KR102324275B1 - Etching composition for silicone nitride and method for etching using the same - Google Patents
Etching composition for silicone nitride and method for etching using the same Download PDFInfo
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- KR102324275B1 KR102324275B1 KR1020180051448A KR20180051448A KR102324275B1 KR 102324275 B1 KR102324275 B1 KR 102324275B1 KR 1020180051448 A KR1020180051448 A KR 1020180051448A KR 20180051448 A KR20180051448 A KR 20180051448A KR 102324275 B1 KR102324275 B1 KR 102324275B1
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- 238000005530 etching Methods 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 20
- 229920001296 polysiloxane Polymers 0.000 title description 2
- 150000004767 nitrides Chemical class 0.000 title 1
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 51
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MDYOLVRUBBJPFM-UHFFFAOYSA-N tropolone Chemical group OC1=CC=CC=CC1=O MDYOLVRUBBJPFM-UHFFFAOYSA-N 0.000 claims description 16
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- 239000002210 silicon-based material Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 8
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 12
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229930007845 β-thujaplicin Natural products 0.000 description 2
- NRDYZLSIZYUHNH-UHFFFAOYSA-N 3-(methylhydrazinylidene)inden-1-one Chemical compound C1=CC=C2C(=NNC)CC(=O)C2=C1 NRDYZLSIZYUHNH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
본 발명의 실리콘 질화막 에칭 조성물은 인산 화합물; 치환되거나 치환되지 않은 탄소수 7-8의 고리형 탄화수소; 및 물을 포함한다. 상기 실리콘 질화막 에칭 조성물은 실리콘산화막에 대한 실리콘 질화막의 선택비가 높고, 실리콘 화합물의 석출을 억제할 수 있다. The silicon nitride film etching composition of this invention is a phosphoric acid compound; substituted or unsubstituted cyclic hydrocarbons having 7-8 carbon atoms; and water. The silicon nitride film etching composition has a high selectivity ratio of the silicon nitride film to the silicon oxide film, and can suppress precipitation of the silicon compound.
Description
본 발명은 실리콘 질화막 에칭 조성물 및 이를 이용한 에칭 방법에 관한 것이다. 보다 상세하게는 본 발명은 실리콘 질화막에 대한 에칭 속도를 높이고, 실리콘 질화막과 실리콘 산화막에 대한 에칭 선택비를 향상시키며, 에칭 과정에서 생성되는 부산물의 석출을 억제할 수 있는 실리콘 질화막 에칭 조성물에 관한 것이다.The present invention relates to a silicon nitride film etching composition and an etching method using the same. More particularly, the present invention relates to a silicon nitride film etching composition capable of increasing the etching rate for the silicon nitride film, improving the etching selectivity for the silicon nitride film and the silicon oxide film, and suppressing the precipitation of by-products generated in the etching process. .
실리콘 산화막 및 실리콘 질화막은 반도체 제조 공정에서 대표적인 절연막으로 사용되고 있다. 이러한 절연막은 단일층 혹은 복수층의 형태로 사용된다. 또한 실리콘 산화막 및 실리콘 질화막은 금속 배선과 같은 도전성 패턴을 형성하기 위한 하드마스크(Hard mask)로서도 사용된다.A silicon oxide film and a silicon nitride film are used as representative insulating films in a semiconductor manufacturing process. This insulating film is used in the form of a single layer or a plurality of layers. In addition, the silicon oxide film and the silicon nitride film are also used as a hard mask for forming a conductive pattern such as a metal wiring.
이러한 실리콘 질화막을 에칭 공정을 통해 제거할 때 주로 인산이 사용되고 있다. 그러나, 인산은 부식성이 있으며, 에칭 과정에서 Si(OH)4 등의 부산물이 석출되는 등 안정적인 공정 유지가 어려운 문제가 있다.When the silicon nitride film is removed through an etching process, phosphoric acid is mainly used. However, phosphoric acid is corrosive, and there is a problem in that it is difficult to maintain a stable process such as by-products such as Si(OH) 4 being precipitated during the etching process.
따라서, 실리콘 질화막에 대한 에칭 속도를 높이고, 실리콘 질화막과 실리콘 산화막에 대한 에칭 선택비를 향상시키며, 에칭 과정에서 생성되는 부산물의 석출을 억제할 수 있는 에칭 조성물의 개발이 필요하다.Therefore, it is necessary to develop an etching composition capable of increasing the etching rate for the silicon nitride film, improving the etching selectivity between the silicon nitride film and the silicon oxide film, and suppressing the precipitation of by-products generated in the etching process.
본 발명의 목적은 실리콘 질화막에 대한 에칭 속도를 높이고, 실리콘 질화막과 실리콘 산화막에 대한 에칭 선택비를 향상시키며, 에칭 과정에서 생성되는 부산물의 석출을 억제할 수 있는, 실리콘 질화막 에칭 조성물을 제공하는 것이다.SUMMARY OF THE INVENTION It is an object of the present invention to provide a silicon nitride film etching composition capable of increasing an etching rate for a silicon nitride film, improving an etching selectivity for a silicon nitride film and a silicon oxide film, and suppressing precipitation of by-products generated in the etching process. .
본 발명의 다른 목적은 상기 실리콘 질화막 에칭 조성물을 이용한 에칭 방법을 제공하는 것이다.Another object of the present invention is to provide an etching method using the silicon nitride film etching composition.
본 발명의 실리콘 질화막 에칭 조성물은 인산 화합물; 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소; 및 물을 포함한다.The silicon nitride film etching composition of the present invention is phosphoric acid compounds; substituted or unsubstituted cyclic hydrocarbons having 7-8 carbon atoms; and water.
구체예에서, 상기 인산 화합물은 오르토인산, 메타인산, 피로인산, 아인산, 차인산 및 폴리인산 중 하나 이상을 포함할 수 있다.In embodiments, the phosphoric acid compound may include at least one of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid.
구체예에서, 상기 치환되거나 치환되지 않은 탄소 수 7~8의 고리형 탄화수소는 작용기를 2개 이상 포함할 수 있다.In embodiments, the substituted or unsubstituted cyclic hydrocarbon having 7 to 8 carbon atoms may include two or more functional groups.
구체예에서 상기 작용기는 카르보닐기 또는 수산기일 수 있다. In an embodiment, the functional group may be a carbonyl group or a hydroxyl group.
구체예에서, 상기 치환되거나 치환되지 않은 탄소 수 7~8의 고리형 탄화수소는 트로폴론(tropolone) 또는 그의 유도체일 수 있다. In an embodiment, the substituted or unsubstituted cyclic hydrocarbon having 7 to 8 carbon atoms may be tropolone or a derivative thereof.
상기 실리콘 질화막 에칭 조성물은, 인산 화합물 60~95 중량%; 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소 0.0001~10 중량%; 및 잔량의 물을 포함할 수 있다.The silicon nitride film etching composition, 60 to 95% by weight of a phosphoric acid compound; 0.0001 to 10 wt% of a substituted or unsubstituted cyclic hydrocarbon having 7-8 carbon atoms; and the remainder of water.
상기 실리콘 질화막 에칭 조성물은 실리콘 함유 화합물을 0 초과 10 중량% 이하의 범위로 더 포함할 수 있다.The silicon nitride film etching composition may further include a silicon-containing compound in an amount of greater than 0 to 10% by weight or less.
상기 실리콘 함유 화합물은 하기 화학식 2로 표시되는 화합물을 포함할 수 있다:The silicon-containing compound may include a compound represented by the following Chemical Formula 2:
[화학식 2][Formula 2]
(상기 화학식 2에서, R1, R2, R3 및 R4는 각각 독립적으로 수소, 탄소 수 1~10의 알킬기, 탄소 수 1~10의 알콕시기, 탄소 수 3~10의 고리형 알킬기 또는 탄소수 6~12의 아릴기이며, R1, R2, R3 및 R4 중 하나 이상은 수소 또는 탄소 수 1~10의 알콕시기임).(In Formula 2, R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 6 to 12 carbon atoms. of an aryl group, and at least one of R1, R2, R3 and R4 is hydrogen or an alkoxy group having 1 to 10 carbon atoms).
본 발명의 다른 관점은 반도체 소자의 에칭 방법에 관한 것이다. 상기 방법은 상기 실리콘 질화막 에칭 조성물을 사용하여 실리콘 질화막을 에칭하는 것을 특징으로 한다. Another aspect of the present invention relates to a method of etching a semiconductor device. The method is characterized in that the silicon nitride film is etched using the silicon nitride film etching composition.
본 발명은 실리콘 질화막에 대한 에칭 속도를 높이고, 실리콘 질화막과 실리콘 산화막에 대한 에칭 선택비를 향상시키며, 에칭 과정에서 생성되는 부산물의 석출을 억제할 수 있는, 실리콘 질화막 에칭 조성물 및 상기 실리콘 질화막 에칭 조성물을 이용한 에칭 방법을 제공하는 효과가 있다.The present invention increases the etching rate for the silicon nitride film, improves the etching selectivity for the silicon nitride film and the silicon oxide film, and can suppress the precipitation of by-products generated in the etching process, a silicon nitride film etching composition and the silicon nitride film etching composition There is an effect of providing an etching method using
본 발명의 실리콘 질화막 에칭 조성물은 인산 화합물; 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소; 및 물을 포함한다.The silicon nitride film etching composition of the present invention is phosphoric acid compounds; substituted or unsubstituted cyclic hydrocarbons having 7-8 carbon atoms; and water.
인산 화합물phosphate compound
상기 인산 화합물은 실리콘 질화막에 대한 에칭 속도를 높일 수 있다. 구체예에서 상기 인산 화합물은 오르토인산, 메타인산, 피로인산, 아인산, 차인산 및 폴리인산 중 하나 이상을 포함할 수 있다.The phosphoric acid compound may increase the etching rate of the silicon nitride layer. In an embodiment, the phosphoric acid compound may include at least one of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid.
상기 인산 화합물은 실리콘 질화막 에칭 조성물 중 60~95 중량%, 예를 들면 75~90 중량%로 포함될 수 있다. 상기 범위 내에서 실리콘 질화막에 대한 에칭 속도를 확보할 수 있다.The phosphoric acid compound may be included in an amount of 60 to 95% by weight, for example, 75 to 90% by weight of the silicon nitride film etching composition. The etching rate for the silicon nitride film can be secured within the above range.
치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소substituted or unsubstituted cyclic hydrocarbons having 7-8 carbon atoms
상기 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소는 에칭 과정에서 Si(OH)4 등의 부산물의 석출을 억제할 수 있다.The substituted or unsubstituted cyclic hydrocarbon having 7-8 carbon atoms may suppress precipitation of by-products such as Si(OH) 4 in the etching process.
구체예에서, 상기 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소는 작용기를 2개 이상 포함할 수 있다.In an embodiment, the substituted or unsubstituted cyclic hydrocarbon having 7-8 carbon atoms may include two or more functional groups.
구체예에서 상기 작용기는 카르보닐기 또는 수산기일 수 있으며, 상기 치환되거나 치환되지 않은 탄소 수 7-8의 고리형 탄화수소는 카르보닐기 또는 수산기를 각각 최소한 1개 이상 포함할 수 있다.In embodiments, the functional group may be a carbonyl group or a hydroxyl group, and the substituted or unsubstituted cyclic hydrocarbon having 7-8 carbon atoms may include at least one carbonyl group or a hydroxyl group, respectively.
예를 들면, 상기 치환되거나 치환되지 않은 탄소 수 7~8의 고리형 탄화수소는 하기 화학식 1로 표시되는 트로폴론(tropolone) 또는 그의 유도체가 사용될 수 있다:For example, as the substituted or unsubstituted cyclic hydrocarbon having 7 to 8 carbon atoms, tropolone represented by the following formula (1) or a derivative thereof may be used:
[화학식 1][Formula 1]
상기 치환되거나 치환되지 않은 탄소 수 7~8의 고리형 탄화수소는 상기 실리콘 질화막 에칭 조성물 중 0.0001~10 중량%, 예를 들면, 0.1~7 중량%, 또는 0.5~5 중량%로 포함될 수 있다. 상기 범위에서 Si(OH)4 등의 부산물의 석출을 대폭 억제할 수 있다.The substituted or unsubstituted cyclic hydrocarbon having 7 to 8 carbon atoms may be included in an amount of 0.0001 to 10% by weight, for example, 0.1 to 7% by weight, or 0.5 to 5% by weight of the silicon nitride film etching composition. In the above range, precipitation of by-products such as Si(OH) 4 can be significantly suppressed.
본 발명의 실리콘 질화막 에칭 조성물은 실리콘 함유 화합물을 더 포함할 수 있다. The silicon nitride film etching composition of the present invention may further include a silicon-containing compound.
상기 실리콘 함유 화합물은 하기 화학식 2로 표시되는 화합물을 포함할 수 있다:The silicon-containing compound may include a compound represented by the following Chemical Formula 2:
[화학식 2][Formula 2]
(상기 화학식 2에서, R1, R2, R3 및 R4는 각각 독립적으로 수소, 탄소 수 1~10의 알킬기, 탄소 수 1~10의 알콕시기, 탄소 수 3~10의 고리형 알킬기 또는 탄소 수 6~12의 아릴기이며, R1, R2, R3 및 R4 중 하나 이상은 수소 또는 탄소 수 1~10의 알콕시기임).(In Formula 2, R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 6 to carbon atoms. an aryl group of 12, and at least one of R1, R2, R3 and R4 is hydrogen or an alkoxy group having 1 to 10 carbon atoms).
상기 실리콘 함유 화합물의 구체예로는 테트라에톡시실란 (tetraethoxysilane, TEOS) 등이 사용될 수 있다.Specific examples of the silicon-containing compound include tetraethoxysilane (TEOS) and the like.
상기 실리콘 함유 화합물은 상기 실리콘 질화막 에칭 조성물 중 0 초과 10 중량% 이하의 범위로 포함될 수 있다. 상기 범위에서 실리콘 질화막에 대한 에칭 속도를 높일 수 있다.The silicon-containing compound may be included in an amount of greater than 0 to 10% by weight or less in the silicon nitride etching composition. In the above range, the etching rate for the silicon nitride film may be increased.
본 발명의 다른 관점은 반도체 소자의 에칭 방법에 관한 것이다. 상기 에칭 방법은 상기 실리콘 질화막 에칭 조성물을 사용해서 에칭하는 단계를 포함할 수 있다.Another aspect of the present invention relates to a method of etching a semiconductor device. The etching method may include etching using the silicon nitride etching composition.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.
실시예Example
하기 실시예와 비교예에서 사용된 성분의 구체적인 사양은 다음과 같다.Specific specifications of the components used in the following Examples and Comparative Examples are as follows.
(A) 인산 화합물: 인산(H3PO4)(농도 85%의 수용액, 삼전화학 제조)을 사용하였다.(A) Phosphoric acid compound: phosphoric acid (H 3 PO 4 ) (aqueous solution having a concentration of 85%, manufactured by Samchun Chemical) was used.
(B1) 탄소 수 7의 고리형 탄화수소: 트로폴론(TCI사 제조)을 사용하였다.(B1) Cyclic hydrocarbon having 7 carbon atoms: Tropolone (manufactured by TCI) was used.
(B2) 이소프로필기로 치환된 트로폴론(4-isopropyltropolone, 히노키티올)(TCI사 제조)을 사용하였다.(B2) Tropolone (4-isopropyltropolone, hinokitiol) substituted with an isopropyl group (manufactured by TCI) was used.
(B3) 탄소 수 6의 고리형 탄화수소: 1,3-사이클로헥산디온(TCI사)을 사용하였다.(B3) Cyclic hydrocarbon having 6 carbon atoms: 1,3-cyclohexanedione (TCI) was used.
(B4) 탄소수 9의 고리형 탄화수소: 1H-INDENE-1,3(2H)-DIONE-1-(METHYLHYDRAZONE)(SIGMA사 제조)을 사용하였다.(B4) Cyclic hydrocarbon having 9 carbon atoms: 1H-INDENE-1,3(2H)-DIONE-1-(METHYLHYDRAZONE) (manufactured by SIGMA) was used.
(C) 물: 초순수를 사용하였다.(C) Water: Ultrapure water was used.
(D) 실리콘 함유 화합물: TEOS(TCI사 제조)를 사용하였다.(D) Silicone-containing compound: TEOS (manufactured by TCI) was used.
실시예Example 1~6 1-6
하기 표 1의 조성에 잔량의 물을 혼합하여 100 중량%가 되도록 실리콘 질화막 에칭 조성물을 제조하고, 하기 방법으로 물성을 측정하였다.A silicon nitride film etching composition was prepared by mixing the remaining amount of water with the composition shown in Table 1 below to be 100% by weight, and physical properties were measured by the following method.
실시예와 비교예에서 제조한 에칭 조성물에 대하여 에칭 평가를 하고, 그 결과를 하기 표 2에 나타내었다.Etching was evaluated for the etching compositions prepared in Examples and Comparative Examples, and the results are shown in Table 2 below.
(1) 실리콘 질화막 에칭 속도(Å/min): 비커에 식각용 조성물을 넣고 가열하여 온도가 165℃가 되었을 때 SiN 막질을 넣고 30분간 식각한 후, 전후 두께 차이를 측정하여 에칭 속도를 계산하였다.(1) Silicon nitride film etching rate (Å/min): After putting an etching composition in a beaker and heating it, when the temperature reached 165° C., SiN film material was put and etched for 30 minutes, and the etching rate was calculated by measuring the difference in thickness before and after .
(2) 실리콘 산화막 에칭 속도(Å/min): SiN 막질 대신에 SiO 막질을 사용한 것을 제외하고 실리콘 질화막 에칭 속도와 동일한 방법으로 평가하였다.(2) Silicon oxide film etching rate (Å/min): The evaluation was performed in the same manner as the silicon nitride film etching rate except that SiO film quality was used instead of SiN film quality.
(3) 선택비: 상기 실리콘 산화막 에칭속도에 대한 실리콘 질화막 에칭속도 선택비를 계산하여 하기 표 2에 나타내었다.(3) Selectivity: The silicon nitride film etch rate selectivity with respect to the silicon oxide film etch rate was calculated and shown in Table 2 below.
(4) 부산물 측정 방법: 실리콘 질화막과 산화막을 포함하는 웨이퍼를 165℃의 식각액을 이용하여 4매 연속 에칭한 후 5매째 웨이퍼에 대해 부산물을 측정하였다. 실리콘 산화막의 에칭 속도가 음의 값을 가질 경우 실리콘 산화막 표면에 부산물이 생성된 것으로 판단하였으며, 추가적으로 주사전자 현미경을 통하여 실리콘 산화막의 표면을 분석하여 부산물 생성 여부를 확인하였다.(4) Method for measuring by-products: After etching a wafer including a silicon nitride film and an oxide film four successively using an etchant at 165° C., the by-products were measured for the fifth wafer. When the etching rate of the silicon oxide film had a negative value, it was determined that by-products were generated on the surface of the silicon oxide film. Additionally, by analyzing the surface of the silicon oxide film through a scanning electron microscope, it was confirmed whether by-products were generated.
상기 표 2에서와 같이, 본 발명의 실리콘 질화막 에칭 조성물은 실리콘 질화막에 대한 에칭 속도가 높고, 실리콘 질화막과 실리콘 산화막에 대한 에칭 선택비가 향상되며, 에칭 과정에서 생성되는 부산물의 석출을 억제할 수 있는 것을 알 수 있다.As shown in Table 2, the silicon nitride film etching composition of the present invention has a high etching rate for the silicon nitride film, improves the etching selectivity for the silicon nitride film and the silicon oxide film, and can suppress the precipitation of by-products generated in the etching process. it can be seen that
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. Simple modifications or changes of the present invention can be easily carried out by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.
Claims (9)
트로폴론(tropolone) 또는 이소프로필기로 치환된 트로폴론; 및
물;을 포함하는 것인, 실리콘 질화막 에칭 조성물.
phosphoric acid compounds;
Tropolone or tropolone substituted with an isopropyl group; and
Water; containing, the silicon nitride film etching composition.
The silicon nitride film etching composition according to claim 1, wherein the phosphoric acid compound includes at least one of orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphoric acid, and polyphosphoric acid.
상기 인산 화합물 60~95 중량%;
상기 트로폴론 또는 이소프로필기로 치환된 트로폴론 0.0001~10 중량%; 및
잔량의 상기 물;을 포함하는 실리콘 질화막 에칭 조성물.
According to claim 1, The silicon nitride film etching composition,
60-95 wt% of the phosphoric acid compound;
0.0001 to 10% by weight of the tropolone or tropolone substituted with an isopropyl group; and
A silicon nitride film etching composition comprising a; remaining amount of the water.
The silicon nitride film etching composition according to claim 6, wherein the silicon nitride film etching composition further comprises a silicon-containing compound in an amount of greater than 0 to 10% by weight or less.
[화학식 2]
(상기 화학식 2에서, R1, R2, R3 및 R4는 각각 독립적으로 수소, 탄소수 1-10의 알킬기, 탄소수 1-10의 알콕시기, 탄소수 3-10의 고리형알킬기 또는 탄소수 6-12의 아릴기이며, R1, R2, R3 및 R4 중 하나 이상은 수소 또는 탄소수 1-10의 알콕시기임).
The silicon nitride film etching composition according to claim 7, wherein the silicon-containing compound includes a compound represented by the following Chemical Formula 2:
[Formula 2]
(In Formula 2, R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, a cyclic alkyl group having 3-10 carbon atoms, or an aryl group having 6-12 carbon atoms. and at least one of R1, R2, R3 and R4 is hydrogen or an alkoxy group having 1-10 carbon atoms).
A method for etching a semiconductor device, characterized in that the silicon nitride film is etched using the silicon nitride film etching composition according to any one of claims 1, 2, and 6 to 8.
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