JP6303020B2 - PATTERN FORMING METHOD, ELECTRONIC DEVICE MANUFACTURING METHOD, BLOCK COPOLYMER, AND BLOCK COPOLYMER MANUFACTURING METHOD - Google Patents

Description

  The present invention is suitable for use in ultra-microlithography processes such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes, pattern formation methods, electronic device manufacturing methods, electronic devices, block copolymers, And it is related with the manufacturing method of a block copolymer.

In recent years, with the increasing integration of integrated circuits, pattern miniaturization has progressed, and technological development of microfabrication by lithography using radiation such as EUF light, electron beam, and X-ray from ArF excimer laser light has progressed. With the demand for higher integration, development of patterning techniques that do not use photolithography, such as the development of self-organized lithography using nanoimprinting and microphase separation of block copolymers, is also in progress.
In addition, as the recording density of hard disk drives increases, the technological development of bit patterned media that processes magnetic films to the size of each bit is progressing. For example, in order to obtain a recording density of 5 Tbits / inch, it is necessary to form an ultrafine dot pattern of about 12 nm, and here too, development of self-organized lithography using microphase separation of a block copolymer is advanced. Yes.
Various processes have been proposed for self-assembled lithography. For example, in order to control the arrangement and arrangement of self-assembled nanostructures formed by microphase separation, they are provided on a base substrate on which a block copolymer is applied. There have been proposed a graphoepitaxy method in which a microphase separation pattern is controlled by a guide pattern, and a chemical registration method in which the microphase separation pattern is controlled by a difference in chemical characteristics of a substrate surface.
In self-assembled lithography, after a self-assembled resist film containing a block copolymer is formed on a substrate provided with a guide pattern as described above, a microphase separation structure is formed by annealing treatment in a solvent atmosphere or heating. The pattern can be formed by selectively removing specific blocks of the block copolymer by oxygen plasma treatment, ozone treatment, UV irradiation treatment, thermal decomposition treatment, or chemical decomposition treatment.
As the block copolymer used in the pattern formation method by self-organization, a copolymer having two or more segments capable of causing microphase separation can be used. In order to form microphase separation, it is advantageous to use, for the block copolymer, blocks whose values of interaction parameters of Flory-Huggins are separated from each other. As such a block copolymer, a block copolymer of polystyrene or a derivative thereof and polymethacrylic acid acrylate or a derivative thereof has been reported (for example, see Non-Patent Documents 1 and 2).

Macromolecules. 1994, 27, 35 Proc. of SPIE Vol. 8680 86801W

  However, in recent years, with the demand for further miniaturization of patterns, there is a demand for the development of a technique that can achieve further miniaturization of the pattern as compared with the technique described in the prior art.

  The present invention has been made in view of the above, and an object of the present invention is to achieve high-quality pattern refinement in self-organized lithography using a graphoepitaxy method (for example, a pitch of 40 nm or less). A line and space pattern and a hole pattern with a hole diameter of 20 nm or less can be formed with high quality), a pattern forming method, an electronic device manufacturing method and an electronic device using the pattern forming method, and a pattern forming method. Another object of the present invention is to provide a block copolymer and a method for producing the same.

That is, the present invention is as follows.
<1>
(I) On a substrate on which a guide pattern is formed, a block of a repeating unit represented by any one of the following general formulas (I-1) to (I-3) and a repeating represented by the following general formula (II) Forming a block copolymer layer containing a block copolymer having a block of units;
(Ii) phase-separating the block copolymer layer; and
(Iii) A pattern forming method including a step of selectively removing at least one of a plurality of phases in the block copolymer layer.

In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having a group represented by any of the following formulas (R ₆ -1) to (R ₆ -4).

<2>
The block copolymer is a block copolymer having a block of a repeating unit represented by the general formula (I-1) and a block of a repeating unit represented by the general formula (II), <1 The pattern formation method as described in>.
<3>
The solubility parameter (SP value) of the repeating unit represented by any one of the general formulas (I-1) to (I-3) in the block copolymer and the repeating unit represented by the general formula (II) The pattern forming method according to <1> or <2>, wherein an absolute value of a difference from the solubility parameter (SP value) is 6.0 (MPa ^1/2 ) or more.
<4>
The guide pattern exposes the actinic ray-sensitive or radiation-sensitive film with an ArF excimer laser, extreme ultraviolet light, or an electron beam, and develops the exposed actinic ray-sensitive or radiation-sensitive film using a developer. The pattern formation method according to any one of <1> to <3>, which is a guide pattern formed by the above.
<5>
The pattern forming method according to any one of <1> to <4>, wherein a base layer containing a base agent is formed on the substrate, and the block copolymer layer is formed on the base layer. .
<6>
The pattern forming method according to any one of <1> to <5>, wherein a topcoat layer is formed on the block copolymer layer between the step (i) and the step (ii). .
<7>
<1>-<6> The manufacturing method of an electronic device containing the pattern formation method of any one of <6>.
<8>
<1>-<6> The block of the repeating unit represented by any one of the following general formulas (I-1) to (I-3) and the following, which is provided for the pattern forming method according to any one of A block copolymer having a repeating unit block represented by formula (II).

In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having a group represented by any of the following formulas (R ₆ -1) to (R ₆ -4).

<9>
A method for producing a block copolymer, wherein the block copolymer according to <8> is synthesized by living polymerization.
<10>
The method for producing a block copolymer according to <9>, wherein the living polymerization is living anionic polymerization.
Although this invention is invention concerning said <1>-<10>, below, other matters (for example, following [1]-[14]) are also described.

[1]
(I) On a substrate on which a guide pattern is formed, a block of a repeating unit represented by any one of the following general formulas (I-1) to (I-3) and a repeating represented by the following general formula (II) Forming a block copolymer layer containing a block copolymer having a block of units;
(Ii) a step of phase-separating the block copolymer layer, and
(Iii) A pattern forming method including a step of selectively removing at least one of a plurality of phases in the block copolymer layer.


In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having at least one of the following (a) to (e).
(A) two or more hydroxyl groups (b) amino group (c) carboxyl group (d) thiol group (e) sulfonic acid group [2]
The block copolymer is a block copolymer having a repeating unit block represented by the general formula (I-1) and a repeating unit block represented by the general formula (II). [1].
[3]
The pattern forming method according to the above [1] or [2], wherein R ₆ in the general formula (II) is an alkyl or cycloalkyl group having two or more hydroxyl groups.
[4]
The pattern formation method according to the above [3], wherein the two or more hydroxyl groups include two hydroxyl groups linked to each other via 2 or 3 atoms.
[5]
In the above [4], R ₆ in the general formula (II) is an alkyl or cycloalkyl group having a group represented by any of the following formulas (R ₆ -1) to (R ₆ -4). The pattern formation method as described.


[6]
The solubility parameter (SP value) of the repeating unit represented by any one of the general formulas (I-1) to (I-3) in the block copolymer and the repeating unit represented by the general formula (II) The pattern forming method according to any one of [1] to [5] above, wherein an absolute value of a difference from the solubility parameter (SP value) is 6.0 (MPa ^1/2 ) or more.
[7]
The guide pattern exposes the actinic ray-sensitive or radiation-sensitive film with an ArF excimer laser, extreme ultraviolet light, or an electron beam, and develops the exposed actinic ray-sensitive or radiation-sensitive film using a developer. The pattern formation method of any one of said [1]-[6] which is a guide pattern formed by this.
[8]
The pattern formation according to any one of [1] to [7], wherein a base layer containing a base agent is formed on the substrate, and the block copolymer layer is formed on the base layer. Method.
[9]
The pattern formation according to any one of [1] to [8], wherein a topcoat layer is formed on the block copolymer layer between the step (i) and the step (ii). Method.
[10]
The manufacturing method of an electronic device containing the pattern formation method of any one of said [1]-[9].
[11]
The electronic device manufactured by the manufacturing method of the electronic device as described in said [10].
[12]
A block of repeating units represented by any one of the following general formulas (I-1) to (I-3), which is provided for the pattern forming method according to any one of [1] to [9] above; The block copolymer which has a block of the repeating unit represented by the following general formula (II).


In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having at least one of the following (a) to (e).
(A) two or more hydroxyl groups (b) amino group (c) carboxyl group (d) thiol group (e) sulfonic acid group [13]
A method for producing a block copolymer, wherein the block copolymer according to [12] is synthesized by living polymerization.
[14]
The method for producing a block copolymer according to [13], wherein the living polymerization is living anion polymerization.

  According to the present invention, in the self-organized lithography using the graphoepitaxy method, it is possible to achieve a high-quality pattern with high quality (for example, a line-and-space pattern with a pitch of 40 nm or less or a hole diameter of 20 nm or less. A pattern forming method capable of forming a hole pattern with high quality), an electronic device manufacturing method and electronic device using the pattern forming method, a block copolymer used in the pattern forming method, and a manufacturing method thereof can be provided. .

FIGS. 1A to 1D are schematic cross-sectional views for explaining a form in which a highly refined line and space pattern is formed by a graphoepitaxy method using a line and space pattern as a guide pattern. 1 (e) is a schematic top view of the same. FIGS. 2A to 2D are schematic cross-sectional views for explaining a form in which a highly refined hole pattern is formed by a graphoepitaxy method using the hole pattern as a guide pattern, and FIG. FIG. 2 is a schematic top view of the same.

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

The pattern forming method of the present invention comprises:
(I) On a substrate on which a guide pattern is formed, a block of a repeating unit represented by any one of the following general formulas (I-1) to (I-3) and a repeating represented by the following general formula (II) Forming a block copolymer layer containing a block copolymer having a block of units;
(Ii) phase-separating the block copolymer layer; and
(Iii) A pattern forming method including a step of selectively removing at least one of a plurality of phases in the block copolymer layer.

In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having at least one of the following (a) to (e).
(A) two or more hydroxyl groups (OH groups),
(B) an amino group (NH ₂ group),
(C) a carboxyl group (COOH group),
(D) a thiol group (SH group),
(E) Sulfonic acid group (SO ₃ H group)

  With the pattern formation method of the present invention, high-quality pattern refinement can be achieved with high quality in self-organized lithography using the graphoepitaxy method (for example, a line-and-space pattern with a pitch of 40 nm or less or a hole diameter of 20 nm or less The reason why the hole pattern can be formed with high quality is not clear, but is estimated as follows, for example.

As described above, in the pattern formation method of the present invention, the block copolymer layer subjected to phase separation is a repeating unit represented by any one of the general formulas (I-1) to (I-3). And a block copolymer having a repeating unit block represented by the general formula (II).
Here, while the repeating unit represented by any one of the above general formulas (I-1) to (I-3) has a hydrophobic structure, it is represented by the above general formula (II). The repeating unit to be used is particularly high in the polarities of the above (a) to (e) which the alkyl group or cycloalkyl group as R ₆ has. Therefore, the repeating unit represented by any one of the general formulas (I-1) to (I-3) has a very high hydrophobicity compared to the repeating unit represented by the general formula (II). large. Thereby, the phase separation property between the block of the repeating unit represented by any one of the general formulas (I-1) to (I-3) and the block of the repeating unit represented by the general formula (II) is extremely high. Very expensive.
As described above, the block of the repeating unit represented by any one of the general formulas (I-1) to (I-3) and the block of the repeating unit represented by the general formula (II) Since the phase separation property is very high, a block copolymer layer containing these copolymers (particularly, a block copolymer containing a block copolymer having a low number average molecular weight in order to achieve a finer pattern). Even when the guide pattern is formed on the substrate, the phase separation of the block copolymer layer can be surely caused. As a result, according to the present invention, it is possible to achieve high-quality pattern refinement (for example, a line-and-space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less can be formed with high quality). It is considered a thing.

<Pattern formation method>
FIGS. 1A to 1D are schematic cross-sectional views for explaining a form in which a highly refined line and space pattern is formed by a graphoepitaxy method using a line and space pattern as a guide pattern. 1 (e) is a schematic top view of the same.
FIGS. 2A to 2D are schematic cross-sectional views for explaining a form in which a highly refined hole pattern is formed by a graphoepitaxy method using the hole pattern as a guide pattern, and FIG. These are the same schematic top views.

  Hereinafter, the pattern forming method of the present invention will be described in detail with reference to these drawings as appropriate. In the embodiments described below, the members and the like described in the drawings already referred to are denoted by the same or corresponding reference numerals in the drawings, and the description is simplified or omitted.

[(I) On a substrate on which a guide pattern is formed, a block of a repeating unit represented by any one of the general formulas (I-1) to (I-3) and a repeating unit represented by the general formula (II) Step of forming a block copolymer layer containing a block copolymer having a block of
The substrate in the “substrate on which the guide pattern is formed” used in the step (i) is not particularly limited, and is an inorganic substrate such as silicon, SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG, and the like. A substrate generally used in a semiconductor manufacturing process such as an IC, a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes can be used. Further, if necessary, an antireflection film may be formed between the film and the substrate.

  As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

In addition, a base layer containing a base agent may be provided on the substrate.
By providing such a base layer, there are cases where phase separation of the block copolymer layer can be caused more reliably in step (ii) described in detail later. For example, by providing a base layer containing as a base material a material having affinity for any block constituting the block copolymer, it is possible to prevent only a specific phase from contacting the substrate. May be possible. Specifically, for example, a random copolymer having each component of a block copolymer used for self-assembly (DSA), and in addition, a crosslinkable / polymerizable group such as an epoxy group or a vinyl group. Polymers obtained by copolymerizing monomer components are preferably used as the underlayer.
Such a base agent is not particularly limited as long as the functions described above are expressed, and the description of paragraphs [0331] to [0333] of International Publication No. 2012/169620 can be referred to. The contents are incorporated herein.
The base layer containing the base agent is suitably formed by applying a liquid obtained by dissolving the base agent with a solvent using a spinner, a coater or the like and drying.
The thickness of the underlayer is preferably 3 to 100 nm, more preferably 5 to 50 nm, and still more preferably 10 to 30 nm.

The guide pattern provided on the substrate is not particularly limited. For example, the guide pattern 21 that forms a line and space pattern (see the schematic sectional view of FIG. 1A) and the guide pattern 22 that forms a hole pattern (FIG. 2). (See the schematic cross-sectional view of (a)).
The thickness of the guide pattern is preferably 10 to 250 nm, more preferably 20 to 200 nm, and still more preferably 30 to 100 nm.

  The guide pattern is preferably a guide pattern formed by exposing an actinic ray-sensitive or radiation-sensitive film and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

The actinic ray-sensitive or radiation-sensitive film is obtained by applying an actinic ray-sensitive or radiation-sensitive resin composition, which will be described in detail later, to a substrate (for example, a substrate used for manufacturing precision integrated circuit elements, imprint molds, etc. (Example: the above-mentioned substrate, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate, etc.) are applied using a spinner, coater, etc., and then dried to obtain It is preferred that
Examples of the actinic ray or radiation used for exposure include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and electron beams. Preferable actinic rays or radiation include, for example, KrF excimer laser, ArF excimer laser, electron beam, X-ray and extreme ultraviolet light (EUV light). More preferred are ArF excimer laser, electron beam and extreme ultraviolet light.

Further, in the exposure step, when performing exposure using an ArF excimer laser, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

  Regarding the immersion liquid used in the immersion exposure, the description in paragraphs [0059] and [0060] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.

  The receding contact angle of the actinic ray-sensitive or radiation-sensitive film is 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, which is suitable for exposure through an immersion medium, and at 75 ° or more. It is preferable that the angle is 75 to 85 °.

  If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable that a hydrophobic resin (HR) described later is included in the actinic ray-sensitive or radiation-sensitive resin composition described later. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the actinic ray-sensitive or radiation-sensitive film.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with respect to the actinic ray-sensitive or radiation-sensitive film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

In the exposure with an electron beam or extreme ultraviolet rays, the actinic ray sensitivity or sensation of the present invention is used for the purpose of suppressing outgas, the purpose of suppressing blob defects, the deterioration of collapse due to reverse taper shape improvement, the deterioration of LWR due to surface roughness, and the like. You may form a topcoat in the upper layer of the film | membrane formed from a radiation resin composition. Moreover, when the actinic ray-sensitive or radiation-sensitive composition is for electron beam or extreme ultraviolet exposure, a hydrophobic resin (HR) described later may be added. By adding the hydrophobic resin (HR), effects such as outgas suppression can be obtained as in the case where the top coat is formed.
Hereinafter, the topcoat composition used for forming the topcoat will be described.

In the top coat composition, the solvent is preferably water or an organic solvent. More preferred is water or an alcohol solvent.
When the solvent is an organic solvent, it is preferably a solvent that does not dissolve the film formed from the actinic ray-sensitive or radiation-sensitive resin composition. As the solvent that can be used, an alcohol solvent, a fluorine solvent, or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used. The alcohol solvent is preferably a primary alcohol from the viewpoint of applicability, more preferably a primary alcohol having 4 to 8 carbon atoms. As the primary alcohol having 4 to 8 carbon atoms, linear, branched, and cyclic alcohols can be used, and linear and branched alcohols are preferable. Specific examples include 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1-butanol.
The solvent for the topcoat composition may be one type or a combination of two or more types.

When the solvent of the top coat composition is water, an alcohol solvent or the like, it is preferable to contain a water-soluble resin. By containing a water-soluble resin, it is considered that the uniformity of solubility in a developer can be further improved. Preferred water-soluble resins include polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ether, polyvinyl acetal, polyacrylimide, polyethylene glycol, polyethylene oxide, polyethyleneimine, polyester polyol and polyether polyol. , Polysaccharides, and the like. Particularly preferred are polyacrylic acid, polymethacrylic acid, polyhydroxystyrene, polyvinylpyrrolidone, and polyvinyl alcohol. The water-soluble resin is not limited to a homopolymer, and may be a copolymer. For example, it may be a copolymer having monomers corresponding to the repeating units of the homopolymers listed above and other monomer units. Specifically, acrylic acid-methacrylic acid copolymer, acrylic acid-hydroxystyrene copolymer and the like can be used in the present invention.
Further, as the resin for the top coat composition, resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can be preferably used.
The weight average molecular weight of the water-soluble resin is not particularly limited, but is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 100,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)). One type of resin for the top coat composition may be used, or two or more types may be used in combination.

  Although there is no restriction | limiting in particular in pH of a topcoat composition, Preferably it is 0-10, More preferably, it is 0-8, Most preferably, it is 1-7.

  When the solvent of the topcoat composition is an organic solvent, the topcoat composition contains a hydrophobic resin such as the hydrophobic resin (E) described above in the actinic ray-sensitive or radiation-sensitive resin composition section. You may do it. As the hydrophobic resin, it is also preferable to use a hydrophobic resin described in JP-A-2008-209889.

The concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass.
The topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably Is from 95 to 100% by weight.
The solid content concentration of the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and still more preferably 0.3 to 5% by mass. . By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied on the resist film.

  Examples of components other than the resin that can be added to the top coat material include surfactants, acid generators, and basic compounds. Specific examples of the acid generator and the basic compound include compounds that generate an acid upon irradiation with actinic rays or radiation described later and compounds similar to the basic compound.

When using surfactant, the usage-amount of surfactant becomes like this. Preferably it is 0.0001-2 mass% with respect to the whole quantity of a topcoat composition, More preferably, it is 0.001-1 mass%.
By adding a surfactant to the topcoat composition, applicability when the topcoat composition is applied can be improved. Examples of the surfactant include nonionic, anionic, cationic and amphoteric surfactants.
Nonionic surfactants include BALF's Plufrac series, Aoki Yushi Kogyo's ELEBASE series, Finesurf series, Braunon series, Asahi Denka Kogyo's Adekapluronic P-103, Kao Chemical's Emulgen Series, Amit series, Aminone PK-02S, Emanon CH-25, Rheodor series, Surflon S-141 from AGC Seimi Chemical Co., Neugen series from Daiichi Kogyo Seiyaku, New Calgen series from Takemoto Yushi DYNOL604 manufactured by Nissin Chemical Industry Co., Ltd., Envirogem AD01, Olphine EXP series, Surfynol series, Footage 300 manufactured by Hishie Chemical Co., etc. can be used.
As an anionic surfactant, Kao Chemical's Emar 20T, Poise 532A, TOHO's Phosphanol ML-200, Clariant Japan's EMULSOGEN series, AGC Seimi Chemical's Surflon S-111N, Surflon S -211, Prisurf series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Pionein series manufactured by Takemoto Yushi Co., Ltd., Orphine PD-201 manufactured by Nissin Chemical Industry Co., Ltd. -3, a Lion made by Lion, etc. can be used.
As the cationic surfactant, Acetamine 24, Acetamine 86, etc. manufactured by Kao Chemical Co., Ltd. can be used.
As an amphoteric surfactant, Surflon S-131 (manufactured by AGC Seimi Chemical Co., Ltd.), Enagicol C-40H, Lipomin LA (manufactured by Kao Chemical Co., Ltd.) or the like can be used.
These surfactants can also be mixed and used.

The top coat is formed by applying and drying the top coat composition by the same means as the method for forming the actinic ray sensitive or radiation sensitive film formed from the actinic ray sensitive or radiation sensitive resin composition. The film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
The film having the top coat as an upper layer is usually irradiated with an electron beam (EB), X-rays or EUV light through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
The performance required for the top coat and how to use it are described in Chapter 7 of CM Publishing “Immersion Lithography Processes and Materials”.

  When the topcoat is peeled after exposure, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed simultaneously with the development processing step of the film, it is preferable that the peeling step can be performed with a developer.

  In the formation of the guide pattern, the step of exposing the actinic ray-sensitive or radiation-sensitive film may be performed a plurality of times.

After film formation, a preheating step (PB; Prebake) may be performed before the exposure step. Here, a plurality of preheating steps may be performed.
It is also preferable to carry out a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step. Here, a plurality of post-exposure heating steps may be performed.
The heating temperature is preferably 70 to 130 ° C, more preferably 80 to 120 ° C for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

The developer used for forming the guide pattern may be a developer containing an organic solvent or an alkali developer.
When a developer containing an organic solvent is used, a negative guide pattern can be formed.
When an alkaline developer is used, a positive guide pattern can be formed.

In the case where the developer is a developer containing an organic solvent, a step of developing using an alkali developer may be further carried out, whereas in the case where the developer is an alkali developer, an organic solvent is included. You may further implement the process developed using a developing solution.
In this case, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by performing an alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] And the same mechanism).
In this case, the order of the alkali development step and the organic solvent development step is not particularly limited, but the alkali development is more preferably performed before the organic solvent development step.

When carrying out the step of developing with an alkaline developer in the formation of the guide pattern, examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic alkalis, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine Alcohol amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. Ammonium salts, pyrrole, an alkaline aqueous solution such as cyclic amines such as piperidine, can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

After the step of developing with an alkaline developer, a step of washing with a rinsing solution may be performed, but from the viewpoint of throughput (productivity), the amount of rinsing solution used, etc., washing with a rinsing solution is performed. It is not necessary to carry out the process of.
As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

When carrying out the step of developing using a developer containing an organic solvent in the formation of the guide pattern, as the developer in the step (hereinafter also referred to as an organic developer), a ketone solvent, an ester solvent, Polar solvents such as alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid Mention may be made of propyl, butyl butanoate, methyl 2-hydroxyisobutyrate and the like.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
Examples of the ether solvent include anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, alcohol solvents such as n-heptyl alcohol, n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxyme Glycol ether solvents such as rubutanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic carbonization such as toluene and xylene Examples thereof include aliphatic hydrocarbon solvents such as hydrogen solvents, octane, and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio , Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, etc. Glycol solvents, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol ether solvents such as methoxymethyl butanol, N- Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide Amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

  The organic developing solution may contain a basic compound as described in JP-A-2013-11833, particularly [0032] to [0063]. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition described later.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and particularly preferably 0.0005 to 1% by mass with respect to the total amount of the developer. One type of surfactant may be used, or two or more types may be used in combination.

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

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

  Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

  After the step of developing with a developer containing an organic solvent, a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is not necessary to carry out the step of using and washing.

The rinsing solution used in the rinsing step after the step of developing using a developer containing an organic solvent is not particularly limited as long as the guide pattern is not dissolved, and a solution containing a general organic solvent can be used. . The rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents (preferably decane), ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. It is preferable to use a rinse solution.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

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

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

  It is also preferable to carry out a heating step (Post Bake) after the rinsing step that can be carried out after each of the step of developing with an alkali developer and the step of developing with an organic developer. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  In particular, when the actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) having a group that generates a polar group by being decomposed by the action of an acid described in detail later, the guide pattern is organic as a developer. It is preferably a negative type guide pattern formed using a system developer. This negative type guide pattern has a polar group generated by decomposition of the resin in the pattern due to the action of an acid, so it is difficult to dissolve in an organic solvent in a composition containing a block copolymer to be described in detail later. It is.

On the other hand, in particular, when an alkaline developer is used as a developer to form a positive guide pattern, it is also preferable to perform a freezing treatment on the positive guide pattern as necessary.
Regarding the freezing treatment, “New development of photoresist material, CMC Publishing” P138-175 (especially P165-175), JP2009-294630A, JP2009-271259A, and JP2009-A. Known methods described in JP-A No. 294264, JP-A 2010-039034, JP-A 2010-039035 and the like can be preferably used.
In addition, the guide pattern may be created by nanoimprint. For details, refer to “Basics of Nanoimprint and Technology Development / Application Deployment-Nanoimprint Substrate Technology and Latest Technology Deployment-Editing: Yoshihiko Hirai (Frontier Publishing)” You can refer to it.

For example, on the substrate on which the guide pattern obtained as described above is formed, a block of repeating units represented by any one of the general formulas (I-1) to (I-3) and the following general formula (II) Step (i) of forming a block copolymer layer containing a block copolymer (described in detail later) having a block of repeating units represented is carried out.
For example, in the case of a graphoepitaxy method using a line and space pattern as a guide pattern, a block copolymer is formed on a substrate 10 on which a guide pattern 21 is formed as shown in the schematic cross-sectional view of FIG. Layer 31 is formed.
Further, for example, in the case of a graphoepitaxy method using a hole pattern as a guide pattern, a block copolymer is formed on the substrate 10 on which the guide pattern 22 is formed, as shown in the schematic sectional view of FIG. Layer 35 is formed.

  Typically, a composition containing a block copolymer is applied onto the substrate 10 using a spinner, a coater, or the like. Then, this can be dried and the block copolymer layers 31 and 35 can be formed.

  The thickness of the block copolymer layers 31 and 35 is not particularly limited as long as phase separation occurs in the step (ii), but the thickness is preferably 10 to 250 nm, and used at a thickness of 20 to 200 nm. More preferably, the thickness is 30 to 100 nm.

[(Ii) Step of phase-separating block copolymer layer]
Next, the step (ii) of phase-separating the block copolymer layer is performed.
Step (ii) typically develops a phase separation structure in which at least a portion of the substrate is exposed by heating the block copolymer layer and selectively removing phases in step (iii) described in detail later It is a process to make.
The heating temperature is preferably not less than the glass transition temperature of the block copolymer and not more than the thermal decomposition temperature of the block copolymer. Preferably it is 50-300 degreeC as heating temperature, More preferably, it is 100-270 degreeC, More preferably, it is 150-250 degreeC.
The heating time is preferably 1 second to 10 hours.

Among the plurality of phases constituting the phase-separated block copolymer layer, a phase that is not selectively removed in step (ii) is a non-removed phase, and a phase that is selectively removed is a removed phase. In the graphoepitaxy method using a line and space pattern as a guide pattern, the removed phase 32 and the non-removed phase 33 are arranged along the guide patterns 21 and 21 as shown in the schematic sectional view of FIG. An alternately arranged lamella structure can be formed between the guide patterns 21 and 21. Here, typically, the phase containing the block of the repeating unit represented by the general formula (II) constitutes the removed phase 32, and any one of the general formulas (I-1) to (I-3) The phase containing the block of repeating units represented constitutes the non-removed phase 33.
Further, for example, in the case of a graphoepitaxy method using a hole pattern as a guide pattern, as shown in the schematic cross-sectional view of FIG. A cylinder structure in which the removal phase 37 is arranged on the center side of the guide pattern 22 can be formed. Here, typically, a phase containing a block of repeating units represented by any one of the general formulas (I-1) to (I-3) constitutes the non-removed phase 36, and the general formula (II) The phase containing a block of repeating units represented by

  The shape and size of the removed phase and the non-removed phase are defined by the component ratio of each block constituting the block copolymer, the molecular weight of the block copolymer, and the like.

[(Iii) Step of selectively removing at least one of a plurality of phases in the block copolymer layer]
Next, the step (iii) of selectively removing at least one of the plurality of phases in the block copolymer layer is performed.
Step (iii) is typically a step of exposing at least a portion of the substrate by selective removal of the phase (ie, the removal phase described above).

  Examples of the method for removing the removal phase include oxygen plasma treatment, ozone treatment, ultraviolet irradiation treatment, thermal decomposition treatment, and chemical decomposition treatment. As the chemical decomposition treatment, a fluorine treatment such as dry etching with fluorine can be preferably exemplified.

For example, in the graphoepitaxy method using a line and space pattern as a guide pattern, as shown in the schematic cross-sectional view of FIG. 1D and the schematic top view of FIG. The pattern is selectively removed and the non-removed phase 33 is left, so that the pattern is made finer (for example, a line and space pattern with a pitch of 40 nm or less).
Further, for example, in the graphoepitaxy method using a hole pattern as a guide pattern, the removal phase 37 in the cylinder structure is formed as shown in the schematic cross-sectional view of FIG. 2D and the schematic top view of FIG. By selectively removing and leaving the non-removed phase 36, pattern refinement (for example, a hole pattern with a hole diameter of 20 nm or less) is realized. In addition, it can be said that the refinement | miniaturization of this pattern respond | corresponds to performing what is called a shrink process with respect to a guide pattern.

In the pattern forming method of the present invention, a top coat layer may be formed on the block copolymer layer between step (i) and step (ii).
By providing such a topcoat layer, in some cases, the phase separation of the block copolymer layer can be more reliably caused in the above-described step (ii). For example, by providing a topcoat layer containing a material having affinity for any block constituting the block copolymer, only a specific phase is unevenly distributed in the surface layer of the block copolymer layer. It may be possible to suppress.
The material, the forming method, and the preferred thickness of such a top coat layer are the same as those described in the above underlayer.

  As a preferable example of the form for forming the line and space pattern by the graphoepitaxy method using the line and space pattern as the guide pattern described with reference to FIGS. 1A to 1E, for example, EUV exposure And a guide pattern of a 2: 9 line and space pattern having a line width of 20 nm and a space width of 90 nm is formed by the development, and the step (ii) and the step (iii) are performed in the space of the guide pattern. In another embodiment, four non-removed phases each having a line width of 10 nm are formed with a pitch of 20 nm.

[Usage]
The pattern forming method of the present invention is suitably used for the production of semiconductor microcircuits such as the production of VLSI and high-capacity microchips. When creating a semiconductor microcircuit, the patterned resist film is used for circuit formation and etching, and the remaining resist film portion is finally removed with a solvent or the like. Unlike so-called permanent resists, the resist film derived from the actinic ray-sensitive or radiation-sensitive resin composition described in the present invention does not remain in the final product such as a microchip.

The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

[Composition Containing Block Copolymer]
Hereinafter, the block copolymer contained in the block copolymer layer and the composition containing the block copolymer for forming the block copolymer layer will be described in detail.

  The block copolymer has a repeating unit block represented by any one of the following general formulas (I-1) to (I-3) and a repeating unit block represented by the following general formula (II). ing.

In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ represents an alkyl group or a cycloalkyl group having at least one of the following (a) to (e).
(A) two or more hydroxyl groups (b) amino group (c) carboxyl group (d) thiol group (e) sulfonic acid group

The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group or aralkyl group in R ₁ may further have a substituent.
Examples of the further substituent include an alkoxy group, a hydroxyl group, a halogen atom (fluorine atom, chlorine atom, etc.), a nitro group, an aryl group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group. And heterocyclic residues such as a group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a pyrrolidone residue.
Carbon number of the alkyl group which may have a substituent becomes like this. Preferably it is 1-12, More preferably, it is 2-9, More preferably, it is 4-6.
The carbon number of the alkenyl group and alkynyl group which may have a substituent is preferably 2 to 12, more preferably 2 to 9, and still more preferably 4 to 6.
Carbon number of the cycloalkyl group which may have a substituent becomes like this. Preferably it is 3-12, More preferably, it is 3-9, More preferably, it is 3-6.
Carbon number of the aryl group which may have a substituent becomes like this. Preferably it is 6-12, More preferably, it is 6-9.
The carbon number of the aralkyl group which may have a substituent is preferably 7 to 12, and more preferably 7 to 9.
The number of carbon atoms in R _{1 being} within the above-described preferable range is a further improvement in non-removability (typically etching resistance) in step (iii), and general formulas (I-1) to (I−) 3) represented by the block of the repeating unit represented by the general formulas (I-1) to (I-3) and the above general formula (II), as the hydrophobicity of the repeating unit represented by 3) is further improved. From the viewpoint of further improving the phase separation property with the block of repeating units.

R ₁ is bonded to the carbon atom adjacent to the carbon atom to which R ₁ is bonded (that is, the ortho-positioned carbon atom constituting the benzene ring when R ₁ is used as a reference), and is condensed with the benzene ring. In some cases, the additionally formed ring is preferably a benzene ring (that is, a naphthalene ring is preferably formed as the whole condensed ring structure).

The alkyl group, cycloalkyl group and aryl group as R ₂ may further have a substituent.
Specific examples of the further substituent include the same groups as those described in the further substituent that each group in R ₁ may have.
Carbon number of the alkyl group which may have a substituent becomes like this. Preferably it is 1-6, More preferably, it is 1-4, More preferably, it is 1.
Carbon number of the cycloalkyl group which may have a substituent becomes like this. Preferably it is 3-12, More preferably, it is 5-12, More preferably, it is 6-10.
Carbon number of the aryl group which may have a substituent becomes like this. Preferably it is 3-20, More preferably, it is 5-15, More preferably, it is 6-10.

The alkyl group and aryl group as R ₃ and R ₄ may further have a substituent.
Specific examples of the further substituent include the same groups as those described in the further substituent that each group in R ₁ may have.
Carbon number of the alkyl group which may have a substituent becomes like this. Preferably it is 1-6, More preferably, it is 1-3, More preferably, it is 1 or 2.
Carbon number of the aryl group which may have a substituent becomes like this. Preferably it is 3-20, More preferably, it is 5-15, More preferably, it is 6-10.

The alkyl group and cycloalkyl group in R ₅ may further have a substituent.
Specific examples of the further substituent include the same groups as those described in the further substituent that each group in R ₁ may have.
Carbon number of the alkyl group which may have a substituent becomes like this. Preferably it is 1-6, More preferably, it is 1-3, More preferably, it is 1 or 2.

R ₅ can further reduce the non-removability (typically etching resistance) in step (iii) (ie, further improve the removability) and further improve the glass point transfer (Tg) of the block copolymer. From the viewpoint that the phase separation structure of the block copolymer layer can be prevented from deteriorating, the alkyl group which may have a substituent or the cycloalkyl group which may have a substituent An alkyl group which may have a substituent is more preferable, and a methyl group is still more preferable.

As described above, the alkyl group and cycloalkyl group represented by R ₆ include (a) two or more hydroxyl groups (OH groups); (b) amino groups (NH ₂ groups); (c) carboxyl groups ( COOH group); (d) a thiol group (SH group); and (e) a sulfonic acid group (SO ₃ H group).
The above R ₆ has a higher polarity than, for example, an alkyl group or a cycloalkyl group having only one hydroxyl group. As a result, the absolute value of the difference between the dissolution parameters between the blocks can be increased, and further refinement of the pattern can be achieved (for example, a line and space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less can be increased). Can be formed to a high grade).

R ₆ is preferably an alkyl or cycloalkyl group having two or more hydroxyl groups, and in this case, two hydroxyl groups in which two or more hydroxyl groups are connected to each other via two or three atoms The form containing is preferable. Here, the number of the atoms is determined by the number of atoms in the shortest route connecting two hydroxyl groups (that is, the minimum number of atoms connecting two hydroxyl groups). In such a form, R ₆ is preferably an alkyl or cycloalkyl group having a group represented by any of the following formulas (R ₆ -1) to (R ₆ -4).

The alkyl group and cycloalkyl group as R ₆ may further have another substituent in addition to at least one of the above (a) to (e).
Specific examples of this further substituent include the same groups as those described for the further substituent that each group in R ₁ may have, but are a halogen atom, an oxygen atom or a sulfur atom. A group containing can be preferably mentioned.
Preferred examples of the halogen atom include a fluorine atom and a chlorine atom.
Examples of the group containing an oxygen atom or sulfur atom include an alkoxy group, a hydroxyl group, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, and a thiophenemethylcarbonyl group. Examples thereof include an oxy group and a heterocyclic residue having an oxygen atom or a sulfur atom as a hetero atom.

Phase separation from the block of the repeating unit represented by any one of the general formulas (I-1) to (I-3) accompanying the further improvement of the hydrophilicity of the repeating unit represented by the general formula (II) From the viewpoint of further improving the property, the carbon number of the alkyl group having at least one of the above (a) to (e) as R ₆ is preferably 1 to 12, more preferably 1 to 12. 8, more preferably 1-4. For the same reason, the number of carbon atoms of the cycloalkyl group having at least one of the above (a) to (e) as R ₆ is preferably 3 to 12, more preferably 3 to 8. . In addition, the carbon atom which comprises an alkyl group, and the carbon atom as a ring member in the alicyclic structure of a cycloalkyl group may each be substituted by hetero atoms, such as an oxygen atom.

  Hereinafter, although the specific example of a repeating unit represented by general formula (I-1) is shown, this invention is not limited to these.

  Hereinafter, although the specific example of the repeating unit represented by general formula (I-2) is shown, this invention is not limited to these.

  Hereinafter, although the specific example of the repeating unit represented by general formula (I-3) is shown, this invention is not limited to these.

  Hereinafter, although the specific example of the repeating unit represented by general formula (II) is shown, this invention is not limited to these.

  The block copolymer is preferably a block copolymer having a repeating unit block represented by formula (I-1) and a repeating unit block represented by formula (II).

The solubility parameter (SP value) of the repeating unit represented by any one of the general formulas (I-1) to (I-3) in the block copolymer and the solubility parameter of the repeating unit represented by the general formula (II) ( The absolute value of the difference from the (SP value) is preferably 6.0 (MPa ^1/2 ) or more, more preferably 7.0 (MPa ^1/2 ) or more, and 8.0 (MPa ^{1 / 2} ) or more is more preferable. The absolute value is typically 12.0 (MPa ^1/2 ) or less. When the absolute value of the difference is less than 6.0 (MPa ^1/2 ), the pattern is particularly fine (for example, formation of a line and space pattern with a pitch of 40 nm or less or a hole pattern with a hole diameter of 20 nm or less). In the use of a block polymer having a low number average molecular weight (for example, a number average molecular weight of less than 25,000), which is advantageous in the above, the block polymer layer tends to be difficult to phase-separate. On the other hand, when the absolute value exceeds 12.0 (MPa ^1/2 ), the diffusion rate of the block copolymer becomes too slow, and the phase separation of the block copolymer layer tends not to be performed with high quality. . Moreover, when preparing the composition containing this, a block copolymer tends to become difficult to melt | dissolve in a solvent.

When the solubility of the block copolymer in the solvent is low due to the large absolute value, etc., it is selected from the group consisting of the repeating unit represented by (I), heating, and irradiation with actinic rays or radiation The block copolymer having the repeating unit (II ′) converted into the repeating unit represented by the general formula (II) is dissolved in a solvent by using at least one external stimulus as described above, A composition containing a copolymer may be prepared.
The repeating unit (II ′) typically has a group that generates the above (a) to (e) in R ₆ of the above general formula (II), triggered by the above external stimulus, Is a repeating unit obtained by substituting the hydrogen atom in each of the groups (a) to (e) in the general formula (II) with a group capable of leaving when triggered by the external stimulus.
According to such a block copolymer, the absolute value of the difference between the solubility parameter (SP value) of the repeating unit represented by (I) and the solubility parameter (SP value) of the repeating unit (II ′). Therefore, at the time of preparing the composition, the solubility of the block copolymer in the solvent can be increased, and as a result, the applicability of the composition solution can be improved.
Moreover, when such a block copolymer is used, after forming a block copolymer layer with the composition containing a block copolymer, before implementing said process (ii), a block copolymer By applying the external stimulus to the layer, the repeating unit (II ′) is replaced with the repeating unit represented by the general formula (II). From the viewpoint of efficiently performing this substitution, a composition containing a block copolymer contains a compound that generates an acid by the external stimulus or a compound that generates a base by the external stimulus, and the external stimulus. It is preferable that the group that is released by the action of is a group that is released by the action of an acid or a group that is released by the action of a base.

Here, the solubility parameter (SP value) is obtained by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)), which is one of the methods for calculating the SP value known in the industry. be able to.
The solubility parameter (SP value) of the repeating unit constituting the specific block of the block copolymer corresponds to the solubility parameter (SP value) of the specific block (in other words, a homopolymer composed only of the repeating unit). For example, the SP value of a t-butylstyrene unit constituting poly-t-butylstyrene as a homopolymer is 16.9 (MPa ^1/2 ), and poly (2,3-dihydroxy) propyl methacrylate as a homopolymer Since the SP value of (2,3-dihydroxy) propyl methacrylate constituting 24.6 (MPa ^1/2 ), the SP value between blocks of a block copolymer composed of polystyrene and polymethyl methacrylate is The difference is 7.7 (MPa ^1/2 ).

  The block copolymer is a range in which phase separation of the block of the repeating unit represented by any one of the general formulas (I-1) to (I-3) and the block of the repeating unit represented by the general formula (II) occurs. And may further have a repeating unit different from the repeating unit represented by any one of the general formulas (I-1) to (I-3) and the repeating unit represented by the general formula (II).

  The mass ratio of each block constituting the block copolymer is appropriately determined according to the type of the phase separation structure to be developed in the step (ii), but the general formula (I-1) in the block copolymer is not limited. The mass ratio of the repeating unit block represented by any of (I) to (I-3) to the repeating unit block represented by the general formula (II) is preferably 30:70 to 90:10. 40:60 to 80:20 is more preferable.

The number average molecular weight (Mn) of the block copolymer is preferably 100000 or less, more preferably 50000 or less, further preferably less than 25000, and more preferably less than 20000 as a polystyrene-converted value by the GPC method. More preferably it is.
The number average molecular weight (Mn) of the block copolymer and polystyrene is preferably 3000 or more, more preferably 5000 or more, and still more preferably 6000 or more as a polystyrene converted value by the GPC method.

  The dispersity (Mw / Mn) of the block copolymer is preferably 1.0 to 1.5, more preferably 1.0 to 1.2, and 1.0 to 1.1. More preferably.

  In this specification, the number average molecular weight (Mn), weight average molecular weight (Mw) and dispersity of the resin including the block copolymer are, for example, HLC-8120 (manufactured by Tosoh Corporation), As TSK gel Multipore HXL-M (Tosoh Co., Ltd., 7.8 mm HD × 30.0 cm), and THF (tetrahydrofuran) or NMP (N-methyl-2-pyrrolidone) as an eluent. .

The block copolymer can be synthesized by a known method by radical polymerization or anionic polymerization. In order to lower the degree of dispersion of the block copolymer (that is, monodisperse), it is preferable to use living polymerization such as known living anion polymerization and living radical polymerization. Specifically, the block of the repeating unit represented by any one of the general formulas (I-1) to (I-3) and the block of the repeating unit represented by the general formula (II) are each living. More preferably, it is formed by polymerization.
As living polymerization, living anionic polymerization is particularly advantageous and more preferable for monodispersion.
Moreover, it is also preferable to perform living anion polymerization using a microreactor apparatus (flow reaction system) as described in JP2009-67999A.

Hereinafter, although the specific example (The composition ratio of a repeating unit is a mass ratio) of the block copolymer in this invention is shown, this invention is not limited to these. ΔSP represents the absolute value (MPa ^1/2 ) of the difference between the above SP values.

  The content of the block copolymer relative to the total solid content of the composition containing the block copolymer is preferably 90% by mass to 100% by mass, more preferably 95% by mass to 100% by mass, More preferably, it is 97 mass%-100 mass%.

It is preferable that the composition containing a block copolymer contains a solvent. The solvent is not particularly limited as long as it can dissolve the block copolymer. Usually, the solvent that dissolves the block copolymer well can be determined using the solubility parameter (SP value). Typically, a solvent having an SP value close to the median SP value of the repeating units constituting each block of the block copolymer is a solvent that dissolves the block copolymer well.
The composition containing the block copolymer may contain one type of solvent or two or more types of solvents.
The solvent is preferably an organic solvent. Examples of the organic solvent include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, di- Polyhydric alcohols such as propylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond Monoalkyl ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having an ether bond [in these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, and lactic acid Esters such as methyl, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; halogen organic solvents such as chloroform; anisole, ethyl Benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, tolue And aromatic organic solvents such as ethylene, xylene, cymene and mesitylene.
In particular, the solvent is preferably a highly hydrophobic solvent such as toluene, xylene, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and chloroform.

  The solid content concentration of the composition containing the block copolymer is usually 1.0 to 10% by mass, preferably 1.5 to 6.0% by mass, more preferably 1.5 to 5.5% by mass. %.

  The present invention provides a block of a repeating unit represented by any one of the above general formulas (I-1) to (I-3) and the above general formula (II), which is provided for the pattern forming method of the present invention described above. It also relates to block copolymers having blocks of repeating units represented.

In addition, resin is a block copolymer, when the resin is measured based on differential scanning calorimetry (DSC), each glass transition temperature (Tg) corresponding to each block constituting the block copolymer. Can be confirmed by measuring.
Specifically, when the resin is a diblock block copolymer having a first repeating unit block and a second repeating unit block, the glass transition temperature corresponding to the first repeating unit block. (Tg ₁ ) and the glass transition temperature (Tg ₂ ) corresponding to the second repeating unit block are confirmed. In this case, for example, in a polystyrene-polymethyl methacrylate block copolymer, a Tg of 105 ° C. corresponding to polystyrene and a Tg of 120 ° C. corresponding to polymethyl methacrylate are confirmed.
On the other hand, when the resin is a random copolymer having a first repeating unit and a second repeating unit, the glass transition temperature (Tg ₁ ) and the glass transition temperature (Tg ₂ ) are the glass transition temperatures. The glass transition temperature (Tm) during is confirmed. In this case, in a random copolymer having a styrene repeating unit and a methyl methacrylate repeating unit, only Tg at 112 ° C. is observed.
In addition, in this specification, a glass transition temperature is temperature measured on temperature increase rate conditions of 10 degree-C / min in model number Q1000 which is a scanning scanning calorimeter (DSC) made from TA instruments.

[Actinic ray-sensitive or radiation-sensitive resin composition]
Next, the actinic ray-sensitive or radiation-sensitive resin composition that is preferably used in the formation of the guide pattern will be described.
When an alkaline developer is used as the developer, the actinic ray-sensitive or radiation-sensitive resin composition is positively developed (when exposed, the solubility in the developer increases, and the unexposed area is patterned. And development for removing the exposed portion). That is, in this case, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for alkali development used for development using an alkali developer. Can do. Here, the term “for alkali development” means at least an application provided for a development process using an alkali developer.
On the other hand, when an actinic ray-sensitive or radiation-sensitive resin composition uses an organic developer as a developer, negative-type development (when exposed, the solubility in the developer decreases and the exposed portion is exposed). Remains as a pattern and is used for development in which unexposed portions are removed. That is, in this case, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for developing an organic solvent used in development using a developer containing an organic solvent. It can be a thing. Here, the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and even a negative resist composition (that is, a resist composition for developing an organic solvent) is positive. It may be a mold resist composition (that is, a resist composition for alkali development).
The composition according to the present invention is typically a chemically amplified resist composition.

[1] (A) Resin having a group that decomposes by the action of an acid to generate a polar group The actinic ray-sensitive or radiation-sensitive resin composition is a group that decomposes by the action of an acid to generate a polar group (hereinafter, “ It is preferable to contain a resin (A) (hereinafter also referred to as “resin (A)”) having an “acid-decomposable group”.
The resin (A) is, for example, a resin having an acid-decomposable group in the main chain or side chain of the resin or in both the main chain and the side chain.
The definition of the polar group is synonymous with the definition described in the section of the repeating unit (c) described later. Examples of the polar group generated by the decomposition of the acid-decomposable group include an alcoholic hydroxyl group, an amino group, and an acidic group. Is mentioned.

The polar group generated by the decomposition of the acid-decomposable group is preferably an acidic group.
The acidic group is not particularly limited as long as it is a group that is insolubilized in a developer containing an organic solvent, but is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group, a sulfonamide group, a sulfonyl group. Imido group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (Alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, more preferably carboxylic acid group, fluorinated alcohol group (preferably hexafluoroisopropanol), phenolic hydro Sill group, (used as a developer for conventional resist, a group dissociated in 2.38 mass% tetramethylammonium hydroxide aqueous solution) acidic group such as a sulfonic acid group include.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group capable of leaving by the action of an acid _{include, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like.

(A) Repeating unit having acid-decomposable group The resin (A) preferably has a repeating unit (a) having an acid-decomposable group.

  The repeating unit (a) is preferably a repeating unit represented by the following general formula (V).

In general formula (V),
R ₅₁ , R ₅₂ , and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, and R ₅₂ in this case represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
As the alkyl group of R _{51 to} R ₅₃ in the general formula (V), a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R _{51 to} R ₅₃ .
The cycloalkyl group may be monocyclic or polycyclic. Preferably, a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

When R ₅₂ is an alkylene group and forms a ring with L ₅ , the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable. The ring formed by combining R ₅₂ and L ₅ is particularly preferably a 5- or 6-membered ring.

R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₅ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₅ ), and an ethylene group (forms a ring with L ₅ ). .

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
L ₅ is preferably a single bond, a group represented by —COO—L ₁ —, or a divalent aromatic ring group. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group are preferable, and a 1,4-phenylene group is more preferable.
In the case of which L ₅ to form a ring with R _52, examples of the trivalent linking group represented by L _5, a specific example described above divalent linking group represented by L ₅ 1 single Preferable examples include groups formed by removing any hydrogen atom.
The alkyl group for R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, and n-butyl Particularly preferred are those having 1 to 4 carbon atoms such as a group, an isobutyl group and a t-butyl group.
The cycloalkyl group represented by R ₅₅ and R _56, preferably one having 3 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
The aryl group represented by R ₅₅ and R _56, preferably has 6 to 20 carbon atoms, may be monocyclic or polycyclic, may have a substituent. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group and the like can be mentioned. When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably an aryl group.
The aralkyl group represented by R ₅₅ and R ₅₆ may be monocyclic or polycyclic and may have a substituent. Preferably it is C7-21, and a benzyl group, 1-naphthylmethyl group, etc. are mentioned.

  Moreover, since the effect of this invention is more excellent, resin (A) is resin which has a repeating unit represented by the following general formula (V-1) as a repeating unit represented by general formula (V). It is also preferable that there is.

In the general formula (V-1),
R ₁ and R ₂ each independently represent an alkyl group, R ₁₁ and R ₁₂ each independently represent an alkyl group, and R ₁₃ represents a hydrogen atom or an alkyl group. R ₁₁ and R ₁₂ may be linked to form a ring, and R ₁₁ and R ₁₃ may be linked to form a ring.
Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, and L ₅ represents a single bond or a divalent linking group.

In the general formula (V-1), the alkyl group as R ₁ , R ₂ , R _{11 to} R ₁₃ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or propyl. Group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group.
The alkyl group for R ₁ and R ₂ is more preferably an alkyl group having 2 to 10 carbon atoms from the viewpoint of more reliably achieving the effects of the present invention.
Preferably, at least one of R ₁ and _{R 2} is an alkyl group having 2 to 10 carbon atoms, more preferably both of _{R 1} and _{R 2} is an alkyl group having 2 to 10 carbon atoms, _{R 1} and More preferably, any of R ₂ is an ethyl group.
The alkyl group for R ₁₁ and R ₁₂ is more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₁₃ is more preferably a hydrogen atom or a methyl group.
It is particularly preferable R ₁₁ and _{R 12} are linked to form a _{ring, R 11} and _{R 13} are linked may form a ring.
The ring formed by connecting R ₁₁ and R ₁₂ is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
The ring formed by connecting R ₁₁ and R ₁₃ is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
When R ₁₁ and R ₁₃ are linked to form a ring, it is preferably when R ₁₁ and R ₁₂ are linked to form a ring.
The ring formed by connecting R ₁₁ and R ₁₂ (or R ₁₁ and R ₁₃ ) is more preferably an alicyclic group described later as X in the general formula (V-2).

The ring formed by linking R ₁ , R ₂ , an alkyl group as R _{11 to} R ₁₃ , R ₁₁ and R ₁₂ (or R ₁₁ and R ₁₃ ) may further have a substituent.
Examples of the substituent that the alkyl group as R ₁ , R ₂ , R _{11 to} R ₁₃ and the ring formed by linking R ₁₁ and R ₁₂ (or R ₁₁ and R ₁₃ ) may further include cycloalkyl Group, aryl group, amino group, hydroxy group, carboxy group, halogen atom, alkoxy group, aralkyloxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group. The above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .

The alkyl group for Ra may have a substituent and is preferably an alkyl group having 1 to 4 carbon atoms.
Preferable substituents that the alkyl group of Ra may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms (for example, a trifluoromethyl group), and the glass transition point (Tg) of the resin (A). ) And a methyl group is particularly preferable from the viewpoint of improving resolution and space width roughness.
However, when L ₅ is a phenylene group, Ra is preferably a hydrogen atom.

Specific examples and preferred examples of L ₅ represents the same as those described in L ₅ of the general formula (V).

From the viewpoint that the effect of the present invention can be expressed more reliably by achieving higher contrast (high γ value), R ₁₁ and R ₁₂ in the general formula (V-1) are linked to form a ring. The repeating unit represented by the general formula (V-1) is more preferably a repeating unit represented by the following general formula (V-2).

In the general formula (V-2),
X represents an alicyclic group.
R _{1, R} 2, Ra and _{L 5,} respectively, have the same meaning as _{R 1,} R 2, Ra and _{L 5} in formula (V-1), specific example, also general formula for preferred embodiments (V-1 And R ₁ , R ₂ , Ra and L _{5 in} the formula ( ₁ ).

The alicyclic group as X may be monocyclic, polycyclic or bridged, and preferably represents an alicyclic group having 3 to 25 carbon atoms.
The alicyclic group may have a substituent, and examples of the substituent include an alkyl group as R ₁ , R ₂ , R _{11 to} R ₁₃ , R ₁₁ and R ₁₂ (or R ₁₁ and R _{11). 13} ) The same substituents as those described above as the substituent which the ring formed by linking may have, and alkyl groups (methyl group, ethyl group, propyl group, butyl group, perfluoroalkyl group (for example, trifluoro) Methyl group) and the like.
X preferably represents an alicyclic group having 3 to 25 carbon atoms, more preferably an alicyclic group having 5 to 20 carbon atoms, and particularly preferably a cycloalkyl group having 5 to 15 carbon atoms.
X is preferably a 3- to 8-membered alicyclic group or a condensed ring group thereof, more preferably a 5- or 6-membered ring or a condensed ring group thereof.
Below, the structural example of the alicyclic group as X is shown.

  Preferred examples of the alicyclic group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be exemplified. A cyclohexyl group, a cyclopentyl group, an adamantyl group and a norbornyl group are more preferred, a cyclohexyl group and a cyclopentyl group are more preferred, and a cyclohexyl group is particularly preferred.

As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.
Specific examples of the repeating unit represented by the general formula (V) are shown below, but the present invention is not limited thereto.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms. Z represents a substituent. p represents 0 or a positive integer, preferably 0 to 2, and more preferably 0 or 1. When a plurality of Z are present, they may be the same as or different from each other. Z is preferably a group consisting of only a hydrogen atom and a carbon atom from the viewpoint of increasing the dissolution contrast with respect to the developer before and after acid decomposition, for example, a linear or branched alkyl group or a cycloalkyl group. It is preferable.

  The repeating unit (a) is also preferably a repeating unit represented by the following general formula (VI).

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.

General formula (VI) will be described in more detail.
As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.
The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 10 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent. A cycloalkyl group is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

If R ₆₂ represents an alkylene group, the alkylene group, preferably a methylene group which may have a substituent group, an ethylene group, a propylene group, butylene group, hexylene group, 1 to 8 carbon atoms such as octylene Can be mentioned.
_-CONR 64 represented by X ₆ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64 in,} the same as the alkyl group of R 61 _{to R 63.}
X ₆ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.
The alkylene group for L ₆ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group. The ring formed by combining R ₆₂ and L ₆ is particularly preferably a 5- or 6-membered ring.
Ar ₆ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent. Ar ₆ may have a plurality of substituents, and in this case, the plurality of substituents may be bonded to each other to form a ring.

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have are represented by R _{51 to} R ₅₃ in the general formula (V). Specific examples similar to the substituents that the group may have are exemplified.
n is preferably 1 or 2, and more preferably 1.
n Y ₂ each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y ₂ leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R _{38), - C (R 01} ) (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38) , —CH (R ₃₆ ) (Ar) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a group in which an alkylene group and an aryl group are combined, or an alkenyl group.

Ar represents an aryl group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be linear or branched and is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, A propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group, etc. can be mentioned.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably an aryl group having 6 to 10 carbon atoms, such as an aryl group such as a phenyl group, a naphthyl group and an anthryl group, thiophene, furan, pyrrole, Mention may be made of divalent aromatic ring groups containing heterocycles such as benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.
The group in which the alkylene group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and the aryl group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. be able to.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. As the monocyclic type, a cycloalkyl structure having 3 to 10 carbon atoms is preferable, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkyl structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.
Each of the groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, and an amino group. Amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. The number of carbon atoms is preferably 8 or less.
As the group Y ₂ leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).
The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Preferred examples include a group and an octyl group.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms. Specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like are preferable examples. Can do.

The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and the like. .
Group formed by combining an alkylene group and an aryl group represented by L ₁ and L ₂ are, for example, a 6 to 20 carbon atoms, a benzyl group, an aralkyl group such as a phenethyl group.
The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group). Group, adamantylene group, etc.), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O _{-, - CO -, - SO} 2 -, - N (R 0) -, and a divalent linking group formed by combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).

The alkyl group as Q is the same as each group as L ₁ and L ₂ described above.
In the cycloalkyl group which may contain a hetero atom as Q and the aryl group which may contain a hetero atom, an aliphatic hydrocarbon ring group containing no hetero atom and an aryl group containing no hetero atom Includes the cycloalkyl group as L ₁ and L ₂ described above, an aryl group, and the like, and preferably has 3 to 15 carbon atoms.
Examples of the cycloalkyl group containing a hetero atom and the aryl group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, Examples thereof include groups having a heterocyclic structure such as pyrrolidone, but are not limited thereto as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom or a ring formed of a heteroatom).

Q, M, as a ring which may be formed by combining at least two L _1, Q, M, by combining at least two L _1, for example, a propylene group, to form a butylene group, an oxygen atom The case where a 5-membered or 6-membered ring containing is formed is mentioned.
Each group represented by L ₁ , L ₂ , M, and Q in the general formula (VI-A) may have a substituent, for example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ described above. And those described as the substituent that Ar may have, and the carbon number of the substituent is preferably 8 or less.
The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

  The resin (A) is preferably a resin having a repeating unit represented by the following general formula (3) as the repeating unit represented by the general formula (VI).

In general formula (3),
Ar ₃ represents an aromatic ring group.
R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₃ represents a single bond or a divalent linking group.
Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
At least two of Q ₃ , M ₃ and R ₃ may be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group. More preferred is a phenylene group.
Ar ₃ may have a substituent, and examples of the substituent that Ar ₃ may have include the same substituents that Ar ₆ in General Formula (VI) may have.

The alkyl group or cycloalkyl group represented by R ₃ has the same meaning as the alkyl group or cycloalkyl group represented by R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ described above.
The aryl group represented by R ₃ has the same meaning as the aryl group represented by R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.
The aralkyl group represented by R ₃ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkyl group part of the alkoxy group represented by R ₃ is the same as the alkyl group represented by R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ described above, and the preferred range is also the same.
Examples of the acyl group represented by R ₃ include aliphatic acyl groups having 1 to 10 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, benzoyl group and naphthoyl group. , An acetyl group or a benzoyl group is preferred.
Examples of the heterocyclic group represented by R ₃ include the aforementioned cycloalkyl groups containing a hetero atom and aryl groups containing a hetero atom, and a pyridine ring group or a pyran ring group is preferable.

R ₃ is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group, and a linear or branched alkyl group having 1 to 8 carbon atoms (specifically, Is a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group), a carbon number of 3 More preferably, it is 15 cycloalkyl groups (specifically, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc.). R ₃ is more preferably a methyl group, an ethyl group, an i-propyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a cyclohexyl group, an adamantyl group, a cyclohexylmethyl group or an adamantanemethyl group, , Sec-butyl group, neopentyl group, cyclohexylmethyl group or adamantanemethyl group is particularly preferable.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, acyl group or heterocyclic group described above may further have a substituent, and examples of the substituent that may be included include the aforementioned R ₃₆ to R ₃₆ to. _{R 39, R 01, R 02} , and Ar can be mentioned those described as the substituent which may have.

The divalent linking group represented by M ₃ has the same meaning as M in the structure represented by the aforementioned general formula (VI-A), and the preferred range is also the same. M ₃ may have a substituent, and the substituent that M ₃ may have is the same group as the substituent that M in the group represented by the general formula (VI-A) can have Is mentioned.

The alkyl group, cycloalkyl group and aryl group represented by Q ₃ have the same meanings as those in Q in the structure represented by the general formula (VI-A), and the preferred ranges are also the same.
Examples of the heterocyclic group represented by Q ₃ include a cycloalkyl group containing a hetero atom as Q and an aryl group containing a hetero atom in the structure represented by the aforementioned general formula (VI-A), and a preferred range is also included. It is the same.
Q ₃ may have a substituent, and the substituent that Q ₃ may have is the same group as the substituent that Q in the group represented by the general formula (VI-A) can have Is mentioned.

The ring formed by combining at least two of Q ₃ , M ₃ and R ₃ is a ring which may be formed by combining at least two of Q, M and L ₁ in the general formula (VI-A). It is synonymous and the preferable range is also the same.

  Specific examples of the repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

  The repeating unit (a) is also preferably a repeating unit represented by the following general formula (4).

In general formula (4),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.
L ₄ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₄₂ , represents a trivalent linking group.
R ₄₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
M ₄ represents a single bond or a divalent linking group.
Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring.

R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₅₁ , R ₅₂ and R _{53 in} the general formula (V), and preferred ranges are also the same.

L ₄ has the same meaning as L _{5 in} the general formula (V), and the preferred range is also the same.

R ₄₄ has the same meaning as R _{3 in} the general formula (3), and the preferred range is also the same.

M ₄ has the same meaning as M _{3 in} the general formula (3), and the preferred range is also the same.

Q ₄ has the same meaning as Q _{3 in} the general formula (3), and the preferred range is also the same. Examples of the ring formed by combining at least two of Q ₄ , M ₄ and R ₄₄ include rings formed by combining at least two of Q ₃ , M ₃ and R ₃ , and the preferred range is the same. It is.

  Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

  The repeating unit (a) is also preferably a repeating unit represented by the following general formula (BZ).

In general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

The aryl group for AR is preferably a group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.
When AR is a naphthyl group, anthryl group, or fluorene group, the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited. For example, when AR is a naphthyl group, this carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.
Each of the aryl groups as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group. A linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group containing these alkyl group parts, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkoxy group containing these cycloalkyl group parts, a hydroxyl group , Halogen atom, aryl group, cyano group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy group, thiophenemethylcarbonyloxy group, and pyrrolidone residue And heterocyclic residues such as groups. As this substituent, a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group portion are preferable, and a paramethyl group or a paramethoxy group is more preferable.

When the aryl group as AR has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. Moreover, this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
Furthermore, this ring may have a substituent. As this substituent, the thing similar to what is mentioned later about the further substituent which Rn may have is mentioned.
Moreover, it is preferable that the repeating unit (a) represented by general formula (BZ) contains two or more aromatic rings from a viewpoint of roughness performance. The number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.
In the repeating unit (a) represented by the general formula (BZ), from the viewpoint of roughness performance, AR preferably contains two or more aromatic rings, and AR is a naphthyl group or a biphenyl group. Is more preferable. The number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.

As described above, Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group or a dodecyl group. A thing with 1-20 carbon atoms is mentioned. The alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.
Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
As the aryl group of Rn, for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.

Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group. , Thiophenemethylcarbonyloxy group, and heterocyclic residues such as pyrrolidone residues. Among these, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group as described above.
Examples of the alkyl group and cycloalkyl group for R ₁ include the same groups as those described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.

When R ₁ is an alkyl group or a cycloalkyl group having a substituent, particularly preferable R ₁ includes, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group. Groups.
Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.
The alkyl group moiety contained in the alkyloxycarbonyl group of R _1, for example, it is possible to adopt a configuration in which previously mentioned as the alkyl group of R _1.
Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.

The non-aromatic ring that may be formed by bonding Rn and AR to each other is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
The non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
The non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.

  Specific examples of the repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.

  Moreover, the aspect of the repeating unit which produces an alcoholic hydroxyl group may be sufficient as the aspect of the repeating unit which has an acid-decomposable group different from the repeating unit illustrated above. In this case, it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). The repeating unit is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3), and is represented by the following general formula (I-1). More preferably.

Where
Each Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group.
R ₁ represents an (n + 1) valent organic group.
R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.
OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.
W represents a methylene group, an oxygen atom or a sulfur atom.
n and m represent an integer of 1 or more. In general formula (I-2), (I-3) or (I-8), n is 1 when R ₂ represents a single bond.
l represents an integer of 0 or more.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.
Each R independently represents a hydrogen atom or an alkyl group.
R ₀ represents a hydrogen atom or an organic group.
L ₃ represents a (m + 2) -valent linking group.
R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.
R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.
p represents an integer of 0 to 3.

Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a methyl group.
W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.
R ₁ represents an (n + 1) valent organic group. R ₁ is preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an alicyclic hydrocarbon group. R ₁ is more preferably an alicyclic hydrocarbon group.
R ₂ represents a single bond or an (n + 1) valent organic group. R ₂ is preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
When R ₁ and / or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. The chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, when R ₁ and / or R ₂ is an alkylene group, R ₁ and / or R ₂ are methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.
When R ₁ and / or R ₂ is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number of this alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.

Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent. In each of these partial structures, the methylene group (—CH ₂ —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C (═O) —], a sulfonyl group [ -S (= O) _2- ], a sulfinyl group [-S (= O)-], or an imino group [-N (R)-] (R is a hydrogen atom or an alkyl group).

For example, when R ₁ and / or R ₂ is a cycloalkylene group, R ₁ and / or R ₂ may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group. Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferable that they are a len group, a tetracyclododecanylene group, or a tricyclodecanylene group.
The non-aromatic hydrocarbon group of R ₁ and / or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent. As this substituent, a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group. L ₁ is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.
R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. Carbon number of this alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-3. R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R ₀ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.
L ₃ represents a (m + 2) -valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.
R ^L represents a (n + 1) -valent linking group. That is, R ^L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and corresponding groups in the specific examples described below. R ^L may be bonded to each other or bonded to the following R ^S to form a ring structure.
R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.
n is an integer of 1 or more. n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent. Accordingly, in this way, the limit resolution and roughness characteristics can be further improved.
m is an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably 1 or 2.
l is an integer of 0 or more. l is preferably 0 or 1.
p is an integer of 0-3.
Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In specific examples, Ra and OP have the same meanings as in general formulas (I-1) to (I-3). Further, when a plurality of OPs are bonded to each other to form a ring, the corresponding ring structure is represented as “OPO” for convenience.

  The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.
The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).

Where
R ₄ has the same meaning as in general formulas (II-1) to (II-3).
R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring.
The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is more preferably represented by at least one selected from the general formulas (II-1) to (II-3). More preferably, it is represented by 1) or (II-3), and particularly preferably represented by formula (II-1).

R ₃ represents a hydrogen atom or a monovalent organic group as described above. R ₃ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.
The alkyl group for R ₃ may be linear or branched. The number of carbon atoms in the alkyl group of R ₃ is preferably 1 to 10, and more preferably 1 to 3. Examples of the alkyl group for R ₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
The cycloalkyl group for R ₃ may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group represented by R ₃ is preferably 3 to 10, and more preferably 4 to 8. Examples of the cycloalkyl group represented by R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

In the general formula (II-1), at least one of R ₃ is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.
R ₄ represents a monovalent organic group. R ₄ is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.
The alkyl group represented by R ₄ preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents. The carbon number of the unsubstituted alkyl group is preferably 1-20. It is preferable that carbon number of the alkyl group part in the alkyl group substituted by one or more aryl groups is 1-25. It is preferable that carbon number of the alkyl group part in the alkyl group substituted by the 1 or more silyl group is 1-30. Also, if the cycloalkyl group R ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.
R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group. R ₅ is preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may not have a substituent. When the alkyl group does not have a substituent, the carbon number is preferably 1 to 6, and preferably 1 to 3.
R ₆ represents a hydrogen atom or a monovalent organic group as described above. R ₆ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent. R ₆ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
Examples of the alkyl group and cycloalkyl group of R ₄ , R _5, and R ₆ include the same as those described above for R ₃ .
Below, the specific example of the group which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxy group is shown.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  The resin (A) is a resin having a repeating unit represented by the general formula (V), the general formula (VI) or the general formula (4) as the repeating unit (a) having an acid-decomposable group. It is preferable.

As a preferred embodiment of the present invention, the resin (A) is a resin having the repeating unit represented by the general formula (VI) as the repeating unit (a), and an alkaline developer is used as a developer. A form in which a positive guide pattern is formed may be mentioned.
In another preferred embodiment of the present invention, the resin (A) is a resin having a repeating unit represented by the general formula (V) or the general formula (4) as the repeating unit (a), and The negative guide pattern is formed using a developer containing an organic solvent as the developer.

  One type of repeating unit (a) having an acid-decomposable group may be used, or two or more types may be used in combination.

The content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 15 mol% to 95 mol% with respect to all the repeating units in the resin (A). However, it is more preferable that it is 20 mol%-95 mol%.
In particular, when organic solvent development is performed, the content of repeating units having an acid-decomposable group in the resin (A) (the total when there are a plurality of types) is 20 with respect to all repeating units in the resin (A). It is preferably at least mol%, more preferably at least 45 mol%. The content of the repeating unit having an acid-decomposable group is preferably 80 mol% or less, more preferably 75 mol% or less, based on all repeating units in the resin (A).

(B) Repeating unit represented by the general formula (1) Especially when irradiating KrF excimer laser, electron beam, X-ray, high energy beam (EUV light etc.) with a wavelength of 50 nm or less, the resin (A) It is preferable to have a repeating unit represented by Formula (1).

In general formula (1),
R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ may be bonded to Ar ₁ to form a ring, in which case R ₁₃ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₁ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₁₃ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.

Specific examples of the alkyl group, cycloalkyl group, halogen atom, alkoxycarbonyl group of R ₁₁ , R ₁₂ , and R ₁₃ in formula (1), and the substituents that these groups may have include those represented by the general formula (V). Are the same as the specific examples described for the groups represented by R ₅₁ , R ₅₂ , and R ₅₃ .

Ar ₁ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the above-described alkylene group and (n + 1) -valent aromatic ring group may have include the alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, and propoxy groups mentioned as R _{51 to} R ₅₃ in formula (V). Group, an alkoxy group such as a hydroxypropoxy group and a butoxy group, and an aryl group such as a phenyl group.

As the divalent linking group for X ₁ , —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —CONR— (wherein R is A hydrogen atom or an alkyl group), an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms) or a plurality of these. Examples thereof include a combined divalent linking group.
X ₁ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

As Ar ₁ , an aromatic ring group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
The repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar ₁ is preferably a benzene ring group.

  n represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

  Specific examples of the repeating unit represented by the general formula (1) are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

  The resin (A) may contain two or more types of repeating units represented by the general formula (1).

  The content of the repeating unit represented by the general formula (1) (the total when containing a plurality of types) is within the range of 3 to 98 mol% with respect to all the repeating units in the resin (A). Is preferable, more preferably in the range of 10 to 80 mol%, still more preferably in the range of 25 to 70 mol%.

(C) Repeating unit having a polar group other than the repeating unit represented by formula (1) The resin (A) preferably contains a repeating unit (c) having a polar group. By including the repeating unit (c), for example, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. The repeating unit (c) is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).
As the “polar group” that can be contained in the repeating unit (c), and the repeating unit having a polar group, the description in paragraphs [0149] to [0157] of JP2013-76991A can be referred to. It is incorporated herein.

  When the repeating unit (c) has an alcoholic hydroxy group or a cyano group as a polar group, it is a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group as one preferred repeating unit. Can be mentioned. At this time, it is preferable not to have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIIc) are preferable. This improves the substrate adhesion and developer compatibility.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms.

  Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIIc) include the repeating units represented by the following general formulas (AIIa) to (AIIc).

In the general formulas (AIIa) to (AIIc),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group is in the resin (A). The total repeating unit is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

The repeating unit (c) may be a repeating unit having a lactone structure as a polar group.
The repeating unit having a lactone structure is more preferably a repeating unit represented by the following general formula (AII).

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

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group having a lactone structure.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), and (LC1-14).

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

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

The resin (A) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is The range of 1 to 70 mol% is preferable with respect to the repeating unit, more preferably 3 to 65 mol%, and still more preferably 5 to 60 mol%.
Specific examples of the repeating unit having a lactone structure in the resin (A) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The repeating unit (c) may be a repeating unit having a sultone structure as a polar group.
The sultone structure is preferably a structure represented by the following general formula (SL1-1) or (SL1-2). Rb ₂ and n ₂ in the formula are synonymous with the above-described general formulas (LC1-1) to (LC1-17).

  As the repeating unit containing a sultone group that the resin (A) has, a lactone group in the repeating unit having a lactone group described above is preferably substituted with a sultone group.

  The repeating unit (c) may be a repeating unit having a cyclic carbonate structure as a polar group.

  The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In General Formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ² each independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.
n represents an integer of 0 or more.

General formula (A-1) is demonstrated in detail.
The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.
The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group. Preferably it is a C1-C5 alkyl group, and a C1-C5 linear alkyl group; C3-C5 branched alkyl group etc. can be mentioned. The alkyl group may have a substituent such as a hydroxyl group.
n is an integer of 0 or more representing the number of substituents. For example, n is preferably 0 to 4, and more preferably 0.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As an alkylene group, a C1-C10 alkylene group is preferable and a C1-C5 alkylene group is more preferable.
In one embodiment of the present invention, A is preferably a single bond or an alkylene group.

As a monocycle containing -O-C (= O) -O- represented by Z, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 to 7-membered ring, and it is preferably a 5- or 6-membered ring _(n a = 2 or 3), more preferably a 5-membered ring _(n a = 2).
Examples of the polycycle including —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures. Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .

In the resin (A), one type of repeating units having a cyclic carbonate structure may be contained alone, or two or more types may be contained.
In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). 3 to 80 mol%, preferably 3 to 60 mol%, more preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such content rate, developability, low defect property, low LWR, low PEB temperature dependency, profile, etc. can be improved in the formation of the guide pattern.

Although the specific example of the repeating unit represented by general formula (A-1) below is given, this invention is not limited to these.
Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the general formula (A-1).

  Moreover, it is also one of the especially preferable aspects that the polar group which a repeating unit (c) can have is an acidic group. Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (eg hexafluoroisopropanol group), sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned. Of these, the repeating unit (c) is more preferably a repeating unit having a carboxyl group. By containing the repeating unit having an acidic group, the resolution in the contact hole application is increased. The repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The acidic group that the repeating unit (c) may have may or may not contain an aromatic ring, but when it has an aromatic ring, it is preferably selected from acidic groups other than phenolic hydroxyl groups. When the repeating unit (c) has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, and 20 mol% or less with respect to all the repeating units in the resin (A). More preferably. When resin (A) contains the repeating unit which has an acidic group, content of the repeating unit which has an acidic group in resin (A) is 1 mol% or more normally.
Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(D) Repeating unit having a plurality of aromatic rings The resin (A) may have a repeating unit (d) having a plurality of aromatic rings represented by the following general formula (c1).
As the repeating unit (d) having a plurality of aromatic rings, the description in paragraphs [0194] to [0207] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.

  The resin (A) may or may not contain the repeating unit (d), but when it is contained, the content of the repeating unit (d) is 1 to 30 with respect to the total repeating unit of the resin (A). It is preferably in the range of mol%, more preferably in the range of 1 to 20 mol%, and still more preferably in the range of 1 to 15 mol%. The repeating unit (d) contained in the resin (A) may contain a combination of two or more types.

  The resin (A) in the present invention may appropriately have a repeating unit other than the repeating units (a) to (d). As an example of such a repeating unit, a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, or cyano group) and does not exhibit acid decomposability can be included. Thereby, the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

  Description of each group in general formula (IV) can consider the description of Paragraph [0212]-[0216] of Unexamined-Japanese-Patent No. 2013-76991, The content of these is integrated in this-application specification.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content is preferably 1 to 20 mol%, more preferably 5 to 15 mol%, based on all repeating units in the resin (A).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  In addition, the resin (A) may further include a repeating unit represented by the following general formula (5).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. S represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

  Although the specific example of the repeating unit represented by General formula (5) below is shown, this invention is not limited to this. Specific examples of the repeating unit represented by the general formula (P) include paragraphs [0168] to [0210] of JP2013-80002A and paragraphs [0191] to [0191] of JP2013-137537A. [0203] can also be considered, and the contents thereof are incorporated in the present specification.

  The content of the repeating unit represented by the general formula (5) in the resin (A) is preferably in the range of 1 to 40 mol%, and in the range of 2 to 30 mol% with respect to all the repeating units of the resin (A). Is more preferable, and the range of 5 to 25 mol% is particularly preferable.

  Further, the resin (A) may contain the following monomer components in view of the effects such as improvement of Tg, improvement of dry etching resistance, the above-mentioned internal filter of out-of-band light, and the like.

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

  Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.

The form of the resin (A) may be any of random type, block type, comb type, and star type.
Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of an unsaturated monomer and a polymerization initiator in a heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).

The reaction concentration is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.
After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

In particular, when an actinic ray-sensitive or radiation-sensitive film obtained from an actinic ray-sensitive or radiation-sensitive resin composition is irradiated with ArF excimer laser light, the composition of the present invention is used from the viewpoint of transparency to ArF light. The resin (A) used has substantially no aromatic ring (specifically, the content of the repeating unit having an aromatic group is preferably 5 mol% or less, based on the total repeating units of the resin, More preferably, it is preferably 3 mol% or less, ideally 0 mol%, that is, having no aromatic group), and the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure. preferable.
When the composition of the present invention contains a hydrophobic resin (HR) described later, the resin (A) does not contain a fluorine atom and a silicon atom from the viewpoint of compatibility with the hydrophobic resin (HR). Is preferred.
In this case, the resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  In particular, an actinic ray-sensitive or radiation-sensitive film obtained from an actinic ray-sensitive or radiation-sensitive resin composition is applied to a KrF excimer laser, an electron beam, an X-ray, a high-energy ray having a wavelength of 50 nm or less (such as EUV light ), The resin (A) may have a repeating unit having an aromatic ring, and preferably has a repeating unit represented by the general formula (1) as described above. The repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate. Examples include units. As the resin (A) in this case, more specifically, a resin having a hydroxystyrene repeating unit and a hydroxystyrene repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of (meth) acrylic acid is protected by an acid-decomposable group.

  The molecular weight of the resin (A) is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and particularly in the range of 2000 to 30000. preferable. By setting the weight average molecular weight in the range of 1000 to 100,000, it is possible to prevent heat resistance and dry etching resistance from being deteriorated, and also to prevent developability from being deteriorated and the film forming property from being deteriorated due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

  Moreover, dispersity (Mw / Mn) becomes like this. Preferably it is 1.00-5.00, More preferably, it is 1.00-3.50, More preferably, it is 1.00-2.50. The smaller the molecular weight distribution, the better the resolution and resist shape, the smoother the side walls of the guide pattern, and the better the roughness.

  Resin (A) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (A) is preferably 20 to 99 mass%, more preferably 30 to 99 mass%, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 40-99 mass% is still more preferable.

[2] (B) Compound that generates acid upon irradiation with actinic ray or radiation Actinic ray-sensitive or radiation-sensitive resin composition is usually a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generation”). It is preferable to contain "agent" or "compound (B)".
The acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.
The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in a form incorporated in a part of the polymer, the resin (A) is incorporated into a part of the resin (A) described above. You may comprise, You may incorporate in resin different from resin (A).
More preferred examples include compounds represented by the following general formula (ZI), (ZII) or (ZIII).

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

  Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  Examples of the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion and the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion are described in paragraphs [0234] and [0234] of JP2013-76991A. [0235], the contents of which are incorporated herein by reference.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. As specific examples, the description in paragraph [0236] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.

  As the aralkylcarboxylate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, and tris (alkylsulfonyl) methide anion, the description in paragraphs [0237] to [0239] of JP2013-76991A can be referred to. These contents are incorporated herein.

  As other non-nucleophilic anions, the description in paragraph [0240] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.

  Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

  Moreover, as a non-nucleophilic anion, the anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.

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

The general formula (AN1) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ may be mentioned, among which a fluorine atom and CF ₃ are preferable. In particular, it is preferable that both Xf are fluorine atoms.

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

x is preferably 1 to 10, and more preferably 1 to 5.
y is preferably 0 to 4, and more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having 12 or less carbon atoms is preferred. Among these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.

  In addition, examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that the resin (A) may have. Can be mentioned.

  The cyclic organic group may have a substituent, and the description of paragraph [0251] of JP2013-76991A can be referred to as the substituent, and the contents thereof are incorporated in the present specification. It is.

_Examples of the organic group for R ₂₀₁ , R _202, and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, the alkyl group, and the cycloalkyl group, the description in paragraph [0252] of JP2013-76991A can be referred to, and the contents thereof are incorporated in the present specification.

In addition, in the case where two of R _{201 to} R ₂₀₃ are bonded to form a ring structure, the structure represented by the general formula (A1) is described in paragraphs [0253] to [0257] of JP2013-76991A. And the contents thereof are incorporated in the present specification.

In addition, as a preferable structure when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, paragraphs 0046 to 0048 of JP-A-2004-233661, paragraphs 0040 to 340 of JP-A-2003-35948 Compounds exemplified as formulas (I-1) to (I-70) in U.S. Patent Application Publication No. 2003 / 0224288A1, and formula (IA-1) in U.S. Patent Application Publication No. 2003 / 0077540A1. ) To (IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

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

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by general formulas (ZIV), (ZV), and (ZVI) described in paragraphs [0262] to [0264] of JP2013-76991A.

  Among acid generators, particularly preferred examples are given below.

In the present invention, the compound (B) has a volume of 240 to ³ or more by irradiation with actinic rays or radiation from the viewpoint of improving the resolution by suppressing the diffusion of the acid generated by exposure to the non-exposed portion. It is preferably a compound that generates an acid having a size, more preferably a compound that generates an acid having a volume of 300 to ³ or more, and a compound that generates an acid having a volume of 350 to ³ or more. Is more preferable, and a compound that generates an acid having a volume of 400 ³ or more is particularly preferable. However, from the viewpoint of sensitivity and coating solvent solubility, the volume is preferably 2000 ³ or less, and more preferably 1500 ³ or less. The volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the total solid content of the composition. %, More preferably 1 to 30% by mass.

[3] (C) Solvent (coating solvent)
The solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited as long as it can dissolve each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether) Acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.), lactate alkyl ester (ethyl lactate, methyl lactate) Etc.), cyclic lactones (γ-butyrolactone, etc., preferably 4 to 10 carbon atoms), chain or cyclic ketones (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (e. Ren carbonate, propylene carbonate), alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), alkoxy alkyl acetates (ethyl ethoxypropionate), and methyl 2-hydroxyisobutyrate and the like. Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.
The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.

[4] (D) Basic compound The actinic ray-sensitive or radiation-sensitive resin composition preferably further contains a basic compound (D). The basic compound (D) is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(7) can be used.

  (1) Compound represented by general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be given. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

  Among the basic compounds represented by the general formula (BS-1), examples of those having such a hydroxyl group or oxygen atom include the following.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  Examples of compounds having a preferred nitrogen-containing heterocyclic structure include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine is mentioned. These may further have a substituent.

  Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferred basic compounds include, for example, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2 -Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) ) Piperazine, N- (2-aminoethyl) ) Piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3 -Pyrazolin, N-aminomorpholine and N- (2-aminoethyl) morpholine.

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.
The cation of the ammonium salt is preferably a tetraalkylammonium cation substituted with an alkyl group having 1 to 18 carbon atoms, such as a tetramethylammonium cation, a tetraethylammonium cation, a tetra (n-butyl) ammonium cation, or a tetra (n-heptyl) ammonium. A cation, a tetra (n-octyl) ammonium cation, a dimethylhexadecylammonium cation, a benzyltrimethyl cation, and the like are more preferable, and a tetra (n-butyl) ammonium cation is most preferable.
Examples of the anion of the ammonium salt include hydroxide, carboxylate, halide, sulfonate, borate, and phosphate. Of these, hydroxide or carboxylate is particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

The carboxylate may be an aliphatic carboxylate or an aromatic carboxylate, and examples thereof include acetate, lactate, birubate, trifluoroacetate, adamantane carboxylate, hydroxyadamantane carboxylate, benzoate, naphthoate, salicylate, phthalate, phenolate, and the like. In particular, benzoate, naphthoate, phenolate and the like are preferable, and benzoate is most preferable.
In this case, as the ammonium salt, tetra (n-butyl) ammonium benzoate, tetra (n-butyl) ammonium phenolate and the like are preferable.
In the case of hydroxide, this ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred that

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The actinic ray-sensitive or radiation-sensitive resin composition has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or It may further contain a compound that generates a compound that has been changed from proton acceptor property to acidity (hereinafter also referred to as compound (PA)).
As a compound (PA) having a proton acceptor functional group and decomposing upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity Can be referred to the descriptions in paragraphs [0379] to [0425] of JP 2012-32762 A (corresponding to [0386] to [0435] of the corresponding US Patent Application Publication No. 2012/0003590). Is incorporated herein.

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.
The basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is highly neutralizing reactivity with the acid, Since it is excellent in a roughness characteristic, it is preferable and it is more preferable that it is 8.0-16.0.

  Due to such strong basicity, it is possible to suppress acid diffusibility and contribute to the formation of an excellent pattern shape.

  Here, “pKa” means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

  Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

  In the present invention, log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. In general, the distribution coefficient is obtained by calculation without experimentation. In the present invention, CSChemDrawUltraVer. The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.

  Moreover, it is preferable that logP of a guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.

  The log P of the guanidine compound (A) in the present invention is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, still more preferably in the range of 4 to 8.

  Moreover, it is preferable that the guanidine compound (A) in this invention does not have a nitrogen atom other than a guanidine structure.

  Hereinafter, although the specific example of a guanidine compound is shown, it is not limited to these.

(7) A low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The actinic ray-sensitive or radiation-sensitive resin composition has a group having a nitrogen atom and leaving by the action of an acid. And a low molecular compound (hereinafter, also referred to as “low molecular compound (D)” or “compound (D)”). The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.
As the low molecular weight compound (D), the description in paragraphs [0324] to [0337] of JP2012-133331A can be referred to, and the contents thereof are incorporated in the present specification.
In the present invention, the low molecular compound (D) can be used singly or in combination of two or more.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

  These basic compounds (D) may be used alone or in combination of two or more.

  The content of the basic compound (D) contained in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.01 to 8.0% by mass based on the total solid content of the composition. More preferably, it is 0.1-5.0 mass%, and it is especially preferable that it is 0.2-4.0 mass%.

  The molar ratio of the basic compound (D) to the acid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3. The acid generator in the molar ratio is the total of the repeating unit represented by the general formula (5) of the resin (A) and the acid generator that the resin (A) may further contain. It is based on quantity.

[5] Compound that decomposes by the action of an acid to generate an acid The actinic ray-sensitive or radiation-sensitive resin composition further contains one or more compounds that decompose by the action of an acid to generate an acid. You may go out. The acid generated from the compound that decomposes by the action of the acid to generate an acid is preferably a sulfonic acid, a methide acid, or an imido acid.

  Although the example of the compound which decomposes | disassembles by the effect | action of the acid which can be used for this invention and generate | occur | produces an acid is shown below, it is not limited to these.

The compound which decomposes | disassembles by the effect | action of the said acid and generate | occur | produces an acid can be used individually by 1 type or in combination of 2 or more types.
In addition, content of the compound which decomposes | disassembles by the effect | action of an acid and generate | occur | produces an acid may be 0.1-40 mass% on the basis of the total solid of the said actinic-ray-sensitive or radiation-sensitive resin composition. Preferably, it is 0.5-30 mass%, More preferably, it is 1.0-20 mass%.

[6] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (A).
Since the hydrophobic resin (HR) is unevenly distributed on the film surface, the hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a silicon atom, or a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.

  In addition, as the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.

[7] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

  Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.
Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate is composed of a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation). Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ Copolymerization of a group-containing acrylate or methacrylate with (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate Body, and the like.

Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
One of these surfactants may be used alone, or two or more thereof may be used in combination.
When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001, based on the total solid content of the composition. ˜2 mass%, more preferably 0.0005 to 1 mass%.

[8] Other additives In addition to the components described above, the actinic ray-sensitive or radiation-sensitive resin composition is described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996) and the like. These may contain a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like.
In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.
The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0 in the total solid concentration of the actinic ray-sensitive or radiation-sensitive resin composition. 0.01 to 3% by mass.

As described above, the actinic ray-sensitive or radiation-sensitive resin composition is preferably used at a film thickness of 10 to 250 nm, more preferably at a film thickness of 20 to 200 nm, from the viewpoint of improving resolution. It is preferable to use at 30 to 100 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0. It is -5.3 mass%. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a guide pattern having excellent line width roughness can be formed. The reason for this is not clear, but it is likely that the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, so that the material in the actinic ray-sensitive or radiation-sensitive resin composition solution, in particular, It is considered that agglomeration of the photoacid generator was suppressed, and as a result, a uniform actinic ray-sensitive or radiation-sensitive film could be formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  The actinic ray-sensitive or radiation-sensitive resin composition is used by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Resin>
[Synthesis Example 1: Synthesis of Resin (BP-1)]
Under a nitrogen atmosphere, s-butyllithium was added to 50 mL of tetrahydrofuran (THF), and the mixture was stirred at room temperature for 1 hour to remove moisture and the like in the system. After cooling to -78 ° C, 0.27 mL (0.40 mmol) of n-butyllithium (n-BuLi) and 4.76 mL (26.0 mmol) of t-butylstyrene (TBSt) were added to initiate polymerization. After aging for 10 minutes, a THF solution of 1,1-diphenylethylene (DPE) 0.11 mL (0.60 mmol) and lithium chloride (LiCl) 52.6 mg (1.24 mmol) was added, and the mixture was further stirred for 5 minutes. Next, 1.84 g (9.20 mmol) of methyl (2,2-dimethyl-1,3-dioxolan-4-yl) methacrylate was added to the reaction solution, and the mixture was further stirred for 1 hour. Methanol was added to this reaction solution to stop the reaction, and then reprecipitation operation was carried out with a methanol solvent, followed by filtration. The obtained block copolymer was dissolved in 15 mL of THF, 5 mL of 1N HCl was added, and the mixture was reacted at room temperature for 24 hours. A reprecipitation operation was performed with a methanol solvent, and the resultant was collected by filtration. The obtained filtrate was air-dried to obtain a resin (BP-1) (Mn = 11,400, Mw / Mn = 1.11, general formula). Block of repeating unit represented by (I-1) / Block of repeating unit represented by general formula (II) = 53/47 wt%, Tg = 85, 145 ° C., 1H-NMR (400 MHz, CDCl ₃ ) δ (Ppm) 7.3-6.2 (m, 4H), 4.3 (s, 0.5H), 4.2-3.7 (m, 2.2H), 2.2-0.7 ( m, 16.7H)).
A synthesis scheme of the resin (BP-1) is shown below. Hereinafter, Me represents a methyl group, and Ph represents a phenyl group.

[Synthesis Example 2: Synthesis of Resin (BP-2)]
Under a nitrogen atmosphere, s-butyllithium (s-BuLi) was added to 50 mL of THF, and the mixture was stirred at room temperature for 1 hour to remove moisture and the like in the system. After cooling to −78 ° C., 0.27 mL (0.40 mmol) of n-butyllithium and 4.76 mL (26.0 mmol) of t-butylstyrene (TBSt) were added to initiate polymerization. After aging for 10 minutes, a THF solution of 1,1-diphenylethylene (DPE) 0.11 mL (0.60 mmol) and lithium chloride (LiCl) 52.6 mg (1.24 mmol) was added, and the mixture was further stirred for 5 minutes. Next, 2.10 g (9.20 mmol) of methacrylic acid (1-methyl-2,6,7-trioxabicyclo [2,2,2] -octane-4-yl) methyl was added to the reaction solution, and Stir for 1 hour. Methanol was added to this reaction solution to stop the reaction, and then reprecipitation operation was carried out with a methanol solvent, followed by filtration. The obtained block copolymer was dissolved in 15 mL of THF, 5 mL of 1N HCl was added, and the mixture was reacted at room temperature for 24 hours. A reprecipitation operation was performed with a methanol solvent, and the resultant was collected by filtration. The obtained filtrate was air-dried to obtain a resin (BP-2) (Mn = 11,700, Mw / Mn = 1.12, general formula). Block of repeating unit represented by (I-1) / Block of repeating unit represented by general formula (II) = 51/49 wt%, Tg = 93, 140 ° C., 1H-NMR (400 MHz, CDCl ₃ ) δ (Ppm) 7.3-6.2 (m, 4H), 4.0 (s, 1.7H), 3.2 (s, 0.6H), 2.2-0.7 (m, 18. 4H)).
A synthesis scheme of the resin (BP-2) is shown below. Hereinafter, Me represents a methyl group, and Ph represents a phenyl group.

[Synthesis Example 3: Synthesis of Resin (BP-3)]
Under a nitrogen atmosphere, s-butyllithium was added to 50 mL of THF, and the mixture was stirred at room temperature for 1 hour to remove moisture and the like in the system. After cooling to −78 ° C., 0.27 mL (0.40 mmol) of n-butyllithium and 4.76 mL (26.0 mmol) of t-butylstyrene (TBSt) were added to initiate polymerization. After aging for 10 minutes, a THF solution of 1,1-diphenylethylene 0.11 mL (0.60 mmol) and lithium chloride 52.6 mg (1.24 mmol) was added, and the mixture was further stirred for 5 minutes. Next, 3.02 g (9.20 mmol) of 1,2,5,6-diisopropylidine-D-glycosyl methacrylate was added to the reaction solution, and the mixture was further stirred for 1 hour. Methanol was added to this reaction solution to stop the reaction, and then reprecipitation operation was carried out with a methanol solvent, followed by filtration. The obtained block copolymer was dissolved in 15 mL of THF, 5 mL of 1N HCl was added, and the mixture was reacted at room temperature for 24 hours. Resin (BP-3) was obtained by performing reprecipitation operation with a methanol solvent, filtering, and air-drying the obtained filtrate. (Mn = 11,000, Mw / Mn = 1.12, block of repeating unit represented by general formula (I-1) / block of repeating unit represented by general formula (II) = 50/50 wt%, 4. Tg = 110, 142 ° C., 1H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 7.3-6.2 (m, 4H), 6.0-5.6 (m, 0.3H), 1-3.4 (m, 1.8H), 2.2-0.7 (m, 17H).
A synthesis scheme of the resin (BP-3) is shown below. Hereinafter, Me represents a methyl group, and Ph represents a phenyl group.

  Resins (BP-4) to (BP-9) and resins (CBP-1) to (CBP-3) were synthesized in the same manner as in Synthesis Example 1.

In any of the synthesis examples described above, the block of the repeating unit represented by any one of the above general formulas (I-1) to (I-3) and the repeating represented by the above general formula (II) This is a synthesis example in which a unit block is formed by living polymerization.
Although these block copolymers contained 1-1000 ppm of metal ions, the amount of metal ions was reduced to 1-50 ppb or less by using a known filtration method. The metal was quantified by diluting the sample 10 times with MEK and using an ICP-OES apparatus (Perkin Elmer Optima 7300 DV, organic solvent mode) by the absolute calibration method.

  Hereinafter, including the resins synthesized in the above synthesis examples, the chemical structures of resins (BP-1) to (BP-9) and resins (CBP-1) to (CBP-3) (composition ratio of repeating units) Is a mass ratio), number average molecular weight (Mn) and dispersity (Mw / Mn). Hereinafter, Me represents a methyl group. ΔSP represents the absolute value of the difference between the above SP values.

[Synthesis Example 4: Synthesis of Resin (P-1)]
20.0 g of poly (p-hydroxystyrene) (VP-2500, manufactured by Nippon Soda Co., Ltd.) was dissolved in 80.0 g of propylene glycol monomethyl ether acetate (PGMEA). To this solution, 10.3 g of 2-cyclohexylethyl vinyl ether and 10 mg of camphorsulfonic acid were added and stirred at room temperature (25 ° C.) for 3 hours. After adding 84 mg of triethylamine and stirring for a while, the reaction solution was transferred to a separatory funnel containing 100 mL of ethyl acetate. This organic layer was washed with 50 mL of distilled water three times, and then the organic layer was concentrated with an evaporator. After dissolving the obtained polymer in 300 mL of acetone, it was dropped again in 3000 g of hexane, and 17.5 g of Resin (P-1) was obtained by filtering the precipitate.

[Synthesis Example 5: Synthesis of Resin (P-11)]
10.00 g of p-acetoxystyrene was dissolved in 40 g of ethyl acetate, cooled to 0 ° C., 4.76 g of sodium methoxide (28 mass% methanol solution) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 5 hours. . Ethyl acetate was added and the organic phase was washed three times with distilled water, then dried over anhydrous sodium sulfate, the solvent was distilled off, and p-hydroxystyrene (a compound represented by the following formula (1), 54 masses). % Ethyl acetate solution) 13.17 g was obtained. 6.66 g (containing 3.6 g of p-hydroxystyrene (1)) of a 54 mass% ethyl acetate solution of the obtained p-hydroxystyrene (1), a compound represented by the following formula (2) (Kobe Natural Product Chemistry) 14.3 g (manufactured by Co., Ltd.), 2.2 g of a compound represented by the following formula (3) (manufactured by Daicel Corporation) and 2.3 g of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) It was dissolved in 14.2 g of propylene glycol monomethyl ether (PGME). 3.6 g of PGME was placed in the reaction vessel, and the solution prepared previously at 85 ° C. was added dropwise over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours and then allowed to cool to room temperature. The obtained reaction solution was dropped and reprecipitated into 889 g of a mixed solution of hexane / ethyl acetate (8/2 (mass ratio)), and 14.9 g of Resin (P-11) was obtained by filtering the precipitate. .

Hereinafter, Resins (P-2) to (P-10) and Resins (P-12) to (P-42) were synthesized using the same method as in Synthesis Examples 4 and 5.
Hereinafter, the polymer structure, weight average molecular weight (Mw), and dispersity (Mw / Mn) of resins (P-1) to (P-42) are shown. Moreover, the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.

<Acid generator>
The acid generator was appropriately selected from the acid generators z1 to z141 listed above.

<Basic compound>
As the basic compound, any one of the following compounds (N-1) to (N-11) was used.

<Surfactant>
The following W-1 to W-4 were used as the surfactant.
W-1: Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon-based)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

<Coating solvent>
As the coating solvent, the following were used.
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)
S3: Ethyl lactate S4: Cyclohexanone

<Developer>
As the developer, the following was used.
SG-1: Anisole SG-2: Methyl amyl ketone (2-heptanone)
SG-3: Butyl acetate

<Rinse solution>
When using a rinse solution, the following was used.
SR-1: 2-pentanol SR-2: 1-hexanol SR-3: methyl isobutyl carbinol

[Phase separation of block copolymer layer using line and space pattern as guide pattern]
(1) Coating liquid preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition The coating liquid composition having the composition of Example 1-3 shown in Table 2 below is precisely filtered with a membrane filter having a pore size of 0.05 μm. Filtration was performed to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution (solid content concentration: 1.5% by mass).
This actinic ray-sensitive or radiation-sensitive resin composition solution was applied onto a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and 100 ° C. for 60 seconds. It dried on the hotplate and obtained the actinic-ray-sensitive or radiation-sensitive film | membrane with a film thickness of 50 nm.

(2) EUV exposure and development The wafer coated with the resist film obtained in the above (1) is subjected to an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0, manufactured by Exitech) .36) and pattern exposure was performed using an exposure mask (line width / space width = 2/9). After irradiation, heated on a hot plate at 110 ° C. for 60 seconds, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds, and dried. A guide pattern of a 2: 9 line and space pattern having a line width of 20 nm and a space width of 90 nm was obtained.

(3) Formation of block copolymer layer and implementation of phase separation On the substrate on which the 2: 9 line and space pattern having a line width of 20 nm and a space width of 90 nm was formed, each DSA resin described in Table 3 below was formed. A 1.9% by weight toluene solution was applied using a spinner (rotation speed: 1000 rpm, 60 seconds), baked on a hot plate at 110 ° C. for 60 seconds, and dried to form a block copolymer having a thickness of 25 nm. A layer was formed.
Next, the substrate on which the block copolymer layer was formed was heated under a nitrogen stream at 240 ° C. until a phase separation structure was formed.
Thereafter, using TCA-3822 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the substrate was subjected to oxygen plasma treatment (200 sccm, 40 Pa, 200 W, 30 seconds), and the repetition represented by the general formula (II) A phase consisting of a block of units was selectively removed.

(4) Evaluation of pattern The surface of the obtained substrate was observed using a scanning electron microscope SU8000 (manufactured by Hitachi High-Technologies Corporation). Is observed relatively cleanly, B is a vertical lamella observed in a non-problematic grade, C is a vertical lamella observed dirty, and E is a vertical lamella not observed. Regarding the lamella shape, the vertical lamella interface is clean A, the vertical lamella interface is relatively clean B, the vertical lamella interface is dirty C, the vertical lamella is not observed Was D.
The evaluation results are shown in Table 3 below. In Table 3, “ΔSP value” is represented by the solubility parameter (SP value) of the repeating unit represented by any one of the above general formulas (I-1) to (I-3) and the above general formula (II). The absolute value of the difference from the solubility parameter (SP value) of the repeating unit. The “block ratio of the repeating units of the general formulas (I-1) to (I-3)” is the block of the repeating unit represented by any one of the above general formulas (I-1) to (I-3) The content (% by mass) of the block of the repeating unit represented by any one of the above general formulas (I-1) to (I-3) with respect to the total amount of the repeating unit block represented by the general formula (II) Represent.

Example 2-9 shall be read as Reference Example 2-9.
From Table 3 above, in Examples 2-1 to 2-9 using the block copolymer in the present invention, the pattern is highly refined (see lamella formation and lamella shape with a pitch of 20 nm in the table). ) Was achieved with high quality.
On the other hand, Comparative Examples 2-1 to 2-3 using a block copolymer not corresponding to the block copolymer in the present invention could not achieve formation of a highly refined pattern with high quality. .

  The coating liquid composition (solid content concentration: 1.5 mass%) which has a composition of Example 1-3 used for formation of the guide pattern in Examples 2-1 to 2-9 is shown in Table 2 above. Example 1-1 was carried out in the same manner as in Examples 2-1 to 2-9 except that the coating liquid compositions having the compositions of 1-1, 1-2, and 1-4 to 1-20 were used. Evaluation results similar to those of 2-1 to 2-9 were obtained.

  In the formation of the guide pattern in Examples 2-1 to 2-9, when the pattern was formed under the same conditions as in Examples 2-1 to 2-9, except that the developer was changed to butyl butanoate. Also, a good guide pattern was obtained, and the same evaluation results as in Examples 2-1 to 2-9 could be obtained.

  Each coating composition having the composition of Examples 3-1 to 3-36 shown in Table 4 is the coating liquid composition having the composition of Example 1-3 used for the formation of the guide pattern in Examples 2-1 to 2-9. Liquid composition (solid content concentration: 1.5% by mass) is used, and exposure mask (line width / space width = 5/1) is used instead of exposure mask (line width / space width = 1/5). Then, in place of the alkaline aqueous solution (TMAH; 2.38 mass% tetramethylammonium hydroxide aqueous solution), development was performed with the developer (organic developer) described in Table 4, and instead of water, the developer was listed in Table 4. The 1.9% by weight toluene solution of each DSA resin listed in Table 3 was replaced with 1.9% by weight propylene glycol monomethyl ether acetate (PGMEA) of each DSA resin listed in Table 3. Except for the solution, Preparation of the actinic ray-sensitive or radiation-sensitive resin composition in the same manner as 施例 2-1 to 2-9, the formation of the guide patterns, and was carried out formation and phase separation of the block copolymer layer. In Table 4, in the examples not described in the column of the rinsing liquid, rinsing is not performed. As a result, the same evaluation results as in Examples 2-1 to 2-9 could be obtained.

  In the above example, even when the guide pattern was replaced with a contact hole pattern having a hole portion diameter of 20 nm and a pitch between holes of 40 nm, the same evaluation as in the above example could be obtained. .

  According to the present invention, in the self-organized lithography using the graphoepitaxy method, it is possible to achieve a high-quality pattern with high quality (for example, a line-and-space pattern with a pitch of 40 nm or less or a hole diameter of 20 nm or less. A pattern forming method capable of forming a hole pattern with high quality), an electronic device manufacturing method and electronic device using the pattern forming method, a block copolymer used in the pattern forming method, and a manufacturing method thereof can be provided. .

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 17, 2014 (Japanese Patent Application No. 2014-189424), the contents of which are incorporated herein by reference.

10 Substrate 21, 22 Guide pattern 31, 35 Block copolymer layer 32, 37 Removal phase 33, 36 Non-removal phase

Claims (10)

(I) On a substrate on which a guide pattern is formed, a block of a repeating unit represented by any one of the following general formulas (I-1) to (I-3) and a repeating represented by the following general formula (II) Forming a block copolymer layer containing a block copolymer having a block of units;
(Ii) phase-separating the block copolymer layer; and
(Iii) A pattern forming method including a step of selectively removing at least one of a plurality of phases in the block copolymer layer.


In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ has the group represented by any one of the following formulas _{(R 6 -1) ~ (R} 6 -4), represents an alkyl group or a cycloalkyl group.
  The block copolymer is a block copolymer having a repeating unit block represented by the general formula (I-1) and a repeating unit block represented by the general formula (II). 2. The pattern forming method according to 1. The solubility parameter (SP value) of the repeating unit represented by any one of the general formulas (I-1) to (I-3) in the block copolymer and the repeating unit represented by the general formula (II) The pattern forming method according to claim 1, wherein an absolute value of a difference from the solubility parameter (SP value) is 6.0 (MPa ^1/2 ) or more. The guide pattern exposes the actinic ray-sensitive or radiation-sensitive film with an ArF excimer laser, extreme ultraviolet light, or an electron beam, and develops the exposed actinic ray-sensitive or radiation-sensitive film using a developer. The pattern formation method of any one of Claims 1-3 which is a guide pattern formed by this. The pattern formation method of any one of Claims 1-4 which forms the base layer containing a base agent on the said board | substrate, and forms the said block copolymer layer on the said base layer. Wherein between steps (i) and the step (ii), to form the topcoat layer on the block copolymer layer, a pattern forming method according to any one of claims 1-5. The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-6 . A block of repeating units represented by any one of the following general formulas (I-1) to (I-3) and the following general formula, which is provided for the pattern forming method according to any one of claims 1 to 6. A block copolymer having a block of repeating units represented by (II).

In General Formula (I-1), R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and bonded to a carbon atom adjacent to the carbon atom to which R ₁ is bonded. The ring may be condensed with a benzene ring.
In General Formula (I-2), R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
In general formula (I-3), R ₃ and R ₄ each independently represents an alkyl group or an aryl group.
In general formula (II), R ₅ represents a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₆ has the group represented by any one of the following formulas _{(R 6 -1) ~ (R} 6 -4), represents an alkyl group or a cycloalkyl group.
A method for producing a block copolymer, wherein the block copolymer according to claim 8 is synthesized by living polymerization. The manufacturing method of the block copolymer of Claim 9 whose said living polymerization is living anion polymerization.