JP2006169302A - Polymer and positive type resist material and method for forming pattern therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist material, especially a chemical amplification positive type resist material, which has high resolution, high exposure margin, small compressional dimension difference, and process adaptability, forms good patterns, after exposed to light, and exhibits excellent etching resistance. <P>SOLUTION: This polymer containing at least copolymerization repeating units represented by general formula (1) and having a weight-average mol. wt. of 1,000 to 500,000. The positive resist material containing the polymer as a base resin. A method for forming a pattern includes a process for coating a substrate with the polymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is obtained by copolymerizing a resist material with a polymer compound obtained by copolymerizing substituted acenaphthylene and substituted hydroxystyrene and having improved alkali solubility by the action of an acid as a base resin. Fine pattern forming material, especially for VLSI manufacturing or photomasks, with significantly high dissolution rate contrast, high sensitivity and high resolution, good pattern shape after exposure, and excellent etching resistance In particular, the present invention relates to a positive resist material suitable as a chemical amplification positive resist material.

  In recent years, along with the high integration and high speed of LSIs, far ultraviolet lithography is considered promising as a next-generation microfabrication technique, while miniaturization of pattern rules is required. Far-ultraviolet lithography can process 0.5 μm or less, and when a resist material with low light absorption is used, it is possible to form a pattern having sidewalls that are nearly perpendicular to the substrate.

  A recently developed acid-catalyzed chemically amplified positive resist material uses a high-brightness KrF excimer laser as a deep ultraviolet light source, and has excellent sensitivity, resolution, dry etching resistance, and excellent characteristics. It is used as a resist material particularly promising for deep ultraviolet lithography (Patent Documents 1 and 2).

As such a chemically amplified positive resist material, a two-component system comprising a base polymer and an acid generator, a three-component system comprising a base polymer, an acid generator and a dissolution inhibitor having an acid labile group are known. .
For example, a resist material composed of poly-p-tert-butoxystyrene and an acid generator has been proposed (Patent Document 3). As similar to this proposal, a resist material composed of a resin having a tert-butoxy group in the molecule and an acid generator is proposed. A two-component resist material (Patent Document 4) and a two-component resist material composed of polyhydroxystyrene containing a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group, and a trimethylsilyl group and an acid generator have been proposed. (Patent Document 5).
Furthermore, poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], poly [3,4-bis (2-tetrahydropyranyl) A resist material composed of a polydihydroxystyrene derivative such as (oxy) styrene] and an acid generator has been proposed (Patent Document 6).

  However, the base resin of these resist materials has an acid labile group in the side chain, and the acid labile group is decomposed with a strong acid such as tert-butyl group and tert-butoxycarbonyl group. The pattern shape of the resist material tends to be a T-top shape. On the other hand, since an alkoxyalkyl group such as an ethoxyethyl group is decomposed by a weak acid, it has a drawback that the pattern shape becomes extremely thin with the passage of time from exposure to heat treatment. In addition, since the side chain has a bulky group, the heat resistance is not lowered, and the sensitivity and resolution are not satisfactory. Thus, both have problems.

  In addition, a resist material using a copolymer of hydroxystyrene and (meth) acrylic acid tertiary ester to realize higher transparency and adhesion to the substrate, to improve the tailing to the substrate, and to improve etching resistance. However, this type of resist material has problems such as heat resistance and poor pattern shape after exposure, and etching resistance is not satisfactory (Patent Documents 7 to 8).

  Here, in order to improve etching resistance, hydroxystyrene-styrene- (meth) acrylic acid tertiary ester copolymers have been proposed (Patent Documents 9 to 10). By introducing styrene, not only the etching resistance is improved, but also the margin of the isolated residual pattern is enlarged, and the dimensional difference (dense dimensional difference) between the group pattern and the isolated residual pattern is reduced. The phenomenon in which the density difference between the density and the density is reduced is considered to be because the acid diffusion distance is reduced. In order to reduce the acid diffusion distance, it is considered to be effective to add an acid generator having a higher molecular weight and generating a bulky acid. However, it is also possible to reduce the acid diffusion distance by introducing an acid inert group such as styrene.

  In recent years, the mass production of 150 nm design rules has become full-scale in KrF lithography, and mass production of 130 nm is about to start, and the extension of life to 100 nm is being studied. Here, in order to resolve a dimension much smaller than the wavelength, it is essential to increase the NA of the projection lens of the exposure machine, but super-resolution technology such as modified illumination or a phase shift mask is necessary. However, in the dimension close to the wavelength limit, the problem that the sparse / dense dimensional difference increases becomes serious. At the same time, further higher contrast is required to increase the resolution.

For example, in the above terpolymer of hydroxystyrene-styrene-tert-butyl (meth) acrylate, it is necessary to increase the ratio of tert-butyl (meth) acrylate in order to increase the dissolution contrast. However, if the ratio of tert-butyl (meth) acrylate is too high, there is a disadvantage that the dimensional difference in density is very large. Increasing the proportion of styrene and decreasing the proportion of tert-butyl (meth) acrylate reduces the density difference but decreases the dissolution contrast. Therefore, it is necessary to optimize the proportion of styrene and tert-butyl (meth) acrylate to balance the dissolution contrast and the density difference.
However, with the progress of miniaturization, required performance cannot be achieved only by balancing styrene and tert-butyl (meth) acrylate.
Thus, further breakthroughs have been required to achieve minimum acid diffusion and maximum dissolution contrast.

  It has been shown that reducing the molecular weight of the base polymer is effective for reducing line edge roughness. Therefore, resists based on low molecular weight polymers such as calixarene, low molecular weight novolak, and low molecular weight hydroxystyrene have been reported. However, since a low molecular polymer generally has a low glass transition point (Tg), it is difficult to control acid diffusion in a post-exposure bake (PEB) of a low molecular novolak or hydroxystyrene. A polymer having a low molecular weight and a high Tg is desired.

JP-B-2-27660 JP 63-27829 A JP 62-115440 A JP-A-3-223858 JP-A-4-21258 Japanese Patent Laid-Open No. 6-1000048 JP-A-3-275149 JP-A-6-289608 Japanese Patent Laid-Open No. 10-186665 JP-A-11-305441

  The present invention has been made in view of the above circumstances, has high resolution, exposure margin, small density difference, process adaptability, and a good pattern shape after exposure, compared to conventional positive resist materials. It is another object of the present invention to provide a positive resist material exhibiting excellent etching resistance, particularly a chemically amplified positive resist material.

(上式中、Ｒ¹は同一又は非同一の水素原子、ヒドロキシ基、炭素数１〜４の直鎖状、分岐状のアルキル基、アセトキシ基、ヒドロキシメチル基、ハロゲン原子、又は−ＯＲ⁴（式中、Ｒ⁴は炭素数１〜６の直鎖状、分岐状のアルキル基、又は酸不安定基を表す。）を表し、ｍは０又は１〜６の正の整数であり、ｎは１〜５の整数であり、Ｒ²は水素原子又はメチル基を表し、Ｒ³は酸不安定基又は水素原子を表すが、Ｒ³とＲ⁴が併存するときはそのうちの少なくとも一つが酸不安定基であり、Ｒ⁴が存在しないときはＲ³のうちの少なくとも一つが酸不安定基であり、ｐとｑはモル分率を表し各々１未満の正数であり、ｐ＋ｑ≦１の関係を満たす。) In order to solve the above-mentioned problems, according to the present invention, at least a repeating unit by copolymerization represented by the following general formula (1) having a weight average molecular weight in the range of 1,000 to 500,000 is high. Molecular compounds are provided.

(In the above formula, R ¹ is the same or non-identical hydrogen atom, hydroxy group, linear or branched alkyl group having 1 to 4 carbon atoms, acetoxy group, hydroxymethyl group, halogen atom, or —OR ⁴ ( In the formula, R ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an acid labile group.), M is 0 or a positive integer of 1 to 6, and n is R ² represents a hydrogen atom or a methyl group, R ³ represents an acid labile group or a hydrogen atom, and when R ³ and R ⁴ coexist, at least one of them is an acid-immobilized group. When R ⁴ is not present, at least one of R ³ is an acid labile group, p and q are mole fractions, each being a positive number less than 1, and p + q ≦ 1 Meet.)

Moreover, the present invention provides a positive resist material comprising a high molecular compound having a repeating unit represented by the general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000 as a base resin. This positive resist material has a resist film with high dissolution contrast, high sensitivity and high resolution, exposure margin, excellent process adaptability, good pattern shape after exposure, especially dense patterns And the sparse pattern have a small dimensional difference and exhibit better etching resistance. Therefore, since it has these excellent characteristics, it is extremely practical and is very effective as a resist material for VLSI.
Such a positive resist material of the present invention includes at least a step of coating the resist material on a substrate, a step of heat-treating the obtained coating film, and exposing the heat-treated coating film with high energy rays. It can be used as a method for forming a pattern on a semiconductor substrate, a mask substrate or the like by performing a step of developing and a step of developing the exposed coating film using a developer.
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.
Examples of the use of the positive resist material of the present invention as described above, particularly the chemically amplified positive resist material, include not only lithography in semiconductor circuit formation, but also mask circuit pattern formation, micromachines, and thin film magnetic head circuits. It can also be applied to formation.

  In the present invention, a polymer compound obtained by copolymerizing substituted acenaphthylene and substituted hydroxystyrene is blended with a resist material as a base resin, so that the alkali dissolution rate contrast before and after exposure is significantly high, and the sensitivity is high. It has resolution, has a good pattern shape after exposure, and particularly suppresses the acid diffusion rate and exhibits excellent etching resistance. Accordingly, it is possible to obtain a positive resist material, particularly a chemically amplified positive resist material, which is particularly suitable as a material for forming a fine pattern for VLSI manufacturing or a photomask.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.
As a result of intensive studies to obtain a positive resist material having high sensitivity and high resolution, exposure margin, etc. that have been recently requested, good etching shape, and excellent etching resistance, For this purpose, it is extremely effective if a polymer obtained by copolymerization of hydroxystyrene in which a hydrogen atom of a hydroxy group is substituted with an acid labile group and acenaphthylene is used as a base resin of a positive resist material, particularly a chemically amplified positive resist material. Thus, the present invention has been completed.

That is, the present inventors examined the copolymerization of acenaphthylene prior to the present invention. These materials not only have improved etching resistance, but also have a feature of reducing the density difference by suppressing acid diffusion, and the effect is higher than that of styrene. This is considered to be because acenaphthylene is a cycloolefin, and the thermal motion in the molecule is suppressed by the main chain of the polymer being rigid, thereby suppressing acid diffusion.
From the above, the present inventors further developed a polymer obtained by copolymerizing hydroxystyrene in which a hydrogen atom of a hydroxy group is substituted with an acid labile group and acenaphthylene in order to suppress acid diffusion, as a positive resist material. In particular, the idea was to use it as a base resin for chemically amplified positive resist materials.

  The polymer compound according to the present invention is a polymer compound having a weight average molecular weight in the range of 1,000 to 500,000, comprising at least a repeating unit by copolymerization represented by the general formula (1). .

  Using such a high molecular compound as a base resin, an organic solvent, an acid generator, a dissolution inhibitor, a basic compound, a surfactant and the like are appropriately combined according to the purpose to form a positive resist material. Resist resist film has high dissolution contrast and resolution, exposure margin, excellent process adaptability, good pattern shape after exposure, and better etching resistance, especially suppressing acid diffusion Therefore, the dimensional difference is small, and these facts are highly practical and can be very effective as a resist material for VLSI. In particular, when a chemically amplified positive resist material containing an acid generator and utilizing an acid catalytic reaction is used, it can be made more sensitive and have excellent properties and is extremely useful. .

According to the present invention, it is preferable to use a chemically amplified resist material containing the polymer compound as a base resin and further containing an organic solvent and an acid generator. Thus, by using the polymer compound as a base resin, and further blending an organic solvent and an acid generator, the dissolution rate of the polymer compound in the developing solution is accelerated by a catalytic reaction in the exposed area. A highly sensitive positive resist material can be obtained.
In this case, the positive resist material of the present invention can preferably further contain a dissolution inhibitor. Thus, by adding a dissolution inhibitor to the positive resist material, the difference in dissolution rate between the exposed area and the unexposed area can be further increased, and the resolution can be further improved.
In the present invention, preferably, a basic compound and / or a surfactant can be further added as an 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, and by adding a surfactant, the coatability of the resist material can be improved. It can be further improved or controlled.

In R ³ or R ⁴ in the general formula (1), when they exhibit the function of an acid labile group, they are variously selected and may be the same or non-identical. A group represented by the following formula (AL11), a tertiary alkyl group having 4 to 40 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, or a carbon number represented by the following formula (AL12): It is preferably substituted with 4 to 20 oxoalkyl groups or the like.

In the formulas (AL10) and (AL11), R ⁶ and R ⁹ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms and may contain heteroatoms such as oxygen, sulfur, nitrogen or fluorine. Good.
R ⁷ and R ⁸ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a heteroatom such as oxygen, sulfur, nitrogen, or fluorine, and a is It is an integer of 0-10. R ⁷ and R ⁸ , R ⁷ and R ⁹ , or R ⁸ and R ⁹ may be bonded to each other to form a ring.

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

In formulas (AL10) -1 to (AL10) -9, R ¹⁴ is the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or aryl group having 6 to 20 carbon atoms. Or an aralkyl group having 6 to 20 carbon atoms. R ¹⁵ does not exist, or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ¹⁶ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 6 to 20 carbon atoms.

  Examples of the acetal compound represented by the formula (AL11) are the following (AL11) -1 to (AL11) -30.

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

In the above formula, R ³³ and R ³⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ³³ and R ³⁴ may combine to form a ring, and when forming a ring, R ³³ and R ³⁴ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ³⁵ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and b and d are 0 or 1 to 10, preferably 0 or an integer of 1 to 5. c is an integer of 1-7. A represents a (c + 1) -valent C1-C50 aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, and these groups are heteroatoms such as O, S or 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-C20 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 or N, 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. It may be. C is preferably an integer of 1 to 3.

  Specific examples of the cross-linked acetal groups represented by the general formulas (AL-11a) and (AL-11b) include those represented by the following formulas (AL-11) -31 to (AL-11) -38.

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

In the above formula, R ¹⁰ represents the same or non-identical 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 6 to 20 carbon atoms. Show. R ¹¹ and R ¹³ are not present or represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ¹² represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 6 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL12) -19 and (AL12) -20, a polymer having a divalent or higher valent alkylene group or an arylene group, R ¹⁷ , is crosslinked within or between the molecules of the polymer. Also good. In the formulas (AL12) -19 and (AL12) -20, R ¹⁰ is the same as described above, and R ¹⁷ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group. It may contain a hetero atom such as a sulfur atom or a nitrogen atom. e is an integer of 1-3.

Furthermore, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may have a heteroatom such as oxygen, nitrogen, or sulfur, and specifically include the following (AL13) -1 to (AL13) -7. Can show.

  Examples of the trialkylsilyl group having 1 to 6 carbon atoms that can be used as the acid labile group of the polymer compound of the present invention include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolan-5-yl group.

  The substitution rate of the acid labile group depends on the type of the acid labile group and the concentration of the alkaline water to be developed, but 5 to 50 mol% of the hydroxyl atom of hydroxystyrene or hydroxyacenaphthylene is used. Substitution is a preferred range. In this case, the polymer film becomes insoluble or hardly soluble in the alkaline developer.

Next, considering the characteristics of the resist material, in the above formula (1), p and q are each positive numbers, and are desirably numbers satisfying the following formula.
That is, 0 <p / (p + q) ≦ 0.7, preferably 0.03 ≦ p / (p + q) ≦ 0.6, 0.1 <q / (p + q) ≦ 0.97, preferably The range is 0.3 ≦ q / (p + q) ≦ 0.95. The range is 0.5 ≦ p + q ≦ 1, preferably 0.6 ≦ p + q ≦ 1. Therefore, in the present invention, another unit may be copolymerized in addition to the p and q units.
On the other hand, when q is 0.4 or less, in normal radical polymerization, the polymerization rate of the p unit alone is considerably slow, and it may be difficult to obtain a polymer. In this case, polymerization by cationic polymerization is performed. Further, when the p unit is less than 0.03, the effect of the present invention may be lost.

  The polymer compound of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000. If the weight average molecular weight is too small, the resist material is inferior in heat resistance. If the weight average molecular weight is too large, the alkali solubility is lowered, and a trailing phenomenon is likely to occur after pattern formation. In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are obtained by polystyrene conversion using GPC (gel permeation chromatograph).

Furthermore, in the polymer compound of the present invention, when the molecular weight distribution (Mw / Mn) of the multi-component copolymer of the above formula (1) is wide, a low molecular weight or high molecular weight polymer is present. Foreign matter is seen on the pattern or the shape of the pattern is deteriorated. 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 the general formula (1) of the present invention, the substituted acenaphthylene shown in the repeating unit having a molar fraction p can be specifically shown below.

  In the general formula (1) of the present invention, the substituted hydroxystyrene shown in the repeating unit having a molar fraction q can be specifically shown below. In the following examples, Ra represents an acid labile group.

In addition to the repeating unit having the molar fractions p and q represented by the general formula (1), other components for improving adhesion, dry etching resistance, and transparency can be added.
Additional components include, for example, (meth) acrylic acid derivatives, (meth) acrylamide derivatives, itaconic acid derivatives, norbornene derivatives, maleic anhydride, maleimide derivatives, indene derivatives, styrene, vinyl naphthalene derivatives, vinyl anthracene derivatives, nortricyclene, acetic acid Examples include vinyl, (meth) acrylonitrile, vinyl pyrrolidone, and tetrafluoroethylene. In addition, (meth) acryl means methacryl or acryl.

In order to synthesize these polymer compounds, as one method, an acetoxystyrene monomer and a substitutable acenaphthylene monomer are added to a radical initiator or a cationic initiator in an organic solvent and subjected to heat polymerization, and the resulting polymer is obtained. The compound is subjected to alkaline hydrolysis in an organic solvent to deprotect the acetoxy group, and a polymer compound of a two-component copolymer of hydroxystyrene and one of substituted acenaphthylenes can be obtained.
In addition, a hydroxystyrene monomer substituted with an acid labile group and acenaphthylene are heated in an organic solvent by adding a radical initiator, and the resulting polymer compound is deprotected with an acid catalyst in an organic solvent to produce hydroxystyrene and There is also a method of obtaining a polymer compound of a two-component copolymer of acenaphthylene.
The acid labile group may substitute a hydrogen atom of the hydroxy group of hydroxystyrene, or may substitute a hydroxy group of hydroxyacenaphthylene.

Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like.
As radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), Examples include benzoyl peroxide and lauroyl peroxide.
Examples of the cationic polymerization initiator include sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, hypochlorous acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, tosylic acid and the like, BF ₃ , AlCl _3, TiCl _4, SnCl ₄ other Friedel-Crafts catalyst such _{as, I 2, (C 6 H} 5) 3 generated material susceptible to cationic as CCl can be exemplified.
The polymerization is preferably performed by heating from 50 ° C to 80 ° C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

A styrene monomer in which the hydrogen atom of the hydroxy group of hydroxystyrene is substituted with an acid labile group, an acetoxystyrene monomer, and an acenaphthylene monomer are polymerized, and after the polymerization, only acetoxystyrene is deprotected by the above alkaline hydrolysis to produce hydroxy. There is also a method of using styrene. Further, acetoxyacenaphthylene can be used instead of acetoxystyrene.
Ammonia water, triethylamine, etc. can be used as the base during the alkali hydrolysis. Moreover, as reaction temperature, it becomes like this. Preferably it is -20-100 degreeC, More preferably, it is 0-60 degreeC, As reaction time, Preferably it is 0.2-100 hours, More preferably, it is 0.5-20 hours.

After isolating the obtained polymer compound, acid labile groups represented by R ³ and R ⁴ in the general formula (1) can be introduced into the phenolic hydroxyl group. For example, it is possible to obtain a polymer compound in which the phenolic hydroxyl group is partially protected with an alkoxyalkyl group by reacting the phenolic hydroxyl group of the polymer compound with an alkenyl ether compound in the presence of an acid catalyst.
At this time, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate, and may be used alone or in combination. As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt and the like are preferable, and the amount used thereof is the phenolic hydroxyl group of the polymer compound to be reacted. It is preferable that a hydrogen atom is 0.1-10 mol% with respect to 1 mol of the whole hydroxyl group. The reaction temperature is preferably −20 to 100 ° C., more preferably 0 to 60 ° C., and the reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours.

It is also possible to obtain a polymer compound in which a phenolic hydroxyl group is partially protected with an alkoxyalkyl group by reacting with a polymer compound in the presence of a base using a halogenated alkyl ether compound.
At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, or dimethylsulfoxide, and may be used alone or in combination. As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable, and the amount used is 10 mol% or more of the hydrogen atom of the phenolic hydroxyl group of the polymer compound to be reacted with respect to 1 mol of the total hydroxyl group. Is preferred. The reaction temperature is preferably −50 to 100 ° C., more preferably 0 to 60 ° C., and the reaction time is preferably 0.5 to 100 hours, more preferably 1 to 20 hours.

Furthermore, introduction of an acid labile group represented by R ³ in the general formula (1) is possible by reacting a dialkyl dicarbonate compound or alkoxycarbonylalkyl halide with a polymer compound in a solvent in the presence of a base. It is.
At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran, or dimethylsulfoxide, and may be used alone or in combination. As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount used is 10 mol% or more of the hydrogen atom of the phenolic hydroxyl group of the original polymer compound with respect to 1 mol of the total hydroxyl group. Preferably there is. The reaction temperature is preferably 0 to 100 ° C, more preferably 0 to 60 ° C. The reaction time is preferably 0.2 to 100 hours, more preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride, tert-amyloxycarbonylmethyl chloride, tert-butoxycarbonylmethyl bromide, tert-butoxycarbonylethyl chloride and the like.
However, it is not limited to these synthesis methods.

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

  The organic solvent used in the positive 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 monomethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate, although lactones such as γ- butyl lactone, not being limited thereto.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types. 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 by mass, more preferably 400 to 800 parts by mass with respect to 100 parts by mass of the base resin.

As an acid generator blended in the positive resist material of the present invention,
i) Onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
ii) a diazomethane derivative represented by 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) sulfonic acid ester derivatives and the like.

(In the above formula, 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 or an oxoalkenyl group, and having 6 to 20 carbon atoms. An aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, part or all of hydrogen atoms of which may be substituted with an alkoxy group, etc. R ^101b and R ^101c And 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 aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkyl sulfonates such as 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate, tosylate, and benzene. Examples thereof include aryl sulfonates such as sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（上式中、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 above 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 group having 1 to 10 carbon atoms. Represents an alkylene group, 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 methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. Examples of K ⁻ include the same ones as described in the formulas (P1a-1) and (P1a-2).

（上式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は、炭素数１〜１２の直鎖状、分岐状もしく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 above formula, R ¹⁰⁵ and R ¹⁰⁶ 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 is shown.)

^Examples of the alkyl group represented by 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, Examples include amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group 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, an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, or an m-tert-butoxyphenyl group. And alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（上式中、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、Ｐ２式のものと同様である。）

(In the above formula, 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 aryl halide 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 when forming a cyclic structure, each of R ¹⁰⁸ and R ¹⁰⁹ is 1 carbon atom. And represents a linear or branched alkylene group of ˜6, and R ¹⁰⁵ is the same as that of the 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.

（上式中、Ｒ^101a、Ｒ^101bは前記と同様である。）

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

（上式中、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 above 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 part or all of the hydrogen atoms of these groups are Further, 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 straight chain having 1 to 8 carbon atoms. A branched or substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, wherein some 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 by an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a substituent which may be substituted by a chlorine atom or a fluorine atom Good.)

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.
In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

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

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

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

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

Examples of β-ketosulfone derivatives include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Examples of the disulfone derivative include disulfone derivatives such as diphenyl disulfone derivatives and dicyclohexyl disulfone derivatives.

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

Examples of sulfonic acid ester derivatives include 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy). Mention may be made of sulfonic acid ester derivatives such as benzene.
Further, 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-hydroxy Succinimide 2-chloroethane sulfonate, N-hydroxysuccinimide benzene sulfonate N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid Ester, N-hydroxymaleimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimide benzenesulfone Acid ester, N-hydroxyphthalimidomethanesulfonic acid ester, N-hydroxyphthalimidobenzenesulfonic acid ester, N-hydroxyl Phthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimidebenzenesulfonate, N-hydroxy-5-norbornene-2,3- Dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonate Examples thereof include sulfonic acid ester derivatives of N-hydroxyimide compounds.

  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, bisnaphthy 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.

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

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

The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably 80 mol%. Mol%. The substitution rate of the hydrogen atom of the carboxy group with an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.
In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

In the above 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. ^R207 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.

  In addition, the weight average molecular weight of the compound is preferably 100 to 1,000, and more preferably 150 to 800. The blending amount of the dissolution inhibitor is preferably 0 to 50 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the base resin. Can be used in combination. 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 in the positive resist material of the present invention, particularly in 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- Examples include amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.
Secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, Examples include dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.
Tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, tri Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, Examples thereof include N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.
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.

上式中、ｎは１、２又は３である。側鎖Ｘは同一でも異なっていても良く、下記一般式（Ｘ）−１〜（Ｘ）−３で表すことができる。側鎖Ｙは同一又は異種の、水素原子もしくは直鎖状、分岐状又は環状の炭素数１〜２０のアルキル基を示し、エーテル基もしくはヒドロキシル基を含んでもよい。また、Ｘ同士が結合して環を形成しても良い。 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.

In the above formula, n is 1, 2 or 3. The side chains X may be the same or different, and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y 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. Xs may be bonded to form a ring.

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

Specific examples of the compound represented by formula (B) -1 are given below.
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] amine 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-acetoxy) Ethoxycarbonyl) 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- (tetrahydrofurfuryl Oxycarbonyl) 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-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2- Toxiethyl) 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- (methoxy Carbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butyl Rubis [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.

（上式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は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、又はスルフィドを１個あるいは複数個含んでいても良い。） 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 and contains one or more carbonyl groups, ether groups, ester groups, or sulfides. You may leave.)

  (B) -2 is specifically 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, methoxy 2- (1-pyrrolidinyl) ethyl acetate, 4- [2- (methoxycarbonyloxy) ethyl] morpholine 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidino Methyl propionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropionic acid Methoxycarbonylmethyl, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholinopropion Tetrahydrofurfuryl acid, 3 Glycidyl piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-piperidinopropionic acid Cyclohexyl, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate , Ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

（上式中、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 general formulas (B) -3 to (B) -6 can be added.

(In the above formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear and branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the base 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-aminopropiononitrile, N, N -Bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopro Methyl onate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- ( 2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- (2 -Cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- ( 2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propyl) -N- (2 Cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofur Furyl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis ( 2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl Aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) ) Methyl 3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N -Cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl -N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl) -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, cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate, N, Cyanomethyl N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxyethyl) Cyanomethyl 3-aminopropionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate 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), 1-pyrrolidinepropionate cyanomethyl, 1-piperidinepropionate cyano Examples include methyl, 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 the basic compound in this invention is 0.001-2 mass part with respect to 100 mass parts of all base resins, Especially 0.01-1 mass part is suitable. If the blending amount is less than 0.001 part by mass, there is no blending effect, and if it exceeds 2 parts by mass, the sensitivity may decrease too much.

  As 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, for example, one or more compounds selected from the following groups I and II are used. However, the present invention is not limited to these. By blending this component, the PED 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.

However, in the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R ⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a — (R ⁴⁰⁹ ) h-COOR ′ group (R ′ is a hydrogen atom or —R ⁴⁰⁹ —COOH). Indicates. R ⁴⁰⁵ represents — (CH ₂ ) _i — (i represents an integer of 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 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 ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group. R ⁴⁰⁹ represents a linear or branched alkyl group, alkenyl group or —R ⁴¹¹ —COOH group having 1 to 10 carbon atoms. R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a —R ⁴¹¹ —COOH group. R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. u is 0 or 1. h is an integer of 1 to 4. j is 0 to 3, s1 to 4, and t1 to 4 are numbers satisfying s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, respectively, and having at least one hydroxyl group in each phenyl skeleton It is. u is an integer of 1-4. κ is a number that makes the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000. λ is a number that makes the compound of formula (A7) a weight average molecular weight of 1,000 to 10,000.

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

R ⁴⁰² , R ⁴⁰³ , and R ⁴¹¹ have the same meaning as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. s5 and t5 are numbers satisfying s5 + t5 = 5 with s5 ≧ 0 and t5 ≧ 0. h ′ is 0 or 1.

  Specific examples of this component include compounds represented by the following general formulas AI-1 to 14 and AII-1 to 10. However, it is not limited to these.

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

  The amount of the compound having a group represented by ≡C—COOH in the molecule is 0 to 5 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0 to 100 parts by mass of the base resin. 0.1-3 parts by mass, more preferably 0.1-2 parts by mass. If it exceeds 5 parts by mass, 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 Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF352 (Tochemputtoc), MegaFuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH -10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymers-KP-341, X-70-092, X-70-093 ( Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Co., Ltd.), among which FC430, 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 by mass or less, preferably 1 mass with respect to 100 parts by mass of the solid content in the resist material composition. Or less.

When the positive resist material of the present invention, for example, a chemically amplified positive resist material containing an organic solvent, a polymer compound represented by the general formula (1), an acid generator, and a basic compound is used for manufacturing various integrated circuits. Although not particularly limited, a known lithography technique can be applied.
For example, the positive resist material of the present invention is applied to a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, etc.) or a substrate for manufacturing a mask circuit (Cr , CrO, CrON, MoSi, etc.) by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., so that the coating film thickness is preferably 0.1 to 2.0 μm. Apply to. This is preferably pre-baked on a hot plate at 60 to 150 ° C. for 1 to 30 minutes, more preferably at 80 to 120 ° C. for 1 to 20 minutes. Next, a light source selected from high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, etc. Direct exposure is performed. In the case of light exposure, the exposure is preferably about 1 to 200 mJ / cm ² , more preferably about 10 to 100 mJ / cm ^2, and in the case of electron beam exposure, preferably 0. .1~100μC / cm ² or so, more preferably it is exposed so that 0.2~50μC / cm ² approximately. Next, post-exposure baking (PEB) is preferably performed on a hot plate at 60 to 150 ° C. for 1 to 30 minutes, more preferably at 80 to 120 ° C. for 1 to 20 minutes.

  Furthermore, it is preferably 0.1 to 5% by mass, more preferably 2 to 3% by mass, using an aqueous developer such as tetramethylammonium hydroxide (TMAH), preferably 0.1 to 3 minutes, more preferably By developing by a conventional method such as a dip method, a paddle method, or a spray method for 0.5 to 2 minutes, a portion irradiated with light dissolves in the developer and is not exposed. The desired portion is not dissolved, and the desired positive pattern is formed on the substrate. The resist material of the present invention is particularly suitable for fine patterning by far ultraviolet rays of 254 to 193 nm, vacuum ultraviolet rays of 157 nm, electron beams, soft X-rays, X-rays, excimer lasers, γ rays and synchrotron radiation among high energy rays. Is optimal.

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.
(Synthesis Example 1)
To a 1 L flask, 25.6 g of acenaphthylene, 106 g of 4-acetoxystyrene, 38.0 g of 4-t-butoxystyrene, and 200 g of toluene 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, 4.1 g of AIBN (azobisisobutylnitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 32 g of a white polymer. It was. This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added to perform a deprotection reaction, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain 128 g of a white polymer.

The obtained polymer was subjected to ¹³ C-NMR, ¹ H-NMR and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio Acenaphthylene: 4-hydroxystyrene: 4-t-butoxystyrene = 12.3: 65.7: 22.0
Weight average molecular weight (Mw) = 4400
Molecular weight distribution (Mw / Mn) = 1.82
This polymer compound is referred to as (Polymer 1).

(Synthesis Example 2)
25.6 g of acenaphthylene, 106 g of 4-acetoxystyrene, 38.0 g of 4-t-amyloxystyrene and 200 g of toluene as a solvent were added to a 1 L flask. 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, 4.1 g of AIBN (azobisisobutylnitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C. and reacted for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 32 g of a white polymer. It was. This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added to perform a deprotection reaction, and neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and precipitation, filtration and drying were performed in the same manner as above to obtain 123 g of a white polymer.

The obtained polymer was subjected to ¹³ C-NMR, ¹ H-NMR and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio Acenaphthylene: 4-hydroxystyrene: 4-t-amyloxystyrene = 13.0: 67.0: 20.0
Weight average molecular weight (Mw) = 3800
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 2).

(Synthesis Example 3)
To a 1 L flask, 60.8 g of acenaphthylene, 72 g of 4-hydroxystyrene and 80 g of 1,2-dichloroethane as a solvent were added. In a nitrogen atmosphere, 1 g of trifluoroboron was added as a polymerization initiator to the reaction vessel, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 2.5 L of methanol and 0.2 L of water, and the resulting white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 102 g of a white polymer. It was.

The obtained polymer was subjected to ¹³ C-NMR, ¹ H-NMR and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio Acenaphthylene: 4-hydroxystyrene = 40.4: 59.6
Weight average molecular weight (Mw) = 4300
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as (Polymer 3).

(Synthesis Example 4)
40 g of polymer 3 was dissolved in 400 ml of pyridine, and 22.6 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After making it react for 1 hour, when the reaction liquid was dripped at 3 L of water, white solid was obtained. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and dried in vacuo to obtain polymer 4.
Copolymerization composition ratio Acenaphthylene: 4-hydroxystyrene: 4-tbutoxycarbonylstyrene = 40.4: 47.1: 12.5
Weight average molecular weight (Mw) = 4400
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as (Polymer 4).

(Comparative Synthesis Example 1)
A two-component polymer was synthesized in the same manner as in the above synthesis example. The product names and analysis results are shown below.
Hydroxystyrene: Methacrylic acid 1-ethylcyclopentyl ester = 71: 29
Weight average molecular weight (Mw) = 16,100
Molecular weight distribution (Mw / Mn) = 1.70
This polymer compound is referred to as (Comparative Polymer 1).

(Comparative Synthesis Example 2)
Using a 2 L flask, 40 g of polyhydroxystyrene (Mw = 11000, Mw / Mn = 1.08) was dissolved in 400 mL of tetrahydrofuran, and 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether were added. The reaction was stopped by adding 2.5 g of aqueous ammonia (30%), the reaction solution was crystallized and precipitated with 5 L of acetic acid water, washed twice with water, and the resulting white solid was filtered. And dried under reduced pressure at 40 ° C. to obtain 47 g of a white polymer.

The obtained polymer was subjected to ¹³ C-NMR, ¹ H-NMR and GPC measurement, and the following analysis results were obtained.
Copolymerization composition ratio Hydroxystyrene: p-ethoxyethoxystyrene = 63.5: 36.5
Weight average molecular weight (Mw) = 13000
Molecular weight distribution (Mw / Mn) = 1.10
This polymer compound is referred to as (Comparative Polymer 2).

Examples 1-6 and Comparative Examples 1-2
Using the polymer compound synthesized above, a solution dissolved in the composition shown in Table 1 below was filtered through a 0.2 μm size filter to prepare a positive resist material.
Each composition in Table 1 is as follows.

Polymers 1, 2, and 4: From Synthesis Examples 1, 2, and 4,
Comparative polymer 1 and comparative polymer 2: From comparative synthesis example 1 and comparative synthesis example 2,
Organic solvent: PGMEA (propylene glycol methyl ether acetate)
Acid generator: PAG1, PAG2 (see structural formula below)

Basic compound: TMMEA (see the following structural formula)

Dissolution inhibitor: DRI1 (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate),
EL (ethyl lactate (ethyl lactate))

<Electron beam drawing evaluation>
In the drawing evaluation, a positive resist material was prepared by filtering a solution dissolved in the composition shown in Table 1 using a polymer compound synthesized above with a 0.2 μm size filter.
The obtained positive resist material was spin-coated using a clean track Mark5 (manufactured by Tokyo Electron) on a 6-inch diameter Si substrate treated with a vapor of hexamethyldisilazane (HMDS) and heated on a hot plate. A 200 nm resist film was prepared by pre-baking at 110 ° C. for 90 seconds. For this, drawing in a vacuum chamber was performed with an HV voltage of 50 keV using Hitachi Ltd. HL-800D.
Immediately after drawing, post-exposure baking (PEB) was performed at 110 ° C. for 90 seconds on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron), and paddle development was performed for 30 seconds with a 2.38 mass% TMAH aqueous solution. A positive pattern was obtained.
The obtained resist pattern was evaluated as follows.
The exposure amount for resolving 0.12 μm line and space at 1: 1 was taken as the sensitivity of the resist, and the edge roughness was observed by SEM.
Table 1 shows the results of resist composition, sensitivity and resolution in EB exposure.

Examples 7-9 and Comparative Examples 3-4
<Dry etching resistance evaluation>
In the dry etching resistance test, 10 g of PGMEA was dissolved in 2 g of each of the above polymers, 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 200 nm. Evaluation was carried out under such two conditions.

(1) Etching test with CHF ₃ / CF ₄ gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
60 sec

₍₂₎ Cl ₂ / BCl ₃ system using an etching test Nichiden Anelva Co., Ltd. dry etching apparatus L-507D-L Gas was calculated the difference between the film thickness of before and after etching of the polymer film.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 300W
Gap 9mm
Cl ₂ gas flow rate 30ml / min
BCl ₃ gas flow rate 30ml / min
CHF ₃ gas flow rate 100ml / min
O ₂ gas flow rate 2ml / min
60 sec

This evaluation shows that a film having a small difference in film thickness, that is, a film having a small decrease amount has etching resistance.
The results are shown in Table 2.

  From the results of Tables 1 and 2, the resist material using the polymer compound of the present invention satisfies sufficient resolution and sensitivity, the pattern shape after exposure is good, and the film thickness difference after etching is small. It can be seen that it has excellent dry etching resistance.

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.
For example, in the above description, the case where a chemically amplified positive resist material is formed by mixing a positive resist material with an acid generator, a basic compound, a dissolution inhibitor, and an organic solvent has been described. However, it is optional to add these additives and the like, and if necessary, surfactants and other additives may be added, or a part of the composition may be omitted.

Claims (6)

A polymer compound comprising at least a repeating unit by copolymerization represented by the following general formula (1) and having a weight average molecular weight in the range of 1,000 to 500,000.

(In the above formula, R ¹ is the same or non-identical hydrogen atom, hydroxy group, linear or branched alkyl group having 1 to 4 carbon atoms, acetoxy group, hydroxymethyl group, halogen atom, or —OR ⁴ ( In the formula, R ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms or an acid labile group.), M is 0 or a positive integer of 1 to 6, and n is An integer of 1 to 5, R ² represents a hydrogen atom or a methyl group, R ³ represents the same or non-identical acid labile group or a hydrogen atom, and when R ³ and R ⁴ coexist, At least one is an acid labile group, and when R ⁴ is not present, at least one of R ³ is an acid labile group, p and q each represents a mole fraction and is a positive number less than 1; (P + q ≦ 1 is satisfied)   A positive resist material comprising the polymer compound according to claim 1 as a base resin.   The positive resist composition according to claim 2, further comprising an organic solvent and an acid generator, and is of a chemical amplification type.   The positive resist material according to claim 2 or 3, further comprising a dissolution inhibitor.   The positive resist material according to claim 2, further comprising a basic compound and / or a surfactant.   A step of applying the positive resist material according to claim 2 on a substrate, a step of heat-treating the obtained coating film, and exposing the heat-treated coating film with a high energy beam A pattern forming method comprising a step and a step of developing the exposed coating film using a developer.