SILICON-CONTAINING FILM-FORMING COMPOSITION, SILICON-CONTAINING FILM-FORMED SUBSTRATE, AND PATTERNING PROCESS

• US 20120052685A1
• Filed: 08/08/2011
• Published: 03/01/2012
• Est. Priority Date: 09/01/2010
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: OGIHARA, Tsutomu, UEDA, Takafumi, YANO, Toshiharu, HASEGAWA, Koji
• Granted Patent: US 8,501,386 B2
• Time in Patent Office: Days
• US Class Current: 438/702
• CPC Class Codes: G03F 7/0752 in non photosensitive layers or as additives, e.g. for dry lithography
• CPC Class Codes: G03F 7/091 characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• CPC Class Codes: G03F 7/094 Multilayer resist systems, e.g. planarising layers
• CPC Class Codes: G03F 7/11 having cover layers or intermediate layers, e.g. subbing layers G03F7/091 - G03F7/093, B41N3/03 take precedence

Abstract

A thermosetting silicon-containing film-forming composition for forming a silicon-containing film to be formed in a multi-layer resist process used in lithography, the composition including at least: (A) a silicon-containing compound obtained by hydrolysis-condensation of a hydrolyzable silicon compound and compound(s) selected from the group consisting of a hydrolyzable silicon compound and a reactive compound; (B) a thermal crosslinking accelerator; (C) an organic acid with one, or two or more valency having 1 to 30 carbon atoms; and (D) an organic solvent.

Claims

1. A thermosetting silicon-containing film-forming composition for forming a silicon-containing film to be formed in a multilayer resist process used in a lithography, wherein the composition comprises at least:

(A) a silicon-containing compound obtained by hydrolysis-condensation of one, or two or more kinds of a hydrolyzable silicon compound represented by the following general formula (1) and one, or two or more compounds selected from the group consisting of a hydrolyzable silicon compound represented by the following general formula (2-1) and a reactive compound represented by the following general formula (2-2),

R¹_m1Si(OR²)_(4-m1) 

 

(1)

R³_m3Si (OR⁴)_(4-m3) 

 

(2-1)

U(OR⁵)_m5(OR⁶)_m6(O)_m7/2 

 

(2-2)

wherein R¹ represents a monovalent organic group substituted with one or more fluorine atoms and having 1 to 30 carbon atoms;

R³ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, wherein R¹ and R³ may be the same or different with each other;

R² and R⁴ represent an alkyl group having 1 to 6 carbon atoms;

m1 and m3 are integers satisfying m1≦

3 and 0≦

m3≦

3, respectively;

R⁵ and R⁶ represent an organic group having 1 to 30 carbon atoms;

m5+m6+m7/2 is a valency determined by the kind of U;

each of m5, m6, and m7 is an integer of 0 or more; and

U is any element belonging to the groups of III, IV, or V in the periodic table, except for carbon and silicon,

(B) one, or two or more kinds of a thermal crosslinking accelerator represented by the following general formula (3) or (4)

L_aH_bX 

 

(3)

wherein L represents any of lithium, sodium, potassium, rubidium, and cesium;

X represents a hydroxyl group or an organic acid group with one, or two or more valency having 1 to 30 carbon atoms;

a represents an integer of 1 or more, b represents 0 or an integer of 1 or more, and a+b is a valency of the hydroxyl group or the organic acid group,

M_aH_b,A 

 

(4)

wherein M represents any of a sulfonium group, an iodonium group, and an ammonium group;

A represents a hydroxyl group, or an organic acid group with one, or two or more valency having 1 to 30 carbon atoms, or an non-nucleophilic counter ion;

a′

represents an integer of 1 or more, b′

represents 0 or an integer of 1 or more, and is a valency of the hydroxyl group, the organic acid group, or the non-nucleophilic counter ion,

(C) an organic acid with one, or two or more valency having 1 to 30 carbon atoms, and

(D) an organic solvent.

2. The thermosetting silicon-containing film-forming composition according to claim 1, wherein the silicon-containing compound of the component (A) is a compound obtained by hydrolysis-condensation using an acid as a catalyst.

3. The thermosetting silicon-containing film-forming composition according to claim 2, wherein the acid catalyst is one or more compounds selected from inorganic acids and sulfonic acid derivatives.

4. The thermosetting silicon-containing film-forming composition according to claim 1, wherein M in the general formula (4) is any of a tertiary sulfonium, a secondary iodonium, and a quaternary ammonium.

5. The thermosetting silicon-containing film-forming composition according to claim 2, wherein M in the general formula (4) is any of a tertiary sulfonium, a secondary iodonium, and a quaternary ammonium.

6. The thermosetting silicon-containing film-forming composition according to claim 3, wherein M in the general formula (4) is any of a tertiary sulfonium, a secondary iodonium, and a quaternary ammonium.

7. The thermosetting silicon-containing film-forming composition according to claim 1, wherein U in the general formula (2-2) is any of boron, aluminum, gallium, yttrium, germanium, titanium, zirconium, hafnium, bismuth, tin, phosphorous, vanadium, arsenic, antimony, niobium, and tantalum.

8. The thermosetting silicon-containing film-forming composition according to claim 6, wherein U in the general formula (2-2) is any of boron, aluminum, gallium, yttrium, germanium, titanium, zirconium, hafnium, bismuth, tin, phosphorous, vanadium, arsenic, antimony, niobium, and tantalum.

9. A substrate, wherein the substrate is formed of successively at least an organic film formed on a processing substrate, a silicon-containing film formed on the organic film by using the thermosetting silicon-containing film-forming composition according to claim 1, and a photoresist film formed on the silicon-containing film.

10. A substrate, wherein the substrate is formed of successively at least an organic film formed on a processing substrate, a silicon-containing film formed on the organic film by using the thermosetting silicon-containing film-forming composition according to claim 8, and a photoresist film formed on the silicon-containing film.

11. A patterning process for forming a pattern on a substrate, wherein the patterning process is effected by at least:

forming an organic film on a processing substrate,

forming a silicon-containing film on the organic film by using the thermosetting silicon-containing film-forming composition according to claim 1,

forming a resist film on the silicon-containing film by using a resist composition of a chemically amplification type not containing silicon,

after exposure of the resist film and then alkaline development, pattern-processing of the silicon-containing film by dry etching by using the obtained resist film pattern as an etching mask,

pattern-processing of the underlayer organic film by using the processed silicon-containing film pattern as an etching mask, and

pattern-processing of the processing substrate by using the processed organic film as an etching mask to form a pattern on a substrate.

12. A patterning process for forming a pattern on a substrate, wherein the patterning process is effected by at least:

forming an organic film on a processing substrate,

forming a silicon-containing film on the organic film by using the thermosetting silicon-containing film-forming composition according to claim 8,

forming a resist film on the silicon-containing film by using a resist composition of a chemically amplification type not containing silicon,

after exposure of the resist film and then alkaline development, pattern-processing of the silicon-containing film by dry etching by using the obtained resist film pattern as an etching mask,

pattern-processing of the underlayer organic film by using the processed silicon-containing film pattern as an etching mask, and

pattern-processing of the processing substrate by using the processed organic film as an etching mask to form a pattern on a substrate.

13. The patterning process according to claim 11, wherein, in patterning of the resist film, a photo lithography method in which a light having wavelength of 300 nm or shorter or an EUV light is used, or an electron beam drawing method is used.

14. The patterning process according to claim 12, wherein, in patterning of the resist film, a photo lithography method in which a light having wavelength of 300 nm or shorter or an EUV light is used, or an electron beam drawing method is used.