JP5141459B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photolithography processes. More specifically, a chemically amplified radiation-sensitive resin composition that can be suitably used in a photolithography process using far ultraviolet rays having a wavelength of 250 nm or less or an electron beam as an exposure light source, such as KrF excimer laser and ArF excimer laser. It is about.

  The chemically amplified radiation-sensitive resin composition generates an acid in an exposed portion by irradiation with far ultraviolet rays or electron beams typified by a KrF excimer laser or an ArF excimer laser, and is exposed by a chemical reaction using this acid as a catalyst. It is a composition that causes a difference in the dissolution rate of the part and the unexposed part in the developer to form a resist pattern on the substrate.

  For example, when a KrF excimer laser (wavelength 248 nm) is used as a light source, a polymer having a basic skeleton of poly (hydroxystyrene) (hereinafter sometimes referred to as “PHS”) that has low absorption in the 248 nm region. A chemically amplified radiation-sensitive resin composition containing as a constituent is used. According to this composition, high sensitivity, high resolution, and good pattern formation can be realized.

  However, when a shorter wavelength light source, for example, an ArF excimer laser (wavelength 193 nm) is used as a light source for the purpose of further microfabrication, an aromatic compound such as PHS having a large absorption in the 193 nm region should be used. There was a problem that was difficult.

  Therefore, as a lithography material using an ArF excimer laser as a light source, a polymer having an alicyclic hydrocarbon having no large absorption in the 193 nm region in its skeleton, particularly a polymer having a lactone skeleton in its repeating unit is constituted. A resin composition as a component is used.

  As the radiation sensitive resin composition as described above, for example, a radiation sensitive resin composition containing a polymer having a mevalonic lactone skeleton or a γ-butyrolactone skeleton in its repeating unit is disclosed. (See Patent Documents 1 and 2). Moreover, the resin composition which uses the polymer which has an alicyclic lactone skeleton in the repeating unit as a structural component is also disclosed (for example, refer patent documents 3-13).

JP-A-9-73173 US Pat. No. 6,388,101B JP 2000-159758 A JP 2001-109154 A JP 2004-101642 A JP 2003-113174 A Japanese Patent Laid-Open No. 2003-147023 JP 2002-308866 A JP 2002-371114 A JP 2003-64134 A JP 2003-270787 A JP 2000-26446 A JP 2000-122294 A

  It has been found that the above-mentioned composition has a lactone skeleton in its repeating unit, so that the resolution performance as a resist is remarkably improved. However, at the present time when the miniaturization of resist patterns has progressed to a level of 90 nm or less, not only high resolution performance but also other performance has been required. For example, as one of the resist pattern miniaturization techniques, liquid immersion exposure is currently being put into practical use, and a resist material that can cope with this liquid immersion exposure is demanded. Specifically, the depth of focus (DOF), the roughness of the line width (LWR: Line Width Roughness), the amplification factor (MEEF: Mask Error Enhancement Factor) of the deviation of the line width due to the deviation of the mask width, and the pattern There is a demand for the development of materials that satisfy various required characteristics such as fall resistance and development defect performance.

  The present invention has been made in view of such problems of the prior art, and has a wide focal depth, a small LWR and MEEF, excellent pattern collapse characteristics, and excellent development defect performance. A composition is provided.

  As a result of intensive studies to solve the problems of the prior art as described above, the present inventors have found that a resin comprising a polymer having a repeating unit containing a cyclic carbonate structure and an acid diffusion inhibitor having a carbamate structure. It has been found that the above-mentioned problems can be solved by using an agent as a constituent of the radiation-sensitive resin composition, and the present invention has been completed. Specifically, the present invention provides the following radiation-sensitive resin composition.

〔一般式（ａ−１）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基を示し、Ｒ^１９は相互に独立して、水素原子、炭素数１〜５の鎖状炭化水素基を示し、Ａは単結合、炭素数が１〜３０である２価若しくは３価の鎖状炭化水素基、炭素数が３〜３０である２価若しくは３価の脂環式炭化水素基又は炭素数が６〜３０である２価若しくは３価の芳香族炭化水素基を示し、Ａが３価の場合、Ａに含まれる炭素原子と環状炭酸エステルを構成する炭素原子とが結合されて、環構造が形成されている。ｎは２〜４の整数を示す。〕

〔一般式（Ｃ−１）中、Ｒ^２，Ｒ^３は相互に独立して、水素原子、炭素数が１〜２０である１価の鎖状炭化水素基、炭素数が３〜２０である１価の脂環式炭化水素基又は炭素数が６〜２０である１価の芳香族炭化水素基を示す。２つのＲ^２が結合されて、環構造が形成されていてもよい。〕 [1] A resin (A), a radiation-sensitive acid generator (B), an acid diffusion inhibitor (C), and a solvent (D), and the resin (A) is represented by the following general formula ( a polymer having a repeating unit (a-1) represented by a-1), wherein the acid diffusion inhibitor (C) is a nitrogen-containing compound represented by the following general formula (C-1) Resin composition.

[In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁹ independently represents a hydrogen atom, which has 1 to 5 carbon atoms. A chain hydrocarbon group, A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic group having 3 to 30 carbon atoms A hydrocarbon group or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and when A is trivalent, the carbon atoms contained in A and the carbon atoms constituting the cyclic carbonate are Combined, a ring structure is formed. n shows the integer of 2-4. ]

[In General Formula (C-1), R ² and R ³ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 3 to 20. A monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is shown. Two R ² may be bonded to form a ring structure. ]

[2] The radiation-sensitive resin according to [1], wherein the resin (A) is a polymer having a repeating unit (a-2) containing a lactone structure in addition to the repeating unit (a-1). Composition.

〔一般式（ａ−１）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基を示し、Ｒ^１９は相互に独立して、水素原子、炭素数１〜５の鎖状炭化水素基を示し、Ａは単結合、炭素数が１〜３０である２価若しくは３価の鎖状炭化水素基、炭素数が３〜３０である２価若しくは３価の脂環式炭化水素基又は炭素数が６〜３０である２価若しくは３価の芳香族炭化水素基を示し、Ａが３価の場合、Ａに含まれる炭素原子と環状炭酸エステルを構成する炭素原子とが結合されて、環構造が形成されている。ｎは２〜４の整数を示す。〕

〔一般式（ａ−３ａ），（ａ−３ｂ）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基、Ｒ^１７は相互に独立して炭素数１〜１０のアルキル基、Ｒ^１８は炭素数２〜４のアルキル基を示す。２つのＲ^１７が結合されて、３〜１０員環が形成されていてもよい。〕 [3] The repeating unit (a-1) represented by the following general formula (a-1) and at least one repeating unit (a-3) of the following general formulas (a-3a) and (a-3b) And a copolymer.

[In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁹ independently represents a hydrogen atom, which has 1 to 5 carbon atoms. A chain hydrocarbon group, A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic group having 3 to 30 carbon atoms A hydrocarbon group or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and when A is trivalent, the carbon atoms contained in A and the carbon atoms constituting the cyclic carbonate are Combined, a ring structure is formed. n shows the integer of 2-4. ]

[In General Formulas (a-3a) and (a-3b), R ¹ is independently of each other a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁷ is independently of each other of 1 to 10 carbon atoms. An alkyl group, R ¹⁸ represents an alkyl group having 2 to 4 carbon atoms. Two R < ¹⁷ > may be couple | bonded and the 3-10 membered ring may be formed. ]

  The radiation sensitive resin composition of the present invention has a wide depth of focus, a small LWR and MEEF, excellent pattern collapse characteristics, and excellent development defect performance. Therefore, it can be suitably used as a lithography material using an ArF excimer laser as a light source. Moreover, it can respond also to the lithography material which uses immersion exposure and a KrF excimer laser as a light source.

  Hereinafter, the best mode for carrying out the radiation-sensitive resin composition of the present invention will be specifically described. However, the present invention includes all embodiments including the invention-specific matters, and is not limited to the embodiments described below. In the following description, the same type of substituent is given the same reference numeral, and the description is omitted.

  In addition, in this specification, “... group” means “optionally substituted ... group”. For example, when “alkyl group” is described, it includes not only an unsubstituted alkyl group but also an alkyl group in which a hydrogen atom is substituted with another functional group. Further, the term “... Group” means “a group that may have a branch ...”. For example, “alkylcarbonyl group” includes not only a linear alkylcarbonyl group but also a branched alkylcarbonyl group.

  The radiation-sensitive resin composition of the present invention comprises a resin (A), an acid generator (B), an acid diffusion inhibitor (C), and a solvent (D) as essential components, and an additive (E) depending on the purpose. Is included. Hereinafter, each component will be described.

〔一般式（ａ−１）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基を示し、Ｒ^１９は相互に独立して、水素原子、炭素数１〜５の鎖状炭化水素基を示し、Ａは単結合、炭素数が１〜３０である２価若しくは３価の鎖状炭化水素基、炭素数が３〜３０である２価若しくは３価の脂環式炭化水素基又は炭素数が６〜３０である２価若しくは３価の芳香族炭化水素基を示し、Ａが３価の場合、Ａに含まれる炭素原子と環状炭酸エステルを構成する炭素原子とが結合されて、環構造が形成されている。ｎは２〜４の整数を示す。〕 [1] Resin (A):
The resin (A) in the present invention is a polymer having a repeating unit (a-1) represented by the following general formula (a-1).

[In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁹ independently represents a hydrogen atom, which has 1 to 5 carbon atoms. A chain hydrocarbon group, A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic group having 3 to 30 carbon atoms A hydrocarbon group or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and when A is trivalent, the carbon atoms contained in A and the carbon atoms constituting the cyclic carbonate are Combined, a ring structure is formed. n shows the integer of 2-4. ]

[1-1] Repeating unit (a-1):
A repeating unit (a-1) is a repeating unit containing the cyclic carbonate structure shown by the said general formula (a-1), and is an essential repeating unit of resin (A).

Examples thereof include repeating units (a-1a) to (a-1v) represented by the following general formulas (a-1a) to (a-1v).

In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Of these, a methyl group is preferred. R ¹⁹ independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 5 carbon atoms. Examples of the “chain hydrocarbon group having 1 to 5 carbon atoms” include linear alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, and butyl group; isopropyl group, isobutyl group, t -C3-C5 branched alkyl groups, such as a butyl group, etc. can be mentioned.

  In general formula (a-1), n shows the integer of 2-4. That is, the cyclic carbonate is a 5-membered ring structure when n = 2 (ethylene group), a 6-membered ring structure when n = 3 (propylene group), and a 7-membered ring when n = 4 (butylene group). It becomes a structure. For example, the repeating unit a-1a is a 5-membered ring structure, and a-1j is a 6-membered ring structure.

  In general formula (a-1), A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, or a divalent or trivalent alicyclic ring having 3 to 30 carbon atoms. And a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

  When A is a single bond, the oxygen atom of (meth) acrylic acid constituting the polymer and the carbon atom constituting the cyclic carbonate are directly bonded.

  The “chain hydrocarbon group” referred to in the present specification means a hydrocarbon group composed of only a chain structure without including a cyclic structure in the main chain. Examples of the “divalent chain hydrocarbon group having 1 to 30 carbon atoms” include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a tetramethylene group, and a pentamethylene group. , Hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadeca Linear alkylene groups such as methylene, octadecamethylene, nonadecamethylene, icosalen; 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1 , 2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, methylidene group, ethylide And the like can be given; group, propylidene group, and a 2-propylidene group branched alkylene group. Examples of the “trivalent chain hydrocarbon group having 1 to 30 carbon atoms” include a group in which one hydrogen atom is eliminated from the functional group.

  As the structure when A is a chain hydrocarbon group, the oxygen atom of (meth) acrylic acid constituting the polymer and the carbon atom constituting the cyclic carbonate are linear alkyl having 1 to 5 carbon atoms. The structure couple | bonded through group can be mentioned (repeating unit a-1a-a-1f). In this structure, a cyclic structure may be included as a substituent of A (a-1p).

  The carbon atom contained in A and the carbon atom which comprises cyclic carbonate may be couple | bonded, and the ring structure may be formed. In other words, the cyclic carbonate may form part of a condensed ring or a spiro ring. When the ring structure contains two carbon atoms in the cyclic carbonate, a condensed ring is formed, and when only one carbon atom in the cyclic carbonate is contained, a spiro ring is formed. The repeating units a-1g, a-1q, a-1t, a-1u, a-1i, a-1r, a-1s, a-1v are the two carbon atoms contained in A and the cyclic carbonate. This is an example in which a condensed ring containing a carbon atom is formed. On the other hand, a-1j is an example in which a spiro ring is formed by the carbon atom contained in A and one carbon atom constituting the cyclic carbonate. The ring structure may be a heterocycle (a-1q to a-1v).

  The “alicyclic hydrocarbon group” in the present specification means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be constituted only by the structure of the alicyclic hydrocarbon, and a part thereof may include a chain structure.

  Examples of the “divalent alicyclic hydrocarbon group” include a 1,3-cyclobutylene group, a 1,3-cyclopentylene group, a 1,4-cyclohexylene group, and a 1,5-cyclooctylene group. A monocyclic cycloalkylene group having 3 to 10 carbon atoms such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc. An alkylene group; and the like. Examples of the “trivalent alicyclic hydrocarbon group” include a group in which one hydrogen atom is eliminated from the functional group.

  As the structure when A is an alicyclic hydrocarbon group, an oxygen atom of (meth) acrylic acid constituting a polymer and a carbon atom constituting a cyclic carbonate are bonded via a cyclopentylene group. (Repeating unit a-1j), those bonded via a norbornylene group (a-1k, a-1l), those bonded via a substituted tetradecahydrophenanthryl group (a- 1n) and the like.

  The repeating units a-1k and a-1l are examples in which a condensed ring including the carbon atom contained in A and the two carbon atoms constituting the cyclic carbonate is formed. On the other hand, a-1j and a-1n are examples in which a spiro ring is formed by the carbon atom contained in A and one carbon atom constituting the cyclic carbonate.

  The “aromatic hydrocarbon group” in the present specification means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.

  Examples of the “divalent aromatic hydrocarbon group” include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group. Examples of the “trivalent aromatic hydrocarbon group” include a group in which one hydrogen atom is eliminated from the functional group.

  As an example in which A is an aromatic hydrocarbon group, an oxygen atom of (meth) acrylic acid constituting a polymer and a carbon atom constituting a cyclic carbonate are bonded via a benzylene group (repeatedly) And units a-1o). The repeating unit a-1o is an example in which a condensed ring including a carbon atom contained in A and two carbon atoms constituting a cyclic carbonate is formed.

  Examples of the monomer include Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002) and the like, and can be synthesized by a conventionally known method.

  In the resin (A), one of the exemplified repeating units (a-1) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-1) is preferably from 5 to 80 mol%, and preferably from 10 to 70 mol%, based on all repeating units constituting the resin (A). It is still more preferable, and it is especially preferable that it is 10-50 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR, low PEB temperature dependence, etc. can be improved. On the other hand, if the content of a-1 is less than 5 mol%, the developability and low defectivity as a resist may be lowered. Moreover, when it exceeds 80 mol%, there exists a possibility that the resolution as a resist, low LWR, and low PEB temperature dependence may fall.

  Note that “low defectivity” means that defects are less likely to occur in the photolithography process. Examples of the “defect” in the photolithography process include a watermark defect, a blob defect, a bubble defect, and the like. If a large number of these defects occur in device manufacturing, the device yield is greatly affected, which is not preferable.

  Furthermore, the “watermark defect” is a defect in which a droplet trace of the immersion liquid remains on the resist pattern, and the “blob defect” is a resin once dissolved in the developer, which is deposited by the rinse shock, The “bubble defect” refers to a defect in which a desired pattern cannot be obtained due to a change in optical path caused by the immersion liquid containing bubbles at the time of immersion exposure.

[1-2] Repeating unit (a-2):
The resin (A) is preferably a polymer having a repeating unit (a-2) containing a lactone structure in addition to the repeating unit (a-1).

〔一般式（ａ−２ａ）〜（ａ−２ｐ）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基を示す。〕 Examples of the repeating unit (a-2) include repeating units (a-2a) to (a-2p) represented by the following general formulas (a-2a) to (a-2p).

[In the general formulas (a-2a) to (a-2p), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

  The repeating unit (a-2) is preferably a repeating unit containing a lactone ring bonded to an alicyclic hydrocarbon group. The repeating unit a-2b is an example of a repeating unit including a lactone ring bonded to a cyclopentane ring, and a-2e and a-2f are examples of a repeating unit including a lactone ring bonded to a cyclohexane ring.

  The repeating unit (a-2) is particularly preferably a repeating unit containing a lactone ring bonded to a polycyclic alicyclic hydrocarbon group. The repeating units a-2a, a-2c, a-2g to a-2m are examples of a repeating unit containing a lactone ring bonded to a norbornene ring, and a-2d is a bicyclo [2.2.2] octane. It is an example of the repeating unit containing a ring.

As a monomer that gives the repeating unit (a-2), (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester, (Meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester, (meth) acrylic acid-5-oxo-4- Oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl ester, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] Nona-2-yl ester, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-4-methoxycarbonyl -6-oxo-7-oki -Bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ester, (meth) acrylic acid -4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester, (meth) acrylic Acid-4-methyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-propyl-2- Oxotetrahydropyran-4-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2,2-di Methyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, (Meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid- 2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester, (Meth) acrylic acid-4,4-dimethyl-5-oxote Rahidorofuran 2-yl methyl ester, and the like.

  In the resin (A), one of the exemplified repeating units (a-2) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-2) is preferably 0 to 90 mol%, and preferably 0 to 80 mol%, based on all repeating units constituting the resin (A). Is more preferable, and it is especially preferable that it is 0-70 mol%. When the content rate of a repeating unit (a-2) exceeds 90 mol%, there exists a possibility that the resolution as a resist, LWR, and PEB temperature dependence may fall.

〔一般式（ａ−３ａ），（ａ−３ｂ）中、Ｒ^１は相互に独立して、水素原子、メチル基又はトリフルオロメチル基、Ｒ^１７は相互に独立して炭素数１〜１０のアルキル基、Ｒ^１８は炭素数２〜４のアルキル基を示す。２つのＲ^１７が結合されて、３〜１０員環が形成されていてもよい。〕 [1-3] Repeating unit (a-3):
The resin (A) is a polymer having at least one repeating unit (a-3) of the following general formulas (a-3a) and (a-3b) in addition to the repeating unit (a-1). Preferably there is.

[In General Formulas (a-3a) and (a-3b), R ¹ is independently of each other a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁷ is independently of each other of 1 to 10 carbon atoms. An alkyl group, R ¹⁸ represents an alkyl group having 2 to 4 carbon atoms. Two R < ¹⁷ > may be couple | bonded and the 3-10 membered ring may be formed. ]

As the repeating unit (a-3a), repeating units represented by the following general formulas (a-3a1) to (a-3a10), and as the repeating unit (a-3b), the following general formulas (a-3b1), ( The repeating unit represented by a-3b2) is particularly preferred.

  In the resin (A), one of the exemplified repeating units (a-3) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-3) is preferably 5 to 80 mol%, and preferably 10 to 80 mol%, based on all repeating units constituting the resin (A). It is further more preferable that it is 20 to 70%. When the content rate of a repeating unit (a-3) exceeds 80 mol%, the adhesiveness of a resist film will fall and there exists a possibility of causing pattern collapse and pattern peeling.

（一般式（ａ−４ａ），（ａ−４ｂ）中、Ｒ^４は相互に独立して、炭素数１〜４のアルキル基を示す。） [1-4] Repeating unit (a-4):
The resin (A) is a polymer having at least one repeating unit (a-4) of the following general formulas (a-4a) to (a-4b) in addition to the repeating unit (a-1). Preferably there is. The repeating unit (a-4) is a repeating unit having an adamantane skeleton at the ester moiety.

(In the general formulas (a-4a) and (a-4b), R ⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.)

In the general formulas (a-4a) and (a-4b), the “alkyl group having 1 to 4 carbon atoms” represented by R ⁴ has 1 to 3 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group. A branched alkyl group having 3 to 4 carbon atoms such as isopropyl group, isobutyl group and t-butyl group. Of these, a methyl group or an ethyl group is preferable.

  As a monomer which gives the repeating unit (a-4a), (meth) acrylic acid 2-methyladamantyl-2-yl ester, (meth) acrylic acid 2-ethyladamantyl-2-yl ester, (meth) acrylic acid 2-ethyl-3-hydroxyadamantyl-2-yl ester, (meth) acrylic acid 2-n-propyladamantyl-2-yl ester, (meth) acrylic acid 2-isopropyladamantyl-2-yl ester and the like are preferable, More preferred are (meth) acrylic acid 2-methyladamantyl-2-yl ester and (meth) acrylic acid 2-ethyladamantyl-2-yl ester.

  As a monomer which gives the repeating unit (a-4b), (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-ethyl ethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylpropyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-ethylpropyl ester, etc. preferable.

  In the resin (A), one type of the exemplified repeating units (a-4) may be contained alone, or two or more types may be contained. In the resin (A), the content of the repeating unit (a-4) is such that the total amount of the repeating unit (a-4) is 5 to 70 mol% with respect to all the repeating units constituting the resin (A). It is preferably 5 to 60 mol%, more preferably 10 to 50 mol%. By setting it as such a content rate, the developability as a resist, defect property, low LWR, low PEB temperature dependence, etc. can be improved. On the other hand, when the content of the repeating unit (a-4) is less than 5 mol%, the pattern collapse performance as a resist may be lowered. Moreover, when it exceeds 70 mol%, there exists a possibility that the resolution as a resist, LWR, and PEB temperature dependence may fall.

（一般式（ａ−５）中、Ｒ^６は炭素数７〜２０の多環型シクロアルキル基を示す。） [1-5] Repeating unit (a-5):
Resin (A) is a polymer having a repeating unit (a-5) having a polycyclic cycloalkyl group in the structure, represented by general formula (a-5), in addition to repeating unit (a-1) It is preferable that

(In general formula (a-5), R ⁶ represents a polycyclic cycloalkyl group having 7 to 20 carbon atoms.)

In the general formula (a-5), examples of the “polycyclic cycloalkyl group having 7 to 20 carbon atoms” represented by R ⁶ include bicyclo [2.2.1] heptane and bicyclo [2.2.2] octane. , Tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . And a cycloalkyl group having a plurality of ring structures such as 0 ^2,7 ] dodecane and tricyclo [3.3.1.1 ^3,7 ] decane.

  In this polycyclic cycloalkyl group, at least one hydrogen atom is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, a cyano group, or a hydroxyalkyl having 1 to 10 carbon atoms. It may be substituted with at least one substituent selected from the group consisting of a group and a carboxyl group.

  Examples of the “alkyl group having 1 to 4 carbon atoms” include linear alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group; an i-propyl group and 2-methyl And a branched alkyl group having 3 to 4 carbon atoms such as a propyl group, a 1-methylpropyl group and a t-butyl group. Examples of the “C3-C12 cycloalkyl group” include a cyclopropyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.

As a monomer which gives the repeating unit (a-6), (meth) acrylic acid-bicyclo [2.2.1] heptyl ester, (meth) acrylic acid-cyclohexyl ester, (meth) acrylic acid-bicyclo [4] .4.0] decanyl ester, (meth) acrylic acid-bicyclo [2.2.2] octyl ester, (meth) acrylic acid-tricyclo [5.2.1.0 ^2,6 ] decanyl ester, ( (Meth) acrylic acid-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecanyl ester, (meth) acrylic acid-tricyclo [3.3.1.1 ^3,7 ] decanyl ester, and the like.

  In the resin (A), one of the exemplified repeating units (a-5) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-5) is preferably 0 to 30 mol%, and preferably 0 to 25 mol%, based on all repeating units constituting the resin (A). More preferably. When the content of the repeating unit (a-5) exceeds 30 mol%, the resist film tends to swell with an alkali developer, or the developability as a resist may be reduced.

（一般式（ａ−６）中、Ｒ^７は水素原子、炭素数１〜４のアルキル基、トリフルオロメチル基又はヒドロキシメチル基を示し、Ｒ^８は、２価の鎖状炭化水素基又は２価の環状炭化水素基を示す。） [1-6] Repeating unit (a-6):
Resin (A) has a repeating unit (a-1) and a repeating unit having a carbon atom represented by the general formula (a-6) in which two trifluoromethyl groups and one hydroxyl group are bonded in the structure. It is preferable that it is a polymer which has a unit (a-6).

(In General Formula (a-6), R ⁷ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or a hydroxymethyl group, and R ⁸ represents a divalent chain hydrocarbon group or 2 Valent cyclic hydrocarbon group.)

In the general formula (a-6), the “divalent chain hydrocarbon group” represented by R ⁸ includes a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group Linear alkylene groups such as 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2; heptadecamethylene group, octadecamethylene group, nonadecamethylene group, icosalen group, etc. -Methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, methylidene group, ethyl And branched alkylene groups such as a lidene group, a propylidene group, and a 2-propylidene group.

  The “divalent cyclic hydrocarbon group” includes 1,3-cyclobutylene group, 1,3-cyclopentylene group, etc., 1,4-cyclohexylene group, 1,5-cyclooctylene group, etc. 3-10 monocyclic cycloalkylene groups; polycyclic cycloalkylene groups such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group; etc. Can be mentioned.

  The “divalent chain hydrocarbon group” or “divalent cyclic hydrocarbon group” may contain other atoms as long as it contains carbon atoms and hydrogen atoms. For example, an alkylene glycol group, an alkylene ester group and the like are also included in the “divalent chain hydrocarbon group”.

  Monomers that give the repeating unit (a-6) include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) acrylic Acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2- Hydroxy-5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester,

(Meth) acrylic acid 2-{[5- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] bicyclo [2.2.1] heptyl} ester, (Meth) acrylic acid 3-{[8- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecyl} ester and the like are preferable.

  In the resin (A), one of the exemplified repeating units (a-6) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-6) is preferably 0 to 30 mol%, and preferably 0 to 25 mol% with respect to all repeating units constituting the resin (A). More preferably. When the content rate of a repeating unit (a-6) exceeds 30 mol%, there exists a possibility that the top loss of a resist pattern may arise and a pattern shape may deteriorate.

（一般式（ａ−７）中、Ｒ^９は水素原子又はメチル基を示し、Ｙは相互に独立して単結合又はメチレン基、炭素数２〜３の２価のアルキレン基を示し、Ｒ^１０は相互に独立して水素原子、水酸基、シアノ基又はＣＯＯＲ^１１基を示す。但し、Ｒ^１１は水素原子、炭素数１〜４のアルキル基又は炭素数３〜２０のシクロアルキル基を示す。）。 [1-7] Repeating unit (a-7):
The resin (A) is a polymer having a repeating unit (a-7) having a structure of an adamantane ring in the structure represented by the general formula (a-7) in addition to the repeating unit (a-1). It is preferable.

(In the general formula (a-7), R ⁹ represents a hydrogen atom or a methyl group, Y represents a single bond or a methylene group, independently of one another, it represents a divalent alkylene group having 2 to 3 carbon atoms, R ¹⁰ Each independently represents a hydrogen atom, a hydroxyl group, a cyano group or a COOR ¹¹ group, provided that R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.) .

  In the general formula (a-7), examples of the “divalent alkylene group having 2 to 3 carbon atoms” represented by Y include divalent linear saturated alkylene groups such as an ethylene group and a propylene group; Can do.

In General Formula (a-7), when Y is a single bond and there is a group in which R ^{10 which} is not a hydrogen atom is bonded to the single bond, at least one of the other Y is a methylene group, and has 2 to 3 carbon atoms. It is preferable that it is an alkylene group.

In R ^{10 of} general formula (a-7), the “alkyl group having 1 to 4 carbon atoms” represented by R ¹¹ has the same meaning as that represented by R ³ in general formula (a-2).

As the “cycloalkyl group having 3 to 20 carbon atoms”, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group represented by a general formula: —C _x H _2x-1 (x: an integer of 3 to 20), Monocyclic cycloalkyl groups such as cycloheptyl and cyclooctyl; bicyclo [2.2.1] heptyl, tricyclo [5.2.1.0 ^2,6 ] decyl, tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] a polycyclic cycloalkyl group such as a dodecanyl group or an adamantyl group; or a group in which a part of hydrogen atoms of these groups is substituted with an alkyl group or a cycloalkyl group.

  Monomers that give the repeating unit (a-7) include (meth) acrylic acid 3-hydroxyadamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dihydroxyadamantan-1-ylmethyl ester, (Meth) acrylic acid 3-hydroxy-5-methyladamantan-1-yl ester, (meth) acrylic acid 3,5-dihydroxy-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5, 7-dimethyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5,7-dimethyladamantan-1-ylmethyl ester, and the like are preferable.

  In the resin (A), one of the exemplified repeating units (a-7) may be contained alone, or two or more thereof may be contained. In the resin (A), the content of the repeating unit (a-7) is preferably 0 to 30 mol%, and preferably 0 to 25 mol%, based on all repeating units constituting the resin (A). More preferably. When the content of the repeating unit (a-7) exceeds 30 mol%, the resist film tends to swell with an alkali developer, or the developability as a resist may be reduced.

[1-8] Repeating unit (a-8):
The polymer constituting the resin (A) may further have a repeating unit (a-8) other than the repeating units (a-1) to (a-7) so as to impart a desired function.

  Examples of the repeating unit (a-8) include (meth) acrylic acid esters having a bridged hydrocarbon skeleton such as dicyclopentenyl (meth) acrylate and adamantylmethyl (meth) acrylate; (meth) acrylic Carboxyl group-containing esters having a bridged hydrocarbon skeleton of unsaturated carboxylic acid such as carboxynorbornyl acid, carboxytricyclodecanyl (meth) acrylate, carboxytetracycloundecanyl (meth) acrylate;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, 1-methyl (meth) acrylate Propyl, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclopropyl (meth) acrylate, ( (Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 4-methoxycyclohexyl, (meth) acrylic acid 2-cyclopentyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) 2- (4-Methoxycyclohexyl) acrylic acid No bridged hydrocarbon skeleton such as aryloxycarbonyl ethyl (meth) acrylate;

  α-hydroxymethyl acrylate esters such as methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, n-butyl α-hydroxymethyl acrylate; (meth) acrylonitrile , Α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconitrile, citraconitrile, itaconnitrile, and other unsaturated nitrile compounds; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide , Fumaramide, mesaconamide, citraconic amide, itaconic amide, etc .; N- (meth) acryloylmorpholine, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinyl Other nitrogen-containing vinyl compounds such as lysine and vinylimidazole; (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc. Unsaturated carboxylic acids (anhydrides); 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, Carboxyl group-containing esters having no bridged hydrocarbon skeleton of unsaturated carboxylic acid such as (meth) acrylic acid 4-carboxycyclohexyl;

  1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, etc. A polyfunctional monomer having a bridged hydrocarbon skeleton;

  Methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di ( (Meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzenedi (meth) acrylate, 1,3-bis List units in which a polymerizable unsaturated bond of a polyfunctional monomer such as a polyfunctional monomer having no bridged hydrocarbon skeleton such as (2-hydroxypropyl) benzenedi (meth) acrylate is cleaved Can do.

  In the resin (A), the content of the repeating unit (a-8) is preferably 0 to 50 mol%, and preferably 0 to 40 mol%, based on all repeating units constituting the resin (A). More preferably.

[1-4] Manufacturing method:
Next, the manufacturing method of resin (A) is demonstrated.

  The resin (A) can be synthesized according to a conventional method such as radical polymerization. For example, (1) a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; (2) a solution containing the monomer and a radical A method in which a solution containing an initiator is dropped into a reaction solvent or a solution containing a monomer separately to cause a polymerization reaction; (3) a plurality of types of solutions containing each monomer, and radical initiation It is preferable to synthesize | combine by the method of dripping the solution containing an agent separately to the solution containing a reaction solvent or a monomer, respectively, and carrying out a polymerization reaction.

  In addition, when the monomer solution is dropped and reacted with respect to the monomer solution, the amount of the monomer in the dropped monomer solution is 30 mol% with respect to the total amount of monomers used for polymerization. Preferably, it is more preferably 50 mol% or more, and particularly preferably 70 mol% or more.

  What is necessary is just to determine the reaction temperature in these methods suitably with initiator seed | species. Usually, it is 30-180 degreeC, 40-160 degreeC is preferable and 50-140 degreeC is still more preferable. Although dripping time changes with conditions, such as reaction temperature, the kind of initiator, and the monomer made to react, it is 30 minutes-8 hours normally, 45 minutes-6 hours are preferable, and 1-5 hours are still more preferable. Further, the total reaction time including the dropping time varies depending on the conditions as well as the dropping time, but is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 to 6 hours.

  Examples of the radical initiator used in the polymerization include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2, 2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2-methyl-N [1,1-bis (hydroxymethyl) 2-hydroxyethyl] propionamide}, dimethyl-2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2- (hydroxymethyl) propionitrile) and the like can be mentioned. These initiators can be used alone or in admixture of two or more.

  As the polymerization solvent, any solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and capable of dissolving the monomer may be used. it can. Examples thereof include alcohols, ethers, ketones, amides, esters / lactones, nitriles, and mixed solvents thereof.

  Examples of the “alcohols” include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol and the like. Examples of the “ethers” include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 1,3-dioxane and the like.

  Examples of “ketones” include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. Examples of “amides” include N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples of the “ester / lactone” include ethyl acetate, methyl acetate, isobutyl acetate, γ-butyrolactone and the like. Examples of “nitriles” include acetonitrile, propionitrile, butyronitrile and the like. These solvents can be used alone or in admixture of two or more.

  The resin obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the target resin is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent. As a reprecipitation solvent, the solvent illustrated as the said polymerization solvent can be used individually or in mixture of 2 or more types.

  In addition, although the resin (A) contains a low molecular weight component derived from a monomer, the content thereof is 0.1% by mass or less with respect to the total amount (100% by mass) of the resin (A). It is preferably 0.07% by mass or less, and particularly preferably 0.05% by mass or less.

  When the content of this low molecular weight component is 0.1% by mass or less, a resist film is prepared using this resin (A), and water is brought into contact with the resist film when performing immersion exposure. It is possible to reduce the amount of eluate. Furthermore, no foreign matter is deposited in the resist during resist storage, and coating unevenness does not occur during resist application. Therefore, it is possible to sufficiently suppress the occurrence of defects when forming a resist pattern.

  In the present specification, when the term “low molecular weight component” derived from a monomer is used, the polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as “Mw”) by gel permeation chromatography (GPC) is Mw500. It shall mean the following ingredients. Specifically, it is a component such as a monomer, dimer, trimer or oligomer. This “low molecular weight component” can be removed by, for example, chemical purification methods such as washing with water, liquid-liquid extraction, and the like, and chemical purification methods combined with physical purification methods such as ultrafiltration and centrifugation. it can.

  Further, the low molecular weight component can be quantified by analyzing the resin (A) by high performance liquid chromatography (HPLC). In addition to the low molecular weight component, the resin (A) is preferably as low as possible impurities such as halogen and metal, thereby further improving the sensitivity, resolution, process stability, pattern shape, etc. when used as a resist. it can.

  On the other hand, the polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) of the resin (A) is not particularly limited, but is preferably 1,000 to 100,000. More preferably, it is 1,000 to 30,000, and particularly preferably 1,000 to 20,000. If the Mw of the resin (A) is less than 1,000, the heat resistance when used as a resist tends to decrease. On the other hand, if the Mw of the resin (A) exceeds 100,000, the developability when used as a resist tends to decrease.

  The ratio (Mw / Mn) of Mw to the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) by gel permeation chromatography (GPC) of the resin (A) is usually 1.0 to 5.0. It is preferable that it is 1.0-3.0, and it is still more preferable that it is 1.0-2.0.

  In the resin composition of this invention, resin (A) can be used individually or in mixture of 2 or more types.

[2] Acid generator (B):
The acid generator (B) is a radiation-sensitive acid generator that generates an acid upon exposure. This acid generator uses an acid generated by exposure to dissociate an acid-dissociable group present in the resin (A) contained in the radiation-sensitive resin composition (eliminate a protective group), and (A) is alkali-soluble. As a result, the exposed portion of the resist film becomes readily soluble in an alkaline developer, thereby forming a positive resist pattern.

As an acid generator (B) in this embodiment, what contains the compound shown by the following general formula (B-1) is preferable.

（一般式（ｂ−３），（ｂ−４）中、Ｒ^１６は相互に独立して炭素数１〜１０のフッ素置換アルキル基を示す。但し、２個のＲ^１６が相互に結合して炭素数２〜１０の２価のフッ素置換アルキレン基を形成していてもよい。） In the general formula (B-1), R ¹² represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 11 carbon atoms, R ¹³ represents an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkanesulfonyl group having 1 to 10 carbon atoms, R ¹⁴ is independently an alkyl group having 1 to 10 carbon atoms, A phenyl group and a naphthyl group are shown. However, two R ^14s may be bonded to each other to form a divalent group having 2 to 10 carbon atoms. k represents an integer of 0 to 2, r represents an integer of 0 to 10, and X ⁻ represents an anion represented by the following general formulas (b-1) to (b-4). )
_{^{R 15 C y F 2y SO 3}} -: (b-1)
R ¹⁵ SO ₃ ⁻ : (b-2)
(In the general formulas (b-1) and (b-2), R ¹⁵ represents a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 12 carbon atoms, and y represents an integer of 1 to 10.)

(In the general formulas (b-3) and (b-4), R ¹⁶ independently represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms, provided that two R ¹⁶ are bonded to each other. A divalent fluorine-substituted alkylene group having 2 to 10 carbon atoms may be formed.)

In the general formula (B-1), examples of the “alkyl group having 1 to 10 carbon atoms” represented by R ¹² , R ¹³ and R ¹⁴ include n already mentioned “alkyl group having 1 to 4 carbon atoms”, n -Linear alkyl group such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group; branched alkyl group such as neopentyl group, 2-ethylhexyl group; Etc. In these, a methyl group, an ethyl group, n-butyl group, t-butyl group etc. are preferable.

Moreover, as the “C1-C10 alkoxyl group” represented by R ¹² and R ¹³ , a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group Linear alkoxyl groups such as n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group; i-propoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy A branched alkoxyl group such as a group, neopentyloxy group, 2-ethylhexyloxy group, and the like. In these, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group etc. are preferable.

In addition, as the “C2-C11 alkoxycarbonyl group” represented by R ¹² , a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an n-pentyloxycarbonyl group, n- Linear alkoxycarbonyl groups such as hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group; i-propoxycarbonyl group, 2-methyl And branched alkoxycarbonyl groups such as propoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, neopentyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, and the like. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the “alkanesulfonyl group having 1 to 10 carbon atoms” represented by R ¹³ include methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, n-pentanesulfonyl group, n -Linear alkanesulfonyl group such as hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, n-nonanesulfonyl group, n-decanesulfonyl group; tert-butanesulfonyl group, neopentanesulfonyl group, 2- And branched alkanesulfonyl groups such as ethylhexanesulfonyl group; cycloalkanesulfonyl groups such as cyclopentanesulfonyl group and cyclohexanesulfonyl group; and the like. Among these, 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.

  Moreover, in general formula (B-1), it is preferable that r is an integer of 0-2.

In the general formula (B-1), the “phenyl group” represented by R ¹⁴ includes a phenyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2 , 4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4 -Substituted phenyl groups such as ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, 4-fluorophenyl group; the hydrogen atom of these groups is replaced by hydroxyl group, carboxyl group, cyano group, nitro group, A group substituted with at least one group selected from the group consisting of an alkoxyl group, an alkoxyalkyl group, an alkoxycarbonyl group and an alkoxycarbonyloxy group; Can.

  Among the groups that substitute a hydrogen atom of a phenyl group or a substituted phenyl group, the “alkoxyl group” includes a linear alkoxyl group such as a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group; i-propoxy group And branched alkoxyl groups such as 2-methylpropoxy group, 1-methylpropoxy group and t-butoxy group; cycloalkyloxy groups such as cyclopentyloxy group and cyclohexyloxy group. These groups preferably have 1 to 20 carbon atoms.

  Examples of the “alkoxyalkyl group” include linear alkoxyalkyl groups such as methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group and 2-ethoxyethyl group; branched groups such as 1-methoxyethyl group and 1-ethoxyethyl group An alkoxyalkyl group having a cycloalkane structure; and the like. These groups preferably have 1 to 20 carbon atoms.

  Examples of the “alkoxycarbonyl group” include linear alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group; i-propoxycarbonyl group, 2-methylpropoxycarbonyl group, 1 -Branched alkoxycarbonyl groups such as methylpropoxycarbonyl group and t-butoxycarbonyl group; cycloalkyloxycarbonyl groups such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl; These groups preferably have 2 to 21 carbon atoms.

  Examples of the “alkoxycarbonyloxy group” include linear alkoxycarbonyloxy groups such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyloxy group; i-propoxycarbonyloxy group, t -Branched alkoxycarbonyloxy groups such as butoxycarbonyloxy group; cycloalkyloxycarbonyl groups such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl; and the like. These groups preferably have 2 to 21 carbon atoms.

As the “phenyl group” represented by R ¹⁴ , a phenyl group, 4-cyclohexylphenyl group, 4-t-butylphenyl group, 4-methoxyphenyl group, 4-t-butoxyphenyl group and the like are preferable.

In addition, examples of the “naphthyl group” represented by R ¹⁴ include 1-naphthyl group; 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 2,3-dimethyl -1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7-dimethyl-1-naphthyl group, 2,8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl group, 3,7-dimethyl- 1-naphthyl group, 3,8-dimethyl-1-naphthyl Group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 2-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl Substituted naphthyl groups such as 2-naphthyl group and 4-methyl-2-naphthyl group; the hydrogen atom of these groups is replaced by hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group And a group substituted with at least one group selected from the group consisting of alkoxycarbonyloxy groups.

  Examples of the “alkoxyl group”, “alkoxyalkyl group”, “alkoxycarbonyl group”, and “alkoxycarbonyloxy group” that replace the hydrogen atom of the naphthyl group or substituted naphthyl group include the groups exemplified in the section of the phenyl group Can do.

Examples of the “naphthyl group” represented by R ¹⁴ include a 1-naphthyl group, 1- (4-methoxynaphthyl) group, 1- (4-ethoxynaphthyl) group, 1- (4-n-propoxynaphthyl) group, 1 -(4-n-butoxynaphthyl) group, 2- (7-methoxynaphthyl) group, 2- (7-ethoxynaphthyl) group, 2- (7-n-propoxynaphthyl) group, 2- (7-n- Butoxynaphthyl) group and the like are preferable.

In addition, as a “divalent group having 2 to 10 carbon atoms” formed by bonding two R ¹⁴ to each other, two R ¹⁴ are bonded to each other, in the general formula (B-1) A structure in which a 5-membered ring or a 6-membered ring is formed with the sulfur atom, and a structure in which a 5-membered ring (tetrahydrothiophene ring) is formed is preferable.

  This “divalent group” has at least one hydrogen atom selected from the group consisting of hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group and alkoxycarbonyloxy group. It may be substituted with a group. A part of hydrogen atoms may be substituted. Examples of the “alkoxyl group”, “alkoxyalkyl group”, “alkoxycarbonyl group”, and “alkoxycarbonyloxy group” include the groups exemplified in the section of the phenyl group.

As R ¹⁴ , a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, a 1-naphthyl group, two R ^14s are bonded to each other, and together with the sulfur atom in the general formula (B-1), tetrahydrothiophene A structure in which a ring is formed is preferable.

Examples of the cation of the general formula (B-1) include triphenylsulfonium cation, tri-1-naphthylsulfonium cation, tri-tert-butylphenylsulfonium cation, 4-fluorophenyl-diphenylsulfonium cation, di-4-fluorophenyl- Phenylsulfonium cation, tri-4-fluorophenylsulfonium cation, 4-cyclohexylphenyl-diphenylsulfonium cation, 4-methanesulfonylphenyl-diphenylsulfonium cation, 4-cyclohexanesulfonyl-diphenylsulfonium cation, 1-naphthyldimethylsulfonium cation, 1- Naphthyldiethylsulfonium cation, 1- (4-hydroxynaphthyl) dimethylsulfonium cation, 1- (4-methylnaphthane Til) dimethylsulfonium cation, 1- (4-methylnaphthyl) diethylsulfonium cation, 1- (4-cyanonaphthyl) dimethylsulfonium cation, 1- (4-cyanonaphthyl) diethylsulfonium cation, 1- (3,5-dimethyl) -4-hydroxyphenyl) tetrahydrothiophenium cation, 1- (4-methoxynaphthyl) tetrahydrothiophenium cation, 1- (4-ethoxynaphthyl) tetrahydrothiophenium cation, 1- (4-n-propoxynaphthyl)
Tetrahydrothiophenium cation, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium cation, 2- (7-methoxynaphthyl) tetrahydrothiophenium cation, 2- (7-ethoxynaphthyl) tetrahydrothiophenium cation, 2- (7-n-propoxynaphthyl) tetrahydrothiophenium cation, 2- (7-n-butoxynaphthyl) tetrahydrothiophenium cation and the like are preferable.

In the general formula (b-1), “—C _y F _2y —” is a perfluoroalkylene group having a carbon number y and may be linear or branched. And y is preferably 1, 2, 4 or 8.

In the general formulas (b-1) and (b-2), as the “hydrocarbon group having 1 to 12 carbon atoms” represented by R ¹⁵ , an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and Arihi Bridge A cyclic hydrocarbon group is preferred. Specifically, methyl group, 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, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl group, hydroxynorbornyl group, adamantyl group Etc.

In the general formulas (b-3) and (b-4), examples of the “fluorine-substituted alkyl group having 1 to 10 carbon atoms” represented by R ¹⁶ include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, Nonafluorobutyl group, dodecafluoropentyl group, perfluorooctyl group and the like can be mentioned.

Examples of the “divalent fluorine-substituted alkylene group having 2 to 10 carbon atoms” formed by bonding two R ¹⁶ to each other include a tetrafluoroethylene group, a hexafluoropropylene group, an octafluorobutylene group, and decafluoropentylene. Examples include a len group and an undecafluorohexylene group.

As an anion site of the general formula (B-1), trifluoromethanesulfonate anion, perfluoro-n-butanesulfonate anion, perfluoro-n-octanesulfonate anion, 2- (bicyclo [2.2.1] hepta-2 -Yl) -1,1,2,2-tetrafluoroethanesulfonate anion, 2- (bicyclo [2.2.1] hept-2-yl) -1,1-difluoroethanesulfonate anion, 1-adamantylsulfonate anion In addition, anions represented by the following formulas (b-3a) to (b-3g) are preferable.

  The acid generator (B) is composed of combinations of cations and anions already exemplified. However, the combination is not particularly limited. In the resin composition of this invention, an acid generator (B) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In addition, in the resin composition of this invention, you may use together acid generators other than an acid generator (B). Examples of such acid generators include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds. Specifically, the following can be mentioned.

Examples of the “onium salt compound” include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. More specifically, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl)
Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) Iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium Examples thereof include trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, and the like.

  Examples of the “halogen-containing compound” include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like. More specifically, (trichloromethyl) -s such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine, etc. -Triazine derivatives; 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane;

  Examples of “diazoketone compounds” include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. More specifically, 1,2-naphthoquinonediazide of 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonylchloride, 2,3,4,4′-tetrahydroxybenzophenone 4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane, 1,2, -Naphthoquinonediazide-5-sulfonic acid ester etc. can be mentioned.

  Examples of the “sulfone compound” include β-ketosulfone, β-sulfonylsulfone, α-diazo compounds of these compounds, and the like. More specifically, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like can be given.

  Examples of the “sulfonic acid compound” include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like.

  More specifically, benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene -2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2.1] Hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo [2.2.1] hept -5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyloxy) succini N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1, 1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarboxylic imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic imidononafluoro-n-butanesulfonate, 1,8-naphthalenedicarboxylic imide Examples include perfluoro-n-octane sulfonate.

  These acid generators can be used singly or in combination of two or more.

  In the resin composition of the present invention, the total amount of the acid generator (B) and the other acid generator used is 100 parts by mass of the resin (A) from the viewpoint of ensuring sensitivity and developability as a resist. Usually, it is 0.1-30 mass parts, and it is preferable that it is 0.5-20 mass parts. In this case, if the total amount used is less than 0.1 parts by mass, the sensitivity and developability tend to be lowered. On the other hand, when it exceeds 30 parts by mass, the transparency to radiation is lowered, and it tends to be difficult to obtain a rectangular resist pattern. Moreover, it is preferable that the usage-amount of another acid generator is 80 mass% or less with respect to the total amount of an acid generator (B) and another acid generator, and it is further 60 mass% or less. preferable.

[3] Acid diffusion inhibitor (C):
The radiation sensitive resin composition of the present invention further contains an acid diffusion inhibitor (C) in addition to the resin (A) and the acid generator (B) described so far. This acid diffusion inhibitor (C) controls the diffusion phenomenon in the resist film of the acid generated from the acid generator upon exposure, and suppresses an undesirable chemical reaction in the non-exposed region. By blending such an acid diffusion inhibitor (C), the storage stability of the resulting radiation-sensitive resin composition is improved, the resolution as a resist is further improved, and the heat treatment from exposure to exposure is performed. The change in the line width of the resist pattern due to the fluctuation of the holding time (PED) up to the above can be suppressed, and a composition having excellent process stability can be obtained.

〔一般式（Ｃ−１）中、Ｒ^２，Ｒ^３は相互に独立して、水素原子、炭素数が１〜２０である１価の鎖状炭化水素基、炭素数が３〜２０である１価の脂環式炭化水素基又は炭素数が６〜２０である１価の芳香族炭化水素基を示す。２つのＲ^２が結合されて、環構造が形成されていてもよい。〕 In the radiation sensitive resin composition of the present invention, a nitrogen-containing compound (C-1) represented by the following general formula (C-1) is used as the acid diffusion inhibitor (C).

[In General Formula (C-1), R ² and R ³ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 3 to 20. A monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is shown. Two R ² may be bonded to form a ring structure. ]

In the general formula (C-1), the group represented by R ³ is preferably a tert-butyl group or a tert-amyl group.

In the general formula (C-1), two R ² may be bonded to form a ring structure. For example, the nitrogen compound (C-1) in which the nitrogen atom in C-1 forms part of a cyclic amine is also included (for example, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl-2-phenyl) Benzimidazole).

  Examples of the nitrogen-containing compound represented by the general formula (C-1) include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, and Nt-butoxy. Carbonyl di-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, N'-di-t-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, N- t-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-butoxycarbonyl 1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N -N-tert-butyl group-containing amino compounds such as t-butoxycarbonyl-2-phenylbenzimidazole;

  Nt-amyloxycarbonyldi-n-octylamine, Nt-amyloxycarbonyldi-n-nonylamine, Nt-amyloxycarbonyldi-n-decylamine, Nt-amyloxycarbonyldicyclohexylamine, Nt-amyloxycarbonyl-1-adamantylamine, Nt-amyloxycarbonyl-2-adamantylamine, Nt-amyloxycarbonyl-N-methyl-1-adamantylamine, (S)-(−) -1- (t-amyloxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-amyloxycarbonyl) -2-pyrrolidinemethanol, Nt-amyloxycarbonyl-4-hydroxy Piperidine, Nt-amyloxycarbonylpyrrolidine, N, N′-di-t-amyloxycarbonylpirine Razine, N, N-di-t-amyloxycarbonyl-1-adamantylamine, N, N-di-t-amyloxycarbonyl-N-methyl-1-adamantylamine, Nt-amyloxycarbonyl-4, 4'-diaminodiphenylmethane, N, N'-di-t-amyloxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-amyloxycarbonylhexamethylenediamine, N, N'-di-t -Amyloxycarbonyl-1,7-diaminoheptane, N, N'-di-t-amyloxycarbonyl-1,8-diaminooctane, N, N'-di-t-amyloxycarbonyl-1,9-diaminononane N, N′-di-t-amyloxycarbonyl-1,10-diaminodecane, N, N′-di-t-amyloxycarbonyl-1,12-diamy Dodecane, N, N′-di-t-amyloxycarbonyl-4,4′-diaminodiphenylmethane, Nt-amyloxycarbonylbenzimidazole, Nt-amyloxycarbonyl-2-methylbenzimidazole, Nt -N-tert-amyl group-containing amino compounds such as amyloxycarbonyl-2-phenylbenzimidazole; and the like.

  Among these compounds, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, (S)-(−)-1- (T-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl-4 -Hydroxypiperidine, Nt-butoxycarbonyl-2-phenylbenzimidazole, Nt-amyloxycarbonyldicyclohexylamine, Nt-amyloxycarbonyl-1-adamantylamine, Nt-amyloxycarbonyl-2- Adamantylamine, (S)-(−)-1- (t-a Roxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-amyloxycarbonyl) -2-pyrrolidinemethanol, Nt-amyloxycarbonylpyrrolidine, Nt-amyloxycarbonyl-4 -Hydroxypiperidine, Nt-amyloxycarbonyl-2-phenylbenzimidazole are preferred, Nt-butoxycarbonyldicyclohexylamine, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl-4-hydroxypiperidine, and Nt-butoxycarbonyl-2-phenylbenzimidazole are more preferable.

  Examples of the acid diffusion inhibitor (C) other than the nitrogen-containing compound (C-1) include nitrogen-containing compounds such as tertiary amine compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds.

  Examples of the “tertiary amine compound” include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n. -Tri (cyclo) alkylamines such as octylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4 -Aromatic amines such as methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline; alkanolamines such as triethanolamine, N, N-di (hydroxyethyl) aniline; N , N, N ′, N′-Tetramethylethylene Diamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzenetetramethylenediamine, bis (2- Examples thereof include dimethylaminoethyl) ether and bis (2-diethylaminoethyl) ether.

  Examples of the “quaternary ammonium hydroxide compound” include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide.

  Examples of the “nitrogen-containing heterocyclic compound” include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4- Pyridines such as phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine; piperazines such as piperazine, 1- (2-hydroxyethyl) piperazine; pyrazine, pyrazole, Pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, imidazole 4-methylimidazole, 1- N-di-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt -Butoxycarbonyl-2-phenylbenzimidazole etc. can be mentioned.

  An acid diffusion inhibitor (C) can be used individually by 1 type or in mixture of 2 or more types.

  In the resin composition of the present invention, the total amount of the acid diffusion inhibitor (C) used is preferably less than 10 parts by mass with respect to 100 parts by mass of the resin (A) from the viewpoint of ensuring high sensitivity as a resist. More preferably, it is less than 5 parts by mass. When the total amount used exceeds 10 parts by mass, the sensitivity as a resist tends to be remarkably reduced. In addition, if the usage-amount of an acid diffusion inhibitor (C) is less than 0.001 mass part, there exists a possibility that the pattern shape and dimensional fidelity as a resist may fall depending on process conditions.

[4] Solvent (D):
The solvent (D) is not particularly limited as long as it is a solvent that can dissolve at least the resin (A), the acid generator (B), the acid diffusion inhibitor (C), and, if desired, the additive (E). Absent.

  Examples of the solvent (D) include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate. Propylene glycol monoalkyl ether acetates such as propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate;

  Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2 -Ketones such as hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone; methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, Such as t-butyl 2-hydroxypropionate - hydroxypropionic acid alkyls; methyl 3-methoxypropionate, 3-methoxy propionic acid ethyl, methyl 3-ethoxypropionate, other ethyl 3-ethoxypropionate and the like of 3-alkoxy propionic acid alkyl ethers,

  n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl Ether, propylene glycol mono -n- propyl ether,

  Toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-o Pentanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, .gamma.-butyrolactone, ethylene carbonate, and propylene carbonate.

  Among these, it is preferable to use propylene glycol monoalkyl ether acetates, particularly propylene glycol monomethyl ether acetate. Besides, ketones, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, γ-butyrolactone and the like are preferable. These solvent can be used individually by 1 type or in mixture of 2 or more types.

[5] Additive (E):
In the radiation sensitive resin composition of the present invention, various additives (E) such as a fluorine-containing resin, an alicyclic skeleton-containing resin, a surfactant, and a sensitizer can be blended as necessary. . The amount of each additive can be determined as appropriate according to the purpose.

  The fluorine-containing resin exhibits an action of developing water repellency on the resist film surface particularly in immersion exposure. In addition, it suppresses the elution of components from the resist film to the immersion liquid, and does not leave droplets even if immersion exposure is performed by high-speed scanning, and as a result, suppresses immersion-derived defects such as watermark defects. It is an effective ingredient.

  The structure of the fluorine-containing resin is not particularly limited. (1) Fluorine-containing resin that itself is insoluble in the developer and becomes alkali-soluble by the action of acid, and (2) itself is soluble in the developer. Fluorine-containing resin whose alkali solubility is increased by the action of acid, (3) Fluorine-containing resin which is itself insoluble in the developer and becomes alkali-soluble by the action of alkali, (4) itself is soluble in the developer And fluorine-containing resins whose alkali solubility is increased by the action of alkali.

  Examples of the “fluorine-containing resin” include a resin comprising a polymer having at least one repeating unit selected from the repeating unit (a-7) and the fluorine-containing repeating unit. ) To (a-4), (a-6), (a-8) and a polymer further having at least one repeating unit selected from the group of (a-9) is preferred.

  Examples of the “fluorine-containing repeating unit” include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, and perfluoro n-propyl (meth) acrylate. Perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2 -(1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) pentyl (meth) acrylate , 1- (2,2,3,3,4,4,5,5-octafluoro) hex (Meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1- (2,2,3,3,3-pentafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4, 4,4-Heptafluoro) penta (meth) acrylate, 1- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Examples include heptadecafluoro) decyl (meth) acrylate and 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro) hexyl (meth) acrylate.

As the fluorine-containing resin, for example, polymers represented by the following general formulas (D-1a) to (D-1f) are preferable. These fluorine-containing resins can be used alone or in combination of two or more.

  The alicyclic skeleton-containing resin is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.

  Examples of the alicyclic skeleton-containing resin include 1-adamantanecarboxylic acid, 2-adamantanone, 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone. Ester, 1,3-adamantane dicarboxylate di-t-butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantane diacetate di-t-butyl, 2,5- Adamantane derivatives such as dimethyl-2,5-di (adamantylcarbonyloxy) hexane;

  Deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxycholate 2-ethoxyethyl, deoxycholate 2-cyclohexyloxyethyl, deoxycholate 3-oxocyclohexyl, deoxycholate tetrahydropyranyl, deoxychol Deoxycholic acid esters such as acid mevalonolactone ester; t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, lithocholic acid Lithocholic acid esters such as tetrahydropyranyl acid, lithocholic acid mevalonolactone ester; dimethyl adipate, diethyl adipate, dipropyl adipate, di-n-adipate Chill, alkyl carboxylic acid esters such as adipate t- butyl;

3- [2-Hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane, and the like. These alicyclic skeleton-containing resins can be used singly or in combination of two or more.

  A surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (made by Asahi Glass Co., Ltd.), etc. Can do. These surfactants can be used individually by 1 type or in mixture of 2 or more types.

  The sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced. It has the effect of improving the “apparent sensitivity”.

  Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers can be used individually by 1 type or in mixture of 2 or more types.

  As the additive (E), dyes, pigments, adhesion assistants and the like can also be used. For example, by using a dye or a pigment, the latent image of the exposed area can be visualized, and the influence of halation during exposure can be reduced. Moreover, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid. Examples of other additives include alkali-soluble resins, low-molecular alkali solubility control agents having an acid-dissociable protecting group, antihalation agents, storage stabilizers, and antifoaming agents.

  As the additive (E), one of the various additives described above may be used alone, or two or more of them may be used in combination.

[6] Photoresist pattern forming method:
The radiation sensitive resin composition of the present invention is useful as a chemically amplified resist. In a chemically amplified resist, a resin component, mainly an acid dissociable group in the resin (A), is dissociated by the action of an acid generated from an acid generator by exposure to generate a carboxyl group. As a result, the solubility of the exposed portion of the resist in the alkaline developer is increased, and the exposed portion is dissolved and removed by the alkaline developer to obtain a positive photoresist pattern.

  In the method for forming a photoresist pattern of the present invention, (1) a step of forming a photoresist film on a substrate using the radiation sensitive resin composition (hereinafter sometimes referred to as “step (1)”). And (2) a step of irradiating the exposed photoresist film with radiation through a mask having a predetermined pattern (if necessary, through an immersion medium) and exposing (hereinafter referred to as “step (2)”). And (3) a step of developing the exposed photoresist film to form a photoresist pattern (hereinafter sometimes referred to as “step (3)”). is there.

  Also, when performing immersion exposure, before the step (2), in order to protect the direct contact between the immersion liquid and the resist film, an immersion liquid insoluble immersion protective film is formed on the resist film. It may be provided. As the protective film for immersion, a solvent-peelable protective film (see, for example, JP-A-2006-227632) that is peeled off by a solvent before the step (3), a development that peels off simultaneously with the development in the step (3) Any of liquid-removable protective films (see, for example, WO2005-069096 and WO2006-035790) may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type immersion protective film.

  In the step (1), a resin composition solution obtained by dissolving the resin composition of the present invention in a solvent is applied to a substrate (silicon wafer, dioxide dioxide) by an appropriate application means such as spin coating, cast coating, roll coating or the like. A photoresist film is formed by coating on a silicon-coated wafer or the like. Specifically, after applying the resin composition solution so that the obtained resist film has a predetermined film thickness, the solvent in the coating film is volatilized by pre-baking (PB) to form a resist film.

  Although the thickness of a resist film is not specifically limited, It is preferable that it is 0.1-5 micrometers, and it is still more preferable that it is 0.1-2 micrometers.

  Moreover, although the prebaking heating conditions change with composition of a radiation sensitive resin composition, it is preferable that it is 30-200 degreeC, and it is still more preferable that it is 50-150 degreeC.

  In forming a photoresist pattern using the radiation-sensitive resin composition of the present invention, in order to maximize the potential of the radiation-sensitive resin composition, organic or inorganic reflection is performed on the substrate to be used. A prevention film may be formed (see Japanese Patent Publication No. 6-12458). Further, a protective film may be provided on the photoresist film in order to prevent the influence of basic impurities and the like contained in the environmental atmosphere (see Japanese Patent Application Laid-Open No. 5-188598). Furthermore, the immersion protective film may be provided on the photoresist film. These techniques can be used in combination.

  In step (2), the photoresist film formed in step (1) is irradiated with radiation (possibly through an immersion medium such as water) and exposed. In this case, radiation is irradiated through a mask having a predetermined pattern.

  The radiation is selected appropriately from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like according to the type of acid generator. Far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is particularly preferable.

  Moreover, exposure conditions, such as exposure amount, are suitably set according to the compounding composition of a radiation sensitive resin composition, the kind of additive, etc. In the present invention, it is preferable to perform post-exposure heat treatment (PEB). By PEB, the dissociation reaction of the acid dissociable group in the resin component proceeds smoothly. The heating conditions for this PEB vary depending on the composition of the radiation sensitive resin composition, but are preferably 30 to 200 ° C, more preferably 50 to 170 ° C.

  In step (3), the exposed photoresist film is developed with a developer to form a predetermined photoresist pattern. After development, it is common to wash with water and dry.

  As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3. 0] An aqueous alkaline solution in which at least one of alkaline compounds such as 5-nonene is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 10% by mass or less. If it exceeds 10% by mass, the unexposed area may be dissolved in the developer, which is not preferable.

  Further, the developer may be a solution obtained by adding an organic solvent to an alkaline aqueous solution. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol Alcohols such as i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; Examples thereof include esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylformamide. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  The amount of the organic solvent used is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the amount of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the development residue in the exposed part increases. An appropriate amount of a surfactant or the like may be added to the developer.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Mw, Mn, and Mw / Mn]:
Mw and Mn use GPC columns (trade name “G2000HXL”, product name “G3000HXL”, product name “G4000HXL”, 1 each, manufactured by Tosoh Corporation), flow rate: 1.0 mL / min, Elution solvent: Tetrahydrofuran, Column temperature: It was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C. Further, the degree of dispersion “Mw / Mn” was calculated from the measurement results of Mw and Mn.

[ ¹³ C-NMR analysis]:
The ¹³ C-NMR analysis of each polymer was measured using a nuclear magnetic resonance apparatus (trade name: JNM-ECX400, manufactured by JEOL Ltd.).

[Remaining ratio of low molecular weight components]:
Using an ODS column (trade name: Inertsil ODS-25 μm column (4.6 mmφ × 250 mm), manufactured by GL Sciences Inc.), flow rate: 1.0 mL / min, elution solvent: acrylonitrile / 0.1% phosphoric acid aqueous solution The measurement was performed by high performance liquid chromatography (HPLC) under conditions. The low molecular weight component is a component having a monomer as a main component and a molecular weight of less than 1,000 (that is, a trimer molecular weight or less).

(Synthesis of resin (A))
Resins (A-1) to (A-25) were synthesized using the following monomers (M-1) to (M-15) in the respective synthesis examples. The monomers (M-12) to (M-15) are monomers corresponding to the repeating unit (a-1), and the monomers (M-1) and (M-8) are repeating units (a-2). ), Monomers (M-7) and (M-10) are monomers, monomers (M-2) and (M-3) corresponding to repeating units (a-3b). ) And (M-11) are monomers corresponding to the repeating unit (a-3a).

(Synthesis Example 1: Resin (A-1))
Monomer (M-6) 26.50 g (50 mol%), monomer (M-12) 8.42 g (20 mol%), monomer (M-8) 15.08 g (30 mol%) Was dissolved in 100 g of 2-butanone, and a monomer solution in which 1.91 g (5 mol%) of dimethyl 2,2′-azobis (2-methylpropionate) was added as an initiator was prepared.

  Next, 50 g of 2-butanone was charged into a 500 ml three-necked flask equipped with a thermometer and a dropping funnel, and purged with nitrogen for 30 minutes. After purging with nitrogen, the inside of the flask was heated to 80 ° C. while stirring with a magnetic stirrer. Using a dropping funnel, a monomer solution prepared in advance was added dropwise over 3 hours. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or less by water cooling. After cooling, it was poured into 1000 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was slurried with 200 g of methanol and washed twice. Thereafter, the white powder was again filtered off and dried at 50 ° C. for 17 hours to obtain a white powder copolymer (37 g, yield 74%). This copolymer was referred to as “resin (A-1)”.

This copolymer has Mw of 7321, Mw / Mn of 1.70, and as a result of ¹³ C-NMR analysis, the monomer (M-6), monomer (M-12) and monomer The content rate of each repeating unit derived from a body (M-8) was 45.2: 19.5: 35.3 (mol%). The residual ratio of the low molecular weight component in this copolymer was 0.05% by mass. The measurement results are shown in Table 1.

(Synthesis Examples 2 to 25: Resins (A-2) to (A-25))
Resins (A-2) to (A-25) were synthesized in the same manner as in Synthesis Example 1 except that the formulation shown in Tables 1 and 2 was used.

Moreover, about the obtained resin (A-2)-(A-25), the ratio (mol%) of each repeating unit by ¹³ C-NMR analysis, a yield (%), Mw, and dispersity (Mw / The measurement results of Mn) are shown in Tables 1 and 2. Moreover, the ¹³ C-NMR measurement chart of resin A-5 and A-7 is shown in FIG.1 and FIG.2.

(Preparation of radiation-sensitive resin composition)
Table 3 shows the compositions of the radiation-sensitive resin compositions prepared in each example and comparative example. Moreover, each component (an acid generator (B), an acid diffusion inhibitor (C), and a component constituting a radiation sensitive resin composition other than the resins (A-1) to (A-25) synthesized in the above synthesis example). The solvent (D)) is shown below.

<Acid generator (B)>
(B-1): 4-cyclohexylphenyl, diphenylsulfonium, nonafluoro-n-butanesulfonate,
(B-2): Triphenylsulfonium nonafluoro-n-butanesulfonate (B-3): 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate,
(B-4): 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. 2- (bicyclo [2.2.1] hept-2-yl) -1,1,2,2 -Tetrafluoroethanesulfonate,
(B-5): Triphenylsulfonium · 2- (bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate,
(B-6): Triphenylsulfonium 2- (bicyclo [2.2.1] hept-2-yl) -1,1-difluoroethanesulfonate.

<Acid diffusion inhibitor (C)>
(C-1): Nt-butoxycarbonyl-4-hydroxypiperidine,
(C-2): R-(+)-(t-butoxycarbonyl) -2-piperidinemethanol,
(C-3): Nt-butoxycarbonylpyrrolidine,
(C-4): Nt-butoxycarbonyl-2-phenylbenzimidazole,
(C-5): tri-n-octylamine,
(C-6): Phenyldiethanolamine.

<Solvent (D)>
(D-1): Propylene glycol monomethyl ether acetate,
(D-2): cyclohexanone,
(D-3): γ-butyrolactone.

Example 1
100 parts by mass of the resin (A-1) obtained in Synthesis Example 1, 8.4 parts by mass of (B-2) triphenylsulfonium / nonafluoro-n-butanesulfonate, and acid diffusion inhibitor as the acid generator (B) As (C), 0.9 part by mass of (C-2) R-(+)-(t-butoxycarbonyl) -2-piperidinemethanol is mixed, and (D-1) is added to this mixture as the solvent (D). ) 1500 parts by weight of propylene glycol monomethyl ether acetate, 650 parts by weight of (D-2) cyclohexanone and 40 parts by weight of (D-3) γ-butyrolactone were added to dissolve the above mixture to obtain a mixed solution. The solution was filtered through a filter having a pore size of 0.20 μm to prepare a radiation sensitive resin composition. Table 3 shows the formulation of the radiation sensitive resin composition.

(Examples 2 to 13, Comparative Examples 1 to 11)
Except having changed the composition of each component which prepares a radiation sensitive resin composition as shown in Table 3, it is the same as that of Example 1, and the radiation sensitive resin composition (Examples 2-13, comparison) Examples 1 to 11) were obtained.

[Evaluation method]
About the obtained radiation sensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 11, using ArF excimer laser as a light source, sensitivity, dense line focal depth, isolated space focal depth, LWR, MEEF, minimum pre-collapse dimensions And the number of development defects were evaluated. The evaluation results are shown in Table 4.

(1) Sensitivity (unit: mJ / cm ² ):
A lower antireflection film having a film thickness of 77 nm was formed on an 8-inch wafer surface using a lower antireflection film forming agent (trade name: ARC29A, manufactured by Nissan Chemical Industries, Ltd.). The radiation-sensitive resin compositions of Examples and Comparative Examples were applied to the surface of this substrate by spin coating, and subjected to SB (Soft Bake) for 90 seconds at a temperature shown in Table 4 on a hot plate, and the film thickness was 120 nm. A resist film was formed.

  This resist film was exposed through a mask pattern using a full-field reduction projection exposure apparatus (trade name: S306C, Nikon Corporation, numerical aperture 0.78). Thereafter, PEB was performed for 90 seconds at the temperature shown in Table 4, and then developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution (hereinafter referred to as “TMAH aqueous solution”) at 25 ° C. for 60 seconds and washed with water. And dried to form a positive resist pattern.

At this time, the exposure amount (mJ / cm ² ) formed in a one-to-one line and space with a line width of 90 nm is defined as an optimum exposure amount through a mask with a one-to-one line and space with a dimension of 90 nm. The optimum exposure amount (mJ / cm ² ) was defined as “sensitivity”. A scanning electron microscope (trade name: S9220, manufactured by Hitachi High-Technologies Corporation) was used for length measurement.

(2) Dense line depth of focus (unit: μm)
The focus fluctuation width when the pattern dimension resolved with the 90 nm 1L / 1S mask pattern at the optimum exposure dose is within ± 10% of the mask design dimension was defined as the dense line focal depth. Specifically, it was evaluated as “good” when the dense line focal depth was 0.40 μm or more, and “bad” when it was less than 0.40 μm. The scanning electron microscope was used for observing the pattern dimensions.

(3) Isolated space depth of focus (unit: μm)
The focus fluctuation width when the 90 nmS / 1150 nmP pattern dimension resolved with the mask pattern of 115 nmS / 1150 nmP at the optimum exposure dose falls within the range of 81 to 99 nmS / 1150 nmP was defined as the isolated line focal depth. Specifically, it was evaluated as “good” when the isolated space focal depth was 0.20 μm or more, and “bad” when it was less than 0.20 μm. The scanning electron microscope was used for observing the pattern dimensions.

(4) LWR (unit: nm)
Using the scanning electron microscope, when observing a 90 nm 1L / 1S pattern resolved at the optimum exposure amount from the top of the pattern, the line width was measured at 10 points at arbitrary points, and the 3 sigma value of the measured value (Variation) was defined as LWR. Specifically, when the LWR was 8.0 nm or less, it was evaluated as “good”, and when it exceeded 8.0 nm, it was evaluated as “bad”.

(5) MEEF:
Using the scanning electron microscope, with the optimum exposure dose, five mask sizes (85.0 nmL / 180 nmP, 87.5 nmL / 180 nmP, 90.0 nmL / 180 nmP, 92.5 nmL / 180 nmP, 95.0 nmL / 180 nmP) Resolved pattern dimensions were measured. The measurement results were plotted with the horizontal axis representing the mask size and the vertical axis representing the line width, and the slope of the graph was determined by the least square method. This inclination was defined as MEEF. Specifically, it was evaluated as “good” when the MEEF was 4.0 or more and “bad” when it was less than 4.0.

(6) Minimum collapse size (nm):
When observing a 90 nm line and space pattern resolved with the optimum exposure amount for sensitivity evaluation, the line width of the resulting pattern is narrow when exposure is performed with an exposure amount larger than the optimum exposure amount. As a result, the resist pattern is finally collapsed. The line width at the maximum exposure amount at which the resist pattern was not confirmed to be collapsed was defined as the minimum dimension before collapse (nm), which was used as an index of pattern collapse resistance. Specifically, when the dimension before the minimum collapse was 40.0 nm or less, it was evaluated as “good”, and when it exceeded 40.0 nm, “bad”. In addition, the said scanning electron microscope was used for the measurement of the dimension before minimum collapse.

(7) Number of development defects (unit: pieces / Wafer)
The number of development defects was evaluated by the following method using a defect inspection apparatus (trade name: KLA2351, manufactured by KLA Tencor).
A wafer for defect inspection was prepared as follows. A lower-layer antireflection film forming agent (trade name: ARC25, manufactured by Brewer Science Co., Ltd.) was coated to a film thickness of 820 mm to produce a wafer substrate. On this board | substrate, the radiation sensitive resin composition of the Example and the comparative example was apply | coated with the film thickness of 0.30 micrometer, and SB (SoftBake) was performed for 90 second at the temperature shown in Table 4.
Using a full field exposure apparatus (trade name: S306C, manufactured by Nikon Corporation), 5 mm × 5 mm blank exposure was performed to expose the entire wafer surface. After the exposure, PEB was performed under the conditions of 130 ° C./90 seconds, and then developed with a 2.38 wt% TMAH aqueous solution at 25 ° C. for 30 seconds, washed with water, and dried to prepare a wafer for defect inspection. The above coating, baking and development were all carried out in-line using a coater / developer (trade name: CLEAN TRACK ACT8, manufactured by Tokyo Electron Ltd.).

  Using the defect inspection apparatus, the total number of defects of development defects in the exposed portion of the wafer for defect inspection produced by the method was inspected. The inspection of the total number of defects was performed by observing in the array mode and detecting the total number of defects of clusters and unclusters extracted from the difference caused by the comparison image and the pixel unit overlap. The sensitivity was set so that the defect inspection apparatus could detect defects of 0.15 μm or more. By this inspection, it was evaluated as “good” when the number of development defects was 30 / wafer or less, and “defect” when it exceeded 30 / wafer.

(Examples 15 and 16, Comparative Examples 12 and 13)
Further, the radiation-sensitive resin composition (Examples 15 and 16) was prepared in the same manner as in Example 1 except that the composition of each component for preparing the radiation-sensitive resin composition was changed as shown in Table 5. Comparative Examples 12 and 13) were obtained.

[Evaluation method]
The radiation sensitive resin compositions of Examples 15 and 16 and Comparative Examples 12 and 13 thus obtained were evaluated for sensitivity, dense line focal depth, and minimum pre-collapse dimensions using a KrF excimer laser as a light source. The evaluation results are shown in Table 6.

(1) Sensitivity (unit: mJ / cm ² )
An 8-inch wafer surface was coated with a lower-layer antireflection film forming agent (trade name: DUV42P, manufactured by Brewer Science) to a film thickness of 60 nm to form a film. The radiation sensitive resin compositions of Examples and Comparative Examples were applied to the surface of this substrate by spin coating, and SB was performed for 90 seconds at a temperature shown in Table 1 on a hot plate to form a resist film having a thickness of 335 nm. Formed. The resist film was exposed through a mask pattern using a full-field reduction projection exposure apparatus (trade name: PASS 5500/750, manufactured by ASML, numerical aperture 0.70, exposure wavelength 248 nm).

Thereafter, PEB was carried out at a temperature shown in Table 6 for 90 seconds, and then developed with a 2.38 mass% TMAH aqueous solution at 25 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount (mJ / cm ² ) formed in a one-to-one line-and-space with a line width of 130 nm is defined as an optimum exposure amount through a 130-nm one-to-one line-and-space mask. The optimum exposure amount (mJ / cm ² ) was defined as “sensitivity”. The scanning electron microscope was used for length measurement.

(2) Dense line depth of focus (unit: μm)
The focus fluctuation width when the pattern dimension resolved with the 130 nm 1L / 1S mask pattern at the optimum exposure amount is within ± 10% of the mask design dimension was defined as the dense line focal depth. The scanning electron microscope was used for observing the pattern dimensions. Specifically, it was evaluated as “good” when the dense line focal depth was 0.70 μm or more, and “bad” when it was less than 0.70 μm.

(3) Minimum resolution size (nm)
The minimum dimension that can be resolved with the optimal exposure dose of the 130 nm 1L / 1S pattern is observed from above the pattern using the scanning electron microscope. The minimum line width that can be resolved by this resist is defined as the minimum resolution dimension, which is used as an index of resolution. Specifically, it was evaluated as “good” when the dimension before the minimum collapse was 110 nm or less, and “bad” when it exceeded 110 nm.

  As is clear from Tables 4 and 6, it was found that when the radiation-sensitive resin composition of the present invention was used, various resist performances such as depth of focus, LWR, MEEF, pattern collapse characteristics, and development defect performance were improved. .

  The radiation sensitive resin composition of the present invention can be suitably used as a lithography material using a KrF excimer laser and an ArF excimer laser as a light source. Moreover, it can respond also to immersion exposure.

It is an analysis chart by ¹³ C-NMR of resin (A-5) which is a component of the radiation sensitive resin composition of the present invention. It is an analysis chart by ¹³ C-NMR of resin (A-7) which is a component of the radiation sensitive resin composition of the present invention.

Claims (3)

A resin (A), a radiation sensitive acid generator (B), an acid diffusion inhibitor (C), and a solvent (D),
The resin (A) is a polymer having a repeating unit (a-1) represented by the following general formula (a-1),
The radiation sensitive resin composition whose said acid diffusion inhibitor (C) is a nitrogen containing compound shown by the following general formula (C-1).

[In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁹ independently represents a hydrogen atom, which has 1 to 5 carbon atoms. A chain hydrocarbon group, A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic group having 3 to 30 carbon atoms A hydrocarbon group or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and when A is trivalent, the carbon atoms contained in A and the carbon atoms constituting the cyclic carbonate are Combined, a ring structure is formed. n shows the integer of 2-4. ]

[In General Formula (C-1), R ² and R ³ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, or a carbon number of 3 to 20. A monovalent alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is shown. Two R ² may be bonded to form a ring structure. ]   The radiation sensitive resin composition of Claim 1 whose resin (A) is a polymer which has the repeating unit (a-2) containing a lactone structure in addition to the said repeating unit (a-1). A repeating unit (a-1) represented by the following general formula (a-1), at least one repeating unit (a-3) of the following general formulas (a-3a) and (a-3b); A copolymer having

[In General Formula (a-1), R ¹ independently represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁹ independently represents a hydrogen atom, which has 1 to 5 carbon atoms. A chain hydrocarbon group, A is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent or trivalent alicyclic group having 3 to 30 carbon atoms A hydrocarbon group or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and when A is trivalent, the carbon atoms contained in A and the carbon atoms constituting the cyclic carbonate are Combined, a ring structure is formed. n shows the integer of 2-4. ]

[In General Formulas (a-3a) and (a-3b), R ¹ is independently of each other a hydrogen atom, a methyl group or a trifluoromethyl group, and R ¹⁷ is independently of each other of 1 to 10 carbon atoms. An alkyl group, R ¹⁸ represents an alkyl group having 2 to 4 carbon atoms. Two R < ¹⁷ > may be couple | bonded and the 3-10 membered ring may be formed. ]

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