Chemical solution-resistant protective film forming composition containing polymerization product having diol structure at terminal thereof

Patent metadata

Field	Value
Publication number	US-12344758-B2
Application number	US-202017433523-A
Country	US
Kind code	B2
Filing date	Mar 3, 2020
Priority date	Mar 4, 2019
Publication date	Jul 1, 2025
Grant date	Jul 1, 2025

Abstract

A protective film forming composition which has good mask (protection) function against a wet etching liquid and a high dry etching rate during processing of a semiconductor substrate and also has good coverage even in a stepped substrate, and from which a flat film can be formed due to a small difference in film thickness after being embedded; a protective film produced using said composition; a substrate with a resist pattern; and a method for manufacturing a semiconductor device. This protective film forming composition against a wet etching liquid for semiconductors contains an organic solvent and a polymer having, at a terminal thereof, a structure containing at least one pair of two adjacent hydroxyl groups in a molecule. The structure containing two adjacent hydroxyl groups in a molecule may be 1,2-ethanediol structure (A).

First claim

The invention claimed is:

1. A composition for forming a protective film against a wet etching liquid for a semiconductor, comprising:
a polymer having at a terminal thereof a 1,2-ethanediol structure (A); and
an organic solvent;
wherein the 1,2-ethanediol structure is represented by formula (I):

where:
X is —S—;
Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms which may be substituted;
R 2 , R 3 , and R 4 each are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 40 carbon atoms which may be substituted; and
R 2 may form a ring together with R 3 or R 4 ; and
wherein the polymer is a reaction product of a diepoxy compound (B) and a bi- or higher-functional proton generating compound (C) wherein the bi- or higher functional proton generating compound (C) is an acid anhydride.

2. A composition for forming a protective film against a wet etching liquid for a semiconductor, comprising:
a polymer having at a terminal thereof a 1,2-ethanediol structure (A); and
an organic solvent;
wherein the 1,2-ethanediol structure includes a structure represented by formula (1):

where:
X represents any of —COO—, —OCO—, —O—, —S—, and —NR 1 —;
R 1 represents a hydrogen atom or a methyl group;
Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms which may be substituted; and
R 2 , R 3 , and R 4 are a hydrogen atom; and
wherein the polymer is a reaction product of a diepoxy compound (B) and a bi- or higher-functional proton generating compound (C) wherein the bi- or higher functional proton generating compound (C) is an acid anhydride.

3. The composition for forming a protective film according to claim 1 , wherein in formula (1), Y is a methylene group.

4. The composition for forming a protective film according to claim 2 , wherein in formula (1), X is —S—.

5. The composition for forming a protective film according to claim 1 , wherein the polymer has a partial structure represented by formula (2) below:

where:
R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom, a methyl group, or an ethyl group;
Q 1 represents a divalent organic group between two carbon atoms; and
m1 and m2 each independently represent 0 or 1.

6. The composition for forming a protective film according to claim 5 , wherein in formula (2) above, Q 1 is represented by formula (3) below:
—Z 1 -Q 2 -Z 2 —  Formula (3)

where:
Q2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms which may be interrupted with —O—, —S—, or —S—S—, an alkenylene group having 2 to 6 carbon atoms which may be interrupted with —O—, —S—, or —S—S—, or a divalent organic group having at least one of an alicyclic hydrocarbon ring having 3 to 10 carbon atoms and an aromatic hydrocarbon ring having 6 to 14 carbon atoms,
the divalent organic group may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a halogen atom, a hydroxy group, a nitro group, a cyano group, a methylidene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxy carbonyl group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms, and Z 1 and Z 2 each represent any of —COO—, —OCO—, —O—, and —S—.

7. The composition for forming a protective film according to claim 5 , wherein in formula (2) above, Q1 is represented by formula (4) below:

where Q 3 represents formula (5), formula (6), or formula (7) below:

where:
R 11 , R 12 , R 13 , R 14 , and R 15 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group,
the phenyl group may be substituted with at least one member selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms, and
R 13 and R 14 may be bonded to each other to form a ring having 3 to 6 carbon atoms.

8. The composition for forming a protective film according to claim 1 , further comprising a cross-linking catalyst.

9. The composition for forming a protective film according to claim 1 , further comprising a cross-linking agent.

10. The composition for forming a protective film according to claim 1 , further comprising a surfactant.

11. A protective film, which is a calcined product of a coating film from the composition for forming a protective film according to claim 1 .

12. A method for producing a resist-patterned substrate for use in manufacturing of a semiconductor, comprising the steps of:
applying the composition for forming a protective film according to claim 1 onto a semiconductor substrate and baking the applied composition to form a protective film as a resist underlayer film;
forming a resist film on the protective film; and then,
subjecting the semiconductor substrate to exposure and development to form a resist pattern.

13. A method for manufacturing a semiconductor device, comprising the steps of:
forming a protective film on a semiconductor substrate, which may have an inorganic film formed on a surface thereof, with the composition for forming a protective film according to claim 1 ;
forming a resist pattern on the protective film;
dry etching the protective film through the resist pattern as a mask so as to expose the inorganic film or a surface of the semiconductor substrate;
wet etching the inorganic film or the semiconductor substrate with a wet etching liquid for a semiconductor through the dry-etched protective film as a mask and washing the wet-etched inorganic film or the semiconductor substrate.

14. The composition for forming a protective film according to claim 2 , wherein in formula (1), Y is a methylene group.

15. The composition for forming a protective film according to claim 2 , wherein the polymer has a partial structure represented by formula (2) below:

where:
R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom, a methyl group, or an ethyl group;
Q 1 represents a divalent organic group between two carbon atoms; and
m1 and m2 each independently represent 0 or 1.

16. The composition for forming a protective film according to claim 2 , further comprising a cross-linking catalyst.

17. The composition for forming a protective film according to claim 2 , further comprising a cross-linking agent.

18. The composition for forming a protective film according to claim 2 , further comprising a surfactant.

19. A protective film, which is a calcined product of a co

Assignees

• Nissan Chemical Corp

Inventors

• Endo Takafumi
• Nishita Tokio

Classifications

• H10P50/692

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

• H10P50/642

  Chemical etching · CPC title

• H10P50/287

  by chemical means · CPC title

• H10P50/283

  by chemical means · CPC title

• H10P50/73

  using masks for insulating materials · CPC title