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

Abstract

The present invention provides a film forming material for lithography comprising a compound having: a group of formula (0A):

##STR00001## and a group of formula (0B):

##STR00002##

wherein each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, provided that at least one R is an alkyl group having 1 to 4 carbon atoms.

Claims

1. A film forming material for lithography comprising a compound having: a group of formula (0A): ##STR00052## and a group of formula (0B): ##STR00053## wherein each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, provided that at least one R is an alkyl group having 1 to 4 carbon atoms.

2. The film forming material for lithography according to claim 1, wherein the compound is represented by formula (1A.sub.0): ##STR00054## wherein each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, provided that at least one R is an alkyl group having 1 to 4 carbon atoms; and Z is a divalent group having 1 to 100 carbon atoms and optionally containing a heteroatom.

3. The film forming material for lithography according to claim 1, wherein the compound is represented by formula (1A): ##STR00055## wherein each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, provided that at least one R is an alkyl group having 1 to 4 carbon atoms; each X is independently selected from the group consisting of a single bond, —O—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —CO—, —C(CF.sub.3).sub.2—, —CONH—, and —COO—; A is selected from the group consisting of a single bond, an oxygen atom, and a divalent group having 1 to 80 carbon atoms and optionally containing a heteroatom; each R1 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.

4. The film forming material for lithography according to claim 3, wherein: A is a single bond, an oxygen atom, —(CH2).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.6H4)).sub.p—, or any of the following structures: ##STR00056## Y is a single bond, —O—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, ##STR00057## p is an integer of 0 to 20; and q is an integer of 0 to 4.

5. The film forming material for lithography according to claim 3, wherein: each X is independently a single bond, —O—, —C(CH.sub.3).sub.2—, —CO—, or —COO—; A is a single bond, an oxygen atom, or the following structures: ##STR00058## and Y is —C(CH.sub.3).sub.2— or —C(CF.sub.3).sub.2—.

6. The film forming material for lithography according to claim 1, wherein the compound is represented by formula (2A): ##STR00059## wherein each R′ is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; each R.sub.2 is independently a group haying 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; n is an integer of 0 to 4; and a plurality of groups represented by: ##STR00060## comprise at least a group of formula (0A) and a group of formula (0B).

7. The film forming material for lithography according to claim 1, wherein the compound is represented by formula (3A): ##STR00061## wherein each R′ is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; 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; n is an integer of 1 to 4; and a plurality of groups represented by: ##STR00062## comprise at least a group of formula (0A) and a group of formula (0B).

8. The film forming material for lithography according to claim 2, wherein the heteroatom is selected from the group consisting of oxygen, fluorine, and silicon.

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

10. (canceled)

11. The film forming material for lithography according to claim 9, wherein the crosslinking agent has at least one allyl group.

12. (canceled)

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

14. (canceled)

15. (canceled)

16. The film forming material for lithography according to claim 1, further comprising a radical polymerization initiator.

17. (canceled)

18. (canceled)

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

20. The composition for film formation for lithography according to claim 19, further comprising an acid generating agent.

21. The composition for film formation for lithography according to claim 19, further comprising a basic compound.

22. The composition for film formation for lithography according to claim 19, wherein the film for lithography is an underlayer film for lithography.

23. An underlayer film for lithography formed by using the composition for film formation for lithography according to claim 22.

24. A method for forming a resist pattern, comprising the steps of: forming an underlayer film on a substrate by using the composition for film formation for lithography according to claim 22; forming at least one photoresist layer on the underlayer film; and irradiating a predetermined region of the photoresist layer with radiation for development.

25. A method for forming a pattern, comprising the steps of: forming an underlayer film on a substrate by using the composition for film formation for lithography according to claim 22; 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 substrate with the obtained underlayer film pattern as an etching mask, thereby forming a pattern on the substrate.

26. A purification method comprising the steps of: obtaining an organic phase by dissolving the film forming material for lithography according to claim 1 in a solvent; and extracting impurities in the film forming material for lithography by bringing the organic phase into contact with an acidic aqueous solution (a first extraction step), wherein the solvent used in the step of obtaining the organic phase contains a solvent that does not inadvertently mix with water.

27. (canceled)

28. (canceled)

29. (canceled)

Description

EXAMPLES

[0273] Hereinafter, the present invention will be described in further detail with reference to Synthetic Working Examples, Examples, Production Examples, and Comparative Examples, but the present invention is not limited by these examples in any way.

[Molecular Weight]

[0274] 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]

[0275] 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.

[0276] A: The amount of thermogravimetric weight loss at 400° C. is less than 10%

[0277] B: The amount of thermogravimetric weight loss at 400° C. is 10% to 25%

[0278] C: The amount of thermogravimetric weight loss at 400° C. is greater than 25%

[Evaluation of Solubility]

[0279] Propylene glycol monomethyl ether acetate (PGMEA) and the compound and/or the resin were added to 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 PGMEA 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. When the evaluation is S, A, or B, the sample has high storage stability in the solution state, and can be satisfyingly applied to an edge bead rinse solution (mixed liquid of PGME/PGMEA) widely used for a fine processing process of semiconductors.

[0280] S: 15% by mass or more and less than 35% by mass

[0281] A: 5% by mass or more and less than 15% by mass

[0282] B: less than 5% by mass

(Synthetic Working Example 1) Synthesis of BAPP Citramaleimide

[0283] 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.), 2.07 g (20.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 2.07 g (20.0 mmol) of maleic 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 3.8 g of the target compound, citramaleimide, represented by the following formula:

##STR00028##

[0284] The following peaks were found by 400 MHz-.sup.1H-NMR, and the citramaleimide was confirmed to have a chemical structure of the above formula.

[0285] .sup.1H-NMR: (d-DMSO, internal standard TMS) 6 (ppm) 7.0-7.3 (18.0H, Ph-H, ═CH—), 6.8 (1.0H, ═CH—), 2.0 (3.0H, —CH.sub.3 (citraconimide ring)), 1.7 (6H, —CH.sub.3).

[0286] As a result of measuring the molecular weight of the obtained product by the above method, it was found that the product is a mixture of three compounds: 584 (citramaleimide), 570 (bismaleimide), and 598 (biscitraconimide). Also, the composition ratio (584 (citramaleimide)/570 (bismaleimide)/598 (biscitraconimide)) was 50/25/25.

[0287] Note that, in the following Examples, a single compound of citramaleimide was used to prepare a film forming material for lithography.

[0288] In the following Synthetic Working Examples 2 to 4 as well, the product was obtained as a mixture of citramaleimide/bismaleimide/biscitraconimide in a ratio of 50/25/25, but in Examples, a single compound of citramaleimide was used to prepare a film forming material for lithography.

Synthetic Working Example 2

Synthesis of APB-N Citramaleimide

[0289] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 2.92 g (10.0 mmol) of 3,3′-(1,3-phenylenebis)oxydianiline (product name: APB-N, manufactured by MITSUI FINE CHEMICALS, Inc.), 2.07 g (20.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 2.07 g (20.0 mmol) of maleic 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 110° 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 methanol and subjected to separation and purification with column chromatography to acquire 3.52 g of the target compound (APB-N citramaleimide) represented by the following formula:

##STR00029##

[0290] 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.

[0291] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.3 (12H, Ph-H), 7.0 (3H, —CH═C), 2.1 (3H, C—CH.sub.3). As a result of measuring the molecular weight of the obtained compound by the above method, it was 466.

Synthetic Working Example 3

Synthesis of HFBAPP Citramaleimide

[0292] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 5.18 g (10.0 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (product name: HFBAPP, manufactured by Wakayama Seika Kogyo Co., Ltd.), 2.27 g (22.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 2.27 g (22.0 mmol) of maleic 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 110° C. for 5.0 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 methanol and subjected to separation and purification with column chromatography to acquire 3.9 g of the target compound (HFBAPP citramaleimide) represented by the following formula:

##STR00030##

[0293] 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.

[0294] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.6-7.35 (16H, Ph-H), 2.1 (3H, C—CH.sub.3), 6.4 (3H, —CH═CH—).

[0295] As a result of measuring the molecular weight of the obtained compound by the above method, it was 691.

Synthetic Working Example 4

Synthesis of BisAP Citramaleimide

[0296] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 5.18 g (10.0 mmol) of 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene (product name: Bisaniline-P, manufactured by MITSUI FINE CHEMICALS, Inc.), 2.27 g (22.0 mmol) of citraconic anhydride (manufactured by KANTO CHEMICAL CO., INC.), 2.27 g (22.0 mmol) of maleic 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 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, 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 methanol and subjected to separation and purification with column chromatography to acquire 4.2 g of the target compound (BisAP citramaleimide) represented by the following formula:

##STR00031##

[0297] The following peaks were found by 400 MHz-.sup.1H-NMR, and the compound was confirmed to have a chemical structure of the formula described above.

[0298] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.35 (12H, Ph-H), 6.7 (3H, —CH═C), 2.1 (3H, C—CH.sub.3), 1.6-1.7 (12H, —C (CH.sub.3).sub.2).

[0299] As a result of measuring the molecular weight of the obtained compound by the above method, it was 517.

Synthetic Working Example 5

Synthesis of BMI Citramaleimide Resin

[0300] 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, a mixture of citraconic anhydride and maleic anhydride (22.0 mmol/22.0 mmol), 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, 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 methanol to acquire 4.6 g of a BMI citramaleimide resin.

Synthetic Working Example 6

Synthesis of BAN Citramaleimide Resin

[0301] 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.), a mixture of citraconic anhydride and maleic anhydride (22.0 mmol/22.0 mmol), 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 perform 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 methanol and subjected to separation and purification with column chromatography to acquire 4.6 g of a BAN citramaleimide resin.

Synthetic Working Example 7

Synthesis of High Molecular Weight BMI Citramaleimide Polymer

[0302] To a 300 mL flask container, 30 g of diaminodiphenylmethane oligomers (DDMO) obtained by following up on Synthetic Example 1 in Japanese Patent Application Laid-Open No. 2001-26571 was charged, and 60 g of methyl ethyl ketone was added as a solvent. By heating the resultant mixture to 60° C. for dissolution, a solution was obtained. The above solution was adsorbed on a neutral silica gel (manufactured by Kanto Chemical Co., Inc.), and by using silica gel column chromatography and developing a mixed solvent of ethyl acetate (20% by mass)/hexane (80% by mass), only the component of the repeating unit represented by the following formula was separated. After concentration, vacuum drying was performed to remove the solvent, thereby obtaining 9.6 g of a high molecular weight DDMO polymer.

##STR00032##

(High molecular weight DDMO polymer; in the formula, n represents an integer of 1 to 4)

[0303] To a container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette, 4.0 g of the above high molecular weight diaminodiphenylmethane oligomer polymer, a mixture of citraconic anhydride and maleic anhydride (22.0 mmol/22.0 mmol), 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 perform 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 methanol to acquire 5.5 g of a high molecular weight BMI citramaleimide polymer.

Synthetic Working Example 8

Synthesis of High Molecular Weight BAN Citramaleimide Polymer

[0304] To a 300 mL flask container, 40 g of a biphenyl aralkyl-based polyaniline resin (product name: BAN, manufactured by Nippon Kayaku Co., Ltd.) was charged, and 60 g of methyl ethyl ketone was added as a solvent. By heating the resultant mixture to 60° C. for dissolution, a solution was obtained. The above solution was adsorbed on a neutral silica gel (manufactured by Kanto Chemical Co., Inc.), and by using silica gel column chromatography and developing a mixed solvent of ethyl acetate (20% by mass)/hexane (80% by mass), only the component of the repeating unit represented by the following formula was separated. After concentration, vacuum drying was performed to remove the solvent, thereby obtaining 11.6 g of a high molecular weight BAN polymer.

##STR00033##

(High molecular weight BAN polymer; in the formula, n represents an integer of 2 to 4)

[0305] To a container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette, 5.0 g of the above high molecular weight BAN polymer, a mixture of citraconic anhydride and maleic anhydride (22.0 mmol/22.0 mmol), 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 perform 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 methanol to acquire 6.6 g of a high molecular weight BAN citramaleimide polymer.

Example 1

[0306] The BAPP citramaleimide obtained in Synthetic Working Example 1 was used as 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 PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0308] By using 5 parts by mass of the BAPP citramaleimide obtained in Synthetic Working Example 1, that is, 5 parts by mass of the above film forming material for lithography, adding 95 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent thereto, and stirring the resultant mixture with a stirrer at room temperature for at least 3 hours, a composition for film formation for lithography was prepared.

Example 2

[0309] The APB-N citramaleimide obtained in Synthetic Working Example 2 was used as 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 PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 3

[0312] The HFBAPP citramaleimide obtained in Synthetic Working Example 3 was used as 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 4

[0315] The BisAP citramaleimide obtained in Synthetic Working Example 4 was used as 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 5

[0318] The BMI citramaleimide resin obtained in Synthetic Working Example 5 was used as 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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 5A

[0321] The high molecular weight BMI citramaleimide polymer obtained in Synthetic Working Example 7 was used as 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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 6

[0324] The BAN citramaleimide resin obtained in Synthetic Working Example 6 was used as 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). Furthermore, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 6A

[0327] The high molecular weight BAN citramaleimide polymer obtained in Synthetic Working Example 8 was used as a film forming material for lithography.

[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). Furthermore, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

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

Example 7

[0330] 5 parts by mass of the BAPP citramaleimide and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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 PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0332] A composition for film formation for lithography was prepared by the same operations as in the above Example 1 except that the above film forming material for lithography was used.

Example 8

[0333] 5 parts by mass of the APB-N citramaleimide and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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 PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0335] A composition for film formation for lithography was prepared by the same operations as in the above Example 1, except that the above film forming material for lithography was used.

Example 9

[0336] 5 parts by mass of the HFBAPP citramaleimide and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0338] Except that the above film forming material for lithography was used, a composition for film formation for lithography was prepared by the same operations as in the above Example 1.

Example 10>

[0339] 5 parts by mass of the BisAP citramaleimide and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0341] Except that the above film forming material for lithography was used, a composition for film formation for lithography was prepared according to the same operations as in the above Example 1.

Example 11>

[0342] 5 parts by mass of the BMI citramaleimide resin and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0344] A composition for film formation for lithography was prepared according to the same operations as in the above Example 1, except that the above film forming material for lithography was used.

Example 11A

[0345] 5 parts by mass of the high molecular weight BMI citramaleimide polymer and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0347] A composition for film formation for lithography was prepared according to the same operations as in the above Example 1 except that the above film forming material for lithography was used.

Example 12

[0348] 5 parts by mass of the BAN citramaleimide resin and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[0349] 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). Furthermore, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0350] A composition for film formation for lithography was prepared according to the same operations as in the Example 1 described above except that the above film forming material for lithography was used.

Example 12A

[0351] 5 parts by mass of the high molecular weight BAN citramaleimide polymer and 0.1 parts by mass of TPIZ as a crosslinking promoting agent were compounded to prepare a film forming material for lithography.

[0352] 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). Furthermore, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0353] A composition for film formation for lithography was prepared according to the same operations as in the Example 1 described above, except that the above film forming material for lithography was used.

Example 13

[0354] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of benzoxazine (BF-BXZ; manufactured by KONISHI CHEMICAL IND. CO., LTD.) represented by the formula described below was also used as the crosslinking agent, and 0.1 parts by mass of 2,4,5-triphenylimidazole (TPIZ) was compounded as the crosslinking promoting agent to prepare a film forming material for lithography.

##STR00034##

[0355] 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, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0356] A composition for film formation for lithography was prepared by the same operations as in the Example 1 described above, except that the above film forming material for lithography was used.

Example 14

[0357] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of a biphenyl aralkyl-based epoxy resin (NC-3000-L; manufactured by Nippon Kayaku Co., Ltd.) represented by the formula described below was also used as the crosslinking agent, and 0.1 parts by mass of TPIZ was compounded as the crosslinking promoting agent to prepare a film forming material for lithography.

##STR00035##

[0358] 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, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0359] A composition for film formation for lithography was prepared by the same operations as in the Example 1 described above except that the above film forming material for lithography was used.

Example 15

[0360] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of a diallylbisphenol A-based cyanate (DABPA-CN; manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.) represented by the formula described below was also used as the crosslinking agent, and 0.1 parts by mass of 2,4,5-triphenylimidazole (TPIZ) was compounded as the crosslinking promoting agent to prepare a film forming material for lithography.

##STR00036##

[0361] 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0362] Except that the above film forming material for lithography was used, a composition for film formation for lithography was prepared by the same operations as in the Example 1 described above.

Example 16

[0363] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of diallylbisphenol A (BPA-CA; manufactured by KONISHI CHEMICAL IND. CO., LTD.) represented by the formula described below was also used as the crosslinking agent, and 0.1 parts by mass of 2,4,5-triphenylimidazole (TPIZ) was compounded as the crosslinking promoting agent to prepare a film forming material for lithography.

##STR00037##

[0364] 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0365] Except that the above film forming material for lithography was used, a composition for film formation for lithography was prepared through the same operations as in the Example 1 described above.

Example 17

[0366] In addition to 5 parts by mass of the BAPP citramaleimide, 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 also used as the crosslinking agent to prepare a film forming material for lithography.

##STR00038##

[0367] 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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0368] A composition for film formation for lithography was prepared through the same operations as in the Example 1 described above, except that the above film forming material for lithography was used.

Example 18

[0369] In addition to 5 parts by mass of the BAPP citramaleimide, 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 also used as the crosslinking agent to prepare a film forming material for lithography.

##STR00039##

[0370] 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). Moreover, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0371] A composition for film formation for lithography was prepared through the same operations as in the Example 1 described above except that the above film forming material for lithography was used.

Example 19

[0372] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of 4,4′-diaminodiphenylmethane (DDM; manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the formula described below was also used as the crosslinking agent to prepare a film forming material for lithography.

##STR00040##

[0373] 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). Furthermore, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0374] A composition for film formation for lithography was prepared through the same operations as in the above Example 1, except that the above film forming material for lithography was used.

Production Example 1

[0375] A four necked flask (internal capacity: 10 L) equipped with a Dimroth condenser tube, a thermometer, and a stirring blade, and having a detachable bottom was prepared. To this four necked flask, 1.09 kg (7 mol) of 1,5-dimethylnaphthalene (manufactured by Mitsubishi Gas Chemical Company, Inc.), 2.1 kg (28 mol as formaldehyde) of a 40 mass % aqueous formalin solution (manufactured by Mitsubishi Gas Chemical Company, Inc.), and 0.97 ml of a 98 mass % sulfuric acid (manufactured by Kanto Chemical Co., Inc.) were added in a nitrogen stream, and the mixture was allowed to react for 7 hours while being refluxed at 100° C. at normal pressure. Subsequently, 1.8 kg of ethylbenzene (manufactured by Wako Pure Chemical Industries, Ltd., a special grade reagent) was added as a diluting solvent to the reaction solution, and the mixture was left to stand still, followed by removal of an aqueous phase as a lower phase. Neutralization and washing with water were further performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a dimethylnaphthalene formaldehyde resin as a light brown solid.

[0376] The molecular weight of the obtained dimethylnaphthalene formaldehyde resin was as follows: number average molecular weight (Mn): 562, weight average molecular weight (Mw): 1168, and dispersity (Mw/Mn): 2.08.

[0377] Subsequently, a four necked flask (internal capacity: 0.5 L) equipped with a Dimroth condenser tube, a thermometer, and a stirring blade was prepared. To this four necked flask, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as mentioned above, and 0.05 g of p-toluenesulfonic acid were added in a nitrogen stream, and the temperature was raised to 190° C. at which the mixture was then heated for 2 hours, followed by stirring. Subsequently, 52.0 g (0.36 mol) of 1-naphthol was further added thereto, and the temperature was further raised to 220° C. at which the mixture was allowed to react for 2 hours. After dilution with a solvent, neutralization and washing with water were performed, and the solvent was distilled off under reduced pressure to obtain 126.1 g of a modified resin (CR-1) as a black-brown solid.

[0378] The obtained resin (CR-1) had Mn: 885, Mw: 2220, and Mw/Mn: 2.51.

[0379] As a result of thermogravimetry (TG), the amount of thermogravimetric weight loss at 400° C. of the obtained resin was greater than 25% (evaluation C). Therefore, it was evaluated that application to high temperature baking was difficult.

[0380] As a result of evaluation of solubility in PGMEA, the solubility was 10% by mass or more (evaluation A), and the obtained resin was evaluated to have sufficient solubility.

[0381] Note that the Mn, Mw, and Mw/Mn described above were measured by carrying out gel permeation chromatography (GPC) analysis under the following conditions to determine the molecular weight in terms of polystyrene.

[0382] Apparatus: Shodex GPC-101 model (manufactured by SHOWA DENKO K.K.)

[0383] Column: KF-80M×3

[0384] Eluent: 1 mL/min THF

[0385] Temperature: 40° C.

Production Example 2

Synthesis of BAPP Citraconimide

[0386] 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 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 3.76 g of the target compound (BAPP citraconimide) represented by the following formula:

##STR00041##

[0387] The following peaks were found by 400 MHz-.sup.1H-NMR and the compound was confirmed to have a chemical structure of the formula described above.

[0388] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.4 (16H, Ph-H), 6.7 (2H, —CH═C), 2.1 (6H, C—CH.sub.3), 1.6 (6H, —C (CH.sub.3).sub.2).

As a result of measuring the molecular weight of the obtained compound by the above method, it was 598.

Production Example 3

Synthesis of APB-N Citraconimide

[0389] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 2.92 g (10.0 mmol) of 3,3′-(1, 3-phenylenebis)oxydianiline (product name: APB-N, manufactured by MITSUI FINE CHEMICALS, Inc.), 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 110° 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 methanol and subjected to separation and purification with column chromatography to acquire 3.52 g of the target compound (APB-N citraconimide) represented by the following formula:

##STR00042##

[0390] Note that the following peaks were found by 400 MHz-.sup.1H-NMR and the compound was confirmed to have a chemical structure of the formula described above.

[0391] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.7-7.4 (12H, Ph-H), 6.4 (2H, —CH═C) , 2.2 (6H, C—CH.sub.3. As a result of measuring the molecular weight of the obtained compound by the above method, it was 480.

Production Example 4

Synthesis of HFBAPP Citraconimide

[0392] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 5.18 g (10.0 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (product name: HFBAPP, manufactured by Wakayama Seika Kogyo Co., Ltd.), 4.56 g (44.0 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 110° C. for 5.0 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 methanol and subjected to separation and purification with column chromatography to acquire 3.9 g of the target compound (HFBAPP citraconimide) represented by the following formula:

##STR00043##

[0393] Note that 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.

[0394] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.6-7.3 (16H, Ph-H), 6.4 (2H, —CH═C) , 2.2 (6H, C—CH.sub.3).

[0395] As a result of measuring the molecular weight of the obtained compound by the above method, it was 706.

Production Example 5

Synthesis of BisAP Citraconimide

[0396] A container (internal capacity: 100 ml) equipped with a stirrer, a condenser tube, and a burette was prepared. To this container, 5.18 g (10.0 mmol) of 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene (product name: Bisaniline-P, manufactured by MITSUI FINE CHEMICALS, Inc.), 4.56 g (44.0 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 110° C. for 6.0 hours to perform 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 methanol and subjected to separation and purification with column chromatography to acquire 4.2 g of the target compound

(BisAP citraconimide) represented by the following formula:

##STR00044##

[0397] Note that 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.

[0398] .sup.1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.4 (12H, Ph-H), 6.7 (2H, —CH=C), 2.1 (6H, C-CH.sub.3), 1.6-1.7 (12H, —C (CH.sub.3).sub.2).

[0399] As a result of measuring the molecular weight of the obtained compound by the above method, it was 532.

Production Example 6

Synthesis of BMI Citraconimide Resin

[0400] 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, 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 methanol to acquire 4.7 g of a citraconimide resin (BMI citraconimide resin) represented by the following formula:

##STR00045##

[0401] Note that, as a result of measuring the molecular weight by the above method, it was 446.

Production Example 7

Synthesis of BAN Citraconimide Resin

[0402] 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 carry out 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 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:

##STR00046##

Comparative Example 1

[0403] In addition to 5 parts by mass of CR-1, 2 parts by mass of a biphenyl aralkyl-based epoxy resin (NC-3000-L; manufactured by Nippon Kayaku Co., Ltd.) represented by the formula described below was also used as the crosslinking agent, and 0.1 parts by mass of TPIZ was compounded as the crosslinking promoting agent to prepare a film forming material for lithography.

[0404] A composition for film formation for lithography was prepared through the same operations as in the above Example 1 except that the above film forming material for lithography was used.

Comparative Example 2

[0405] CR-1 was used as a film forming material for lithography.

[0406] Except that the above film forming material for lithography was used, a composition for film formation for lithography was prepared through the same operations as in the above Example 1.

Comparative Example 3

[0407] The BAPP citraconimide was used as a film forming material for lithography.

[0408] 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, the solubility was 15% by mass or more and less than 35% by mass (evaluation S), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0409] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 4

[0410] The APB-N citraconimide was used as a film forming material for lithography.

[0411] 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, the solubility was 15% by mass or more and less than 35% by mass (evaluation S) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0412] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 5

[0413] The HFBAPP citraconimide was used as a film forming material for lithography.

[0414] 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 15% by mass or more and less than 35% by mass (evaluation S), and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0415] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 6

[0416] The BisAP citraconimide was used as a film forming material for lithography.

[0417] 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). Also, as a result of evaluation of solubility in PGMEA, the solubility was 15% by mass or more and less than 35% by mass (evaluation S) and the obtained film forming material for lithography was evaluated to have sufficient solubility.

[0418] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 7

[0419] The BMI citraconimide resin was used as a film forming material for lithography.

[0420] 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, the solubility was 5% by mass or more and less than 15% by mass (evaluation A) and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0421] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 8

[0422] The BAM citraconimide resin was used as a film forming material for lithography.

[0423] 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, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0424] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 9

[0425] A phenylmethane maleimide oligomer (BMI oligomer; BMI-2300; manufactured by Daiwa Kasei Industry Co., Ltd.) represented by the formula described below was used to prepare a film forming material for lithography.

##STR00047##

[0426] 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, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility. The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Comparative Example 10

[0427] As a bismaleimide compound, bismaleimide (BMI-80; manufactured by K.I Chemical Industry Co., LTD.) represented by the formula described below was used to prepare a film forming material for lithography.

##STR00048##

[0428] 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). Besides, as a result of evaluation of solubility in PGMEA, the solubility was 5% by mass or more and less than 15% by mass (evaluation A), and it was evaluated that the obtained film forming material for lithography has sufficient solubility.

[0429] The same operations as in the above Example 1 were carried out, thereby preparing a composition for film formation for lithography.

Example 20

[0430] In addition to 5 parts by mass of the BAPP citramaleimide, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) represented by the formula described below was also compounded as the photopolymerization initiator to prepare a film forming material for lithography.

[0431] To 5 parts by mass of the film forming material for lithography, 95 parts by mass of PGMEA as a 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.

##STR00049##

Example 21

[0432] In addition to 5 parts by mass of the APB-N citramaleimide, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0433] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 22

[0434] In addition to 5 parts by mass of the HFBAPP citramaleimide, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0435] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 23

[0436] In addition to 5 parts by mass of the BisAP citramaleimide, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0437] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 24

[0438] In addition to 5 parts by mass of the BMI citramaleimide resin, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0439] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 24A

[0440] In addition to 5 parts by mass of the high molecular weight BMI citramaleimide polymer, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0441] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 25

[0442] In addition to 5 parts by mass of the BAN citramaleimide resin, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0443] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 25A

[0444] In addition to 5 parts by mass of the high molecular weight BAN citramaleimide polymer, 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was also compounded as the photopolymerization initiator, thereby preparing a film forming material for lithography.

[0445] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 26

[0446] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of BF-BXZ was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0447] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 27

[0448] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of NC-3000-L was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0449] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 28

[0450] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of DABPA-CN was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a material for film formation for lithography.

[0451] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 29

[0452] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of BPA-CA was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0453] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 30

[0454] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of APG-1 was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0455] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 31

[0456] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of APG-2 was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0457] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 32

[0458] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of DDM was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator to prepare a film forming material for lithography.

[0459] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 20-2

[0460] In addition to 5 parts by mass of the BAPP citramaleimide, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) represented by the formula described below was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0461] To 5 parts by mass of the film forming material for lithography, 95 parts by mass of PGMEA as a solvent was added, and the resultant mixture was stirred with a stirrer for at least 3 hours or longer at room temperature, thereby preparing a composition for film formation for lithography.

##STR00050##

Example 21-2

[0462] In addition to 5 parts by mass of the APB-N citramaleimide, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0463] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 22-2

[0464] In addition to 5 parts by mass of the HFBAPP citramaleimide, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0465] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 23-2

[0466] In addition to 5 parts by mass of the BisAP citramaleimide, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0467] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 24-2

[0468] In addition to 5 parts by mass of the BMI citramaleimide resin, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0469] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 24A-2

[0470] In addition to 5 parts by mass of the high molecular weight BMI citramaleimide polymer, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0471] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 25-2

[0472] In addition to 5 parts by mass of the BAN citramaleimide resin, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0473] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 25A-2

[0474] In addition to 5 parts by mass of the high molecular weight BAN citramaleimide polymer, 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was also compounded as the photobase generating agent to prepare a film forming material for lithography.

[0475] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 26-2

[0476] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of BF-BXZ was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a film forming material for lithography.

[0477] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 27-2

[0478] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of NC-3000-L was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a film forming material for lithography.

[0479] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 28-2

[0480] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of DABPA-CN was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a material for film formation for lithography.

[0481] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 29-2

[0482] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of BPA-CA was also used as the crosslinking agent and 0.1 parts by mass of IRGACURE 184 (manufactured by BASF SE) was compounded as the photo-radical polymerization initiator, thereby preparing a film forming material for lithography.

[0483] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 30-2

[0484] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of APG-1 was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a film forming material for lithography.

[0485] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 31-2

[0486] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of APG-2 was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a film forming material for lithography.

[0487] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

Example 32-2

[0488] In addition to 5 parts by mass of the BAPP citramaleimide, 2 parts by mass of DDM was also used as the crosslinking agent and 0.1 parts by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) was compounded as the photobase generating agent to prepare a film forming material for lithography.

[0489] The same operations as in the above Example 20 were carried out to prepare a composition for film formation for lithography.

[0490] A silicon substrate was spin coated with each of the compositions for film formation for lithography of Examples 1 to 19 and Comparative Examples 1 to 10, which have the compositions shown in Table 1, and then baked at 240° C. for 60 seconds. Then, the film thickness of the resultant coated film was measured. Thereafter, the silicon substrate was immersed in a mixed solvent of 70% PGMEA/30% PGME for 60 seconds, the adhered solvent was removed with an Aero Duster, and then the substrate was 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 under the evaluation criteria shown below.

[0491] The underlayer films after the curing baking at 240° C. were further baked at 400° C. for 120 seconds, and 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 under the evaluation criteria shown below. Then, under the conditions shown below, the etching resistance was evaluated.

[0492] In addition, the embedding properties to a substrate having difference in level and the flatness were evaluated under the conditions shown below. <Preparation of underlayer film from compositions for film formation for lithography of Examples 20 to 32 and Examples 20-2 to 32-2>

[0493] A silicon substrate was spin coated with each of the compositions for film formation for lithography of Examples 20 to 32, and 20-2 to 32-2, which have the compositions shown in Table 2, 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 substrate was immersed in a mixed solvent of 70% PGMEA/30% PGME for 60 seconds, the adhered solvent was removed with an Aero Duster, and then the substrate was 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 under the evaluation criteria shown below.

[0494] The underlayer films were further baked at 400° C. for 120 seconds, and 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 under the evaluation criteria shown below. Then, under the conditions shown below, the etching resistance was evaluated.

[0495] In addition, the embedding properties to a substrate having difference in level and the flatness were evaluated under the conditions shown below.

[Evaluation of Curability]

[0496] S: Decreasing rate of film thickness before and after solvent immersion ≤1%

[0497] A: 1%<Decreasing rate of film thickness before and after solvent immersion ≤5%

[0498] B: Decreasing rate of film thickness before and after solvent immersion>5%

[Evaluation of Film Heat Resistance]

[0499] S: Decreasing rate of film thickness before and after baking at 400° C. ≤10%

[0500] A: 10%<Decreasing rate of film thickness before and after baking at 400° C. ≤15%

[0501] B: 15%<Decreasing rate of film thickness before and after baking at 400° C. ≤20%

[0502] C: Decreasing rate of film thickness before and after baking at 400° C.>20%

[Etching Test]

[0503] Etching apparatus: RIE-10NR manufactured by Samco International, Inc.

[0504] Output: 50 W

[0505] Pressure: 4 Pa

[0506] Time: 2 min

[0507] Etching gas

[0508] CF.sub.4 gas flow rate:O.sub.2 gas flow rate=5:15 (sccm)

[Evaluation of Etching Resistance]

[0509] The evaluation of etching resistance was carried out by the following procedures.

[0510] First, an underlayer film of novolac was prepared under the same conditions as in Example 1 except that novolac (PSM 4357 manufactured by Gun Ei Chemical Industry Co., Ltd.) was used instead of the film forming material for lithography in Example 1 and the drying temperature was 110° C. Then, this underlayer film of novolac was subjected to the etching test mentioned above, and the etching rate was measured.

[0511] Next, the underlayer films of Examples 1 to 19 and Comparative Examples 1 to 10 were subjected to the etching test described above in the same way as above, and the etching rate was measured.

[0512] Then, the etching resistance was evaluated according to the following evaluation criteria on the basis of the etching rate of the underlayer film of novolac. From a practical viewpoint, evaluation S described below is particularly preferable, and evaluation A and evaluation B are preferable.

[0513] S: The etching rate was less than −30% as compared with the underlayer film of novolac. [0514] A: The etching rate was −30% or more to less than −20% as compared with the underlayer film of novolac. [0515] B: The etching rate was −20% or more to less than −10% as compared with the underlayer film of novolac. [0516] C: The etching rate was −10% or more and 0% or less as compared with the underlayer film of novolac.

[Evaluation of Embedding Properties to Substrate Having Difference in Level]

[0517] The embedding properties to a substrate having difference in level were evaluated by the following procedures.

[0518] A SiO.sub.2 substrate having a film thickness of 80 nm and a line and space pattern of 60 nm was coated with a composition for underlayer film formation for lithography, and baked at 240° C. for 60 seconds to form a 90 nm underlayer film. The cross section of the obtained film was cut out and observed under an electron microscope to evaluate the embedding properties to a substrate having difference in level.

[0519] A: The underlayer film was embedded without defects in the asperities of the SiO.sub.2 substrate having a line and space pattern of 60 nm.

[0520] C: The asperities of the SiO2 substrate having a line and space pattern of 60 nm had defects which hindered the embedding of the underlayer film.

[Evaluation of Flatness]

[0521] Onto a SiO.sub.2 substrate 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 obtained compositions for film formation 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.

[0522] S: ΔFT<10 nm (best flatness)

[0523] A: 10 nm≤ΔFT<20 nm (good flatness)

[0524] B: 20 nm≤ΔFT<40 nm (partially good flatness)

[0525] C: 40 nm≤ΔFT (poor flatness)

TABLE-US-00001 TABLE 1 Crosslinking Maleimide Crosslinking promoting Film heat Etching Embedding compound agent agent Solvent Curability resistance resistance properties Flatness Example 1 BAPP — — PGMEA(95) S A S A S citramaleimide (5) Example 2 APB-N — — PGMEA(95) S A S A S citramaleimide (5) Example 3 HFBAPP — — PGMEA(95) S A S A S citramaleimide (5) Example 4 BisAP — — PGMEA(95) S A S A S citramaleimide (5) Example 5 BMI — — PGMEA(95) A A S A S citramaleimide resin (5) Example 5A High — — PGMEA(95) A S S A S molecular weight BMI citramaleimide polymer (5) Example 6 BAN — — PGMEA(95) A A A A S citramaleimide resin (5) Example 6A High — — PGMEA(95) A S A A S molecular weight BAN citramaleimide polymer (5) Example 7 BAPP — TPIZ PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 8 APB-N — TPIZ PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 9 HFBAPP — TPIZ PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 10 BisAP — TPIZ PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 11 BMI — TPIZ PGMEA(95) S A S A S citramaleimide (0.1) resin (5) Example 11A High — TPIZ PGMEA(95) S S S A S molecular (0.1) weight BMI citramaleimide polymer (5) Example 12 BAN — TPIZ PGMEA(95) S A S A S citramaleimide (0.1) resin (5) Example 12A High — TPIZ PGMEA(95) S S S A S molecular (0.1) weight BAN citramaleimide polymer (5) Example 13 BAPP BF-BXZ(2) TPIZ PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 14 BAPP NC-3000- TPIZ PGMEA(95) S S S A S citramaleimide L(2) (0.1) (5) Example 15 BAPP DABPA- TPIZ PGMEA(95) S S S A S citramaleimide CN (0.1) (5) (2) Example 16 BAPP BPA-CN TPIZ PGMEA(95) S S S A S citramaleimide (2) (0.1) (5) Example 17 BAPP APG-1 — PGMEA(95) S S S A S citramaleimide (2) (5) Example 18 BAPP APG-2 — PGMEA(95) S S S A S citramaleimide (2) (5) Example 19 BAPP DDM — PGMEA(95) S S S A S citramaleimide (2) (5) Comparative CR-1 NC-3000- TPIZ PGMEA(95) A C C C C Example 1 (5) L(2) (0.1) Comparative CR-1 — — PGMEA(95) A C C C C Example 2 (5) Comparative BAPP — — PGMEA(95) B B A A S Example 3 citraconimide (5) Comparative APB-N — — PGMEA(95) B B S A S Example 4 citraconimide (5) Comparative HFBAPP — — PGMEA(95) B B S A S Example 5 citraconimide (5) Comparative BisAP — — PGMEA(95) B B A A S Example 6 citraconimide (5) Comparative BMI — — PGMEA(95) B B A A S Example 7 citraconimide resin (5) Comparative BAN — — PGMEA(95) B B B A S Example 8 citraconimide resin (5) Comparative BMI-2300(5) — — PGMEA(95) S A A A B Example 9 Comparative BMI-80(5) — — PGMEA(95) S A A A A Example 10

[0526] As is evident from Table 1, it was confirmed that Examples 1 to 19, in which the compositions for film formation for lithography of the present embodiment comprising citramaleimides and citramaleimide resins were used, have superior curability, film heat resistance, and etching resistance compared to the citraconimides of Comparative Examples 3 to 8, and superior flatness compared to the maleimides of Comparative Examples 9 to 10. In particular, it was confirmed that the use of high molecular weight BMI citramaleimide polymer or high molecular weight BAN citramaleimide polymer achieves both high film heat resistance and excellent flatness.

[0527] In addition, the compositions of Examples 1 to 6 and Comparative Examples 3 to 10 were subjected to a storage stability test at room temperature of 25° C. for one month, and the presence or absence of precipitates was visually confirmed. As a result, it was confirmed that there is no precipitation in the compositions of Examples 1 to 6, but precipitates were visually confirmed in the compositions of Comparative Examples 3 to 10.

[0528] Accordingly, it was confirmed that the compositions for film formation for lithography of the present embodiment comprising citramaleimides and citramaleimide resins have superior solvent solubility and storage stability compared to the citraconimides of Comparative Examples 3 to 8 and the maleimides of Comparative Examples 9 to 10.

TABLE-US-00002 TABLE 2 Radical Maleimide Crosslinking polymerization Film heat Etching Embedding compound agent initiator Solvent Curability resistance resistance properties Flatness Example 20 BAPP — IRGACURE184 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 21 APB-N — IRGACURE184 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 22 HFBAPP — IRGACURE184 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 23 BisAP — IRGACURE184 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 24 BMI — IRGACURE184 PGMEA(95) A A B A S citramaleimide (0.1) resin (5) Example 24A High — IRGACURE184 PGMEA(95) A S B A S molecular (0.1) weight BMI citramaleimide polymer (5) Example 25 BAN — IRGACURE184 PGMEA(95) A A B A S citramaleimide (0.1) resin (5) Example 25A High — IRGACURE184 PGMEA(95) A S B A S molecular (0.1) weight BAN citramaleimide polymer (5) Example 26 BAPP BF-BXZ(2) IRGACURE184 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 27 BAPP NC-3000- IRGACURE184 PGMEA(95) S S S A S citramaleimide L(2) (0.1) (5) Example 28 BAPP DABPA- IRGACURE184 PGMEA(95) S S S A S citramaleimide CN(2) (0.1) (5) Example 29 BAPP BPA-CN(2) IRGACURE184 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 30 BAPP APG-1(2) IRGACURE184 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 31 BAPP APG-2(2) IRGACURE184 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 32 BAPP DDM(2) IRGACURE184 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 20-2 BAPP — WPBG-300 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 21-2 APB-N — WPBG-300 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 22-2 HFBAPP — WPBG-300 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 23-2 BisAP — WPBG-300 PGMEA(95) S A B A S citramaleimide (0.1) (5) Example 24-2 BMI — WPBG-300 PGMEA(95) S S B A S citramaleimide (0.1) resin (5) Example 24A-2 High — WPBG-300 PGMEA(95) S S B A S molecular (0.1) weight BMI citramaleimide polymer (5) Example 25-2 BAN — WPBG-300 PGMEA(95) S S B A S citramaleimide (0.1) resin (5) Example 25A-2 High — WPBG-300 PGMEA(95) S S B A S molecular (0.1) weight BAN citramaleimide polymer (5) Example 26-2 BAPP BF-BXZ(2) WPBG-300 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 27-2 BAPP NC-3000- WPBG-300 PGMEA(95) S S S A S citramaleimide L(2) (0.1) (5) Example 28-2 BAPP DABPA- WPBG-300 PGMEA(95) S S S A S citramaleimide CN(2) (0.1) (5) Example 29-2 BAPP BPA-CN(2) WPBG-300 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 30-2 BAPP APG-1(2) WPBG-300 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 31-2 BAPP APG-2(2) WPBG-300 PGMEA(95) S S S A S citramaleimide (0.1) (5) Example 32-2 BAPP DDM(2) WPBG-300 PGMEA(95) S S S A S citramaleimide (0.1) (5)

Example 33

[0529] A SiO.sub.2 substrate 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.

[0530] Note that the compound of the following formula (22) was prepared as follows. That is, 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.

##STR00051##

[0531] In the above formula (22), 40, 40, and 20 represent the ratio of each constituent unit and do not represent a block copolymer.

[0532] 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 34

[0533] A positive type resist pattern was obtained in the same way as Example 33 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 35

[0534] A positive type resist pattern was obtained in the same way as Example 33 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.

Example 36

[0535] A positive type resist pattern was obtained in the same way as Example 33 except that the composition for underlayer film formation for lithography in Example 4 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 11

[0536] The same operations as in Example 33 were performed except that no underlayer film was formed so that a photoresist layer was formed directly on a SiO.sub.2 substrate to obtain a positive type resist pattern. The evaluation results are shown in Table 3.

[Evaluation]

[0537] Concerning each of Examples 33 to 36 and Comparative Example 11, 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 (nm L/S) (μC/cm.sup.2) development Example 33 Composition 53 17 Goodness described in Example 1 Example 34 Composition 61 17 Goodness described in Example 2 Example 35 Composition 54 16 Goodness described in Example 3 Example 36 Composition 48 16 Goodness described in Example 4 Comparative — 90 41 Poorness Example 11

[0538] As is evident from Table 3, it was confirmed that Examples 33 to 36, in which the compositions for film formation for lithography of the present embodiment comprising citramaleimides and citramaleimide resins were used, are significantly superior in both resolution and sensitivity to Comparative Example 11. 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 33 to 36 obtained from the compositions for film formation for lithography of Examples 1, 2, 3, and 4 have good adhesiveness to a resist material.

[0539] The present application is based on Japanese Patent Application No. 2018-218042 filed on November 21, 2018, the contents of which are incorporated herein by reference.

INDUSTRIAL APPLICABILITY

[0540] The film forming material for lithography of the present embodiment has relatively high heat resistance, relatively high solvent solubility, and excellent embedding properties to a substrate having difference in level and film flatness, and is applicable to a wet process. 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.

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

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Abstract

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