FILM FORMING MATERIAL FOR LITHOGRAPHY, COMPOSITION FOR FILM FORMATION FOR LITHOGRAPHY, UNDERLAYER FILM FOR LITHOGRAPHY, AND METHOD FOR FORMING PATTERN

Abstract

The present invention has an object to provide a film forming material for lithography that is applicable to a wet process, has excellent heat resistance and film flatness in a supporting material having difference in level, and has excellent solubility in a solvent and long term storage stability in a solution form; and the like. The above object can be achieved by a film forming material for lithography comprising: a compound having a group of formula (0A):

##STR00001##

(In formula (0A), R.sup.A and R.sup.B are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms); and a latent curing accelerator.

Claims

1. A film forming material for lithography comprising: a compound having a group of formula (0A): ##STR00037## wherein R.sup.A and R.sup.B are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and a latent curing accelerator.

2. The film forming material for lithography according to claim 1, wherein the decomposition temperature of the latent curing accelerator is 600° C. or lower.

3. The film forming material for lithography according to claim 1, wherein the latent curing accelerator is a latent base generating agent.

4. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) has two or more groups of formula (0A).

5. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) is a compound having two groups of formula (0A) or an addition polymerization resin of a compound having a group of formula (0A).

6. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) is represented by formula (1A.sub.0): ##STR00038## wherein R.sup.A and R.sup.B are as defined above; and Z is a divalent hydrocarbon group having 1 to 100 carbon atoms and optionally containing a heteroatom.

7. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) is represented by formula (1A): ##STR00039## wherein R.sup.A and R.sup.B are as defined above; each X is independently a single bond, —O—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —CO—, —C(CF.sub.3).sub.2—, —CONH—, or —COO—; A is a single bond, an oxygen atom, or a divalent hydrocarbon group having 1 to 80 carbon atoms and optionally containing a heteroatom; each R.sub.1 is independently a group having 0 to 30 carbon atoms and optionally containing a heteroatom; and each m1 is independently an integer of 0 to 4.

8. The film forming material for lithography according to claim 7, wherein: A is a single bond, an oxygen atom, —(CH.sub.2).sub.p—, —CH.sub.2C(CH.sub.3).sub.2CH.sub.2—, —(C(CH.sub.3).sub.2).sub.p—, —(O(CH.sub.2).sub.q).sub.p—, —(O(C.sub.6H.sub.4)).sub.p—, or any of the following structures: ##STR00040## Y is a single bond, —O—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, ##STR00041## p is an integer of 0 to 20; and q is an integer of 0 to 4.

9. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) is represented by formula (2A): ##STR00042## wherein R.sup.A and R.sup.B are as defined above; each R.sub.2 is independently a group having 0 to 10 carbon atoms and optionally containing a heteroatom; each m2 is independently an integer of 0 to 3; each m2′ is independently an integer of 0 to 4; and n is an integer of 0 to 4.

10. The film forming material for lithography according to claim 1, wherein the compound having a group of formula (0A) is represented by formula (3A): ##STR00043## wherein R.sup.A and R.sup.B are as defined above; R.sub.3 and R.sub.4 are each independently a group having 0 to 10 carbon atoms and optionally containing a heteroatom; each m3 is independently an integer of 0 to 4; each m4 is independently an integer of 0 to 4; and n is an integer of 1 to 4.

11. The film forming material for lithography according to claim 1, wherein a content ratio of the latent curing accelerator is 1 to 25 parts by mass based on 100 parts by mass of a total mass of the compound having a group of formula (0A).

12. The film forming material for lithography according to claim 1, further comprising a crosslinking agent.

13. The film forming material for lithography according to claim 12, wherein the crosslinking agent is at least one selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound, and an azide compound.

14. The film forming material for lithography according to claim 12, wherein the crosslinking agent has at least one allyl group.

15. The film forming material for lithography according to claim 12, wherein a content ratio of the crosslinking agent is 0.1 to 100 parts by mass based on 100 parts by mass of a total mass of the compound having a group of formula (0A).

16. A composition for film formation for lithography comprising the film forming material for lithography according to claim 1 and a solvent.

17. The composition for film formation for lithography according to claim 16, wherein the film for lithography is an underlayer film for lithography.

18. An underlayer film for lithography formed by using the composition for film formation for lithography according to claim 17.

19. The composition for film formation for lithography according to claim 16, wherein the film for lithography is a resist film.

20. A resist film formed by using the composition for film formation for lithography according to claim 19.

21. A method for forming a resist pattern, comprising: a resist film forming step of forming a resist film on a supporting material by using the composition for film formation for lithography according to claim 19; and a development step of irradiating a predetermined region of the resist film formed by the resist film forming step with radiation for development.

22. The method for forming a resist pattern according to claim 21, wherein the method is a method for forming an insulating film pattern.

23. A method for forming a resist pattern, comprising the steps of: forming an underlayer film on a supporting material by using the composition for film formation for lithography according to claim 17; forming at least one photoresist layer on the underlayer film; and irradiating a predetermined region of the photoresist layer with radiation for development.

24. A method for forming a circuit pattern, comprising the steps of: forming an underlayer film on a supporting material by using the composition for film formation for lithography according to claim 17; forming an intermediate layer film on the underlayer film by using a resist intermediate layer film material containing a silicon atom; forming at least one photoresist layer on the intermediate layer film; irradiating a predetermined region of the photoresist layer with radiation for development, thereby forming a resist pattern; etching the intermediate layer film with the resist pattern as a mask; etching the underlayer film with the obtained intermediate layer film pattern as an etching mask; and etching the supporting material with the obtained underlayer film pattern as an etching mask, thereby forming a pattern on the supporting material.

Description

EXAMPLES

[0246] Hereinafter, the present invention will be described in further detail with reference to Synthetic Working Examples, Examples, and Comparative Examples, but the present invention is not limited by these examples in any way.

[Molecular Weight]

[0247] The molecular weight of the synthesized compound was measured by LC-MS analysis using Acquity UPLC/MALDI-Synapt HDMS manufactured by Waters Corporation.

[Evaluation of Heat Resistance]

[0248] EXSTAR 6000 TG-DTA apparatus manufactured by SII NanoTechnology Inc. was used. About 5 mg of a sample was placed in an unsealed container made of aluminum, and the temperature was raised to 500° C. at a temperature increase rate of 10° C./min in a nitrogen gas stream (100 ml/min), thereby measuring the amount of thermogravimetric weight loss. From a practical viewpoint, evaluation A or B described below is preferable. When the evaluation is A or B, the sample has high heat resistance and is applicable to high temperature baking.

<Evaluation Criteria>

[0249] A: The amount of thermogravimetric weight loss at 400° C. is less than 10%

[0250] B: The amount of thermogravimetric weight loss at 400° C. is 10% to 25%

[0251] C: The amount of thermogravimetric weight loss at 400° C. is greater than 25%

[Evaluation of Solubility]

[0252] A mixed solvent adjusted to have a weight ratio of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CHN) of 1:1 and the compound and/or the resin were charged into a 50 ml screw bottle and stirred at 23° C. for 1 hour using a magnetic stirrer. Then, the amount of the compound and/or the resin dissolved in the above mixed solvent was measured and the result was evaluated according to the following criteria. From a practical viewpoint, evaluation S, A, or B described below is preferable.

<Evaluation Criteria>

[0253] S: 20% by mass or more and less than 30% by mass

[0254] A: 10% by mass or more and less than 20% by mass

[0255] B: 5% by mass or more and less than 10% by mass

[0256] C: less than 5% by mass

(Synthetic Working Example 1) Synthesis of BAPP Citraconimide

[0257] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 4.10 g (10.0 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (product name: BAPP, manufactured by Wakayama Seika Kogyo Co., Ltd.), 4.15 g (40.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 30 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 120° C. for 5 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, after cooling the reaction solution to 40° C., it was added dropwise into a beaker in which 300 m1 of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with acetone and subjected to separation and purification with column chromatography to acquire 3.76 g of the target compound (BAPP citraconimide) represented by the following formula:

##STR00019##

[0258] The following peaks were found by 400 MHz-.sup.1H-NMR, and the compound was confirmed to have a chemical structure of the above formula.

.sup.1H-NMR: (d-DMSO, Internal Standard TMS)

[0259] δ (ppm) 6.8-7.4 (16H, Ph-H), 6.7 (2H, —CH═C) 2.1 (6H, C—CH3), 1.6 (6H, —C(CH3)2). As a result of measuring the molecular weight of the obtained compound by the above method, it was 598.

(Synthetic Working Example 2) Synthesis of m-BAPP Bismaleimide

[0260] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 4.10 g (10.0 mmol) of 2,2-bis[4-(3-aminophenoxy)phenyl]propane (product name: m-BAPP, manufactured by TECNO CHEM CO., LTD.), 2.15 g (22.0 mmol) of maleic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 40 ml of dimethylformamide, and 30 ml of m-xylene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid was added, thereby preparing a reaction solution. The reaction solution was stirred at 130° C. for 4.0 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, the reaction solution was cooled to 40° C. and it was then added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol and subjected to separation and purification with column chromatography to acquire 3.10 g of the target compound (m-BAPP bismaleimide) represented by the following formula:

##STR00020##

[0261] The following peaks were found by 400 MHz-.sup.1H-NMR, and the compound was confirmed to have a chemical structure of the above formula.

.sup.1H-NMR: (d-DMSO, Internal Standard TMS)

[0262] δ (ppm) 6.8-7.4 (16H, Ph-H), 6.9 (4H, —CH═CH), 1.6 (6H, —C(CH3)2). As a result of measuring the molecular weight of the obtained compound by the above method, it was 598.

(Synthetic Working Example 3) Synthesis of m-BAPP Citraconimide

[0263] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 4.10 g (10.0 mmol) of 2,2-bis[4-(3-aminophenoxy)phenyl]propane (product name: m-BAPP, manufactured by TECNO CHEM CO., LTD.), 4.15 g (40.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 30 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 120° C. for 5 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, after cooling the reaction solution to 40° C., it was added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with acetone and subjected to separation and purification with column chromatography to acquire 3.52 g of the target compound (m-BAPP citraconimide) represented by the following formula:

##STR00021##

[0264] The following peaks were found by 400 MHz-.sup.1H-NMR, and the compound was confirmed to have a chemical structure of the above formula.

.sup.1H-NMR: (d-DMSO, Internal Standard TMS)

[0265] δ (ppm) 6.8-7.4 (16H, Ph-H), 6.7 (2H, —CH═C), 2.0 (6H, C—CH3), 1.6 (6H, —C(CH3).sub.2). As a result of measuring the molecular weight of the obtained compound by the above method, it was 598.

(Synthetic Working Example 4) Synthesis of BMI Citraconimide Resin

[0266] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 2.4 g of diaminodiphenylmethane oligomers obtained by following up on Synthetic Example 1 in Japanese Patent Application Laid-Open No. 2001-26571, 4.56 g (44.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 40 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 110° C. for 8.0 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, the reaction solution was cooled to 40° C. and it was then added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol to acquire 4.7 g of a citraconimide resin (BMI citraconimide resin) represented by the following formula:

##STR00022##

[0267] Note that, as a result of measuring the molecular weight by the above method, it was 446.

(Synthetic Working Example 5) Synthesis of BAN Citraconimide Resin

[0268] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 6.30 g of a biphenyl aralkyl-based polyaniline resin (product name: BAN, manufactured by Nippon Kayaku Co., Ltd.), 4.56 g (44.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 40 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 110° C. for 6.0 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, the reaction solution was cooled to 40° C., and it was then added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol and subjected to separation and purification with column chromatography to acquire 5.5 g of the target compound (BAN citraconimide resin) represented by the following formula:

##STR00023##

(Synthetic Working Example 6) Synthesis of Monomer-Removed BMI Maleimide Resin

[0269] A container (internal capacity: 300 ml) equipped with a distillation column capable of retaining heat was prepared. To this container, 100 g of diaminodiphenylmethane oligomers obtained by following up on Synthetic Example 1 in Japanese Patent Application Laid-Open No. 2001-26571 were charged, and water and low boiling impurities were first distilled off by atmospheric distillation. The degree of reduced pressure was gradually increased to 30 Pa, and the diaminodiphenylmethane monomers were mainly removed at a column top temperature of 200 to 230° C. to obtain 32 g of monomer-removed diaminomethane oligomers.

[0270] Next, 2.4 g of monomer-removed diaminodiphenylmethane oligomers obtained above were charged into a container (internal capacity: 200 ml) equipped with a stirrer and a condenser tube, then 4.56 g (44.0 mmol) of maleic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 40 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 100° C. for 6.0 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, the reaction solution was cooled to 40° C., and it was then added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol to acquire 5.6 g of a monomer-removed BMI maleimide resin represented by the following formula. As a result of measuring the molecular weight of the resin by the above method, it was 836.

##STR00024##

(Synthetic Working Example 7) Synthesis of Monomer-Removed BMI Citraconimide Resin

[0271] A container (internal capacity: 300 ml) equipped with a distillation column capable of retaining heat was prepared. To this container, 100 g of diaminodiphenylmethane oligomers obtained by following up on Synthetic Example 1 in Japanese Patent Application Laid-Open No. 2001-26571 were charged, and water and low boiling impurities were first distilled off by atmospheric distillation. The degree of reduced pressure was gradually increased to 30 Pa, and the diaminodiphenylmethane monomers were mainly removed at a column top temperature of 200 to 230° C. to obtain 32 g of monomer-removed diaminomethane oligomers.

[0272] Next, 2.4 g of monomer-removed diaminodiphenylmethane oligomers obtained above were charged into a container (internal capacity: 200 ml) equipped with a stirrer and a condenser tube, then 4.56 g (44.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 40 ml of dimethylformamide, and 60 ml of toluene were charged, and 0.4 g (2.3 mmol) of p-toluenesulfonic acid and 0.1 g of a polymerization inhibitor BHT were added, thereby preparing a reaction solution. The reaction solution was stirred at 110° C. for 8.0 hours to conduct reaction, and the produced water was recovered with a Dean-and-stark trap through azeotropic dehydration. Next, the reaction solution was cooled to 40° C. and it was then added dropwise into a beaker in which 300 ml of distilled water was placed to precipitate the product. After filtering the obtained slurry solution, the residue was washed with methanol to acquire 6.3 g of a monomer-removed BMI citraconimide resin represented by the following formula. As a result of measuring the molecular weight of the resin by the above method, it was 857.

##STR00025##

Example 1

[0273] As a maleimide compound, 9 parts by mass of a bismaleimide (BMI-80; manufactured by K⋅I Chemical Industry Co., LTD.) represented by the formula described below and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

##STR00026##

[0274] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0275] To 10 parts by mass of the film forming material for lithography, 90 parts by mass of the above mixed solvent was added, and the resultant mixture was stirred with a stirrer for at least 3 hours or longer at room temperature to prepare a composition for film formation for lithography.

Example 2

[0276] As a maleimide compound, 9 parts by mass of the m-BAPP bismaleimide obtained in Synthetic Working Example 2 and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

[0277] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0278] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 3

[0279] As a bismaleimide resin, 9 parts by mass of BMI maleimide oligomers (BMI-2300; manufactured by Daiwakasei Industry Co., LTD.) represented by the formula described below and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

##STR00027##

[0280] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0281] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 4

[0282] As a bismaleimide resin, 9 parts by mass of a biphenyl aralkyl-based maleimide resin (MIR-3000-L; manufactured by Nippon Kayaku Co., Ltd.) represented by the formula described below and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

##STR00028##

[0283] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0284] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 5

[0285] As a biscitraconimide compound, 9 parts by mass of the BAPP citraconimide obtained in Synthetic Working Example 1 and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0286] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have good solubility.

[0287] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 6

[0288] As a biscitraconimide compound, 9 parts by mass of the m-BAPP citraconimide obtained in Synthetic Working Example 3 and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0289] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have good solubility.

[0290] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 7

[0291] As a citraconimide resin, 9 parts by mass of the BMI citraconimide resin obtained in Synthetic Working Example 4 and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0292] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0293] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 8

[0294] As a citraconimide resin, 9 parts by mass of the BAN citraconimide resin obtained in Synthetic Working Example 5 and 1 part by mass of a latent base generating agent (WPBG-300; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0295] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0296] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 9

[0297] As a maleimide compound, 9 parts by mass of the above BMI-80 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

[0298] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0299] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 10

[0300] As a maleimide compound, 9 parts by mass of the above m-BAPP bismaleimide and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

[0301] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0302] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 11

[0303] As a bismaleimide resin, 9 parts by mass of the above BMI maleimide oligomers and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

[0304] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0305] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 11A

[0306] As a maleimide resin, 9 parts by mass of the monomer-removed BMI maleimide resin obtained in Synthetic Working Example 6 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0307] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0308] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 12

[0309] As a bismaleimide resin, 9 parts by mass of the above MIR-3000-L and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were used to prepare a film forming material for lithography.

[0310] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0311] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 13

[0312] As a biscitraconimide compound, 9 parts by mass of the BAPP citraconimide obtained in Synthetic Working Example 1 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0313] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have good solubility.

[0314] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 14

[0315] As a biscitraconimide compound, 9 parts by mass of the m-BAPP citraconimide obtained in Synthetic Working Example 3 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0316] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have good solubility.

[0317] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 15

[0318] As a citraconimide resin, 9 parts by mass of the BMI citraconimide resin obtained in Synthetic Working Example 4 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0319] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0320] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 15A

[0321] As a citraconimide resin, 9 parts by mass of the monomer-removed BMI citraconimide resin obtained in Synthetic Working Example 7 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0322] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0323] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 16

[0324] As a citraconimide resin, 9 parts by mass of the BAN citraconimide resin obtained in Synthetic Working Example 5 and 1 part by mass of a latent base generating agent (WPBG-266; manufactured by FUJIFILM Wako Pure Chemical Corporation) were compounded to prepare a film forming material for lithography.

[0325] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0326] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 17

[0327] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of benzoxazine (BF-BXZ; manufactured by KONISHI CHEMICAL IND. CO., LTD.) represented by the formula described above was compounded as a crosslinking agent to prepare a film forming material for lithography.

##STR00029##

[0328] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0329] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 18

[0330] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of a biphenyl aralkyl-based epoxy resin (NC-3000-L; manufactured by Nippon Kayaku Co., Ltd.) represented by the following formula was used as a crosslinking agent to prepare a film forming material for lithography.

##STR00030##

[0331] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 10% by mass or more and less than 20% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0332] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 19

[0333] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of a diallylbisphenol A-based cyanate (DABPA-CN; manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) represented by the following formula was compounded as a crosslinking agent to prepare a film forming material for lithography.

##STR00031##

[0334] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0335] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 20

[0336] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of a diallylbisphenol A (BPA-CA; manufactured by KONISHI CHEMICAL IND. CO., LTD.) represented by the following formula was compounded as a crosslinking agent to prepare a film forming material for lithography.

##STR00032##

[0337] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0338] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 21

[0339] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of a diphenylmethane-based allylphenolic resin (APG-1; manufactured by Gun Ei Chemical Industry Co., Ltd.) represented by the formula described below was used as the crosslinking agent to prepare a film forming material for lithography.

##STR00033##

[0340] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in a mixed solvent of PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0341] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 22

[0342] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of a diphenylmethane-based propenylphenolic resin (APG-2; manufactured by Gun Ei Chemical Industry Co., Ltd.) represented by the formula described below was used as the crosslinking agent to prepare a film forming material for lithography.

##STR00034##

[0343] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility.

[0344] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 23

[0345] As a maleimide compound, 9 parts by mass of BMI-80 and 1 part by mass of the latent base generating agent WPBG-300 were used. In addition, 2 parts by mass of 4,4′-diaminodiphenylmethane (DDM; manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula described below was used as the crosslinking agent to prepare a film forming material for lithography.

##STR00035##

[0346] As a result of thermogravimetry, the amount of thermogravimetric weight loss at 400° C. of the obtained film forming material for lithography was less than 10% (evaluation A). In addition, as a result of evaluation of solubility in PGMEA/CHN, the solubility was 20% by mass or more (evaluation S) and the obtained film forming material for lithography was evaluated to have excellent solubility. In addition, the same operations as in Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Examples 1 to 6

[0347] A film forming material for lithography was prepared in the same manner as in Examples 1, 3 to 5, 7 and 8 except that 1 part by mass of 2,4,5-triphenylimidazole (TPIZ; manufactured by Shikoku Chemicals Corporation) was compounded as a curing accelerator instead of the latent base generating agent WPBG-300. In addition, the same operations as in Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Examples 7 to 13

[0348] A film forming material for lithography was prepared in the same manner as in Examples 17 to 23 except that 1 part by mass of 2,4,5-triphenylimidazole (TPIZ; manufactured by Shikoku Chemicals Corporation) was compounded as a curing accelerator instead of the latent base generating agent WPBG-300. In addition, the same operations as in Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Examples 24 to 37

[0349] Compositions for film formation for lithography were each prepared according to the composition shown in Table 2.

<Evaluation of Compositions for Film Formation for Lithography of Examples 1 to 23 and Comparative Examples

[0350] 1 to 13>[Evaluation of storage stability]

[0351] After storing the composition for film formation for lithography in a thermostatic bath at 40° C. for 1 month, the hue change ΔYI of the solution was measured by using a colorimeter/turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.) and a quartz glass cell with an optical path length of 1 cm. Storage stability was evaluated according to the evaluation criteria shown below.

(Evaluation Criteria)

[0352] S: After storage at 40° C. for 1 month ΔYI≤1.0

[0353] A: After storage at 40° C. for 1 month 1.0<ΔYI≤3.0

[0354] B: After storage at 40° C. for 1 month 3.0<ΔYI

[Evaluation of Curability]

[0355] A silicon supporting material was spin coated with a composition for film formation for lithography, and then baked at 240° C. for 60 seconds. Then, the film thickness of the resultant coated film was measured. Thereafter, the silicon supporting material was immersed in a mixed solvent of 70% PGMEA/30% PGME for 60 seconds, the adhered solvent was removed with an Aero Duster, and the supporting material was then subjected to solvent drying at 110° C. From the difference in film thickness before and after the immersion, the decreasing rate of film thickness (%) was calculated, and the curability of each underlayer film was evaluated according to the evaluation criteria shown below.

(Evaluation Criteria)

[0356] S: Decreasing rate of film thickness before and after solvent immersion≤1% (Good)

[0357] A: Decreasing rate of film thickness before and after solvent immersion≤5% (Partially good)

[0358] B: Decreasing rate of film thickness before and after solvent immersion≤10%

[0359] C: Decreasing rate of film thickness before and after solvent immersion>10%

[Evaluation of Film Heat Resistance]

[0360] The underlayer film after the curing baking at 240° C. in the evaluation of curability was further baked at 450° C. for 120 seconds. From the difference in film thickness before and after the baking, the decreasing rate of film thickness (%) was calculated, and the film heat resistance of each underlayer film was evaluated according to the evaluation criteria shown below.

(Evaluation Criteria)

[0361] SS: Decreasing rate of film thickness after baking at 450° C.≤5%

[0362] S: Decreasing rate of film thickness before and after baking at 450° C.≤10% (Good)

[0363] A: Decreasing rate of film thickness before and after baking at 450° C.≤15% (Partially good)

[0364] B: Decreasing rate of film thickness before and after baking at 450° C.≤20%

[0365] C: Decreasing rate of film thickness before and after baking at 450° C.>20%

[Evaluation of Flatness]

[0366] Onto a SiO.sub.2 supporting material having difference in level on which trenches with a width of 100 nm, a pitch of 150 nm, and a depth of 150 nm (aspect ratio: 1.5) and trenches with a width of 5 μm and a depth of 180 nm (open space) were mixedly present, each of the compositions for film formation for lithography was coated. Subsequently, it was calcined at 240° C. for 120 seconds under the air atmosphere to form a resist underlayer film having a film thickness of 200 nm. The shape of this resist underlayer film was observed with a scanning electron microscope (“S-4800” from Hitachi High-Technologies Corporation), and the difference between the maximum value and the minimum value of the film thickness of the resist underlayer film on the trench or space (ΔFT) was measured. Flatness on a supporting material having difference in level was evaluated according to the evaluation criteria shown below.

(Evaluation Criteria)

[0367] S: ΔFT<10 nm (best flatness)

[0368] A: 10 nm≤ΔFT<20 nm (good flatness)

[0369] B: 20 nm≤ΔFT<40 nm (partially good flatness)

[0370] C: 40 nm≤ΔFT (poor flatness)

Evaluation of Compositions for Film Formation for Lithography of Examples 24 to 37

[Evaluation of Storage Stability]

[0371] The procedures performed were the same as those in the evaluation of the compositions for film formation for lithography of Examples 1 to 23 and Comparative Examples 1 to 13.

[Evaluation of Curability]

[0372] A silicon supporting material was spin coated with a composition for film formation for lithography, and then baked at 150° C. for 60 seconds to remove the solvent in the coated film. Subsequently, the film was cured using a high pressure mercury lamp with an accumulated light exposure of 1500 mJ/cm.sup.2 and an irradiation time of 60 seconds, and then the film thickness of the coated film was measured. Thereafter, the silicon supporting material was immersed in a mixed solvent of 70% PGMEA/30% PGME for 60 seconds, the adhered solvent was removed with an Aero Duster, and the supporting material was then subjected to solvent drying at 110° C. From the difference in film thickness before and after the immersion, the decreasing rate of film thickness (%) was calculated, and the curability of each underlayer film was evaluated according to the evaluation criteria shown below.

(Evaluation Criteria)

[0373] S: Decreasing rate of film thickness before and after solvent immersion≤1% (Good)

[0374] A: Decreasing rate of film thickness before and after solvent immersion≤5% (Partially good)

[0375] B: Decreasing rate of film thickness before and after solvent immersion≤10%

[0376] C: Decreasing rate of film thickness before and after solvent immersion>10%

[Evaluation of Film Heat Resistance]

[0377] The underlayer films after the curing with a high pressure mercury lamp in the evaluation of curability were further baked at 450° C. for 120 seconds, and from the difference in film thickness before and after the baking, the decreasing rate of film thickness (%) was calculated to evaluate the film heat resistance of each underlayer film according to the evaluation criteria shown below.

(Evaluation Criteria)

[0378] SS: Decreasing rate of film thickness before and after baking at 450° C.≤5%

[0379] S: Decreasing rate of film thickness before and after baking at 450° C.≤10% (Good)

[0380] A: Decreasing rate of film thickness before and after baking at 450° C.≤15% (Partially good)

[0381] B: Decreasing rate of film thickness before and after baking at 450° C.≤20%

[0382] C: Decreasing rate of film thickness before and after baking at 450° C.>20%

[Evaluation of Flatness]

[0383] The procedures performed were the same as those in the evaluation of the compositions for film formation for lithography of Examples 1 to 23 and Comparative Examples 1 to 13.

TABLE-US-00001 TABLE 1 Maleimide Crosslinking Curing Storage Film heat Citraconimide agent accelerator Solvent stability Curability resistance Flatness Example BMI-80 — WPBG-300 PGMEA/ S S S A  1 (9) (1) CHN (90) Example m-BAPP — WPBG-300 PGMEA/ S S S A  2 bismaleimide (1) N CHN (9) (90) Example BMI-2300 — WPBG-300 PGMEA/ S S S A  3 (9) (1) CHN (90) Example MIR-3000-L — WPBG-300 PGMEA/ S S S A  4 (9) (1) CHN (90) Example BAPP — WPBG-300 PGMEA/ S A A S  5 citraconimide (1) CHN (9) (90) Example m-BAPP — WPBG-300 PGMEA/ S A A S  6 citraconimide (1) CHN (9) (90) Example BMI — WPBG-300 PGMEA/ S A A S  7 citraconimide (1) CHN (9) (90) Example BAN — WPBG-300 PGMEA/ S A A S  8 citraconimide (1) CHN (9) (90) Example BMI-80 — WPBG-266 PGMEA/ A S S A  9 (9) (1) CHN (90) Example m-BAPP — WPBG-266 PGMEA/ A S S A 10 bismaleimide (1) CHN (9) (90) Example BMI-2300 — WPBG-266 PGMEA/ A S S A 11 (9) (1) CHN (90) Example Monomer- — WPBG-266 PGMEA/ A S SS S 11A removed (1) CHN BMI-2300 (90) (9) Example MIR-3000-L — WPBG-266 PGMEA/ A S S A 12 (9) (1) CHN (90) Example BAPP — WPBG-266 PGMEA/ A A A S 13 citraconimide (1) CHN (9) (90) Example m-BAPP — WPBG-266 PGMEA/ A A A S 14 citraconimide (1) CHN (9) (90) Example BMI — WPBG-266 PGMEA/ A A A S 15 citraconimide (1) CHN (9) (90) Example Monomer- — WPBG-266 PGMEA/ A A S S 15A removed (1) CHN BMI (90) citraconimide (9) Example BAN WPBG-266 PGMEA/ A A A S 16 citraconimide (1) CHN (9) (90) Example BMI-80 BF-BXZ WPBG-300 PGMEA/ A S S A 17 (9) (2) (1) CHN (90) Example BMI-80 NC-3000-L WPBG-300 PGMEA/ A S S A 18 (9) (2) (1) CHN (90) Example BMI-80 DABPA-CN WPBG-300 PGMEA/ A S S A 19 (9) (2) (1) CHN (90) Example BMI-80 BPA-CA WPBG-300 PGMEA/ A S S A 20 (9) (2) (1) CHN (90) Example BMI-80 APG-1 WPBG-300 PGMEA/ A S S A 21 (9) (2) (1) CHN (90) Example BMI-80 APG-2 WPBG-300 PGMEA/ A S S A 22 (9) (2) (1) CHN (90) Example BMI-80 DDM WPBG-300 PGMEA/ A S S A 23 (9) (2) (1) CHN (90) Comparative BMI-80 — TPIZ PGMEA/ B S A S Example (9) (1) CHN  1 (90) Comparative BMI-2300 — TPIZ PGMEA/ B S A S Example (9) (1) CHN  2 (90) Comparative MIR-3000-L — TPIZ PGMEA/ B S A S Example (9) (1) CHN  3 (90) Comparative BAPP — TPIZ PGMEA/ B A C S Example citraconimide (1) CHN  4 (9) (90) Comparative BMI — TPIZ PGMEA/ B A C S Example citraconimide (1) CHN  5 (9) (90) Comparative BAN — TPIZ PGMEA/ B S C A Example citraconimide (1) CHN  6 (9) (90) Comparative BMI-80 BF-BXZ TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN  7 (90) Comparative BMI-80 NC-3000-L TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN  8 (90) Comparative BMI-80 DABPA-CN TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN  9 (90) Comparative BMI-80 BPA-CA TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN 10 (90) Comparative BMI-80 APG-1 TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN 11 (90) Comparative BMI-80 APG-2 TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN 12 (90) Comparative BMI-80 DDM TPIZ PGMEA/ B A B B Example (9) (2) (1) CHN 13 (90) Number in brackets represents part by mass of each component

TABLE-US-00002 TABLE 2 Maleimide Crosslinking Curing Storage Film heat Citraconimide agent accelerator Solvent stability Curability resistance Flatness Example BMI-80 — WPBG-300 PGMEA/ S S S A 24 (9) (1) CHN (90) Example m-BAPP — WPBG-300 PGMEA/ S S S A 25 bismaleimide (1) CHN (9) (90) Example BMI-2300 — WPBG-300 PGMEA/ S S S A 26 (9) (1) CHN (90) Example Monomer- — WPBG-300 PGMEA/ S S SS A 26A removed (1) CHN BMI (90) maleimide (9) Example MIR-3000-L — WPBG-300 PGMEA/ S S S A 27 (9) (1) CHN (90) Example BAPP — WPBG-300 PGMEA/ S S A S 28 citraconimide (1) CHN (9) (90) Example m-BAPP — WPBG-300 PGMEA/ S S A S 29 citraconimide (1) CHN (9) (90) Example BMI — WPBG-300 PGMEA/ S S A S 30 citraconimide (1) CHN (9) (90) Example Monomer- — WPBG-300 PGMEA/ S S S S 30A removed BMI (1) CHN citraconimide (90) (9) Example BAN — WPBG-300 PGMEA/CHN S S A S 31 citraconimide (1) (90) (9) Example BMI-80 BF-BXZ WPBG-300 PGMEA/CHN A S S A 32 (9) (2) (1) (90) Example BMI-80 NC-3000-L WPBG-300 PGMEA/CHN A S S A 33 (9) (2) (1) (90) Example BMI-80 DABPA-CN WPBG-300 PGMEA/CHN A S S A 34 (9) (2) (1) (90) Example BMI-80 BPA-CN WPBG-300 PGMEA/CHN A S S A 35 (9) (2) (1) (90) Example BMI-80 APG-1 WPBG-300 PGMEA/CHN A S S A 36 (9) (2) (1) (90) Example BMI-80 APG-2 WPBG-300 PGMENCHN A S S A 37 (9) (2) (1) (90) Number in brackets represents part by mass of each component

Example 38

[0384] A SiO.sub.2 supporting material with a film thickness of 300 nm was coated with the composition for film formation for lithography in Example 1, and baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to form an underlayer film with a film thickness of 70 nm. This underlayer film was coated with a resist solution for ArF and baked at 130° C. for 60 seconds to form a photoresist layer with a film thickness of 140 nm. The resist solution for ArF used was prepared by compounding 5 parts by mass of a compound of the following formula (22), 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA.

[0385] Note that the compound of the following formula (22) was prepared as follows. 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. This reaction solution was polymerized for 22 hours with the reaction temperature kept at 63° C. in a nitrogen atmosphere. Then, the reaction solution was added dropwise into 400 mL of n-hexane. The product resin thus obtained was solidified and purified, and the resulting white powder was filtered and dried overnight at 40° C. under reduced pressure to obtain a compound represented by the following formula.

##STR00036##

[0386] In the above formula (22), 40, 40, and 20 represent the ratio of each constituent unit and do not represent a block copolymer.

[0387] Subsequently, the photoresist layer was exposed using an electron beam lithography system (manufactured by ELIONIX INC.; ELS-7500, 50 keV), baked (PEB) at 115° C. for 90 seconds, and developed for 60 seconds in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution to obtain a positive type resist pattern. The evaluation results are shown in Table 3.

Example 39

[0388] A positive type resist pattern was obtained in the same way as Example 38 except that the composition for underlayer film formation for lithography in Example 2 was used instead of the composition for underlayer film formation for lithography in the above Example 1. The evaluation results are shown in Table 3.

Example 40

[0389] A positive type resist pattern was obtained in the same way as Example 38 except that the composition for underlayer film formation for lithography in Example 3 was used instead of the composition for underlayer film formation for lithography in the above Example 1. The evaluation results are shown in Table 3.

Comparative Example 14

[0390] The same operations as in Example 38 were carried out except that no underlayer film was formed so that a photoresist layer was formed directly on a SiO.sub.2 supporting material to obtain a positive type resist pattern. The evaluation results are shown in Table 3.

[Evaluation]

[0391] Concerning each of Examples 38 to 40 and Comparative Example 14, the shapes of the obtained 55 nm L/S (1:1) and 80 nm L/S (1:1) resist patterns were observed under an electron microscope (S-4800) manufactured by Hitachi, Ltd. The shapes of the resist patterns after development were evaluated as goodness when having good rectangularity without pattern collapse, and as poorness if this was not the case. The smallest line width having good rectangularity without pattern collapse as a result of this observation was used as an index for resolution evaluation. The smallest electron beam energy quantity capable of lithographing good pattern shapes was used as an index for sensitivity evaluation.

TABLE-US-00003 TABLE 3 Composition for film Resist pattern formation for Resolution Sensitivity shape after lithography (nmL/S) (μC/cm.sup.2) development Example 38 As described 50 16 Good in Example 1 Example 39 As described 60 15 Good in Example 2 Example 40 As described 50 15 Good in Example 3 Comparative None 90 42 Poor Example 14

[0392] As is evident from Table 3, Examples 38 to 40 using the composition for film formation for lithography of the present embodiment including a citraconimide or a maleimide were confirmed to be significantly superior in both resolution and sensitivity to Comparative Example 14. Also, the resist pattern shapes after development were confirmed to have good rectangularity without pattern collapse. Furthermore, the difference in the resist pattern shapes after development indicated that the underlayer films of Examples 38 to 40 obtained from the compositions for film formation for lithography of Examples 1 to 3 have good adhesiveness to a resist material.

(Method for Evaluating Resist Performance of Resist Composition)

[0393] Using the above film forming material, a resist composition was prepared according to the formulation shown in Table 4. A clean silicon wafer was spin coated with the homogeneous resist composition, and then prebaked (PB) before exposure in an oven of 110° C. to form a resist film with a thickness of 60 nm. The obtained resist film was irradiated with electron beams of 1:1 line and space setting with an 80 nm interval using an electron beam lithography system (ELS-7500 manufactured by ELIONIX INC.). After irradiation, the resist film was heated at each predetermined temperature for 90 seconds, and immersed in a 2.38 mass % TMAH alkaline developing solution for 60 seconds for development. Subsequently, the resist film was washed with ultrapure water for 30 seconds, and dried to form a negative type resist pattern.

[0394] Concerning the formed resist pattern, the line and space were observed under a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Corporation) to evaluate the reactivity by electron beam irradiation of the resist composition.

TABLE-US-00004 TABLE 4 Resist composition Maleimide Base Solvent Evaluation Citraconimide generating PGME of resist [g] agent [g] [g] performance Example 41 BMI-80 WPBG-300 100.0 Good [1.0] [0.3] Example 42 BAPP WPBG-300 100.0 Good citraconimide [0.3] [1.0] Example 43 BMI-80 WPBG-266 100.0 Good [1.0] [0.3] Example 44 BAPP WPBG-266 100.0 Good citraconimide [0.3] [1.0] Comparative BMI-80 — — Poor Example 15 [1.0]

[0395] As is evident from Table 4, in the resist pattern evaluation, a good resist pattern could be obtained by irradiation with electron beams of 1:1 line and space setting with an 80 nm interval in each of Examples 41 to 44. On the other hand, it was not possible to obtain a good resist pattern in Comparative Example 15, which contained no latent base generating agent.

[0396] The film forming material for lithography of the present embodiment is applicable to a wet process, and is useful for forming a photoresist underlayer film that is not only excellent in heat resistance and film flatness in a supporting material having difference in level, but also has solubility in a solvent, long term storage stability in a solution form, and curability at low temperature.

[0397] Therefore, the composition for film formation for lithography comprising the film forming material for lithography can be utilized widely and effectively in various applications that require such performances. In particular, the present invention can be utilized particularly effectively in the field of underlayer films for lithography and underlayer films for multilayer resist.