Metal-containing resist underlayer film-forming composition containing polyacid
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 1 a R 2 b Si(R 3 ) 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 4 ) 4 Formula (2) and the zirconium oxide is a hydrolysis-condensation product of hydrolyzable zirconium of Formula (3) or Formula (4): Zr(R 5 ) 4 Formula (3) ZrO(R 6 ) 2 Formula (4) or a hydrolysis-condensation product of a combination thereof.
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 1 a R 2 b Si(R 3 ) 4−(a+b) Formula (1)
wherein:
R 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 1 binds to a silicon atom with a Si—C bond;
R 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 2 binds to a silicon atom with a Si—C bond;
R 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 4 ) 4 Formula (2)
wherein R 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 5 ) 4 Formula (3)
ZrO(R 6 ) 2 Formula (4)
wherein each of R 5 and R 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 1 a R 2 b Si(R 3 ) 4−(a+b) Formula (1)
wherein:
R 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 1 binds to a silicon atom with a Si—C bond;
R 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 2 binds to a silicon atom with a Si—C bond;
R 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 4 ) 4 Formula (2)
wherein R 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 5 ) 4 Formula (3)
ZrO(R 6 ) 2 Formula (4)
wherein each of R 5 and R 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 1 a R 2 b Si(R 3 ) 4−(a+b) Formula (1)
wherein:
R 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 1 binds to a silicon atom with a Si—C bond;
R 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 2 binds to a silicon atom with a Si—C bond;
R 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 4 ) 4 Formula (2)
wherein R 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 5 ) 4 Formula (3)
ZrO(R 6 ) 2 Formula (4)
wherein each of R 5 and R 6 is an alkoxy group, an acyloxy group, a halogen group, or a nitrate ion, or a hydrolysis-condensation product of a combination thereof.