JP5182468B2 - Polymer compound, 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. Polymer compound suitable as fine pattern forming material for LSI production or photomask pattern production, positive resist material containing the polymer compound, especially chemically amplified positive resist material, and pattern forming method using the same About.

  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 performance of resist materials, 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 micron rule devices has become possible. To increase the resolution and sensitivity of a resist material, an acid-catalyzed chemically amplified positive resist material (for example, Patent Documents 1 and 2: JP-B-2-27660, JP-A-63-27829) Has a superior characteristic, and has become a mainstream resist material particularly in deep ultraviolet lithography.

  Resist materials for KrF excimer lasers are generally used in 0.3 micron processes, passed through the 0.25 micron rule, and are now applied to mass production of the 0.18 micron rule. Has also begun, and 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 reduce the design rule to 0.13 μm or less, but conventionally used novolak 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 and cycloolefin-based alicyclic resins have been studied (for example, Patent Documents 3 to 6: JP-A-9-73173, JP-A-10-10739, JP-A-9-230595, pamphlet of International Publication No. 97/33198).

  In particular, a (meth) acrylic-based resin resist material having high resolution has been studied. As a (meth) acrylic resin, a combination of a (meth) acrylic unit having a methyladamantane ester as an acid labile group unit and a (meth) acrylic unit having a lactone ring ester as an adhesive group unit has been proposed ( For example, see Patent Document 7: JP-A-9-90637). Furthermore, norbornyl lactone has been proposed as an adhesive group with enhanced etching resistance (for example, Patent Documents 8 to 10: JP 2000-26446 A, JP 2000-159758 A, and JP 2002). -371114).

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

  The naphthalene ring is an aromatic having a small absorption at a wavelength of 193 nm, and an ArF resist material based on a vinyl naphthalene copolymer has been proposed (Non-Patent Document 1: J. Photopolym. Sci. Technol., Vol. 11). No. 3, p489 (1998), Patent Documents 11 and 12: Japanese Patent Application Laid-Open Nos. 2004-163877 and 2002-107933). A naphthalene ring having a hydroxy group is expected to be effective in preventing swelling during development because it exhibits weak acidity such as phenol. Furthermore, the naphthalene ring has a high etching resistance and has a merit of high transmittance in vacuum ultraviolet rays (EUV) having a wavelength of 13.5 nm.

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 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 2004-163877 A JP 2002-107933 A J. et al. Photopolym. Sci. Technol. , Vol. 11, no. 3, p489 (1998)

  The present invention has been made in view of such problems, and has high sensitivity, high resolution, high dry etching resistance, and low swelling during development, in exposure with high energy rays. A positive resist material having a small line edge roughness and a small amount of residue after development, particularly a polymer compound useful for a chemically amplified positive resist material, and a positive resist material and a pattern forming method using the polymer compound as a base resin The purpose is to provide.

（式中、Ｒ¹は同一又は異種の水素原子又はメチル基を示す。Ｒ²は水素原子、炭素数１〜１０のアシル基又は酸不安定基である。Ｒ³は水素原子、メチル基、又は−ＣＯ₂Ｒ⁸を示し、Ｒ⁴は水素原子、メチル基、又は−ＣＨ₂ＣＯ₂Ｒ⁸を示す。Ｒ⁸は同一又は異種の水素原子又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。Ｘは−ＣＨ₂−、−Ｏ−又は−Ｓ−であるが、Ｒ⁵〜Ｒ⁷の全てが水素原子の場合、−ＣＨ₂−とはならない。Ｒ⁵〜Ｒ⁷は水素原子、メチル基、トリフルオロメチル基、又は−ＣＯ₂Ｒ⁹であり、Ｒ⁹は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はフッ素化されたアルキル基、又は酸不安定基である。ｎは１〜３の整数、ａ１、ｂ１はモル比を意味し、０＜ａ１＜１．０、０＜ｂ１≦０．８の範囲である。） In order to solve the above problems, according to the present invention, Ru is effective der to use a polymer compound comprising a repeating unit represented by the following general formula (1a) and (1b).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a hydrogen atom, an acyl group having 1 to 10 carbon atoms, or an acid labile group. R ³ represents a hydrogen atom, a methyl group, Or —CO ₂ R ⁸ , 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 linear or branched group having 1 to 15 carbon atoms. Jo or .X showing a cyclic alkyl group is -CH ₂ -, - is a O- or -S-, when all R ⁵ to R ⁷ is a hydrogen atom, -CH ₂ - and not .R ⁵ to R ⁷ is a hydrogen atom, a methyl group, a trifluoromethyl group, or a -CO ₂ R ^9, R ⁹ is a hydrogen atom, a straight alkyl group or a fluorinated branched or cyclic alkyl group, or an acid labile group .n is an integer of 1 to 3, a1, b1 denotes a molar ratio, 0 <a1 <1.0 0 <a range of b1 ≦ 0.8.)

（式中、Ｒ³、Ｒ⁴は上記の通り、Ｒ¹⁰は酸不安定基を示す。ｃ１はモル比を意味し、０＜ｃ１≦０．８の範囲である。） In this case, particularly when R ² and R ⁹ are not acid labile groups, that is, when any of the repeating units of formulas (1a) and (1b) does not contain an acid labile group, the polymer compound is represented by the following general formula: it preferred to contain a repeating unit represented by (1c).

(In the formula, R ³ and R ⁴ are as described above, R ¹⁰ represents an acid labile group. C1 means a molar ratio, and 0 <c1 ≦ 0.8.)

Positive resist materials containing the polymer compound of the present invention as a base resin, in the exposure of high-energy radiation, contrast of alkali dissolution rate before and after exposure is significantly higher, it has a high resolution with high sensitivity In addition, since the 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.

Then, the positive resist composition of the present invention, have preferably be a resist material chemically amplified further contains 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.

In this case, a positive type resist composition of the invention, Ru can be those containing a further 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.

Further, a positive type resist composition of the invention, Ru can be assumed that a basic compound and / or a surfactant is blended as a further additive.

  Thus, by adding a basic compound, for example, the acid diffusion rate in the resist film can be suppressed and the resolution can be further improved. By adding a surfactant, the resist material can be applied. Can be further improved or controlled.

Such a resist material of the present invention comprises a step of applying the resist material on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. Ru can be used as a method for forming a pattern on a substrate or the mask substrate.

  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 radiation, Ru can be of a range of wavelengths 180 and 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, there is provided a polymer compound copolymerizing a repeating unit of hydroxyvinylnaphthalene, a (meth) acrylic unit having a bridged lactone ring, and a (meth) acrylic unit having an acid labile group. By blending this polymer compound into a resist material as a base resin, it has the characteristics of high sensitivity, high resolution, low line edge roughness, and high etching resistance. It is possible to provide a positive resist material such as a chemically amplified positive resist material suitable as a fine pattern forming material in mask pattern production.

  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.

  Therefore, as a result of various studies, the present inventors have not been able to have sufficient adhesion only by having naphthol as an adhesive group, and in particular, repeatedly having a lactone having a specific structure and high hydrophilicity as an adhesive group. It has been found that the hydrophilicity, alkali solubility and adhesion can be balanced by copolymerizing with the unit. In particular, a (meth) acrylate having a bridged cyclic lactone group, a (meth) acrylate having an acid labile group, and a repeating unit having an adhesive group having alkali solubility represented by naphthol are combined. By using the resulting polymer compound as a base resin, it has high sensitivity and high resolution, and has little line edge roughness due to swelling during development, little residue after development, and excellent dry etching resistance. The present invention has been completed by conceiving that a positive resist material can be provided.

（式中、Ｒ¹は同一又は異種の水素原子又はメチル基を示す。Ｒ²は水素原子、炭素数１〜１０のアシル基又は酸不安定基である。Ｒ³は水素原子、メチル基、又は−ＣＯ₂Ｒ⁸を示し、Ｒ⁴は水素原子、メチル基、又は−ＣＨ₂ＣＯ₂Ｒ⁸を示す。Ｒ⁸は同一又は異種の水素原子又は炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。Ｘは−ＣＨ₂−、−Ｏ−又は−Ｓ−であるが、Ｒ⁵〜Ｒ⁷の全てが水素原子の場合、−ＣＨ₂−とはならない。Ｒ⁵〜Ｒ⁷は水素原子、メチル基、トリフルオロメチル基、又は−ＣＯ₂Ｒ⁹であり、Ｒ⁹は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はフッ素化されたアルキル基、又は酸不安定基である。ｎは１〜３の整数、ａ１、ｂ１は０＜ａ１＜１．０、０＜ｂ１≦０．８の範囲である。） The polymer compound according to the present invention has a repeating unit represented by the following general formulas (1a) and (1b).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a hydrogen atom, an acyl group having 1 to 10 carbon atoms, or an acid labile group. R ³ represents a hydrogen atom, a methyl group, Or —CO ₂ R ⁸ , 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 linear or branched group having 1 to 15 carbon atoms. Jo or .X showing a cyclic alkyl group is -CH ₂ -, - is a O- or -S-, when all R ⁵ to R ⁷ is a hydrogen atom, -CH ₂ - and not .R ⁵ to R ⁷ is a hydrogen atom, a methyl group, a trifluoromethyl group, or a -CO ₂ R ^9, R ⁹ is a hydrogen atom, a straight alkyl group or a fluorinated branched or cyclic And n is an integer of 1 to 3, a1 and b1 are 0 <a1 <1.0 and 0 <b1 ≦ 0.8. Range.)

  Here, examples of the acyl group having 1 to 10 carbon atoms include an acetyl group and a pivaloyl group. Examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and decyl. Group, norbornyl group, adamantyl group and the like. Examples of the alkyl group having 1 to 10 carbon atoms are the same as those described above, and examples of the fluorinated alkyl group include those in which part or all of the hydrogen atoms of these alkyl groups are substituted with fluorine atoms. The acid labile group will be described later.

  Such a positive resist material containing the polymer compound of the present invention as a base resin 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 the swelling during development is suppressed, the line edge roughness is small, the residue after development 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.

（式中、Ｒ¹、Ｒ²、ｎは上記の通り。）
このモノマーＭ（１ａ）としては、下記のものが例示される。 The monomer M (1a) for obtaining the repeating unit represented by the general formula (1a) is represented by the following formula.

(In the formula, R ¹ , R ² and n are as described above.)
Examples of the monomer M (1a) include the following.

As a monomer before polymerization, R ² may be an acetyl group, which may be converted into a hydroxy group by alkali hydrolysis after polymerization, and in some cases, the hydrogen atom of the hydroxy group may be substituted with an acid labile group thereafter. R ² is an acid labile group such as acetal and may be converted to a hydroxy group by hydrolysis with a weak acid such as acetic acid or oxalic acid after polymerization.

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘは上記の通り。）
上記モノマーＭ（１ｂ）の具体例としては、下記のものが挙げられるが、これに限定されるものではない。 On the other hand, the monomer M (1b) for obtaining the repeating unit represented by the general formula (1b) is represented by the following formula.

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are as described above.)
Specific examples of the monomer M (1b) include the following, but are not limited thereto.

The polymer compound of the present invention contains the above repeating units (1a) and (1b) obtained by copolymerizing the monomers M (1a) and M (1b). In order to obtain a positive resist material, when R ² in the repeating unit represented by the formula (1a) and R ⁹ in the repeating unit represented by the formula (1b) are not acid labile groups, an acid labile group is used. It is preferable to copolymerize with the monomer M (1c) having a repeating unit represented by the following general formula (1c).

（式中、Ｒ³、Ｒ⁴は前述の通り、Ｒ¹⁰は酸不安定基である。ｃ１は、本発明の高分子化合物がこの繰り返し単位（１ｃ）を含む場合、０＜ｃ１≦０．８の範囲である。）

(In the formula, R ³ and R ⁴ are as described above, and R ¹⁰ is an acid labile group. When c1 is a polymer compound of the present invention containing this repeating unit (1c), 0 <c1 ≦ 0. The range is 8.)

Next, in the general formulas (1a), (1b) and (1c), the acid labile groups represented by R ² , R ⁹ and R ¹⁰ are variously selected. Group or a hydroxyl group of a carboxyl group, particularly a group represented by the following formulas (AL-10) and (AL-11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL-12) And those having a structure substituted with an oxoalkyl group having 4 to 20 carbon atoms and the like.

In the formulas (AL-10) and (AL-11), R ⁵¹ and R ⁵⁴ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 40 carbon atoms, particularly 1 to 20 carbon atoms. And may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ⁵² and R ⁵³ are each a monovalent hydrocarbon group such as a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. Well, a5 is an integer of 0-10. R ⁵² and R ⁵³ , R ⁵² and R ⁵⁴ , R ⁵³ and R ⁵⁴ are bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms together with the carbon atom or carbon atom and oxygen atom to which they are bonded. May be.
R ⁵⁵ , R ⁵⁶ , and R ⁵⁷ are each a monovalent hydrocarbon group such as a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and include heteroatoms such as oxygen, sulfur, nitrogen, and fluorine. But you can. Alternatively, R ⁵⁵ and R ⁵⁶ , R ⁵⁵ and R ⁵⁷ , R ⁵⁶ and R ⁵⁷ may be bonded to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms, together with the carbon atom to which they are bonded.

  Specific examples of the compound represented by the formula (AL-10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonyl. Examples include a methyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL-10) -1 to (AL-10) -10. .

In the formulas (AL-10) -1 to (AL-10) -10, R ⁵⁸ is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl having 6 to 20 carbon atoms. Group or a C7-20 aralkyl group is shown. R ⁵⁹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁰ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

  Examples of the acetal compound represented by the formula (AL-11) are (AL-11) -1 to (AL-11) -34.

  In addition, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (AL-11a) or (AL-11b).

In the above formula, R ⁶¹ and R ⁶² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶¹ and R ⁶² may be bonded to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R ⁶¹ and R ⁶² are linear or branched having 1 to 8 carbon atoms. -Like alkylene group. R ⁶³ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b5 and d5 are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. . A represents a (c5 + 1) -valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, and these groups are heteroatoms such as O, S, and N. 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, A is preferably 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 O, S, N, etc., and a part of the hydrogen atoms bonded to the carbon atoms are substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Also good. C5 is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (AL-11a) and (AL-11b) include those represented by the following formulas (AL-11) -35 to (AL-11) -42.

  Next, examples of the tertiary alkyl group represented by the formula (AL-12) include tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, tert -An amyl group etc., or the following general formula (AL-12) -1-(AL-12) -16 can be mentioned.

In the above formula, R ⁶⁴ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁶⁵ and R ^{67 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁶ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL-12) -17 and (AL-12) -18, a divalent or higher valent alkylene group or an arylene group R ⁶⁸ is included, and the polymer within or between the molecules is It may be cross-linked. In the formulas (AL-12) -17 and (AL-12) -18, R ⁶⁴ represents the same as described above, and R ⁶⁸ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group. And may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. b6 is an integer of 1 to 3.

Further, R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ may have a heteroatom such as oxygen, nitrogen and sulfur, specifically, the following formulas (AL-13) -1 to (AL-13) It can be shown in -7.

  In particular, as the acid labile group of the above formula (AL-12), those having an exo structure represented by the following formula (AL-12) -19 are preferable.

（式中、Ｒ⁶⁹は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ⁷⁰〜Ｒ⁷⁵及びＲ⁷⁸、Ｒ⁷⁹はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示し、Ｒ⁷⁶、Ｒ⁷⁷は水素原子を示す。あるいは、Ｒ⁷⁰とＲ⁷¹、Ｒ⁷²とＲ⁷⁴、Ｒ⁷²とＲ⁷⁵、Ｒ⁷³とＲ⁷⁵、Ｒ⁷³とＲ⁷⁹、Ｒ⁷⁴とＲ⁷⁸、Ｒ⁷⁶とＲ⁷⁷又はＲ⁷⁷とＲ⁷⁸は互いに環を形成していてもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。またＲ⁷⁰とＲ⁷⁹、Ｒ⁷⁶とＲ⁷⁹又はＲ⁷²とＲ⁷⁴は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。Ｒ⁷⁷は水素原子、炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。また、本式により、鏡像体も表す。）

(In the formula, R ⁶⁹ 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 ^{70 to} R ⁷⁵ and R ^78. , R ⁷⁹ each independently represents a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁷⁶ and R ^{77 each} represents a hydrogen atom, or R ⁷⁰ and R ⁷¹ , R ⁷² and R ⁷⁴ , R ⁷² and R ⁷⁵ , R ⁷³ and R ⁷⁵ , R ⁷³ and R ⁷⁹ , R ⁷⁴ and R ⁷⁸ , R ⁷⁶ and R ^77, or R ⁷⁷ and R ⁷⁸ may form a ring with each other In this case, it is a divalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, and R ⁷⁰ and R ⁷⁹ , R ⁷⁶ and R ^79, or R ⁷² and R ⁷⁴ are attached to adjacent carbon atoms. R ⁷⁷ may be a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. In addition, this formula also represents an enantiomer.)

を得るためのエステル体のモノマーとしては、特開２０００−３２７６３３号公報に示されている。具体的には下記に示すものを挙げることができるが、これらに限定されることはない。 Here, the repeating unit having an exo-body structure represented by the general formula (AL-12) -19

JP-A-2000-327633 discloses an ester monomer for obtaining the above. Specific examples include the following, but are not limited thereto.

  Furthermore, examples of the acid labile group of the above formula (AL-12) include an acid labile group having frangiyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the following formula (AL-12) -20.

（式中、Ｒ⁸⁰、Ｒ⁸¹はそれぞれ独立に炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。又は、Ｒ⁸⁰、Ｒ⁸¹は互いに結合してこれらが結合する炭素原子と共に炭素数３〜２０の脂肪族炭化水素環を形成してもよい。Ｒ⁸²はフランジイル、テトラヒドロフランジイル又はオキサノルボルナンジイルから選ばれる２価の基を示す。Ｒ⁸³は水素原子又はヘテロ原子を含んでもよい炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。）

(In the formula, R ⁸⁰ and R ⁸¹ each independently represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. Or, R ⁸⁰ and R ⁸¹ are bonded to each other to form a monovalent hydrocarbon group. An aliphatic hydrocarbon ring having 3 to 20 carbon atoms may be formed together with the carbon atom to be bonded, R ⁸² represents a divalent group selected from flangedyl, tetrahydrofurandiyl or oxanorbornanediyl, and R ⁸³ represents a hydrogen atom. Or a C1-C10 linear, branched or cyclic monovalent hydrocarbon group which may contain a hetero atom.

を得るためのモノマーとしては、下記に例示される。なお、下記式中Ｍｅはメチル基、Ａｃはアセチル基を示す。 Repeating units substituted with acid labile groups having frangyl, tetrahydrofurandiyl or oxanorbornanediyl

Examples of the monomer for obtaining the are as follows. In the following formulae, Me represents a methyl group, and Ac represents an acetyl group.

In the polymer compound of the present invention, the repeating unit represented by the general formulas (1a) and (1b) is essential, and the repeating unit having an acid labile group represented by the formula (1c) may be copolymerized. The repeating unit (1d) derived from the monomer M (1d) having an adhesive group such as a hydroxy group other than 1a) and (1b), a cyano group, a carbonyl group, and an ester group may be copolymerized.
Specific examples of the monomer M (1d) for obtaining the repeating unit (1d) include the following.

In the repeating units (1a), (1b), (1c), (1d), the ratio of the number of repeating units a1, b1, c1, d1 is 0 <a1 <1.0, 0 <b1 ≦ 0.8, 0 ≦ c1 ≦ 0.8, 0 ≦ d1 ≦ 0.8, preferably 0.05 ≦ a1 ≦ 0.9, 0.05 ≦ b1 ≦ 0.7, 0 <c1 ≦ 0.8, especially 0.15 ≦ The range is c1 ≦ 0.7 and 0 ≦ d1 ≦ 0.7.
Here, a1 + b1 + c1 + d1 = 1, and a1 + b1 + c1 + d1 = 1 means that the total amount of these repeating units (1a), (1b), (1c) and (1d) is the total amount of all repeating units. It shows that it is 100 mol%.

  The polymer compound of the present invention preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 30,000, as determined by gel permeation chromatography (GPC). 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.

  Furthermore, in the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer exists, so that after exposure, foreign matter is seen on the pattern or the pattern shape is It 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.

  It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

  In order to synthesize these polymer compounds, as one method, there is a method in which a monomer having an unsaturated bond for obtaining the repeating units a1, b1, c1, and d1 is added to a radical initiator in an organic solvent and subjected to heat polymerization. Yes, 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 positive resist material of the present invention comprises an organic solvent, a compound that generates acid in response to high energy rays (acid generator), and if necessary, a dissolution inhibitor, a basic compound, a surfactant, and other components. 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.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基、オキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基、アリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

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, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group, etc. 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. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate 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.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(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. K ^- is can be exemplified the same ones as described in the formulas (P1a-1) and (P1a-2).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

(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.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状、分岐状のアルキレン基を示す。Ｒ¹⁰⁵は式（Ｐ２）のものと同様である。）

(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.

（式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

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

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(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 exemplified above include the following.
Examples of onium salts include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl. Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenyl nonafluorobutanesulfonate Sulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) ) Sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, di-p-toluenesulfonic acid Tylphenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ And onium salts such as 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-ketosulfonic acid 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 -Sulphonic 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, bisnaphthyl Bissulfone derivatives such as sulfonylmethane, 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, etc. Derivatives are preferably used.
Furthermore, an oxime type acid generator represented by WO2004 / 074242 A2 may be added.

  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 to be 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 in the molecule. The compound having two or more phenolic hydroxyl groups, the hydrogen atom of the phenolic hydroxyl group substituted with an acid labile group in an average of 0 to 100 mol% as a whole, or the carboxy group of a compound having a carboxy group in the molecule In which the hydrogen atom is substituted with an acid labile group in an average ratio of 50 to 100 mol%.

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

However, in the formula, 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, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or — (R ²⁰⁷ ) _h COOH. R ²⁰⁴ is _{- (CH 2) i - (} i = 2~10), shows an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. 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 naphthyl group each substituted with a hydroxyl group. R ²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ²⁰⁸ represents a hydrogen atom or a hydroxyl group. j is an integer of 0-5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and at least 1 in each phenyl skeleton The number has two hydroxyl groups. α is a number that makes the molecular weight of the compounds of formulas (D8) and (D9) 100 to 1,000.

  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 capable of suppressing 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 Examples of tertiary aliphatic amines include 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-pyridone, 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 imide derivatives 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 above formula, n = 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. Side chain Y Represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and X may be bonded to form a ring. May be.)

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, linear and branched chains having 1 to 20 carbon atoms. Or a cyclic alkyl group, which 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, a hydroxy group, One or more ether groups, ester groups and lactone rings 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.

（上記式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状、分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

(In the above formula, X is as described above, and R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, including one or more carbonyl groups, ether groups, ester groups, and sulfides. May be.)

  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, Examples thereof include methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

（上記式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状、分岐状のアルキレン基である。） Furthermore, a basic compound containing a cyano group represented by the following general formulas (B) -3 to (B) -6 can be added.

(In the above formulas, 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, and N, N-bis. (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropi Ononitrile, methyl 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-cyanoe ) Methyl 3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropi Ononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiono Nitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropi Ononitrile, 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) amino Acetonitrile, 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-methoxyethyl) -3-aminopropionic acid methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N-cyanomethyl-3- Methyl 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) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3 -Cyanomethyl aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis 2-methoxyethyl) -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-piperi Examples thereof include cyanomethyl dinpropionate, 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 base resins, and 0.01-1 part is especially 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.

（式中、Ｒ⁴⁰⁸は水素原子又はメチル基を示す。Ｒ⁴⁰²、Ｒ⁴⁰³はそれぞれ水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基を示す。Ｒ⁴⁰⁴は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基、あるいは−（Ｒ⁴⁰⁹）_h−ＣＯＯＲ’基（Ｒ’は水素原子又は−Ｒ⁴⁰⁹−ＣＯＯＨ）を示す。Ｒ⁴⁰⁵は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す、Ｒ⁴⁰⁶は炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す。Ｒ⁴⁰⁷は水素原子又は炭素数１〜８の直鎖状又は分岐状のアルキル基、アルケニル基、それぞれ水酸基で置換されたフェニル基又はナフチル基を示す。Ｒ⁴⁰⁹は炭素数１〜１０の直鎖状又は分岐状のアルキル基又はアルケニル基又は−Ｒ⁴¹¹−ＣＯＯＨ基を示す。Ｒ⁴¹⁰は水素原子、炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基又は−Ｒ⁴¹¹−ＣＯＯＨ基を示す。Ｒ⁴¹¹は炭素数１〜１０の直鎖状又は分岐状のアルキレン基を示す。ｈは１〜４の整数である。ｊは０〜３、ｓ１〜ｓ４、ｔ１〜ｔ４はそれぞれｓ１＋ｔ１＝８、ｓ２＋ｔ２＝５、ｓ３＋ｔ３＝４、ｓ４＋ｔ４＝６を満足し、かつ各フェニル骨格中に少なくとも１つの水酸基を有するような数である。ｕは１〜４の整数である。κは式（Ａ６）の化合物を重量平均分子量１，０００〜５，０００とする数である。λは式（Ａ７）の化合物を重量平均分子量１，０００〜１０，０００とする数である。）

(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 .R ⁴⁰⁹ showing a naphthyl group is a straight or branched alkyl or alkenyl group or a -R ⁴¹¹ -COOH group having 1 to 10 carbon atoms .R ⁴¹⁰ represents a hydrogen atom, a straight-chain having 1 to 8 carbon atoms Represents a linear or branched alkyl group or alkenyl group or —R ⁴¹¹ —COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and h is an integer of 1 to 4. J is a number such that 0 to 3, s1 to s4, and t1 to t4 satisfy s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, and each phenyl skeleton has at least one hydroxyl group. U is an integer of 1 to 4. 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 weight average molecular weight of the compound of formula (A7). 1,000 to 10,000 )

（式中、Ｒ⁴⁰²、Ｒ⁴⁰³、Ｒ⁴¹¹は上記と同様の意味を示す。Ｒ⁴¹²は水素原子又は水酸基を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。ｈ’は０又は１である。） [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.

（式中、Ｒ’’は水素原子又は−ＣＨ₂ＣＯＯＨ基を示し、各化合物においてＲ’’の１０〜１００モル％は−ＣＨ₂ＣＯＯＨ基である。κ、λは上記と同様の意味を示す。）

(Wherein 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. 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 improving the coating property can be further 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 monovalmitate, sorbitan monostearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monovalmitate, polyoxyethylene sorbitan monostearate Non-ionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (Tokemuputtokutsu), Megafuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC-430, FC-431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, Fluorosurfactants such as KH-10, KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-70-093 (Shin-Etsu) Manabu Industry), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Industry Co., Ltd.), etc., among which FC-430, Surflon S-381, Surfynol 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 composition. is there.

  The positive resist material of the present invention, in particular, a chemical containing an organic solvent, a polymer compound having a repeating unit represented by the general formula (1a) and a repeating unit represented by the general formula (1b), an acid generator, etc. When the 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 coat, roll coat, flow coat, dip coat, spray coat, doctor coat, etc. so that the coating film thickness is 0.01 to 2.0 μm, and 60 to 150 ° C. on a hot plate, Pre-bake for 1 to 10 minutes, preferably 80 to 120 ° C. for 1 to 5 minutes.

As the resist thickness becomes thinner, the processing becomes stricter due to the etching selectivity of the substrate to be processed. The silicon-containing intermediate film is formed under the resist, the underlying carbon film has a high carbon density and high etching resistance, and the processed film is formed thereunder. A three-layer process for laminating substrates has been studied. The etching selectivity between the silicon-containing intermediate film using oxygen gas, hydrogen gas, ammonia gas, or the like and the lower layer film is high, and the silicon-containing intermediate film can be thinned. The etching selectivity between the single layer resist and the silicon-containing intermediate layer is also relatively high, and the single layer resist can be thinned. In this case, examples of the method for forming the lower layer film include a method using coating and baking, and a method using CVD. In the case of the coating type, a novolak resin or a resin obtained by polymerizing an olefin having a condensed ring is used, and a gas such as butane, ethane, propane, ethylene, acetylene, or the like is used for producing a CVD film. In the case of the silicon-containing intermediate layer, there are a coating type and a CVD type. Examples of the coating type include silsesquioxane and POSS (registered trademark). Various types of silane gases are used as a raw material for CVD. The silicon-containing intermediate layer may have an antireflection function having light absorption, and may be a light-absorbing group such as a phenyl group or a SiON film. An organic film may be formed between the silicon-containing intermediate film and the photoresist, and the organic film in this case may be an organic antireflection film.
After the formation of the photoresist film, pure water rinsing (post-soak) may be performed to extract the acid generator or the like from the film surface, or the particles may be washed away, or a protective film may be applied.

Next, a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, gamma 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 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes The target pattern is formed on the substrate by development by a conventional method such as a dip method, a paddle method, or a spray method. In addition, 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 or a solution such as alkane having a refractive index of 1 or more and a highly transparent exposure wavelength is used as an immersion solvent. In immersion lithography, water is inserted between a pre-baked resist film and a projection lens. This makes it possible to design a lens having an NA of 1.0 or more, and to form a finer pattern. Immersion lithography is an important technique for extending the life of ArF lithography to the 45 nm node, and its development has been accelerated. In the case of immersion exposure, pure water rinsing (post-soak) after exposure to remove the remaining water droplets on the resist film may be performed, and elution from the resist is prevented, and the film surface is lubricated. In order to increase the thickness, a protective film can be applied on the resist film after pre-baking. The resist protective film used in immersion lithography is based on a high molecular compound having an α-trifluoromethylhydroxy group that is insoluble in water and dissolved in an alkaline developer, an alcohol having 4 or more carbon atoms, and an ether having 8 to 12 carbon atoms. And the material dissolved in these mixed solvents can be used preferably.

  Furthermore, as a technique for extending the life of ArF lithography up to 32 nm, a double patterning method can be mentioned. As the double patterning method, the base of the 1: 3 trench pattern is processed by the first exposure and etching, the position is shifted, the 1: 3 trench pattern is formed by the second exposure, and the 1: 1 pattern is formed. The first base of the 1: 3 isolated residual pattern is processed by the trench method, the first exposure and the etching, and the 1: 3 isolated residual pattern is formed under the first base by shifting the position and the second exposure. Further, there is a line method in which the second base is processed to form a 1: 1 pattern with a half pitch.

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, naphthol dissolves in an alkaline aqueous solution, but does not dissolve in water at all. Therefore, it is considered that the influence of dissolution and swelling by the above-mentioned immersion is small.
Furthermore, the resist material of the present invention can also be used for EB and EUV lithography. In particular, the polymer of the present invention having a naphthalene ring having a high carbon ratio is expected to have a high transmittance in EUV light having a wavelength of 13.5 nm.

  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 addition, a weight average molecular weight (Mw) shows the polystyrene conversion weight average molecular weight by GPC.

[Synthesis Example 1]
In a 100 mL flask, 8.1 g of methacrylate-2-ethyl-2-adamantane, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclo methacrylate [4.2 .1.0 ^4,8] nonan-9-yl 6.7 g, 2-vinyl-6-ethoxy-ethoxy-naphthalene 2.6 g, of tetrahydrofuran as a solvent 20g. 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 (2,2′-azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 2-vinyl-6-hydroxynaphthalene = 0.30: 0.25: 0.30: 0.15
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.72

この高分子化合物をポリマー１とする。

This polymer compound is designated as Polymer 1.

[Synthesis Example 2]
In a 100 mL flask, 8.1 g of methacrylic acid-2-ethyl-2-adamantane, 6.3 g of methacrylic acid-3-hydroxy-1-adamantyl, methacrylic acid-3-oxo-5-methoxycarbonyl-2-oxatricyclo [ 4.2.1.0 ^4,8 ] -9-nonyl 8.4 g, 2-vinyl-6-ethoxyethoxynaphthalene 2.6 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 2-vinyl-6-hydroxynaphthalene = 0.30: 0.25: 0.30: 0.15
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.65

この高分子化合物をポリマー２とする。

This polymer compound is designated as Polymer 2.

[Synthesis Example 3]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecanyl 6.9 g, methacrylic acid 3-hydroxy-1-adamantyl 6.3 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8] 7.8 g of nonan-9-yl, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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-hydroxy-1-adamantyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: 2-vinyl-6-hydroxynaphthalene = 0.25: 0.25: 0.35: 0.15
Weight average molecular weight (Mw) = 7,500
Molecular weight distribution (Mw / Mn) = 1.71

この高分子化合物をポリマー３とする。

This polymer compound is designated as Polymer 3.

[Synthesis Example 4]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 11.2 g, methacrylic acid-3, 5.0 g of 5-di (2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, 20 g of tetrahydrofuran as a solvent 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: methacrylate 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl: methacrylate-3,5-di (2- Hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) cyclohexyl: 2-vinyl-6-hydroxynaphthalene = 0.25: 0.50: 0.10: 0.15
Weight average molecular weight (Mw) = 8,300
Molecular weight distribution (Mw / Mn) = 1.66

この高分子化合物をポリマー４とする。

This polymer compound is designated as polymer 4.

[Synthesis Example 5]
In a 100 mL flask, 6.0 g of 1-ethylcyclopentyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclo methacrylate [4.2.1. 0 ^4,8 ] nonane-9-yl, 6.1 g, 2-vinyl-6-ethoxyethoxynaphthalene, 2.6 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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 : 2-vinyl-6-hydroxynaphthalene = 0.33: 0.25: 0.27: 0.15
Weight average molecular weight (Mw) = 7,100
Molecular weight distribution (Mw / Mn) = 1.82

この高分子化合物をポリマー５とする。

This polymer compound is designated as polymer 5.

[Synthesis Example 6]
In a 100 mL flask, 6.3 g of 1- (7-oxanorbornan-2-yl) cyclopentyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatri methacrylate 7.8 g of cyclo [4.2.1.0 ^4,8 ] nonane-9-yl, 2.6 g of 2-vinyl-6-ethoxyethoxynaphthalene, 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 2-vinyl-6-hydroxynaphthalene = 0.25: 0.25: 0.35: 0.15
Weight average molecular weight (Mw) = 7,400
Molecular weight distribution (Mw / Mn) = 1.73

この高分子化合物をポリマー６とする。

This polymer compound is designated as polymer 6.

[Synthesis Example 7]
In a 100 mL flask, 6.3 g of 2-adamantyloxymethyl methacrylate, 6.3 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclomethacrylate [4.2. ^1.04,8 ] Nonane-9-yl 7.8 g, 2-vinyl-6-ethoxyethoxynaphthalene 2.6 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 2-vinyl-6-hydroxynaphthalene = 0.25: 0.25: 0.35: 0.15
Weight average molecular weight (Mw) = 9,000
Molecular weight distribution (Mw / Mn) = 1.91

この高分子化合物をポリマー７とする。

This polymer compound is designated as polymer 7.

[Synthesis Example 8]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 5.6 g, 2-vinyl-7 -8.5 g of ethoxyethoxynaphthalene 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 2-vinyl-7-hydroxynaphthalene = 0. 25: 0.25: 0.50
Weight average molecular weight (Mw) = 8,100
Molecular weight distribution (Mw / Mn) = 1.72

この高分子化合物をポリマー８とする。

This polymer compound is designated as polymer 8.

[Synthesis Example 9]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanyl 6.9 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl 5.6 g, 1-vinyl-5 -8.9 g of ethoxyethoxynaphthalene 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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: 1-vinyl-5-hydroxynaphthalene = 0. 25: 0.25: 0.50
Weight average molecular weight (Mw) = 8,700
Molecular weight distribution (Mw / Mn) = 1.77

この高分子化合物をポリマー９とする。

This polymer compound is designated as polymer 9.

[Synthesis Example 10]
In a 100 mL flask, 10.8 g of methacrylic acid-3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl, 2-vinyl-7-ethoxy 11.9 g of ethoxynaphthalene 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, the obtained white solid was dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water were added, and an ethoxyethoxy group was deprotected at 60 ° C. for 5 hours. Liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl: 2-vinyl-7-hydroxynaphthalene = 0.30: 0 .70
Weight average molecular weight (Mw) = 9,900
Molecular weight distribution (Mw / Mn) = 1.87

この高分子化合物をポリマー１０とする。

This polymer compound is designated as polymer 10.

[Synthesis Example 11]
In a 100 mL flask, 3.6 g of methacrylic acid-3-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl, 2-vinyl-7-acetoxy 11.9 g of naphthalene, 4.8 g of 2-vinyl-7-ethoxyethoxynaphthalene, 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran. 5 g of triethylamine and 3 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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-oxo-5-ethylcyclopentyloxycarbonyl-2-oxatricyclo [4.2.1.0 ^4,8 ] -9-nonyl: 2-vinyl-7-hydroxynaphthalene: 2-vinyl-7 -Ethoxyethoxynaphthalene = 0.10: 0.70: 0.20
Weight average molecular weight (Mw) = 9,100
Molecular weight distribution (Mw / Mn) = 1.90

この高分子化合物をポリマー１１とする。

This polymer compound is designated as polymer 11.

[Synthesis Example 12]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecanyl 6.9 g, methacrylic acid 3-hydroxy-1-adamantyl 3.8 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8] Nonane-9-yl 3.3 g, methacrylate-2-oxooxofuran-4-yl 5.1 g, 2-vinyl-6-ethoxyethoxynaphthalene 2.6 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 is precipitated in 500 mL of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 200 mL of methyl ethyl ketone, 5 g of oxalic acid and 3 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 500 mL of water. The reaction solution was concentrated and then dissolved in 100 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain 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-hydroxy-1-adamantyl methacrylate: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate: Methacrylic acid-2-oxooxofuran-4-yl: 2-vinyl-6-hydroxynaphthalene = 0.25: 0.15: 0.15: 0.30: 0.15
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.79

この高分子化合物をポリマー１２とする。

This polymer compound is designated as polymer 12.

[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 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 obtained 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 γ-butyrolactone = 0.48: 0.52
Weight average molecular weight (Mw) = 12,500
Molecular weight distribution (Mw / Mn) = 1.88

この高分子化合物を比較例ポリマー１とする。

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

[Comparative Synthesis Example 2]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 8.2 g of dodecanyl, 8.2 g of 3-hydroxy-1-adamantyl methacrylate, 3-oxo-2,7-dioxatricyclo methacrylate [4.2.1.0 ^4,8 ] Nonane-9-yl (9.2 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 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: 8.2 g methacrylate-3-hydroxy-1-adamantyl, 3-oxo-2,7-dioxatricyclo methacrylate [4.2.1.0 ^4,8 ] nonane-9 -Ile = 0.30: 0.25: 0.45
Weight average molecular weight (Mw) = 8,400
Molecular weight distribution (Mw / Mn) = 1.63

この高分子化合物を比較例ポリマー２とする。

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

[Comparative Synthesis Example 3]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecanyl 6.9 g, methacrylic acid 3-hydroxy-1-adamantyl 5.9 g, methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7] nonane -2 -7.7 g of yl, 2.6 g of 2-vinyl-6-hydroxynaphthalene, 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 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-hydroxy-1-adamantyl methacrylate: 5-oxo-4-oxatricyclo methacrylate [4.2.1.0 ^3,7 ] nonan-2-yl: 2-vinyl methacrylate -6-hydroxynaphthalene = 0.25: 0.25: 0.35: 0.15
Weight average molecular weight (Mw) = 7,700
Molecular weight distribution (Mw / Mn) = 1.75

この高分子化合物を比較例ポリマー３とする。

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

[Comparative Synthesis Example 4]
In a 100 mL flask, methacrylic acid-3-ethyl-3-exotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecanyl 6.9 g, methacrylic acid 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8] nonan-9-yl 5.6 g, 4-hydroxystyrene 6 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 500 mL of isopropyl alcohol, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 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: 4-hydroxystyrene = 0.25: 0. 25: 0.50
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.65

この高分子化合物を比較例ポリマー４とする。

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

塩基性化合物：Ｑｕｅｎｃｈｅｒ１、Ｑｕｅｎｃｈｅｒ２（下記構造式参照）

溶解阻止剤：ＤＲＩ１（下記構造式参照）

溶解制御剤：ＤＲＲ１（下記構造式参照）

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート） Preparation of positive resist material Using the polymer compounds synthesized above (Polymers 1 to 7 and 12, Comparative Polymers 1 to 3), a solution dissolved in the composition shown in Table 1 below was 0.2 μm in size. A resist solution was prepared by filtration through a filter.
Each composition in Table 1 is as follows.
Polymers 1-7 and 12: Polymers obtained in Synthesis Examples 1-7 and 12 Comparative Example Polymers 1-3: Polymers obtained in Comparative Synthesis Examples 1-3 Acid generators: PAG1, PAG2 (see the following structural formula)

Basic compounds: Quencher1, Quencher2 (see structural formula below)

Dissolution inhibitor: DRI1 (see structural formula below)

Dissolution control agent: DRR1 (see the following structural formula)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)

[Examples 1 to 11 and Comparative Examples 1 to 3]
Evaluation of ArF exposure patterning The resist material prepared above was spin-coated on a silicon wafer with a film thickness of AR-19 (made by Shipley Co., Ltd.) having a thickness of 82 nm, and baked at 120 ° C. for 60 seconds using a hot plate. The resist thickness was set to 150 nm.
This was exposed in steps of 1 mJ / cm ² using an ArF excimer laser stepper (Nikon Corporation, NSR-S307E, NA 0.85, σ 0.93, 2/3 annular illumination), and immediately after exposure The film was baked at 110 ° C. for 60 seconds and developed with an aqueous solution of 2.38 mass% tetramethylammonium hydroxide for 60 seconds to obtain a positive pattern.
The obtained resist pattern was evaluated as follows.
Using an exposure amount that resolves 0.08 μm line and space at 1: 1 as the sensitivity of the resist, 0.08 μm line edge roughness at this exposure amount is measured with a length measuring SEM (S-9380 manufactured by Hitachi, Ltd.). did.
Next, the dimensional variation within the range of the optimum exposure dose ± ² mJ / cm ² was determined and used as the exposure dose margin.
Table 1 shows the results of resist composition, sensitivity in ArF exposure, exposure amount margin, and line edge roughness.

  From the results in Table 1, it can be seen that the resist materials of Examples 1 to 11 have a wide exposure amount margin and a small line edge roughness.

[Examples 12 to 15, Comparative Examples 4 and 5]
EB exposure patterning evaluation In the EB drawing evaluation, a solution dissolved in the composition shown in Table 2 using the polymer compound synthesized above (Polymers 8 to 10 and Comparative Polymers 3 and 4) was 0.2 μm in size. The positive resist material was prepared by filtering with a filter.
The obtained positive resist material was spin-coated on a Si substrate having a diameter of 6 inches φ using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), prebaked on a hot plate at 110 ° C. for 90 seconds, and 100 nm. A resist film was prepared. To this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using HL-800D manufactured by Hitachi, Ltd.
Immediately after drawing, PEB is performed for 90 seconds at 80 ° C. on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), and paddle development is performed for 30 seconds with 2.38 mass% TMAH aqueous solution. Got the pattern.
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 resist sensitivity, and the minimum dimension resolved at this time was defined as resolution.
Results of resist composition, sensitivity and resolution in EB exposure are shown in 2.

  From the results in Table 2, it can be seen that the resist materials of Examples 12 to 15 have high sensitivity and high resolution.

[Examples 16 to 25, Comparative Examples 6 to 9]
In the dry etching resistance test, 10 g of PGMEA was dissolved in 2 g of polymer and a polymer solution 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 performed under two conditions.
(1) Etching test with CHF ₃ / CF ₄ -based 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. 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 results of dry etching resistance are shown in Table 3.

  From the results shown in Tables 1 to 3, the resist material using the polymer compound of the present invention satisfies the sufficient resolution and sensitivity, has a small line edge roughness, and a small film thickness difference after etching. It turns out that it has etching property.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Claims (9)

The high molecular compound which has a repeating unit shown by the following general formula (1a) and (1b).

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. R ² represents a hydrogen atom, an acyl group having 1 to 10 carbon atoms, or an acid labile group. R ³ represents a hydrogen atom, a methyl group, Or —CO ₂ R ⁸ , 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 linear or branched group having 1 to 15 carbon atoms. Jo or .X showing a cyclic alkyl group is -CH ₂ -, - is a O- or -S-, when all R ⁵ to R ⁷ is a hydrogen atom, -CH ₂ - and not .R ⁵ to R ⁷ is a hydrogen atom, a methyl group, a trifluoromethyl group, or a -CO ₂ R ^9, R ⁹ is a hydrogen atom, a straight alkyl group or a fluorinated branched or cyclic An alkyl group or an acid labile group, n is an integer of 1 to 3, a1 and b1 are molar ratios, 0 <a1 <1.0, (The range is 0 <b1 ≦ 0.8.) Furthermore, the high molecular compound of Claim 1 which has a repeating unit shown by the following general formula (1c).

(In the formula, R ³ and R ⁴ are as described above, R ¹⁰ represents an acid labile group. C1 means a molar ratio, and 0 <c1 ≦ 0.8.) Furthermore, the high molecular compound of Claim 1 or 2 which has a repeating unit derived from the monomer chosen from the monomer which has a hydroxyl group shown by a following formula .

Positive resist composition, characterized in that those comprising as a base resin a polymer compound according to any one of claims 1 to 3. 5. The positive resist material according to claim 4 , which is a chemically amplified resist material containing an organic solvent and an acid generator. Furthermore, positive resist composition according to claim 4 or 5, characterized in that those containing a dissolution inhibitor. Furthermore, positive resist composition according to any one of claims 4 to 6 basic compound and / or surfactant is characterized in that formulated as an additive. It includes a step of applying the resist material according to any one of claims 4 to 7 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. A characteristic pattern forming method. The pattern forming method according to claim 8 , wherein the high energy ray has a wavelength in a range of 180 to 200 nm.