JP5223168B2 - Chemically amplified positive resist material and pattern forming method using the same - Google Patents

Description

The present invention relates to a chemical amplification positive resist materials及 beauty pattern forming method.

With the high integration and high speed of LSI, pattern rule miniaturization is progressing rapidly. ArF (193 nm) lithography was the main focus for 180 nm devices, but KrF (248 nm) lithography was extended, and the 150 nm generation and even 130 nm were mass-produced with KrF lithography. With the maturation of KrF lithography, acceleration of miniaturization was spurred. ArF started from fine processing of 90 nm, and mass production of 65 nm is approaching. F ₂ lithography, which was initially regarded as the 45nm technology, is due to various problems such as the quality of CaF ₂ single crystals used for projection lenses, changes in lens design associated with heart pellicle application, resist resolution, and etching resistance. The study was stopped and immersion lithography using an ArF excimer laser emerged rapidly. Further, in the 32 nm node beyond that, EB reduced projection exposure (PREVAIL, SCALPEL) and EUV using soft X-rays as light sources are listed as candidates. Conventionally, the resist polymer has changed greatly each time the wavelength of light changes. This is to ensure the necessary transmittance. For example, from g-line to i-line, the base of the photosensitizer changed from benzophenone to non-benzophenone type. The transition from i-line to KrF was accompanied by a change from a novolak resin that had been used for a long time to a hydroxystyrene system. From KrF to ArF, which is dramatic, a polymer having a double bond does not transmit light at all, so that it is changed to an alicyclic polymer. Further, in F ₂ , an alicyclic polymer into which fluorine atoms such as polytetrafluoroethylene were introduced was examined for further improvement in transmittance.

In the case of high energy rays having very short wavelengths such as EB and X-rays, light elements such as hydrocarbons used in resist materials hardly absorb, and polyhydroxystyrene-based resist materials have been studied.
The resist material for EB has been practically used for mask drawing. In recent years, mask manufacturing techniques have become a problem. A reduction projection exposure apparatus has been used since the era of g-line, and its reduction magnification has been 1/5. Recently, a 1/4 magnification has been used for both increasing the chip size and increasing the diameter of the projection lens. It has become like this. Not only reducing the line width due to the progress of microfabrication, but also reducing the line width by changing the magnification is a big problem for the mask manufacturing technique.
In order to increase the accuracy of the line width in the mask manufacturing exposure apparatus, an exposure apparatus using an electron beam (EB) has been used from an exposure apparatus using a laser beam. Further, by increasing the acceleration voltage in the electron gun of EB, further miniaturization becomes possible, so that 10 keV to 30 keV, and recently 50 keV is becoming mainstream.

  Here, as the acceleration voltage increases, lowering the sensitivity of the resist film has become a problem. When the acceleration voltage is improved, the influence of forward scattering in the resist film is reduced, so that the contrast of the electron drawing energy is improved and the resolution and dimensional controllability are improved. Since it passes, the sensitivity of the resist film decreases. Since the mask exposure machine exposes with one stroke of direct drawing, a decrease in sensitivity of the resist leads to a decrease in productivity, which is not preferable. Due to the demand for higher sensitivity, chemically amplified resist materials have been studied.

With the improvement of the acceleration voltage and the application of a high-contrast chemically amplified resist material, the size of 500 nm of 125 nm on the wafer can be accurately drawn with a 1/4 reduction. However, KrF extends the device size to 130 nm, ArF is said to be applied from 90 nm, and ArF immersion is predicted to be 65 nm. The limit of ArF immersion lithography using water is predicted to be 45 nm. The dimension on the mask at this time is 180 nm. At present, dimensional control of 180 nm is difficult only by improving the resolution of the resist film. In the case of photolithography, the thinning of the resist film greatly contributes to the improvement of the resolution. This is because the planarization of the device has progressed with the introduction of CMP or the like. In the case of mask production, the substrate is flat, and the thickness of the substrate to be processed (for example, Cr, MoSi, SiO ₂ ) is determined for light shielding rate and phase difference control. In order to reduce the thickness, a method for improving the dry etching resistance of the resist film is effective.

  Here, it is generally said that there is a correlation between the carbon density of the resist film and the dry etching resistance. In EB drawing that is not affected by absorption, a resist material based on a novolak polymer having excellent etching resistance has been developed. However, novolak polymers are difficult to control the molecular weight and dispersibility, and are considered not suitable materials for microfabrication. Here, the naphthalene ring is 94% with respect to the carbon density of 92% of the benzene ring, and the material containing the naphthalene ring is expected to improve the dry etching resistance. Originally, a naphthalene ring has high light absorption, and thus has not been attracting much attention in the past. However, it can be said that it is a promising material in ultrashort wavelength exposure without influence of absorption.

  Further, it is reported that the absorption of carbon atoms is small in difficult X-ray (EUV) exposure at a wavelength of 5 to 20 nm, which is expected as an exposure method in fine processing of 65 nm or later, along with ArF immersion exposure. . It has been found that increasing the carbon density is effective not only for improving dry etching resistance but also for improving transmittance in the soft X-ray wavelength region (N. Matsuzawa et. Al .; Jp. J. Appl. Phys., Vol.38 p7109-7113 (1999): Non-Patent Document 1).

  Conventionally, a polystyrene having a carboxyl group substituted with an acid labile group has been proposed (Microelectronic Engineering 1 (1983) 269-293 North Holland: Non-Patent Document 2). Since the carbonyl group of the carboxyl group and the benzene ring of styrene are conjugated, they have strong absorption at a wavelength of 248 nm and have not been used for lithography with a KrF excimer laser, but are highly transparent in EB and EUV exposure. A high-resolution resist material having high etching resistance and high dissolution contrast can be obtained by pendating a carboxyl group having high dissolution contrast with styrene having high etching resistance as a base skeleton. Furthermore, the etching resistance can be further increased by copolymerization with hydroxyvinylnaphthalene.

Japanese Patent Publication No. 7-69611 Jp. J. et al. Appl. Phys. Vol. 38 p7109-7113 (1999) Microelectronic Engineering 1 (1983) 269-293 North Holland

The present invention has been made in view of the above circumstances, and has higher resolution, exposure margin, smaller density difference, process adaptability than conventional positive resist materials, good pattern shape after exposure, and and to provide a indicates to chemical amplification positive resist materials及 beauty pattern forming method excellent etching resistance.

  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, a polymer obtained by copolymerizing styrene pendant with a carboxylate substituted with an acid labile group and a replaceable hydroxyvinylnaphthalene is used as a base resin of a positive resist material, particularly a chemically amplified positive resist material. It has been found that the present invention is extremely effective, and the present invention has been completed.

  That is, the present inventors first studied the copolymerization of hydroxyvinylnaphthalene. These have not only improved etching resistance, but also featured high dissolution contrast and reduced sparse dimensional difference by suppressing acid diffusion, which is more effective than hydroxystyrene substituted with acid labile groups. It was. This is considered to be because hydroxyvinylnaphthalene is a condensed hydrocarbon, and the bonding portion becomes rigid to the hydroxy group of the polymer, thereby suppressing the thermal motion in the molecule and suppressing acid diffusion.

  In view of the above, the present inventors further carried out copolymerization of styrene and hydroxyvinyl naphthalene pendant with a carboxylate substituted with an acid labile group to further suppress acid diffusion and improve dissolution contrast and etching resistance. By using the resulting polymer as a base resin for a positive resist material, especially a chemically amplified positive resist material, the alkali dissolution rate contrast before and after exposure is significantly high, and it has high sensitivity and high resolution. Finding that positive resist materials, especially chemically amplified positive resist materials, which have good pattern shapes and exhibit excellent etching resistance, are suitable for ultra-LSI manufacturing or photomask fine pattern forming materials. It is a thing.

  The positive resist material of the present invention has particularly high resist contrast, high sensitivity and high resolution, exposure margin, excellent process adaptability, and good pattern shape after exposure. In particular, the dimensional difference between the dense pattern and the sparse pattern is small, and more excellent etching resistance is exhibited. Therefore, since it has these excellent characteristics, it is very practical and is very effective as a resist material mask pattern forming material for VLSI.

（式中、Ｒ¹、Ｒ³は水素原子又はメチル基を表し、Ｒ²はｔｅｒｔ−ブチル基又はｔｅｒｔ−アミル基、Ｒ⁴は水素原子又は酸不安定基である。ｍ、ｎは１又は２である。０＜ａ／（ａ＋ｂ）≦０．７、０＜ｂ／（ａ＋ｂ）＜１．０の範囲である。）
請求項２：
更に、有機溶剤及び酸発生剤を含有する化学増幅型のレジスト材料であることを特徴とする請求項１記載のポジ型レジスト材料。
請求項３：
更に、溶解阻止剤を含有するものであることを特徴とする請求項１又は２記載のポジ型レジスト材料。
請求項４：
更に、添加剤として塩基性化合物及び／又は界面活性剤を配合してなることを特徴とする請求項１、２又は３記載のポジ型レジスト材料。
請求項５：
請求項１乃至４のいずれか１項記載のポジ型レジスト材料を基板上に塗布する工程と、加熱処理後、高エネルギー線で露光する工程と、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。 That is, the present invention provides the following chemically amplified positive resist material and a pattern forming method using the same.
Claim 1:
A polymer having a weight average molecular weight in the range of 1,000 to 500,000 represented by the following general formula (1) having a repeating unit a and a repeating unit b of a substituted hydroxyvinylnaphthalene is included as a base resin. A chemically amplified positive resist material .

(In the formula, R ^1, R ³ represents a hydrogen atom or a methyl group, R ² is tert- butyl or tert- amyl group, R ⁴ is hydrogen atoms Komata is an acid labile group .m, n is 1 or 2. 0 <a / (a + b) ≦ 0.7, 0 <b / (a + b) <1.0.
Claim 2 :
Furthermore, positive resist composition according to claim 1, characterized in that the resist material of chemical amplification type which contains an organic solvent and an acid generator.
Claim 3 :
Furthermore, positive resist composition according to claim 1 or 2, wherein the those containing a dissolution inhibitor.
Claim 4 :
The positive resist composition according to claim 1 , 2 or 3 , further comprising a basic compound and / or a surfactant as an additive.
Claim 5 :
Comprise the steps of: a positive resist composition of any one of claims 1 to 4 onto a substrate, heat treating, exposing the resist coating to high-energy radiation, and a step of developing with a developer A pattern forming method characterized by the above.

  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.

  The positive resist material of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, high sensitivity and high resolution, good pattern shape after exposure, and particularly suppresses the acid diffusion rate. Excellent etching resistance. Therefore, it is possible to obtain a positive resist material, particularly a chemically amplified positive resist material, which is particularly suitable for ultra-LSI manufacturing or as a photomask fine pattern forming material.

（式中、Ｒ¹、Ｒ³は水素原子又はメチル基を表し、Ｒ²は酸不安定基、Ｒ⁴は水素原子、アセチル基、アルキル基、又は酸不安定基である。ｍ、ｎは１又は２である。０＜ａ／（ａ＋ｂ）≦０．７、０＜ｂ／（ａ＋ｂ）＜１．０、好ましくは０．０５≦ａ／（ａ＋ｂ）≦０．６、０．１≦ｂ／（ａ＋ｂ）≦０．９の範囲である。） The polymer compound according to the present invention has a weight average molecular weight of 1,000 to 500,000, represented by the following general formula (1) having a repeating unit a and a repeating unit b of a substituted hydroxyvinylnaphthalene. Is.

Wherein R ¹ and R ³ represent a hydrogen atom or a methyl group, R ² represents an acid labile group, R ⁴ represents a hydrogen atom, an acetyl group, an alkyl group, or an acid labile group. 1 or 2. 0 <a / (a + b) ≦ 0.7, 0 <b / (a + b) <1.0, preferably 0.05 ≦ a / (a + b) ≦ 0.6, 0.1 ≦ b / (a + b) ≦ 0.9.)

  Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. It is done.

  Next, specific examples of the monomer for obtaining the repeating unit b can be given below.

As the monomer before polymerization, R may be the same as R ⁴ , or an acetyl group, which is converted into a hydroxy group by alkali hydrolysis after polymerization, and in some cases, the hydrogen atom of the hydroxy group is then converted to an acid-immobilized group. You may substitute by a stable group. R may be an acid labile group such as acetal, and may be converted to a hydroxy group by hydrolysis with a weak acid such as acetic acid or oxalic acid after polymerization.

  In the present invention, it is essential to have a and b repeating units, and the repeating unit c of (meth) acrylic acid ester substituted with an acid labile group represented by the following general formula (2), hydroxystyrene The repeating unit d can be additionally copolymerized.

（式中、Ｒ⁵、Ｒ⁷は水素原子又はメチル基を表し、Ｒ⁶、Ｒ⁸は酸不安定基、ｐは１又は２である。０≦ｃ／（ａ＋ｂ＋ｃ＋ｄ）≦０．７、０≦ｄ／（ａ＋ｂ＋ｃ＋ｄ）＜１．０の範囲である。）

(Wherein R ⁵ and R ⁷ represent a hydrogen atom or a methyl group, R ⁶ and R ⁸ are acid labile groups, and p is 1 or 2. 0 ≦ c / (a + b + c + d) ≦ 0.7, 0 ≦ d / (a + b + c + d) <1.0.)

  Monomers that give repeatable units other than the repeating units a, b, c, and d are hydroxystyrene, indene, hydroxyindene, styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, indole, acenaphthylene, norbornadiene, norbornene, tricyclo Decene, tetracyclododecene, methyleneindane, chromone, coumarone, (meth) acrylates having lactone, (meth) acrylic acid, 3-hydroxyadamantane (meth) acrylic acid ester, maleic anhydride, itaconic anhydride, maleimides And vinyl ethers.

  Furthermore, as a unit that can be copolymerized, an acid generator having a polymerizable unsaturated bond can be mentioned. A sulfonium salt is mentioned as an acid generator which has a polymerizable unsaturated bond, It can show to following General formula (3).

（式中、Ｒ¹¹は水素原子又はメチル基、Ｒ¹²はフェニレン基、−Ｏ−Ｒ¹⁵−、−Ｃ（＝Ｏ）−Ｘ−Ｒ¹⁵−である。Ｘは酸素原子又はＮＨ、Ｒ¹⁵は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基、フェニレン基、又はアルケニレン基であり、カルボニル基、エステル基又はエーテル基、ヒドロキシ基を含んでいてもよい。Ｒ¹³、Ｒ¹⁴は同一又は異種の炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６〜１２のアリール基もしくは炭素数７〜２０のアラルキル基、又はチオフェニル基を表す。Ｋ^-非求核性対向イオンを表す。）

Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a phenylene group, —O—R ¹⁵ —, —C (═O) —X—R ¹⁵ —, X is an oxygen atom or NH, R ¹⁵ linear 1-6 carbon atoms, branched or cyclic alkylene group, a phenylene group, or an alkenylene group, a carbonyl group, an ester group or an ether group, which may contain a hydroxy group .R ^13, R ¹⁴ is the same or different linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms. or an aralkyl group, or a thiophenyl group having a carbon number of 7 to 20 .K ^- represents a non-nucleophilic counter ion).

Various acid labile groups (acid labile groups in which hydrogen atoms of hydroxyl groups of R ² , R ⁴ , R ⁶ , and R ⁸ in general formulas (1) and (2) are substituted) are selected. However, they may be the same or different, and examples thereof include those represented by the following formulas (A-1) to (A-3).

In the formula (A-1), R ³⁰ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms. An oxoalkyl group or a group represented by the above general formula (A-3) is shown. Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, and 1-ethyl. Cyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, etc. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like. Specifically oxoalkyl group, 3-oxo-cyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolan-5-yl group. a1 is an integer of 0-6.

In the formula (A-2), R ³¹ and R ³² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, Examples thereof include an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ³³ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ³¹ and R ^32, R ³¹ and R ^33, R ³² and the R ³³ may bond together to form a ring with the carbon atoms to which they are attached, R ³¹ in the case of forming a ring, R ^32, R ³³ represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and preferably the ring has 3 to 10 carbon atoms, particularly 4 to 10 carbon atoms.

  Specific examples of the acid labile group of the above formula (A-1) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1 -Diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl Examples include 2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Furthermore, the substituent shown by following formula (A-1) -1-(A-1) -10 can also be mentioned.

Here, R ³⁷ is the same or different from each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ³⁸ is a hydrogen atom, or 1 to 1 carbon atoms. 10 linear, branched or cyclic alkyl groups.
R ³⁹ is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms which is the same or different from each other, or an aryl group having 6 to 20 carbon atoms.

  Of the acid labile groups represented by the above formula (A-2), examples of the linear or branched groups include those of the following formulas (A-2) -1 to (A-2) -35. be able to.

  Among the acid labile groups represented by the above formula (A-2), the cyclic ones include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2- Examples thereof include a methyltetrahydropyran-2-yl group.

  Further, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (A-2a) or (A-2b).

In the formula, R ⁴⁰ and R ⁴¹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁴⁰ and R ⁴¹ may be bonded to form a ring together with the carbon atom to which they are bonded. When forming a ring, R ⁴⁰ and R ⁴¹ are linear or branched having 1 to 8 carbon atoms. -Like alkylene group. R ⁴² is a straight-chain having 1 to 10 carbon atoms, branched or cyclic alkylene group, b1, d1 is 0 or 1 to 10, preferably 0 or an integer of 1 to 5, c1 is an integer of 1-7 . A represents a (c1 + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a hetero atom, Alternatively, a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, preferably, A is a divalent to tetravalent C1-20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms. In these groups, a hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group, or a halogen atom. C1 is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (A-2a) and (A-2b) include those represented by the following formulas (A-2) -36 to (A-2) -43.

Next, in the formula (A-3), R ³⁴ , R ³⁵ and R ³⁶ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, oxygen, sulfur, Hetero atoms such as nitrogen and fluorine may be contained, and R ³⁴ and R ³⁵ , R ³⁴ and R ³⁶ , R ³⁵ and R ³⁶ are bonded to each other, and a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. May be formed.

  As the tertiary alkyl group represented by the formula (A-3), a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, 2- (2- A methyl) adamantyl group, a 2- (2-ethyl) adamantyl group, a tert-amyl group, and the like.

Specific examples of the tertiary alkyl group include the following formulas (A-3) -1 to (A-3) -18.

In formulas (A-3) -1 to (A-3) -18, R ⁴³ is the same or different, linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or having 6 to 20 carbon atoms. An aryl group such as a phenyl group is shown. R ⁴⁴ and R ⁴⁶ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁴⁵ represents an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Furthermore, as shown in the following formulas (A-3) -19 and (A-3) -20, a divalent or higher valent alkylene group and an arylene group R ⁴⁷ are included, and the polymer within or between the molecules is crosslinked. May be.

In formulas (A-3) -19 and (A-3) -20, R ⁴³ is the same as described above, and R ⁴⁷ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, a phenylene group, or the like. And may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. e1 is an integer of 1 to 3.

Further, R ³⁰ , R ³³ and R ³⁶ in formulas (A-1), (A-2) and (A-3) are a phenyl group, a p-methylphenyl group, a p-ethylphenyl group, and p-methoxy. An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as a phenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a hydrogen atom having an oxygen atom in these groups or bonded to a carbon atom is substituted with a hydroxyl group Or an alkyl group represented by the following formula in which two hydrogen atoms are substituted with an oxygen atom to form a carbonyl group, or an oxoalkyl group.

  In particular, the acid labile group of the formula (A-3) is preferably a repeating unit having an exo structure represented by the following formula (A-3) -21.

（式中、Ｒ^c3は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ^c4〜Ｒ^c9及びＲ^c12、Ｒ^c13はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよい１価の炭化水素基を示し、Ｒ^c10、Ｒ^c11は水素原子を示す。あるいは、Ｒ^c4とＲ^c5、Ｒ^c6とＲ^c8、Ｒ^c6とＲ^c9、Ｒ^c7とＲ^c9、Ｒ^c7とＲ^c13、Ｒ^c8とＲ^c12、Ｒ^c10とＲ^c11又はＲ^c11とＲ^c12は互いに環を形成していてもよく、その場合には炭素数１〜１５のヘテロ原子を含んでもよい２価の炭化水素基を示す。またＲ^c4とＲ^c13、Ｒ^c10とＲ^c13又はＲ^c6とＲ^c8は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。Ｒ^c14は水素原子、炭素数１〜１５の直鎖状、分岐状又は環状のアルキル基を示す。また、本式により、鏡像体も表す。）

(In the formula, R ^c3 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{c4 to} R ^c9 and R ^c12. , R ^c13 each independently represents a hydrogen atom or a monovalent hydrocarbon group that may contain a heteroatom having 1 to 15 carbon atoms, and R ^c10 and R ^{c11 each} represent a hydrogen atom, or R ^c4 and R ^c5 , R ^c6 and R ^c8 , R ^c6 and R ^c9 , R ^c7 and R ^c9 , R ^c7 and R ^c13 , R ^c8 and R ^c12 , R ^c10 and R ^c11 or R ^c11 and R ^c12 may form a ring with each other In this case, it is a divalent hydrocarbon group that may contain a hetero atom having 1 to 15 carbon atoms, and R ^c4 and R ^c13 , R ^c10 and R ^c13, or R ^c6 and R ^c8 are bonded to adjacent carbon atoms. nothing binds not through with each other that bind, may form a double bond .R ^c14 is a hydrogen atom, of the straight, branched or cyclic It shows the alkyl group. The formula also represents enantiomer.)

  Here, an ester monomer for obtaining a repeating unit having an acid labile group having an exo structure represented by the general formula (A-3) -21 is disclosed in JP-A No. 2000-327633. Specific examples include the following, but are not limited thereto.

  Next, examples of the acid labile group represented by the formula (A-3) include an acid labile group having frangiyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the formula (A-3) -22. .

（式中、Ｒ^c14、Ｒ^c15はそれぞれ独立に炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。又は、Ｒ^c14、Ｒ^c15は互いに結合してこれらが結合する炭素原子と共に脂肪族炭化水素環を形成してもよい。Ｒ^c16はフランジイル、テトラヒドロフランジイル又はオキサノルボルナンジイルから選ばれる２価の基を示す。Ｒ^c17は水素原子又はヘテロ原子を含んでもよい炭素数１〜１０の直鎖状、分岐状又は環状の１価炭化水素基を示す。）

( ^Wherein R ^c14 and R ^c15 each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, or R ^c14 and R ^c15 are bonded to each other to form An aliphatic hydrocarbon ring may be formed together with the carbon atom to be bonded, R ^c16 represents a divalent group selected from ^frangyl , tetrahydrofurandiyl or ^{oxanorbornanediyl,} and R ^c17 may contain a hydrogen atom or a hetero atom. A good straight chain, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms is shown.)

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

  Examples of the trialkylsilyl group having 1 to 6 carbon atoms as the acid labile group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

  In order to synthesize these polymer compounds, as one method, styrene carboxylic acid substituted with an acid labile group represented by the following formula (1a), a monomer represented by the following formula (1b), and if necessary Hydroxystyrene, the unit of formula (2), the monomer that gives the unit of formula (3), and other copolymerizable monomers are subjected to heat polymerization in an organic solvent with the addition of a radical polymerization initiator. Molecular compounds can be obtained.

（式中、Ｒ¹〜Ｒ⁴、ｍ、ｎは上記の通り。）

(Wherein R ^{1 to} R ⁴ , m and n are as described above.)

In this case, assuming that the repeating unit of a, b, c, d and other repeating units are e, the ratio thereof is as follows.
When a + b + c + d + e = Z, 0 <a / Z ≦ 0.7, preferably 0.05 ≦ a / Z ≦ 0.6, more preferably 0.1 ≦ a / Z ≦ 0.5, 0 <b / Z <1.0, preferably 0.1 ≦ b / Z ≦ 0.9, more preferably 0.15 ≦ b / Z ≦ 0.85, 0 ≦ c / Z ≦ 0.7, preferably 0 ≦ c / Z ≦ 0.6, more preferably 0 ≦ c / Z ≦ 0.5, 0 ≦ d / Z <1.0, preferably 0 ≦ d / Z ≦ 0.6, more preferably 0 ≦ d / Z ≦ 0.5, 0 ≦ e / Z <0.7, preferably 0 ≦ e / Z ≦ 0.6, more preferably 0 ≦ e / Z ≦ 0.5.

  Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), benzoyl A peroxide, a lauroyl peroxide, etc. can be illustrated, Preferably it can superpose | polymerize by heating to 50-80 degreeC. The reaction time is 2 to 100 hours, preferably 5 to 20 hours.

  There is also a method in which acetoxyvinylnaphthalene is used in place of hydroxyvinylnaphthalene, and after polymerization, the acetoxy group is deprotected by alkali hydrolysis to form hydroxypolyvinylnaphthalene.

  Ammonia water, triethylamine, etc. can be used as the base during the alkali hydrolysis. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20 hours.

  It is also possible to introduce an acid labile group into the phenolic hydroxyl group after isolating the obtained polymer compound. 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 −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 100 hours, 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 −50 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

  Furthermore, an acid labile group can be introduced by reacting a dialkyl dicarbonate compound or alkoxycarbonylalkyl halide with a polymer compound in a solvent in the presence of a base.

  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 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time is 0.2 to 100 hours, 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, and tert-butoxy. Examples thereof include carbonylmethyl bromide and tert-butoxycarbonylethyl chloride.
However, it is not limited to these synthesis methods.

  The polymer compound of the present invention has a polystyrene-reduced weight average molecular weight of 1,000 to 500,000 by gel permeation chromatography (GPC), 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.

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.

  The polymer compound of the present invention is suitable as a base resin for a positive resist material. Such a polymer compound is used as a base resin, and an organic solvent, an acid generator, a dissolution inhibitor, a basic compound, and a surfactant. In the exposed part, the dissolution rate of the polymer compound in the developing solution is accelerated by a catalytic reaction, so that a highly sensitive positive resist is prepared. It can be a material, resist film has high dissolution contrast and resolution, exposure margin, excellent process adaptability, good pattern shape after exposure, and better etching resistance, In particular, since acid diffusion can be suppressed, the dimensional difference in density is small, and from these facts, it is highly practical and very effective as a resist material for VLSI. Rukoto can. In particular, when a chemically amplified positive resist material containing an acid generator and utilizing an acid catalyzed reaction is used, the sensitivity can be increased, and various characteristics are further improved and extremely useful. .

  Further, by adding a dissolution inhibitor to the positive resist material, the difference in dissolution rate between the exposed portion and the unexposed portion can be further increased, and the resolution can be further improved.

  Furthermore, by adding a basic compound, for example, the acid diffusion rate in the resist film can be suppressed to further improve the resolution, and by adding a surfactant, the coatability of the resist material can be further improved. Alternatively, it can be controlled.

  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, if necessary, Other components can be contained, but as the organic solvent used in the positive resist material of the present invention, particularly the chemically amplified positive resist material, a base resin, an acid generator, and other additives are dissolved. Any organic solvent can be used. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy 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, particularly 400 to 800 parts, with respect to 100 parts (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 of the following general formula (P2):
(Iii) a glyoxime derivative of the following general formula (P3),
(Iv) a bissulfone derivative of the following general formula (P4),
(V) a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
(Vi) β-ketosulfonic acid derivative,
(Vii) a disulfone derivative,
(Viii) a nitrobenzyl sulfonate derivative,
(Ix) sulfonic acid ester derivatives and the like.

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

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

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

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

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

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

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

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

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include 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.

（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。）

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

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

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

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

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

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

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

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

  Examples of onium salts include diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl. Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenyl nonafluorobutanesulfonate Sulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) ) Sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, di-p-toluenesulfonic acid Tylphenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ And onium salts such as methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] and 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate.

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

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

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

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

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

  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.

（但し、上記式中Ｒ²⁰¹、Ｒ²⁰²はそれぞれ水素原子、又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基を示す。Ｒ²⁰³は水素原子、又は炭素数１〜８の直鎖状又は分岐状のアルキル基又はアルケニル基、あるいは−（Ｒ²⁰⁷）_hＣＯＯＨを示す。Ｒ²⁰⁴は−（ＣＨ₂）_i−（ｉ＝２〜１０）、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す。Ｒ²⁰⁵が炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、カルボニル基、スルホニル基、酸素原子又は硫黄原子を示す。Ｒ²⁰⁶は水素原子、炭素数１〜８の直鎖状又は分岐状のアルキル基、アルケニル基又はそれぞれ水酸基で置換されたフェニル基又はナフチル基を示す。Ｒ²⁰⁷は炭素数１〜１０の直鎖状又は分岐状のアルキレン基を示す。Ｒ²⁰⁸は水素原子又は水酸基を示す。ｊは０〜５の整数である。ｕ、ｈは０又は１である。ｓ、ｔ、ｓ’、ｔ’、ｓ’’、ｔ’’はそれぞれｓ＋ｔ＝８、ｓ’＋ｔ’＝５、ｓ’’＋ｔ’’＝４を満足し、かつ各フェニル骨格中に少なくとも１つの水酸基を有するような数である。αは式（Ｄ８）、（Ｄ９）の化合物の分子量を１００〜１，０００とする数である。）

(In the above formulae, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or 1 to 8 carbon atoms. Represents a linear or branched alkyl group or alkenyl group, or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i — (i = 2 to 10), arylene having 6 to 10 carbon atoms. A group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or naphthyl group each substituted with a hydroxyl group, and R ²⁰⁷ represents a straight chain having 1 to 10 carbon atoms. Chain or branched alkyl R ²⁰⁸ represents a hydrogen atom or a hydroxyl group, j is an integer of 0 to 5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ Is a number satisfying s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and having at least one hydroxyl group in each phenyl skeleton. Α is a formula (D8 ), (D9) is a number that makes the molecular weight of the compound of 100 to 1,000.)

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

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

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

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

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

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

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

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

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

Specific examples of the compound represented by the general 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.

（上記式中、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よい。） Furthermore, 1 type, or 2 or more types of the basic compound which has the cyclic structure shown by the following general formula (B) -2 can also be added.

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

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

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

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

  Specific examples of the 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).

  In addition, the compounding quantity of the basic compound of this invention is 0.001-2 parts with respect to 100 parts of base resins, Especially 0.01-1 part is suitable. If the blending amount is less than 0.001 part, there is no blending effect, and if it exceeds 2 parts, the sensitivity may be too low.

  Examples of the compound having a group represented by ≡C—COOH in the molecule that can be added to the positive resist material of the present invention include one or more selected from the following [Group I] and [Group II]. Compounds can be used, but are 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.

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

(In the above 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 It 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 ′ represents a hydrogen atom or —R ⁴⁰⁹ —COOH). ⁴⁰⁵ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁴⁰⁶ represents an alkylene having 1 to 10 carbon atoms. Group, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, Phenyls each substituted with a hydroxyl group Or .R ⁴⁰⁹ showing a naphthyl group is a straight or branched alkyl or alkenyl group or -R showing a ⁴¹¹ -COOH groups .R ⁴¹⁰ is hydrogen atom or a straight-1 to 8 carbon atoms A chain or branched alkyl group, an alkenyl group, or —R ⁴¹¹ —COOH group, R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms, j is 0 to 3, s1 s4 and t1 to t4 satisfy s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, and s4 + t4 = 6, respectively, and each phenyl skeleton has at least one hydroxyl group, and κ is a formula (A6). Is a number with a weight average molecular weight of 1,000 to 5,000. Λ is a number with a weight average molecular weight of 1,000 to 10,000 for the compound of formula (A7).)

（上記式中、Ｒ⁴⁰²、Ｒ⁴⁰³、Ｒ⁴¹¹は上記と同様の意味を示す。Ｒ⁴¹²は水素原子又は水酸基を示す。ｓ５、ｔ５は、ｓ５≧０、ｔ５≧０で、ｓ５＋ｔ５＝５を満足する数である。ｈ’は０又は１である。） [Group II]
Compounds represented by the following general formulas (A11) to (A15).

(In the above formula, R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ have the same meaning as above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5 and t5 are s5 ≧ 0, t5 ≧ 0, and s5 + t5 = 5. (It is a satisfactory number. H ′ is 0 or 1.)

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

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

(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. Α and κ have the same meanings as described above. .)

  In addition, the compound which has group shown by (≡C-COOH) in the said molecule | numerator can be used individually by 1 type or in combination of 2 or more types.

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

  To the positive resist material of the present invention, a dissolution control agent comprising a compound having a plurality of bisphenol groups substituted with an acid labile group represented by the following general formula (BP) -1 can be added.

（上記式中、Ｒ⁵⁰¹は同一又は異種の水素原子、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、炭素数６〜１０のアリール基、炭素数２〜１０のアルケニル基又はハロゲン原子であり、Ｒ⁵⁰²は同一又は異種の独立して水素原子又は酸不安定基であり、ｎは２〜４の整数である。Ｚは式中の炭素原子を合わせて炭素数５〜４０の環状構造を有するアルキル基、有橋環式炭化水素基、又は縮合多環式炭化水素基であり、硫黄などのヘテロ原子を有していてもよい。）

(In the above formula, R ⁵⁰¹ is the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. Or a halogen atom, R ⁵⁰² is the same or different independently a hydrogen atom or an acid labile group, and n is an integer of 2 to 4. Z is a carbon number of 5 to 5 including the carbon atoms in the formula. An alkyl group having 40 cyclic structures, a bridged cyclic hydrocarbon group, or a condensed polycyclic hydrocarbon group, which may have a heteroatom such as sulfur.)

As the acid labile group in the general formula (BP) -1, those selected from the above-described formulas (A-1) to (A-3) can be used. Specific examples of the compound represented by the general formula (BP) -1 include the following (R ⁵⁰¹ and R ⁵⁰² are as described above).

  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, F-top EF301, EF303, EF352 (Tokemuputtokutsu), MegaFuck F171, F172, F173 (Dainippon Ink Chemical Co., Ltd.), Florard FC-430, FC-431, FC-4430 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106, Fluorosurfactants such as Surfynol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass), organosiloxane polymers KP-341, X-70-092, X-7 -093 (Shin-Etsu Chemical), acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Co., Ltd.), among which FC-430, FC-4430, Surflon S-381, Surfynol E1004, KH-20, KH-30 are preferred. These can be used alone or in combination of two or more.

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

  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 an integrated circuit manufacturing substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflection film, etc.) or a mask circuit manufacturing substrate (Cr , CrO, CrON, MoSi, etc.) by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., so that the coating film thickness is 0.1 to 2.0 μm. To do. This is pre-baked on a hot plate at 60 to 150 ° C. for 10 seconds to 30 minutes, preferably 80 to 120 ° C. for 30 seconds to 20 minutes. Next, a target pattern is exposed through a predetermined mask or directly with a light source selected from high energy rays such as ultraviolet rays, far ultraviolet rays, electron beams, soft X-rays, X-rays, excimer lasers, gamma rays, and synchrotron radiation. . It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , or 0.1 to 100 μC, preferably about 0.5 to 50 μC. Next, post-exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 30 minutes, preferably 70 to 130 ° C. for 30 seconds to 20 minutes.

  Further, 0.1 to 5% by mass, preferably 2 to 3% by mass of a developer of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) is used for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes. By developing by a conventional method such as a dip method, a paddle method, or a spray method, a portion irradiated with light is dissolved in the developer, and a portion not exposed to light is not dissolved. The desired positive pattern is formed on the top. The resist material of the present invention is particularly suitable for fine patterning by electron beam, soft X-ray, X-ray, γ-ray and synchrotron radiation among high energy rays.

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

[Synthesis Example 1]
To a 2 L flask, 18.3 g of styrene-4-carboxylate t-amyl, 99.2 g of 6-ethoxyethoxy-2-vinylnaphthalene, 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 blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Styrene-4-carboxylic acid t-amyl: 6-hydroxy-2-vinylnaphthalene = 18: 82
Weight average molecular weight (Mw) = 12,000
Molecular weight distribution (Mw / Mn) = 1.75
This polymer compound is referred to as (Polymer 1).

[Synthesis Example 2]
To a 2 L flask was added 20.4 g of t-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene = 20: 80
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.84
This polymer compound is referred to as (Polymer 2).

[Synthesis Example 3]
To a 2 L flask were added 26.0 g of cyclohexyloxymethyl styrene-4-carboxylate, 64.0 g of 7-ethoxyethoxy-2-vinylnaphthalene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
Styrene-4-carboxylic acid cyclohexyloxymethyl: 7-hydroxy-2-vinylnaphthalene = 20: 80
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as “ Reference polymer 3”.

[Synthesis Example 4]
To a 2 L flask, 24.5 g of t-butyl styrene-4-carboxylate, 48.4 g of 6-ethoxyethoxy-2-vinylnaphthalene, 34.5 g of 4-ethoxyethoxystyrene, and 100 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 blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 4-hydroxystyrene = 24: 40: 36
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.84
This polymer compound is referred to as (Polymer 4).

[Synthesis Example 5]
To a 2 L flask was added 15.3 g of tert-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, 1.7 g of indene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: indene = 15: 80: 5
Weight average molecular weight (Mw) = 6,800
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as (Polymer 5).

[Synthesis Example 6]
To a 2 L flask, 24.2 g of tert-butyl styrene-4-carboxylate, 78.6 g of 6-ethoxyethoxy-2-vinylnaphthalene, 15.3 g of 7-ethoxyethoxyindene, 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 blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 7-hydroxyindene = 20: 65: 15
Weight average molecular weight (Mw) = 6,800
Molecular weight distribution (Mw / Mn) = 1.77
This polymer compound is referred to as (Polymer 6).

[Synthesis Example 7]
Add 24.2 g of t-butyl styrene-4-carboxylate, 78.6 g of 6-ethoxyethoxy-2-vinylnaphthalene, 17.6 g of 3-hydroxy-1-adamantyl methacrylate, and 200 g of toluene as a solvent to a 2 L flask. did. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
Copolymer composition ratio (molar ratio)
T-Butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 3-hydroxy-1-adamantyl methacrylate = 20: 65: 15
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.73
This polymer compound is referred to as (Polymer 7).

[Synthesis Example 8]
In a 2 L flask, 25.5 g of tert-butyl styrene-4-carboxylate, 66.6 g of 6-ethoxyethoxy-2-vinylnaphthalene, 3-oxo-2,7-dioxatricyclomethacrylate [4.2.1 .0 ^4,8] nonan-9-yl 22.4 g, toluene was added 200g as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-Butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate = 25: 55: 20
Weight average molecular weight (Mw) = 8,200
Molecular weight distribution (Mw / Mn) = 1.78
This polymer compound is referred to as (Polymer 8).

[Synthesis Example 9]
Add 13.5 g of methacrylic acid-2-ethyl-2-adamantane, 10.2 g of tert-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, and 200 g of toluene as a solvent to a 2 L flask. did. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
2-ethyl-2-adamantane methacrylate: t-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene = 10: 10: 80
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.73
This polymer compound is referred to as (Polymer 9).

[Synthesis Example 10]
To a 2 L flask were added 18.2 g of tert-butyl styrene-4-carboxylate, 9.7 g of 6-ethoxyethoxy-2-vinylnaphthalene, 81.6 g of 6-acetoxy-2-vinylnaphthalene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in a solution of 500 mL of isopropyl alcohol, and the resulting white solid is dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran. 12 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-ethoxyethoxy-2-vinylnaphthalene: 6-hydroxy-2-vinylnaphthalene = 15: 8: 77
Weight average molecular weight (Mw) = 7,900
Molecular weight distribution (Mw / Mn) = 1.88
This polymer compound is referred to as (Polymer 10).

[Synthesis Example 11]
To a 2 L flask was added 18.2 g of tert-butyl styrene-4-carboxylate, 7.4 g of 6-methoxy-2-vinylnaphthalene, 81.6 g of 6-acetoxy-2-vinylnaphthalene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in a solution of 500 mL of isopropyl alcohol, and the resulting white solid is dissolved again in 50 mL of methanol and 80 mL of tetrahydrofuran. 12 g of triethylamine and 10 g of water are added, and the acetyl group is deprotected at 70 ° C. for 5 hours. And neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-methoxy-2-vinylnaphthalene: 6-hydroxy-2-vinylnaphthalene = 15: 8: 77
Weight average molecular weight (Mw) = 7,100
Molecular weight distribution (Mw / Mn) = 1.81
This polymer compound is referred to as (Polymer 11).

[Synthesis Example 12]
To a 2 L flask was added 15.3 g of tert-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, 3.9 g of 2-vinylnaphthalene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 2-vinylnaphthalene = 15: 80: 5
Weight average molecular weight (Mw) = 8,900
Molecular weight distribution (Mw / Mn) = 1.72
This polymer compound is referred to as (Polymer 12).

[Synthesis Example 13]
To a 2 L flask was added 15.3 g of tert-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, 5.1 g of 2-vinylanthracene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 2-vinylanthracene = 15: 80: 5
Weight average molecular weight (Mw) = 9,100
Molecular weight distribution (Mw / Mn) = 1.75
This polymer is designated as (Polymer 13).

[Synthesis Example 14]
To a 2 L flask was added 15.3 g of tert-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, 5.7 g of 1-vinylpyrene, and 200 g of toluene as a solvent. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 1-vinylpyrene = 15: 80: 5
Weight average molecular weight (Mw) = 7,300
Molecular weight distribution (Mw / Mn) = 1.66
This polymer compound is referred to as (Polymer 14).

[Synthesis Example 15]
In a 2 L flask, 20.4 g of t-butyl styrene-4-carboxylate, 96.8 g of 6-ethoxyethoxy-2-vinylnaphthalene, 22.1 g of 4-acryloxyoxyphenyldiphenylsulfonium, perfluorononafluorobutanesulfonate, solvent As a result, 200 g of toluene was added. The reaction vessel was cooled to −70 ° C. in a nitrogen atmosphere, and vacuum degassing and nitrogen blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
T-butyl styrene-4-carboxylate: 6-hydroxy-2-vinylnaphthalene: 4-oxyphenyldiphenylsulfonium acrylate, perfluorononafluorobutanesulfonate = 20: 73: 7
Weight average molecular weight (Mw) = 8,400
Molecular weight distribution (Mw / Mn) = 1.81
This polymer compound is referred to as (Polymer 15).

[Comparative Synthesis Example 1]
To a 2 L flask, 21.4 g of t-butyl methacrylate, 67.2 g of 4-ethoxyethoxystyrene, 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 blowing were repeated three times. After raising the temperature to room temperature, 8.5 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, and the temperature was raised to 60 ° C., followed by reaction for 15 hours. This reaction solution is precipitated in 1 L of isopropyl alcohol, and the resulting white solid is filtered, then dissolved again in 400 mL of methyl ethyl ketone, 12 g of oxalic acid and 10 g of water are added, and the ethoxyethoxy group is deprotected at 60 ° C. for 5 hours. And liquid separation washing was performed 3 times with 1 L of water. The reaction solution was concentrated and then dissolved in 200 mL of acetone, followed by precipitation, filtration and drying at 60 ° C. as described above to obtain a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
4-hydroxystyrene: tert-butyl methacrylate = 69: 31
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 4-polyhydroxystyrene (Mw = 11,000, Mw / Mn = 1.08) was dissolved in 400 mL of tetrahydrofuran, 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether were added, The mixture was reacted at room temperature for 1 hour, 2.5 g of aqueous ammonia (30%) was added to stop the reaction, and the reaction solution was crystallized and precipitated with 5 L of acetic acid water, and further washed twice with water. The white solid was filtered and dried under reduced pressure at 40 ° C. to obtain 47 g of a white polymer.
When the obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, the following analysis results were obtained.
Copolymer composition ratio (molar ratio)
4-hydroxystyrene: 4-ethoxyethoxystyrene = 63.5: 36.5
Weight average molecular weight (Mw) = 13,000
Molecular weight distribution (Mw / Mn) = 1.10
This polymer compound is referred to as (Comparative Polymer 2).

[Examples and Comparative Examples]
Using the polymer compound synthesized above, a positive resist material was prepared by filtering a solution dissolved in the composition shown in Table 1 through a 0.2 μm size filter.
Each composition in Table 1 is as follows.
Polymers 1 to 15: Polymers obtained in Synthesis Examples 1 to 15 Comparative polymers 1 and 2: Polymers obtained in Comparative Synthesis Examples 1 and 2 Organic solvent: PGMEA (propylene glycol monomethyl ether acetate), EL (ethyl lactate)
Acid generator: PAG1, PAG2 (see structural formula below)
Basic compounds: Quencher1, Quencher2, Quencher3 (see the structural formula below)
Dissolution inhibitor: DRI 1 (see the following structural formula), dissolution control agent: DRR 1 (see the following structural formula)

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 through a 0.2 μm size filter using the polymer compound synthesized above.
The obtained positive resist material was spin-coated on a Si substrate having a diameter of 6 inches φ using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.), prebaked on a hot plate at 110 ° C. for 90 seconds, and 100 nm. A resist film was prepared. To this, drawing in a vacuum chamber was performed at an HV voltage of 50 keV using HL-800D manufactured by Hitachi, Ltd.
Immediately after drawing, post-exposure baking (PEB) at 90 ° C. for 90 seconds on a hot plate using a clean track Mark 5 (manufactured by Tokyo Electron Ltd.) and paddle development with 2.38 mass% TMAH aqueous solution for 30 seconds And a positive pattern was obtained.
The obtained resist pattern was evaluated as follows.
The minimum dimension at the exposure amount for resolving 0.12 μm line and space at 1: 1 was taken as the resolution, and the edge roughness of 120 nm LS was measured by SEM.
Table 1 shows the results of resist composition, sensitivity and resolution in EB exposure.

Evaluation of dry etching resistance 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. Membranes were evaluated under the following two conditions.
(1) Etching test with CHF ₃ / CF ₄ -based gas Using a dry etching apparatus TE-8500P manufactured by Tokyo Electron Co., Ltd., the difference in film thickness of the polymer film before and after etching was determined.
Etching conditions are as shown below.
Chamber pressure 40.0Pa
RF power 1,000W
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. 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 with a small difference in film thickness, that is, a film with a small amount of decrease has etching resistance.
The results of dry etching resistance are shown in Table 2.

  From the results of Tables 1 and 2, the resist material using the polymer compound of the present invention has sufficient resolution and sensitivity, and has excellent dry etching resistance due to a small difference in film thickness after etching. I found out.

Claims (5)

A polymer having a weight average molecular weight in the range of 1,000 to 500,000 represented by the following general formula (1) having a repeating unit a and a repeating unit b of a substituted hydroxyvinylnaphthalene is included as a base resin. A chemically amplified positive resist material .

(In the formula, R ^1, R ³ represents a hydrogen atom or a methyl group, R ² is tert- butyl or tert- amyl group, R ⁴ is hydrogen atoms Komata is an acid labile group .m, n is 1 or 2. 0 <a / (a + b) ≦ 0.7, 0 <b / (a + b) <1.0. Furthermore, positive resist composition according to claim 1, characterized in that the resist material of chemical amplification type which contains an organic solvent and an acid generator. Furthermore, positive resist composition according to claim 1 or 2, wherein the those containing a dissolution inhibitor. The positive resist composition according to claim 1 , 2 or 3 , further comprising a basic compound and / or a surfactant as an additive. Comprise the steps of: a positive resist composition of any one of claims 1 to 4 onto a substrate, heat treating, exposing the resist coating to high-energy radiation, and a step of developing with a developer A pattern forming method characterized by the above.