Method for forming multi-layer film and patterning process

Patent metadata

Field	Value
Publication number	US-9804492-B2
Application number	US-201514857231-A
Country	US
Kind code	B2
Filing date	Sep 17, 2015
Priority date	Oct 16, 2014
Publication date	Oct 31, 2017
Grant date	Oct 31, 2017

Abstract

A method for forming multi-layer film on substrate, which includes steps ( 1 ) forming under layer film on substrate by applying under layer film material containing resin having repeating unit represented by the general formula (1) or (2) in which fluorene structure is contained, and curing the same by heat treatment, ( 2 ) forming metal oxide film on the under layer film by applying metal oxide film material selected from titanium oxide film material, zirconium oxide film material, and hafnium oxide film material, ( 3 ) forming hydrocarbon film on metal oxide film by applying hydrocarbon film material, and ( 4 ) forming silicon oxide film on the hydrocarbon film by applying silicon oxide film material. There can be provided a method for forming multi-layer film that can reduce reflectance, and useful for a patterning process with high dimensional accuracy of dry etching.

First claim

The invention claimed is:

1. A method for forming a multi-layer film on a substrate, comprising the steps of:
( 1 ) forming an under layer film on the substrate by applying an under layer film material containing a resin having a repeating unit represented by the general formula (1) or (2) in which a fluorene structure is contained, and curing the same by heat treatment;
( 2 ) forming a metal oxide film on the under layer film by applying a metal oxide film material selected from a titanium oxide film material, a zirconium oxide film material, and a hafnium oxide film material;
( 3 ) forming a hydrocarbon film on the metal oxide film by applying a hydrocarbon film material; and
( 4 ) forming a silicon oxide film on the hydrocarbon film by applying a silicon oxide film material,

wherein X represents a benzene ring, a naphthalene ring, or a carbazole ring; R 1 represents a hydrogen atom, a glycidyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; R 2 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; each R 3 independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and optionally contains one or more groups selected from an ether group, an ester group, a hydroxyl group, a carboxyl group, an alkoxy group, and a glycidylether group; R 4 and R 5 independently represent a benzene ring or a naphthalene ring, and a hydrogen atom(s) in the benzene ring or the naphthalene ring may be substituted by a hydrocarbon group having 1 to 6 carbon atoms; and “p” and “q” independently represent an integer of 0 to 2.

2. The method for forming a multi-layer film according to claim 1 , wherein the heat treatment in the step ( 1 ) is carried out at a temperature of 250° C. or higher and 800° C. or lower for 10 seconds to 4,000 seconds.

3. The method for forming a multi-layer film according to claim 2 , wherein the heat treatment in the step ( 1 ) is carried out at a temperature of 250° C. or higher and 700° C. or lower for 10 seconds to 600 seconds.

4. The method for forming a multi-layer film according to claim 3 , wherein applying of the materials in the steps ( 1 ) to ( 4 ) is carried out by a spin coating method.

5. The method for forming a multi-layer film according to claim 4 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

6. The method for forming a multi-layer film according to claim 3 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

7. The method for forming a multi-layer film according to claim 2 , wherein applying of the materials in the steps ( 1 ) to ( 4 ) is carried out by a spin coating method.

8. The method for forming a multi-layer film according to claim 7 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

9. The method for forming a multi-layer film according to claim 2 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

10. The method for forming a multi-layer film according to claim 1 , wherein applying of the materials in the steps ( 1 ) to ( 4 ) is carried out by a spin coating method.

11. The method for forming a multi-layer film according to claim 10 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

12. The method for forming a multi-layer film according to claim 1 , wherein the under layer film having a film thickness of 30 to 20,000 nm is formed in the step ( 1 ), the metal oxide film having a film thickness of 3 to 100 nm is formed in the step ( 2 ), the hydrocarbon film having a film thickness of 5 to 100 nm is formed in the step ( 3 ), and the silicon oxide film having a film thickness of 10 to 20 nm is formed in the step ( 4 ).

13. A patterning process comprising the steps of:
(A) forming a photoresist film on a multi-layer film which has been formed on a substrate by the method for forming a multi-layer film according to claim 1 ;
(B) forming a photoresist pattern by subjecting the photoresist film to exposure and development;
(C) transferring the pattern to the silicon oxide film by dry etching using the photoresist pattern as a mask;
(D) transferring the pattern to the hydrocarbon film by dry etching using the silicon oxide film to which the pattern has been transferred as a mask;
(E) transferring the pattern to the metal oxide film by dry etching using the hydrocarbon film to which the pattern has been transferred as a mask; and
(F) transferring the pattern to the under layer film by dry etching using the metal oxide film to which the pattern has been transferred as a mask.

14. The patterning process according to claim 13 , wherein the dry etching in the step (F) is carried out by using one or more etching gases selected from an oxygen gas, a hydrogen gas, an ammonia gas, a carbon dioxide gas, a carbon monoxide gas, and a sulfur dioxide gas.

15. A patterning process comprising the steps of:
(A) forming a photoresist film on a multi-layer film which has been formed on a substrate by the method for forming a multi-layer film according to claim 2 ;
(B) forming a photoresist pattern by subjecting the photoresist film to exposure and development;
(C) transferring the pattern to the silicon oxide film by dry etching using the photoresist pattern as a mask;
(D) transferring the pattern to the hydrocarbon film by dry etching using the silicon oxide film to which the pattern has been transferred as a mask;
(E) transferring the pattern to the metal oxide film by dry etching using the hydrocarbon film to which the pattern has been transferred as a mask; and
(F) transferring the pattern to the under layer film by dry etching using the metal oxide film to which the pattern has been transferred as a mask.

Assignees

• Shinetsu Chemical Co

Inventors

• Hatakeyama Jun
• Ogihara Tsutomu

Classifications

• H10P76/405

  characterised by their composition, e.g. multilayer masks · CPC title

• H10P50/287

  by chemical means · CPC title

• H10P50/285

  of materials not containing Si, e.g. PZT or Al2O3 · CPC title

• H10P50/283

  by chemical means · CPC title

• H10P50/73

  using masks for insulating materials · CPC title