JP4539847B2 - Positive resist material and pattern forming method using the same - Google Patents

Description

  In the exposure with a high energy beam, the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, low line edge roughness, and excellent etching resistance. The present invention relates to a positive resist material suitable as a fine pattern forming material for LSI manufacturing or photomask pattern fabrication, in particular, a chemically amplified positive resist material, and a pattern forming method using the same.

  In recent years, along with higher integration and higher speed of LSI, pattern rule miniaturization is progressing rapidly. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved resist performance, and shorter wavelengths. In particular, the shortening of the wavelength from i-line (365 nm) to KrF (248 nm) has brought about a major change, and the mass production of 0.18 μm rule devices has become possible. Chemically amplified positive resist materials using acid as a catalyst (for example, see Patent Documents 1 and 2) have excellent characteristics for increasing the resolution and sensitivity of resists, and are particularly mainstream in deep ultraviolet lithography. Resist material.

  Resist materials for KrF excimer lasers are generally used in 0.3 μm processes, and after passing through the 0.25 μm rule, application to the mass production of the 0.18 μm rule is now underway, and further studies on the 0.15 μm rule have begun. The momentum of miniaturization is increasingly accelerated. The shortening of the wavelength from the KrF excimer laser to the ArF excimer laser (193 nm) is expected to make the design rule finer to 0.13 μm or less, but conventionally used novolac and polyvinylphenol resins Has a very strong absorption in the vicinity of a wavelength of 193 nm, so it was difficult to use as a base resin for resist. Therefore, in order to ensure transparency and necessary dry etching resistance, acrylic resins and cycloolefin-based alicyclic resins have been studied (for example, see Patent Documents 3 to 6).

  In particular, a (meth) acrylic-based resin resist having high resolution has been studied. As the (meth) acrylic resin, a combination of (meth) acryl having a methyladamantane ester as an acid labile group unit and (meth) acryl having an ester of a lactone ring as an adhesive group unit has been proposed (for example, (See Patent Document 7). Furthermore, norbornyl lactone has been proposed as an adhesive group with enhanced etching resistance (see, for example, Patent Documents 8 to 10).

  One of the problems in ArF lithography is the reduction of line edge roughness and the reduction of residues after development. One factor of line edge roughness is swelling during development. Polyhydroxystyrene phenol used as a resist for KrF lithography is a weakly acidic group and has a moderate alkali solubility, so it is difficult to swell, but a polymer containing a highly hydrophobic alicyclic group is highly acidic. Since it is dissolved by carboxylic acid, swelling during development is likely to occur.

Here, the amount of swelling during development has been reported by measuring the development characteristics of a resist by a QCM (Quartz Crystal Microbalance) method (see, for example, Non-Patent Document 1). In the conventional optical interference type film thickness measurement method, the swelling of the film during development could not be observed, but in the QCM method, in order to electrically measure the change in the weight of the film, an increase in the weight of the film due to the swelling is observed. It is possible. Non-Patent Document 1 shows swelling of a cycloolefin polymer-based ArF resist. In particular, intense swelling has been observed when carboxylic acid is used as the adhesive group.
It has been reported that hexafluorocarbinol groups are effective in reducing swelling. A norbornene having a hexafluorocarbinol group has a small swelling, and a resist using polynorbornene using this as an adhesive group has been reported (see Non-Patent Documents 2 and 3). An acrylate having a hexafluorocarbinol group has also been reported (Patent Document 11).

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 JP-A-10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Pamphlet JP-A-9-90637 JP 2000-26446 A JP 2000-159758 A JP 2002-371114 A JP 2003-40480 A Proc. SPIE Vol. 3999, p2 (2000) Proc. SPIE Vol. 5039, p70 (2003) Proc. SPIE Vol. 5039, p61 (2003)

  The present invention has been made in view of such problems, and has high sensitivity and high resolution in exposure with a high energy beam, and also has low line edge roughness because swelling during development is suppressed. It is an object of the present invention to provide a positive resist material and a pattern forming method with little residue after development.

The present inventors have a positive resist that has high sensitivity and high resolution in exposure with a high energy beam, and has low line edge roughness due to suppression of swelling during development, and few residues after development. In order to obtain the material, intensive study was conducted.
In addition, a resist using hexafluoroalcohol has been studied for F ₂ lithography. It has been reported that hexafluoroalcohol has the same acidity as phenol and little swelling in the developer (J. Photopolym. Sci. Technol., Vol. 16, No. 4, p523 (2003)). ). In addition, polynorbornene having hexafluoroalcohol, α trifluoromethyl acrylate having hexafluoroalcohol as a pendant were introduced, and exposure characteristics in exposure by ArF excimer laser were introduced. As a result, it is not possible to have sufficient adhesion only by having hexafluoroalcohol as an adhesive group, and in particular, by copolymerizing with a repeating unit having lactone as an adhesive group, hydrophilicity and alkali solubility, adhesiveness It turns out that you can balance. In particular, it is obtained by combining (meth) acrylate having a bridged lactone group, (meth) acrylate having an acid-eliminable group, and an adhesive group having alkali solubility represented by hexafluoroalcohol. By using the polymer compound as a base resin, it has a high sensitivity and high resolution, has little line edge roughness due to swelling during development, little residue after development, and excellent dry etching resistance. The present inventors have found that a mold resist material can be provided and completed the present invention.

Accordingly, the present invention provides a resist material containing a polymer compound having, respectively the repeating units represented de following general formula (1a) and / or a (2a) and (1b).
(Wherein R ¹ represents the same or different hydrogen atom or methyl group; R ² represents the same or different hydrogen atom, an acyl group having 1 to 10 carbon atoms or an acid labile group; R ³ represents hydrogen; An atom, a methyl group, or —CO ₂ R ⁸ , wherein R ⁴ represents a hydrogen atom, a methyl group, or —CH ₂ CO ₂ R ⁸ , where R ⁸ is the same or different hydrogen atom or a carbon number of 1 to 15; A linear, branched or cyclic alkyl group, wherein X is —CH ₂ —, —O— or —S—, and when all of R ^{5 to} R ⁷ are hydrogen atoms, —CH ₂ — R ^{5 to} R ⁷ are a hydrogen atom, a methyl group, or —CO ₂ R ⁹ , and R ⁹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. a1, a2, b1 are
0 ≦ a1 / (a1 + a2 + b1) ≦ 0.9
0 ≦ a2 / (a1 + a2 + b1) ≦ 0.9
0 <(a1 + a2) / (a1 + a2 + b1) ≦ 0.9
0 <(b1) / (a1 + a2 + b1) ≦ 0.8
It is a number that satisfies )

Such a positive resist material containing the polymer compound of the present invention as a base resin (Claim 4 ) has a significantly high alkali dissolution rate contrast before and after exposure, and high sensitivity and high resolution in exposure with a high energy beam. Since it has image quality and swelling during development is suppressed, the line edge roughness is small, the etching residue is small, and the etching resistance is excellent. Therefore, since it has these characteristics, it is extremely practical and suitable as a fine pattern forming material for VLSI manufacturing or photomask pattern production.

  In this case, the positive resist material of the present invention is preferably a chemically amplified resist material further containing an organic solvent and an acid generator. Thus, by using the polymer compound of the present invention as a base resin, and further blending an organic solvent and an acid generator, the dissolution rate of the polymer compound in the developer is accelerated by an acid-catalyzed reaction in the exposed area. Therefore, a chemically amplified positive resist material with extremely high sensitivity can be obtained, and it is very suitable as a fine pattern forming material for ultra-LSI manufacturing or the like that is required in recent years. The positive resist material of the present invention may further contain a dissolution inhibitor. Thus, by mix | blending a dissolution inhibitor with a positive resist material, the difference of the dissolution rate of an exposed part and an unexposed part can be enlarged further, and the resolution can be improved further. In the positive resist material of the present invention, a basic compound and / or a surfactant can be further added as an additive. Thus, by adding a basic compound, for example, the resolution of the acid can be further improved by suppressing the acid diffusion rate in the resist film, and by adding a surfactant, the coating property of the resist material can be improved. Can be further improved or controlled.

  Such a resist material of the present invention includes at least a step of applying the resist material on the substrate, a step of exposing to high energy rays after the heat treatment, and a step of developing using a developer. It can be used as a method for forming a pattern on a semiconductor substrate, a mask substrate or the like. Needless to say, development may be performed after the post-exposure heat treatment, and various other processes such as an etching process, a resist removal process, and a cleaning process may be performed. In this case, the high energy ray can have a wavelength in the range of 180 to 200 nm. The resist material containing the polymer compound of the present invention as a base resin can be suitably used particularly for exposure with high energy rays in the wavelength range of 180 to 200 nm, and has excellent sensitivity at exposure wavelengths in this range.

  According to the present invention, a polymer in which a specific repeating unit having a hexafluorocarbinol group, a (meth) acryl unit having a bridged lactone ring, and a (meth) acryl unit having an acid-decomposable group are copolymerized. A compound is provided, and by blending this polymer compound in a resist material as a base resin, it has high sensitivity, high resolution, low line edge roughness, and reduced residue after development. Swelling during development due to measurement by the above or the like can be suppressed. Accordingly, it is possible to provide a positive resist material such as a chemically amplified positive resist material that is suitable as a fine pattern forming material particularly for VLSI manufacturing or photomask pattern fabrication.

Resist material of the present invention contains a polymer compound having, respectively the repeating units represented de following general formula (1a) and / or a (2a) and (1b).
(Wherein R ¹ represents the same or different hydrogen atom or methyl group; R ² represents the same or different hydrogen atom, an acyl group having 1 to 10 carbon atoms or an acid labile group; R ³ represents hydrogen; An atom, a methyl group, or —CO ₂ R ⁸ , wherein R ⁴ represents a hydrogen atom, a methyl group, or —CH ₂ CO ₂ R ⁸ , where R ⁸ is the same or different hydrogen atom or a carbon number of 1 to 15; A linear, branched or cyclic alkyl group, wherein X is —CH ₂ —, —O— or —S—, and when all of R ^{5 to} R ⁷ are hydrogen atoms, —CH ₂ — R ^{5 to} R ⁷ are a hydrogen atom, a methyl group, or —CO ₂ R ⁹ , and R ⁹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. a1, a2, b1 are
0 ≦ a1 / (a1 + a2 + b1) ≦ 0.9
0 ≦ a2 / (a1 + a2 + b1) ≦ 0.9
0 <(a1 + a2) / (a1 + a2 + b1) ≦ 0.9
0 <(b1) / (a1 + a2 + b1) ≦ 0.8
It is a number that satisfies )

Here, examples of the acyl group of R ² include an acetyl group and a pivaloyl group, and those having 1 to 6 carbon atoms are particularly preferable. The acid labile group will be described later. Examples of the alkyl group for R ⁸ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group and the like. Particularly, those having 1 to 12 carbon atoms are preferable. Examples of the alkyl group for R ⁹ include the same as those exemplified for R ⁸ above, and those having 1 to 12 carbon atoms are particularly preferable.

  Examples of the monomer for obtaining the repeating unit represented by the general formulas (1a) and (2a) include the following.

As the monomer before polymerization, the group bonded to the carbon atom of —C (CF ₃ ) ₂ — is an acetyl group, which is converted into a hydroxy group by alkali hydrolysis after polymerization, and in some cases, a hydrogen atom of the hydroxy group thereafter. May be substituted with an acid labile group.

The polymer compound of the present invention comprises an ester monomer having a repeating unit having hexafluorocarbinol represented by general formulas (1a) and (2a) and a specific lactone ring represented by general formula (1b) (repeating). It is essential to copolymerize the unit b1).
Here, the monomer (1b) can be specifically exemplified below.

  The polymer compound to be blended with the resist material of the present invention is preferably copolymerized with a monomer (1c) represented by the following general formula having an acid labile group in order to obtain a positive resist.

(Here, R ¹ and R ² are as described above, and R ⁷ is an acid labile group.)

Next, in the general formulas (1a) and (1c), various acid labile groups represented by R ³ and R ⁷ may be selected, but they may be the same or different. In particular, the following formulas (AL10), ( A group represented by AL11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL12), an oxoalkyl group having 4 to 20 carbon atoms, and the like.

In the formulas (AL10) and (AL11), R ⁰⁰¹ and R ⁰⁰⁴ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. . a is an integer of 0-10. R ⁰⁰² and R ⁰⁰³ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as oxygen, sulfur, nitrogen and fluorine. R ⁰⁰² and R ⁰⁰³ , R ⁰⁰² and R ⁰⁰⁴ , R ⁰⁰³ and R ⁰⁰⁴ may be bonded together to form a ring having 3 to 10 carbon atoms, particularly 3 to 8 carbon atoms, together with the carbon atom to which they are bonded. R ^005, R ^006, R ⁰⁰⁷ is a straight, a branched or cyclic alkyl group. Alternatively, R ⁰⁰⁵ and R ⁰⁰⁶ , R ⁰⁰⁵ and R ⁰⁰⁷ , R ⁰⁰⁶ and R ⁰⁰⁷ may be bonded together to form a ring having 3 to 16 carbon atoms, particularly 3 to 12 carbon atoms, together with the carbon atoms to which they are bonded.

  Specific examples of the compound represented by the formula (AL10) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group, and a 1-ethoxyethoxycarbonylmethyl group. , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following formulas (AL10) -1 to (AL10) -9.

In the formulas (AL10) -1 to (AL10) -9, R ⁰⁰⁸ is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group or aralkyl having 6 to 20 carbon atoms. Indicates a group. R ⁰⁰⁹ is a straight, branched or cyclic alkyl group of a hydrogen atom or 1 to 20 carbon atoms. R ⁰¹⁰ represents an aryl group or aralkyl group having 6 to 20 carbon atoms. a is an integer of 0-10.

  Acetal compounds represented by formula (AL11) are exemplified by formulas (AL11) -1 to (AL11) -34.

  Further, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (AL11a) or (AL11b).

In the above formula, R ⁰¹¹ and R ^{012 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁰¹¹ and R ⁰¹² may combine to form a ring, and in the case of forming a ring, R ⁰¹¹ and R ⁰¹² represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁰¹³ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and c is an integer of 1 to 7. . A represents a (c + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups are heteroatoms such as oxygen, sulfur and nitrogen. Or a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, preferably, A is a divalent to tetravalent C1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms. These groups may have intervening heteroatoms such as oxygen, sulfur, nitrogen, etc., and some of the hydrogen atoms bonded to the carbon atoms are substituted by hydroxyl groups, carboxyl groups, acyl groups or halogen atoms. May be. C is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal group represented by the general formulas (AL11a) and (AL11b) include those represented by the following formulas (AL11) -35 to (AL11) -42.

  Next, examples of the tertiary alkyl group represented by the formula (AL12) include a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, 2- ( Examples include 2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group, and the following general formulas (AL12) -1 to (AL12) -18.

In the above formula, R ⁰¹⁴ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group or aralkyl group having 6 to 20 carbon atoms. R ⁰¹⁵ and R ^{017 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁰¹⁶ represents an aryl group or aralkyl group having 6 to 20 carbon atoms.

Further, the formula (AL12) -19, as shown in (AL12) -20, 2 or more valences alkylene group, include R ⁰¹⁸ is an arylene group, within the molecule or between molecules of the polymer may be cross-linked . In this case, R ⁰¹⁴ is the same as described above, and R ⁰¹⁸ represents a linear, branched, or cyclic alkylene group or arylene group having 1 to 20 carbon atoms, and includes a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. You may go out. c is an integer of 1 to 3.

Further, R ⁰¹⁴ , R ⁰¹⁵ , R ⁰¹⁶ , and R ⁰¹⁷ may have heteroatoms such as oxygen, nitrogen, sulfur, and the like, and specifically are represented by the following formulas (13) -1 to (13) -7. be able to.

  In particular, the acid labile group of the formula (AL12) is preferably a repeating unit having an exo structure represented by the following formula (AL12) -21.

(Wherein R ⁰¹⁹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{020 to} R ⁰²⁵ and R ^028. , R ⁰²⁹ each independently represents a hydrogen atom or a monovalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, and R ⁰²⁶ and R ^{027 each} represents a hydrogen atom, or R ⁰²⁰ and R ⁰²¹ , R ⁰²² and R ⁰²⁴ , R ⁰²² and R ⁰²⁵ , R ⁰²³ and R ⁰²⁵ , R ⁰²³ and R ⁰²⁹ , R ⁰²⁴ and R ⁰²⁸ , R ⁰²⁶ and R ^027, or R ⁰²⁷ and R ⁰²⁸ may form a ring with each other. In this case, it is a divalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁰²⁰ and R ⁰²⁹ , R ⁰²⁶ and R ⁰²⁹ or R ⁰²² and R ⁰²⁴ are adjacent carbon atoms. May be bonded to each other without any interposition to form a double bond, and this formula also represents an enantiomer.)

Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and an octyl group. In particular, those having 1 to 12 carbon atoms are preferred. Examples of the aryl group include a phenyl group. Examples of the monovalent hydrocarbon group that may contain a hetero atom include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, and the like in addition to the same alkyl group as exemplified above. Are preferred. Examples of the divalent hydrocarbon group that may contain a hetero atom include a group in which one hydrogen atom bonded to a carbon atom is eliminated from the monovalent hydrocarbon group. When R ⁰²⁰ and R ⁰²¹ form a ring, the ring is preferably a ring having 3 to 10 carbon atoms, particularly 3 to 8 carbon atoms.

  Examples of the monomer of the above formula (1c) include those shown in JP-A No. 2000-327633, and specific examples thereof include, but are not limited to, the following.

  In addition, examples of the acid labile group represented by the formula (AL12) include an acid labile group having frangyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the formula (AL12) -22. The acid labile group of the repeating unit derived from (1c) is preferred.

(Wherein R ⁰³⁰ and R ⁰³¹ each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Alternatively, R ⁰³⁰ and R ⁰³¹ are bonded to each other to form An aliphatic hydrocarbon ring may be formed together with the carbon atom to which R is bonded, R ⁰³² represents a divalent group selected from frangyl, tetrahydrofurandiyl or oxanorbornanediyl, and R ⁰³³ may include a hydrogen atom or a hetero atom. A good straight chain, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms is shown.)

  Here, examples of the monovalent hydrocarbon group include an alkyl group, and examples of the aliphatic hydrocarbon ring include those having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like. Is mentioned.

  Monomers for obtaining repeating units substituted with acid labile groups having frangyl, tetrahydrofuraniyl or oxanorbornanediyl are exemplified below. In the following formulae, Me represents a methyl group, and Ac represents an acetyl group.

  The polymer compound blended in the resist material of the present invention requires the repeating units represented by the general formulas (1a), (2a), and (1b), but other than the formulas (1a), (2a), and (1b) The repeating unit having the adhesive group may be copolymerized. Specifically, a repeating unit obtained by polymerizing the monomer (1d) exemplified below can be introduced.

In the present invention, the above formula (1a), (2a), the unit 1a, 2a, the molar ratio of 1b in (1b), when the _{a1 + a2 + b1 = T 1} ,
0 ≦ a1 / T ₁ ≦ 0.9, preferably 0 ≦ a1 / T ₁ ≦ 0.8
0 ≦ a2 / T ₁ ≦ 0.9, preferably 0 ≦ a2 / T ₁ ≦ 0.8
0 <(a1 + a2) / T ₁ ≦ 0.9, preferably 0.03 ≦ (a1 + a2) / T ₁ ≦
0.8
0 <b1 / T ₁ ≦ 0.8, preferably 0.1 ≦ b1 / T ₁ ≦ 0.7
It is. Further, when the unit 1c derived from the monomer of the formula (1c) and the unit 1d derived from the monomer of the formula (1d) are introduced, a1 + a2 + b1 + 1c + 1d = T ₂
0 ≦ 1c / T ₂ ≦ 0.8, especially 0.1 ≦ 1c / T ₂ ≦ 0.7
0 ≦ 1d / T ₂ ≦ 0.7, especially 0 ≦ 1d / T ₂ ≦ 0.6
It is. The repeating units 1a, 2a, and 1b are the same as those in the case of T ₁ even if the denominator is T ₂ .

  The polymer compound of the present invention needs to have a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000 by gel permeation chromatography. If the weight average molecular weight is too small, the resist material is inferior in heat resistance, and if it is too large, the alkali solubility is lowered, and a trailing phenomenon may easily occur after pattern formation.

  Further, in the polymer compound according to the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer exists, so that foreign matter is seen on the pattern after exposure or the shape of the pattern. May get worse. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitably used for fine pattern dimensions, the multi-component copolymer to be used is obtained. The molecular weight distribution is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5 and narrow dispersion.

  In order to synthesize the polymer compound according to the present invention, as one method, a monomer having an unsaturated bond for obtaining the repeating units 1a, 2a, 1b, 1c, etc. is added to a radical initiator in an organic solvent, There is a method of performing heat polymerization, whereby a polymer compound can be obtained. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As polymerization initiators, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) ), Benzoyl peroxide, lauroyl peroxide and the like, and preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. As the acid labile group, those introduced into the monomer may be used as they are, or the acid labile group may be once removed by an acid catalyst and then protected or partially protected.

  The polymer compound according to the present invention can be suitably used as a base resin for resist materials, particularly chemically amplified positive resist materials. In this case, when the polymer compound (polymer) of the present invention is used as a base resin, it is possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

  The positive resist material of the present invention includes an organic solvent, a compound that generates an acid in response to high energy rays (acid generator), a dissolution inhibitor, a basic compound, a surfactant, and other components as necessary. Can be contained.

  The organic solvent used in the resist material of the present invention, particularly the chemically amplified positive resist material, may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Examples thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyl lactone, one kind of these alone or two or more kinds. However, the present invention is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. .

  The amount of the organic solvent used is preferably 200 to 1,000 parts, particularly 400 to 800 parts, with respect to 100 parts (parts by mass) of the base resin.

As the acid generator used in the present invention,
i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii. A diazomethane derivative of the following general formula (P2):
iii. A glyoxime derivative of the following general formula (P3):
iv. A bissulfone derivative of the following general formula (P4):
v. A sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
vi. β-ketosulfonic acid derivatives,
vii. Disulfone derivatives,
viii. Nitrobenzyl sulfonate derivatives,
ix. Examples thereof include sulfonic acid ester derivatives.

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group, an oxoalkenyl group or an aryl having 6 to 20 carbon atoms. group, or an aralkyl group having 7 to 12 carbon atoms, a group selected from aryl oxoalkyl group, a part or all of the hydrogen atoms of these groups may be replaced by alkoxy or other groups. also, R ^101b And R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion. .)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the oxoalkenyl group include 2-oxo-4-cyclohexenyl group and 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

(In the formula, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. Examples of K ⁻ are the same as those described in the formulas (P1a-1) and (P1a-2).

(In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups having 6 to 20 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. As the aryl group for R ¹⁰⁵ and R ^106, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Is mentioned. Examples of the halogenated aryl group for R ¹⁰⁵ and R ¹⁰⁶ include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. ^Examples of the aralkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a benzyl group and a phenethyl group.

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. And R ¹⁰⁵ is the same as that in formula (P2).

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

(In the formula, R ^101a and R ^101b are the same as described above.)

(In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups are further carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a linear or branched chain having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group of 4 to 4, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a phenyl group which may be substituted with a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specific examples of the acid generator include onium salts such as diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfone. Acid (p-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate , Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nona Triphenylsulfonium fluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexyl p-toluenesulfonate Methyl (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, -Toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium And onium salts such as ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate.

  Diazomethane derivatives include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane Bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane Bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfur) Nyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane And the like.

  Examples of glyoxime derivatives include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)- α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, Bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime Bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- ( -Butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis -O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl)- α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α- Dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) α- dimethylglyoxime, bis -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, and bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

  Examples of bissulfone derivatives include bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane. Bissulfone derivatives can be mentioned.

  Examples of β-ketosulfone derivatives include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.

  Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

  Examples of the nitrobenzyl sulfonate derivative include nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

  Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.

  Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid. Ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N- Hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ester, N-hydroxyglutarimide benzenesulfonic acid ester, N-hydroxyphthalimide methanesulfonic acid ester, N-hydro Siphthalimidobenzenesulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N- Hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3 Examples thereof include sulfonic acid ester derivatives of N-hydroxyimide compounds such as dicarboximide p-toluenesulfonic acid ester.

  In particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p -Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonyl trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O -Glyoxime derivatives such as-(p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphth Bissulfone derivatives such as rusulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N -Hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester and other sulfonic acids of N-hydroxyimide compounds Ester derivatives are preferably used.

  In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since onium salts are excellent in rectangularity improving effect and diazomethane derivatives and glyoxime derivatives are excellent in standing wave reducing effect, it is possible to finely adjust the profile by combining both.

  The addition amount of the acid generator is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts with respect to 100 parts of the base resin. If the amount is less than 0.1 part, the amount of acid generated during exposure is small and the sensitivity and resolution may be inferior. If the amount exceeds 50 parts, the transmittance of the resist may be lowered and the resolution may be inferior.

  Next, as a dissolution inhibitor (dissolution control agent) blended in the positive resist material of the present invention, particularly a chemically amplified positive resist material, the weight average molecular weight is 100 to 1,000, preferably 150 to 800. And a compound in which the hydrogen atom of the phenolic hydroxyl group of the compound having two or more phenolic hydroxyl groups in the molecule is substituted with an acid labile group in an average of 0 to 100 mol% as a whole, or a carboxy group in the molecule A compound in which the hydrogen atom of the carboxy group of the compound is substituted with an acid labile group as a whole in an average ratio of 50 to 100 mol% is blended.

  The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably 80 mol%. Mol%. The substitution rate of the hydrogen atom of the carboxy group with an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.

  In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

(In the above formulae, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or 1 to 8 carbon atoms. Represents a linear or branched alkyl group or alkenyl group, or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i — (i = 2 to 10), arylene having 6 to 10 carbon atoms. A group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ²⁰⁷ has 1 to 10 carbon atoms. Linear or branched al .R ²⁰⁸ indicating the Killen groups are .j represents a hydrogen atom or a hydroxyl group is an integer of 0 to 5 .u, h is 0 or 1 .s, t, s ', t', s '', t ″ Is a number satisfying s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and having at least one hydroxyl group in each phenyl skeleton. Α is a formula (D8 ), (D9) is a number that makes the molecular weight of the compound of 100 to 1,000.)

  In addition, the weight average molecular weight of the said compound is 100-1,000, Preferably it is 150-800. The compounding quantity of a dissolution inhibitor is 0-50 parts with respect to 100 parts of base resins, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. If the blending amount is small, the resolution may not be improved. If the blending amount is too large, the pattern film is reduced and the resolution tends to decrease.

Furthermore, a basic compound can be blended with the positive resist material of the present invention, particularly with the chemically amplified positive resist material.
As the basic compound, a compound that can suppress the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By adding a basic compound, the acid diffusion rate in the resist film is suppressed and resolution is improved, sensitivity change after exposure is suppressed, and substrate and environment dependency is reduced, and exposure margin and pattern profile are reduced. Etc. can be improved.

  Examples of such basic compounds include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. A nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta The tertiary aliphatic amines are exemplified by trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine.

  Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinoline carbo Nitriles), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Examples include derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated.

Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.
Examples of the imide derivative include phthalimide, succinimide, maleimide and the like.

Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by the following general formula (B) -1 can also be added.
N (X) _n (Y) _3-n (B) -1
(In the formula, n is 1, 2 or 3. The side chain X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is The same or different hydrogen atom, or a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain an ether group or a hydroxyl group, and Xs combine to form a ring. You may do it.)

Here, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, or linear groups having 1 to 20 carbon atoms, It is a branched or cyclic alkyl group and may contain one or a plurality of hydroxy groups, ether groups, ester groups, and lactone rings.
R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a hydroxy group , An ether group, an ester group, or a lactone ring may be contained.

Specific examples of the compound represented by the general formula (B) -1 include the following.
Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, Tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, Tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyethyl) amine, N, N- Bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl Amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amino , Tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) Amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl ) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2- Acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] Ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N- Bis (2-hydroxyethyl) 2- (tetrahydrofurf Ruoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3- Yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- ( 4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyl) Oxyethoxycarbonyl) ethylamine, N, N-bis (2 Methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1- Propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- ( Methoxycarbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Tylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N -Butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone can be exemplified, but are not limited thereto.

Furthermore, 1 type, or 2 or more types of the basic compound which has a cyclic structure shown by the following general formula (B) -2 can also be added.
(In the formula, as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and contains one or more carbonyl groups, ether groups, ester groups or sulfides. May be good.)

  Specific examples of the formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl]. Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) Methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl] Ruphorin, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidi Methyl nopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropion Methoxycarbonylmethyl acid, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholino Propionate tetrahydrofurf Glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Mention may be made of methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

Furthermore, a basic compound containing a cyano group represented by the following general formulas (B) -3 to (B) -6 can be added.
(In the formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the basic compound containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2- Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3 Methyl aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2 -(Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-me Methyl toxiethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N- Cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile N- (3-acetoxy-1-propyl Pyr) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1- Piperidine propiononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropion Cyanomethyl acid, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2- Meto Cyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2 -Hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropiate Examples include cyanomethyl onate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl) and the like.

  In addition, the compounding quantity of a basic compound is 0.001-2 parts with respect to 100 parts of all base resins, Especially 0.01-1 part is suitable. If the blending amount is less than 0.001 part, the blending effect is small, and if it exceeds 2 parts, the sensitivity may be too low.

  Examples of the compound having a group represented by ≡C—COOH in the molecule that can be added to the positive resist material of the present invention include one or more selected from the following [Group I] and [Group II]. However, it is not limited to these. By blending this component, the PED (Post Exposure Delay) stability of the resist is improved, and the edge roughness on the nitride film substrate is improved.

[Group I]
A part or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the following general formulas (A1) to (A10) are converted to —R ⁴⁰¹ —COOH (where R ⁴⁰¹ is a linear or branched alkylene having 1 to 10 carbon atoms). The molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1 to 1.0. Compound.

(In the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents hydrogen. atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms _{^{or, - (R 409) h -COOR}} ' group (R' is a hydrogen atom or -R ⁴⁰⁹ -COOH) shows a .R ⁴⁰⁵ Is — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁶ is an alkylene group having 1 to 10 carbon atoms. Represents an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁴⁰⁷ represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, A phenyl group substituted by a hydroxyl group or It shows a naphthyl group .R ⁴⁰⁹ is a linear or showing a branched alkylene group .R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl or alkenyl of 1 to 8 carbon atoms having 1 to 10 carbon atoms Or -R ⁴¹¹ -COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, h is an integer of 1 to 4, j is 0 to 3, s1 to 4 , T1 to t4 are numbers satisfying s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, respectively, and having at least one hydroxyl group in each phenyl skeleton. Κ is a number that makes the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000, and λ is a number that makes the compound of formula (A7) a weight average molecular weight of 1,000 to 10,000. .)

[Group II]
Compounds represented by the following general formulas (A11) to (A15).

(Wherein R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meanings as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 satisfy s5 + t5 = 5 with s5 ≧ 0 and t5 ≧ 0. H 'is 0 or 1.)

  Specific examples of this component include, but are not limited to, compounds represented by the following general formulas (AI-1) to (AI-14) and (AII-1) to (AII-10). It is not a thing.

(In the formula, R ″ represents a hydrogen atom or a —CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is a —CH ₂ COOH group. Κ and λ have the same meanings as described above. Show.)

  The amount of the compound having a group represented by ≡C—COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 100 parts of the base resin. 3 parts, more preferably 0.1 to 2 parts. If it exceeds 5 parts, the resolution of the resist material may be lowered.

  In the positive resist material of the present invention, particularly a chemically amplified positive resist material, a surfactant for further improving the coating property can be added.

  Examples of the surfactant include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and polyoxyethylene Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tochemputtoc), MegaFuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Fluorard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, Fluorosurfactants such as KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-093 (Shin-Etsu Chemical) Work), acrylic acid-based or methacrylic acid-based Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Industry Co., Ltd.), etc., among which FC430, Surflon S-381, Surfinol E1004, KH-20, KH-30 are preferred. These can be used alone or in combination of two or more.

  The addition amount of the surfactant in the positive resist material of the present invention, particularly the chemically amplified positive resist material, is 2 parts or less, preferably 1 part or less with respect to 100 parts of the base resin in the resist material.

  When the positive resist material of the present invention, in particular, the chemically amplified positive resist material is used for manufacturing various integrated circuits, a known lithography technique can be used, although not particularly limited.

For example, the resist material of the present invention is spun onto a substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, Cr, CrO, CrON, MoSi, etc.) for manufacturing an integrated circuit. It is applied by a suitable coating method such as coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. so that the coating film thickness is 0.1 to 2.0 μm, on a hot plate at 60 to 150 ° C., Pre-bake for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes. Then, a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, etc., preferably with an exposure wavelength of 300 nm or less, more preferably with an exposure wavelength in the range of 180 to 200 nm. The pattern is exposed through a predetermined mask. It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

  Further, 0.1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) or other alkaline aqueous developer is used for 0.1-3 minutes, preferably 0.5-2 minutes. The target pattern is formed on the substrate by developing by a conventional method such as a (dip) method, a paddle method, or a spray method. The resist material of the present invention is a far ultraviolet ray having a wavelength of 254 to 193 nm, a vacuum ultraviolet ray having a wavelength of 157 nm, an electron beam, a soft X-ray, an X-ray, an excimer laser, a γ ray, a synchrotron radiation, among high energy rays. Preferably, it is most suitable for fine patterning with high energy rays in the wavelength range of 180 to 200 nm.

  The resist material of the present invention can also be applied to immersion lithography. In ArF immersion lithography, pure water is used as an immersion solvent. In immersion lithography, exposure is performed by inserting water between a pre-baked resist film and a projection lens. The exposure wavelength is 135 nm obtained by dividing the refractive index of water at a wavelength of 193 nm by 1.43, and the wavelength can be shortened. This is an important technology for extending the life of ArF lithography to the 65 nm node, and its development has been accelerated. The lactone ring conventionally used as the hydrophilic group of ArF resist is soluble in both alkaline aqueous solution and water. When water-soluble lactones or acid anhydrides such as maleic anhydride or itaconic anhydride are used as hydrophilic groups, water permeates from the resist surface due to immersion in water, causing the resist surface to swell. Will occur. However, although hexafluoroalcohol dissolves in an alkaline aqueous solution but does not dissolve in water at all, it is considered that the influence of dissolution and swelling by the above-mentioned immersion is small.

  EXAMPLES Hereinafter, although a synthesis example, a comparative synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc. In the following examples, the molecular weight measurement is a molecular weight in terms of polystyrene by GPC (gel permeation chromatography).

[Synthesis Example 1]
100mL methacrylic acid to the flask of 3-ethyl-3-exo-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodecanyl 8.2 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 9.2 g, methacrylic acid-2- 14.8 g of (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 25.8 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: methacrylic acid-2- (2-hydroxy-1) , 1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.30: 0.40: 0.30
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.78

This polymer compound is referred to as Example polymer 1.

[Synthesis Example 2]
In a 100 mL flask, 9.8 g of 2-ethyl-2-adamantane methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2 1.0 ^4,8 ] nonane-9-yl, 5.3 g, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 5.0 g and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2-ethyl-2-adamantane: Methacrylic acid-3-hydroxy-1-adamantyl: Methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane- 9-yl: methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.35: 0.30: 0.25: 0.10
Weight average molecular weight (Mw) = 8,600
Molecular weight distribution (Mw / Mn) = 1.88

This polymer compound is referred to as Example polymer 2.

[Synthesis Example 3]
In a 100 mL flask, 9.8 g of methacrylic acid-2-ethyl-2-adamantane, 8.8 g of methacrylic acid-3-hydroxy-1-adamantyl, methacrylic acid-3-oxo-5-methoxycarbonyl-2-oxatricyclo [ 4.2.1.0 ^4,8 ] -9-nonyl, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl ) 5.0 g of cyclohexyl and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2-ethyl-2-adamantane: Methacrylic acid-3-hydroxy-1-adamantyl: Methacrylic acid-3-oxo-5-methoxycarbonyl-2-oxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl: methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.35: 0.30: 0. 25: 0.10
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.83

This polymer compound is referred to as Example polymer 3.

[Synthesis Example 4]
In a 100 mL flask, 9.8 g of 2-ethyl-2-adamantane methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2 .1.0 ^4,8] nonan-9-yl 5.3 g, methacrylic acid-2- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 8.0g 20 g of tetrahydrofuran was added as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2-ethyl-2-adamantane: Methacrylic acid-3-hydroxy-1-adamantyl: Methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane- 9-yl: methacrylic acid-2- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.35: 0.20: 0.20: 0.25
Weight average molecular weight (Mw) = 9,200
Molecular weight distribution (Mw / Mn) = 1.81

This polymer compound is referred to as Example polymer 4.

[Synthesis Example 5]
In a 100 mL flask, 11.8 g of 1-cyclopentylcyclohexyl methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1. 0 ^4,8 ] nonane-9-yl 5.3 g, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 5.0 g 20 g of tetrahydrofuran was added as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-1-cyclopentylcyclohexyl: methacrylate-3-hydroxy-1-adamantyl: methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl : Methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.22: 0.30: 0.38: 0.10
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.73

This polymer compound is referred to as Example polymer 5.

[Synthesis Example 6]
In a 100 mL flask, 8.6 g of 1-ethylcyclopentyl methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1. 0 ^4,8 ] nonane-9-yl 5.3 g, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 5.0 g 20 g of tetrahydrofuran was added as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-1-ethylcyclopentyl: Methacrylic acid-3-hydroxy-1-adamantyl: Methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl : Methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.33: 0.30: 0.27: 0.10
Weight average molecular weight (Mw) = 7,200
Molecular weight distribution (Mw / Mn) = 1.76

This polymer compound is referred to as Example polymer 6.

[Synthesis Example 7]
In a 100 mL flask, 10.5 g of 1- (7-oxanorbornan-2-yl) cyclopentyl methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatri methacrylate Cyclo [4.2.1.0 ^4,8 ] nonan-9-yl 5.3 g, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro- 2-propyl) cyclohexyl 5.0 g and tetrahydrofuran 20 g as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
1- (7-oxanorbornane-2-yl) cyclopentyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1.0 ^{4 , 8} ] nonan-9-yl: methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.25: 0.30 : 0.35: 0.10
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.88

This polymer compound is referred to as Example polymer 7.

[Synthesis Example 8]
In a 100 mL flask, 7.9 g of 2-adamantyloxymethyl methacrylate, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2. 1.0 ^4,8 ] nonane-9-yl 5.3 g, methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 5 0.0 g and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 23.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
2-Adamantyloxymethyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonane-9 methacrylate -Yl: methacrylic acid-3,5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.21: 0.30: 0.41: 0 .08
Weight average molecular weight (Mw) = 9,100
Molecular weight distribution (Mw / Mn) = 1.83

This polymer compound is referred to as Example polymer 8.

[Comparative Synthesis Example 1]
To a 100 mL flask was added 24.4 g of methacrylic acid-2-ethyl-2-adamantane, 17.1 g of γ-butyrolactone methacrylate, and 40 g of tetrahydrofuran as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated 3 times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 36.1 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2-ethyl-2-adamantane: methacrylic acid gamma butyrolactone = 0.48: 0.52
Weight average molecular weight (Mw) = 12,500
Molecular weight distribution (Mw / Mn) = 1.88

This polymer compound is referred to as Comparative Example Polymer 1.

[Comparative Synthesis Example 2]
In a 100 mL flask, 8.7 g of methacrylic acid-2- (2-methoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl, methacrylic acid-2- (2-hydroxy-1) , 1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl and 25.7 g of tetrahydrofuran as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 20.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2- (2-methoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl: methacrylic acid-2- (2-hydroxy-1,1,1,3,3) 3,3-hexafluoro-2-propyl) cyclohexyl = 0.77: 0.23
Weight average molecular weight (Mw) = 6,700
Molecular weight distribution (Mw / Mn) = 1.56

This polymer compound is referred to as Comparative Example Polymer 2.

[Comparative Synthesis Example 3]
In a 100 mL flask, 8.6 g of methacrylic acid-2-ethyl-2-adamantane, methacrylic acid-2- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl 30. 3 g and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 28.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-2-ethyl-2-adamantane: Methacrylic acid-2- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.35: 0.65
Weight average molecular weight (Mw) = 7,800
Molecular weight distribution (Mw / Mn) = 1.66

This polymer compound is referred to as Comparative Example Polymer 3.

[Comparative Synthesis Example 4]
In a 100 mL flask, 11.8 g of methacrylic acid-3,5-di (2-methoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl, methacrylic acid-2- (2- Hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl (35.6 g) and 20 g of tetrahydrofuran as a solvent were added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen flow were repeated three times. After raising the temperature to room temperature, 0.2 g of AIBN was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution was precipitated in a 500 mL solution of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 32.3 g of a white polymer.

When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Methacrylic acid-3,5-di (2-methoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl: methacrylic acid-2- (2-hydroxy-1,1,1) , 3,3,3-hexafluoro-2-propyl) cyclohexyl = 0.20: 0.80
Weight average molecular weight (Mw) = 6,800
Molecular weight distribution (Mw / Mn) = 1.55

This polymer compound is referred to as Comparative Example Polymer 4.

[Examples and Comparative Examples]
Preparation of Positive Resist Material A 0.2 μm sized filter was prepared by dissolving a solution dissolved in the composition shown in Table 1 below using the synthesized polymer compounds (Example polymers 1 to 8, Comparative polymers 1 to 4). To prepare a resist solution.
Each composition in Table 1 is as follows.
Examples Polymers 1 to 8: From Synthesis Examples 1 to 8 Comparative Examples Polymers 1 to 4: From Comparative Synthesis Examples 1 to 4 Acid generator: PAG1 (see the following structural formula)
Basic compounds: Triethanolamine, TMMEA, AAA, AACN (see the following structural formula)
Dissolution inhibitor: DRI1 (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

Exposure patterning evaluation The above-prepared resist materials (Examples 1 to 12 and Comparative Examples 1 to 4) were spin-coated on a substrate in which AR-19 (made by Shipley Co., Ltd.) was formed to a film thickness of 82 nm on a silicon wafer, The resist was baked at 120 ° C. for 60 seconds using a hot plate to a resist thickness of 250 nm.
This is exposed using an ArF excimer laser stepper (Nikon Corporation, NSR-S305B, NA-0.68, σ0.85, 2/3 annular illumination), and baked immediately after exposure at 110 ° C. for 60 seconds. Development was performed with an aqueous solution of 38% tetramethylammonium hydroxide for 60 seconds to obtain a positive pattern.
And the obtained resist pattern was evaluated as follows.
The exposure amount for resolving 0.12 μm line and space at 1: 1 was defined as the resist sensitivity, and the minimum line width of the line and space separated at this exposure amount was defined as the resolution of the evaluation resist.
Further, the line edge roughness of a 0.12 μm line and space was measured using a length measuring SEM (S-9220 manufactured by Hitachi, Ltd.), and the resist cross section was observed by SEM (S4200 manufactured by Hitachi, Ltd.).
The results are also shown in Table 1.

  From the results in Table 1, it can be seen that the resist materials of Examples 1 to 12 have high sensitivity and high resolution and small line edge roughness.

Evaluation of Dissolution Properties in Developer Using QCM Method A resist solution obtained by filtering the solution of the resist material prepared above (Example 1, Comparative Example 1) through a 0.2 μm size filter is used, and the base is gold and a chromium electrode is provided on the surface. The deposited quartz substrate having a size of 1 inch (about 2.5 cm) was spin-coated, and baked at 130 ° C. for 60 seconds using a hot plate, so that the resist thickness was 250 nm.

Exposure was performed with an ArF exposure apparatus ArFES3000 (manufactured by RISOTEC Japan), and PEB was performed at 110 ° C. for 60 seconds. A substrate is mounted on the crystal oscillator microbalance device RDA-Qz3 (manufactured by RISOTEC Japan) for resist development analyzer, developed with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds, and developed with vibration mode AT cut. Swelling and dissolution were measured. Exposure was performed with different exposure amounts, and QCM was measured.
The results are shown in FIGS. In the figure, when the film thickness increases with respect to the development time, it indicates swelling and when the film thickness decreases, it indicates that the film is dissolved.
1 and 2, it can be seen that the swelling during development is significantly suppressed in the resist material of Example 1 by the measurement by the QCM method.

Next, in the dry etching resistance test, a polymer solution obtained by dissolving 10 g of PGMEA in 2 g of a polymer and filtered through a 0.2 μm size filter was formed on a Si substrate by spin coating to form a film having a thickness of 300 nm. Evaluation was made under the conditions of the strain.
(1) Etching test with CHF ₃ / CF ₄ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec
₍₂₎ Cl ₂ / BCl ₃ system using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L Gas was calculated the difference between the film thickness of before and after etching of the polymer film.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec
The etching results are shown in Table 2.

  From the results shown in Tables 1 and 2, the resist material using the polymer compound of the present invention has sufficient resolution and sensitivity, low line edge roughness, and small film thickness difference after etching. It was found to have etching properties.

6 is a graph showing the results of measurement by a QCM method on a resist formed from the resist material of Example 1. 5 is a graph showing the results of measurement by a QCM method for a resist formed from the resist material of Comparative Example 1.

Claims (8)

Resist material containing a polymer compound having the following general formula (1a) and / or a (2a) repeating units represented out with the (1b), respectively.
(Wherein R ¹ represents the same or different hydrogen atom or methyl group; R ² represents the same or different hydrogen atom, an acyl group having 1 to 10 carbon atoms or an acid labile group; R ³ represents hydrogen; An atom, a methyl group, or —CO ₂ R ⁸ , wherein R ⁴ represents a hydrogen atom, a methyl group, or —CH ₂ CO ₂ R ⁸ , where R ⁸ is the same or different hydrogen atom, or having 1 to 15 carbon atoms; A linear, branched or cyclic alkyl group, wherein X is —CH ₂ —, —O— or —S—, and —CH ₂ — is the case where all of R ^{5 to} R ⁷ are hydrogen atoms. R ^{5 to} R ⁷ are a hydrogen atom, a methyl group, or —CO ₂ R ⁹ , and R ⁹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. a1, a2, b1 are
0 ≦ a1 / (a1 + a2 + b1) ≦ 0.9
0 ≦ a2 / (a1 + a2 + b1) ≦ 0.9
0 <(a1 + a2) / (a1 + a2 + b1) ≦ 0.9
0 <(b1) / (a1 + a2 + b1) ≦ 0.8
It is a number that satisfies ) The resist material according to claim 1, wherein the polymer compound further has a repeating unit based on a monomer represented by the following general formula (1c) having an acid labile group.
(Where R ¹ , R ² Is as defined in claim 1 and R ⁷ Is an acid labile group. )
The resist material according to claim 1, wherein the polymer compound further has a repeating unit based on any of the following monomers.
(A) The polymer compound according to any one of claims 1 to 3 as a base resin,
(B) an organic solvent,
(C) A chemically amplified positive resist material containing an acid generator. The positive resist material according to claim 4 , further comprising a dissolution inhibitor. The positive resist composition according to claim 4 or 5 , further comprising a basic compound and / or a surfactant. A step of applying the positive resist material according to any one of claims 1 to 6 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. The pattern formation method characterized by the above-mentioned. The pattern forming method according to claim 7 , wherein the high energy ray is in a wavelength range of 180 to 200 nm.