Method for forming multi-layer film and patterning process

• US 9,804,492 B2
• Filed: 09/17/2015
• Issued: 10/31/2017
• Est. Priority Date: 10/16/2014
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Hatakeyama, Jun, Ogihara, Tsutomu
• Primary Examiner(s): Duda, Kathleen
• Application Number:
  US14/857,231
• Publication Number:
  US 20160111287A1
• Time in Patent Office: 775 Days
• 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: H01L 21/02115 the material being carbon, e.g. alpha-C, diamond or hydrogen doped carbon
• CPC Class Codes: H01L 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/0212 the material being fluoro carbon compounds, e.g.(CFx) n, (CHxFy) n or polytetrafluoroethylene
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/0332 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/31116 by dry-etching
• CPC Class Codes: H01L 21/31122 of layers not containing Si, e.g. PZT, Al2O3
• CPC Class Codes: H01L 21/31138 by dry-etching
• CPC Class Codes: H01L 21/31144 using masks
• CPC Class Codes: H01L 21/32139 using masks

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.

Claims

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,

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.

16. The patterning process according to claim 15, 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.

17. 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 3;

(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.

18. The patterning process according to claim 17, 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.

19. 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 10;

(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.

20. 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 12;

(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.