# US 12,183,591 B2 · Etching gas compositions, methods of forming micropatterns, and methods of manufacturing semiconductor device

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- Number: US 12,183,591 B2
- Document ID: US12183591B2
- Status: Granted
- Kind: B2
- Application number: 17/701,846
- Filed: 2022-03-23
- Published: 2022-09-29
- Granted: 2024-12-31
- Earliest claimed: 2021-03-24
- Assignees: Samsung Electronics Co., Ltd.; Wonik Materials
- Applicants: Samsung Electronics Co., Ltd.
- Inventors: Dohoon Kim; Wonwoong Chung; Taehyung Kim; Heejun Park; Handuck Song; Heonjong Jeong; Younglae Kim; Byeongok Cho
- Web page: https://patentgrep.com/patent/US12183591B2

## CPC

- H10P 50/69: {using masks for semiconductor materials}
- C09K 13/00: Etching, surface-brightening or pickling compositions (for glass C03C15/00, {C03C25/66; for mortars, concrete, artificial or natural stone or ceramics C04B41/5338}; for metallic material C23F, C23G1/00, C25F1/00; {for semi-conductors H10P52/40})
- H10B 41/27: the channels comprising vertical portions, e.g. U-shaped channels
- H10B 41/50: characterised by the boundary region between the core region and the peripheral circuit region
- H10B 43/27: the channels comprising vertical portions, e.g. U-shaped channels
- H10B 43/50: characterised by the boundary region between the core and peripheral circuit regions
- H10P 50/268: {of silicon-containing layers}
- H10P 50/283: {by chemical means}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H10B: ELECTRONIC MEMORY DEVICES

## Abstract

An etching gas composition includes a first organofluorine compound having 3 to 6 carbon atoms, and an organosulfur compound having 1 to 4 sulfur atoms. The organosulfur compound may include a carbon-fluorine (C—F) bond, a carbon-sulfur (C—S) bond, at least one carbon-carbon double (—C═C—) bond. When the etching gas composition is used, excellent etch selectivity may be obtained, and the linearity and verticality of a pattern may be greatly increased by improving line edge roughness (LER) and line width roughness (LWR) due to an improvement in the roughness of an etched surface.

## Claims

### Claim 1

An etching gas composition comprising:
a first organofluorine compound having a formula of CaFbHc, wherein a is an integer of 3 to 6, b is an integer of 1 to 10, and c is an integer of 1 to 6;
an organosulfur compound having 1 to 4 sulfur atoms, the organosulfur compound comprising a carbon-fluorine (C—F) bond, a carbon-sulfur (C—S) bond and at least one carbon-carbon double (—C═C—) bond, and
a second organofluorine compound and a third organofluorine compound, wherein the second and third organofluorine compound are each different from the first organofluorine compound,
wherein the organosulfur compound is present in the etching gas composition in an amount of about 1 part to about 100 parts by mole based on 100 parts by mole of the first organofluorine compound,
wherein the second organofluorine compound comprises a C1 to C6 perfluorocarbon compound, and the third organofluorine compound include at least one selected from the group of C3H4F4, C3H3F5, C3H2F6, C3H1F7, C3H3F3, C3H2F4, C3H1F5, C4H4F6, C4H3F7, C4H2F8, C4H1F9, C4H4F4, C4H3F5, C4H2F6, C4H1F7, C4H2F4, and C4H1F5.

### Claim 2 (depends on 1)

The etching gas composition of claim 1, wherein the organosulfur compound has a formula of CxFySz, wherein x is an integer of 1 to 6, y is an integer of 1 to 16, and z is an integer of 1 to 4.

### Claim 3 (depends on 1)

The etching gas composition of claim 1, wherein
the organosulfur compound comprises at least one selected from the group consisting of methanethioyl fluoride, difluoromethanethione, trifluormethanthiyl-radical, trifluoro(trifluoromethyl)sulfur(IV), pentafluoro(trifluoromethyl)-λ6-sulfane, trifluoromethylmercaptothiocarbonyl fluoride, 2,2,4,4-tetrafluoro-1,3-dithietane, trifluoro(trifluoromethylsulfanyl)methane, trifluoro-(trifluoromethyldisulfanyl)methane, trifluoro-(trifluoromethyltrisulfanyl)methane, trifluoro-(trifluoromethyltetrasulfanyl) methane, difluorobis(trifluoromethyl)sulfur(IV), 1,1,2-trifluoro-2-pentafluorosulfanylethene, bis(trifluoromethyl)tetrafluorosulfur(VI), pentafluoro(1,1,2,2,2-pentafluoroethyl)-λ6-sulfane, hexafluorothioacetone, bis(trifluoromethylsulfanyl) methanethione, 3,3,3-trifluoro-1-pentafluorosulfanyl-1-propyne, hexadecafluoro-octahydro-1,4-dithiane, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene-1-thione, 3,4-bis(trifluoromethyl)dithiete, bis(trifluoromethylmercapto)acetylene, perfluorotetrahydrothiophene, 2,2-difluoro-3,3-bis(trifluoromethyl)thiirane, and perfluorocyclohexanesulfurpentafluoride.

### Claim 4 (depends on 1)

The etching gas composition of claim 1, wherein the first organofluorine compound comprises at least one selected from the group consisting of 1h-heptafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,2,2,3,3-hexafluoropropane, 1,1,2,2,3-pentafluoropropane, 1, 1,1,2,2-pentafluoropropane, 1,1,2,3,3-pentafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,2,2-tetrafluoropropane, 1,1,1,2-tetrafluoropropane, 1,2,2,3-tetrafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,3,3-tetrafluoropropane, 1,1,2,3-tetrafluoropropane, 1,1,3-trifluoropropane, 1,1,2-trifluoropropane, 1,2,3-trifluoropropane, 1,1,2-trifluoropropane, 1,1,1-trifluoropropane, 1,1-difluoropropane, 1,2-difluoropropane, 2,2-difluoropropane, 1-fluoropropane, 2-fluoropropane, 1,1,3,3,3-pentafluoroprop-1-ene, 1,1,2,3,3-pentafluoroprop-1-ene, 1,2,3,3,3-pentafluoroprop-1-ene, 1,3,3,3-tetrafluoroprop-1-ene, 1,1,3,3-tetrafluoroprop-1-ene, 2,3,3,3-tetrafluoroprop-1-ene, 1,2,3,3-tetrafluoroprop-1-ene, 1,1,2,3-tetrafluoroprop-1-ene, 3,3,3-trifluoroprop-1-ene, 1,1,3-trifluoroprop-1-ene, 1,3,3-trifluoroprop-1-ene, 1,1,2-trifluoroprop-1-ene, 1,2,3-trifluoroprop-1-ene, 2,3,3-trifluoroprop-1-ene, 1,1-difluoroprop-1-ene, 1,3-difluoroprop-1-ene, 3,3-difluoroprop-1-ene, 1,2-difluoroprop-1-ene, 2,3-difluoroprop-1-ene, 1-fluoroprop-1-ene, 2-fluoroprop-1-ene, 3-fluoroprop-1-ene, 1,1,1,2,2,3,3,4,4-nonafluorobutane, 1,1,1,2,2,3,4,4,4-nonafluorobutane, 1,1,1,2,2,3,3,4-octafluorobutane, 1,1,1,2,2,4,4,4-octafluorobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,4-octafluorobutane, 1,1,1,2,3,4,4,4-octafluorobutane, 1,1,1,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,3-heptafluorobutane, 1,1,1,2,2,4,4-heptafluorobutane, 1,1,1,3,3,4,4-heptafluorobutane, 1,1,2,2,3,3,4-heptafluorobutane, 1,1,1,2,4,4,4-heptafluorobutane, 1,1,1,2,2,3,4-heptafluorobutane, 1,1,1,2,3,4,4-heptafluorobutane, 1,1,2,2,3,4,4-heptafluorobutane, 1, 1,1,2,2,3-hexafluorobutane, 1,1,1,2,3,3-hexafluorobutane, 1,1,2,2,3,3-hexafluorobutane, 1,1,1,2,2,4-hexafluorobutane, 1,1,1,3,3,4-hexafluorobutane, 1,2,2,3,3,4-hexafluorobutane, 1,1,1,4,4,4-hexafluorobutane, 1,1,1,2,3,4-hexafluorobutane, 1,1,2,2,3,4-hexafluorobutane, 1,1,2,3,3,4-hexafluorobutane, 1,1,1,3,4,4-hexafluorobutane, 1,1,1,2,4,4-hexafluorobutane, 1,1,2,2,4,4-hexafluorobutane, 1,1,2,3,4,4-hexafluorobutane, 1,1,1,2,2-pentafluorobutane, 1,1,1,3,3-pentafluorobutane, 1,1,1,4,4-pentafluorobutane, 1,1,1,2,3-pentafluorobutane, 1, 1,1,2,4-pentafluorobutane, 1,1,1,3,4-pentafluorobutane, 1,1,2,2,3-pentafluorobutane, 1,1,2,2,4-pentafluorobutane, 1,1,3,3,4-pentafluorobutane, 1,1,2,3,3-pentafluorobutane, 1,1,2,4,4-pentafluorobutane, 1,2,2,3,3-pentafluorobutane, 1,1,2,3,4-pentafluorobutane, 1,2,2,3,4-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,3-hexafluorocyclopentane, 1h,2h-octafluorocyclopentane, 3,3,4,4,5,5-hexafluorocyclopentene, 1,3,3,4,4,5,5-heptafluorocyclopentene, 2h,3h-decafluoropentane, and 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene.

### Claim 5 (depends on 1)

The etching gas composition of claim 1, wherein
the organosulfur compound comprises a compound having a formula of C4F6S.

### Claim 6 (depends on 1)

The etching gas composition of claim 1, wherein
the first organofluorine compound comprises hexafluorobutene.

### Claim 7 (depends on 1)

The etching gas composition of claim 1, wherein
the first organofluorine compound comprises at least one selected from the group consisting of 1,1,3,3,3-pentafluoro-2-(fluoromethyl)prop-1-ene, (3S,4R)-1,1,2,2,3,4-hexafluorocyclobutane, 2,3,3,4,4,4-hexafluoro-1-butene, 1,1,2,2,3,3-hexafluorocyclobutane, (2Z)-1,1,1,2,4,4-hexafluoro-2-butene, and (2E)-1,1,2,3,4,4-hexafluoro-2-butene.

### Claim 8 (depends on 1)

The etching gas composition of claim 1, wherein
the organosulfur compound is present in the etching gas composition in an amount of about 10 parts to about 60 parts by mole based on 100 parts by mole of the first organofluorine compound.

### Claim 9 (depends on 1)

The etching gas composition of claim 1, wherein
the second organofluorine compound and/or the third organofluorine compound is present in the etching gas composition in an amount of about 1 part to about 60 parts by mole based on 100 parts by mole of the first organofluorine compound.

### Claim 10 (depends on 9)

The etching gas composition of claim 9, wherein
a ratio of a molar number of the second organofluorine compound to a molar number of the third organofluorine compound is in a range of about 10 to about 32.

### Claim 11 (depends on 1)

A method of forming patterns, the method comprising:
forming a film on a substrate;
forming an etch mask on the film; and
etching the film by performing an etch process on the etch mask using the etching gas composition of claim 1.

### Claim 12

An etching gas composition comprising:
a first organofluorine compound having a formula of CaFbHc; and
an organosulfur compound having a formula of CxFySz, the organosulfur compound comprising at least one carbon-carbon double (—C═C—) bond,
wherein the organosulfur compound is present in the etching gas composition in an amount of about 10 parts to about 60 parts by mole based on 100 parts by mole of the first organofluorine compound,
wherein a is an integer of 3 to 6, b is an integer of 1 to 10, c is an integer of 1 to 6, x is an integer of 1 to 6, y is an integer of 1 to 16, and z is an integer of 1 to 4,
wherein the etching gas composition comprises both a second organofluorine compound and a third organofluorine compound, wherein the first, second and third organofluorine compounds are different from each other,
wherein the second organofluorine compound and/or the third organofluorine compound is present in the etching gas composition in an amount of about 1 part to about 60 parts by mole based on 100 parts by mole of the first organofluorine compound, and
wherein a ratio of a molar number of the second organofluorine compound to a molar number of the third organofluorine compound is in a range of about 10 to about 32.

### Claim 13 (depends on 12)

The etching gas composition of claim 12, wherein
the organosulfur compound comprises a compound having a formula of C4F6S, and
the first organofluorine compound comprises at least one selected from the group consisting of trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, tetrafluoropropene, difluoropropane, pentafluorobutane, heptafluorobutane, octafluorobutane, hexafluorobutene, decafluoropentane, hexafluorocyclopentane, heptafluorocyclopentane, octafluorocyclopentane, heptafluorocyclopentene, and nonafluorohexene.

### Claim 14 (depends on 12)

The etching gas composition of claim 12,
wherein the second organofluorine compound comprises a C1 to C6 perfluorocarbon compound, and the third organofluorine compound comprises a C1 to C4 hydrofluorocarbon compound.

### Claim 15 (depends on 14)

The etching gas composition of claim 14, wherein
the second organofluorine compound comprises tetrafluoromethane, tetrafluoroethene, hexafluoroethane, octafluoropropane, hexafluoropropene, octafluorobutene, hexafluorobutadiene, or decafluorocyclopentane.

### Claim 16 (depends on 15)

The etching gas composition of claim 15, wherein the third organofluorine compound has a formula of CpHqFr, wherein p is an integer of 1 to 4, each of q and r is an integer of 1 or more, q+r is an integer of 2p+2 or less, and r is greater than or equal to q.