JP4365172B2 - Polymer compound, resist material, and pattern forming method using the same - Google Patents

Description

  The present invention relates to a polymer material useful as a base resin for a resist material suitable for microfabrication technology, particularly a chemically amplified resist material, a resist material, and a pattern forming method using the same.

In recent years, along with higher integration and higher speed of LSI, pattern rule miniaturization has been demanded, and technology for miniaturization has been rapidly progressing.
The background of the rapid progress in miniaturization includes high NA (Numerical Aperture) of the projection lens, improved performance of the resist material, shorter exposure light wavelength, and the like. Among these, regarding the performance improvement such as higher resolution and higher sensitivity of the resist material, the chemically amplified positive resist material catalyzed by the acid generated by light irradiation has excellent performance, particularly in deep ultraviolet lithography. It became a mainstream resist material (see, for example, Patent Documents 1 and 2).

  Moreover, the shortening of the wavelength from exposure using i-line (wavelength 365 nm) to exposure using a KrF excimer laser (wavelength 248 nm) as a light source has brought about a great change. Resist materials for exposure (hereinafter referred to as KrF) using a KrF excimer laser as a light source start from the 0.30 micron process, and go through the 0.25 micron rule to the current mass production of the 0.18 micron rule. It has been developed to apply. Furthermore, the investigation below the 0.10 micron rule has begun, and the momentum of miniaturization is further accelerated.

  Furthermore, in the exposure using an ArF excimer laser (wavelength 193 nm) as a light source, it is expected that the refinement of the design rule will be 0.09 μm or less. However, conventionally used resins such as novolak resins and polyvinylphenols have very strong absorption near a wavelength of 193 nm, and are difficult to use as a base resin for resist materials. Therefore, in order to ensure transparency and necessary dry etching resistance, acrylic resins and cycloolefin-based alicyclic resins have been studied (for example, see Patent Documents 3 to 5).

Furthermore, with respect to exposure using an F ₂ laser (wavelength of 157 nm) as a light source, miniaturization of a design rule of 0.07 μm or less is expected. However, it becomes increasingly difficult to ensure transparency, and acrylic resin, which is a base resin of resist material for exposure (hereinafter referred to as ArF) using an ArF excimer laser as a light source, does not transmit light at all. Even in the olefin system, those having a carbonyl bond were found to have strong absorption. It was also found that polyvinylphenol, which is the base resin of the resist material for KrF, has an absorption window in the vicinity of a wavelength of 160 nm and slightly improves the transmittance, but is far from a practical level.

In order to improve the transmittance in the vicinity of the wavelength (157 nm) of the F ₂ laser, one effective method is to reduce the number of carbonyl groups and carbon-carbon double bonds having strong absorption in the vicinity. is there. However, more recent research results have shown that the introduction of fluorine atoms into the base resin is effective in improving the transmittance in the wavelength region of exposure using an F ₂ laser as a light source. For example, a copolymer of tert-butyl α-trifluoromethyl acrylate and 5- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-2-norbornene, and tert-butyl α-trifluoromethyl acrylate It has been reported that a resist material using a copolymer of styrene and 4- (2-hydroxy-2,2-bistrifluoromethyl) methylstyrene as a base resin improves the absorbance of the polymer to about 3 at a wavelength of 157 nm. (For example, refer nonpatent literature 1.).

However, in order to obtain a rectangular pattern with a film thickness of 2000 mm or more by exposure using an F ₂ laser as a light source, it is considered that an absorbance of 2 or less is necessary, so the above resin is still insufficient in transparency. On the other hand, an extremely highly transparent resin having an absorbance of 1 or less has been proposed (for example, see Non-Patent Document 2). This polymer is not only highly transparent but also excellent in substrate adhesion and affinity with a developer, but its dry etching resistance is decisively lower than general-purpose polymers for KrF and ArF. ing

JP-B-2-27660 JP 63-27829 A JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/333981 Pamphlet “Polymer design for 157 nm chemically amplified resists”, Proc. SPIE. 4345, pp. 273-284, 2001. “Synthesis of novel fluoropolymers for 157 nm photo-sensitives by cyclo-polymerization”, Proc. SPIE. 4690, pp. 76-83, 2002.

The present invention has been made in view of the above circumstances, and has excellent transparency in etching at a wavelength of 300 nm or less, particularly at a wavelength of 160 nm or less, for example, exposure using an F ₂ laser as a light source, and etching resistance to dry etching. It is an object of the present invention to provide a novel polymer compound useful as a base resin of a resist material having excellent development characteristics and a resist material and a pattern forming method using the same.

（式中、Ｒ¹及びＲ²は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。上記一般式（１ｂ）ではＲ¹とＲ²が結合してもよく、その場合はＲ¹とＲ²は炭素数１〜２０の直鎖状、分枝状、環状のアルキレン基又はフッ素化アルキレン基を表す。Ｒ³は水素原子、水酸基、又は水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１５の直鎖状、分枝状、環状のアルキル基、アルコキシ基、アシルオキシ基、アルキルチオ基、アシルアミノ基、アルキルスルフォニルアミノ基、を表す。ただし、Ｒ^２が水素原子である場合は、Ｒ^３は水酸基とはならない。） In order to solve the above problems, according to the present invention, at least a compound having one or more partial structures represented by the following general formula (1a) or (1b) is included as a repeating unit, and the weight average molecular weight is 1,000. polymer compounds characterized in that in a range of 500,000 is Ru are provided.

(Wherein R ¹ and R ² are a hydrogen atom, an acid labile group, a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. The above general formula (1b ), R ¹ and R ² may be bonded, in which case R ¹ and R ² represent a linear, branched or cyclic alkylene group or fluorinated alkylene group having 1 to 20 carbon atoms. ³ is a hydrogen atom, a hydroxyl group, or a linear, branched, or cyclic alkyl group, an alkoxy group, an acyloxy group having 1 to 15 carbon atoms in which part or all of the hydrogen atoms may be substituted with a halogen atom, Represents an alkylthio group, an acylamino group, or an alkylsulfonylamino group, provided that when R ² is a hydrogen atom, R ³ is not a hydroxyl group.)

Such a polymer compound has high transparency and high etching resistance even in exposure at a wavelength of 200 nm or less, particularly 160 nm or less, and can suppress hydrophobicity while containing fluorine atoms. It has excellent development characteristics. Furthermore, the polymer compound containing, as a repeating unit, a compound having one or more partial structures represented by the general formula (1a) or (1b) can be selected by selecting an optimal compound as R ^{1 to} R ^3.・ Performance such as hydrophilicity can be adjusted optimally.

（式中、Ｒ¹〜Ｒ³は前記と同じである。Ｒ⁴は単結合、もしくは水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１０の直鎖状、分枝状、環状のアルキレン基を表す。Ｒ⁵は水素原子、もしくは水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１０の直鎖状、分枝状、環状のアルキル基を表す。ａ１〜ａ４はそれぞれ０又は１である。） The polymer compound containing as a repeating unit a compound having one or more partial structures represented by the general formula (1a) or (1b) is at least one of the following general formulas (2a) to (2d). compounds intended containing as a repeating unit and even not preferable more.

(In the formula, R ^{1 to} R ³ are the same as defined above. R ⁴ is a single bond or a straight chain having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with halogen atoms, Represents a branched or cyclic alkylene group, and R ⁵ represents a hydrogen atom or a linear, branched or cyclic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms. And a1 to a4 are each 0 or 1.)

The polymer compound containing any one or more compounds represented by the general formulas (2a) to (2d) as a repeating unit has particularly high etching resistance against dry etching, and has transparency in exposure at a wavelength of 160 nm or less. In addition, the hydrophobicity is sufficiently suppressed. Furthermore, the compounds represented by the above general formulas (2a) to (2d) can be selected as R ^{1 to} R ⁵ depending on the application, and the performance can be adjusted.

（式中、Ｒ⁶及びＲ¹³は水素原子、フッ素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ⁷は水素原子、酸不安定基、密着性基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ⁸はメチレン基又は酸素原子である。Ｒ⁹〜Ｒ¹²は、水素原子、フッ素原子、−Ｒ¹⁶−Ｏ−Ｒ⁷、−Ｒ¹⁶−ＣＯ₂Ｒ⁷、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ¹⁴及びＲ¹⁶は単結合、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキレン基又はフッ素化アルキレン基である。Ｒ⁹〜Ｒ¹²は結合してエーテル環、ラクトン環、炭化水素環を形成しても良い。Ｒ¹⁵はフッ素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のフッ素化アルキル基である。ｂは０又は１、ｃは１又は２、ｄは０〜４の整数であり、１≦ｃ＋ｄ≦５である。） Then, the polymer compound of the present invention, further, and even not preferable those containing as a repeating unit of any one or more of the compounds represented by the following general formula (3a) ~ (3e).

(Wherein R ⁶ and R ¹³ are a hydrogen atom, a fluorine atom, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. R ⁷ is a hydrogen atom, an acid, or an acid. An unstable group, an adhesive group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ⁸ is a methylene group or an oxygen atom, and R ^{9 to} R. ¹² represents a hydrogen atom, a fluorine atom, —R ¹⁶ —O—R ⁷ , —R ¹⁶ —CO ₂ R ⁷ , or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl. R ¹⁴ and R ¹⁶ are a single bond, a linear, branched, or cyclic alkylene group or a fluorinated alkylene group having 1 to 20 carbon atoms, and R ^{9 to} R ¹² are bonded to ether. ring, lactone ring, may also form a hydrocarbon ring .R ¹⁵ is fluorine atom, or a straight, minutes Jo, the .b a cyclic fluorinated alkyl group is 0 or 1, c is 1 or 2, d is 0 to 4 integer, a 1 ≦ c + d ≦ 5.)

  As described above, when one or more compounds represented by the general formulas (3a) to (3e) are included as a repeating unit, the polymer compound is used as a base resin of a resist material. Performances such as dissolution contrast and substrate adhesion can be improved.

Furthermore, the present invention is a polymer compound of the present invention, that provides a resist material characterized in that those comprising as a base resin.

  As described above, the polymer compound of the present invention has high transparency at a wavelength of 300 nm or less, particularly 160 nm or less, and high etching resistance against dry etching. Is suppressed. Therefore, a resist material using this as a base resin has very good resolution, and can be suitably used as a fine pattern forming material for manufacturing VLSI in particular.

Then, in the resist material of the present invention, furthermore, it has the preferred to the chemical amplification type positive resist composition containing an organic solvent and an acid generator.

  In this way, by using the polymer compound as a base resin and further blending an organic solvent and an acid generator, the dissolution rate of the polymer compound in the developer is accelerated by an acid catalyst reaction in the exposed portion. It can be an extremely sensitive chemically amplified positive resist material, and is extremely useful as a highly sensitive positive resist material required in recent years.

In this case, the resist material of the present invention, furthermore, a basic compound, a dissolution inhibitor, Ru can be those containing any one or more surfactants.

  Of these, by adding a basic compound, the resolution can be further improved by, for example, suppressing the rate of acid diffusion in the resist film, and by adding a dissolution inhibitor, The difference in dissolution rate from the exposed portion can be further increased, and the coating property of the resist material can be further improved or controlled by adding a surfactant.

Such a resist material of the present invention includes at least a step of applying the resist material on a substrate, a step of exposing to high energy rays through a photomask after heat treatment, and a step of developing using a developer. by performing, Ru can be used as a method for forming a pattern on a semiconductor substrate or a mask substrate.
Needless to say, development may be performed after the post-exposure heat treatment, and various other processes such as an etching process, a resist removal process, and a cleaning process may be performed. Moreover, exposure can be performed with high energy rays, such as a wavelength 100-300 nm band or a 1-30 nm band, for example.

In this case, the high-energy-line, KrF excimer laser, ArF excimer laser, F ₂ laser, Ar ₂ laser, Ru can be either soft X-ray.

  The resist material containing the polymer compound of the present invention as a base resin is sensitive to these high energy rays and has excellent sensitivity at a wavelength of 300 nm or less, particularly 200 nm or less, and even 160 nm or less.

The resist material containing the polymer compound of the present invention as a base resin is sensitive to high energy rays, has excellent sensitivity at a wavelength of 300 nm or less, particularly 200 nm or less, and also has transparency of the resin, substrate adhesion, and development. Sufficient dry etching resistance can be ensured without impairing liquid affinity. Therefore, the resist material containing the polymer compound of the present invention as a base resin is a resist material that has a small absorption particularly at the exposure wavelength of the F ₂ laser due to these characteristics, and is fine and perpendicular to the substrate. A pattern can be easily formed, and is therefore suitable as a material for forming a fine pattern for VLSI manufacturing.

Hereinafter, the present invention will be described in more detail.
One of the major problems with conventional resist materials for exposure (hereinafter referred to as F ₂ ) using an F ₂ laser as a light source is that the transmittance of the base resin is low. As described above, since a resin containing a substituent such as a carbonyl group or an aromatic ring has a strong absorption in the vicinity of an exposure wavelength with an F ₂ laser, it is possible to realize an absorbance of 2 or less required for an F ₂ resist. difficult. Although it is possible to improve the resin transmittance by introducing fluorine atoms into the resin, increasing the fluorine content to ensure transparency generally increases the water repellency of the resin. Developer affinity is reduced.
Therefore, as a result of intensive studies, the present inventors have introduced a hydrophilic fluorine-containing unit as a partial structure into a compound contained as a repeating unit of a polymer compound, thereby improving substrate adhesion and developer compatibility. Transparency can be improved without impairing the properties, and in particular, a polymer compound containing a compound obtained by introducing a hydrophilic fluorine-containing unit into a norbornene ring or a tetracyclododecene ring as a repeating unit has a wavelength of 300 nm or less In particular, in the wavelength of 160 nm or less, the inventors have found that it is excellent in transparency, substrate adhesion, and developer compatibility, and that sufficient etching resistance to dry etching can be ensured, thereby completing the present invention.

（式中、Ｒ¹及びＲ²は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。上記一般式（１ｂ）ではＲ¹とＲ²が結合してもよく、その場合はＲ¹とＲ²は炭素数１〜２０の直鎖状、分枝状、環状のアルキレン基又はフッ素化アルキレン基を表す。Ｒ³は水素原子、水酸基、又は水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１５の直鎖状、分枝状、環状のアルキル基、アルコキシ基、アシルオキシ基、アルキルチオ基、アシルアミノ基、アルキルスルフォニルアミノ基、を表す。ただし、Ｒ^２が水素原子である場合は、Ｒ^３は水酸基とはならない。） That is, the polymer compound of the present invention contains at least a compound having at least one partial structure represented by the following general formula (1a) or (1b) as a repeating unit, and has a weight average molecular weight of 1,000 to 500,000. Of the range.

(Wherein R ¹ and R ² are a hydrogen atom, an acid labile group, a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. The above general formula (1b ), R ¹ and R ² may be bonded, in which case R ¹ and R ² represent a linear, branched or cyclic alkylene group or fluorinated alkylene group having 1 to 20 carbon atoms. ³ is a hydrogen atom, a hydroxyl group, or a linear, branched, or cyclic alkyl group, an alkoxy group, an acyloxy group having 1 to 15 carbon atoms in which part or all of the hydrogen atoms may be substituted with a halogen atom, Represents an alkylthio group, an acylamino group, or an alkylsulfonylamino group, provided that when R ² is a hydrogen atom, R ³ is not a hydroxyl group.)

In the partial structure of the compound contained as the repeating unit of the polymer compound, it is considered that the fluorinated alkyl moiety contributes significantly to excellent transparency, and the hydroxyl group and the ketone group contribute to good development characteristics. Therefore, a polymer compound containing a compound having such a partial structure as a repeating unit has high transparency and high etching resistance in exposure at a wavelength of 300 nm or less, particularly at a wavelength of 160 nm or less. While containing atoms, hydrophobicity can be suppressed. Furthermore, the polymer compound containing, as a repeating unit, a compound having one or more partial structures represented by the general formula (1a) or (1b) can be selected by selecting an optimal compound as R ^{1 to} R ^3.・ Performance such as hydrophilicity can be adjusted optimally.
When R ² is a hydrogen atom and R ³ is a hydroxyl group, when the polymer compound is used as a base resin of a resist material, the developer solubility is higher than necessary, and the film in the unexposed area since Verification is hard to use as a resist becomes significant, when R ² is a hydrogen atom, R ³ should not be a hydroxyl group.

（式中、Ｒ¹〜Ｒ³は前記と同じである。Ｒ⁴は単結合、もしくは水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１０の直鎖状、分枝状、環状のアルキレン基を表す。Ｒ⁵は水素原子、もしくは水素原子の一部又は全部がハロゲン原子で置換されていてもよい炭素数１から１０の直鎖状、分枝状、環状のアルキル基を表す。ａ１〜ａ４はそれぞれ０又は１である。） And as a high molecular compound which contains as a repeating unit the compound which has one or more partial structures shown by the said General formula (1a) or (1b), any of following General formula (2a)-(2d) is shown. It is preferable that one or more compounds are contained as a repeating unit.

(In the formula, R ^{1 to} R ³ are the same as defined above. R ⁴ is a single bond or a straight chain having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with halogen atoms, Represents a branched or cyclic alkylene group, and R ⁵ represents a hydrogen atom or a linear, branched or cyclic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms. And a1 to a4 are each 0 or 1.)

As described above, the polymer compound containing any one or more compounds represented by the general formulas (2a) to (2d) as a repeating unit has an etching resistance to dry etching because the compound of the repeating unit includes an alicyclic portion. It is particularly high and has high transparency to radiation having a wavelength of 300 nm or less, particularly 160 nm or less, and the hydrophobicity is sufficiently suppressed. Furthermore, the compounds represented by the above general formulas (2a) to (2d) can be selected as R ^{1 to} R ⁵ depending on the application, and the performance can be adjusted.

The linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms of R ¹ and R ² are methyl group, ethyl group, propyl group, isopropyl group, n-propyl group, and n-butyl group. , Sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, 2-ethylhexyl group, n-octyl group, 1-adamantyl group, 2-adamantyl group, (2-adamantyl) methyl group Etc., and those having 1 to 12 carbon atoms, particularly those having 1 to 10 carbon atoms are preferred.
The linear, branched, and cyclic fluorinated alkyl groups having 1 to 20 carbon atoms of R ¹ and R ² are those in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms. Is used.
Furthermore, as the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms of R ¹ and R ² , those in which one hydrogen in the alkyl group is eliminated are used.

Next, the acid labile group represented by R ¹ and R ² will be described.
Various acid labile groups are selected, and groups such as those represented by the following general formulas (4) to (6) are particularly preferable.

In the above general formula (4), R ¹⁷ represents a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above general formula (6). .
Specific examples of the tertiary alkyl group for R ¹⁷ include tert-butyl, tert-amyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, -Butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group and the like can be mentioned.
Specific examples of the oxoalkyl group for R ¹⁷ include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-5-oxooxolan-4-yl group. It is done.
e is an integer of 0-6.

  Specific examples of the acid labile group of the general formula (4) 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.

Next, in the general formula (5), R ¹⁸ and R ¹⁹ 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 Examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, and n-octyl group.
R ²⁰ 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, and is a linear, branched or cyclic alkyl group. In addition, examples in which a part of these hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like can be given, and specific examples thereof include the following substituted alkyl groups.

R ¹⁸ and R ¹⁹ , R ¹⁸ and R ²⁰ , R ¹⁹ and R ²⁰ may be bonded to each other to form a ring, and in the case of forming a ring, R ¹⁸ , R ¹⁹ and R ²⁰ are each A linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms is shown.

Specific examples of the linear or branched group of the acid labile group represented by the general formula (5) include the following groups.

Further, among the acid labile groups represented by the general formula (5), specific examples of the cyclic group include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, and tetrahydropyran-2-yl. Group, 2-methyltetrahydropyran-2-yl group and the like.
In particular, the group represented by the general formula (5) is preferably a methoxymethyl group, an ethoxyethyl group, a butoxyethyl group, or an ethoxypropyl group.

Next, in the general formula (6), R ²¹ , R ²² and R ²³ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, oxygen, Hetero atoms such as sulfur and nitrogen may be contained, and R ²¹ and R ²² , R ²¹ and R ²³ , R ²² and R ²³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.
The tertiary alkyl group represented by the general formula (6) includes a tert-butyl group, a triethylcarbyl group, a 1-ethylnorbornyl group, a 1-methylcyclohexyl group, a 1-ethylcyclopentyl group, 2- (2 -Methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group and the like, and the groups shown below can be specifically exemplified.

Here, R ²⁴ represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Examples thereof include a butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. R ²⁵ represents a linear, branched, or cyclic alkyl group having 2 to 6 carbon atoms, specifically, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or n-pentyl. Group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. R ²⁶ and R ²⁷ represent a hydrogen atom, a monovalent hydrocarbon group which may contain a C 1-6 hetero atom, or a monovalent hydrocarbon group which may contain a C 1-6 hetero atom, May be linear, branched or cyclic. In this case, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and —OH, —OR ²⁸ , —O—, —S—, —S (═O) —, —NH ₂ , —NHR ²⁸ , —N (R ²⁸ ) ₂ , —NH—, —NR ²⁸ — may be contained or interposed. R ²⁸ represents an alkyl group having 1 to 5 carbon atoms. Specific examples of R ²⁶ and R ²⁷ include methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n- Examples include a hexyl group, a methoxy group, a methoxymethoxy group, an ethoxy group, and a tert-butoxy group.

The acid labile groups represented by the general formulas R ¹ and R ² , linear, branched, and cyclic alkyl groups or fluorinated alkyl groups having 1 to 20 carbon atoms are active hydrogens in the monomer state. Polymerization can be performed after protecting the atoms, or polymerization can be performed while R ¹ and R ² remain as hydrogen atoms, and modification can be performed later. In the case of retrofitting, for example, sodium hydride or potassium tert-butoxide can be reacted with a polymer to anionize an acidic hydroxyl group and react with a corresponding halide, but this is not a limitation. .

  Examples of the compound having one or more partial structures represented by the general formula (1a) include the following compounds in addition to the compounds represented by the general formulas (2a) and (2b). It is not limited.

（式中、Ｒ^１は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ is a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

  The fluorine-containing cyclic unit having one or more partial structures represented by the general formula (1b) preferably has a structure corresponding to the general formulas (2c) and (2d). In addition to the compounds represented by the general formulas (2c) and (2d), the following compounds can be specifically exemplified, but are not limited thereto.

（式中、Ｒ^１及びＲ²は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ and R ² are a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

In the compound represented by the above general formula (2a), R ³ is a hydrogen atom, a hydroxyl group, or a linear or branched group having 1 to 15 carbon atoms in which part or all of the hydrogen atoms may be substituted with halogen atoms. Represents a branched or cyclic alkyl group, an alkoxy group, an acyloxy group, an alkylthio group, an acylamino group or an alkylsulfonylamino group, specifically, a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, decyl group, pentadecyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, methoxy group, ethoxy group, Propyloxy group, isopropoxy group, 2,2,2-trifluoroethoxy group, 1,1,1,3,3,3-hexafluoro Sopropoxy group, formyloxy group, acetoxy group, trifluoroacetoxy group, methylthio group, ethylthio group, t-butylthio group, formylamino group, acetylamino group, trifluoroacetylamino group, N-formyl-N-methylamino group, Examples include, but are not limited to, a methanesulfonylamino group, a trifluoromethanesulfonylamino group, and an N-methanesulfonyl-N-methylamino group.
The following compounds can be illustrated as typical examples of the compound of the general formula (2a), but are not limited thereto.

（式中、Ｒ^１は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ is a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

  Specific examples of the compound represented by the general formula (2b) include, but are not limited to, the following.

（式中、Ｒ^１は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ is a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

  Specific examples of the compound represented by the general formula (2c) include the following compounds, but are not limited thereto.

（式中、Ｒ^１及びＲ²は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ and R ² are a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

  Specific examples of the compound represented by the general formula (2d) include the following compounds, but are not limited thereto.

（式中、Ｒ^１及びＲ²は水素原子、酸不安定基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。）

(In the formula, R ¹ and R ² are a hydrogen atom, an acid labile group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms.)

  The fluorine-containing cyclic monomer corresponding to the compounds represented by the general formulas (2a) and (2b) is 1,1,3,3,3-pentafluoro-2-propenyl for the raw aldehyde or ketone compound as shown below. It can be produced by an addition reaction of an oxymetal compound.

（式中、Ｒ¹〜Ｒ⁵、ａ１及びａ２は前記と同様である。Ｍはアルカリ金属またはハロゲン化マグネシウムを表す。）

(In the formula, R ^{1 to} R ⁵ , a1 and a2 are the same as described above. M represents an alkali metal or a magnesium halide.)

  In this reaction, a starting carbonyl compound is reacted with a 1,1,3,3,3-pentafluoro-2-propenyloxy metal compound in a general-purpose solvent such as tetrahydrofuran (hereinafter abbreviated as THF). The 1,1,3,3,3-pentafluoro-2-propenyloxy metal compound is prepared from 1,1,1,3,3,3-hexafluoro-2-propanol as a raw material. = Li) (Organic Synthesis, 76, 151, 1998). Purification can be performed by a conventional method such as distillation, recrystallization, or chromatography depending on the physical properties of the product.

As shown below, the monomer corresponding to the compound of the general formula (2a) or (2b) is a 4-membered ring hemiacetal (2a ′) or (2b ′), hydrate, during the reaction or after the post-treatment. (2a ″) or (2b ″), or a mixture thereof may be obtained. When obtained as a hydrate (2a ″) or (2b ″), it can be regenerated to the original monomer compound by heat dehydration.
In addition, compounds (2a ′), (2b ′), (2a ″) and (2b ″) can also be used as monomers for polymer production, but compounds (2a ′), (2 The compounds produced using 2b ′), (2a ″) and (2b ″) as monomers have a higher solubility in the developer than necessary, and the weight produced using the monomer of the present invention is high. Compared with coalescence, when used as a base resin of a resist material, there is a disadvantage that film unsettled portions are noticeable and difficult to use.

（式中、Ｒ⁴及びＲ⁵、ａ１及びａ２は前記と同様である。）

(Wherein R ⁴ and R ⁵ , a1 and a2 are the same as described above.)

Formula (2c) and monomer compound corresponding to a compound represented by (2d), the monomeric compounds corresponding to the as shown in the following (2a) or (2b) and R ³ - the anion equivalent R ³ -Z It can be produced by reaction. In this reaction as well, the target compound can be obtained by reacting the starting carbonyl compound with the anion equivalent R ³ -Z in a general-purpose solvent, and purifying by a conventional method such as recrystallization, chromatography, distillation, etc., if necessary. .

（式中Ｒ^１〜Ｒ⁵、ａ３及びａ４は前記と同様である。Ｒ³−ＺはＲ³−アニオン等価体を表す。）

(.R ³ -Z is wherein ^R 1 ^{~R 5,} a3 and a4 is the same as above R ³ - represents an anion equivalent.)

  In the polymer compound of the present invention, the following general formulas (3a) to (3) are added to the repeating units represented by the general formulas (2a) to (2d) in order to improve performance such as resist dissolution contrast and substrate adhesion. Any one or more compounds represented by 3e) can be copolymerized and used.

（式中、Ｒ⁶及びＲ¹³は水素原子、フッ素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ⁷は水素原子、酸不安定基、密着性基、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ⁸はメチレン基又は酸素原子である。Ｒ⁹〜Ｒ¹²は、水素原子、フッ素原子、−Ｒ¹⁶−Ｏ−Ｒ⁷、−Ｒ¹⁶−ＣＯ₂Ｒ⁷、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基又はフッ素化アルキル基である。Ｒ¹⁴及びＲ¹⁶は単結合、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキレン基又はフッ素化アルキレン基である。Ｒ⁹〜Ｒ¹²は結合してエーテル環、ラクトン環、炭化水素環を形成しても良い。Ｒ¹⁵はフッ素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のフッ素化アルキル基である。ｂは０又は１、ｃは１又は２、ｄは０〜４の整数であり、１≦ｃ＋ｄ≦５である。）

(Wherein R ⁶ and R ¹³ are a hydrogen atom, a fluorine atom, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. R ⁷ is a hydrogen atom, an acid, or an acid. An unstable group, an adhesive group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ⁸ is a methylene group or an oxygen atom, and R ^{9 to} R. ¹² represents a hydrogen atom, a fluorine atom, —R ¹⁶ —O—R ⁷ , —R ¹⁶ —CO ₂ R ⁷ , or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl. R ¹⁴ and R ¹⁶ are a single bond, a linear, branched, or cyclic alkylene group or a fluorinated alkylene group having 1 to 20 carbon atoms, and R ^{9 to} R ¹² are bonded to ether. ring, lactone ring, may also form a hydrocarbon ring .R ¹⁵ is fluorine atom, or a straight, minutes Jo, the .b a cyclic fluorinated alkyl group is 0 or 1, c is 1 or 2, d is 0 to 4 integer, a 1 ≦ c + d ≦ 5.)

The acid labile group represented by R ⁷ in the above general formula is the same as described for R ¹ and R ² .
The adhesive group represented by R ⁷ in the above general formula is variously selected, and is particularly preferably a group represented by the following general formula.

（式中、Ｒ²⁹はメチレン基又は酸素原子である。）

(In the formula, R ²⁹ is a methylene group or an oxygen atom.)

  In addition to the above units, the polymer compound of the present invention can introduce the following adhesive units from the viewpoint of improving the adhesiveness.

（式中、Ｒ³⁰及びＲ³¹は水素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基である。Ｒ³²はメチレン基又は酸素原子である。）

(In the formula, R ³⁰ and R ³¹ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³² is a methylene group or an oxygen atom.)

  Furthermore, the polymer compound of the present invention can introduce the following units from the viewpoint of improving the transparency of the resin.

（式中、Ｒ³³〜Ｒ³⁷は水素原子、フッ素原子、又は炭素数１〜４のフッ素化されたアルキル基であり、Ｒ³⁴〜Ｒ³⁷のうち少なくとも１個以上のフッ素原子を含む。Ｒ³⁸及びＲ³⁹は水素原子、メチル基、又はトリフルオロメチル基である。）

(In the formula, R ^{33 to} R ³⁷ are a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, and include at least one fluorine atom of R ^{34 to} R ^{37. 38} and R ³⁹ are a hydrogen atom, a methyl group, or a trifluoromethyl group.)

Next, a method for synthesizing the polymer compound of the present invention will be described.
When synthesizing the polymer compound of the present invention, monomers corresponding to units containing a partial structure represented by the general formula (1a) or (1b), general formulas (2a) to (2d), (3a), (3b) ), (3d), a monomer corresponding to the unit of (3e), and if necessary, one or more of the aforementioned adhesion improving monomer or transparency improving monomer are mixed with a polymerization solvent, and a catalyst is added. In some cases, the polymerization reaction is carried out with heating or cooling. The polymerization reaction is also governed by the type of initiator (or catalyst), the initiation method (light, heat, radiation, plasma, etc.), the polymerization conditions (temperature, pressure, concentration, solvent, additives), etc. In the polymerization of the polymer compound of the present invention, a radical polymerization initiated by a radical derived from 2,2′-azobisisobutyronitrile (hereinafter abbreviated as AIBN) or a catalyst such as alkyl lithium is used. In general, ionic polymerization (anionic polymerization) or the like is generally used, and these polymerizations can be carried out in accordance with conventional methods.

  Although it does not specifically limit as an initiator at the time of performing radical polymerization reaction, For example, AIBN, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis Azo compounds such as (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4,4-trimethylpentane), tert-butylperoxypivalate, lauroyl peroxide, benzoyl peroxide, tert- Peroxide compounds such as butyl peroxylaurate, persulfates such as potassium persulfate as water-soluble initiators, and peroxides such as potassium persulfate and hydrogen peroxide and sodium sulfite Examples are redox initiators comprising a combination of reducing agents. The amount of the polymerization initiator used can be appropriately changed according to the type, polymerization reaction conditions, etc., but is usually 0.001 to 5% by weight, particularly 0.01 to 2%, based on the total amount of monomers to be polymerized. % By weight is employed.

  In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those that do not inhibit the polymerization reaction are preferable, and typical examples include esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, toluene, xylene, cyclohexane, and the like. Aliphatic or aromatic hydrocarbons, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ether solvents such as diethyl ether, dioxane and THF can be used. These solvents can be used alone or in admixture of two or more. Moreover, you may use together well-known molecular weight regulators, such as dodecyl mercaptan.

  The reaction temperature of the polymerization reaction is appropriately changed depending on the kind of the polymerization initiator or the boiling point of the solvent, and is usually preferably 20 to 200 ° C, particularly preferably 50 to 140 ° C. The reaction vessel used for such a polymerization reaction is not particularly limited.

  As a method for removing the organic solvent or water as a medium from the polymer solution or dispersion according to the present invention thus obtained, any known method can be used. For example, reprecipitation filtration may be used. Alternatively, there is a method such as heating distillation under reduced pressure.

  The polymer compound preferably has a weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 100,000.

In the polymer compound of the present invention, U1 represents a repeating unit having a partial structure represented by the general formulas (1a) and (1b) or a unit represented by the general formulas (2a) to (2d), and the general formula (3a) When the unit represented by (3e) is U2, and the other adhesion improving unit and the unit for improving transparency are U3,
-(U1) u1- (U2) u2- (U3) u3-
It can be expressed as. Here, when u = u1 + u2 + u3,
0 <u1 / u ≦ 1, preferably 0.2 <u1 / u <0.6,
0 ≦ u2 / u <1, preferably 0.2 <u2 / u <0.8,
0 ≦ u3 / u ≦ 0.3, preferably 0 ≦ u3 / u <0.1
It is preferable that

  The polymer compound of the present invention can be used as a base resin for resist materials, particularly chemically amplified, particularly chemically amplified positive resist materials. However, the polymer physical properties, thermal properties, alkali solubility, and other physical properties of the film can be used. Other polymer compounds can be mixed for the purpose of changing. In this case, the range of the polymer compound to be mixed is not particularly limited, but it can be mixed with a known polymer compound for resist in an arbitrary range.

The resist material of the present invention is preferably a chemically amplified positive resist material containing an organic solvent and an acid generator.
Further, the resist material of the present invention may further contain a basic compound, a dissolution inhibitor, a surfactant, and other components.

  The organic solvent used in the present invention may be any as long as it can dissolve the base resin, acid generator, other additives, and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol. Alcohols, 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 monoethyl ether acetate, lactic acid Ethyl, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropion Ethyl acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate.

These organic solvents can be used alone or in combination of two or more, but are not limited thereto. In the present invention, among these organic solvents, propylene glycol monomethyl acetate, which is a safety solvent, and mixed solvents thereof, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the acid generator in the resist component Are preferably used.
In addition, the usage-amount of the said organic solvent is 300-10,000 parts with respect to 100 parts (parts by weight, the same hereafter) of base resin, Especially 500-5,000 parts are preferable.

  Next, as an acid generator used in the present invention, an onium salt of the following general formula (7), a diazomethane derivative of the formula (8), a glyoxime derivative of the formula (9), a β-ketosulfonic acid derivative, a disulfone derivative, Examples thereof include nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, imidoyl sulfonate derivatives and the like.

(R ⁴⁰ ) _f M ⁺ K ⁻ (7)
(Wherein, R ⁴⁰ each represent 1 to 12 linear, branched, cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having a carbon number of 7 to 12, M ⁺ Represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and f is 2 or 3.)

Examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ⁴⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-oxocyclopentyl group, a norbornyl group and an adamantyl group. Etc.
Examples of the aryl group having 6 to 20 carbon atoms of R ⁴⁰ include phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert. -Alkoxyphenyl groups such as butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, etc. And an alkylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms of R ⁴⁰ include a benzyl group and a phenethyl group.
Also, K ^- of the 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, Examples thereof include aryl sulfonates such as benzene sulfonate, 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ⁴¹及びＲ⁴²は炭素数１〜１２の直鎖状、分枝状、環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２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。）

(Wherein R ⁴¹ and R ⁴² 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 12 carbon atoms, or carbon atoms. 7 to 12 aralkyl groups are shown.)

Examples of the linear, branched, and cyclic alkyl groups having 1 to 12 carbon atoms of R ⁴¹ and R ⁴² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, and a norbornyl group. And an adamantyl group.
Examples of the linear, branched or cyclic halogenated alkyl group having 1 to 12 carbon atoms of R ⁴¹ and R ⁴² include trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,2 -A trichloroethyl group, a nonafluorobutyl group, etc. are mentioned.
Examples of the aryl group having 6 to 12 carbon atoms of R ⁴¹ and R ⁴² include a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethyl Examples thereof include an alkylphenyl group such as a phenyl group.
Examples of the halogenated aryl group having 6 to 12 carbon atoms of R ⁴¹ and R ⁴² include a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group and the like.
Examples of the aralkyl group having 7 to 12 carbon atoms of R ⁴¹ and R ⁴² include a benzyl group and a phenethyl group.

（式中、Ｒ⁴³〜Ｒ⁴⁵は炭素数１〜１２の直鎖状、分枝状、環状のアルキル基又はハロゲン化アルキル基、炭素数６〜１２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。Ｒ⁴⁴及びＲ⁴⁵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、Ｒ⁴⁴及びＲ⁴⁵はそれぞれ炭素数１〜６の直鎖状、分枝状のアルキレン基を示す。）

(In the formula, R ^{43 to} R ⁴⁵ 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 12 carbon atoms, or carbon. Represents an aralkyl group having a number of 7 to 12. R ⁴⁴ and R ⁴⁵ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ⁴⁴ and R ⁴⁵ are each a straight chain having 1 to 6 carbon atoms. Shows a chain or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ^{43 to} R ⁴⁵ include the same groups as those described for R ⁴¹ and R ⁴² .
Incidentally, R ⁴⁴ and R 1 to 6 carbon atoms of ⁴⁵ linear, branched methylene group as the alkylene group, an ethylene group, a propylene group, butylene group, hexylene group and the like.

Specific examples of acid generators include, for example, onium salts such as diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) phenyliodonium, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid. (P-tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, Tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate P-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, Nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluenesulfonic acid trimethylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid Cyclohexylmethyl (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate p-Toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) Onium salts such as sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 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 Diazomethane derivatives such as
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, bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethyl glyoxime,
β-ketosulfone derivatives include β-ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane,
As disulfone derivatives, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone,
As the nitrobenzyl sulfonate derivative, nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate, 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). Sulfonic acid ester derivatives such as benzene,
Examples of imidoylsulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboxyimido-yl -Imidoyl sulfonate derivatives such as tosylate and 5-norbornene-2,3-dicarboxyimido-yl-n-butyl triflate sulfonate.

In particular, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 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, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfoni Arm, 1,2'-naphthyl carbonyl methyl tetrahydrothiophenium triflate onium salts such as,
Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis ( diazomethane derivatives such as n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane,
Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime 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 amount of the acid generator added is preferably 0.2 to 15 parts with respect to 100 parts of the base resin. If the amount is less than 0.2 parts, the amount of acid generated during exposure is small, and the sensitivity and resolution may be poor. If it is more than 15 parts, the transparency may be lowered and the resolution may be lowered.

  As the basic compound used in the present invention, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By blending such a basic compound, the acid diffusion rate in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate and environment dependency is reduced, and the exposure margin is reduced. And a pattern profile can be improved (for example, JP-A-5-232706, JP-A-5-249683, JP-A-5-158239, JP-A-5-249662, JP-A-5-257282, JP-A-5-289322, (See JP-A-5-289340, etc.).

  Examples of such basic compounds include ammonia, primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, Examples thereof include nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

  Specific examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentyl. Examples include amine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine. , Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, etc. Illustrated.

  Specific examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tripentylamine, Cyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, Examples thereof include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Specific examples of the hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

  Specific examples of aromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline and ethyl. Aniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine And aniline derivatives such as diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, and diaminonaphthalene.

  Specific examples of the heterocyclic amines include pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, oxazole, isoxazole and the like. Oxazole derivatives, thiazole derivatives such as thiazole, isothiazole, imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, pyrazole derivatives, furazane derivatives, pyrroline, pyrroline such as 2-methyl-1-pyrroline Derivatives, pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, imidazoline derivatives, imidazolidine derivatives, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4 (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine Pyridine derivatives such as 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, pyridazine derivatives, pyrimidine derivatives , Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline Conductors, quinoline, quinoline derivatives such as 3-quinolinecarbonitrile, 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 derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative, uridine derivative and the like.

  Specific examples of nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine. And amino acid derivatives such as threonine, lysine, 3-aminopyrazine-2-carboxylic acid and methoxyalanine.

  Specific examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Specific examples of the nitrogen-containing compound and alcoholic nitrogen-containing compound containing a hydroxyl group and a hydroxyphenyl group include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, 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, piperidine ethanol, 1 − 2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyeurolidine, 3- Examples include quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide.

  Specific examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

  Specific examples of the imide derivative include phthalimide, succinimide, maleimide and the like.

  Furthermore, 1 type, or 2 or more types chosen from the basic compound shown by following General formula (10) can also be added.

（式中、側鎖Ｒ⁴⁶は同一でも異なっていてもよく、互いに結合して環を形成することもでき、上記一般式（１０ａ）、（１０ｂ）及び（１０ｃ）で表すことができる。側鎖Ｒ⁴⁷は同一又は異種の、水素原子、又は直鎖状、分枝状、環状の炭素数１〜２０のアルキル基を示し、エーテル基もしくはヒドロキシル基を含んでもよい。Ｒ⁴⁸、Ｒ⁵⁰、Ｒ⁵³は炭素数１〜４の直鎖状又は分枝状のアルキレン基であり、Ｒ⁴⁹及びＲ⁵²は水素原子、又は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、ラクトン環を１あるいは複数含んでいてもよい。Ｒ⁵¹は単結合、又は炭素数１〜４の直鎖状又は分枝状のアルキレン基であり、Ｒ⁵⁴は炭素数１〜２０の直鎖状、分枝状、環状のアルキル基であり、ヒドロキシ基、エーテル、エステル基、ラクトン環を１あるいは複数含んでいてもよい。ｇ＝１、２又は３である。）

(In the formula, the side chains R ⁴⁶ may be the same or different, and may be bonded to each other to form a ring, which can be represented by the general formulas (10a), (10b) and (10c)). chains R ⁴⁷ may be the same or different, a hydrogen atom, or a linear, branched, an alkyl group having 1 to 20 carbon atoms cyclic may contain an ether or hydroxyl group .R ^48, R ^50, R ⁵³ is a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁴⁹ and R ⁵² are a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. And may contain one or more of a hydroxy group, an ether group, an ester group, and a lactone ring, R ⁵¹ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R ⁵⁴ is a straight, branched, or cyclic alkyl group, human Proxy group, an ether, an ester group, it is also good .g = 1, 2 or 3 include 1 or more lactone ring.)

  Specific examples of the compound represented by the general formula (10) include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2-methoxyethoxy). Methoxy) 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-diazabi Crooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxy) Ethyl) 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-o Sopropoxy) 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- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] Ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N -Bis (2-acetoxyethyl) 2- (2-oxopropo Sicarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) 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-formi) Oxyethyl) 2- (2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl ], N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) ) Bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2 -(Methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) Rubonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [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, β- (diethylamino) -δ-valero Lactone etc. Although it can illustrate, it is not restricted to these.

  Further, one or more basic compounds having a cyclic structure represented by the following general formula (11) can be added.

（式中、Ｒ⁴⁶は前述の通り、Ｒ⁵⁵は炭素数２〜２０の直鎖状又は分枝状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを１個あるいは複数個含んでいてもよい。）

(Wherein R ⁴⁶ is as described above, R ⁵⁵ is a linear or branched alkylene group having 2 to 20 carbon atoms, and includes one or more carbonyl groups, ether groups, ester groups, and sulfides. You may go out.)

  Specific examples of the base represented by the general formula (11) 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, acetoxyacetic acid 2-morpholinoethyl, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbo Ruoxy) ethyl] morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, Methyl 3-piperidinopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3- Methoxycarbonylmethyl piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate , 3-morpholinopropion Tetrahydrofurfuryl, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morphonopropionate, Cyclohexyl 3-piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, morpholino Examples include methyl acetate, methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate and the like.

  Furthermore, a basic compound containing a cyano group represented by the following general formulas (12) to (15) can be added.

（式中、Ｒ⁴⁶、Ｒ⁴⁸、Ｒ⁵⁵、及びｇは前述の通り、Ｒ⁵⁶及びＲ⁵⁷は同一又は異種の炭素数１〜４の直鎖状又は分枝状のアルキレン基である。）

(In the formula, R ⁴⁶ , R ⁴⁸ , R ⁵⁵ , and g are as described above, and R ⁵⁶ and R ⁵⁷ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the basic compound containing a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxy). Ethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2- Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-a Methyl nopropionate, 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)- -(2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl)- N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- ( Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-methoxy Methyl) -3-ethylpropionate, 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-propi ) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidine Propiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropionic acid Cyanomethyl, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxy) Til) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2 -Hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) ) -3-Aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropion Examples thereof include cyanomethyl acid, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl) and the like.

  In addition, the said basic compound can be used individually by 1 type or in combination of 2 or more types, The compounding quantity is 0.01-2 parts with respect to 100 parts of all base resins, Especially 0.01-1 part. Is preferred. If the blending amount is less than 0.01 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 2 parts, resolution and sensitivity may be lowered.

  The dissolution inhibitor used in the present invention is a compound having a molecular weight of 3,000 or less, particularly a phenol having a molecular weight of 2,500 or less and a part of the hydroxyl group of the carboxylic acid derivative, whose solubility in an alkaline developer is changed by the action of an acid Alternatively, compounds in which all are substituted with acid labile groups are suitable.

  Examples of phenol or carboxylic acid derivatives having a molecular weight of 2,500 or less include 4,4 ′-(1-methylethylidene) bisphenol, [1,1′-biphenyl-4,4′-diol] -2,2′-methylenebis [ 4-methylphenol], 4,4-bis (4′-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1, 2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, 3,3′-difluoro [(1,1′-biphenyl) -4,4′-diol], 3,3 ′, 5 , 5′-tetrafluoro [(1,1′-biphenyl-4,4′-diol], 4,4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ester Ridene] bisphenol, 4,4′-methylenebis [2-fluorophenol], 2,2′-methylenebis [4-fluorophenol], 4,4′-isopropylidenebis [2-fluorophenol], cyclohexylidenebis [ 2-fluorophenol], 4,4 ′-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4′-methylenebis [2,6-difluorophenol], 4,4 ′-(4 -Fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [(4-hydroxy-3 -Fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-hydro Shifeniru) methyl] -6-methylphenol and the like, the acid labile groups are the same as those for the above general formula (4) to (6).

  Specific examples of the dissolution inhibitor suitably used include 3,3 ′, 5,5′-tetrafluoro [(1,1′-biphenyl) -4,4′-di-tert-butoxycarbonyl], 4, 4 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol-4,4′-di-tert-butoxycarbonyl, bis (4- (2′-tetrahydropyranyloxy) phenyl ) Methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxy) Carbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1′-e Xypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) Propane, 2,2-bis (4′-tert-butoxyphenyl) propane, 2,2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxy) Phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4 -Bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tert-butyl 4,4-bis (4 ′-(2 ″ -teto) Hydrofuranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxyphenyl) tert-butyl valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valeric acid tert-butyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate tert-butyl Butyl, 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) tert-butyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- ( 2'-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris ( 4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyl) Oxy) phenyl) methane, 1,1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) ) Phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′- Toxiethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane, 1,1-tert-butyl 2-trifluoromethylbenzenecarboxylate, 2-trifluoro Tert-butyl methylcyclohexanecarboxylate, tert-butyl decahydronaphthalene-2,6-dicarboxylate, tert-butyl cholate, tert-butyl deoxycholate, tert-butyl adamantanecarboxylate, tert-butyl adamantane acetate, 1, Examples thereof include tetra-tert-butyl 1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylate.

  The addition amount of the dissolution inhibitor in the resist material of the present invention is 20 parts or less, preferably 15 parts or less with respect to 100 parts of the base resin in the resist material. If it exceeds 20 parts, the monomer component increases, so the heat resistance of the resist material may decrease.

  In addition to the above components, a surfactant conventionally used for improving the coating property can be added to the resist material of the present invention. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, and the like. Can be mentioned. For example, Florard “FC-430”, “FC-431” (both manufactured by Sumitomo 3M), Surflon “S-141”, “S-145” (both manufactured by Asahi Glass Co., Ltd.), Unidyne “DS-” 401 "," DS-403 "," DS-451 "(manufactured by Daikin Industries, Ltd.), MegaFuck" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 " , “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Co., Ltd.), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

Resist material of the present invention, for example, a resist material comprising a polymer compound represented by the general formula (1a) and / or (1b) and an organic solvent, an acid generator, a basic compound, a dissolution inhibitor, a surfactant, and the like In particular, in order to form a pattern using a chemically amplified positive resist material, a known lithography technique can be employed.
For example, it is applied on a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.1 to 1.0 μm, and this is applied on a hot plate at 60 to 200 ° C. for 10 seconds to 10 minutes, preferably Heat treatment (prebaking) at 80 to 150 ° C. for 30 seconds to 5 minutes.
Next, a mask for forming a target pattern is placed over the resist film, and high energy rays such as a wavelength range of 100 to 300 nm or 1 to 30 nm, such as deep ultraviolet rays, excimer lasers, X-rays, electron beams, etc. the high-energy radiation, the exposure amount 1 to 200 mJ / cm ^2, preferably about after irradiation so that 10 to 100 mJ / cm ² or so, 60 to 150 ° C. on a hot plate at 10 seconds to 5 minutes, preferably 80 Post exposure bake (PEB) at ~ 130 ° C for 30 seconds to 3 minutes.

Further, using an aqueous developer solution of 0.1 to 5%, preferably 2 to 3%, such as tetramethylammonium hydroxide (TMAH), immersion for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. The target pattern is formed on the substrate by developing by a conventional method such as a dip method, a paddle method, or a spray method.
The material of the present invention is a 254 to 120 nm deep ultraviolet ray or excimer laser, especially 248 nm KrF, 193 nm ArF, 157 nm F ₂ , 146 nm Kr ₂ , 134 nm KrAr, 126 nm Ar ₂ among high energy rays. It is most suitable for fine patterning by laser, X-ray and electron beam.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
(Example 1)
Copolymerization of the following monomer 1 and tert-butyl α-trifluoromethyl acrylate (40/60)

In a 200 mL flask, 7.29 g of the above monomer 1 and 12.71 g of tert-butyl α-trifluoromethyl acrylate were charged, dissolved in 3.53 g of ethyl acetate, and oxygen was sufficiently removed from the system. 0.33 g of the agent AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was carried out for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 11.7 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 8,800 by a light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 1 and tert-butyl α-trifluoromethyl acrylate in the obtained polymer was 37:63.

(Example 2)
Copolymerization of the following monomer 2 with tert-butyl α-trifluoromethyl acrylate (40/60)

In a 200 mL flask, 7.32 g of the above monomer 2 and 12.68 g of tert-butyl α-trifluoromethyl acrylate were charged, dissolved in 3.53 g of ethyl acetate, and the oxygen in the system was sufficiently removed. 0.33 g of the agent AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was carried out for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 11.9 g of white polymer is a polymer having a weight average molecular weight of 8,200 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 2 and tert-butyl α-trifluoromethyl acrylate in the obtained polymer was 40:60.

(Example 3)
Copolymerization of the following monomer 3 and tert-butyl α-trifluoromethyl acrylate (40/60)

In a 200 mL flask, 7.08 g of the above monomer 3 and 12.92 g of tert-butyl α-trifluoromethyl acrylate were charged, dissolved in 3.53 g of ethyl acetate, and the oxygen in the system was sufficiently removed. 0.34 g of the agent AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was carried out for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 13.4 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 8,400 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of the monomer 3 and tert-butyl α-trifluoromethyl acrylate in the obtained polymer was 39:61.

(Example 4)
Copolymerization of monomer 1 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) (40/60)

In a 200 mL flask, 7.47 g of monomer 1 and 12.53 g of α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) were charged and dissolved in 3.53 g of ethyl acetate. After the removal, 0.34 g of initiator AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was performed for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 11.4 g of white polymer is a polymer having a weight average molecular weight of 8,200 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 1 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) in the obtained polymer was 39:61. It was.

(Example 5)
Copolymerization of monomer 2 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) (40/60)

In a 200 mL flask, 7.50 g of monomer 2 and 12.50 g of α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) were charged, dissolved in 3.53 g of ethyl acetate, and oxygen in the system was sufficiently absorbed. After the removal, 0.34 g of initiator AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was performed for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 11.2 g of the white polymer is a polymer having a weight average molecular weight of 8,900 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 2 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) in the obtained polymer was 38:62. It was.

(Example 6)
Copolymerization of monomer 3 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) (40/60)

Into a 200 mL flask, 7.26 g of monomer 3 and 12.74 g of α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) were charged, dissolved in 3.53 g of ethyl acetate, and oxygen in the system was sufficiently absorbed. After the removal, 0.35 g of initiator AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was performed for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 11.4 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 8,100 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 3 and α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl) in the obtained polymer was 39:61. It was.

(Example 7)
Copolymerization of the following monomer 4, α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and maleic anhydride (40/30/30)

A 200 mL flask was charged with 9.21 g of the following monomer 4, 8.15 g of α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and 2.64 g of maleic anhydride, and 3.53 g of ethyl acetate. After dissolving and sufficiently removing oxygen in the system, 0.44 g of initiator AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was performed for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 12.9 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 9,200 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, the content ratio (molar ratio) of monomer 4, α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and maleic anhydride in the obtained polymer was 41:29: It was found to be 30.

(Example 8)
Copolymerization of monomer 3, α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and monomer 5 below (30/40/30)

A 200 mL flask was charged with 4.80 g of monomer 3, 7.50 g of α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and 7.70 g of monomer 5 and dissolved in 3.53 g of ethyl acetate. After sufficiently removing oxygen in the system, 0.31 g of initiator AIBN was charged, the temperature was raised to 65 ° C., and a polymerization reaction was performed for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 11.5 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 9,200 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, the content ratio (molar ratio) of monomer 3, α-trifluoromethylacrylic acid (2-ethyl-2-adamantyl), and monomer 5 in the obtained polymer was 31:39:30. I found out that

Example 9
Copolymerization of monomer 2 and monomer 5 (40/60), and methoxymethylation of the resulting polymer (methoxymethylation rate 45%)

In a 200 mL flask, 6.09 g of monomer 2 and 13.91 g of monomer 5 were charged and dissolved in 3.53 g of ethyl acetate. After sufficiently removing oxygen in the system, 0.28 g of initiator AIBN was charged. The temperature was raised to ° C. and the polymerization reaction was carried out for 24 hours.
In order to purify the polymer obtained, the reaction mixture was poured into hexane to precipitate the polymer obtained. Further, the operation of dissolving the obtained polymer in THF and pouring it into 2 L of hexane to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The 11.9 g white polymer thus obtained is a polymer having a weight average molecular weight of 8,500 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that the content ratio (molar ratio) of monomer 2 and monomer 5 in the obtained polymer was 40:60.

Next, 0.92 g of sodium hydride (purity 60%) was put into a 200 mL flask, and after washing twice with hexane under a nitrogen stream, 15 g of THF was added. The total amount of the polymer obtained was dissolved in 20 g of THF, dropped into the flask at room temperature with a dropping funnel, and aged at 40 ° C. for 4 hours. After cooling the flask to room temperature, 2.54 g of chloromethyl methyl ether was added dropwise using a dropping funnel and allowed to react at room temperature for 12 hours.
The resulting solution was poured into 1 L of 0.1N hydrochloric acid solution to precipitate the polymer. The operation of dissolving the obtained polymer in acetone and pouring it into 1 L of water to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 10.9 g of white polymer is a polymer having a weight average molecular weight of 8,600 by light scattering method and a dispersity (= Mw / Mn) of 1.5 from the GPC elution curve. It was confirmed that there was. ^From the measurement result of ¹ H-NMR, it was found that 43% of the acidic hydroxyl group of the original polymer was methoxymethylated.

(Comparative Example 1)
A polymer was prepared in which 30% of the hydroxyl groups of monodisperse polyhydroxystyrene having a molecular weight of 10,000 and a dispersity (= Mw / Mn) of 1.1 were substituted with tetrahydropyranyl groups.

(Comparative Example 2)
A polymethyl methacrylate having a molecular weight of 15,000 and a dispersity of 1.7 was prepared.

(Comparative Example 3)
A novolak polymer having a meta / para ratio of 40/60, a molecular weight of 9,000, and a dispersity of 2.5 was prepared.

[Evaluation example]
1) Measurement of transmittance of polymer compound 1 g of the polymer compound prepared as described above (Examples 1 to 9, Comparative Examples 1 to 3) was sufficiently dissolved in 20 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). The solution was filtered through a 0.2 μm filter to prepare polymer solution.

The prepared polymer solution was spin-coated on an MgF ₂ substrate and applied, and then baked at 100 ° C. for 90 seconds using a hot plate to form a polymer compound film having a thickness of 100 nm on the MgF ₂ substrate. This substrate was placed in a vacuum ultraviolet photometer (manufactured by JASCO Corporation, VUV-200S), and transmittances at 248 nm, 193 nm, and 157 nm were measured.
The measurement results are shown in Table 1.

It can be seen from Table 1 that the resist material using the polymer compound of the present invention can ensure sufficient transparency even at a wavelength of 200 nm or less, particularly at a wavelength of F ₂ laser (157 nm).

2) Resist preparation and exposure The above-prepared polymer compounds (Examples 1 to 6, Comparative Example 1), an acid generator (PAG1, 2; the following structural formula), a basic compound (tributylamine, triethanolamine), A resist solution was prepared by a conventional method using a dissolution inhibitor (DRI1; the following structural formula) and an organic solvent (PGMEA) in the amounts shown in Table 2.

Next, after spin-coating a resist solution obtained on a silicon wafer on which DUV-30 (manufactured by Brewer Science) was formed to a film thickness of 85 nm, the resist solution was baked at 100 ° C. for 90 seconds using a hot plate. The thickness was 200 nm. This was exposed with an F ₂ laser (VUVES, manufactured by RISOTEC Co., Ltd.) while changing the exposure amount, immediately after exposure, baked at 120 ° C. for 90 seconds, and developed with an aqueous solution of 2.38% tetramethylammonium hydroxide for 60 seconds. The relationship between the exposure amount and the remaining film rate was determined. The exposure amount at which the film thickness became 0 was determined as Eth, and the sensitivity of the resist and the tan θ of the gradient at that time were determined as γ. As a result of VUVES exposure, it was found that the film thickness decreased as the exposure amount increased and exhibited the characteristics of a positive resist. Further, exposure is performed using a KrF scanner (S203B, manufactured by Nikon, NA 0.68, σ0.75, 2/3 annular illumination, Cr mask), and the minimum resolution is 150 nm line and space 1: 1. The pattern of the mask dimension was obtained and used as the limit resolution.
The results are shown in Table 2.

  From Table 2, it can be seen that the resist material comprising the polymer compound of the present invention as the base resin has excellent substrate adhesion and developer compatibility, and therefore has very excellent development characteristics.

3) Dry etching resistance test 2 g of the polymer compounds prepared above (Examples 1 to 6, Comparative Examples 1 and 2) were dissolved in 10 g of PGMEA, filtered through a 0.2 μm size filter, and then the polymer solution was spin-coated with Si. A film having a thickness of 300 nm was formed on the substrate.
Then, the etching resistance was evaluated using two systems of gases shown in Table 3 below.

Evaluation of etching resistance measured the film thickness of the polymer film before and behind etching, and calculated | required the film thickness difference.
The results are shown in Table 4.

  From Table 4, it can be seen that the resist material comprising the polymer compound of the present invention as a base resin is excellent in etching resistance against dry etching.

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

Claims (10)

It contains at least a compound having at least one partial structure represented by the following general formula (1a) or (1b) as a repeating unit, tert-butyl α-trifluoromethyl acrylate, α-trifluoromethyl acrylic acid (2- A polymer compound having a weight average molecular weight in the range of 1,000 to 500,000 , copolymerized with at least one of ethyl-2-adamantyl) and maleic anhydride .

(Wherein R ¹ and R ² are a hydrogen atom, an acid labile group, a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. The above general formula (1b ) May be bonded to R ¹ and R ² , in which case R ¹ and R ² are bonded to each other in a linear, branched or cyclic alkylene group or fluorinated alkylene group having 1 to 20 carbon atoms. R ³ represents a hydrogen atom, a hydroxyl group, or a linear, branched, or cyclic alkyl group or alkoxy group having 1 to 15 carbon atoms, in which part or all of the hydrogen atoms may be substituted with a halogen atom. Represents an acyloxy group, an alkylthio group, an acylamino group, or an alkylsulfonylamino group, provided that when R ² is a hydrogen atom, R ³ is not a hydroxyl group.) The polymer compound according to claim 1, comprising at least one compound represented by the following general formulas (2a) to (2d) as a repeating unit.

(In the formula, R ^{1 to} R ³ are the same as defined above. R ⁴ is a single bond or a straight chain having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with halogen atoms, Represents a branched or cyclic alkylene group, and R ⁵ represents a hydrogen atom or a linear, branched or cyclic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms. And a1 to a4 are each 0 or 1.) Furthermore, the high molecular compound of Claim 1 or Claim 2 which contains any one or more compounds shown by the following general formula (3a)-(3e) as a repeating unit.

(Wherein R ⁶ and R ¹³ are a hydrogen atom, a fluorine atom, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms. R ⁷ is a hydrogen atom, an acid, or an acid. An unstable group, an adhesive group, or a linear, branched, or cyclic alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms, R ⁸ is a methylene group or an oxygen atom, and R ^{9 to} R. ¹² represents a hydrogen atom, a fluorine atom, —R ¹⁶ —O—R ⁷ , —R ¹⁶ —CO ₂ R ⁷ , or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl. R ¹⁴ and R ¹⁶ are a single bond, a linear, branched, or cyclic alkylene group or a fluorinated alkylene group having 1 to 20 carbon atoms, and R ^{9 to} R ¹² are bonded to ether. ring, lactone ring, may also form a hydrocarbon ring .R ¹⁵ is fluorine atom, or a straight, minutes Jo, the .b a cyclic fluorinated alkyl group is 0 or 1, c is 1 or 2, d is 0 to 4 integer, a 1 ≦ c + d ≦ 5.) The polymer compound according to any one of claims 1 to 3, wherein the acid labile group is a group selected from groups represented by the following general formulas (4) to (6).

(In the formula (4), R ¹⁷ represents a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the general formula (6).
e is an integer of 0-6.
In the formula (5), R ¹⁸ and R ¹⁹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
R ²⁰ 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, and is a linear, branched or cyclic alkyl group. And those in which some of these hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, or the like.
In the formula (6), R ²¹ , R ²² and R ²³ are monovalent hydrocarbon groups such as linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, such as oxygen, sulfur, nitrogen, etc. A hetero atom may be contained, and R ²¹ and R ²² , R ²¹ and R ²³ , R ²² and R ²³ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ) The polymer compound according to any one of claims 1 to 3, wherein the adhesive group is a group selected from groups represented by the following general formula.

(In the formula, R ²⁹ is a methylene group or an oxygen atom.) A resist material comprising the polymer compound according to any one of claims 1 to 5 as a base resin. The resist material according to claim 6 , further comprising a chemically amplified positive resist material containing an organic solvent and an acid generator. The resist material according to claim 6 or 7, further comprising at least one of a basic compound, a dissolution inhibitor, and a surfactant. At least a step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of exposing to high energy rays through a photomask after heat treatment,
And a step of developing using a developer. The pattern forming method according to claim 9 , wherein the high energy beam is any one of a KrF excimer laser, an ArF excimer laser, an F ₂ laser, an Ar ₂ laser, and a soft X-ray.