TWI552993B - Monomer, polymer, resist composition, and patterning process - Google Patents

Description

Monomer, polymer compound, photoresist material and pattern forming method

The present invention relates to a monomer which is useful as a raw material for functional materials, medicines, and agricultural chemicals, a polymer compound containing a repeating unit derived from the monomer, a photoresist material containing the polymer compound, and the use of the photoresist material. Pattern forming method.

With the high integration and speed of LSI, the miniaturization of pattern rules has progressed rapidly. In particular, the expansion of the flash memory market and the increase in memory capacity have led to miniaturization. As a state-of-the-art micronization technique, a film is formed on both side walls of the pattern of the ArF lithography, and a device having a pattern of 20 nm is formed by a double patterning (SADP) in which two patterns are formed in one line by half line width. Production. As a microfabrication technique for the next generation of 10 nm nodes, SAQP with two SADPs repeated is a candidate technique, but the process of forming the sidewall film by CVD repeatedly and processing it by dry etching is very expensive. The extreme ultraviolet (EUV) lithography having a wavelength of 13.5 nm can form a pattern having a size of about 10 nm with one exposure, but the laser power is still low and there is a problem of low productivity. Since the prospect of microfabrication is unknown, the development of 3-dimensional devices such as flash memory in which BiCS is represented in the vertical direction has been carried out, but it is also a high-cost process.

In recent years, organic solvent development has received renewed attention. A positive pattern is formed using a high resolution positive photoresist material to form a negative pattern. As the ArF photoresist material for negative tone development using an organic solvent, a conventional positive type ArF photoresist material can be used, and Patent Document 1 discloses a pattern formation method using the same.

In the method of developing a negative pattern by an organic solvent, a film having a dry etching resistance such as a ring structure having dry etching resistance remains as a negative pattern, and dry etching resistance is insufficient. Therefore, the formation of a negative pattern by the development of an organic solvent has a major problem.

On the other hand, a method of developing a negative pattern by an aqueous alkali solution has also been discussed. The photoresist material to be used in the above-mentioned method is a polar-type negative-type photoresist material which has a γ-hydroxycarboxylic acid in a repeating unit of a base resin and which forms a lactone ring by heating after exposure (Patent Document 2). a copolymer of a (meth) acrylate unit having an alcoholic hydroxyl group and a unit of a fluoroalcohol as a negative-type photoresist material using a crosslinking agent as a base resin (Patent Document 3), and a combination of α-hydroxy acrylate and Lactone unit (Patent Document 4), α-hydroxy acrylate and various fluoroalcohol units (Patent Documents 5 to 7), mono(methyl)acryl decyloxy [product] unit, and fluoroalcohol unit (Patent Document 8) A cross-linked negative photoresist material such as a cross-linking agent.

Among these, Patent Document 1 describes a polarity-transforming negative photoresist material which is not cross-linked, but the γ-hydroxycarboxylic acid unit causes swelling of the pattern after development. On the other hand, in Patent Documents 2 to 7, all are cross-linked negative-type photoresist materials. In the formation of a negative pattern by an alcoholic hydroxyl group or the like and a crosslinking agent, there is a problem that bridging between patterns and pattern collapse due to swelling, but it has been confirmed that the introduction of the fluoroalcohol unit has an effect of reducing swelling. Further, in the recent example of formation of a negative pattern of a polarity change type, a base resin having a polar unit of a polar group such as a 3-stage hydroxyl group, a 3-stage ether bond, a 3-stage ester bond or an acetal bond has been proposed. . Among them, the use of a polar unit having one 3-stage hydroxyl group has been confirmed to be difficult to swell after development, but on the other hand, since the difference in the dissolution speed of the unexposed portion and the exposed portion with respect to the developer is insufficient, there is an online The bottom of the pitch pattern generation pattern is a problem such as a so-called push-out shape (Patent Documents 9 to 10 and Non-Patent Document 1).

The formation method of the above-mentioned series of negative patterns all exerts certain results in forming a pattern of about 100 nm. However, when a pattern is formed thinner than 100 nm, it is inevitable that the pattern swelling causes bridging, collapse, tailing of the pattern, etc., and the performance is not Satisfied. In the negative pattern forming process which has been researched by organic solvent development in recent years, the organic solvent used for the developer is more expensive than the conventional alkali developer. In view of the improvement of etching resistance, it is desirable to have a high-resolution negative-type photoresist material in which a rigid main chain structure remains in a film and can perform conventional alkali development. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-195502 [Patent Document 3] International Publication No. 2004/074936 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-3862 [ Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. 2006-317. [Patent Document 9] US Patent No. 7300739 (Patent Document 10) US Patent No. 7563558 [Non-Patent Document]

[Non-Patent Document 1] Proc. SPIE vol. 5376, p71 (2004)

(The subject to be solved by the invention)

In recent years, in the negative pattern formation in which the development of the organic solvent has been studied, the negative pattern remaining in the photoresist film is reduced in density compared with that before exposure. Therefore, the durability of the etching step and the maintenance of the pattern shape after etching have become problems.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a polymerizable monomer having a substituent which changes polarity due to an acid action, a polymer compound obtained from the monomer, a photoresist material containing the polymer compound as a base resin, and A pattern forming method of the photoresist material is used. (method of solving the problem)

In order to achieve the above object, the inventors of the present invention have conducted an effort to obtain a monomer represented by the following formula (1), which can be formed by using a polymer compound obtained from the monomer as a base resin of a photoresist material. The negative pattern insoluble in an alkali developing solution having high resolution and excellent etching resistance is completed by the present invention.

That is, the present invention provides the following monomers, polymer compounds, photoresist materials, and pattern forming methods. [1] a monomer represented by the following formula (1); In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each independently represent a carbon number of 1 to 10 linear, branched or cyclic monovalent hydrocarbon group of 1, R ² may be bonded to each other with R ³ The knot forms an alicyclic group together with the carbon atoms bonded thereto; X ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ constituting the divalent hydrocarbon group - may also be substituted with -O- or -C(=O)-; Z ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and -CH2- constituting the aliphatic hydrocarbon group It may also be replaced by -O- or -C(=O)-; k ¹ represents 0 or 1; k ² represents an integer of 2 to 4. [2] The monomer according to [1], wherein Z ¹ is a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms. [3] A polymer compound characterized by comprising a repeating unit represented by the following formula (3); In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each independently represent a carbon number of 1 to 10 linear, branched or cyclic monovalent hydrocarbon group of 1, R ² may be bonded to each other with R ³ The knot forms an alicyclic group together with the carbon atoms bonded thereto; X ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH2- constituting the divalent hydrocarbon group It may also be substituted with -O- or -C(=O)-; Z ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the aliphatic hydrocarbon group _; It may also be replaced by -O- or -C(=O)-; k ¹ represents 0 or 1; k ² represents an integer of 2 to 4. [4] The polymer compound according to [3], further comprising at least one selected from the group consisting of repeating units represented by the following formulas (A) to (D); Wherein R ^{1 is the} same as defined above; Z ^A represents a substituent of a fluorine-containing alcohol having 1 to 20 carbon atoms; Z ^B represents a substituent having a phenolic hydroxyl group having 1 to 20 carbon atoms; and Z ^C represents a carbon number of 1 to 20 a carboxyl group-containing substituent; Z ^D represents a lactone skeleton, a sultone skeleton, a carbonate skeleton, a cyclic ether skeleton, an acid anhydride skeleton, an alcoholic hydroxyl group, an alkoxycarbonyl group, an anthranyl group or an amine formazan group. Substituent; X ² represents a single bond, methylene, ethyl, phenyl, fluorinated phenyl, naphthyl, -OR ⁰¹ -, or -C(=O)-Z ² -R ⁰¹ -, Z ² represents an oxygen atom or NH, and R ⁰¹ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclical carbon number of 2 to 6. An alkenyl group, a phenylene group, or a naphthyl group, and may also contain a carbonyl group, an ester group, an ether group or a hydroxyl group. [5] A photoresist material comprising: a base resin comprising a polymer compound such as [3] or [4], an acid generator, and an organic solvent. [6] A pattern forming method, characterized in that: a photoresist material such as [5] is coated on a substrate to form a photoresist film, and after heat treatment, the photoresist film is exposed by high-energy rays, and then developed by heating. The liquid gets a pattern. [7] The pattern forming method according to [6], wherein the unexposed portion is dissolved using an alkali developing solution to obtain a negative pattern in which the exposed portion is insoluble. (Effect of the invention)

The monomer of the present invention is used as a basis for producing a radiation-sensitive photoresist material having excellent transparency to radiation having a wavelength of 500 nm or less, particularly a wavelength of 300 nm or less, for example, KrF laser light, ArF laser light, and F ₂ laser light, and excellent development characteristics. The raw material monomers of the polymer of the resin are very useful. When a polymer compound containing a repeating unit derived from a monomer of the present invention is used as a base resin of a photoresist material, a negative pattern insoluble in an alkali developing solution having high resolution and excellent etching resistance can be formed.

The invention is described in detail below. Further, in the following description, depending on the structure represented by the chemical formula, asymmetric carbon may exist, and an enantiomer or a diastereomer may exist, and in this case, the isoform is represented by a formula. Things. These isomers may be used singly or in the form of a mixture.

[Monomer] The monomer of the present invention is represented by the following formula (1). 【化4】

In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and may also bond R ² and R ^{3 to} each other and bond to the carbon atom. Together, an alicyclic group is formed. X ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with -O- or -C(=O)-. Z ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the aliphatic hydrocarbon group may be substituted with -O- or -C(=O)-. k ¹ represents 0 or 1. k ² represents an integer of 2 to 4.

Examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, and a ring. An alkyl group such as pentyl, cyclohexyl, 2-ethylhexyl, n-octyl, norbornyl, tricyclodecyl, adamantyl or the like.

The linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms is exemplified below, but is not limited thereto. 【化5】 (In the formula, the dashed line represents the keying hand.)

The aliphatic hydrocarbon group having a linear, branched or cyclic carbon number of 1 to 20 is exemplified as follows, but is not limited thereto. 【化6】 (In the formula, the dashed line represents the keying hand.)

Among these, Z ^{1 is} preferably a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and particularly preferably a cyclohexane ring skeleton (including a bridged ring such as a norbornane ring). In this case, the monomer of the present invention is represented by, for example, the following formula (2), but is not limited thereto. 【化7】 (wherein R ¹ to R ³ , X ¹ , k ¹ and k ^{2 are the} same as defined above. R ⁵ and R ⁶ represent a hydrogen atom, or R ⁵ and R ⁶ may be bonded to each other to form a sub-substituent. Methyl or ethyl, or -O-.)

Specific examples of the repeating unit derived from the monomer represented by the formula (1) are as follows, but are not limited thereto. 【化8】

【化9】

The monomer represented by the formula (1) is obtained, for example, by the reaction shown in the following Scheme A, but is not limited thereto. 【化10】 (wherein R ¹ to R ³ , X ¹ , Z ¹ , k ¹ and k ^{2 are the} same as defined above. R ⁴ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. X ³ represents A halogen atom, a hydroxyl group or a mercaptooxy group. M represents Li, Na, K, MgX, or ZnX, and X represents a halogen atom.

The first stage is a step of obtaining a polyol compound (6) by an addition reaction of a hydroxyester compound (4) with an organometallic reagent (5).

The reaction can be carried out according to a usual method. For example, the hydroxy ester compound (4) is dissolved in an ether solvent such as tetrahydrofuran or diethyl ether, and a Grignard reagent such as methylmagnesium chloride or ethylmagnesium chloride or an alkyllithium reagent such as methyllithium is added. The organometallic reagent (5) corresponding to the substituents R ² and R ³ is used, whereby a polyol compound (6) having a tertiary alcohol can be obtained. The organometallic reagent (5) is preferably used in an amount of from 3.0 to 10.0 mol, more preferably from 3.0 to 5.0 mol, based on the ester group of the hydroxyester compound (4). If the organometallic reagent (5) is used in an amount of less than 3.0 mol, since the hydroxyl group compound (4) has a hydroxyl group per 1 mol of the organometallic reagent (5) 1 mol, there will be an ester. In the case where the addition reaction of the base is incomplete, on the other hand, if it exceeds 10.0 mol, there is a case where the cost is disadvantageous due to an increase in the raw material cost. The reaction can be carried out by cooling or heating as necessary, but it is usually carried out at a temperature ranging from 0 ° C to the boiling point of the solvent. If the reaction time is followed by gas chromatography (GC) or silica gel thin layer chromatography (TLC) to complete the reaction, it is preferable from the viewpoint of productivity, and it is usually about 0.5 to 24 hours. The polyol compound (6) can be obtained from the reaction mixture according to a usual aqueous work-up, and if necessary, it can be purified by a usual method such as distillation, chromatography or recrystallization.

The second stage is a step of reacting the esterifying agent (7) with the polyol compound (6) to obtain a monomer (1).

The reaction can be carried out according to the method. The esterifying agent (7) is cerium chloride (in the case where X ³ in the formula (7) is a chlorine atom), a carboxylic acid (in the case where X ³ in the formula (7) is a hydroxyl group), or an acid anhydride (in the formula (7) It is especially preferable that X ³ is a decyloxy group. When ruthenium chloride is used, the polyol compound (6) and methacrylic acid ruthenium chloride, etc., and triethylamine, pyridine, may be used in a solvent-free or solvent such as dichloromethane, acetonitrile, toluene or hexane. A base such as 4-dimethylaminopyridine is added sequentially or simultaneously, and is applied by cooling or heating. When a carboxylic acid is used, the carboxylic acid corresponding to the polyol compound (6) and methacrylic acid may be heated in the presence of an acid catalyst in a solvent such as toluene or hexane, and the generated water may be discharged to the system as needed. Waiting outside. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid; and organic acids such as p-toluenesulfonic acid and benzenesulfonic acid. When an acid anhydride is used, the corresponding acid anhydride of the polyol compound (6), methacrylic anhydride, etc., and triethylamine, pyridine, 4-di can be used in a solvent-free or solvent such as dichloromethane, acetonitrile, toluene or hexane. A base such as methylaminopyridine is added sequentially or simultaneously, and is carried out by cooling or heating as necessary. When the reaction time is followed by gas chromatography (GC) or silica gel thin layer chromatography (TLC) to complete the reaction, it is preferable from the viewpoint of productivity, and it is usually about 0.5 to 24 hours. The monomer (1) can be obtained from the reaction mixture by a usual aqueous work-up, and if necessary, it can be purified by a usual method such as distillation, chromatography or recrystallization.

A specific example of the method for producing a monomer represented by the formula (2), a method of obtaining a monomer (2-1) in the case where both R ² and R ³ are a methyl group and k ² is 2 is shown in the following scheme B. 【化11】 (wherein R ¹ , R ⁵ , R ⁶ , X ¹ , X ³ and k ^{1 are the} same as defined above. R ⁷ represents a hydrogen atom or a fluorenyl group.)

The first stage is a step of obtaining a triol compound (9) by reacting a Grignard reagent with the lactone compound (8). The triol compound (9) having a tertiary alcohol can be obtained by dissolving the lactone compound (8) in an ether solvent such as tetrahydrofuran or diethyl ether and adding methyl magnesium chloride. The amount of methylmagnesium chloride used is preferably 3.0 to 10.0 moles relative to the lactone compound (8), and more preferably 3.0 to 5.0 moles. If the amount of methyl magnesium chloride used is less than 3.0 moles, the substituent-OR ⁷ of the lactone compound (8) will consume 1 to 2 moles of methyl magnesium chloride per 1 mole, and there will be an addition to the lactone. In the case of incomplete reaction, if it exceeds 10.0 m, it will be disadvantageous in terms of cost due to an increase in raw material costs. The reaction can be carried out by cooling or heating as necessary, and is usually carried out at a temperature ranging from 0 ° C to the boiling point of the solvent. If the reaction time is followed by gas chromatography (GC) or silica gel thin layer chromatography (TLC) to complete the reaction, the yield is preferred, and it is usually about 0.5 to 24 hours. The triol compound (9) can be obtained from the reaction mixture by an ordinary aqueous work-up, and if necessary, it can be purified by a usual method such as distillation, chromatography or recrystallization.

The second stage is a step of reacting the esterifying agent (7) with the triol compound (9) to obtain a monomer (2-1). The conditions of the reaction are the same as those of the aforementioned polyol compound (6) and the esterifying agent (7).

[Polymer compound] The polymer compound of the present invention contains a repeating unit represented by the following formula (3), and the repeating unit is derived from a monomer represented by the formula (1). 【化12】 (wherein R ¹ , R ² , R ³ , X ¹ , Z ¹ , k ¹ and k ^{2 are the} same as defined above.)

The polymer compound of the present invention is a (meth) acrylate polymer having a plurality of tertiary alcoholic hydroxyl groups which are acid labile groups. The following scheme is exemplified by the case where the polymer compound (3a) in which R ² and R ³ are a methyl group and k ² is 2, and the polymer compound of the present invention is used as a base resin component of a photoresist material due to an exposure portion. The action of the strong acid produced causes the water molecules to detach (hereinafter referred to as dehydration) and the structural changes of the repeating unit. Depending on the structure of Z ¹ , it is considered that most of the olefin formation (path A) due to dehydration, intramolecular cyclization with dehydration, and formation of a ring such as an oxetane ring or a tetrahydrofuran ring (path B) get on. Since many of the highly polar and hydrophilic groups exist before exposure, the affinity and solubility of the alkali developing solution are high, but the exposed portion loses a plurality of hydroxyl groups after exposure, so the solubility in the alkali developing solution is remarkably lowered and becomes insoluble. In the developer. In addition, only water molecules are lost after the change in polarity, and the change in carbon density is extremely small. In particular, when the skeleton has a cyclic hydrocarbon group, the rigid alicyclic skeleton is maintained and only a polarity change occurs. That is, since the polymer compound of the present invention has an extremely high solubility contrast with an alkali developer, it can be a base resin component which does not necessarily have to be insolubilized by a crosslinking agent. Moreover, since the high carbon density and the resin film thickness can be maintained even after the polarity change, the pattern is caused by the swelling of the conventional polarity-changing negative-type photoresist material or the negative-type photoresist material which requires a crosslinking reaction. The bridging and pattern collapse are not easy to occur, and the etching resistance is also excellent, so that a finer pattern can be solved.

【化13】 (wherein R ¹ , X ¹ , Z ¹ and k ^{1 are the} same as described above.)

As described above, the polymer compound of the present invention has high polarity before dehydration reaction and low polarity after dehydration, so that the dissolution contrast with respect to the alkali aqueous solution is high. In the formula (3), when the number of carbon atoms of the substituents R ² and R ^{3 in} the third-stage alcohol moiety is small, the polarity and hydrophilicity are higher, and the viewpoint of easy introduction of the monomer (1) during production is considered, and R ² and R ^{3 is} each independently preferably a methyl group or an ethyl group. Further, from the viewpoint of maintaining the carbon density and the rigidity of the straightness before and after the dehydration reaction, Z ¹ is preferably a cyclic hydrocarbon group having 3 to 20 carbon atoms. Among them, Z ¹ is an alicyclic group having 3 to 10 carbon atoms and k ² is 2, and it is preferable from the viewpoint of easily obtaining a raw material when producing the monomer (1). When k ² exceeds 4, the difference in polarity change before and after dehydration is larger, but the solubility of the monomer (1) to the polymerization solvent is remarkably lowered, the preparation of the raw material becomes difficult, and the polymer compound of the present invention itself acts as a photoresist. The solvent solubility of the material is also lowered, which is not desirable.

In addition to the repeating unit derived from the monomer represented by the formula (1), the polymer compound of the present invention may further contain at least one selected from the group consisting of the repeating units represented by the following formulas (A) to (D) in order to control the solubility. . 【化14】

Wherein R ^{1 is the} same as defined above. Z ^A represents a substituent of a fluorine-containing alcohol having 1 to 20 carbon atoms. Z ^B represents a substituent having a phenolic hydroxyl group having 1 to 20 carbon atoms. Z ^C represents a carboxyl group-containing substituent having 1 to 20 carbon atoms. Z ^D represents a substituent containing a lactone skeleton, a sultone skeleton, a carbonate skeleton, a cyclic ether skeleton, an acid anhydride skeleton, an alcoholic hydroxyl group, an alkoxycarbonyl group, a decylamino group or an aminecarbamyl group. X ² represents a single bond, a methylene group, an ethyl group, a phenyl group, a phenyl group, a phenyl group, a naphthyl group, -OR ⁰¹ -, or -C(=O)-Z ² -R ⁰¹ -, Z. ² represents an oxygen atom or NH, and R ⁰¹ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, The phenyl group or the naphthyl group may also contain a carbonyl group, an ester group, an ether group or a hydroxyl group.

The repeating unit represented by the formula (A) has a substituent of a fluorine-containing alcohol having high affinity with an aqueous alkali solution. As a preferable example of the unit of the above-mentioned fluorine-containing alcohol, JP-A-2007-297590, JP-A-2008-111103, JP-A-2008-122932, and JP-A-2012-128067 A repeating unit having a 1,1,1,3,3,3-hexafluoro-2-propanol residue or a 2-hydroxy-2-trifluoromethyltetrahydrofuran structure is disclosed. These have a tertiary alcoholic hydroxyl group or a hemiacetal structure, but are not reactive with an acid because they are substituted by fluorine.

The repeating units represented by the formulae (A) to (C) are structural units having a hydroxyl group having a high acidity, and the higher the introduction rate, the higher the alkali solubility of the polymer compound of the present invention. On the other hand, excessive introduction of these units may impair the polarity change due to the dehydration reaction of the repeating unit represented by the formula (1) and the acid, and the effect of insolubilizing the alkali. Therefore, it is preferable that the repeating unit represented by the above formulas (A) to (C) is used to compensate for the alkali solubility of the unexposed portion, and is preferably introduced within a range that does not impair the alkali insolubilization effect of the exposed portion.

The repeating unit represented by the formula (A) is as follows, but is not limited thereto. 【化15】

【化16】

【化17】

The repeating unit represented by the formula (B) is exemplified below, but is not limited thereto. 【化18】

The repeating unit represented by the formula (C) is as follows, but is not limited thereto. 【化19】

Further, the fluoroalcohol may be first protected by a mercapto group or an acid labyrinth group, and the unit which is hydrolyzed by the alkali developing solution and deprotected by the exposed acid to produce a fluorine-containing alcohol corresponding to the above formula (A). In this case, the ideal repeating unit is exemplified in paragraphs [0036] to [0040] of JP-A-2012-128067, and formulas (2a), (2b), and (2f) in paragraph [0041]. Those who represent them, etc.

The repeating unit represented by the formula (D) is exemplified below, but is not limited thereto. Further, in the following formula, Me represents a methyl group. 【化20】

【化21】

【化22】

【化23】

【化24】

【化25】

【化26】

【化27】

Further, the polymer compound of the present invention may contain at least one selected from the group consisting of repeating units represented by the following formulas (f1) to (f3). 【化28】

In the formula, R ¹¹ each independently represents a hydrogen atom or a methyl group. R ¹² represents a single bond, a phenyl group, -OR ²¹ - or -C(=O)-Z ²² -R ²¹ -, Z ²² represents an oxygen atom or NH, and R ²¹ represents a linear chain having a carbon number of 1 to 6, a branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, or a phenyl group, or a carbonyl group (-CO-) or an ester group (-COO) -), ether group (-O-) or hydroxyl group. L represents a single bond or -Z ³³ -C(=O)-O-, and Z ³³ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom. Z ¹¹ represents a single bond, a methylene group, an ethyl group, a phenyl group, a fluorinated phenyl group, -OR ²² -, or -C(=O)-Z ⁴⁴ -R ²² -, and Z ⁴⁴ represents an oxygen atom. Or NH, R ²² represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, or a phenyl group. It may also contain a carbonyl group, an ester group, an ether group or a hydroxyl group. M ^- represents a non-nucleophilic relative ion.

R ¹³ to R ²⁰ each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom. The above monovalent hydrocarbon group may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl or 4-methyl. An alkyl group such as a cyclohexyl group, a cyclohexylmethyl group, a decyl group or an adamantyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group; a phenyl group or a naphthyl group; An aryl group such as an aryl group such as a thienyl group, an aryl group such as a benzyl group, a 1-phenylethyl group or a 2-phenylethyl group, or the like is preferred. Further, a part of the hydrogen atom of the group may be substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, or a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be inserted. A hydroxyl group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride, a haloalkyl group, or the like is formed or inserted. Further, R ¹³ and R ^{14 may} be bonded to each other and form a ring, or both of R ¹⁵ , R ¹⁶ and R ¹⁷ together with the sulfur atom to which they are bonded, or R ¹⁸ , R ¹⁹ and R ^{20 .} Any two or more of them may be bonded to each other and form a ring together with the sulfur atoms bonded thereto.

When L is -Z ³³ -C(=O)-O-, a linear, branched or cyclic divalent hydrocarbon group having a carbon number of 1 to 20 and a hetero atom may be substituted by Z ³³ may be mentioned as follows However, it is not limited to this. 【化29】 (In the formula, the dashed line represents the keying hand.)

When R ¹³ and R ¹⁴ are bonded to each other and form a ring together with the sulfur atom to which they are bonded, or two or more of R ¹⁵ , R ¹⁶ and R ¹⁷ or R ¹⁸ , R ¹⁹ and R ²⁰ When the two or more of the two are bonded to each other and form a ring together with the sulfur atom to be bonded thereto, specific examples thereof are as follows, but are not limited thereto.

【化30】

In the formula, R ²³ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom. The above-mentioned monovalent hydrocarbon group is the same as those described in the description of R ¹³ to R ²⁰ .

Specific structures of the phosphonium cations in the formulae (f2) and (f3) are as follows, but are not limited thereto. 【化31】

The non-nucleophilic relative ions represented by M ^- may be exemplified by halide ions such as chloride ions and bromide ions; trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonate Isofluoroalkylsulfonate; sulfonate such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate; mesylate, butanesulfonate Alkylsulfonate such as acid radical, bis(trifluoromethylsulfonyl) quinone imine, bis(perfluoroethylsulfonyl) quinone imine; bis(perfluorobutylsulfonyl) quinone imide A methylated acid such as imidic acid; ginseng (trifluoromethylsulfonyl) methide or ginseng (perfluoroethylsulfonyl) methide.

Further, the non-nucleophilic relative ion may be exemplified by a sulfonate having a fluorine group substituted at the α-position represented by the following formula (F-1), a sulfonate having a fluorine group substituted at the α and β positions represented by the following formula (F-2). . 【化32】

In the formula (F-1), R ³¹ represents a hydrogen atom, a linear one having a carbon number of 1 to 20, a branched or cyclic alkyl group, a linear or branched or cyclic alkene having a carbon number of 2 to 20. The aryl group having a carbon number of 6 to 20 may have an ether group, an ester group, a carbonyl group, a lactone ring or a fluorine atom. In the formula (F-2), R ³² represents a hydrogen atom, a linear one having a carbon number of 1 to 30, a branched or cyclic alkyl group, a linear chain having a carbon number of 2 to 30, a branched or a cyclic group. a base, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and may have an ether group or an ester group. A carbonyl or lactone ring.

The polymer compound of the present invention may further comprise a repeating unit g having an oxirane ring or an oxetane ring. When the repeating unit g is contained, the exposed portion is crosslinked. Therefore, when the polymer compound of the present invention is used for a photoresist material, the insolubility of the alkali developing solution and the etching resistance of the negative pattern can be expected to be improved. The monomer to which the repeating unit g having an oxirane ring or an oxetane ring is administered is as follows, but is not limited thereto. Further, in the following formula, R ^{1 is the} same as described above.

【化33】

【化34】

The polymer compound of the present invention may further contain a repeating unit h derived from a monomer having a carbon-carbon double bond. Repeating unit h, for example, unsaturated acrylates such as methyl methacrylate, methyl crotonate, dimethyl maleate, dimethyl itaconate, maleic acid, fumaric acid, itaconic acid, etc. a carboxylic acid, a norbornene, a norbornene derivative, a cyclic olefin such as a tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecene derivative, or an unsaturated acid anhydride such as itaconic anhydride, as shown below A repeating unit of a monomer or the like. Further, in the following formula, R ^{1 is the} same as described above.

【化35】

【化36】

In the polymer compound of the present invention, the ideal content ratio of each repeating unit is, for example, the range (mol%) shown below, but is not limited thereto. (I) The content of one or more of the repeating units represented by the formula (3) selected from the monomer of the formula (1) is more than 0 mol%, 100 mol% or less, preferably 5~ 80% by mole, more preferably 10 to 60% by mole. (II) The content of one or more of the repeating units represented by the formulas (A) to (D) is 0 mol% or more and less than 100 mol%, preferably 20 to 95 mol%, More preferably 40 to 90% by mole. (III) The content of one or more of the repeating units represented by the formulas (f1) to (f3) is 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0~ 10 moles %. (IV) The content of one or more selected from the group consisting of repeating units g and h is 0 to 80 mol%, preferably 0 to 70 mol%, more preferably 0 to 50 mol%.

A method of synthesizing the polymer compound of the present invention, for example, a method in which a desired monomer in a monomer of each repeating unit is added to an organic solvent, a radical polymerization initiator is added, and heating polymerization is carried out.

The organic solvent used in the polymerization may, for example, be toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), γ- Butyrolactone (GBL) and the like. The polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis (2) -Methylpropionic acid) dimethyl ester, benzammonium peroxide, lauric acid peroxide, and the like. The polymerization temperature is preferably from 50 to 80 °C. The reaction time is preferably from 2 to 100 hours, more preferably from 5 to 20 hours.

When the hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, the hydroxystyrene or hydroxyvinylnaphthalene and other monomers may be added to the organic solvent, the radical polymerization initiator may be added and heated to polymerize, or acetonitrile may be used. The styrene or ethoxylated vinyl naphthalene is deprotected by alkali hydrolysis to polyhydroxystyrene or hydroxypolyvinylnaphthalene after polymerization.

Alkyl water, triethylamine or the like can be used as the base in the alkaline hydrolysis. Further, the reaction temperature is preferably from -20 to 100 ° C, more preferably from 0 to 60 ° C. The reaction time is preferably from 0.2 to 100 hours, more preferably from 0.5 to 20 hours.

Further, the weight average molecular weight (Mw) of the polymer compound of the present invention is preferably from 1,000 to 500,000, more preferably from 3,000 to 50,000. If it falls outside this range, the etching resistance will fall extremely, or the dissolution rate of the before and after exposure may not be ensured, and the resolution may fall. Further, the degree of dispersion (Mw/Mn) of the polymer compound of the present invention is preferably from 1.20 to 2.20, more preferably from 1.30 to 1.80. Further, in the present invention, Mw is measured by polystyrene conversion using gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

[Photoresist Material] The polymer compound of the present invention is suitable as a base resin of a photoresist material. The polymer compound of the present invention can be used as a base resin, and an organic solvent, an acid generator, a dissolution controlling agent, a basic compound, a surfactant, an acetylene alcohol, or the like can be appropriately combined and used in accordance with the purpose to prepare a photoresist.

When the polymer compound of the present invention is used, the polymer compound in the exposed portion is reduced in the rate of dissolution of the alkali developing solution by the catalyst reaction, so that it can be an extremely high-sensitivity photoresist material. When the photoresist material of the invention is made into a photoresist film, the dissolution contrast and the resolution are high, the exposure margin is excellent, the processing suitability is excellent, the pattern shape after exposure is good, and the etching resistance is better, and the acid is particularly inhibited. Diffusion, so the size difference is small. Because of this, it has high practicability and is very effective as a photoresist material for super LSI. In particular, if an acid generator is contained, a chemically amplified photoresist material which is reacted by an acid catalyst can be used, which is a higher sensitivity and is excellent in various characteristics, and is extremely useful.

Further, by blending the dissolution controlling agent in the photoresist of the present invention, the difference in the dissolution speed between the exposed portion and the unexposed portion can be made larger, and the resolution can be further improved. Further, by adding a basic compound, for example, the diffusion rate of the acid in the photoresist film can be suppressed, the resolution can be further improved, and the coating property can be further improved or controlled by adding a surfactant. .

The photoresist material of the present invention particularly functions as a chemically amplified negative-type photoresist material, and therefore may contain an acid generator. For example, it may contain a compound (photoacid generator) which generates an acid by inducing active light or radiation. In this case, the amount of the photoacid generator to be blended is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the base resin.

The photoacid generator is not particularly limited as long as it is a compound which generates an acid by irradiation with a high-energy ray. The photoacid generator is preferably an onium salt described in JP-A-2009-269953 and a component (F) described in the same publication. The photoacid generator and the photoacid generator described in Japanese Patent No. 3995575 may be a phosphonium salt, a phosphonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimine, or a sulfonium-O-sulfonate. Any of the acid ester type acid generators. These may be used alone or in combination of two or more.

Examples of the acid produced from the acid generator include a sulfonic acid, a ruthenium acid, amethide acid, and the like. Among these, the sulfonic acid which is fluorinated at the α-position is most often used, but in the case of an acetal which is susceptible to deprotection of the acid-unstable group, the α-position does not necessarily have to be fluorinated.

Further, when the base resin contains at least one selected from the group consisting of the repeating units represented by the formulae (f1) to (f3), it is necessary to be an additive type acid generator.

The acid generator is preferably one represented by the following formula (Z1) or (Z2). 【化37】

In the formula, R ¹⁰⁰ represents a hydrogen atom, a fluorine atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms of a hetero atom. X ^a and X ^b each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group. k represents an integer from 1 to 4. R ¹⁰¹ , R ¹⁰² and R ¹⁰³ each independently represent a substituted or unsubstituted linear or branched alkyl or pendant oxyalkyl group having 1 to 10 carbon atoms, or a linear chain having 2 to 10 carbon atoms or A branched alkenyl group, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or an aralkyl group or an aryl-terminated oxyalkyl group having 7 to 19 carbon atoms. Further, any two or more of R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other and form a ring together with the sulfur atoms bonded thereto. R ¹⁰⁴ and R ¹⁰⁵ each independently represent a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom. R ¹⁰⁶ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom. Further, R ¹⁰⁴ and R ^{105 may} be bonded to each other and form a ring together with the sulfur atoms bonded thereto. L' represents a single bond, an ether bond, or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom.

Further, the acid generator is preferably represented by the following formula (Z3) or (Z4). 【化38】

Wherein R ¹⁰¹ , R ¹⁰² and R ^{103 are} as defined above. A represents a hydrogen atom or a trifluoromethyl group. R ¹⁰⁷ represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms of a hetero atom. R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ each independently represent a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms in which a hetero atom is inserted. m and n each independently represent an integer of 0 to 5, and p represents an integer of 0 to 4. L' represents a single bond, an ether bond, or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hetero atom or may be inserted with a hetero atom.

The acid generator is an acid generator represented by the above formula (Z3) or (Z4), and preferably an acid generator of the above formula (Z3) or (Z4) wherein A is a trifluoromethyl group, for example, if it is a line and The pitch pattern can form a pattern with improved acid diffusion length control with low roughness (LWR), and if it is a hole pattern, it can form a pattern with improved roundness and improved dimensional control.

Specific examples of the acid generator represented by the formulae (Z1) to (Z4) are as follows, but are not limited thereto. Further, in the following formula, Ac represents an ethyl group, Ph represents a phenyl group, and Me represents a methyl group. A is the same as above.

【化39】

【化40】

【化41】

【化42】

【化43】

Specific examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentanone, and diacetone; 3-methoxybutanol and 3-methyl-3-methoxy Alcohols such as butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, Ethers such as propylene glycol dimethyl ether and diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, n-butyl lactate, ethyl pyruvate, acetic acid Butyl ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, 2-hydroxyiso Ester such as methyl butyrate, isopropyl 2-hydroxyisobutyrate, isobutyl 2-hydroxyisobutyrate, n-butyl 2-hydroxyisobutyrate; lactones such as γ-butyrolactone; Mix the solvent.

Examples of the basic compound include the first-, second-, and third-order amine compounds described in paragraphs [0146] to [0164] of JP-A-2008-111103, and particularly have a hydroxyl group, an ether group, an ester group, a lactone ring, and a cyanogen group. A compound having a sulfonate group, a compound having a urethane group described in Japanese Patent No. 3790649, and the like.

Further, as the sulfonic acid having an unfluorinated sulfonic acid at the α-position described in JP-A-2008-158339, and the sulfonium salt such as a ruthenium salt, an onium salt or an ammonium salt of the carboxylic acid described in JP-A-2013-37092, Quenching agent. The above-mentioned α-position unfluorinated sulfonate and carboxylate may coexist with the fluorinated sulfonic acid, quinone imidic acid or methylated acid generated from the photoacid generator, and may be exchanged by salt. A sulfonic acid having an alpha fluorination and a carboxylic acid are produced. The acidity of the α-position unfluorinated sulfonic acid and the carboxylic acid does not cause the photoresist resin to undergo a deprotection reaction, so the onium salt, the onium salt and the ammonium salt act as a quencher. In particular, the α-position unfluorinated sulfonic acid, and the carboxylic acid sulfonium salt and sulfonium salt are photodegradable, and the partial quenching ability of the light intensity is lowered, and the fluorinated sulfonic acid and sulfimine at the α position. The concentration of acid and methylated acid increases. Thereby, it is possible to form a pattern in which the contrast of the exposed portion is improved, and the focus margin (DOF) is improved, and the size is well controlled.

When the polarity change unit of the formula (3) in the base resin is sensitive to acid, the acid used to remove it does not necessarily have to be a fluorinated sulfonic acid, sulfamic acid, methyl group. The acid, sometimes the unfluorinated sulfonic acid in the alpha position, also causes the deprotection reaction to proceed. In this case, the sulfonium salt of the sulfonic acid cannot be used as the quencher, and in this case, it is preferred to use the ruthenium salt of the carboxylic acid alone.

Specific examples of the non-fluorinated sulfonate and the carboxylate at the α-position are as follows, but are not limited thereto.

【化44】

【化45】

【化46】

【化47】

【化48】

【化49】

【化50】

【化51】

【化52】

【化53】

【化54】

The surfactant can be described in paragraphs [0165] to [0166] of JP-A-2008-111103. The dissolution control agent can be described in paragraphs [0155] to [0178] of JP-A-2008-122932. The acetylene alcohols can be used in the paragraphs [0179] to [0182].

The blending amount of the organic solvent is preferably 50 to 10,000 parts by mass, more preferably 100 to 5,000 parts by mass, per 100 parts by mass of the base resin. The blending amount of the dissolution controlling agent is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, per 100 parts by mass of the base resin. The blending amount of the basic compound is preferably from 0 to 100 parts by mass, more preferably from 0.001 to 50 parts by mass, per 100 parts by mass of the base resin. The blending amount of the surfactant and acetylene alcohol can be appropriately selected depending on the purpose of blending.

In the photoresist material of the present invention, in order to improve the water repellency of the photoresist surface after spin coating, a water repellency enhancer may be contained. This water borne enhancer can be used to infiltrate lithography without the use of a topcoat. Such a water-repellent enhancer has a specific structure of a 1,1,1,3,3,3-hexafluoro-2-propanol residue, which is described in JP-A-2007-297590, JP-A-2008-111103 Japanese Patent Laid-Open Publication No. 2008-122932, Japanese Laid-Open Patent Publication No. 2012-128067, and Japanese Laid-Open Patent Publication No. 2013-57836.

In addition, when the polymer compound for improving the water repellency is specifically described, it is preferably a polymer composed of one fluorine-containing unit, a copolymer composed of two or more fluorine-containing units, or a fluorine-containing unit and other units. The copolymer formed is preferred. The fluorine-containing unit and other units are exemplified below, but are not limited thereto. Further, in the following formula, R ⁵⁵ is a hydrogen atom or a methyl group.

【化55】

【化56】

【化57】

【化58】

【化59】

【化60】

【化61】

The water repellency enhancer described above must be dissolved in an aqueous alkali solution of the developer. The water-removing agent having the specific 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in a developing solution. As a water-repellent additive, a polymer compound in which an amine group or an amine salt is copolymerized as a repeating unit prevents evaporation of an acid in post-exposure baking (PEB) and prevents opening of a hole pattern after development, line and pitch The effect of the bridge of the pattern is high. The amount of the water-removing agent to be added is preferably 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the base resin.

By the crosslinking reaction by the crosslinking agent, the negative pattern formation by the polarity change of the polymer compound of the present invention can be reinforced. Specific examples of the crosslinking agent include those described in JP-A-2006-145755. When a crosslinking agent is used, it is preferred to use a crosslinking agent insofar as it does not impair the high-resolution performance due to the change in polarity due to the dehydration reaction and the change in solubility by the repeating unit derived from the monomer of the present invention. The blending amount of the crosslinking agent is preferably from 1 to 30 parts by mass, more preferably from 3 to 20 parts by mass, per 100 parts by mass of the base resin.

[Pattern Forming Method] The photoresist material of the present invention, for example, a chemically amplified photoresist material containing a polymer compound, an organic solvent, an acid generator, a basic compound or the like of the present invention can be used in the production of various integrated circuits. It can be applied to the known lithography technology by various steps of coating, heat treatment (prebaking), exposure, heat treatment (exposure baking, PEB) and development. Additional steps can be added as needed.

For example, the negative-type photoresist material of the present invention can be applied to a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, or the like). , SiON, TiN, WSi, BPSG, SOG, multilayer film of antimony-containing anti-reflective film or organic hydrocarbon film) or substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi, SiO _{2 ,} etc.) The film thickness is 0.01 to 2.0 μm. It is prebaked on a hot plate at 60 to 150 ° C for 10 seconds to 30 minutes, more preferably at 80 to 120 ° C for 30 seconds to 20 minutes. Secondly, a light source selected from the group consisting of ultraviolet rays, far ultraviolet rays, electron beams (EB), X-rays, excimer lasers, gamma rays, synchrotron radiation, EUV, soft X-rays, etc., is exposed through a predetermined mask through a target pattern or Direct exposure. Exposure is preferably carried out so that the exposure amount is about 1 to 200 mJ/cm ² , especially 10 to 100 mJ/cm ² , or 0.1 to 100 μC/cm ² , particularly preferably 0.5 to 50 μC/cm ² . Next, the hot plate is preferably 60 to 150 ° C, 10 seconds to 30 minutes, more preferably 80 to 120 ° C for 30 seconds to 20 minutes PEB.

Further, 0.1 to 10% by mass, preferably 2 to 5% by mass, of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylate are used. An alkali developing solution such as ammonium hydroxide (TBAH) is preferably used for 3 seconds to 3 minutes, more preferably 5 seconds to 2 minutes, depending on the dip method, the puddle method, the spray method, and the like. The method develops such that the portion of the illumination is insoluble in the developer, and the exposed portion dissolves and forms a negative pattern of interest on the substrate. Further, water may be used after the development step, preferably for 3 seconds to 3 minutes, more preferably 5 seconds to 2 minutes, by a dipping method such as a dipping method, a dipping method or a spraying method. Further, the photoresist material of the present invention is particularly suitable for fine patterning of KrF excimer lasers, ArF excimer lasers, EB, EUV, soft X-rays, X-rays, gamma rays, synchrotron radiation, etc. in high energy rays. .

The hole pattern and the groove pattern after development can also be shrunk by heat flow, RELACS technique, DSA technique or the like. By applying a shrinking agent to the hole pattern, crosslinking of the shrinking agent occurs on the surface of the resist by diffusion of an acid catalyst from the photoresist layer in the baking, whereby the shrinking agent can be attached to the side wall of the hole pattern. The baking temperature is preferably 70 to 180 ° C, more preferably 80 to 170 ° C, and the baking time is 10 to 300 seconds. Finally, the excess shrinkage agent is removed to shrink the hole pattern. [Examples]

The following examples and comparative examples are specifically described for the present invention, but the present invention is not limited to the following examples and the like. Further, in the following examples, Mw represents tetrahydrofuran (THF) as a solvent, and is converted into polystyrene obtained by GPC.

[1] Synthesis of Monomer [Example 1] Synthesis of Monomer 1 [Chem. 62]

[Example 1-1] Synthesis of triol 1 Under a nitrogen atmosphere, a solution of hydroxyester 1 (56 g) in THF (150 mL) was added dropwise at 25 to 45 ° C at 1.0 mol/L methyl magnesium chloride-THF. Solution (1,080 mL). After stirring at 50 ° C for 10 hours, the reaction solution was ice-cooled, and a mixed aqueous solution of ammonium chloride (108 g) and a 2.4% by mass aqueous hydrochloric acid solution (908 g) was added dropwise to terminate the reaction. The usual aqueous work-up was carried out, and the solvent was distilled off, followed by recrystallization (acetone-diisopropyl ether), filtration, and drying to obtain 48 g of a triol 1 (yield 85%). IR (D-ATR): ν = 3331, 2972, 2930, 2909, 2855, 1453, 1417, 1380, 1367, 1337, 1327, 1275, 1237, 1208, 1175, 1161, 1138, 1119, 1107, 1055, 1032 , 1025, 987, 970, 950, 910, 869, 841, 832, 786, 749, 633, 617, 601, 592 cm ^-1 . ¹ H-NMR (600MHz, DMSO-d ₆ ): δ = 1.00 (12H , s), 1.26-1.38(12H), 2.12(1H, m), 3.84(2H, s), 4.19(1H, s) ppm.

[Example 1-2] Synthesis of Monomer 1 Under a nitrogen atmosphere, methacrylofluorene chloride (23.3 g) was added dropwise at 25 to 45 ° C to triol 1 (37 g), triethylamine (30 g), A mixed solution of N,N-dimethylaminopyridine (1.7 g) and acetonitrile (200 mL). After stirring at 45 ° C for 8 hours, the reaction solution was ice-cooled, and a saturated aqueous sodium hydrogen carbonate solution (100 mL) was added dropwise and the reaction was stopped. After performing normal aqueous work-up and solvent distillation, recrystallization (acetone-hexane), filtration, and drying were carried out to obtain 37 g of monomer 1 (yield 80%). IR (D-ATR): ν = 3385, 2974, 2941, 2885, 2869, 1709, 1636, 1558, 1450, 1409, 1377, 1342, 1323, 1304, 1169, 1139, 1116, 1095, 1010, 995, 986 , 947, 914, 872, 813, 783, 748, 659, 618, 559 cm ^-1 . ¹ H-NMR (600MHz, DMSO-d ₆ ): δ=1.00(12H, s), 1.30-1.38 (3H) , 1.42-1.48(3H), 1.78(2H, d), 1.81(3H, s), 1.89(2H, d), 1.92(2H, s), 2.23(1H, m), 3.99(2H, s), 5.56(1H, s), 5.91(1H, s) ppm.

[Example 2] Synthesis of Monomer 2 [Chem. 63]

[Example 2-1] Synthesis of triol 2 A solution of lactone 1 (50 g) in THF (200 mL) was added dropwise at 25 to 45 ° C in a 1.0 mol/L methyl magnesium chloride-THF solution under a nitrogen atmosphere. (1,150 mL). After stirring at 50 ° C for 10 hours, the reaction solution was ice-cooled, and a mixed aqueous solution of ammonium chloride (115 g) and a 2.4% by mass aqueous hydrochloric acid (960 g) was added dropwise, and the reaction was stopped. After performing a usual aqueous work-up and solvent distillation, recrystallization (ethyl acetate-hexane) was carried out, filtration, and drying to obtain 52 g of a triol 2 (yield 90%). ¹ H-NMR (600MHz, DMSO-d ₆ ): δ = 1.11 (1H, dd), 1.19 (3H, s), 1.28 (1H, m), 1.29 (3H, s), 1.40 (3H, s), 1.50(3H, s), 1.68-1.76(2H), 2.09(1H, d), 2.27-2.35(2H), 2.44(1H, m), 3.98(1H, m), 6.21(1H, s), 6.37 (1H, d), 7.30(1H, s) ppm.

[Example 2-2] Synthesis of Monomer 2 Under a nitrogen atmosphere, methacrylic anhydride (43 g) was added dropwise at 25 to 45 ° C to triol 2 (45 g), triethylamine (40 g), N, A mixed solution of N-dimethylaminopyridine (2.4 g) and THF (200 mL). After stirring at 45 ° C for 10 hours, the reaction solution was ice-cooled, and a saturated aqueous sodium hydrogen carbonate solution (100 mL) was added dropwise, and the reaction was stopped. After performing normal aqueous work-up and solvent distillation, recrystallization (ethyl acetate-hexane) was carried out, filtration, and drying to obtain 53 g of monomer 2 (yield 90%). IR (D-ATR): ν = 3254, 3164, 3022, 2960, 2933, 2883, 1704, 1636, 1498, 1576, 1449, 1412, 1381, 1363, 1328, 1301, 1259, 1202, 1180, 1162, 1135 , 1107, 1047, 1018, 953, 934, 862, 850, 835, 814, 776, 733, 627, 570 cm ^-1 . ¹ H-NMR (600 MHz, DMSO-d ₆ ): δ = 1.12 (3H, s ), 1.25(1H, m), 1.24(3H, s), 1.30(1H, m), 1.41(3H, s), 1.42(3H, s), 1.68(1H, m), 1.86(3H, s) , 2.16(1H, ddd), 2.23(1H, dd), 2.42(1H, m), 2.58(1H, m), 2.63(1H, m), 4.94(1H, m), 5.56(2H), 5.81( 1H, s), 6.31(1H, s) ppm.

[Example 3] Synthesis of Monomer 3 [Chem. 64]

[Example 3-1] Synthesis of triol 3 The triol 3 was synthesized in the same manner as in Example 2-1 except that the hydroxyl lactone 1 was used as a material. Further, the triol 3 was not purified, and was directly used in the next reaction after the reaction.

[Example 3-2] Synthesis of Monomer 3 In the same manner as in Example 2-2, except that the triol 3 was used as a raw material, the monomer 3 was synthesized (white crystal, from the two steps of the hydroxyl lactone 1). The yield was 72%). IR (D-ATR): ν = 3160, 3003, 2977, 2920, 2877, 1709, 1639, 1628, 1498, 1466, 1437, 1393, 1381, 1367, 1322, 1248, 1202, 1153, 1051, 1005, 985 , 956, 933, 902, 857, 847, 814, 779, 729, 701, 645, 610, 599 cm ^-1 . ¹ H-NMR (600 MHz, DMSO-d ₆ ): δ = 1.20 (3H, s), 1.21(6H), 1.22(3H, s), 1.31(1H, d), 1.43(1H, m), 1.47(1H, d), 1.75(1H, m), 1.83(1H, m), 1.84(3H , s), 1.87(1H, m), 2.01(1H, m), 2.05(1H, d), 4.62(1H, d), 5.62(1H, m), 5.97(1H, m), 6.03(1H, s), 6.10(1H, s) ppm.

[Example 4] Synthesis of Monomer 4 [Chem. 65]

[Example 4-1] Synthesis of triol 4 Triol 4 was synthesized in the same manner as in Example 2-1 except that hydroxyester 2 was used as a material. Further, the triol 4 was not purified, and was directly used in the next reaction after the reaction.

[Example 4-2] Synthesis of Monomer 4 In the same manner as in Example 2-2 except that triol 4 was used as a raw material, a monomer 4 (white crystal, 2 steps from hydroxyester 2) was synthesized. The yield was 70%). IR (D-ATR): ν = 3314, 2973, 2922, 2898, 1709, 1636, 1468, 1446, 1421, 1384, 1371, 1338, 1322, 1300, 1206, 1173, 1159, 1141, 1120, 1055, 1038 , 1008, 979, 968, 939, 905, 896, 850, 815, 658, 620, 608 cm ^-1 . ¹ H-NMR (600 MHz, DMSO-d ₆ ): δ = 1.07 (3H, s), 1.17 ( 3H, s), 1.19(3H, s), 1.28(3H, s), 1.34(1H, d), 1.38(1H, d), 1.45(1H, d), 1.48(1H, m), 1.73(1H , m), 1.84(3H, s), 1.88(1H, dd), 2.09(1H, d), 2.29(1H, d), 5.11(1H, d), 5.19(1H, s), 5.29(1H, s), 5.62(1H, m), 5.97(1H, m) ppm.

[Example 5] Synthesis of Monomer 5 [Chem. 66]

Monomer 5 (white crystals, yield 86%) was synthesized in the same manner as in Example 1-2 except that acrylonitrile was used as the material.

[Example 6] Synthesis of Monomer 6 [Chem. 67]

Monomer 6 (white crystals, yield 76%) was synthesized in the same manner as in Example 1-2 except that methacrylic acid was used as the material.

[Example 7] Synthesis of Monomer 7 [Chem. 68]

A solution of hydroxyester 3 (61 g) in THF (500 mL) was added dropwise to a solution of 1.0 mol/L methylmagnesium chloride-THF (1,500 mL) at 25 to 45 ° C under a nitrogen atmosphere. After stirring at 50 ° C for 10 hours, the reaction solution was ice-cooled, and then methacrylic anhydride (58 g) was added dropwise at 30 ° C or lower to a suspension of the alkoxide corresponding to the tetraol 1 in the above formula. After stirring at 25 ° C for 4 hours, the reaction solution was ice-cooled, and a mixed aqueous solution of ammonium chloride (150 g) and a 2.4% by mass aqueous hydrochloric acid solution (1,250 g) was added dropwise, and the reaction was stopped. After performing the usual aqueous work-up and solvent distillation, recrystallization (ethyl acetate-THF-hexane), filtration, and drying were carried out to obtain 37 g of monomer 7 (the yield of the two steps was 51). %).

[Example 8] Synthesis of Monomer 8 [Chem. 69]

[Example 8-1] Synthesis of triol 5 Triol 5 was synthesized in the same manner as in Example 2-1 except that hydroxyester 4 was used as a material. Further, the triol 5 was not purified, and was directly used in the next reaction after the reaction.

[Example 8-2] Synthesis of Monomer 8 In the same manner as in Example 2-2 except that triol 5 was used as a material, a monomer 8 (white crystal, step 2 from hydroxyester 4) was synthesized. Yield 80%). IR (D-ATR): ν = 3471, 3278, 2969, 2864, 1708, 1639, 1452, 1383, 1317, 1300, 1258, 1219, 1177, 1146, 1120, 1091, 1020, 982, 948, 898, 866 , 846, 815, 797, 755, 720, 652, 621, 611, 593, 567, 556 cm ^-1 . ¹ H-NMR (600 MHz, DMSO-d ₆ ): δ = 0.68 (1H, m), 0.96-1.07 (14H), 1.30(2H, m), 1.81-1.86(4H), 2.01(2H, m), 4.12(2H, s), 4.66(1H, m), 5.63(1H, m), 5.99(1H, m) ppm.

[2] Synthesis of polymer compound [Examples 9 to 27, Comparative Examples 1 to 9] In the polymer compound used for the photoresist material, each monomer was combined and copolymerized in a cyclopentanone solvent. The mixture was separated into hexane, washed repeatedly with hexane, and then separated and dried to obtain polymer compounds (polymers 1 to 19 and comparative polymers 1 to 9) shown below. The composition of the obtained polymer compound was confirmed by ¹ H-NMR and ¹³ C-NMR.

[Example 9] Polymer 1 Mw = 8,500 Mw / Mn = 1.67 [Chem. 70]

[Example 10] Polymer 2 Mw = 8,400 Mw / Mn = 1.65 [Chem. 71]

[Example 11] Polymer 3 Mw = 8,300 Mw / Mn = 1.67 [Chem. 72]

[Example 12] Polymer 4 Mw = 8,300 Mw / Mn = 1.66 [Chem. 73]

[Example 13] Polymer 5 Mw = 8,500 Mw / Mn = 1.66 [Chem. 74]

[Example 14] Polymer 6 Mw = 8,600 Mw / Mn = 1.61 [Chem. 75]

[Example 15] Polymer 7 Mw = 8,400 Mw / Mn = 1.67 [Chem. 76]

[Example 16] Polymer 8 Mw = 8,500 Mw / Mn = 1.62 [Chem. 77]

[Example 17] Polymer 9 Mw = 8,500 Mw / Mn = 1.64 [Chem. 78]

[Example 18] Polymer 10 Mw = 8,600 Mw / Mn = 1.62 [Chem. 79]

[Example 19] Polymer 11 Mw = 8,300 Mw / Mn = 1.61 [Chem. 80]

[Example 20] Polymer 12 Mw = 8,500 Mw / Mn = 1.63 [Chem. 81]

[Example 21] Polymer 13 Mw = 8,300 Mw / Mn = 1.62 [Chem. 82]

[Example 22] Polymer 14 Mw = 8,300 Mw / Mn = 1.62 [Chem. 83]

[Example 23] Polymer 15 Mw = 8,500 Mw / Mn = 1.60 [Chem. 84]

[Example 24] Polymer 16 Mw = 8,100 Mw / Mn = 1.65 [Chem. 85]

[Example 25] Polymer 17 Mw = 8,000 Mw / Mn = 1.63 [Chem. 86]

[Example 26] Polymer 18 Mw = 8,200 Mw / Mn = 1.64 [Chem. 87]

[Example 27] Polymer 19 Mw = 8,100 Mw / Mn = 1.63 [Chem. 88]

[Comparative Example 1] Comparative polymer 1 Mw = 8,400 Mw / Mn = 1.65 [Chem. 89]

[Comparative Example 2] Comparative polymer 2 Mw = 8,500 Mw / Mn = 1.63 [Chemical 90]

[Comparative Example 3] Comparative polymer 3 Mw = 8,700 Mw / Mn = 1.65 [Chem. 91]

[Comparative Example 4] Comparative polymer 4 Mw = 8,600 Mw / Mn = 1.62 [Chem. 92]

[Comparative Example 5] Comparative polymer 5 Mw = 8,400 Mw / Mn = 1.66 [Chem. 93]

[Comparative Example 6] Comparative polymer 6 Mw = 8,600 Mw / Mn = 1.63 [Chem. 94]

[Comparative Example 7] Comparative polymer 7 Mw = 8,600 Mw / Mn = 1.63 [Chem. 95]

[Comparative Example 8] Comparative polymer 8 Mw = 8,500 Mw / Mn = 1.61 [Chem. 96]

[Comparative Example 9] Comparative polymer 9 Mw = 8,400 Mw / Mn = 1.65 [Chem. 97]

[3] Preparation of Photoresist Material [Examples 28 to 46, Comparative Examples 10 to 18] The polymer compound obtained by the above examples and comparative examples was formulated with a photoresist as shown in the following Tables 1 and 2 to 0.2. The Teflon (registered trademark) filter of μm was filtered to prepare photoresist materials R-01 to R-28, respectively.

Further, in Tables 1 and 2, a photoacid generator (PAG-1 to PAG-4), a water-repellent polymer (SF-1), a sensitivity adjuster (Q-1 to Q-4), and a crosslinking agent (XL) -1), and the solvent is as follows.

Photoacid generator: PAG-1~PAG-4

Sensitivity modifier: Q-1~Q-4 【化99】

Water-repellent polymer: SF-1 Mw=8,700 Mw/Mn=1.85 【化100】

Crosslinking agent: XL-1 【化101】

PGEE: propylene glycol monoethyl ether GBL: γ-butyrolactone

【Table 1】         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> photoresist material</td><td> resin (mass parts </td><td> Photoacid generator (parts by mass) </td><td> Sensitivity modifier (parts by mass) </td><td> Water-repellent polymer (parts by mass) </td>< Td> Crosslinker (parts by mass) </td><td> Solvent (parts by mass) </td></tr><tr><td> Example 28 </td><td> R-01 </ Td><td> Polymer 1 (100) </td><td> PAG-1 (6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 29 </td><td> R-02 </td><td> Polymer 2 (100) </td><td> PAG-1 (6.0) </td><td> Q-1 (3.5) </td><td> SF-1 ( 5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 30 </td><td> R -03 </td><td> Polymer 3 (100) </td><td> PAG-2 (6.0) </td><td> Q-4 (8.0) </td><td> SF- 1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 31 </td><td > R-04 </td><td> Polymer 4 (100) </td><td> PAG-3 (6.0) </td><td> Q-4 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2 000) GBL(500) </td></tr><tr><td> Example 32 </td><td> R-05 </td><td> Polymer 5 (100) </td> <td> PAG-4 (6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 33 </td><td> R-06 </td><td> Polymer 6 (100) </ Td><td> PAG-1 (6.0) </td><td> Q-2 (3.0) </td><td> SF-1 (5.0) </td><td> - </td>< Td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 34 </td><td> R-07 </td><td> Polymer 7 (100) </td><td> PAG-1 (6.0) </td><td> Q-1 (3.5) </td><td> SF-1 (5.0) </td><td> - </td ><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 35 </td><td> R-08 </td><td> Polymer 8 ( 100) </td><td> PAG-1 (6.0) </td><td> Q-2 (3.0) </td><td> SF-1 (5.0) </td><td> - < /td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 36 </td><td> R-09 </td><td> Polymer 9 (100) </td><td> PAG-1 (6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 37 </td><td> R-10 </td><td> Polymer 10 (100) </td><td> PAG-4 (6.0) </td><td> Q-4 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL( 500) </td></tr><tr><td> Example 38 </td><td> R-11 </td><td> Polymer 11 (100) </td><td> - </td><td> Q-4 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) < /td></tr><tr><td> Example 39 </td><td> R-12 </td><td> Polymer 12 (100) </td><td> PAG-1 ( 6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE( 2000) GBL(500) </td></tr><tr><td> Example 40 </td><td> R-13 </td><td> Polymer 13 (100) </td> <td> PAG-1 (6.0) </td><td> Q-1 (3.5) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE (2000) GBL (500) </td></tr><tr><td> Example 41 </td><td> R-14 </td><td> Polymer 14 (100) </ Td><td> PAG-1 (6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td>< Td> PGEE(2000) GBL(500) </td></tr><tr><td> Example 42 </td><td> R-15 </td><td> Polymer 15 (100) </td><td> PAG-1 (6.0) </td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td ><td> PGEE(2000) GBL(500) </td></tr><t r><td> Example 43 </td><td> R-16 </td><td> Polymer 16 (100) </td><td> PAG-1 (6.0) </td><td > Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr ><tr><td> Example 44 </td><td> R-17 </td><td> Polymer 17 (100) </td><td> PAG-4 (6.0) </td> <td> Q-2 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td>< /tr><tr><td> Example 45 </td><td> R-18 </td><td> Polymer 18 (100) </td><td> PAG-1 (6.0) </ Td><td> Q-3 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td ></tr><tr><td> Example 46 </td><td> R-19 </td><td> Polymer 19 (100) </td><td> PAG-4 (6.0) </td><td> Q-2 (8.0) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) < /td></tr></TBODY></TABLE>

【Table 2】         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> photoresist material</td><td> resin (mass parts </td><td> Photoacid generator (parts by mass) </td><td> Sensitivity modifier (parts by mass) </td><td> Water-repellent polymer (parts by mass) </td>< Td> Crosslinker (parts by mass) </td><td> Solvent (parts by mass) </td></tr><tr><td> Comparative Example 10 </td><td> R-20 </ Td><td> Comparative Polymer 1 (100) </td><td> PAG-2 (12.5) </td><td> Q-4 (1.5) </td><td> SF-1 (5.0 </td><td> - </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Comparative Example 11 </td><td> R- 21 </td><td> Comparative Polymer 2 (100) </td><td> PAG-4 (10.0) </td><td> Q-3 (1.5) </td><td> SF- 1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE(2000) GBL(500) </td></tr><tr><td> Comparative Example 12 < /td><td> R-22 </td><td> Comparative Polymer 3 (100) </td><td> PAG-3 (12.5) </td><td> Q-4 (1.5) < /td><td> SF-1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE(2000) GBL(500) </td></tr><tr ><td> Comparative Example 13 </td><td> R-23 </td><td> Comparative Polymer 4 (100) </td><td> PAG-1 (10.0) </td><td > Q-1 (1.5) </t d><td> SF-1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE(2000) GBL(500) </td></tr><tr> <td> Comparative Example 14 </td><td> R-24 </td><td> Comparative Polymer 5 (100) </td><td> - </td><td> Q-1 (1.5 </td><td> SF-1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE(2000) GBL(500) </td></tr> <tr><td> Comparative Example 15 </td><td> R-25 </td><td> Comparative Polymer 6 (100) </td><td> PAG-1 (10.0) </td> <td> Q-1 (1.5) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </td>< /tr><tr><td> Comparative Example 16 </td><td> R-26 </td><td> Comparative Polymer 7 (100) </td><td> PAG-1 (6.0) < /td><td> Q-1 (3.5) </td><td> SF-1 (5.0) </td><td> - </td><td> PGEE(2000) GBL(500) </ Td></tr><tr><td> Comparative Example 17 </td><td> R-27 </td><td> Comparative Polymer 8 (100) </td><td> PAG-1 ( 10.0) </td><td> Q-3 (1.5) </td><td> SF-1 (5.0) </td><td> XL-1 (5.0) </td><td> PGEE( 2000) GBL(500) </td></tr><tr><td> Comparative Example 18 </td><td> R-28 </td><td> Comparative Polymer 9 (100) </td ><td> PAG-1 (10.0) </td><td> Q-3 (1.5) </td><td> SF-1 (5.0) </td><td> XL-1 (5.0) < /td><td> PGEE(2 000) GBL(500) </td></tr></TBODY></TABLE>

[4] Evaluation of swelling of a photoresist material in development using a QCM (quartz crystal microbalance) method [Examples 47 to 50, Comparative Example 19] Prepared by the compositions shown in Tables 1 and 2 above. The photoresist of the present invention and the photoresist of the comparative example were spin-coated on the QCM substrate to a thickness of 100 nm, and baked at 100 ° C for 60 seconds on a hot plate. After an ArF exposure apparatus in an open frame level 1mJ / cm ² from an exposure amount of 1mJ / cm ² to 13mJ / cm ² exposure, post-exposure using a hot plate, a temperature shown in Table 3 for 60 seconds PEB. Then, the photoresist film on the QCM substrate was subjected to development analysis apparatus RDA-Qz3 (manufactured by Litho Tech Co., Ltd.), and the film thickness of the photoresist film with respect to the development time was observed in a 2.38 mass% TMAH aqueous solution. Table 3 shows the ratio of the exposure amount and the maximum swelling amount (the maximum swelling amount is normalized to the initial film thickness) in which the development time of each exposure amount and the film thickness variation pattern are the maximum swelling amount. The smaller the maximum swelling ratio, the more it inhibits the swelling of the photoresist film.

【table 3】         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist material</td><td> PEB temperature (°C </td><td> Exposure (mJ/cm²) </td><td> Maximum swelling ratio (%) </td></tr><tr><td > Example 47 </td><td> R-02 </td><td> 100 </td><td> 7 </td><td> 133 </td></tr><tr>< Td> Example 48 </td><td> R-05 </td><td> 120 </td><td> 6 </td><td> 110 </td></tr><tr> <td> Example 49 </td><td> R-06 </td><td> 100 </td><td> 7 </td><td> 140 </td></tr><tr ><td> Example 50 </td><td> R-07 </td><td> 100 </td><td> 4 </td><td> 116 </td></tr>< Tr><td> Comparative Example 19 </td><td> R-17 </td><td> 100 </td><td> 7 </td><td> 191 </td></tr> </TBODY></TABLE>

From the results of Table 3, it was confirmed that the photoresist material of the present invention has a smaller maximum swelling amount than the photoresist material of the comparative example.

[5] Evaluation of etching resistance [Examples 51 to 53 and Comparative Examples 20 to 21] Wafer wafers which had been surface-treated (90 ° C, 60 seconds) in the gas phase of hexamethyldioxane (HMDS) The photoresist material of the present invention and the photoresist material of the comparative example shown in Tables 1 and 2 above were spin-coated, and baked at 100 ° C for 60 seconds (PAB) using a hot plate to make the thickness of the photoresist film 100 nm. Thereafter, the wafer was subjected to open frame exposure in an ArF excimer laser scanning exposure machine (NSR-307E, manufactured by Nikon Co., Ltd., NA = 0.85). The amount of exposure at this time was set to 50 mJ/cm ^{2 in} order to generate an acid sufficient for the deprotection reaction from the photoacid generator. Thereafter, PEB was carried out at a temperature shown in Table 4 at 60 seconds to promote a dehydration reaction or a crosslinking reaction in the base resin forming the photoresist film. In the base resin of the present invention, the portion where the dehydration reaction occurs corresponds to the insoluble portion at the time of development. The ratio of the amount of decrease in the thickness of the photoresist film due to exposure and PEB treatment to the film thickness before the treatment was determined as the amount of shrinkage (%) of PEB. Further, development was carried out for 30 seconds in a 2.38 mass% TMAH aqueous solution, and then the thickness of the photoresist film was measured, and the difference between the film thickness after the PEB treatment and the film thickness after development was measured to determine the minimum dissolution rate (nm/sec). When the amount of shrinkage of PEB or the minimum dissolution rate is small, it is preferable to ensure sufficient film thickness required for dry etching or to thin the initial film thickness, thereby being advantageous in resolution. The results are shown in Table 4.

【Table 4】         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist material</td><td> PEB temperature (°C </td><td> PEB shrinkage (%) </td><td> very small dissolution rate (nm/sec) </td></tr><tr><td> Example 51 </td> <td> R-08 </td><td> 95 </td><td> 93 </td><td> 0.03 </td></tr><tr><td> Example 52 </td ><td> R-09 </td><td> 100 </td><td> 92 </td><td> 0.04 </td></tr><tr><td> Example 53 </ Td><td> R-10 </td><td> 90 </td><td> 90 </td><td> 0.06 </td></tr><tr><td> Comparative Example 20 < /td><td> R-21 </td><td> 100 </td><td> 85 </td><td> 0.05 </td></tr><tr><td> Comparative Example 21 </td><td> R-22 </td><td> 100 </td><td> 92 </td><td> 0.1 </td></tr></TBODY></TABLE>

From the results of Table 4, it was confirmed that the photoresist of the present invention has a small amount of PEB shrinkage and a very small dissolution rate. Therefore, it is revealed that the residual pattern film thickness after development is thick, and the etching resistance after patterning is also excellent.

[6] ArF exposure patterning evaluation (1) [Examples 54 to 69, Comparative Examples 22 to 29] The photoresist materials of the present invention prepared according to the compositions shown in Tables 1 and 2 above and the photoresist materials of Comparative Examples were spun. The substrate was coated on a substrate having a thickness of 78 nm on a substrate of ARC29A (manufactured by Nissan Chemical Industries Co., Ltd.), and baked at 100 ° C for 60 seconds using a hot plate to make the thickness of the photoresist film 100 nm. The wafer was mounted on an on-wafer by an ArF excimer laser scanning exposure machine (Nikon NSR-S307E, NA=0.85, σ0.93/0.74, Annular illumination, 6% half-tone phase shifting mask). The dimensions are 90 nm pitch and 180 nm pitch, pitch width 80 nm and 160 nm pitch, and line and pitch pattern (LS pattern) with a pitch width of 70 nm and a pitch of 140 nm, and a trench pattern with a pitch of 90 nm and a pitch of 1,650 nm. In order to change the exposure amount and the focus (exposure pitch: 1 mJ/cm ² , focus pitch: 0.025 μm), after exposure, PEB was performed at a temperature shown in Table 5 at 60 seconds to 2.38 mass% of TMAH. The aqueous solution was immersed and developed for 30 seconds, rinsed with pure water, and spun dry to obtain a negative pattern. The developed LS pattern and the trench pattern were observed by TD-SEM (S-9380 manufactured by Hitachi Advanced Technology Co., Ltd.).

[Sensitivity Evaluation] The sensitivity was obtained by obtaining an optimum exposure amount E _op (mJ/cm ² ) of the LS pattern having the pitch width of 90 nm and a pitch of 180 nm. The results are shown in Table 5. The smaller the score, the higher the sensitivity.

[Exposure margin (EL) evaluation] In terms of exposure margin evaluation, the exposure margin is sequentially obtained from the exposure amount formed by the LS pattern within a range of ±10% (81 to 99 nm) from the width of 90 nm ( unit:%). The results are shown in Table 5. Exposure margin (%)=(|E ₁ -E ₂ |/E _op )×100 E ₁ : Appropriate exposure amount E ₂ of LS pattern having a pitch width of 81 nm and a pitch of 180 nm: a given pitch width of 99 nm and a pitch of 180 nm The optimum exposure amount of the LS pattern E _op : the optimum exposure amount of the LS pattern with a pitch of 90 nm and a pitch of 180 nm

[Line width roughness (LWR) evaluation] The LS pattern obtained by irradiation with the optimum exposure amount in the sensitivity evaluation described above was measured at 10 dimensions along the longitudinal direction of the wide pitch, and the standard deviation (σ) was obtained as a result. Double 値 (3σ), defined as LWR. The results are shown in Table 5. The smaller the ridge, the smaller the roughness, and the more uniform the pattern of the pitch.

[Density of Focus (DOF) Evaluation] In the evaluation of the depth of focus, a focus range formed within a range of ±10% (81 to 99 nm) in width of the 90 nm pitch of the trench pattern was obtained. The results are shown in Table 5. The greater the size, the greater the depth of focus.

[Resolution Force Evaluation] The pattern size of the LS pattern of 70 to 90 nm (pitch 140 to 180 nm) is defined as the resolution. The results are shown in Table 5. The smaller the size, the better the resolution.

【table 5】         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist material</td><td> PEB temperature (°C </td><td> E_op (mJ/cm²) </td><td> EL (%) </td><td> LWR ( Nm) </td><td> DOF (μm) </td><td> resolution (nm) </td></tr><tr><td> Example 54 </td><td> R- 01 </td><td> 100 </td><td> 35.8 </td><td> 15.3 </td><td> 6.5 </td><td> 0.18 </td><td> 70 < /td></tr><tr><td> Example 55 </td><td> R-02 </td><td> 100 </td><td> 32.5 </td><td> 14.5 </td><td> 6.2 </td><td> 0.18 </td><td> 70 </td></tr><tr><td> Example 56 </td><td> R- 03 </td><td> 110 </td><td> 40.3 </td><td> 18.6 </td><td> 6.8 </td><td> 0.18 </td><td> 70 < /td></tr><tr><td> Example 57 </td><td> R-04 </td><td> 100 </td><td> 33 </td><td> 13.2 </td><td> 6.3 </td><td> 0.16 </td><td> 70 </td></tr><tr><td> Example 58 </td><td> R- 05 </td><td> 120 </td><td> 45.2 </td><td> 14.2 </td><td> 7.9 </td><td> 0.14 </td><td> 80 < /td></tr><tr><td> Example 59 </td><td> R-06 </td><td> 100 </td><td> 44.9 </td><td> 13.4 </td>< Td> 7.3 </td><td> 0.18 </td><td> 70 </td></tr><tr><td> Example 60 </td><td> R-07 </td> <td> 105 </td><td> 47.3 </td><td> 15.6 </td><td> 7.5 </td><td> 0.16 </td><td> 80 </td></ Tr><tr><td> Example 61 </td><td> R-08 </td><td> 95 </td><td> 51 </td><td> 16 </td>< Td> 6.1 </td><td> 0.16 </td><td> 70 </td></tr><tr><td> Example 62 </td><td> R-09 </td> <td> 100 </td><td> 53.2 </td><td> 17.2 </td><td> 6.3 </td><td> 0.18 </td><td> 70 </td></ Tr><tr><td> Example 63 </td><td> R-10 </td><td> 90 </td><td> 48.5 </td><td> 15.8 </td>< Td> 5.9 </td><td> 0.18 </td><td> 70 </td></tr><tr><td> Example 64 </td><td> R-12 </td> <td> 95 </td><td> 31.2 </td><td> 17.5 </td><td> 7.2 </td><td> 0.18 </td><td> 80 </td></ Tr><tr><td> Example 65 </td><td> R-13 </td><td> 100 </td><td> 34 </td><td> 15.5 </td>< Td> 6.4 </td><td> 0.18 </td><td> 70 </td></tr><tr><td> Example 66 </td><td> R-25 </td> <td> 100 </td><td> 36 </td><td> 15.1 </td><td> 6.3 </td><td> 0.18 </td><td> 70 </td></ Tr><tr><td> Example 67 </td><td> R-26 </td> <td> 100 </td><td> 38 </td><td> 15.7 </td><td> 5.9 </td><td> 0.14 </td><td> 70 </td></ Tr><tr><td> Example 68 </td><td> R-27 </td><td> 100 </td><td> 35 </td><td> 14.1 </td>< Td> 6.4 </td><td> 0.18 </td><td> 70 </td></tr><tr><td> Example 69 </td><td> R-28 </td> <td> 100 </td><td> 37 </td><td> 15.5 </td><td> 6.1 </td><td> 0.16 </td><td> 70 </td></ Tr><tr><td> Comparative Example 22 </td><td> R-16 </td><td> 100 </td><td> 36.3 </td><td> 9.5 </td>< Td> 10.3 </td><td> 0.1 </td><td> 90 </td></tr><tr><td> Comparative Example 23 </td><td> R-17 </td> <td> 95 </td><td> 25.3 </td><td> 10.5 </td><td> 9.8 </td><td> 0.08 </td><td> 90 </td></ Tr><tr><td> Comparative Example 24 </td><td> R-18 </td><td> 110 </td><td> 28.3 </td><td> 8.3 </td>< Td> 11.5 </td><td> 0.1 </td><td> 90 </td></tr><tr><td> Comparative Example 25 </td><td> R-19 </td> <td> 100 </td><td> 38.5 </td><td> 5.6 </td><td> 15.2 </td><td> 0.12 </td><td> 90 </td></ Tr><tr><td> Comparative Example 26 </td><td> R-20 </td><td> 100 </td><td> 35.6 </td><td> 7.5 </td>< Td> 9.5 </td><td> 0.08 </td><td> 90 </td> </tr><tr><td> Comparative Example 27 </td><td> R-21 </td><td> 110 </td><td> 30.5 </td><td> 6 </td ><td> 16.3 </td><td> 0.1 </td><td> 90 </td></tr><tr><td> Comparative Example 28 </td><td> R-22 </ Td><td> 100 </td><td> 45.3 </td><td> 10.1 </td><td> 13.2 </td><td> 0.1 </td><td> 90 </td> </tr><tr><td> Comparative Example 29 </td><td> R-23 </td><td> 100 </td><td> 33.3 </td><td> 6.6 </td ><td> 10.7 </td><td> 0.08 </td><td> 90 </td></tr></TBODY></TABLE>

From the results of Table 5, it was confirmed that the photoresist material of the present invention has practical sensitivity. Further, it was confirmed that the exposure margin and the depth of focus also have a broad margin, and the LWR is also smaller than the photoresist of the comparative example. And confirm that the resolution is also excellent.

[7] ArF exposure patterning evaluation (2) [Examples 70 to 73, Comparative Example 30] The photoresist materials of the present invention prepared in the compositions shown in Tables 1 and 2 and the photoresist materials of the comparative examples were spin-coated. Formed a Shin Kong Chemical Industry Co., Ltd. spin-on carbon film ODL-180 (carbon content of 80% by mass) 180nm thick, on which a spin-coated hard mask SHB-A940 containing ruthenium was formed On a three-layer processing substrate of 43 mass%) and 35 nm thick, it was baked at 100 ° C for 60 seconds using a hot plate, and the thickness of the photoresist film was 60 nm. It was exposed to an ArF excimer laser-wet scanning exposure machine (Nikon NSR-S610C, NA1.30, σ0.90/0.72, cross-pole opening 35 degrees, Azimuthally polarized illumination, 6% half-tone) Phase shift mask, crosspole illumination), on-wafer size 55nm, pitch while making exposure and focus change (exposure pitch: 1mJ/cm ² , focus pitch: 0.025μm) Exposure of a contact hole pattern (CH pattern) of 110 nm, exposure to a PEB for 60 seconds at a temperature shown in Table 6, and immersion development with a 2.38 mass% aqueous solution of TMAH for 30 seconds, rinsing with pure water, and spinning to obtain Negative pattern. The CH pattern after development was observed by TD-SEM (CG4000 manufactured by Hitachi Advanced Technology Co., Ltd.).

[Sensitivity Evaluation] The sensitivity was obtained by obtaining an optimum exposure amount E _op (mJ/cm ² ) of a CH pattern having a hole size of 55 nm and a pitch of 110 nm. The results are shown in Table 6. The smaller the score, the higher the sensitivity.

[Evaluation of Exposure Margin (EL)] The exposure margin was evaluated by exposing the exposure amount from the above-described CH pattern to a range of ±10% (49.5 to 60.5 nm) in a pore size of 55 nm. %). The results are shown in Table 6. Exposure margin (%)=(|E ₁ -E ₂ |/E _op )×100 E ₁ : optimum exposure amount E ₂ of a CH pattern having a hole size of 49.5 nm and a pitch of 110 nm: a hole size of 60.5 nm, a pitch Optimum exposure amount of CH pattern from 110 nm E _op : optimum exposure amount of CH pattern with a hole size of 55 nm and a pitch of 110 nm

[Evaluation of Dimensional Uniformity (CDU)] For the CH pattern obtained by irradiating with the optimum exposure amount in the above-described sensitivity evaluation, the size of 10 points (9 CH patterns per one shot) in the same exposure amount spot was measured. From the results, 3 times 値 (3σ) of the standard deviation (σ) was obtained, which was defined as size uniformity (CDU). The results are shown in Table 6. The smaller the enthalpy, the better the uniformity of the size of the CH pattern.

[Table 6]         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist material</td><td> PEB temperature (°C </td><td> E_op (mJ/cm²) </td><td> EL (%) </td><td> CDU 3σ (nm) </td></tr><tr><td> Example 70 </td><td> R-02 </td><td> 100 </td><td> 24.3 </td> <td> 9.6 </td><td> 7.1 </td></tr><tr><td> Example 71 </td><td> R-08 </td><td> 95 </td ><td> 35.6 </td><td> 11.1 </td><td> 6.8 </td></tr><tr><td> Example 72 </td><td> R-09 </ Td><td> 100 </td><td> 38 </td><td> 12.5 </td><td> 6.3 </td></tr><tr><td> Example 73 </td ><td> R-10 </td><td> 90 </td><td> 32.2 </td><td> 10.5 </td><td> 6.7 </td></tr><tr> <td> Comparative Example 30 </td><td> R-16 </td><td> 100 </td><td> 22.3 </td><td> 7.2 </td><td> 10.1 </ Td></tr></TBODY></TABLE>

From the results of Table 6, it was confirmed that the photoresist of the present invention has practical sensitivity. Further, it was confirmed that the exposure margin has a wide margin and the dimensional uniformity is also excellent.

[8] EB drawing evaluation [Examples 74 to 77, Comparative Examples 31 to 32] The photoresist materials of the present invention prepared in the compositions shown in Tables 1 and 2 and the photoresist materials of Comparative Examples were spin-coated on HMDS gas. The surface was treated with a surface treatment (90 ° C, 60 seconds), and baked at 100 ° C for 60 seconds using a hot plate to make the thickness of the photoresist film 60 nm. The electron beam drawing device (JBX-9000, Accelerated Voltage 50 kV, manufactured by JEOL Ltd.) was used to change the irradiation amount (the irradiation pitch: ² μC/cm ² ) while the wafer size was 100 nm wide and the pitch was wide. The LS pattern of 200 nm was drawn, and after drawing, PEB was performed for 60 seconds at the temperature shown in Table 7, and it was immersed and developed with a 2.38 mass% TMAH aqueous solution for 30 seconds, rinsed with pure water, and dried to obtain a negative pattern. The developed LS pattern was observed by TD-SEM (S-9380, manufactured by Hitachi Advanced Technology Co., Ltd.).

[Sensitivity Evaluation] With respect to the sensitivity, the optimum exposure amount E _op (μC/cm ² ) of the LS pattern having the above-described pitch width of 100 nm and a pitch of 200 nm was obtained. The results are shown in Table 7. The smaller the score, the higher the sensitivity.

[Evaluation of Exposure Margin (EL)] In terms of exposure margin evaluation, an exposure margin is sequentially obtained from the exposure amount formed by the LS pattern within a range of ±10% (90 to 110 nm) from the width of 100 nm. unit:%). The results are shown in Table 7. Exposure margin (%)=(|E ₁ -E ₂ |/E _op )×100 E ₁ : an optimum exposure amount E ₂ of an LS pattern having a pitch width of 90 nm and a pitch of 200 nm is given: a pitch of 110 nm is given, and a pitch is 200 nm. The optimum exposure amount of the LS pattern E _op : the optimum exposure amount of the LS pattern with a pitch of 100 nm and a pitch of 200 nm

[Line width roughness (LWR) evaluation] The LS pattern obtained by irradiating the optimum sensitivity with the sensitivity is measured, and the dimension in the longitudinal direction 10 along the width is measured, and the standard deviation (σ) is obtained from the result. 3 times 値 (3σ), defined as LWR. The results are shown in Table 7. The smaller the enthalpy, the more the pattern with a small roughness and a uniform width can be obtained.

[Table 7]         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Photoresist material</td><td> PEB temperature (°C </td><td> Exposure (μC/cm²) </td><td> EL (%) </td><td> LWR (nm) </td>< /tr><tr><td> Example 74 </td><td> R-02 </td><td> 100 </td><td> 43.5 </td><td> 13.5 </td> <td> 5.2 </td></tr><tr><td> Example 75 </td><td> R-11 </td><td> 95 </td><td> 50.3 </td ><td> 18.6 </td><td> 4.5 </td></tr><tr><td> Example 76 </td><td> R-14 </td><td> 110 </ Td><td> 35.6 </td><td> 13.8 </td><td> 5.1 </td></tr><tr><td> Example 77 </td><td> R-15 < /td><td> 115 </td><td> 38 </td><td> 14.2 </td><td> 5.8 </td></tr><tr><td> Comparative Example 31 </ Td><td> R-16 </td><td> 100 </td><td> 42.2 </td><td> 8.6 </td><td> 8.9 </td></tr><tr ><td> Comparative Example 32 </td><td> R-24 </td><td> 105 </td><td> 53.5 </td><td> 7.2 </td><td> 9.5 < /td></tr></TBODY></TABLE>

From the results of Table 7, it was confirmed that the photoresist material of the present invention has practical sensitivity. In addition, it can be confirmed that the exposure margin has a wide margin and the LWR is small.

no

Claims (7)

a monomer represented by the following formula (1); In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each independently represent a carbon number of 1 to 10 linear, branched or cyclic monovalent hydrocarbon group of 1, R ² may be bonded to each other with R ³ The knot forms an alicyclic group together with the carbon atoms bonded thereto; X ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ constituting the divalent hydrocarbon group - may also be substituted with -O- or -C(=O)-; Z ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ constituting the aliphatic hydrocarbon group - may also be replaced by -O- or -C(=O)-; k ¹ represents 0 or 1; k ² represents an integer of 2 to 4. The monomer of claim 1, wherein Z ¹ is a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms. A polymer compound characterized by comprising a repeating unit represented by the following formula (3); In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² and R ³ each independently represent a carbon number of 1 to 10 linear, branched or cyclic monovalent hydrocarbon group of 1, R ² may be bonded to each other with R ³ The knot forms an alicyclic group together with the carbon atoms bonded thereto; X ¹ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ constituting the divalent hydrocarbon group - may also be substituted with -O- or -C(=O)-; Z ¹ represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ constituting the aliphatic hydrocarbon group - may also be replaced by -O- or -C(=O)-; k ¹ represents 0 or 1; k ² represents an integer of 2 to 4. The polymer compound of claim 3, further comprising at least one selected from the group consisting of repeating units represented by the following formulas (A) to (D); Wherein R ^{1 is the} same as defined above; Z ^A represents a substituent of a fluorine-containing alcohol having 1 to 20 carbon atoms; Z ^B represents a substituent having a phenolic hydroxyl group having 1 to 20 carbon atoms; and Z ^C represents a carbon number of 1 to 20 a carboxyl group-containing substituent; Z ^D represents a lactone skeleton, a sultone skeleton, a carbonate skeleton, a cyclic ether skeleton, an acid anhydride skeleton, an alcoholic hydroxyl group, an alkoxycarbonyl group, an anthranyl group or an amine formazan group. Substituent; X ² represents a single bond, methylene, ethyl, phenyl, fluorinated phenyl, naphthyl, -OR ⁰¹ -, or -C(=O)-Z ² -R ⁰¹ -, Z ² represents an oxygen atom or NH, and R ⁰¹ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclical carbon number of 2 to 6. An alkenyl group, a phenylene group, or a naphthyl group, and may also contain a carbonyl group, an ester group, an ether group or a hydroxyl group. A photoresist material comprising: a base resin comprising a polymer compound as claimed in claim 3 or 4, an acid generator, and an organic solvent. A pattern forming method, characterized in that: a photoresist material as disclosed in claim 5 is coated on a substrate to form a photoresist film, and the photoresist film is exposed by high-energy rays after heat treatment, and is developed after heat treatment. The liquid gets a pattern. The pattern forming method of claim 6, wherein the unexposed portion is dissolved using an alkali developing solution to obtain a negative pattern in which the exposed portion is insoluble.