon atoms combined with an arbitrary substituent on the cycloalkyl group is 7 or more.
Examples of the polycyclic cycloalkyloxy group having 7 or more total carbon atoms include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl group is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl group is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group which may have the above-mentioned substituent is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituent is 7 or more. Represents things. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.
Examples of the alkoxy group having a polycyclic cycloalkyl group having a total carbon number of 7 or more include a norbornyl methoxy group, a norbornyl ethoxy group, a tricyclodecanyl methoxy group, a tricyclodecanyl ethoxy group, a tetracyclo group. A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantyl methoxy group, an adamantyl ethoxy group, etc. are mentioned, A norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.
The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these alkylsulfonyl groups and cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

Examples of the substituent that each group of R ₁₃ , R ₁₄ , and R ₁₅ may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, and an alkoxy group. Examples thereof include an alkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.
Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group.
Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.
Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include straight-chain, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy group.

As the ring structure that two R ₁₅ may be bonded to each other, a 5- or 6-membered ring, particularly preferably a 5-membered ring (that is, a 5-membered ring together with the sulfur atom in the general formula (ZI-4) (that is, A group that forms a tetrahydrothiophene ring) is particularly preferred. Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc. There may be a plurality of substituents for the ring structure, and they may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or these A polycyclic fused ring formed by combining two or more rings may be formed. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
The alkyl group, cycloalkyl group, alkoxy group, or alkoxycarbonyl group of R _13, the alkyl group, cycloalkyl group, alkoxy group, alkylsulfonyl group, and cycloalkylsulfonyl group of R ₁₄ may be substituted as described above. The substituent is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

  Below, the preferable specific example of the cation in the compound represented by general formula (ZI-4) is shown.

In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.

The aryl group for R _{204 to} R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.

The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ preferably include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group. Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things can be mentioned.
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethynylene group, propenylene group, butenylene group, etc.), and the arylene group of A is an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable. Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group that contains a monovalent fluorine atom or an imido acid that is substituted with a group containing a fluorine atom, and even more preferably, a fluorinated compound It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid, or a fluorinated substituted imido acid whose pKa of the generated acid is −1 or less, and the sensitivity is improved.

  Among acid generators, particularly preferred examples are given below.

  An acid generator can be used individually by 1 type or in combination of 2 or more types. The content of the acid generator in the resist composition is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, and even more preferably from 1 to 20% by mass, based on the total solid content of the resist composition. 7% by mass.

[3] Compound (G) having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid
In general, when a resist film formed using a chemically amplified resist composition containing a compound that generates an acid by light (photoacid generator) is exposed, the surface layer portion of the resist film is compared with the inside. The degree of exposure is high, the concentration of the generated acid is high, and the reaction tends to progress more. If negative development is performed on such an exposure film, the resulting pattern has a T-top shape or a bridge defect.
However, the resist composition of the present invention contains a compound (G) having at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid.
Since the compound (G) has at least one of a fluorine atom and a silicon atom, the surface free energy is low as compared with the case where the compound (G) does not have these atoms, and the compound (G) is likely to be unevenly distributed in the surface layer portion of the resist film. .
Therefore, when a resist film containing such a compound (G) is exposed, a compound having basicity or a compound having increased basicity by the action of an acid is present in a high concentration in the surface layer portion of the resist film. The excess acid generated in the surface layer of the exposed area can be captured. That is, the acid concentration distribution in the thickness direction of the exposed portion of the resist film can be made uniform. As a result, the acid-catalyzed insolubilization or insolubilization reaction of the resist film in the developer containing the organic solvent can be performed more uniformly in the thickness direction of the resist film. And a defect such as a bridge defect can be suppressed.

  Compound (G) is composed of “compound (G-1) having at least one of a fluorine atom and a silicon atom and having basicity” and “base having at least one of a fluorine atom and a silicon atom and an acid. When the compound (G-2) is used, more basic substances are present in regions where the concentration of acid generated in the exposed area is higher. Therefore, the acid-base neutralization reaction is further promoted. Therefore, the acid concentration distribution in the thickness direction of the exposed portion of the resist film can be made more uniform when the compound (G-2) is used than when the compound (G-1) is used. In this respect, the compound (G) is more preferably the compound (G-2).

The compound (G) is preferably a nitrogen-containing compound.
Here, when the compound (G) is a compound having at least one of a fluorine atom and a silicon atom and having basicity, in order for the compound (G) to have sufficient basicity, the compound (G) may be It is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (particularly a fluorine atom), etc.) is not directly connected, and all the atoms adjacent to the nitrogen atom are hydrogen atoms or carbon atoms. It is more preferable.
In addition, when the compound (G) has at least one of a fluorine atom and a silicon atom and the basicity is increased by the action of an acid, the compound having increased basicity by the action of an acid has sufficient basicity. In order to have it, an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (especially a fluorine atom), etc.) is directly connected to a nitrogen atom of a compound whose basicity has been increased by the action of an acid. It is preferred that all atoms adjacent to the nitrogen atom are hydrogen atoms or carbon atoms.

  In addition, in order for compound (G) to express the said effect | action reliably, it is preferable not to be accompanied by the change which the chemical structure does not intend by irradiation of actinic light or a radiation. In other words, it is preferable that the compound (G) does not have photosensitivity (non-photosensitivity).

  Hereinafter, the compound (G) is divided into “a compound (G-1) having at least one of a fluorine atom and a silicon atom and having basicity”, and “an action of an acid having at least one of a fluorine atom and a silicon atom. And the compound (G-2) in which the basicity is increased.

[3-1] A compound having at least one of a fluorine atom and a silicon atom and having basicity (G-1)
The compound (G-1) has at least one of a fluorine atom and a silicon atom and is not particularly limited as long as it is a basic compound. For example, the compound (G-1) has at least one of a fluorine atom and a silicon atom, and The basic compound which has either of the structures shown by general formula (A)-(E) can be mentioned.

In general formula (A), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably Is a C6-C20) or heteroaryl group.
In general formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represents an alkyl group or a cycloalkyl group.
In the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.
In the structures represented by the general formulas (B) to (D), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.
In the structure represented by the general formula (E), two or more of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , a bond from a carbon atom, and a bond from a nitrogen atom are bonded to each other, A ring may be formed.

In the general formula (A), the alkyl group of R ²⁰¹ and R ²⁰² is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, n -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, i-propyl group, i-butyl group, sec-butyl group, t -A butyl group, t-dodecyl group, etc. can be mentioned.
The cycloalkyl group represented by R ²⁰¹ and R ²⁰² is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Among the alkyl groups and cycloalkyl groups represented by R ²⁰¹ and R ^202, a linear alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms are preferable.

The aryl group of R ²⁰¹ and R ²⁰² is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthryl group. It is done.
The heteroaryl group of R ²⁰¹ and R ²⁰² is a group containing one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the aryl group as described above. For example, a pyridyl group, an imidazolyl group, a morpholinyl group , Piperidinyl group, pyrrolidinyl group and the like.

The alkyl group, cycloalkyl group, aryl group, and heteroaryl group of R ²⁰¹ and R ²⁰² may further have a substituent. Examples of such a substituent include a halogen atom, a hydroxyl group, an amino group, and a carboxyl group. Cyano group, nitro group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkylcarbonyloxy group, arylcarbonyloxy group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and the like.

Examples of the alkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. And a linear or branched alkyl group having 1 to 12 carbon atoms such as 1-methylpropyl group and t-butyl group.
Examples of the cycloalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group as a substituent that R ²⁰¹ and R ²⁰² may further include an aryl group having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group.

Examples of the alkoxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a 2-methylpropoxy group. , 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group and the like, such as a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms.

Examples of the aryloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include an aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group and a naphthyloxy group. .

Examples of the acyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an acetyl group, a propionyl group, an n-butanoyl group, an i-butanoyl group, an n-heptanoyl group, and 2-methylbutanoyl. And a linear or branched acyl group having 2 to 12 carbon atoms such as a group, 1-methylbutanoyl group, t-heptanoyl group, and the like.

Examples of the arylcarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an arylcarbonyl group having 6 to 10 carbon atoms such as a phenylcarbonyl group and a naphthylcarbonyl group. .

Examples of the alkoxyalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, and a 1-ethoxyethyl group. And a straight-chain, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as 2-ethoxyethyl group.

Examples of the aryloxyalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a carbon number of 7 such as a phenyloxymethyl group, a phenyloxyethyl group, a naphthyloxymethyl group, a naphthyloxyethyl group, and the like. -12 aryloxyalkyl groups and the like can be mentioned.

Examples of the alkylcarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, C2-C21 straight chain such as n-butylcarbonyloxy group, 2-methylpropylcarbonyloxy group, 1-methylpropylcarbonyloxy group, t-butylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group , Branched, or cyclic alkylcarbonyloxy groups.

Examples of the arylcarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include an arylcarbonyloxy group having 7 to 11 carbon atoms such as a phenylcarbonyloxy group and a naphthylcarbonyloxy group. Can be mentioned.

Examples of the alkoxycarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group. A linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl, etc. Etc.

Examples of the aryloxycarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an aryloxycarbonyl group having 7 to 11 carbon atoms such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group. Can be mentioned.

Examples of the alkoxycarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, List linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy, etc. Can do.

Examples of the aryloxycarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include aryloxycarbonyl having 7 to 11 carbon atoms such as a phenyloxycarbonyloxy group and a naphthyloxycarbonyloxy group. An oxy group etc. can be mentioned.

As the compound (G-1) having the structure represented by the general formula (A),
(A1) A structure represented by the general formula (A) (wherein R ²⁰¹ and R ²⁰² do not include any of a fluorine atom and a silicon atom) and “fluorine positioned outside the structure represented by the general formula (A)” A compound having “a group having at least one of an atom and a silicon atom”;
(A2) The structure represented by the general formula (A) (provided that at least one of R ²⁰¹ and R ²⁰² is an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, which may have a substituent). A compound having one or more hydrogen atoms in which the fluorine atom or a group having a silicon atom is substituted);
(A3) The structure represented by the general formula (A) (provided that at least one of R ²⁰¹ and R ²⁰² is an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group, which may have a substituent). One or more hydrogen atoms is a fluorine atom or a group formed by replacing a silicon atom-containing group) and “at least one of a fluorine atom and a silicon atom located outside the structure represented by the general formula (A)” A compound having a “group having one”;
Can be mentioned.

In the above (A1) and (A3), as the “group having at least one of a fluorine atom and a silicon atom” located outside the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² further have Preferred examples of the above-described specific examples (excluding halogen atoms and hydroxyl groups) as preferred substituents include groups in which one or more hydrogen atoms are replaced by fluorine atoms or groups having silicon atoms. be able to.
Here, the group having a silicon atom is not particularly limited as long as it is a group containing at least one silicon atom, and examples thereof include a silyl group, a silyloxy group, and a group having a siloxane bond. The group having a silicon atom is represented by an alkylsilyl structure or a cyclic siloxane structure (for example, general formulas (CS-1) to (CS-3) to be described later) that the resin (G) to be described later may have. Group). These groups may further have a substituent, and specific examples of such a substituent are the same as the specific examples of the substituent which R ²⁰¹ and R ²⁰² may further have.
Specific examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group.

The compound (G-1) having a structure represented by the general formulas (B) to (D) includes a structure represented by the general formulas (B) to (D) and a group having at least one of a fluorine atom and a silicon atom. (For example, in the specific examples given above as substituents that R ²⁰¹ and R ²⁰² may further have (except for a halogen atom and a hydroxyl group), one or more hydrogen atoms are fluorine atoms or silicon And a compound having a group substituted by a group having an atom).
Here, specific examples of the group having a silicon atom are the same as those described above.

In General Formula (E), specific examples of the alkyl group and cycloalkyl group of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ are the same as the specific examples of the alkyl group and cycloalkyl group of R ²⁰¹ and R ²⁰² , respectively. is there.
The alkyl group and cycloalkyl group of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may further have a substituent, and specific examples of such a substituent are further included in R ²⁰¹ and R ^202. The same as the above specific examples of the substituents that may be present.

As the compound (G-1) having the structure represented by the general formula (E),
(E1) A structure represented by the general formula (E) (wherein R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ do not include any of a fluorine atom and a silicon atom), and a structure represented by the general formula (E) A compound having "a group having at least one of a fluorine atom and a silicon atom" located outside the structure;
(E2) A structure represented by the general formula (E) (provided that at least one of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may have a substituent, 1 in an alkyl group or a cycloalkyl group) A compound having two or more hydrogen atoms replaced with a fluorine atom or a group having a silicon atom);
(E3) A structure represented by the general formula (E) (provided that at least one of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may have a substituent, 1 in an alkyl group or a cycloalkyl group) And at least one of a fluorine atom and a silicon atom located outside the structure represented by the general formula (E), wherein two or more hydrogen atoms are a fluorine atom or a group formed by replacing a group having a silicon atom) A compound having a group having:
Can be mentioned.

In the above (E1) and (E3), as the “group having at least one of a fluorine atom and a silicon atom” located outside the structure represented by the general formula (E), R ²⁰¹ and R ²⁰² further have Preferred examples of the above-described specific examples (excluding halogen atoms and hydroxyl groups) as preferred substituents include groups in which one or more hydrogen atoms are replaced by fluorine atoms or groups having silicon atoms. be able to.
Here, specific examples of the group having a silicon atom are the same as those described above.

In the structures represented by the general formulas (A) to (E), a bond from a carbon atom and / or a nitrogen atom is connected to another atom constituting the compound (G-1).
Further, as described above, in the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring, and are represented by the general formulas (B) to (D). In the structure represented by formula (E), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring. , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.

Examples of the ring include aromatic or non-aromatic nitrogen-containing heterocycles. As such a nitrogen-containing heterocyclic ring, a 3-10 membered ring can be mentioned, It is preferable that it is a 4-8 membered ring, and it is more preferable that it is a 5 or 6 membered ring. Such a ring may further have a substituent, and specific examples thereof are the same as the specific examples described above as substituents which R ²⁰¹ and R ²⁰² may further have.

In other words, preferred examples of the compound (G-1) include compounds having a nitrogen-containing heterocycle, and the heterocycle substituted with a fluorine atom or a group containing a fluorine atom or a silicon atom. be able to. As the group containing a fluorine atom or a silicon atom, one or more hydrogen atoms in the above specific examples (excluding a halogen atom and a hydroxyl group) listed as substituents that R ²⁰¹ and R ²⁰² may further have Is a group formed by replacing with a fluorine atom or a group having the above silicon atom.
Preferable examples of the nitrogen-containing heterocycle include a pyrrole ring, a pyridine ring, and a pyrimidine ring.

When the compound (G-1) is a low-molecular compound (described in detail later), in the structures represented by the general formulas (A) to (E), a bond from a carbon atom and / or a nitrogen atom is Each of them is preferably bonded to a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, and specific examples of these groups are the same as those described for R ²⁰¹ and R ²⁰² .

[3-2] Compound (G-2) having at least one of a fluorine atom and a silicon atom and having increased basicity by the action of an acid
The compound (G-2) is not particularly limited as long as it has at least one of a fluorine atom and a silicon atom and the basicity is increased by the action of an acid. For example, at least one of a fluorine atom and a silicon atom, A compound having a carbamate group having a protecting group can be given.
Such a protecting group constituting the carbamate group is preferably a group represented by the following general formula (P) (the group represented by the general formula (P) is a bond represented by the symbol *). It is bonded to the nitrogen atom at the site).

In general formula (P):
Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Specific examples of the alkyl group, cycloalkyl group and aryl group of Rb ₁ , Rb ₂ and Rb ₃ are the alkyl group, cycloalkyl group and aryl group of R ²⁰¹ and R ^{202 in} the group represented by the general formula (P). This is the same as the above-described specific example.
Specific examples of aralkyl groups of Rb ₁ , Rb ₂ and Rb ₃ are preferably aralkyl groups having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, etc. Can do.
Rb ₁ , Rb ₂ and Rb ₃ are preferably a linear or branched alkyl group, cycloalkyl group or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
The ring formed by combining two members out of Rb _{1 to} Rb ₃ is preferably a cycloalkyl group (monocyclic or polycyclic), and more specifically, a monocyclic cyclohexane such as a cyclopentyl group or a cyclohexyl group. A polycyclic cycloalkyl group such as an alkyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
Rb ₁ , Rb ₂ and Rb ₃ may further have a substituent. Examples of such a substituent include a halogen atom (such as a fluorine atom), a hydroxyl group, a nitro group, a cyano group, a carboxy group, and a carbonyl group. Group, cycloalkyl group (preferably 3 to 10 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 20 carbon atoms) , An acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 20 carbon atoms), an aminoacyl group (preferably 2 to 10 carbon atoms), a group having a silicon atom (specific examples are compounds ( And the like described in G-1). As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10).
When _{two of} Rb ₁ , Rb ₂ and Rb ₃ are both hydrogen atoms, the remaining one is preferably an aryl group, and examples of the aryl group include a phenyl group and a naphthyl group. .

  Compound (G-2) can also be constituted by replacing at least one group connected to the nitrogen atom of compound (G-1) with a group represented by formula (P).

  Although it does not specifically limit as a compound (G-2), As a particularly preferable form, the compound represented by the following general formula (1) which has group represented by the said general formula (P) is mentioned. The compound represented by the following general formula (1) has at least one of a fluorine atom and a silicon atom in a portion other than the group represented by the general formula (P) (protecting group constituting the carbamate group). Therefore, the compound (compound with increased basicity) obtained by the action of an acid on the compound represented by the general formula (1) has at least one of a fluorine atom and a silicon atom. As a result, even in the post-exposure heating step (PEB) described later, the compound with increased basicity is present in a desired position without diffusing in the internal direction of the resist film. It is possible to more reliably “catch the generated excess acid”, and to make the acid concentration distribution in the thickness direction of the exposed portion of the resist film more uniform.

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, two Rc and two Rf may be the same or different, and two Rc may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.

_Ra, alkyl groups as Rb 1, Rb ₂ and Rb _3, cycloalkyl group, specific examples of the aryl group or aralkyl group, the alkyl group of _Rb 1, Rb ₂ and Rb ₃ of the general formula (P), cycloalkyl This is the same as the specific examples of the group, aryl group or aralkyl group.

Rc is preferably a divalent linking group having 2 to 12 carbon atoms (more preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), such as an alkylene group, a phenylene group, an ether group, Examples include an ester group, an amide group, and a group formed by combining two or more of these.
The organic group as Rf is preferably an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
Specific examples of the alkyl group, cycloalkyl group, aryl group or heteroaryl group as Rf are the same as the specific examples of the cycloalkyl group, aryl group or heteroaryl group as R ²⁰¹ and R ^{202 in} the general formula (A). It is.

Ra, Rb ₁ , Rb ₂ , Rb ₃ , Rc and Rf may each further have a substituent, and specific examples of such a substituent include Rb ₁ , Rb of the above general formula (P). _This is the same as the specific examples of the substituent that ₂ and Rb ₃ may further have.

When the organic group as Rf contains a fluorine atom or a silicon atom, Rf is preferably a group formed by replacing one or more hydrogen atoms in the organic group with a fluorine atom or a group having a silicon atom. . Here, specific examples of the group having a silicon atom are the same as the specific examples of the group having a silicon atom described in the compound (G-1).
As Rf when the organic group as Rf contains a fluorine atom or a silicon atom, for example, an alkyl group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is particularly preferable. And a perfluoroalkyl group such as a perfluoropropyl group and a perfluorobutyl group.

Examples of the nitrogen-containing heterocycle formed by bonding Ra and Rc or Rc to each other include aromatic or non-aromatic nitrogen-containing heterocycles (preferably having 3 to 20 carbon atoms). Examples of such nitrogen-containing heterocycle include pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine. , Homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benz Imidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4. 0] deck-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, Include a ring corresponding to the heterocyclic compounds such as 5,9-triazacyclododecane. These rings may further have one or more substituents, and specific examples of such substituents include Rb ₁ , Rb ₂ and Rb _{3 in the} general formula (P). Is the same as the specific examples of the substituent which may further have.

The ring formed by combining two of Rb _{1 to} Rb ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

The compound (G) may be either a low molecular compound or a resin (polymer compound).
Compared to the resin, the low molecular weight compound diffuses to some extent in the post-exposure heating step (PEB), so that it is considered that the acid is captured more uniformly. For that reason, LWR can be more reliably reduced by using a low molecular compound as the compound (G).
On the other hand, compared to low molecular weight compounds, the resin is less likely to diffuse in the internal direction of the resist film even in the post-exposure heating step (PEB). It is thought that it can be captured. For that reason, bridge defects can be more reliably reduced by using a resin as the compound (G).
When the compound (G) is a low molecular compound, the molecular weight is usually 500 or less, preferably 150 to 500, and more preferably 250 to 500.

Moreover, a compound (G-2) is compoundable by the method as described in Protective Groups in Organic Synthesis 4th edition etc. from an amine, for example. For example, the compound represented by the general formula (1) is preferably obtained by allowing a dicarbonate or haloformate to act on an amine as shown in the following scheme. In the formula, X represents a halogen atom. _{Ra, Rb 1, Rb 2,} Rb 3, Rc, Rf , respectively, the same meanings as _{Ra, Rb 1, Rb 2,} Rb 3, Rc, Rf in the general formula (1).

  Specific examples of the low molecular weight compounds (G-1) and (G-2) are listed below, but the present invention is not limited thereto.

When the compound (G) is a resin (hereinafter, such a resin is also referred to as a resin (G)), at least one of a fluorine atom and a silicon atom may be contained in the main chain of the resin, and the side chain It may be included.
Since the resin (G) also has the same function as the hydrophobic resin (E) described later, it is considered effective for reducing development defects resulting from immersion exposure.

When the resin (G) contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to have a group.
The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
The cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The cycloalkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  Preferable examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom include groups represented by the following general formulas (F2) to (F4).

In the general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. These alkyl groups preferably have 1 to 4 carbon atoms.

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms.
R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

  Examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2- Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2, Examples include 3,3-tetrafluorocyclobutyl group and perfluorocyclohexyl group. Among these, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group is more preferable, and a hexafluoroisopropyl group or More preferred is a heptafluoroisopropyl group.

Examples of the group represented by the general formula (F4), for _{example, -C (CF 3) 2 OH} , -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, and -CH (CF ₃ ) OH. Of these, -C _{(CF 3)} 2 OH is particularly preferred.

Specific examples of the repeating unit containing a fluorine atom are shown below.
In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

  When the resin (G) contains a silicon atom, this resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

  Preferable examples of the alkylsilyl structure and the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3), R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group or a cycloalkyl group. This alkyl group preferably has 1 to 20 carbon atoms. This cycloalkyl group preferably has 3 to 20 carbon atoms.

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether group, a carbonyl group, an ester bond, an amide bond, a urethane bond, a urea bond, or a combination thereof.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Below, the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

As resin (G),
A resin (Ga) having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a basic group or a group whose basicity is increased by the action of an acid; and at least one of a fluorine atom and a silicon atom Resin (Gb) having one repeating unit having a basic group or a group whose basicity is increased by the action of an acid
Can be preferably mentioned.

  Specific examples of the repeating unit having at least one of a fluorine atom and a silicon atom in the resin (Ga) include those listed above.

  In the resin (G-a), the repeating unit having a basic group or a group whose basicity is increased by the action of an acid is preferably a repeating unit represented by the following general formula (BI).

In General Formula (BI), Xa represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. An alkyl group, more preferably a methyl group. Xa preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, more preferably a hydrogen atom, a methyl group or a hydroxymethyl group.
Ab represents a group having a basic group or a group having a group whose basicity is increased by the action of an acid.

  In Ab, the group having basicity and the group whose basicity increases by the action of an acid preferably both contain a nitrogen atom.

The group having a basic group as Ab is preferably a group having any one of the structures represented by the general formulas (A) to (E), specifically, the general formulas (A) to (E) Basic compound (low molecular compound) having any of the structures shown (in this case, the basic compound may or may not have at least one of a fluorine atom and a silicon atom) And a monovalent group obtained by removing any one hydrogen from.
The group having a basic group as Ab is more preferably a group represented by the following formula (BI ′).

-L-Ac (B-I ')

In formula (BI ′), L represents a single bond or a divalent linking group, and Ac represents a structure represented by the above general formula (A) (a bond from a nitrogen atom in the above general formula (A)). Binds to L).
Examples of the divalent linking group as L include an alkylene group, a cycloalkylene group, an ether group, a phenylene group, and a group formed by combining two or more of these, more preferably an alkylene group and a cyclo group. An alkylene group, more preferably an alkylene group. The total number of carbon atoms of the divalent linking group as L is preferably 0 to 10, more preferably 1 to 6, and still more preferably 2 or 3.

  The “group whose basicity is increased by the action of an acid” in the group having a group whose basicity is increased by the action of an acid as Ab is the “carbamate group having a protecting group” described in the above compound (G-2). Can be preferably mentioned.

  The group having a group whose basicity is increased by the action of an acid as Ab is more preferably a group represented by the following formula (B-II).

In general formula (B-II),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
x represents 0 or 1, y represents 1 or 2, and x + y = 2.
When x = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.

In general formula (B-II), each group in Ra, Rb ₁ , Rb ₂ , Rb ₃ , Rc, a ring that two of Rb _{1 to} Rb ₃ may be bonded to each other, and Ra and Rc Specific examples of the nitrogen-containing heterocyclic ring that may be bonded to each other are the same as those described in the general formula (1).

In the resin (Gb), the repeating unit having at least one of a fluorine atom and a silicon atom and a basic group or a group whose basicity is increased by the action of an acid is represented by the general formula (B-1). Repeating unit
(I) Xa is a methyl group (for example, trifluoromethyl group) having at least one of a fluorine atom and a silicon atom.
(Ii) Ab has a basic group or a group whose basicity is increased by the action of an acid, and further has at least one of a fluorine atom and a silicon atom, and (iii) (i) and (ii) above ) And
The repeating unit which satisfy | fills either of these can be mentioned.

Regarding the above (ii), examples of the group Ab having a basic group and further having at least one of a fluorine atom and a silicon atom include any of the structures represented by the general formulas (A) to (E) described above. And a monovalent group formed by removing any one hydrogen from a basic compound (low molecular compound) having a hydrogen atom (however, the basic compound has at least one of a fluorine atom and a silicon atom). .
In addition, regarding the above (ii), the group Ab having a group whose basicity is increased by the action of an acid and further having at least one of a fluorine atom and a silicon atom is represented by, for example, the general formula (1) described above. And monovalent groups formed by removing any one hydrogen from any one of Ra, Rc and Rf of the compound to be prepared.

Hereinafter, although the specific example of the repeating unit which has a basic group in resin (G) or a group which basicity increases by the effect | action of an acid is given, this invention is not limited to this. In specific examples, X represents a hydrogen atom, —CH ₃ , —CH ₂ OH, —F or —CF ₃ .

  The resin (G) may further contain a repeating unit represented by the following general formula (III ′).

Rc ₃₁ represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.
Rc ₃₁ is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
Rc ₃₂ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom, or the like.
L _c3 represents a single bond or a divalent linking group.

The alkyl group for R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

L _c3 represents a single bond or a divalent linking group. Examples of the divalent linking group include an ester group, an alkylene group (preferably 1 to 5 carbon atoms), an oxy group, a phenylene group, an ester bond (a group represented by —COO—), or two of these. Examples include a group formed by combining the above, and a linking group having 1 to 12 carbon atoms in total is preferable.

  The hydrophobic resin may further contain a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Zc ′ represents an atomic group necessary for forming an alicyclic structure together with two carbon atoms (C—C) to which R _c11 ′ and R _c12 ′ are bonded.
R _c32 is a substituent for the alicyclic structure, and the definition thereof is the same as R _c32 in the general formula (III ′).
p represents an integer of 0 to 3, and 0 or 1 is preferable.

Specific examples of the repeating unit represented by the general formula (III ′) or (CII-AB) are given below. In specific examples, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  Hereinafter, although the specific example of resin (G) is given below, this invention is not limited to this.

  When the compound (G) (including the resin (G)) contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass based on the molecular weight of the compound (G). More preferably, it is -80 mass%. When the compound (G) is the resin (G), the content of the repeating unit containing a fluorine atom is preferably 10 to 100% by mass based on all the repeating units of the hydrophobic resin, and 30 to 100 More preferably, it is mass%.

  When the compound (G) (resin (including G) contains a silicon atom), the content of the silicon atom is preferably 2 to 50% by mass based on the molecular weight of the compound (G). When the compound (G) is the resin (G), the content of the repeating unit containing a silicon atom is 10 to 100 based on the total repeating unit of the resin (G). It is preferable that it is mass%, and it is more preferable that it is 20-100 mass%.

  Since the fluorine atom or silicon atom content based on the molecular weight of the compound (G) is within the above range, the compound (G) is sufficiently contained in the compound (G). The surface free energy of (G) can be sufficiently reduced, and the compound (G) can be more unevenly distributed in the surface layer portion of the resist film. As a result, excess acid generated in the surface layer of the exposed portion can be more reliably captured, and the acid concentration distribution in the thickness direction of the exposed portion of the resist film can be more reliably made uniform. It is considered that the problem of a T-top shape and a bridge defect can be more reliably suppressed.

  The content of “a repeating unit having at least one of a fluorine atom and a silicon atom” in the resin (G-a) is preferably 20 to 80 mol%, more preferably based on all repeating units constituting the resin (G). Is 25 to 70 mol%, particularly preferably 30 to 60 mol%.

  The content of “a repeating unit having a basic group or a group whose basicity is increased by the action of an acid” in the resin (G-a) is preferably from 20 to the total repeating unit constituting the resin (G). 80 mol%, more preferably 25 to 70 mol%, particularly preferably 30 to 60 mol%.

The content of “a repeating unit having at least one of a fluorine atom and a silicon atom and a basic group or a group whose basicity is increased by the action of an acid” in the resin (Gb) constitutes the resin (G). Preferably it is 20-80 mol% with respect to all the repeating units, More preferably, it is 25-70 mol%, Most preferably, it is 30-60 mol%.
The content of the repeating unit represented by the general formula (III ′) or (CII-AB) in the resin (G) is preferably 20 to 80 mol% with respect to all the repeating units constituting the resin (G). More preferably, it is 25-70 mol%, Most preferably, it is 30-60 mol%.

The weight average molecular weight of the resin (G) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 100,000 as a polystyrene-converted value by the GPC method. 15,000.
The degree of dispersion of the resin (G) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. This makes it possible to achieve better resolution, pattern shape, and roughness characteristics.

As the compound (G) (including the resin (G)), one type may be used alone, or two or more types may be used in combination.
The content of the compound (G) (including the resin (G)) is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass based on the total solid content in the composition. It is more preferable, and it is still more preferable that it is 0.1-5 mass%.

  As the compound (G) (including the resin (G)), a commercially available product may be used, or a compound synthesized according to a conventional method may be used. As a general synthesis method of the resin (G), for example, the same method as described above for the resin (A) can be mentioned.

  As for resin (G), it is natural that there are few impurities, such as a metal, It is preferable that the residual amount of a monomer and an oligomer component is 0-10 mass%, and it is more preferable that it is 0-5 mass%. The content is preferably 0 to 1% by mass. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

[4] Crosslinking agent (C)
The resist composition of the present invention may contain, together with the resin (A), a compound that crosslinks the resin (A) by the action of an acid (hereinafter referred to as a crosslinking agent). Here, a known crosslinking agent can be used effectively. In this case, the resin (A) preferably has a repeating unit (a2) having an alcoholic hydroxyl group as described above.
The crosslinking agent (C) is a compound having a crosslinkable group capable of crosslinking the resin (A). Examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, a vinyl ether group, and an epoxy group. Can do. The crosslinking agent (C) preferably has two or more such crosslinkable groups.
The crosslinking agent (C) is preferably a melamine compound, a urea compound, an alkylene urea compound, or a glycoluril compound.

Examples of preferable crosslinking agents include compounds having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group.
As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, two or more (more preferably 2 to 8) partial structures represented by the following general formula (CLNM-1) are used. ) Is preferred.

In General Formula (CLNM-1), R ^NM1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an oxoalkyl group. In general formula (CLNM-1), the alkyl group of R ^NM1 is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group of R ^NM1 is preferably a cycloalkyl group having 5 to 6 carbon atoms. The oxoalkyl group of R ^NM1 is preferably an oxoalkyl group having 3 to 6 carbon atoms, and examples thereof include a β-oxopropyl group, a β-oxobutyl group, a β-oxopentyl group, and a β-oxohexyl group. it can.

  As a more preferable embodiment of the compound having two or more partial structures represented by the general formula (CLNM-1), a urea-based crosslinking agent represented by the following general formula (CLNM-2), the following general formula (CLNM-3) , A glycoluril crosslinking agent represented by the following general formula (CLNM-4), and a melamine crosslinking agent represented by the following general formula (CLNM-5).

In the general formula (CLNM-2),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM2 each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), or a cycloalkyl group (preferably having 5 to 6 carbon atoms).

  Specific examples of the urea crosslinking agent represented by the general formula (CLNM-2) include, for example, N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, N, N-di (Propoxymethyl) urea, N, N-di (isopropoxymethyl) urea, N, N-di (butoxymethyl) urea, N, N-di (t-butoxymethyl) urea, N, N-di (cyclohexyloxy) And methyl) urea, N, N-di (cyclopentyloxymethyl) urea, N, N-di (adamantyloxymethyl) urea, N, N-di (norbornyloxymethyl) urea and the like.

In the general formula (CLNM-3),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM3 each independently represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbon atoms), an oxoalkyl group (having 3 carbon atoms). To 6), an alkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxy group (preferably having 1 to 6 carbon atoms).
G represents a single bond, an oxygen atom, a sulfur atom, an alkylene group (preferably having 1 to 3 carbon atoms) or a carbonyl group. More specifically, a methylene group, ethylene group, propylene group, 1-methylethylene group, hydroxymethylene group, cyanomethylene group and the like can be mentioned.

  Specific examples of the alkylene urea crosslinking agent represented by the general formula (CLNM-3) include, for example, N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethylene urea, N, N- Di (ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneurea, N, N-di (propoxymethyl) -4,5-di (propoxymethyl) ethyleneurea, N, N-di (isopropoxymethyl) -4,5-di (isopropoxymethyl) ethylene urea, N, N-di (butoxymethyl) -4,5-di (butoxymethyl) ethylene urea, N, N-di (t-butoxymethyl) -4, 5-di (t-butoxymethyl) ethyleneurea, N, N-di (cyclohexyloxymethyl) -4,5-di (cyclohexyloxymethyl) ethyleneurea, N, N-di (cyclo Nthyloxymethyl) -4,5-di (cyclopentyloxymethyl) ethyleneurea, N, N-di (adamantyloxymethyl) -4,5-di (adamantyloxymethyl) ethyleneurea, N, N-di (nor Bornyloxymethyl) -4,5-di (norbornyloxymethyl) ethyleneurea and the like.

In the general formula (CLNM-4),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM4 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group.

R ^NM4 alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms), alkoxy group (preferably having 1 to 6 carbon atoms), more specifically, methyl group, Examples include an ethyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and a butoxy group.

  Specific examples of the glycoluril-based crosslinking agent represented by the general formula (CLNM-4) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra ( Ethoxymethyl) glycoluril, N, N, N, N-tetra (propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (butoxy) Methyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, N, N, N, N-tetra (cyclohexyloxymethyl) glycoluril, N, N, N, N-tetra ( Cyclopentyloxymethyl) glycoluril, N, N, N, N-tetra (adamantyloxymethyl) glycoluril, N, N, N, N- Tiger (norbornyloxymethyl) glycoluril, and the like.

In the general formula (CLNM-5),
, Each R ^NM1 independently, are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
R ^NM5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ′).
R ^NM6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an atomic group represented by the following general formula (CLNM-5 ″).

In the general formula (CLNM-5 ′),
R ^NM1 are those in formula (CLNM-1) ^at, the same as ^{R NM1.}
In the general formula (CLNM-5 ″),
R ^NM1 of the general formula are those (CLNM-1) in ^at, the same as ^{R NM1, R NM5} are those formula (CLNM-5) in the same manner as in ^{R NM5.}

Alkyl group R ^NM5 and ^{R NM6} (1 to 6 carbon atoms is preferred), cycloalkyl groups (5 to 6 carbon atoms is preferred), an aryl group (having 6 to 10 carbon atoms is preferred), and more specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

Examples of the melamine crosslinking agent represented by the general formula (CLNM-5) include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N Hexa (ethoxymethyl) melamine, N, N, N, N, N, N-hexa (propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N , N, N, N, N-hexa (butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine, N, N, N, N, N, N-hexa (Cyclohexyloxymethyl) melamine, N, N, N, N, N, N-hexa (cyclopentyloxymethyl) melamine, N, N, N, N, N, N-hexa (adamantyloxymethyl) melamine, N, N , N, N, N, N-hexa ( Rubornyloxymethyl) melamine, N, N, N, N, N, N-hexa (methoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (isopropoxymethyl) acetoguanamine, N, N, N, N, N, N -Hexa (butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (methoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) benzoguanamine, N, N, N, N, N, N Hexa (isopropoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (butoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) benzoguanamine, etc. Can be mentioned.

The groups represented by R ^{NM1 to} R ^NM6 in the general formulas (CLNM-1) to (CLNM-5) may further have a substituent. Examples of the substituent that R ^{NM1 to} R ^NM6 may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), and an aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), cycloalkoxy group (preferably 4 to 20 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably carbon 2-20) etc. can be mentioned.

The crosslinking agent (C) may be a phenol compound having a benzene ring in the molecule.
The phenolic compound has a molecular weight of 1200 or less, 3 to 5 benzene rings in the molecule, and two or more hydroxymethyl groups or alkoxymethyl groups, and at least any of the hydroxymethyl group and alkoxymethyl group. Phenol derivatives formed by concentrating on these benzene rings or by sorting and binding are preferred. By using such a phenol derivative, the effect of the present invention can be made more remarkable. As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a sec-butoxymethyl group, and a t-butoxymethyl group are preferable. Furthermore, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propyl group are also preferable.

The phenol compound is more preferably a phenol compound having two or more benzene rings in the molecule, and is preferably a phenol compound containing no nitrogen atom.
Specifically, a phenol compound having 2 to 8 crosslinkable groups per molecule that can crosslink the resin (A) is preferable, and 3 to 6 crosslinkable groups are more preferable.

Among these phenol derivatives, particularly preferable ones are listed below. In the formula, L ^{1 to} L ⁸ represent a crosslinkable group and may be the same or different, and the crosslinkable group preferably represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.

A commercially available phenol compound can be used, and it can also be synthesized by a known method. For example, a phenol derivative having a hydroxymethyl group is obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. be able to. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

  A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like. A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

The crosslinking agent (C) may be an epoxy compound having an epoxy group in the molecule.
As an epoxy compound, the compound represented by the following general formula (EP2) is mentioned.

In formula (EP2),
R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group, and the alkyl group and the cycloalkyl group may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure.
Examples of the substituent that the alkyl group and cycloalkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfone group, and an alkylsulfonyl group. Groups, alkylamino groups, alkylamide groups, and the like.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 to R ^EP3 may also form a ring structure with ^{Q EP} not only with each other but.
n ^EP represents an integer of 2 or more, preferably 2 to 10, more preferably 2 to 6. However, ^nEP is 2 when ^QEP is a single bond.

When ^QEP is an ^nEP- valent organic group, a chain or cyclic saturated hydrocarbon structure (preferably having 2 to 20 carbon atoms) or an aromatic ring structure (preferably having 6 to 30 carbon atoms), or these are ethers and esters , Amides, sulfonamides and the like linked structures are preferred.

  Specific examples of the compound having an epoxy structure are illustrated below, but the present invention is not limited thereto.

In this invention, a crosslinking agent may be used independently and may be used in combination of 2 or more type.
When the resist composition contains a crosslinking agent, the content of the crosslinking agent in the resist composition is preferably 3 to 15% by mass, more preferably 4 to 12% by mass, based on the total solid content of the resist composition. More preferably, it is 5 to 10% by mass.

[5] Solvent (D)
The resist composition in the present invention contains a solvent.
Examples of the solvent that can be used in preparing the resist composition in the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, and cyclic lactone (preferably Examples thereof include organic solvents such as carbon atoms having 4 to 10 carbon atoms and monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
Specific examples and preferred examples of these solvents are the same as those described in JP 2008-292975 A [0244] to [0248].

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is generally 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60. / 40. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[6] Hydrophobic resin (HR)
The resist composition of the present invention is a hydrophobic resin having at least one of a fluorine atom and a silicon atom particularly when applied to immersion exposure (however, this hydrophobic resin does not correspond to the resin (G)). It may contain. As a result, the hydrophobic resin (HR) is unevenly distributed on the surface of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion water followability is improved. Can do.
Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. These fluorine atoms and / or silicon atoms may be contained in the main chain of the resin or may be contained in the side chain.

In the case where the hydrophobic resin contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to provide.
The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
The cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The cycloalkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.
An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  Preferred examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom are represented by the general formulas (F2) to (F4) described in the resin (G). Groups.

  Specific examples of the repeating unit containing a fluorine atom are the same as those exemplified in the resin (G).

  When the hydrophobic resin contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

  Preferable examples of the alkylsilyl structure and the cyclic siloxane structure include groups represented by the general formulas (CS-1) to (CS-3) described in the resin (G).

  Specific examples of the repeating unit having a group represented by general formulas (CS-1) to (CS-3) are the same as those exemplified in the resin (G).

The hydrophobic resin may further include at least one group selected from the group consisting of the following (x) to (z).
(X) acid group (y) group having lactone structure, acid anhydride group, or acid imide group (z) acid-decomposable group

(X) As the acid group, for example, phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)
(Alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, A tris (alkylcarbonyl) methylene group and a tris (alkylsulfonyl) methylene group are mentioned. Preferred acid groups include fluorinated alcohol groups, sulfonimide groups, and bis (carbonyl) methylene groups. Preferred fluorinated alcohol groups include hexafluoroisopropanol groups.

  The repeating unit having an acid group is a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid and methacrylic acid. Alternatively, this repeating unit may be a repeating unit in which an acid group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has an acid group at the time of superposition | polymerization.

  The content of the repeating unit having an acid group is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, more preferably 5 to 20 mol, based on all repeating units in the hydrophobic resin. % Is more preferable.

Specific examples of the repeating unit having an acid group are shown below. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

(Y) As the group having a lactone structure, the acid anhydride group, or the acid imide group, a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

  More preferably, the group having the lactone structure has a partial structure represented by the following general formula (KA-1). By having this structure, an improvement in the receding contact angle of the immersion liquid is expected.

In general formula (KA-1),
Z _ka1 each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxy group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group when nka is 2 or more. When nka is 2 or more, a plurality of Z _ka1 may be bonded to each other to form a ring. Examples of this ring include cycloalkyl rings and heterocyclic rings such as cyclic ether rings and lactone rings.
nka represents an integer of 0 to 10. nka is preferably 0 to 8, more preferably 0 to 5, still more preferably 1 to 4, and particularly preferably 1 to 3.

  The structure represented by the general formula (KA-1) is a partial structure existing in the main chain, side chain, terminal, etc. of the resin, and is formed by removing at least one hydrogen atom contained in this structure. It exists as a substituent having a valence or higher.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxy group or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. The ether group is preferably an alkyl ether group or a cycloalkyl ether group.
The alkyl group of Z _ka1 may be linear or branched. This alkyl group may further have a substituent.
The alkyl group of Z _ka1 has 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. Is preferred.
The cycloalkyl group of Z _ka1 may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The monocyclic cycloalkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group , Tetocyclododecyl group and androstanyl group.
These structures may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.
The alkyl group as a substituent is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a methyl group, an ethyl group, a propyl group and an isopropyl group. .
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
These alkyl groups and alkoxy groups as substituents may have further substituents. As this further substituent, a hydroxyl group, a halogen atom, and an alkoxy group (preferably C1-C4) are mentioned, for example.
Examples of the aryl group for Z _ka1 include a phenyl group and a naphthyl group.

Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group of Z _ka1 may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the above alkyl group; a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; benzyl group, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; Acyloxy group such as butyryloxy group; Alkenyl group; Vinyloxy group, propenyloxy group, allyloxy group And butenyl An alkenyloxy group such as an oxy group; the above aryl group; an aryloxy group such as a phenoxy group; and an aryloxycarbonyl group such as a benzoyloxy group.

Examples of the electron withdrawing group for Z _ka1 include a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group, and —C (R _f1 ) (R _f2 ) —R _f3 , a halo (cyclo) alkyl group, a haloaryl group, and combinations thereof. The “halo (cyclo) alkyl group” means a (cyclo) alkyl group in which at least one hydrogen atom is substituted with a halogen atom.
Examples of the halogen atom for Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

In the halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group. R _f1 is more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably a fluorine atom or a trifluoromethyl group.
In the halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. These groups may further have a substituent such as a halogen atom.
At least two of R _{f1 to} R _f3 may be bonded to each other to form a ring. Examples of the ring include a cycloalkyl ring, a halocycloalkyl ring, an aryl ring, and a haloaryl ring.
Examples of the alkyl group and haloalkyl group of R _{f1 to} R _f3 include an alkyl group described above for Z _ka1 and a group in which at least a part of hydrogen atoms of these alkyl groups is substituted with a halogen atom.
Examples of the halocycloalkyl group and haloaryl group include groups in which at least a part of the hydrogen atoms of the cycloalkyl group and aryl group described above for Z _ka1 are substituted with a halogen atom. More preferred examples of the halocycloalkyl group and haloaryl group include a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H, a perfluoroaryl group, and the like. Here, although there is no restriction | limiting in particular in the range of carbon number n, it is preferable that n is an integer of 5-13, and it is especially preferable that n is 6.

More preferably, R _f2 is the same group as R _f1 , or is bonded to R _f3 to form a ring.

The electron withdrawing group is particularly preferably a halogen atom, a halo (cyclo) alkyl group or a haloaryl group.
In the electron withdrawing group, a part of the fluorine atom may be substituted with an electron withdrawing group other than the fluorine atom.
When the electron withdrawing group is a divalent or higher valent group, the remaining bond is used for bonding with an arbitrary atom or substituent. In this case, said partial structure may be couple | bonded with the principal chain of hydrophobic resin through the further substituent.

  Among those represented by the general formula (KA-1), those represented by the following general formula (KY-1) are more preferable.

(KY-1)

In formula (KY-1),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxy group, cyano group, amide group, or aryl. Represents a group. At least two _members out of R _{ky6 to} R _ky10 may be bonded to each other to form a ring.
R _ky5 represents an electron-withdrawing group. Examples of the electron withdrawing group include the same groups as Z _ka1 in the general formula (KA-1). This electron-withdrawing group is preferably a halogen atom, a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , or a haloaryl group. This is the same as the specific example in general formula (KA-1).
nkb represents 0 or 1.
R _kb1 and R _kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group. Specific examples of these atomic groups include the same groups as Z _ka1 in formula (KA-1).

  The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-1-1).

(KY-1-1)

In the formula (KY-1-1), each of Z _ka1 and nka has the same meaning as that in the general formula (KA-1). Each of Rky ₅ , R _kb1 , R _kb2 and nkb is synonymous with that in the general formula (KY-1).
L _ky represents an alkylene group, an oxygen atom, or a sulfur atom. Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
Rs independently represents an alkylene group or a cycloalkylene group. When ns is 2 or more, the plurality of Rs may be the same or different from each other. Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
ns is the number of repeating linking groups represented by-(Rs-Ls)-and represents an integer of 0 to 5.

  Although the preferable specific example of the repeating unit which has a structure represented by general formula (KA-1) is shown below, it is not limited to this. Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 40 mol% based on all repeating units in the hydrophobic resin, and 3 to 30 It is more preferable that it is mol%, and it is still more preferable that it is 5-15 mol%.

Examples of the (z) acid-decomposable group include the same groups as described above in the section of (A) acid-decomposable resin.
The content of the repeating unit having an acid-decomposable group is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin, and more preferably 20 to 20 mol%. More preferably, it is 60 mol%.

  The hydrophobic resin may contain a repeating unit represented by the general formula (III ′) or (CII-AB) described in the resin (G).

Specific examples of the repeating unit represented by the general formula (III ′) or (CII-AB) are the same as those exemplified in the resin (G).
When the hydrophobic resin (HR) includes a repeating unit represented by the general formula (III ′) or (CII-AB), the amount of the repeating unit is based on the total repeating units constituting the hydrophobic resin (HR). The content is preferably 1 to 100 mol%, more preferably 5 to 95 mol%, and still more preferably 20 to 80 mol%.

  Specific examples of the hydrophobic resin are given below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight, and dispersity (Mw / Mn).

  When the hydrophobic resin contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, more preferably 10 to 80% by mass based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on all repeating units of the hydrophobic resin.

  When the hydrophobic resin contains silicon atoms, the silicon atom content is preferably 2 to 50% by mass, more preferably 2 to 30% by mass, based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a silicon atom is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, based on all repeating units of the hydrophobic resin.

The weight average molecular weight of hydrophobic resin becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000.
The degree of dispersion of the hydrophobic resin is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. This makes it possible to achieve better resolution, pattern shape, and roughness characteristics.

One type of hydrophobic resin may be used alone, or two or more types may be used in combination.
The content of the hydrophobic resin is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition, More preferably, it is 5 mass%.

  As the hydrophobic resin, commercially available products may be used, or those synthesized according to a conventional method may be used. As a general method for synthesizing this resin, for example, the same method as described above for the resin (A) can be mentioned.

  It is natural that the hydrophobic resin has few impurities such as metals, and the residual amount of the monomer and oligomer components is preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. More preferably, it is 0 to 1% by mass. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

[7] Surfactant (F)
The resist composition of the present invention may or may not further contain a surfactant. When it is contained, the fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, fluorine-containing surfactant) It is preferable that one or two or more surfactants having both atoms and silicon atoms are contained.

When the composition of the present invention contains the above-described surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, F-top EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), F-top EF121, E 122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the surfactant corresponding to the above, Megafac F-178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.), C ₆ F ₁₃ Copolymer of acrylate (or methacrylate) having a group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate having a C ₃ F ₇ group (or And a copolymer of (methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

  These surfactants may be used alone or in several combinations.

When the resist composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to the total amount of the resist composition (excluding the solvent). 1% by mass.
On the other hand, by making the addition amount of the surfactant 10 ppm or less with respect to the total amount of the resist composition (excluding the solvent), the surface unevenness of the hydrophobic resin is improved, thereby making the resist film surface more hydrophobic. It is possible to improve the water followability at the time of immersion exposure.

[8] Compound (H) other than the above compound (G) having basicity or increasing basicity by the action of an acid
The resist composition of the present invention has basicity other than the above compound (G) (having neither a fluorine atom nor a silicon atom) in order to reduce a change in performance over time from exposure to heating, or You may contain the compound which basicity increases by the effect | action of an acid.

  Specific examples of the basic compound (basic compound) include basic compounds having structures represented by the following general formulas (A) to (E).

In general formulas (A) and (E),
R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group or a cycloalkyl group.
In the structure represented by the general formula (A), R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.
In the structures represented by the general formulas (B) to (D), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.
In the structure represented by the general formula (E), two or more of R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ , R ²⁵⁶ , a bond from an elementary atom, and a bond from a nitrogen atom are bonded to each other, A ring may be formed.

In General Formula (A), specific examples of R ²⁵¹ and R ²⁵² are the same as the definitions and specific examples of R ²⁰¹ and R ^{202 in} the structure represented by General Formula (A) described in Compound (G-1). It is.
In General Formula (E), specific examples of R ²⁵³ , R ²⁵⁴ , R ^255, and R ²⁵⁶ include R ²⁰³ , R ²⁰⁴ , and the like in the structure represented by General Formula (A) described for Compound (G-1). This is the same as the specific examples of R ²⁰⁵ and R ²⁰⁶ .

  In the structures represented by the general formulas (A) to (E), specific examples of the ring that two or more of each group and each bond may form are as described in the above compound (G-1). It is the same.

In addition, each group in the structures represented by the general formulas (A) to (E) and a ring that may be formed by bonding two or more of each group and each bond to each other further have a substituent. Specific examples of such a substituent may be further included in R ²⁰¹ and R ²⁰² described in the structure represented by the general formula (A) of the compound (G-1). It is the same as the specific example of a good substituent.

Examples of the alkyl group having a substituent and the cycloalkyl group having a substituent as R ^{250 to} R ²⁵⁶ include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms. Or a hydroxycycloalkyl group having 3 to 20 carbon atoms is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

  Preferable basic compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, which may have a substituent. Further preferable compounds include an imidazole structure, a diazabicyclo structure, an onium hydroxide structure (particularly preferably, a tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide), an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure. A compound having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like.

  Further, at least one nitrogen-containing compound selected from an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be exemplified. . Examples of these compounds include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of US Patent Application Publication No. 2007/02245539. It is not a thing.

  Examples of the compound whose basicity is increased by the action of an acid include compounds represented by the following general formula (F). In addition, the compound represented by the following general formula (F) exhibits effective basicity in the system when a group capable of leaving by the action of an acid is eliminated.

In the general formula (F), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In general formula (F), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, It may be substituted with an alkoxy group or a halogen atom.
As the alkyl group, cycloalkyl group, aryl group or aralkyl group of R (these alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted with the above functional group, alkoxy group or halogen atom) Is
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group A group substituted with one or more groups derived from an aromatic compound such as an anthracenyl group or the like, or the above substituent is a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group And a group substituted with a functional group such as.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group And a group substituted with one or more functional groups such as a morpholino group and an oxo group.

  Specifically shown in the present invention are particularly preferred examples: Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, ( S)-(−)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl- 4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxy Rubonylmorpholine, Nt-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt -Butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N ' -Di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl-1,9- Diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxy Carbonyl-1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole Nt-butoxycarbonyl-2-phenylbenzimidazole and the like.

The compound represented by the general formula (F) may be a commercially available compound, or may be synthesized from a commercially available amine by the method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom. R _a and R _b have the same meaning as in formula (F).

  The molecular weight of the compound (H) having basicity or increasing basicity by the action of an acid other than the compound (G) is preferably 250 to 2000, and more preferably 400 to 1000.

These compounds (H) are used alone or in combination of two or more.
When the compound (H) is contained, the content thereof is preferably 0.05 to 8.0% by mass, more preferably 0.05 to 5.0%, based on the total solid content of the resist composition. % By mass, particularly preferably 0.05 to 4.0% by mass.

[9] Basic compound or ammonium salt compound that is reduced in basicity by irradiation with actinic light or radiation The resist composition of the present invention is a basic compound or ammonium salt that is reduced in basicity upon irradiation with actinic light or radiation. A compound (hereinafter also referred to as “compound (PA)”) may be contained. That is, the compound (PA) is accompanied by a change in chemical structure upon irradiation with actinic rays or radiation and has photosensitivity.

The compound (PA) is preferably a compound (PA ′) having a basic functional group or an ammonium group and a group capable of generating an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (PA) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with active light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (PA) or (PA ′), which is generated by decomposing upon irradiation with actinic rays or radiation and has a reduced basicity, has the following general formula (PA-I), (PA-II) or (PA- Compounds represented by formula (III), and particularly from the viewpoint that the excellent effects of LWR and DOF can be achieved at a high level, in particular, compounds represented by formula (PA-II) or (PA-III) Is preferred.
First, the compound represented by general formula (PA-I) is demonstrated.

_{Q-A 1 - (X)} n -B-R (PA-I)

In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents _-SO 3 H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

The divalent linking group in A ₁ is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
The alkyl group in Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.
Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .
The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.
The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

Preferable partial structures of basic functional groups include, for example, the structures of crown ethers, primary to tertiary amines, and nitrogen-containing heterocyclic rings (pyridine, imidazole, pyrazine, etc.).
Preferable partial structures of the ammonium group include, for example, primary to tertiary ammonium, pyridinium, imidazolinium, pyrazinium structures and the like.
In addition, as a basic functional group, the functional group which has a nitrogen atom is preferable, and the structure which has a 1-3 primary amino group, or a nitrogen-containing heterocyclic structure is more preferable. In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.
As the monovalent organic group in the monovalent organic group (group R) having such a structure, a preferable carbon number is 4 to 30, and an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. Each group may have a substituent.
The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in the basic functional group or ammonium group in R are each represented by Rx. These are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned.

  Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C20) etc. are mentioned. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms). Examples of the alkyl group having a substituent include perfluoroalkyl groups such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

When B is -N (Rx)-, R and Rx are preferably bonded to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
Examples of the monocyclic structure include a 4- to 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent include 1 or 2 alkyl groups (preferably having 1 to 15 carbon atoms).

  Among the compounds represented by the general formula (PA-I), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

  Next, the compound represented by general formula (PA-II) is demonstrated.

_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)

In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

The monovalent organic group as Q ₁ and Q _{2 in} formula (PA-II) preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, An alkenyl group etc. can be mentioned.
The alkyl group in Q ₁ and Q ₂ may have a substituent, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and an oxygen atom, sulfur atom, nitrogen atom in the alkyl chain You may have.
The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a nitrogen atom in the ring. Good.
The aryl group in Q ₁ and Q ₂ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Q ₁ and Q ₂ may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Q ₁ and Q ₂ may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group.
Examples of the substituent that each of the above groups may have include the same groups as those exemplified above as the substituent that each of the groups in the above formula (PA-1) may have.

Preferable partial structures of the basic functional group possessed by at least one of Q ₁ and Q ₂ include the same partial structures as those described as the basic functional group possessed by R in the general formula (PA-I).

Q ₁ and Q ₂ are combined to form a ring, and the formed ring has a basic functional group. For example, the organic group of Q ₁ and Q ₂ is further an alkylene group, an oxy group, or an imino group. A structure bonded with a group or the like can be given.

In the general formula (PA-II), it is preferable that at least one of X ₁ and X ₂ is —SO ₂ —.

  Next, the compound represented by general formula (PA-III) is demonstrated.

_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)

In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
B is, -N (Qx) - when, _{Q 3} and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Q ₁ has the same meaning as Q _{1 in} formula (PA-II).
Examples of the organic group of Q ₃ include the same organic groups as Q ₁ and Q ₂ in formula (PA-II).

The divalent linking group for A ₂ is preferably a divalent linking group having 1 to 8 carbon atoms, for example, an alkylene group having 1 to 8 carbon atoms, or a phenylene having a fluorine atom. Groups and the like. An alkylene group having a fluorine atom is more preferable, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a C2 to C4 perfluoroalkylene group.

  The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group, the same groups as those described above for Rx in the above formula (PA-I) can be mentioned.

In the general formula (PA-III), X ₁ , X ₂ , and X ₃ are preferably —SO ₂ —.

  As the compound (PA), a sulfonium salt compound of the compound represented by the general formula (PA-I), (PA-II) or (PA-III), the general formula (PA-I), (PA-II) or The iodonium salt compound of the compound represented by (PA-III) is preferable, and the compound represented by the following general formula (PA1) or (PA2) is more preferable.

In general formula (PA1):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group, specifically, the same as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ of the formula ZI in the acid generator.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

In the general formula (PA2),
R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group, and specifically, are the same as R ₂₀₄ and R ₂₀₅ of the formula ZII in the acid generator.
X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate, for example, a compound represented by the general formula (PA-I), (PA-II) or (PA-III).
The compound represented by the general formula (PA-I) has a sulfonic acid group or a carboxylic acid group together with a basic functional group or an ammonium group, so that the basicity is reduced, disappeared, or basic compared to the compound (PA). It is a compound that has changed from acidic to acidic.
The compound represented by the general formula (PA-II) or (PA-III) has an organic sulfonylimino group or an organic carbonylimino group together with a basic functional group, so that the basicity is lower than that of the compound (PA). , Disappearance, or a compound changed from basic to acidic.
In the present invention, the decrease in basicity upon irradiation with actinic rays or radiation means that the acceptor property to protons (acids generated by irradiation with actinic rays or radiation) of compound (PA) upon irradiation with actinic rays or radiation. Means lower. The acceptor property decreases when an equilibrium reaction occurs in which a non-covalent complex that is a proton adduct is formed from a compound having a basic functional group and a proton, or the counter cation of a compound having an ammonium group is exchanged for a proton. This means that when an equilibrium reaction occurs, the equilibrium constant at that chemical equilibrium decreases.
Thus, the compound (PA) whose basicity is reduced by irradiation with actinic rays or radiation is contained in the resist film, so that the acceptor property of the compound (PA) is sufficiently expressed in the unexposed area. In addition, it is possible to suppress an unintended reaction between the acid diffused from the exposed portion and the resin and the resin (A), and in the exposed portion, the acceptor property of the compound (PA) is reduced, so that the acid and the resin (A) It is presumed that the intended reaction of the above occurs more surely and that a pattern excellent in line width variation (LWR), focus margin (DOF) and pattern shape can be obtained due to the contribution of such an action mechanism.
In addition, basicity can be confirmed by performing pH measurement, and it is also possible to calculate a calculated value with commercially available software.

Specific examples of the compound (PA) whose basicity is lowered by irradiation with actinic rays or radiation include those described in, for example, JP-A-2006-208781 and JP-A-2006-330098.
Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented with general formula (PA-I) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

  These compounds are synthesized from a compound represented by the general formula (PA-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide or chloride of iodonium or sulfonium. Or a salt exchange method described in JP-A No. 2003-246786. Further, the synthesis method described in JP-A-7-333851 can also be applied.

  Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented by general formula (PA-II) or (PA-III) by irradiation of actinic light or a radiation is given, this invention is limited to this. is not.

These compounds can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine, alcohol, or the like containing a partial structure represented by the general formula (PA-II) or (PA-III), After forming a sulfonate bond, the other sulfonyl halide moiety is hydrolyzed, or the cyclic sulfonic anhydride is opened with an amine or alcohol containing a partial structure represented by the general formula (PA-II) It can be obtained by a method. The amine or alcohol containing a partial structure represented by the general formula (PA-II) or (PA-III) is an amine or alcohol under basicity (R′O ₂ C) ₂ O or (R′SO _2). ) It can be synthesized by reacting with an anhydride such as ₂ O and an acid chloride compound such as R′O ₂ CCl or R′SO ₂ Cl (R ′ is a methyl group, an n-octyl group, a trifluoromethyl group, etc.) . In particular, it can be applied to the synthesis example of JP-A-2006-330098.
The molecular weight of the compound (PA) is preferably 500 to 1000.

When the resist composition of the present invention contains a compound (PA), its content is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the composition. It is.
Compound (PA) may be used alone or in combination of two or more. In addition, compound (PA) may be used in combination with the aforementioned basic compound.

[10] Other additives (I)
If necessary, the resist composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorber, a dissolution inhibitor, a dissolution accelerator, and the like.

The total solid content concentration of the resist composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0 to 5.3% by mass. is there. By setting the solid content concentration within the above range, it is possible to uniformly apply the resist solution on the substrate and to form a resist pattern having excellent line edge roughness. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film can be formed.
The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the resist composition.

[11] Pattern formation method The pattern formation method of the present invention comprises:
(A) forming a film (resist film) from a chemically amplified resist composition;
(A) a step of exposing the film, and (c) a step of developing using a developer containing an organic solvent,
At least.
The resist film is formed from the above-described chemically amplified resist composition of the present invention, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film of a resist composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 120 ° C., more preferably 80 to 110 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

The light source wavelength limit is not used for the exposure apparatus in the present invention, KrF excimer laser wavelength (248 nm), ArF excimer laser wavelength and (193 nm) _{F 2} can be applied to excimer laser wavelength (157 nm) or the like.

The resist film of the present invention may be exposed (immersion exposure) by filling a liquid (immersion medium) having a higher refractive index than air between the film and the lens during irradiation with actinic rays or radiation. . Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.
In this case, the above-mentioned hydrophobic resin may be added to the resist composition in advance, or after forming the resist film, an immersion liquid hardly soluble film (hereinafter referred to as “top coat”) is formed on the resist film. May be provided).
The performance required for the top coat and how to use it are explained in chapter 7 of CM Publishing “Immersion Lithography Processes and Materials”.
From the viewpoint of transparency to a laser having a wavelength of 193 nm, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer is a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl. Examples include ethers, silicon-containing polymers, fluorine-containing polymers. The aforementioned hydrophobic resin (HR) is also suitable as a top coat. Commercially available top coat materials can also be used as appropriate.
When the topcoat is peeled after exposure, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed simultaneously with the development processing step of the film, it is preferable that the peeling step can be performed with a developer.
In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

・ Development process As an organic developer that can be used when developing with a developer containing an organic solvent, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent, or A developer containing a hydrocarbon solvent can be used, and preferably contains at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. Methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3- Examples include ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. In particular, alkyl acetates such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, and amyl acetate are preferred.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2- Alcohols such as pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water within the range having performance. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used with respect to the developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.
In particular, the developer containing an organic solvent is preferably a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

The vapor pressure of the developer containing the organic solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Agent, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol Alcohol solvents such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether Glycol ether solvents such as triethylene glycol monoethyl ether and methoxymethylbutanol , Ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, octane, decane, etc. And aliphatic hydrocarbon solvents.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol, ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, alcohol solvents such as n-decanol, ethylene glycol, diethylene glycol, Glycol solvents such as triethylene glycol, and glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol Solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Formamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

-Surfactant A proper quantity of surfactant can be added to a developing solution as needed.
As the surfactant, the same surfactants as those used in the resist composition described above can be used.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

・ Resin (A ')
The developer containing the organic solvent and the rinse liquid described later may contain a resin (A ′) that is soluble in the organic solvent. Thereby, it is speculated that the resin (A ′) is dissolved in the processing liquid in advance, so that the dissolution of the resist film into the processing liquid and the penetration of the processing liquid into the resist film are promoted.
The resin (A ′) is not particularly limited as long as it is soluble in an organic solvent, and a resin used for a resist composition can be suitably used. Epoxy resin, melamine resin, urea resin, polyester resin, polyurethane Resin, polyimide resin, etc. can also be used.
Examples of the resin (A ′) soluble in the organic solvent include those having the following repeating units.
-Repeating unit (a1) having an acid-decomposable group
-Repeating unit having alcoholic hydroxyl group (a2)
・ Repeating unit having nonpolar group (a3)
-Repeating unit having a lactone structure (a4)
-Repeating unit having an acid group-Repeating unit derived from hydroxystyrene and its derivatives-(Meth) acrylic ester repeating unit having an aromatic ring in the side chain Specifically, the same resin as that contained in the resist composition may be mentioned. It is done.

The weight average molecular weight of the resin (A ′) of the present invention is preferably 3,000 to 25,000, more preferably 5,000 to 15,000 as a polystyrene conversion value by GPC method.
The dispersity (molecular weight distribution) of the resin (A ′) is preferably 1.2 to 3.0, more preferably 1.4 to 1.8.
The blending amount of the resin (A ′) in the entire treatment liquid is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass with respect to the total amount of the treatment liquid.
Moreover, the resin (A ′) may be included in the treatment liquid or may be included in a plurality.
The resin (A ′) of the present invention can be synthesized according to a conventional method (for example, radical polymerization).

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method for adjusting the discharge pressure with a pump and the like, and a method for changing the pressure by adjusting the pressure by supplying from a pressurized tank.

-Rinse process Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

  After the development with the developer containing an organic solvent, it is preferable to include a step of rinsing with a rinse solution. As the rinse liquid, a rinse liquid containing an organic solvent is preferable.

  The rinsing solution used in the rinsing step after development with a developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . The rinse liquid more preferably contains at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent, and more preferably contains an alcohol solvent or an ester solvent. Even more preferably, it contains a monohydric alcohol, particularly preferably a monohydric alcohol having 5 or more carbon atoms. Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-octanol, and the like. Use methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Rukoto can. Among these, branched alkyl alcohols having 5 or more carbon atoms are preferable.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably less than 10% by mass, more preferably less than 5% by mass, and particularly preferably less than 3% by mass. By setting the water content to less than 10% by mass, good development characteristics can be obtained.
That is, the amount of the organic solvent used in the rinse liquid is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on the total amount of the rinse liquid. Most preferably, it is at least 100% by mass.

  The vapor pressure of the rinsing solution used after development with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less at 20 ° C. Is most preferred. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant and a resin (A ′) can be added to the rinse liquid. The types and addition amounts of the surfactant and the resin (A ′) that can be contained are the same as those in the developer.

In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. The rotation time of the substrate can be set within a range in which the rinsing liquid is removed from the substrate according to the number of rotations, but is usually 10 seconds to 3 minutes.
It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Synthesis Example 1 Synthesis of Resin (P-1) Under a nitrogen stream, 40 g of propylene glycol monomethyl ether acetate and 6/4 (mass ratio) of propylene glycol monomethyl ether mixed solvent were put into a three-necked flask, and this was brought to 80 ° C. Heated (solvent 1). Monomers corresponding to the following repeating units were dissolved in a mixed solvent of 6/4 (mass ratio) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a molar ratio of 40/10/40/10, respectively. A monomer solution (400 g) was prepared. Furthermore, 8 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the monomer, and a dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 3600 ml of hexane / 400 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 74 g of Resin (P-1). The obtained resin (P-1) had a weight average molecular weight of 10,000 and a dispersity (Mw / Mn) of 1.6.

Synthesis Example 2 Synthesis of Hydrophobic Resin Synthesis of Monomer (4) The following compound (1) was synthesized by the method described in International Publication No. 07/037213.
150.00 g of water was added to 35.00 g of compound (1), and 27.30 g of sodium hydroxide was further added. The mixture was stirred for 9 hours under heating and reflux conditions. Hydrochloric acid was added to make it acidic, and the mixture was extracted with ethyl acetate. The organic layers were combined and concentrated to obtain 36.90 g of compound (2) (yield 93%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.56-1.59 (1H), 1.68-1.72 (1H), 2.13-2.15 (1H ), 2.13-2.47 (2H), 3.49-3.51 (1H), 3.68 (1H), 4.45-4.46 (1H)
200 ml of CHCl ₃ was added to 20.00 g of compound (2), and 50.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylaminopyridine were further added and stirred. To the solution, 22.00 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 500 ml of 1N HCl to stop the reaction. The organic layer was further washed with 1N HCl, then with water, and the organic layer was concentrated to obtain 30.00 g of Compound (3) (yield 85%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.62 (1H), 1.91-1.95 (1H), 2.21-2.24 (1H), 2. 45-2.53 (2H), 3.61-3.63 (1H), 3.76 (1H), 4.32-4.58 (1H), 6.46-6.53 (1H)
While adding 300.00 g of toluene to 15.00 g of compound (3), further adding 3.70 g of methacrylic acid and 4.20 g of p-toluenesulfonic acid monohydrate, and removing the produced water by azeotropic distillation, 15 hours Refluxed. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 11.70 g of Compound (4) (yield 65%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.76-1.79 (1H), 1.93 (3H), 2.16-2.22 (2H), 2. 57-2.61 (1H), 2.76-2.81 (1H), 3.73-3.74 (1H), 4.73 (1H), 4.84-4.86 (1H), 5 .69-5.70 (1H), 6.12 (1H), 6.50-6.56 (1H)

-Synthesis | combination of hydrophobic resin (6b) The monomer corresponding to the following repeating unit was prepared in the ratio (molar ratio) of 90/10, respectively, and it melt | dissolved in PGMEA, and prepared 450 g of solutions with a solid content concentration of 15 mass%. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added to this solution, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin (6b).

  The polymer composition ratio determined from NMR was 90/10. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 12000, and dispersion degree 1.5.

  Resins (P-2) to (P-13) and hydrophobicity in the same manner as in Synthesis Example 1 except that the monomers corresponding to the respective repeating units were used so as to have a desired composition ratio (molar ratio). Resins (1b) to (5b) were synthesized.

  Hereinafter, the structures of the resins (P-2) to (P-13) and the hydrophobic resins (1b) to (6b) are shown. In addition, including the resin (P-1) described above, the composition ratio (molar ratio), weight average molecular weight, dispersion of the resins (P-2) to (P-13) and the hydrophobic resins (1b) to (6b) The degrees are shown in Table 1.

Synthesis Example 3 (Synthesis of triphenylsulfonium acetate)
Triphenylsulfonium iodide 5.07 g (13 mmol), silver acetate 2.25 g (13.5 mmol), acetonitrile 120 mL, and water 60 mL were added and stirred at room temperature for 1 hour. The reaction solution was filtered to obtain a triphenylsulfonium acetate solution.

Synthesis Example 4 (Synthesis of Compound PAG-1)
Under a nitrogen stream, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride 28.0 g (88.55 mmol), triethylamine 17.92 g (177.1 mmol), diisopropyl ether 210 mL Was cooled with ice, and a mixed solution of 7.56 g (88.2 mmol) of piperidine and 105 mL of diisopropyl ether was added dropwise thereto over 30 minutes. The mixture was stirred for 1 hour under ice cooling, and further stirred at room temperature for 1 hour. The organic layer was washed successively with water, a saturated aqueous ammonium chloride solution and water, and the organic layer was dried over sodium sulfate. The solvent was removed, 140 mL of ethanol and 1400 mg of sodium hydroxide were added, and the mixture was stirred at room temperature for 2 hours. Dilute hydrochloric acid was added to neutralize the reaction solution to obtain a sulfonic acid ethanol solution.

The triphenylsulfonium acetate solution was added to the sulfonic acid solution and stirred at room temperature for 2 hours. 2100 mL of chloroform was added, and the organic layer was washed successively with water, a saturated aqueous ammonium chloride solution, and water. Purification by column chromatography (SiO ₂ , chloroform / methanol = 5/1) gave 21.0 g (32.76 mmol) of the following formula (PAG-1) as a white solid.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.64 (bs, 6H), 3.29 (bs, 2H), 3.64 (bs, 2H), 7.70 (m, 15H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-111.1 (t, 2F), -114.3 (t, 2F), -119.4 (m, 2F)

  Using the compound corresponding to each component (B), photoacid generators (PAG-2) to (PAG-12) of the following formulas were synthesized in the same manner as in Synthesis Examples 3 and 4 above.

<Preparation of resist and topcoat composition>
The components shown in Table 2 below were dissolved in the solvent shown in Table 2 to give a total solid content concentration of 3.5% by mass, and each was filtered through a polyethylene filter having a pore size of 0.03 μm to obtain resist compositions Ar-1 to Ar. -29 and topcoat composition t-1 were prepared.

  Abbreviations in Table 2 are as follows.

  B-1 to B-19: each represents the following compound. Here, the compounds (B-7) to (B-18) correspond to the compound (G), and among these, the nitrogen-containing resins (B-12) to (B-18) are all the resin (G). It corresponds to. Compound (B-19) corresponds to the above compound (PA). Compound B-10 and Resin B-12 were synthesized based on the following synthesis method, and other compounds were synthesized in the same manner.

Synthesis Example 5 (Synthesis of Compound B-10)
To 2.3 g of 1- (tert-butoxycarbonyl) isonipecotic acid, 50 ml of tetrahydrofuran (THF) was added, and 3.4 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol, 4-dimethylaminopyridine 1 0.7 g was added and stirred. To the solution, 3.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 30 ml of 1N HCl to stop the reaction. The organic layer was further washed with 1N HCl, then with water, and the organic layer was concentrated to obtain 3.2 g of Compound (B-10) (yield 83%).
¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): σ (ppm) = 1.45 (9H), 1.60-1.75 (2H), 1.90-2.00 (2H), 2.70 (1H), 2.85-3.00 (2H), 3.95-4.10 (2H), 5.75 (1H)

Synthesis Example 6 (Synthesis of Resin B-12)
Monomers corresponding to the following repeating units were charged in a ratio (molar ratio) of 39/49/10/2, respectively, and dissolved in PGMEA to prepare 450 g of a solution having a solid content concentration of 15% by mass. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added to this solution, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin B-12.

  The polymer composition ratio determined from NMR was 39/49/10/2. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 4300, and dispersion degree 1.5.

  The composition ratios (molar ratios), weight average molecular weights, and dispersities of resins (B-12) to (B-18) are shown in Table 3 below.

  X-1 to X-7, CL-1: each represents the following compound.

W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)

A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: γ-butyrolactone A3: Cyclohexanone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate B3: 2-Heptanone B4: Propylene carbonate C1: Diisopentyl ether

  A resist pattern was formed by the following method using the prepared resist composition.

Example 1 (exposure → bake → development → rinse: abbreviation E-B-D-R)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-1 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65), an exposure mask (line / space = 1/1) was obtained. Used for pattern exposure. After heating at 100 ° C. for 60 seconds, the developer shown in Table 4 was paddled for 30 seconds for development, padded with the rinse solution shown in Table 4 for 30 seconds, rinsed at 4000 rpm for 30 seconds. The wafer was rotated and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

Examples 2, 3, 5, 10, 11, 14, 15, 18-23, 26, Comparative Examples 1-3
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 1 except that the resists and conditions listed in Table 4 were employed.

Example 4 (immersion exposure → bake → development → rinse: abbreviation tiE-B-D-R)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-4 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Furthermore, the topcoat composition t-1 was applied thereon and baked at 100 ° C. for 60 seconds to form a topcoat film having a thickness of 100 nm. The obtained wafer was exposed using an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), and an exposure mask (line / space = 1/1), pattern exposure was performed. Ultra pure water was used as the immersion liquid. After heating at 100 ° C. for 60 seconds, the developer shown in Table 4 was paddled for 30 seconds for development, padded with the rinse solution shown in Table 4 for 30 seconds, rinsed at 4000 rpm, and 30 minutes. The wafer was rotated for 2 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

Example 6 (immersion exposure → bake → development → rinse: abbreviation iE-B-D-R)
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-6 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. The obtained wafer was exposed using an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), and an exposure mask (line / space = 1/1), pattern exposure was performed. Ultra pure water was used as the immersion liquid. After heating at 100 ° C. for 60 seconds, the developer shown in Table 4 was paddled for 30 seconds for development, padded with the rinse solution shown in Table 4 for 30 seconds, rinsed at 4000 rpm, and 30 minutes. The wafer was rotated for 2 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

Examples 7-9, 12, 24, 25
A line and space resist pattern of 100 nm (1: 1) was obtained in the same manner as in Example 6 except that the resists and conditions described in Table 4 were employed.

Example 13 (Exposure → Bake → Development: Abbreviation EBD)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-13 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65), an exposure mask (line / space = 1/1) was obtained. Used for pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 4 is paddled for 30 seconds for development, the wafer is rotated at 4000 rpm for 30 seconds, and baking is performed at 90 ° C. for 60 seconds. A 100 nm (1: 1) line and space resist pattern was obtained.

Example 16 (exposure → bake → development → rotation rinse: abbreviation E-BD-R2)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-16 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65), an exposure mask (line / space = 1/1) was obtained. Used for pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 4 is paddled for 30 seconds for development, and the rinse liquid described in Table 4 is allowed to flow on the wafer while rotating the wafer at 500 rpm. After rinsing for 30 seconds, the wafer was rotated at 4000 rpm for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

Example 17 (exposure → bake → rotary development → rinse: abbreviation EB-D2-R)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-17 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65), an exposure mask (line / space = 1/1) was obtained. Used for pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 4 was flowed on the wafer while rotating the wafer at a rotation speed of 500 rpm, developed for 30 seconds, and padded with the rinse liquid described in Table 4 for 30 seconds. After rinsing, the wafer was rotated at 4000 rpm for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

Example 27 (Inorganic antireflection film substrate → exposure → bake → development → rinse: abbreviation I-E-B-D-R)
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 2 except that a SiON substrate was used as the substrate having an inorganic antireflection film.

  In Table 4, PB means heating before exposure, and PEB means heating after exposure. Further, in the columns of PB, PEB and top coat baking, for example, “100 ° C. 60 s” means heating at 100 ° C. for 60 seconds. A1 and B1 represent the solvent described above.

<Evaluation method>
Evaluation of resolution [Line width roughness (LWR)]
A 100 nm (1: 1) line-and-space resist pattern was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd., S-9380II), and the range of the space pattern in the longitudinal direction of 2 μm was equally spaced. The 50 dotted line width was measured, and 3σ (nm) was calculated from the standard deviation. A smaller value indicates better performance.

[Focus margin (DOF)]
When the exposure amount and focus for forming a 100 nm (1: 1) line-and-space resist pattern are set to the optimum exposure amount and the optimum focus, respectively, and the focus is changed (defocused) while keeping the exposure amount at the optimum exposure amount. In addition, the width of the focus allowing the pattern size to be 100 nm ± 10% was obtained. The larger the value, the smaller the performance change due to the focus change, and the better the focus margin (DOF).

[Pattern shape]
The pattern shape of a 100 nm (1: 1) line-and-space resist pattern at the optimum exposure and optimum focus was observed. The level of a good pattern shape was indicated by ◯, and the level at which a T-top shape was observed was indicated by ×.

[Dimensions before bridge]
In a 100 nm (1: 1) line-and-space resist pattern at the optimum focus, the minimum space dimension at which no bridge defect occurs was observed by changing the exposure amount. A smaller value indicates that bridge defects are less likely to occur and the performance is better.

  From Table 5, by developing the resist composition of the present invention with a developer containing an organic solvent, a highly accurate fine pattern that is excellent in terms of line width roughness, focus margin, pattern shape and defect performance can be stably obtained. It is clear that it can be formed.

Claims (19)

(A) forming a film with a chemically amplified resist composition;
(A) a step of exposing the film, and (c) a step of developing using a developer containing an organic solvent,
A pattern forming method including:
The resist composition is
(A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) A pattern forming method comprising a compound having at least one of a fluorine atom and a silicon atom and having basicity or increased basicity by the action of an acid.   The pattern forming method according to claim 1, wherein the compound (G) is a nitrogen-containing compound.   The molecular weight of the said compound (G) is 500 or less, The pattern formation method of Claim 1 or 2 characterized by the above-mentioned. The pattern forming method according to claim 2, wherein the compound (G) is a compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different.   The pattern forming method according to claim 1, wherein the compound (G) is a resin.   The compound (G) is a resin having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a basic group or a group whose basicity is increased by the action of an acid. The pattern forming method according to claim 5.   The pattern forming method according to claim 1, wherein the resist composition further contains a crosslinking agent (C).   8. The developer according to claim 1, wherein the developer contains at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. The pattern forming method according to 1.   Furthermore, (d) The pattern formation method in any one of the Claims 1-8 characterized by including the process of rinsing using a rinse liquid.   The rinsing liquid is a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. The pattern forming method according to claim 9.   The pattern forming method according to claim 1, wherein the exposure in the step of exposing the film is immersion exposure. (A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G) a compound having at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid,
A chemically amplified resist composition comprising:
The chemical amplification resist composition, wherein the compound (G) is a compound represented by the following general formula (1).

In general formula (1),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, the organic group as Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom.
When z = 2, the two Rc's and the two Rf's may be the same or different, and the two Rc's may be bonded to each other to form a ring.
When y = 2, two R _b1 , two R _b2 and two R _b3 may be the same or different. (A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) solvent,
(G) a compound having at least one of a fluorine atom and a silicon atom, having basicity or increasing basicity by the action of an acid, and
A chemically amplified resist composition containing a hydrophobic resin having a fluorine atom, which does not correspond to the compound (G).   The chemically amplified resist composition according to claim 12 or 13, wherein the compound (G) has a molecular weight of 500 or less. (A) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(D) a solvent, and
(G- 2 ) a compound having at least one of a fluorine atom and a silicon atom and having increased basicity by the action of an acid ,
A chemically amplified resist composition comprising:
The chemical amplification resist composition, wherein the compound (G- 2 ) is a resin. The compound (G- 2 ) is a resin having a repeating unit having at least one of a fluorine atom and a silicon atom and a repeating unit having a group whose basicity is increased by the action of an acid. 15. The chemically amplified resist composition as described in 15. Furthermore, it contains the hydrophobic resin which does not correspond to the said component (G) or (G-2) and which has at least any one of a fluorine atom and a silicon atom, Any of Claim 12, 15, and 16 characterized by the above-mentioned. A chemically amplified resist composition as described above. The chemically amplified resist composition according to any one of claims 12 to 17 , further comprising a crosslinking agent (C). A resist film formed from the chemical amplification resist composition according to any one of claims 12 to 18.