Metal-containing resist underlayer film-forming composition containing polyacid

Abstract

A resist underlayer film-forming composition including: (A) component: an isopoly or heteropoly acid, or a salt thereof, or a combination thereof; and (B) component: polysiloxan, poly hafnium oxide or zirconium oxide, or a combination thereof, wherein an amount of the (A) component is 0.1 to 85% by mass of a total amount of the (A) component and the (B) component; and polysiloxan is a hydrolysis-condensation product of hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4−(a+b)  Formula (1)
and a hydrolyzable silane whose (a+b) is 0 is contained in a proportion of 60 to 85 mol % of a total hydrolyzable silane in Formula (1); the poly hafnium oxide is a hydrolysis-condensation product of hydrolyzable hafnium of Formula (2):
Hf(R.sup.4).sub.4  Formula (2)
and the zirconium oxide is a hydrolysis-condensation product of hydrolyzable zirconium of Formula (3) or Formula (4):
Zr(R.sup.5).sub.4  Formula (3)
ZrO(R.sup.6).sub.2  Formula (4)
or a hydrolysis-condensation product of a combination thereof.

Claims

1. A resist underlayer film obtained by applying a resist underlayer film-forming composition onto a semiconductor substrate, and then baking the applied resist underlayer film-forming composition, wherein the resist underlayer film-forming composition comprises: (A) component: an isopoly acid or a heteropoly acid, or a salt thereof, or a combination thereof; and (B) component: polysiloxan, poly hafnium oxide or zirconium oxide, or a combination thereof, wherein an amount of the (A) component is 0.1 to 85% by mass of a total amount of the (A) component and the (B) component; and the polysiloxan is a hydrolysis-condensation product of hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4−(a+b)  Formula (1) wherein: R.sup.1 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R.sup.1 binds to a silicon atom with a Si—C bond; R.sup.2 is a nitrogen atom-containing ring or an organic group containing the nitrogen atom-containing ring, a condensed aromatic ring or an organic group containing the condensed aromatic ring, a protected phenolic hydroxyl group or an organic group containing the protected phenolic hydroxyl group, or a bisaryl group or an organic group containing the bisaryl group, and R.sup.2 binds to a silicon atom with a Si—C bond; R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 0 to 3; b is an integer of 0 to 3; (a+b) is an integer of 0 to 3; and a hydrolyzable silane whose (a+b) is 0 is contained in a proportion of 60 to 85 mol % of a total hydrolyzable silane in Formula (1); the poly hafnium oxide is a hydrolysis-condensation product of hydrolyzable hafnium of Formula (2):
Hf(R.sup.4).sub.4  Formula (2) wherein R.sup.4 is an alkoxy group, an acyloxy group, or a halogen group; and the zirconium oxide is a hydrolysis-condensation product of hydrolyzable zirconium of Formula (3) or Formula (4):
Zr(R.sup.5).sub.4  Formula (3)
ZrO(R.sup.6).sub.2  Formula (4) wherein each of R.sup.5 and R.sup.6 is an alkoxy group, an acyloxy group, a halogen group, or a nitrate ion, or a hydrolysis-condensation product of a combination thereof.

2. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the isopoly acid is an oxoacid of tungsten, molybdenum, or vanadium, or a salt thereof.

3. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the isopoly acid is metatungstic acid or ammonium metatungstate.

4. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the heteropoly acid is a combination of an oxoacid of tungsten, molybdenum, or vanadium, or a salt thereof and an oxoacid of silicon or phosphorus, or a salt thereof.

5. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the heteropoly acid is silicotungstic acid, phosphotungstic acid, or phosphomolybdic acid.

6. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the composition further comprises an acid.

7. The resist underlayer film obtained by applying a resist underlayer film-forming composition according to claim 1, wherein the composition further comprises water.

8. A method for manufacturing a semiconductor device comprising: forming a resist underlayer film by applying a resist underlayer film-forming composition onto a semiconductor substrate, and then baking the applied resist underlayer film-forming composition; forming a resist film by applying a composition for resists onto the resist underlayer film; exposing the resist film; obtaining a resist pattern by developing the exposed resist film; etching the resist underlayer film with the resist pattern; and processing the semiconductor substrate with a patterned resist underlayer film, wherein the resist underlayer film-forming composition comprises: (A) component: an isopoly acid or a heteropoly acid, or a salt thereof, or a combination thereof; and (B) component: polysiloxan, poly hafnium oxide or zirconium oxide, or a combination thereof, wherein an amount of the (A) component is 0.1 to 85% by mass of a total amount of the (A) component and the (B) component; and the polysiloxan is a hydrolysis-condensation product of hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4−(a+b)  Formula (1) wherein: R.sup.1 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R.sup.1 binds to a silicon atom with a Si—C bond; R.sup.2 is a nitrogen atom-containing ring or an organic group containing the nitrogen-atom containing ring, a condensed aromatic ring or an organic group containing the condensed aromatic ring, a protected phenolic hydroxyl group or an organic group containing the protected phenolic hydroxyl group, or a bisaryl group or an organic group containing the bisaryl group, and R.sup.2 binds to a silicon atom with a Si—C bond; R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 0 to 3; b is an integer of 0 to 3; (a+b) is an integer of 0 to 3; and a hydrolyzable silane whose (a+b) is 0 is contained in a proportion of 60 to 85 mol % of a total hydrolyzable silane in Formula (1): the poly hafnium oxide is a hydrolysis-condensation product of hydrolyzable hafnium of Formula (2):
Hf(R.sup.4).sub.4  Formula (2) wherein R.sup.4 is an alkoxy group, an acyloxy group, or a halogen group; and the zirconium oxide is a hydrolysis-condensation product of hydrolyzable zirconium of Formula (3) or Formula (4):
Zr(R.sup.5).sub.4  Formula (3)
ZrO(R.sup.6).sub.2  Formula (4) wherein each of R.sup.5 and R.sup.6 is an alkoxy group, an acyloxy group, a halogen group, or a nitrate ion, or a hydrolysis-condensation product of a combination thereof.

9. A method for manufacturing a semiconductor device comprising: forming an organic underlayer film on a semiconductor substrate; forming a resist underlayer film by applying a resist underlayer film-forming composition onto the organic underlayer film, and then baking the applied resist underlayer film-forming composition; forming a resist film by applying a composition for resists onto the resist underlayer film; exposing the resist film; obtaining a resist pattern by developing the exposed resist film; etching the resist underlayer film with the resist pattern; etching the organic underlayer film with the patterned resist underlayer film; and processing the semiconductor substrate with the patterned organic underlayer film, wherein the resist underlayer film-forming composition comprises: (A) component: an isopoly acid or a heteropoly acid, or a salt thereof, or a combination thereof; and (B) component: polysiloxan, poly hafnium oxide or zirconium oxide, or a combination thereof, wherein an amount of the (A) component is 0.1 to 85% by mass of a total amount of the (A) component and the (B) component; and the polysiloxan is a hydrolysis-condensation product of hydrolyzable silane of Formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4−(a+b)  Formula (1) wherein: R.sup.1 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R.sup.1 binds to a silicon atom with a Si—C bond; R.sup.2 is a nitrogen atom-containing ring or an organic group containing the nitrogen atom-containing ring, a condensed aromatic ring or an organic group containing the condensed aromatic ring, a protected phenolic hydroxyl group or an organic group containing the protected phenolic hydroxyl group, or a bisaryl group or an organic group containing the bisaryl group, and R.sup.2 binds to a silicon atom with a Si—C bond; R.sup.3 is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 0 to 3; b is an integer of 0 to 3; (a+b) is an integer of 0 to 3; and a hydrolyzable silane whose (a+b) is 0 is contained in a proportion of 60 to 85 mol % of a total hydrolyzable silane in Formula (1); the poly hafnium oxide is a hydrolysis-condensation product of hydrolyzable hafnium of Formula (2):
Hf(R.sup.4).sub.4  Formula (2) wherein R.sup.4 is an alkoxy group, an acyloxy group, or a halogen group; and the zirconium oxide is a hydrolysis-condensation product of hydrolyzable zirconium of Formula (3) or Formula (4):
Zr(R.sup.5).sub.4  Formula (3)
ZrO(R.sup.6).sub.2  Formula (4) wherein each of R.sup.5 and R.sup.6 is an alkoxy group, an acyloxy group, a halogen group, or a nitrate ion, or a hydrolysis-condensation product of a combination thereof.

Description

EXAMPLES

(1) (Preparation of Metatungstic Acid Aqueous Solution)

(2) 20.0 g of ammonium metatungstate (manufactured by Nippon Inorganic Colour & Chemical Co., Ltd., 90.8% by mass in terms of WO.sub.3) was dissolved in 80.1 g of ion exchange water to prepare an ammonium metatungstate aqueous solution. After 20.0 g of a cation exchange resin (manufactured by Organo Corporation, Amberlist 15JWET) was added thereto, the mixture was stirred at a room temperature for 4 hours, and then filtrated to obtain a metatungstic acid aqueous solution. The pH of the obtained solution was 0.54. The solid residue at 140° C. was 17.0%.

Synthesis Example 1

(3) 18.94 g (30 mol %) of methyltriethoxysilane, 51.62 g (70 mol %) of tetraethoxysilane, and 105.84 g of acetone were placed in a 300 ml flask, and 23.60 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 142.00 g of propylene glycol monomethyl ether was added to the reaction solution to distill off reaction by-products, including ethanol, water, hydrochloric acid, and acetone, under reduced pressure. After condensation, a propylene glycol monomethyl ether solution of a hydrolysis-condensation product (polymer) was obtained. The solution was diluted with propylene glycol monomethyl ether, so that the solid residue at 140° C. was 30.0% by weight. The obtained polymer was represented by Formula (5-1).

Synthesis Example 2

(4) 18.99 g (15 mol %) of 3-(triethoxysilylpropyl)diallyl isocyanurate, 44.65 g (70 mol %) of tetraethoxysilane, 8.19 g (15 mol %) of methyltriethoxysilane, and 71.83 g of acetone were placed in a 300 ml flask, and 20.41 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 142.00 g of propylene glycol monomethyl ether was added to the reaction solution to distill off reaction by-products, including ethanol, water, hydrochloric acid, and acetone, under reduced pressure. After concentration, a propylene glycol monomethyl ether solution of a hydrolysis-condensation product (polymer) was obtained. The solution was diluted with propylene glycol monomethyl ether, so that the solid residue at 140° C. was 30.0% by weight. The obtained polymer was represented by Formula (5-2).

Synthesis Example 3

(5) 9.63 g (14 mol %) of phenyltrimethoxysilane, 9.28 g (15 mol %) of methyltriethoxysilane, 50.59 g (70 mol %) of tetraethoxysilane, 1.25 g (1 mol %) of N-(3-(triethoxysilyl)propyl)benzenesulfonamide, and 106.12 g of acetone were placed in a 300 ml flask, and 23.13 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 142.00 g of propylene glycol monomethyl ether was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, water, hydrochloric acid, and acetone, under reduced pressure. After concentration, a propylene glycol monomethyl ether solution of a hydrolysis-condensation product (polymer) was obtained. The solution was diluted with propylene glycol monomethyl ether, so that the solid residue at 140° C. was 30.0% by weight. The obtained polymer was represented by Formula (5-8).

Synthesis Example 4

(6) 4.48 g of methyltriethoxysilane, 15.73 g of tetraethoxysilane, and 76.31 g of methanol were placed in a 300 ml flask, and a solution in which 17.94 g of zirconyl nitrate dihydrate (ZrO(NO.sub.3).sub.2-2H.sub.2O) was dissolved in 76.31 g of methanol and 9.22 g of ultrapure water was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 120 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 200 g of propylene glycol monomethyl ether was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, and water, under reduced pressure, and finally the solid residue at 140° C. was adjusted to 15.0% by weight. The obtained polymer was represented by Formula (5-7).

(7) (Preparation of Resist Underlayer Film)

(8) Ammonium metatungstate or metatungstic acid, and the silicon-containing polymer obtained in the synthesis example described above, an acid, a curing catalyst, an additive, a solvent, and water were mixed according to the mixing ratio shown in Table 1, and then the mixture was filtrated through a fluororesin filter having a pore size of 0.1 μm to prepare each of the resist underlayer film-forming composition solutions. The addition ratios of the polymers shown in Table 1 represent addition amounts of polymers themselves, and do not represent addition amounts of polymer solutions.

(9) The abbreviations in Table 1 are explained below: MA is maleic acid, MeSO.sub.3 is methanesulfonic acid, HNO.sub.3 is nitric acid, BTEAC is benzyltriethylammonium chloride, TPS105 is triphenylsulfonium trifluoromethane sulfonate, TPSMA is monotriphenylsulfonium maleate, and PGME is propylene glycol monomethyl ether. The water used was ultrapure water. Each of the addition amounts are represented by parts by mass.

(10) TABLE-US-00001 TABLE 1 Tungsten Curing Component Polymer Acid Catalyst Additive Solvent Example 1 Metatungstic Acid Synthesis MA BTEAC PGME Water (Parts by Mass) 1.0 Example 1 0.02 0.006 90 10 1.0 Example 2 Metatungstic Acid Synthesis MA BTEAC PGME Water (Parts by Mass) 0.6 Example 1 0.02 0.006 90 10 1.4 Example 3 Ammonium Synthesis MA BTEAC PGME Water (Parts by Mass) Metatungstate Example 1 0.02 0.006 90 10 1.4 0.6 Example 4 Ammonium Synthesis MA BTEAC PGME Water (Parts by Mass) Metatungstate Example 1 0.02 0.006 90 10 1.0 1.0 Example 5 Ammonium Synthesis MA BTEAC PGME Water (Parts by Mass) Metatungstate Example 1 0.02 0.006 90 10 0.6 1.4 Example 6 Metatungstic Acid Synthesis MA BTEAC PGME Water (Parts by Mass) 1.0 Example 2 0.02 0.006 90 10 1.0 Example 7 Metatungstic Acid Synthesis MA BTEAC PGME Water (Parts by Mass) 0.6 Example 2 0.02 0.006 90 10 1.4 Example 8 Metatungstic Acid Synthesis MeS03 BTEAC PGME Water (Parts by Mass) 0.6 Example 3 0.06 0.006 90 10 1.4 Example 9 Metatungstic Acid Synthesis MeS03 TPSMA PGME Water (Parts by Mass) 0.6 Example 2 0.06 0.006 90 10 1.4 Example 10 Metatungstic Acid Synthesis MeS03 TPSMA TPS105 PGME Water (Parts by Mass) 0.6 Example 2 0.06 0.006 0.02 90 10 1.4 Example 11 Metatungstic Acid Synthesis HN03 PGME Water (Parts by Mass) 0.6 Example 4 2.4 90 10 1.4 Comparative Ammonium MA PGME Water Example 1 Metatungstate 0.02 90 10 (Parts by Mass) 2.0 Comparative Metatungstic Acid MA PGME Water Example 2 2.0 0.02 90 10 (Parts by Mass)

Synthesis Example 5

(11) 25.81 g (70 mol %) of tetraethoxysilane, 9.47 g (30 mol %) of methyltriethoxysilane, and 52.92 g of acetone were placed in a 300 ml flask, and 11.80 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, acetone, water, and hydrochloric acid, under reduced pressure. After concentration, a propylene glycol monomethyl ether acetate solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monoethyl ether was added to the solution, so that the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether was adjusted to 20/80, and the solid residue at 140° C. was adjusted to 20% by weight. The obtained polymer is represented by Formula (5-1), and the weight-average molecular weight determined by GPC was Mw 2,000 in terms of polystyrene.

Synthesis Example 6

(12) 25.59 g (70 mol %) of tetraethoxysilane, 6.26 g (20 mol %) of methyltriethoxysilane, 3.48 g (10 mol %) of phenyltrimethoxysilane, and 52.98 g of acetone were placed in a 300 ml flask, and 11.69 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, acetone, water, and hydrochloric acid, under reduced pressure. After concentration, a propylene glycol monomethyl ether acetate solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monoethyl ether was added to the solution, so that the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether was adjusted to 20/80, and the solid residue at 140° C. was adjusted to 20% by weight. The obtained polymer is represented by Formula (5-3), and the weight-average molecular weight determined by GPC was Mw 2,000 in terms of polystyrene.

Synthesis Example 7

(13) 22.32 g (70 mol %) of tetraethoxysilane, 4.09 g (15 mol %) of methyltriethoxysilane, 9.49 g (1.5 mol %) of 3-(triethoxysilyl)propyl diallyl isocyanurate, and 53.88 g of acetone were placed in a 300 ml flask, and 10.20 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, acetone, water, and hydrochloric acid, under reduced pressure. After concentration, a propylene glycol monomethyl ether acetate solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monoethyl ether was added to the solution, so that the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether was adjusted to 20/80, and the solid residue at 140° C. was adjusted to 20% by weight. The obtained polymer is represented by Formula (5-2), and the weight-average molecular weight determined by GPC was Mw 2,000 in terms of polystyrene.

Synthesis Example 8

(14) 24.81 g (70 mol %) of tetraethoxysilane, 7.58 g (25 mol %) of methyltriethoxysilane, 3.08 g (5 mol %) of N-(3-(triethoxysilyl)propyl)benzenesulfonamide, and 51.20 g of acetone were placed in a 300 ml flask, and 11.36 g of 0.01 mol/l hydrochloric acid was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and 68.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution to distill off reaction by-products, including methanol, ethanol, acetone, water, and hydrochloric acid, under reduced pressure. After concentration, a propylene glycol monomethyl ether acetate solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monoethyl ether was added to the solution, so that the solvent ratio of propylene glycol monomethyl ether acetate/propylene glycol monoethyl ether was adjusted to 20/80, and the solid residue at 140° C. was adjusted to 20% by weight. The obtained polymer is represented by Formula (5-4), and the weight-average molecular weight determined by GPC was Mw 2,000 in terms of polystyrene.

Synthesis Example 9

(15) 11.53 g of silicotungstic acid, 3.48 g of tetraethoxysilane, 4.47 g of methyltriethoxysilane, and 77.95 g of propylene glycol monomethyl ether were placed in a 300 ml flask, and 2.56 g of ultrapure water was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and reaction by-products, including ethanol and water, were distilled off under reduced pressure. After concentration, a propylene glycol monomethyl ether solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monomethyl ether was added to the solution, so that the solid residue at 140° C. was 20% by weight. The obtained polymer was represented by Formula (5-5).

Synthesis Example 10

(16) 11.53 g of silicotungstic acid, 11.98 g of tetra-n-butoxy hafnium, and 75.97 g of propylene glycol monomethyl ether were placed in a 300 ml flask, and 5.04 g of concentrated nitric acid (70 wt %) was added dropwise to the mixed solution with stirring by a magnetic stirrer. After that, the flask was placed in an oil bath whose temperature was adjusted to 85° C., and the solution was warmed to reflux for 240 minutes to be reacted. Then, the reaction solution was cooled to a room temperature, and reaction by-products, including ethanol and water, were distilled off under reduced pressure. After concentration, a propylene glycol monomethyl ether solution of a hydrolysis-condensation product (polymer) was obtained. Propylene glycol monomethyl ether was added to the solution, so that the solid residue at 140° C. was 20% by weight. The obtained polymer was represented by Formula (5-6).

(17) (Preparation of Si—Containing Resist Underlayer Film)

(18) The silicon-containing polymer obtained in the synthesis example described above, an acid, a curing catalyst, a sulfonate additive, a solvent, and water were mixed according to the mixing ratio shown in Table 1, and then the mixture was filtrated through a fluororesin filter having a pore size of 0.1 μm to prepare each of the resist underlayer film-forming composition solutions. The addition ratios of the polymers shown in Table 2 represent addition amounts of polymers themselves, and do not represent addition amounts of polymer solutions.

(19) As heteropoly acids in Table 2, (A) refers to silicotungstic acid, (B) refers to phosphotungstic acid, and (C) refers to phosphomolybdic acid.

(20) The abbreviations in Table 2 are explained below: MA is maleic acid, BTEAC is benzyltriethylammonium chloride, IMIDTEOS is N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, TPSCl is triphenylsulfonium chloride, TPSMA is monotriphenylsulfonium maleate, TPSNO3 is triphenylsulfonium nitrate, TPSTFA is triphenylsulfonium trifluoroacetate, TPSCS is triphenylsulfonium camphorsulfonate, BPS is bisphenylsulfone, PGMEA is propylene glycol monomethyl ether acetate, PGEE is propylene glycol monoethyl ether, and PGME is propylene glycol monomethyl ether. The water used was ultrapure water. Each of the addition amounts is represented by parts by mass.

(21) TABLE-US-00002 TABLE 2 Heteropoly Curing Acid Polymer Acid Catalyst Additive Solvent Example 12 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 1 Example 5 0.02 0.006 15 65 5 15 1 Example 13 (B) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 1 Example 5 0.02 0.006 15 65 5 15 1 Example 14 (C) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 1 Example 5 0.02 0.006 15 65 5 15 1 Example 15 (A) Synthesis MA TPSMA PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 6 0.02 0.006 15 65 5 15 1.8 Example 16 (B) Synthesis MA TPSMA PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 6 0.02 0.006 15 65 5 15 1.8 Example 17 (C) Synthesis MA TPSMA PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 6 0.02 0.006 15 65 5 15 1.8 Example 18 (A) Synthesis MA TPSN03 TPSCS PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 5 0.02 0.006 0.1 15 65 5 15 1.8 Example 19 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 7 0.02 0.006 15 65 5 15 1.8 Example 20 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 0.2 Example 8 0.02 0.006 15 65 5 15 1.8 Example 21 Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) Example 9 0.02 0.006 15 65 5 15 2.0 Example 22 Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) Example 0 0.006 15 65 5 15 10 2.0 Example 23 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 1.6 Example 5 0.02 0.006 15 65 5 15 0.4 Example 24 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 0.6 Example 5 0.02 0.006 15 65 5 15 1.4 Example 25 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 0.1 Example 5 0.02 0.006 15 65 5 15 1.9 Example 26 (A) Synthesis MA BTEAC PGME PGEE PGMEA Water (Parts by Mass) 0.02 Example 5 0.02 0.006 15 65 5 15 1.98 Comparative Synthesis MA TPSMA TPSCS PGME PGEE PGMEA Water Example 3 Example 6 0.02 0.006 0.06 15 65 5 15 (Parts by Mass) 2

(22) (Preparation of Organic Underlayer Film-Forming Composition)

(23) Carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and para-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 100 mL four-neck flask in a nitrogen gas, and then 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Inc.) was added thereto and stirred. The temperature was raised to 100° C. in order to dissolve the content such that polymerization is initiated. After 24 hours, the content was cooled to 60° C. The content was diluted by adding chloroform (34 g, manufactured by Kanto Chemical Co., Inc.), and was re-precipitated in methanol (168 g, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtrated and dried in a vacuum dryer at 80° C. for 24 hours to obtain 9.37 g of the target polymer (Formula (6-1), hereinafter, abbreviated as PCzFL).

(24) ##STR00005##

(25) The PCzFL was measured by .sup.1H-NMR, and the result is shown below.

(26) .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ7.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H), δ 11.18 (br, 1H).

(27) The weight-average molecular weight (Mw) of PCzFL determined by GPC was 2,800 in terms of polystyrene, and polydispersity (Mw/Mn) was 1.77.

(28) 20 g of the obtained resin was mixed with 3.0 g of tetramethoxymethyl glycoluril (trade name: Powder Link 1174, manufactured by Mitsui Cytec, Ltd.) as a cross-linker, 0.30 g of pyridinium para-toluenesulfonate as a catalyst, and 0.06 g of MEGAFACE R-30 (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated) as a surfactant, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the solution was filtrated through a polyethylene microfilter having a pore size of 0.10 μm, followed by a polyethylene microfilter having a pore size of 0.05 μm to prepare a solution of the organic underlayer film-forming composition used for a multilayer film lithography process.

(29) (Measurement of Optical Constant)

(30) Each of the resist underlayer film-forming compositions, which were prepared in Examples 1 to 26 and Comparative Examples 1 to 3, was applied onto a silicon wafer by using a spinner. The silicon wafer was heated on a hot plate at 200° C. for 1 minute to form the resist underlayer film (having a film thickness of 0.05 μm). For each of these resist underlayer films, a refractive index (the “n” value) and an optical absorption coefficient (the “k” value, also referred to as an attenuation coefficient) at the wavelength of 193 nm were measured by using a spectroscopic ellipsometer (VUV-VASEVU-302 manufactured by J.A. Woollam Co. Inc.).

(31) (Measurement of Dry Etching Rate)

(32) The etcher and etching gas used for measuring a dry etching rate are described below.

(33) ES401 (manufactured by Nippon Scientific Co., Ltd.): CF.sub.4

(34) RIE-10NR (manufactured by SAMCO INC.): O.sub.2

(35) Each of the solutions of resist underlayer film-forming compositions prepared in Examples 1 to 26 and Comparative Examples 1 to 3 was applied onto a silicon wafer by using a spinner. The silicon wafer was heated on a hot plate at a temperature shown in Table 3 or Table 4 for 1 minute to form each of resist underlayer films having film thicknesses of 0.08 μm (to measure an etching rate with CF.sub.4 gas), and to form each of resist underlayer films having film thicknesses of 0.05 μm (to measure an etching rate with O.sub.2 gas). Similarly, a silicon wafer was coated with an organic underlayer film-forming composition by using a spinner to form a film (having a film thickness of 0.20 μm). The dry etching rate was measured by using O.sub.2 gas as an etching gas, and the result was compared with each of the dry etching rates of resist underlayer films of Examples 1 to 26 and of Comparative Examples 1 to 3.

(36) Table 3 shows the refractive index “n” at the wavelength of 193 nm and the optical absorption coefficient “k” at the wavelength of 193 nm. About Examples 1 to 11 and Comparative Examples 1 and 2, each of etch rates when fluorine-containing gas (CF.sub.4 gas) and oxygen-containing gas (O.sub.2 gas) was used is shown (an etching rate: nm/minute).

(37) TABLE-US-00003 TABLE 3 Fluorine- Oxygen- Optical Containing Containing Baking Refractive Absorption Gas Etch Rate Gas Etch Rate Temperature Index Coefficient (nm/minute) (nm/minute) Example 1 400° C. 1.54 0.17 23.3 1.35 Example 2 400° C. 1.53 0.09 24.3 1.35 Example 3 400° C. 1.55 0.38 22.3 0.46 Example 4 400° C. 1.59 0.21 25.9 0.69 Example 5 400° C. 1.57 0.09 28.6 0.89 Example 6 300° C. 1.78 0.32 40.0 1.90 Example 7 300° C. 1.76 0.23 39.5 3.10 Example 8 300° C. 1.78 0.32 35.0 3.20 Example 9 300° C. 1.76 0.24 39.7 3.10 Example 10 300° C. 1.76 0.25 39.2 3.10 Example 11 300° C. 1.81 0.32 7.2 0.70 Comparative 400° C. 1.55 0.78 25.5 0.11 Example 1 Comparative 400° C. 1.52 0.98 22.0 0.11 Example 2

(38) Table 4 shows the refractive index “n” at the wavelength of 193 nm, the optical absorption coefficient “k” at the wavelength of 193 nm, etch of the etch rates when fluorine-containing gas (CF.sub.4 gas) was used (an etching rate is nm/minute), and oxygen-containing gas (O.sub.2 gas) resistances as etch rate ratios, that is (the resist underlayer film)/(the organic underlayer film).

(39) TABLE-US-00004 TABLE 4 Fluorine- Oxygen- Optical Containing Containing Gas Baking Refractive Absorption Gas Etch Rate (Ratio to Organic Temperature Index Coefficient (nm/minute) Underlayer Film) Example 12 240° C. 1.62 0.20 32 0.00 Example 13 240° C. 1.63 0.20 40 0.01 Example 14 240° C. 1.61 0.20 54 0.01 Example 15 240° C. 1.56 0.03 39 0.02 Example 16 240° C. 1.55 0.03 42 0.02 Example 17 240° C. 1.55 0.03 44 0.02 Example 18 240° C. 1.60 0.29 39 0.02 Example 19 240° C. 1.70 0.38 43 0.02 Example 20 240° C. 1.62 0.34 40 0.02 Example 21 240° C. 1.61 0.20 35 0.01 Example 22 240° C. 1.91 0.75 40 0.01 Example 23 240° C. 1.57 0.41 40 0.00 Example 24 240° C. 1.57 0.10 30 0.02 Example 25 240° C. 1.53 0.01 25 0.02 Example 26 240° C. 1.52 0.00 25 0.02 Comparative 240° C. 1.69 0.24 22 0.03 Example 3

(40) (Evaluation of Resist Patterning 1)

(41) The obtained organic underlayer film (A layer)-forming composition was applied onto a silicon wafer, and was baked on a hot plate at 400° C. for 60 seconds to obtain the organic underlayer film (A layer). Each of the resist underlayer film (B layer)-forming compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 3 was applied onto the organic underlayer film (A layer), and was baked on a hot plate at a temperature shown in Table 5 or Table 6 for 60 seconds to obtain the resist underlayer film (B layer).

(42) The commercially available photoresist solution (manufactured by JSR Corporation, trade name: AR2772) was applied onto the resist underlayer film (B layer) by using a spinner, and was baked on a hot plate at 110° C. for 60 seconds to form the photoresist film (C layer) having the film thickness of 120 nm. The patterning of the resist was conducted by using the ArF exposure device S-307E (wavelength: 193 nm, NA, σ: 0.85, 0.93/0.85 (Dipole), immersion liquid; water) manufactured by Nikon Corporation. Exposure was conducted through the mask that allows to form a line and space pattern (dense line) in which the line width and the width between the lines of a photoresist are 0.062 μm after development as a target.

(43) Next, baking was conducted on a hot plate at 110° C. for 60 seconds followed by cooling, and then development was conducted with an aqueous solution of concentration of 2.38% by mass tetramethylammonium hydroxide (developing solution) for 60 seconds in the single paddle process. In the skirt shape of the resist pattern after lithography, the rectangle line was evaluated as “straight,” the line having wider bottom was evaluated as “footing,” the line having narrower bottom was evaluated as “undercut,” and the wavy sectional shape of a resist was evaluated as “standing wave.”

(44) In the skirt shape of the resist pattern after resist patterning, if lines are rectangle, it is deemed to be good, and if the skirt shape of the resist is worsen, it is deemed to be defective.

(45) TABLE-US-00005 TABLE 5 (A) layer (B) layer Baking (A) layer Baking (B) layer Temper- Film Temper- Film Shape of ature Thickness ature Thickness Resist Example 1 400° C. 90 nm 400° C. 35 nm Straight Example 2 400° C. 90 nm 400° C. 40 nm Straight Example 3 400° C. 90 nm 400° C. 20 nm Straight Example 4 400° C. 90 nm 400° C. 30 nm Straight Example 5 400° C. 90 nm 400° C. 40 nm Straight Example 6 400° C. 90 nm 300° C. 15 nm Straight Example 7 400° C. 90 nm 300° C. 20 nm Straight Example 8 400° C. 90 nm 300° C. 15 nm Straight Example 9 400° C. 90 nm 300° C. 20 nm Straight Example 10 400° C. 90 nm 300° C. 20 nm Straight Example 11 400° C. 90 nm 300° C. 20 nm Straight Comparative 400° C. 90 nm 400° C. 10 nm Standing Example 1 Wave Comparative 400° C. 90 nm 400° C.  5 nm Standing Example 2 Wave

(46) TABLE-US-00006 TABLE 6 (A) layer (B) layer Baking (A) layer Baking (B) layer Temper- Film Temper- Film Shape of ature Thickness ature Thickness Resist Example 12 400° C. 200 nm 400° C. 45 nm Straight Example 13 400° C. 200 nm 400° C. 45 nm Straight Example 14 400° C. 200 nm 400° C. 45 nm Straight Example 15 400° C. 200 nm 400° C. 45 nm Straight Example 16 400° C. 200 nm 400° C. 45 nm Straight Example 17 400° C. 200 nm 400° C. 45 nm Straight Example 18 400° C. 200 nm 400° C. 45 nm Straight Example 19 400° C. 200 nm 400° C. 45 nm Straight Example 20 400° C. 200 nm 400° C. 45 nm Straight Example 21 400° C. 200 nm 400° C. 45 nm Straight Example 22 400° C. 200 nm 400° C. 45 nm Straight Example 23 400° C. 200 nm 400° C. 45 nm Straight Example 24 400° C. 200 nm 400° C. 45 nm Straight Example 25 400° C. 200 nm 400° C. 45 nm Straight Example 26 400° C. 200 nm 400° C. 45 nm Straight Comparative 400° C. 200 nm 400° C. 45 nm Footing Example 3

(47) (Evaluation of Resist Patterning 2)

(48) The obtained organic underlayer film (A layer)-forming composition was applied onto a silicon wafer, and was baked on a hot plate at 400° C. for 60 seconds to obtain the organic underlayer film (A layer). Each of the resist underlayer film (B layer)-forming compositions obtained in Examples 1 to 26 and Comparative Examples 1 and 2 was applied onto the organic underlayer film (A layer), and was baked on a hot plate at a temperature shown in Table 7 or Table 8 for 60 seconds to obtain the resist underlayer film (B layer).

(49) The commercially available photoresist solution (manufactured by Fujifilm Corporation, trade name: FAiRS-9521NT05) was applied onto the resist underlayer film (B layer) by using a spinner, and was heated on a hot plate at 100° C. for 1 minute to form the photoresist film (C layer) having the film thickness of 85 nm.

(50) By using NSR-S307E scanner manufactured by Nikon Corporation (wavelength: 193 nm, NA, σ: 0.85, 0.93/0.85), exposure was conducted through the mask that allows to form a dense line of 0.060 μm-line and space (L/S)=1/1, in which the line width and the width between the lines of a photoresist are become 0.060 μm after development. Then, baking was conducted on a hot plate at 100° C. for 60 seconds followed by cooling, and then development was conducted with butyl acetate (solvent developing solution) for 60 seconds to form a negative-type pattern on the resist underlayer film (B layer). The obtained photoresist patterns were evaluated as good, if large detachment of patterns, undercut, or the line having wider bottom (footing) was not observed (“straight”).

(51) TABLE-US-00007 TABLE 7 (A) layer (B) layer Baking (A) layer Baking (B) layer Temper- Film Temper- Film Shape of ature Thickness ature Thickness Resist Example 1 400° C. 90 nm 400° C. 35 nm Straight Example 2 400° C. 90 nm 400° C. 40 nm Straight Example 3 400° C. 90 nm 400° C. 20 nm Straight Example 4 400° C. 90 nm 400° C. 30 nm Straight Example 5 400° C. 90 nm 400° C. 40 nm Straight Example 6 400° C. 90 nm 300° C. 15 nm Straight Example 7 400° C. 90 nm 300° C. 20 nm Straight Example 8 400° C. 90 nm 300° C. 15 nm Straight Example 9 400° C. 90 nm 300° C. 20 nm Straight Example 10 400° C. 90 nm 300° C. 20 nm Straight Example 11 400° C. 90 nm 300° C. 20 nm Straight Comparative 400° C. 90 nm 400° C. 10 nm Standing Example 1 Wave Comparative 400° C. 90 nm 400° C.  5 nm Standing Example 2 Wave

(52) TABLE-US-00008 TABLE 8 (A) layer (B) layer Baking (A) layer Baking (B) layer Temper- Film Temper- Film Shape of ature Thickness ature Thickness Resist Example 12 400° C. 200 nm 400° C. 45 nm Straight Example 13 400° C. 200 nm 400° C. 45 nm Straight Example 14 400° C. 200 nm 400° C. 45 nm Straight Example 15 400° C. 200 nm 400° C. 45 nm Straight Example 16 400° C. 200 nm 400° C. 45 nm Straight Example 17 400° C. 200 nm 400° C. 45 nm Straight Example 18 400° C. 200 nm 400° C. 45 nm Straight Example 19 400° C. 200 nm 400° C. 45 nm Straight Example 20 400° C. 200 nm 400° C. 45 nm Straight Example 21 400° C. 200 nm 400° C. 45 nm Straight Example 22 400° C. 200 nm 400° C. 45 nm Straight Example 23 400° C. 200 nm 400° C. 45 nm Straight Example 24 400° C. 200 nm 400° C. 45 nm Straight Example 25 400° C. 200 nm 400° C. 45 nm Straight Example 26 400° C. 200 nm 400° C. 45 nm Straight

INDUSTRIAL APPLICABILITY

(53) The thin film-forming composition of the present invention can be utilized as resist underlayer film-forming compositions for ArF, KrF photoresists and the like; resist underlayer film-forming compositions for EUV resists and the like; resist underlayer film-forming compositions for electron beam resists and the like; and reverse material-forming compositions and the like.