Polymer and composition for forming an anti-reflective film and method of manufacturing an integrated circuit device using the anti-reflective film

Patent metadata

Field	Value
Publication number	US-12405532-B2
Application number	US-202318133166-A
Country	US
Kind code	B2
Filing date	Apr 11, 2023
Priority date	Mar 28, 2019
Publication date	Sep 2, 2025
Grant date	Sep 2, 2025

Abstract

A polymer having a repeating unit represented by Formula 1:

wherein each of R 1 , R 2 , and R 3 is independently selected from a substituted or unsubstituted C1-C6 chain-like saturated or unsaturated hydrocarbon group having 0 to 2 first heteroatoms or a substituted or unsubstituted C3-C6 cyclic saturated or unsaturated hydrocarbon group having 0 to 2 first heteroatoms, wherein at least one of R 1 , R 2 , and R 3 is a hydrocarbon group substituted with a fluorine atom. R 4 is a C1-C10 chain-like saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms. R 5 is a C1-C10 chain-like saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms.

First claim

What is claimed is:

1. A method of manufacturing an integrated circuit device, the method comprising:
forming an anti-reflective film on a feature layer using a composition comprising an organic solvent and a polymer having a repeating unit represented by Formula 1:

wherein each of R 1 , R 2 , and R 3 is independently selected from —CH 2 CF 3 , —OC(CH 3 ) 3 , —OCH 2 CF 3 , —OCF 3 , or —OCF 2 CF 3 , wherein at least one of R 1 , R 2 , and R 3 is a hydrocarbon group that is substituted with at least one fluorine atom,
R 4 is a C1-C10 saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms,
R 5 is a C1-C10 saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms;
forming a photoresist film on the anti-reflective film;
exposing a first resist region of the photoresist film to light, the first resist region covering a first local region of the anti-reflective film; and
developing the photoresist film using a development agent to remove the exposed first resist region and to form a photoresist pattern, wherein the developing of the photoresist film increases a hydrophilicity of a top surface of the first local region of the anti-reflective film.

2. The method of claim 1 , wherein the increase of the hydrophilicity of the top surface of the first local region of the anti-reflective film is performed by a chemical reaction of the at least one of R 1 , R 2 , and R 3 that is the hydrocarbon group that is substituted with the at least one fluorine atom with the development agent.

3. The method of claim 1 , wherein the development agent comprises a basic aqueous solution.

4. The method of claim 1 , wherein
the top surface of the first local region of the anti-reflective film has a first contact angle to deionized water before the photoresist film is developed, and
the top surface of the first local region of the anti-reflective film has a second contact angle to deionized water after the photoresist film is developed, wherein the second contact angle is less than the first contact angle.

5. The method of claim 4 , wherein the second contact angle is at least 4° less than the first contact angle.

6. The method of claim 4 , wherein the second contact angle is at least 9° less than the first contact angle.

7. The method of claim 1 , wherein,
after the photoresist film is developed, a top surface of a second local region of the anti-reflective film, which is covered by the photoresist pattern, has a third contact angle to deionized water, and
the top surface of the first local region of the anti-reflective film has a second contact angle to deionized water, wherein the second contact angle is less than the third contact angle.

8. The method of claim 7 , wherein, after the photoresist film is developed, a difference between a thickness of the first local region of the anti-reflective film and a thickness of the second local region of the anti-reflective film is in a range of 10-25 Å.

9. The method of claim 1 , wherein, the composition for forming the anti-reflective film on the feature layer further comprises a polymer having a repeating unit represented by Formula 2:

wherein R 6 is a C6-C12 saturated or unsaturated hydrocarbon group having 0 to 2 fourth heteroatoms.

10. The method of claim 1 , wherein, the composition for forming the anti-reflective film on the feature layer further comprises at least one of a crosslinking agent and an acid generator.

11. The method of claim 1 , wherein the forming of the anti-reflective film comprises:
coating the composition on the feature layer; and
annealing the coated composition.

12. The method of claim 1 , further comprising:
anisotropically etching the first local region of the anti-reflective film to form an anti-reflective pattern after developing the photoresist film.

13. The method of claim 12 , further comprising:
processing the feature layer that is exposed through the anti-reflective pattern using the anti-reflective pattern and the photoresist pattern as a mask pattern.

14. A method of manufacturing an integrated circuit device, the method comprising:
forming an anti-reflective film on a feature layer using a composition comprising a polymer and an organic solvent, wherein the anti-reflective film includes a top surface having a first contact angle to deionized water, and the polymer has a repeating unit represented by Formula 1:

wherein each of R 1 , R 2 , and R 3 is independently selected from —CH 2 CF 3 , —OC(CH 3 ) 3 , —OCH 2 CF 3 , —OCF 3 , or —OCF 2 CF 3 , wherein at least one of R 1 , R 2 , and R 3 is a hydrocarbon group that is substituted with at least one fluorine atom,
R 4 is a C1-C10 saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 0 to 2 second heteroatoms, and
R 5 is a C1-C10 saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms or a C3-C10 cyclic saturated or unsaturated hydrocarbon group having 1 to 6 third heteroatoms;
forming a photoresist film that covers the top surface of the anti-reflective film;
exposing a partial region of the photoresist film to light;
developing the photoresist film using a development agent to form a photoresist pattern, wherein the developing of the photoresist film increases a hydrophilicity of a top surface of a local region of the anti-reflective film that is not covered by the photoresist pattern.

15. The method of claim 14 , wherein the increase of the hydrophilicity of the top surface of the local region of the anti-reflective film is performed by a chemical reaction of the at least one of R1, R2, and R3 that is the hydrocarbon group that is substituted with the at least one fluorine atom with the development agent.

16. The method of claim 14 , wherein, after the increase of the hydrophilicity of the top surface of the local region of the anti-reflective film, the top surface of the local region has a second contact angle to deionized water, wherein the second contact angle is at least 4° less than the first contact angle.

17. A method of manufacturing an integrated circuit device, the method comprising:
forming an anti-reflective film on a feature layer using a composition comprising an isocyanurate polymer including at least one fluorine-containing substituent;
forming a photoresist film to cover the anti-reflective film;
exposing a first resist region of the photoresist film to light, the first resist region covering a local region of the anti-reflective film; and
developing the photoresist film using a development agent to remove the exposed first resist region and to increase a hydrophilicity of a top surface of the local region of the anti-reflective film,
wherein the isocyanurate polymer has a repeating unit represented by Formula 1:

wherein each of R 1 , R 2 , and R 3 is independently selected

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kang Miyeong
• Hong Sukkoo
• Kim Hyereun
• Kim Jihyun
• Kim Hyunjin
• Roh Hyojung
• Park Jongkyoung
• Lee Jungyoul

Classifications

• C08G18/3802

  having halogens · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• C09D175/04 Primary

  Polyurethanes · CPC title

• G03F7/039

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title

• C08G18/3819

  having nitrogen · CPC title