Thin film forming composition for lithography containing titanium and silicon

1. A thin film forming composition that is used together with a resist in a lithography process, comprising:

a mixture of a titanium compound (A) selected from a group consisting of a compound of Formula (1):

R 0 a Ti(R 1 ) (4-a)   Formula (1)

wherein in Formula (1),

R 0 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, an amino group, or a cyano group and is bonded to a titanium atom through a Ti—C bond;

R 1 is an alkoxy group, an acyloxy group, or a halogen atom; and

a is an integer of 0 to 2,

a titanium chelate compound, and a hydrolyzable titanium dimer, and

a silicon compound (B) of Formula (2):

R 2 a′ R 3 b Si(R 4 ) 4-(a′+b)   Formula (2)

wherein in Formula (2),

R 2 is a nitrogen atom-containing ring group or an organic group containing a nitrogen atom-containing ring group, a condensed aromatic ring group or an organic group containing a condensed aromatic ring group, a protected phenolic hydroxy group or an organic group containing a protected phenolic hydroxy group, or a bisaryl group or an organic group containing a bisaryl group and is bonded to a silicon atom through a Si—C bond;

R 3 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, an amino group, or a cyano group and is bonded to a silicon atom through a Si—C bond or a Si—N bond;

R 4 is an alkoxy group, an acyloxy group, or a halogen atom; and

a′ is an integer of 1, and

b is an integer of 0 or 1,

wherein (a′+b) is an integer of 1 or 2,

a hydrolysis product of the mixture, or a hydrolysis-condensation product of the mixture,

wherein the number of moles of a Ti atom is 50% to 90% relative to the number of total moles in terms of a Ti atom and a Si atom in the composition.

2. The thin film forming composition according to claim 1 , comprising:

a mixture of the titanium compound (A) selected from the group consisting of the compound of Formula (1), a titanium chelate compound, and a hydrolyzable titanium dimer,

the silicon compound (B) of Formula (2), and

a silicon compound (C) of Formula (3):

R 5 a″ Si(R 6 ) 4-a″   Formula (3)

wherein in Formula (3),

R 5 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, an amino group, a sulfonyl group, a sulfide bond, an ether bond, an ester bond, a sulfonamido group, or a cyano group and is bonded to a silicon atom through a Si—C bond;

R 6 is an alkoxy group, an acyloxy group, or a halogen atom; and

a″ is an integer of 0 to 3,

a hydrolysis product of the mixture, or a hydrolysis-condensation product of the mixture.

3. The thin film forming composition according to claim 1 , wherein the nitrogen atom-containing ring group or the organic group containing a nitrogen atom-containing ring group is an organic group of Formula (4):

wherein in Formula (4),

R 7 is a hydrogen atom, a C1-10 alkyl group, an alkenyl group, an epoxy group, a sulfonyl group, or an organic group containing any of a C1-10 alkyl group, an alkenyl group, an epoxy group, and a sulfonyl group;

R 8 is a C1-10 alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of any of a C1-10 alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, and an ester bond; and

X 1 is a group of Formula (5), Formula (6), or Formula (7):

wherein in Formula (5), Formula (6), and Formula (7), R 9 to R 13 are independently a hydrogen atom, a C1-10 alkyl group, an alkenyl group, an epoxy group, a sulfonyl group, or an organic group containing any of a hydrogen atom, a C1-10 alkyl group, an alkenyl group, an epoxy group, and a sulfonyl group, and

is an organic group bonded to a silicon atom through a Si—C bond.

4. The thin film forming composition according to claim 1 , wherein the nitrogen atom-containing ring group or the organic group containing a nitrogen atom-containing ring group is an imidazole group or an organic group containing an imidazole group.

5. The thin film forming composition according to claim 1 , wherein the condensed aromatic ring group or the organic group containing a condensed aromatic ring group is a naphthyl group or an anthryl group.

6. The thin film forming composition according to claim 1 , wherein the protected phenolic hydroxy group or the organic group containing a protected phenolic hydroxy group is an alkoxyalkyl-substituted aryl group or an alkoxyalkoxyalkyl-substituted aryl group.

7. The thin film forming composition according to claim 1 , wherein the bisaryl group or the organic group containing a bisaryl group is a bisphenyl group.

8. The thin film forming composition according to claim 1 , further comprising β-diketone and/or β-ketoester.

9. The thin film forming composition according to claim 1 , further comprising an acid.

10. The thin film forming composition according to claim 1 , further comprising a salt.

11. The thin film forming composition according to claim 1 , further comprising water.

12. A thin film obtained by applying the thin film forming composition as claimed in claim 1 onto a semiconductor substrate and by baking the composition.

13. A method for producing a semiconductor device, comprising:

applying the thin film forming composition as claimed in claim 1 onto a semiconductor substrate and baking the composition to form a thin film;

applying a composition for a resist onto the thin film to form a resist film;

exposing the resist film to light;

developing the resist film after the exposure to obtain a resist pattern;

etching the thin film according to the resist pattern; and

processing the semiconductor substrate according to the patterned resist film and the patterned thin film.

14. The method according to claim 13 , wherein the resist is an EUV resist.

15. A method for producing a semiconductor device, comprising:

forming an organic underlayer film on a semiconductor substrate;

applying the thin film forming composition as claimed in claim 1 onto the organic underlayer film and baking the composition to form a thin film;

applying a composition for a resist onto the thin film to form a resist film;

exposing the resist film to light;

developing the resist film after the exposure to obtain a resist pattern;

etching the thin film according to the resist pattern;

etching the organic underlayer film according to the patterned thin film; and

processing the semiconductor substrate according to the patterned organic underlayer film.

16. A method for producing a semiconductor device, comprising:

forming an organic underlayer film on a semiconductor substrate;

applying the thin film forming composition as claimed in claim 1 onto the organic underlayer film and baking the composition to form a thin film;

applying an organic resist underlayer film forming composition onto the thin film to form an organic resist underlayer film;

applying a composition for a resist onto the organic resist underlayer film to form a resist film;

exposing the resist film to light;

developing the resist film after the exposure to obtain a resist pattern;

etching the organic resist underlayer film according to the resist pattern;

etching the thin film according to the patterned organic resist underlayer film;

etching the organic underlayer film according to the patterned thin film; and

processing the semiconductor substrate according to the patterned organic underlayer film.

17. A method for producing a semiconductor device, comprising:

forming a resist pattern on a substrate;

applying the thin film forming composition as claimed in claim 1 onto the substrate on which the resist pattern is formed and baking the composition to form a thin film;

etching the thin film to expose the resist surface; and

etching the resist pattern to reverse the pattern.

18. A method for producing a semiconductor device, comprising:

applying a composition for an EUV resist onto a semiconductor substrate and baking the composition to form an EUV resist film;

applying the thin film forming composition as claimed in claim 1 onto the EUV resist film to form a thin film;

exposing the thin film to EUV;

developing the EUV resist after the exposure to obtain a resist pattern; and

processing the semiconductor substrate according to the resist pattern.