KR20200092132A - An etchant composition for a silicon nitride layer - Google Patents
An etchant composition for a silicon nitride layer Download PDFInfo
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- KR20200092132A KR20200092132A KR1020190009299A KR20190009299A KR20200092132A KR 20200092132 A KR20200092132 A KR 20200092132A KR 1020190009299 A KR1020190009299 A KR 1020190009299A KR 20190009299 A KR20190009299 A KR 20190009299A KR 20200092132 A KR20200092132 A KR 20200092132A
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 28
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005530 etching Methods 0.000 claims abstract description 31
- 229920002050 silicone resin Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000004767 nitrides Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 22
- 229910052814 silicon oxide Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- -1 methoxy, ethoxy, propoxy, isopropoxy Chemical group 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 실리콘 질화막 식각액 조성물에 관한 것이다.The present invention relates to a silicon nitride film etchant composition.
3D NAND 플래시 메모리는 산화물막 및 질화물막을 포함하는 다층막에서 질화물막만을 선택적으로 제거하는 공정(Wet removal of nitride)을 통해 제조될 수 있으며, 산화물막에는 손상을 주지 않으면서 질화물막을 완전히 제거하는 것이, 질화물막 제거 공정(Wet removal of nitride)의 핵심 기술 중 하나이다.3D NAND flash memory can be manufactured through a process of selectively removing only a nitride film from a multilayer film including an oxide film and a nitride film (Wet removal of nitride), and removing the nitride film completely without damaging the oxide film, It is one of the core technologies of the wet removal process.
일반적으로 질화물막 제거 공정에 사용되는 식각액 조성물은, 산화물막에는 손상을 주지 않으면서 질화물막만을 완전히 제거하는 효과를 얻기 위해, 방식 능력을 갖는 첨가제를 이용한다.In general, the etchant composition used in the nitride film removal process uses an additive having anticorrosive ability to obtain an effect of completely removing the nitride film without damaging the oxide film.
대한민국 공개특허 제10-2018-0004871호 및 대한민국 등록특허 제10-1769349호는 실리콘 산화물막 및 실리콘 질화물막에 대해 실리콘 질화물막만을 선택적으로 식각하는 식각액 조성물에 대해 개시하고 있으나, 첨가제로 실리카를 사용하여 겔화(gelation)가 발생하기 쉽고, 물에 대한 용해도가 낮아 식각 후 린스 공정에서의 입자 생성 및 잔류 문제를 해결하고 있지 못한 실정이다.Korean Patent Publication No. 10-2018-0004871 and Korean Patent Registration No. 10-1769349 disclose an etchant composition for selectively etching only a silicon nitride film with respect to a silicon oxide film and a silicon nitride film, but using silica as an additive Therefore, gelation is likely to occur, and the solubility in water is low, and thus, the problem of particle generation and residual in the rinse process after etching is not solved.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 산화물막 및 질화물막을 포함하는 다층막에서 질화물막에 대한 식각 선택비 조절이 용이하여 질화물막만을 선택적으로 식각할 수 있으며, 처리 매수 증가에도 선택비 변화율이 낮아 식각 성능이 유지되고, 식각 후 린스 공정에서 입자의 발생 및 잔류가 억제된, 실리콘 질화막 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is to improve the above-mentioned problems of the prior art, it is easy to control the etching selectivity for the nitride film in the multilayer film including the oxide film and the nitride film, so that only the nitride film can be selectively etched, and it is also selected to increase the number of treatments. It is an object of the present invention to provide a silicon nitride film etchant composition having a low specific change rate, maintaining etching performance, and suppressing generation and residual of particles in a rinse process after etching.
상기 목적을 달성하기 위해, 본 발명은, (A) 인산, (B) 실리콘 레진 및 (C) 물을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물을 제공한다. To achieve the above object, the present invention provides a silicon nitride film etchant composition comprising (A) phosphoric acid, (B) silicone resin and (C) water.
본 발명의 실리콘 질화막 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서 질화물막에 대한 식각 선택비 조절이 용이하여 질화물막만을 선택적으로 식각할 수 있으며, 처리 매수 증가에도 선택비 변화율이 낮아 식각 성능이 유지되고, 식각 후 린스 공정에서 입자의 발생 및 잔류가 억제되는 효과를 제공한다.The silicon nitride film etchant composition of the present invention is easy to control the etch selectivity to the nitride film in a multilayer film including an oxide film and a nitride film, so that only the nitride film can be selectively etched, and the rate of change in selectivity is low due to an increase in the number of treatments. It is maintained, and provides an effect of suppressing generation and residual of particles in a rinse process after etching.
본 발명은, (A) 인산, (B) 실리콘 레진 및 (C) 물을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물을 제공한다.The present invention provides a silicon nitride film etchant composition comprising (A) phosphoric acid, (B) silicone resin and (C) water.
상기 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각 할 수 있으며, 더 나아가 원하는 선택비로의 조절이 용이한 것을 특징으로 한다. 구체적인 예를 들어, 상기 산화물막은 SiO2을 포함하는 것이 바람직하고, 상기 질화물막은 SiN을 포함하는 것이 바람직하다.The etchant composition is characterized in that it is possible to selectively etch only the nitride film in a multi-layer film including an oxide film and a nitride film, and furthermore, it is easy to control the desired selectivity. For a specific example, the oxide film preferably contains SiO 2 , and the nitride film preferably contains SiN.
상기 식각액 조성물은 3D NAND 플래시 메모리 제조 공정에 이용되며, 상기 질화물막 제거 공정 중 발생하는, 부반응 산화물의 잔류 및 산화물막 손상 불량 문제를 최소화시킬 수 있다.The etchant composition is used in a 3D NAND flash memory manufacturing process, and it is possible to minimize the problem of residual residual oxide and damage to the oxide film occurring during the nitride film removal process.
또한, 상기 식각액 조성물은 상기 실리콘 레진을 포함하여, 물에 대한 용해도가 높고, 이에 따라 식각 후 린스 공정에서 입자 생성 및 잔류 문제가 발생하지 않는다는 이점이 있다.In addition, the etchant composition includes the silicone resin, so it has a high solubility in water, and thus has an advantage that particle generation and residual problems do not occur in a rinse process after etching.
또한, 상기 식각액 조성물은 처리매수 증가에도 식각 성능이 유지되어 조성물의 수명을 증가시킬 수 있다.In addition, the etchant composition may maintain the etch performance even when the number of treatments is increased, thereby increasing the life of the composition.
이하에서, 본 발명의 식각액 조성물에 포함되는, 인산, 실리콘 레진 및 물에 대해 보다 자세하게 설명한다.Hereinafter, phosphoric acid, silicone resin and water included in the etching solution composition of the present invention will be described in more detail.
(A) 인산(A) Phosphoric acid
본 발명의 식각액 조성물에 포함되는 상기 인산(phosphoric acid)은 질화물막 식각을 위한 주 식각 성분으로서, 산화물막 및 질화물막을 포함하는 다층막을 식각시킬 수 있으며, 후술되는 실리콘 레진이 상기 다층막이 포함하는 상기 산화물막의 식각을 방지하여, 상기 질화물막만 선택적으로 식각될 수 있다.The phosphoric acid (phosphoric acid) contained in the etching solution composition of the present invention is a main etching component for etching the nitride film, it is possible to etch a multi-layer film comprising an oxide film and a nitride film, the silicon resin to be described later is included in the multi-layer film By preventing the etching of the oxide film, only the nitride film can be selectively etched.
상기 인산의 함량은 조성물 총 중량에 대하여, 60 내지 95 중량%로 포함되며, 80 내지 90 중량%가 바람직하다. 상기 인산이 상기 함량 범위 내로 포함되는 경우, 적정 수준의 식각 속도를 제공할 수 있으며, 또한 산화물막 및 질화물막을 포함하는 다층막에서 질화물막에 대해 적정 수준의 식각 선택비를 제공할 수 있다.The phosphoric acid content is contained in 60 to 95% by weight, based on the total weight of the composition, preferably 80 to 90% by weight. When the phosphoric acid is included within the content range, an appropriate level of etching rate may be provided, and an appropriate level of etching selectivity may be provided for the nitride film in a multilayer film including an oxide film and a nitride film.
(B) 실리콘 레진(B) Silicone resin
본 발명의 식각액 조성물에 포함되는 상기 실리콘 레진(resin)은 방식제로서, 산화물막 및 질화물막을 포함하는 다층막에서 산화물막이 상기 인산에 의해 식각되는 것을 방지하는 데 사용될 수 있다.The silicone resin contained in the etching solution composition of the present invention is an anticorrosive agent, and may be used to prevent an oxide film from being etched by the phosphoric acid in a multilayer film including an oxide film and a nitride film.
상기 실리콘 레진은 하기 화학식 1 또는 2로 표시되는 화합물 1종 이상을 포함할 수 있다.The silicone resin may include at least one compound represented by the following Chemical Formula 1 or 2.
[화학식 1][Formula 1]
상기 화학식 1에서, R11 내지 R16은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 4의 알콕시기 및 아세톡시기로 이루어진 군에서 선택되며, n은 1 내지 5의 정수일 수 있다.In Formula 1, R11 to R16 are each independently selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 4 carbon atoms and acetoxy group, n can be an integer of 1 to 5 .
바람직하게는, 상기 화학식 1에서, R11 내지 R16은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 5의 알킬기, 메톡시, 에톡시, 프로폭시, 이소프로폭시 및 아세톡시기로 이루어진 군에서 선택되며, n은 1 내지 5의 정수일 수 있다.Preferably, in Formula 1, R11 to R16 are each independently selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, methoxy, ethoxy, propoxy, isopropoxy and acetoxy groups, n may be an integer from 1 to 5.
[화학식 2][Formula 2]
상기 화학식 2에서, R2는 수소, 할로겐, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 4의 알콕시기 및 아세톡시기로 이루어진 군에서 선택되며, R은 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기 및 탄소수 2 내지 10의 알키닐로 이루어진 군에서 선택되며, X는 수소, 할로겐, 하이드록시기, 에테르기, 에스테르기, 아민기, 포스포네이트기, 포스페이트기, 설포네이트기 및 설페이트기로 이루어진 군에서 선택되는 작용기를 포함하며, n은 1 내지 4의 정수일 수 있다.In Chemical Formula 2, R2 is selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an acetoxy group, and R is an alkyl group having 1 to 10 carbon atoms and 2 to 10 carbon atoms. It is selected from the group consisting of an alkenyl group and alkynyl having 2 to 10 carbon atoms, and X is a hydrogen, halogen, hydroxy group, ether group, ester group, amine group, phosphonate group, phosphate group, sulfonate group or sulfate group. It includes a functional group selected from the group consisting of, n may be an integer from 1 to 4.
바람직하게는, 상기 화학식 2에서, R2는 수소, 할로겐, 탄소수 1 내지 5의 알킬기, 메톡시, 에톡시, 프로폭시, 이소프로폭시 및 아세톡시기로 이루어진 군에서 선택되며, R은 탄소수 1 내지 5의 알킬기로 이루어진 군에서 선택되며, X는 하기 화학식 2-1 내지 2-9 로 표시되는 화합물로 이루어진 군에서 선택되며, n은 1 내지 4의 정수일 수 있다.Preferably, in the formula (2), R2 is selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, methoxy, ethoxy, propoxy, isopropoxy and acetoxy group, R is 1 to carbon atoms 5 is selected from the group consisting of alkyl groups, X is selected from the group consisting of compounds represented by the following Chemical Formulas 2-1 to 2-9, and n may be an integer from 1 to 4.
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 2-6][Formula 2-6]
[화학식 2-7][Formula 2-7]
[화학식 2-8][Formula 2-8]
[화학식 2-9][Formula 2-9]
상기 화학식 2-1 내지 2-9에서, Rx는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기, 탄소수 2 내지 10의 알키닐기 및 하이드록시기로 치환된 상기 알킬기, 상기 알케닐기, 상기 알키닐기로 이루어진 군에서 선택될 수 있다.In Formulas 2-1 to 2-9, Rx is each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and the alkyl group substituted with a hydroxyl group, the Alkenyl group, may be selected from the group consisting of the alkynyl group.
상기 실리콘 레진의 함량은 조성물 총 중량에 대하여, 0.001 내지 2.0 중량%로 포함되며, 0.001 내지 1.0 중량%가 바람직하다. 상기 실리콘 레진이 상기 함량 범위 내로 포함되는 경우, 산화물막 및 질화물막을 포함하는 다층막에서 질화물막에 대한 식각 선택비의 조절이 가능하여, 상기 질화물막만을 선택적으로 식각 할 수 있고, 또한 조성물의 겔화가 방지되어 식각 성능이 향상되며, 물에 대한 용해도가 높아, 식각 후 린스 공정에서의 입자 생성 및 잔류에 의한 품질 저하 문제가 개선될 수 있다. The content of the silicone resin is contained in 0.001 to 2.0% by weight relative to the total weight of the composition, preferably 0.001 to 1.0% by weight. When the silicone resin is included within the above content range, it is possible to control the etch selectivity to the nitride film in the multilayer film including the oxide film and the nitride film, so that only the nitride film can be selectively etched, and the gelation of the composition It is prevented to improve the etching performance, the solubility in water is high, and the problem of quality degradation due to particle generation and residual in the rinsing process after etching may be improved.
상기 실리콘 레진은 적어도 한 개 이상의 탄소를 포함하는 실리콘 중합체로, SiO2의 화학식으로 표시되는 무기 입자인 실리카와는 그 특성이 전혀 상이하다. 본 발명의 식각액 조성물이 방식제로서 실리콘 레진을 포함하는 것과 달리, 무기 입자인 실리카를 방식제로 사용할 경우, 실리카가 조성물에서 용해되지 않고 입자로 잔류할 가능성이 높고, 표면 개질 등을 통해 용해시키는 경우에도 겔화가 발생하여 방식제로서 성능이 저하될 우려가 있으며, 물에 용해도가 낮아 식각 후 물 린스 공정에서 입자를 형성하여 반도체 기판 표면에 흡착되어 파티클 문제를 초래할 수 있으며 이는 최종적으로 제품의 품질 저하를 유발할 수 있다.The silicone resin is a silicone polymer containing at least one carbon, and has completely different properties from silica, which is an inorganic particle represented by the formula of SiO 2 . Unlike the etchant composition of the present invention containing silicone resin as an anticorrosive agent, when silica as an inorganic particle is used as an anticorrosive agent, silica is more likely to remain as a particle without dissolving in the composition, and when dissolving through surface modification, etc. Edo gelation occurs, so performance may be deteriorated as an anti-corrosive agent, and the solubility in water is low, forming particles in the water rinsing process after etching to adsorb particles on the surface of the semiconductor substrate, which may cause particle problems. Can cause
또한, 본 발명에서 상기 실리콘 레진은 망상형(network) 구조를 갖는 3관능 및/또는 4관능 실란 화합물을 포함할 수 있고, 실란 화합물의 관능기 수는 단일 실리콘 원자에 대한 관능기 수로 판단될 수 있으며, 예를 들어, 상기 화학식 1의 경우, 두 개의 실리콘 원자를 포함하는 3관능 실란 화합물로 볼 수 있다. 망상형 구조를 갖는 상기 실리콘 레진 대신, 선형(linear, branched, cross-linked) 구조를 갖는 실록산 고분자를 사용하는 경우, 산화물막이 충분히 보호되지 않아, 산화물막 및 질화물막을 포함하는 다층막에서 상기 질화물막만을 선택적으로 식각함에 있어, 산화물막에 손상을 줄 수 있다는 문제가 있다. In addition, in the present invention, the silicone resin may include trifunctional and/or tetrafunctional silane compounds having a network structure, and the number of functional groups of the silane compound may be determined as the number of functional groups for a single silicon atom, For example, in the case of Chemical Formula 1, it can be regarded as a trifunctional silane compound containing two silicon atoms. When the siloxane polymer having a linear (linear, branched, cross-linked) structure is used instead of the silicone resin having a network structure, the oxide film is not sufficiently protected, so that only the nitride film is used in a multilayer film including an oxide film and a nitride film. In selectively etching, there is a problem that the oxide film may be damaged.
(C) 물(C) water
본 발명의 식각액 조성물에 포함되는 상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water contained in the etching solution composition of the present invention may be deionized water for semiconductor processing, and preferably, the deionized water of 18 kPa/cm or more may be used.
상기 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The content of the water may be included as a residual amount to make the total weight of the composition 100% by weight.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.
제조예에 따른 실리콘 레진의 제조Preparation of silicone resin according to the manufacturing example
하기 표 1을 참조하여, 상기 화학식 1 및/또는 2로 표시되는 화합물을 인산(본 발명의 제조예에서는 인산을 촉매로 사용하였으나, 필요에 따라 산 또는 염기 촉매를 선택적으로 사용할 수 있다) 촉매가 존재하는 수용액에 투입하여 실리콘 레진을 1차 형성시키고, 1차 형성된 실리콘 레진을 포집하여 건조시킨 후 인산 85% 수용액에 투입하여 90 내지 200 ℃에서 1 내지 6 시간 조건으로 2차 처리하여, 제조예 1 내지 8에 따른 실리콘 레진을 제조하였다.Referring to Table 1 below, the compound represented by Chemical Formulas 1 and/or 2 is phosphoric acid (phosphoric acid is used as a catalyst in the preparation example of the present invention, but an acid or base catalyst can be optionally used). A silicone resin was first formed by injecting it into an existing aqueous solution, and the first formed silicone resin was collected and dried, and then put into a 85% aqueous solution of phosphoric acid and subjected to secondary treatment at 90 to 200° C. for 1 to 6 hours, thereby preparing an example. Silicone resins according to 1 to 8 were prepared.
수용액Phosphoric acid
Aqueous solution
(℃)Temperature
(℃)
(hr)time
(hr)
1-a : 화학식 1에서 R11 내지 R16이 염소(Cl)이고, n이 1인 화합물1-b : 화학식 1에서 R11 내지 R16이 에톡시기이고, n이 2인 화합물1-a: In Formula 1, R11 to R16 are chlorine (Cl), and n is 1; Compound 1-b: In Formula 1, R11 to R16 is an ethoxy group, and n is 2
1-c : 화학식 1에서 R11이 메틸기이고, R12 내지 R16이 에톡시기이고, n이 2인 화합물1-c: In Formula 1, R11 is a methyl group, R12 to R16 are ethoxy groups, and n is 2
2-a : 화학식 2에서 R2는 에톡시기이고, n이 4인 화합물2-a: In Formula 2, R2 is an ethoxy group, and n is 4
2-b : 화학식 2에서 R2는 아세톡시기이고, R은 X가 수소인 메틸기이고, n은 3인 화합물2-b: In Formula 2, R2 is an acetoxy group, R is a methyl group in which X is hydrogen, and n is 3
2-c : 화학식 2에서 R2는 메톡시기이고, R은 에틸기이고, X는 화학식 2-6에서 Rx가 메틸기이고, n은 3인 화합물 2-c: In Formula 2, R2 is a methoxy group, R is an ethyl group, X is a compound in Formula 2-6, wherein Rx is a methyl group, and n is 3
2-d : 화학식 2에서 R2는 에톡시기이고, R은 프로필기이고, X는 화학식 2-3에서 Rx가 수소이고, n은 3인 화합물2-d: In Formula 2, R2 is an ethoxy group, R is a propyl group, X is a compound in Formula 2-3, Rx is hydrogen, and n is 3
2-e : 화학식 2에서 R2는 에톡시기이고, R은 에틸기이고, X는 화학식 2-2에서 Rx가 에틸기이고, n은 3인 화합물2-e: In Formula 2, R2 is an ethoxy group, R is an ethyl group, and X is a compound in Formula 2-2 where Rx is an ethyl group and n is 3.
2-f : 화학식 2에서 R2는 메톡시기이고, R은 프로필기이고, X는 화학식 2-9에서 Rx는 수소이고, n는 3인 화합물2-f: In Formula 2, R2 is a methoxy group, R is a propyl group, X is a compound in Formula 2-9, Rx is hydrogen, and n is 3
2-g : 화학식 2에서 R2는 메톡시기이고, R은 프로필기이고, X는 화학식 2-7에서 Rx가 수소이고, n은 3인 화합물2-g: In Formula 2, R2 is a methoxy group, R is a propyl group, X is a compound in Formula 2-7, Rx is hydrogen, and n is 3
2-h : 화학식 2에서 R2는 에톡시기이고, R은 X가 수소인 메틸기이고, n은 2인 화합물2-h: In Formula 2, R2 is an ethoxy group, R is a methyl group in which X is hydrogen, and n is a compound of 2
상기 실리콘 레진의 제조예는, 본 발명의 일 실시예에 따른 것으로, 본 발명에서 실리콘 레진의 제조 방법은 이에 제한되지 않는다. 예를 들어, 상기 화학식 1 및/또는 2로 표시되는 화합물을 인산 수용액에 투입하여 실리콘 레진을 1차 형성시키고, 90 내지 200 ℃에서 1 내지 6 시간 조건으로 2차 처리하여 실리콘 레진 용액을 제조할 수도 있다. 또 다른 예를 들어, 상기 실리콘 레진은 인산 외에, 질산, 염산, 황산과 같은 산 촉매 또는 암모니아수, 테트라메틸암모늄히드록시드와 같은 염기 촉매를 이용하여 제조할 수도 있다.The manufacturing example of the silicone resin, according to an embodiment of the present invention, the method of manufacturing a silicone resin in the present invention is not limited thereto. For example, the compound represented by Chemical Formulas 1 and/or 2 is introduced into an aqueous phosphoric acid solution to firstly form a silicone resin, and secondarily treated at 90 to 200° C. for 1 to 6 hours to prepare a silicone resin solution. It might be. For another example, the silicone resin may be prepared using an acid catalyst such as nitric acid, hydrochloric acid, or sulfuric acid, or a base catalyst such as ammonia water or tetramethylammonium hydroxide, in addition to phosphoric acid.
실시예 및 비교예에 따른 식각액 조성물의 제조Preparation of etchant compositions according to Examples and Comparative Examples
하기 표 2를 참조하여, 실시예 및 비교예에 따른 식각액 조성물을 제조하였다. Referring to Table 2, an etchant composition according to Examples and Comparative Examples was prepared.
비교예 1 내지 3은, 본 발명에 따른 실리콘 레진에 대응되는 구성으로, 각각 실리카(SiO2), Poly(dimethylsiloxane) 및 Tetraethyl orthosilicate를 사용하였다. 구체적으로, 비교예 1의 실리카는 Aldrich에서 구매한 실리카를 인산 85% 수용액에 1 중량%가 되도록 투입하여 180℃에서 3시간 가열하여 제조한 뒤, 이를 다시 인산 85% 수용액에 3.5 중량%가 되도록 투입하여 비교예 1의 조성물을 제조하였고, 비교예 2는 Aldrich에서 구매한 폴리 디메틸실록산을 인산 85% 수용액에 0.5 중량%가 되도록 투입하여 제조하였고, 비교예 3은 Aldrich에서 구매한 TEOS를 인산 85% 수용액에 0.1 중량%가 되도록 투입하여 제조하였다.Comparative Examples 1 to 3, as a structure corresponding to the silicone resin according to the present invention, was used for each of silica (SiO 2 ), Poly (dimethylsiloxane) and Tetraethyl orthosilicate. Specifically, the silica of Comparative Example 1 was prepared by adding silica purchased from Aldrich to 85% aqueous solution of phosphoric acid to 1% by weight and heating it at 180°C for 3 hours, and again to make 3.5% by weight of 85% aqueous solution of phosphoric acid. The composition of Comparative Example 1 was prepared by injecting, and Comparative Example 2 was prepared by injecting polydimethylsiloxane purchased from Aldrich so that it was 0.5% by weight in an 85% aqueous solution of phosphoric acid, and Comparative Example 3 obtained 85% TEOS purchased from Aldrich. It was prepared by adding to 0.1% by weight of the aqueous solution.
수용액Phosphoric Acid 85%
Aqueous solution
상기 표 2를 참조하여 제조한 실시예 및 비교예에 따른 식각액 조성물을 25℃에서 1시간 동안 방치 후, 용해 상태를 관찰한 결과, 실시예 1 내지 10 및 비교예 1에 따른 식각액 조성물은 투명한 상태를 유지하였으며, 비교예 2에 따른 식각액 조성물은 입자가 관찰되지는 않았으나, 현탁이 발생하였고, 비교예 3에 따른 식각액 조성물은 입자가 관찰되었다.After the etching solution composition according to the Examples and Comparative Examples prepared with reference to Table 2 was left at 25° C. for 1 hour, the dissolved state was observed, and the etching solution compositions according to Examples 1 to 10 and Comparative Example 1 were transparent. The particles of the etchant composition according to Comparative Example 2 were not observed, but suspension occurred, and particles of the etchant composition according to Comparative Example 3 were observed.
시험예Test example
비교예 3에 따른 식각액 조성물은 입자가 관찰되어 식각액 조성물로 사용할 수 없으므로, 이를 제외한 실시예 1 내지 10 및 비교예 1, 2 에 따른 식각액 조성물에 대해, 성능 평가를 다음과 같이 실시하였다.Since the etchant composition according to Comparative Example 3 cannot be used as an etchant composition because particles are observed, performance evaluations were performed on the etchant compositions according to Examples 1 to 10 and Comparative Examples 1 and 2 except for this.
평가 1 : 실리콘 질화막 및 실리콘 산화막의 Etch rate 측정Evaluation 1: Etch rate measurement of silicon nitride film and silicon oxide film
실시예 및 비교예에 따른 식각액 조성물을 250ml 비커에 200g이 되도록 제조하여 158 내지 160℃로 가열한 후 막 두께가 4500Å인 실리콘 질화막, 막 두께가 500Å 실리콘 산화막을 10분 동안 침지시켜 식각하였다. 식각 후 물로 25℃에서 1분 동안 린스 후 엘립소미터(Elipsometer)로 막 두께를 측정하여 Etch rate(Å/min)을 산출한 뒤, 아래와 같은 계산식으로 선택비(A)를 연산하여, 하기 표 3에 나타내었다.The etchant compositions according to Examples and Comparative Examples were prepared to be 200 g in a 250 ml beaker, heated to 158 to 160° C., and then etched by immersing a silicon nitride film having a film thickness of 4500 Å and a silicon oxide film having a film thickness of 500 동안 for 10 minutes. After etching, rinse for 1 minute at 25°C with water, measure the film thickness with an ellipsometer, calculate the etch rate (Å/min), and calculate the selection ratio (A) using the following calculation formula. It is shown in 3.
선택비 = 실리콘 질화막의 Etch rate/실리콘 산화막의 Etch rateSelectivity = Etch rate of silicon nitride film/Etch rate of silicon oxide film
평가 2 : 실리콘 질화막 및 실리콘 산화막의 Etch rate 측정Evaluation 2: Etch rate measurement of silicon nitride film and silicon oxide film
실시예 및 비교예에 따른 식각액 조성물을 250ml 비커에 200g이 되도록 제조하여 158 내지 160℃로 가열한 후 막 두께가 4500Å인 실리콘 질화막, 막 두께가 500Å 실리콘 산화막을 10분 동안 침지시켜 식각하였다. 이와 같은 방식으로 동일 약액에 실리콘 질화막과 실리콘 산화막 식각을 5회 반복 실시한 후, 기판을 물로 25℃에서 1분 동안 린스 후 엘립소미터로 막 두께를 측정하여 Etch rate(Å/min)을 산출한 뒤, 위의 평가 1과 동일한 계산식으로 선택비(B)를 연산하여, 하기 표 3에 나타내었다.The etchant compositions according to Examples and Comparative Examples were prepared to be 200 g in a 250 ml beaker, heated to 158 to 160° C., and then etched by immersing a silicon nitride film having a film thickness of 4500 Å and a silicon oxide film having a film thickness of 500 동안 for 10 minutes. In this way, after etching the silicon nitride film and the silicon oxide film 5 times in the same chemical solution, the substrate was rinsed at 25°C for 1 minute, and then the film thickness was measured with an ellipsometer to calculate the etch rate (rate/min). Subsequently, the selection ratio (B) was calculated using the same calculation formula as in Evaluation 1 above, and the results are shown in Table 3 below.
평가 3 : 실리콘 질화막 및 실리콘 산화막 처리 횟수에 따른 선택비 변화Evaluation 3: Selection ratio change according to the number of times of silicon nitride film and silicon oxide film treatment
평가 1 및 2에서 산출한 선택비(A) 및 선택비(B)를 이용하여, 아래와 같은 계산식으로 선택비 변화율을 산출한 뒤, 하기 표 3에 나타내었다.Using the selection ratio (A) and the selection ratio (B) calculated in the evaluations 1 and 2, the change ratio of the selection ratio was calculated by the following calculation formula, and then shown in Table 3 below.
선택비 변화율(%) = (B-A)/A x 100Selection ratio change rate (%) = (B-A)/A x 100
A : 1회째 실리콘 질화막과 실리콘 산화막의 식각 선택비A: Etch selectivity of the first silicon nitride film and silicon oxide film
B : 5회째 실리콘 질화막과 실리콘 산화막의 식각 선택비B: Etch selectivity of the fifth silicon nitride film and the silicon oxide film
평가 4 : 물에 대한 용해도 평가Evaluation 4: Evaluation of solubility in water
실시예 및 비교예에 따른 식각액 조성물을 물과 질량비 1:99로 혼합하여 25℃에서 1시간 방치 후 현탁 발생 및 입자 생성 여부를 관찰하였다.The etchant compositions according to Examples and Comparative Examples were mixed with water at a mass ratio of 1:99, and then allowed to stand at 25°C for 1 hour to observe suspension generation and particle generation.
◎ : 투명 상태 유지◎: Keep transparent
○ : 입자가 육안으로 관찰되지 않으나, 현탁 발생○: Particles are not observed with the naked eye, but suspension occurs.
△ : 입자가 육안으로 관찰되나, 침전이 일어나지 않고 현탁 상태로 유지△: Particles are observed with the naked eye, but do not precipitate and remain suspended
X : 입자가 육안으로 관찰되며, 침전 발생X: particles are observed with the naked eye, precipitation occurs
(Å/min)(Å/min)
(Å/min)(Å/min)
(A)Selection
(A)
(B)Selection
(B)
변화율 (%)Selection
Rate of change (%)
상기 표 3을 참조하면, 실시예에 따른 식각액 조성물을 사용하는 경우, 선택비 조절이 용이하며, 선택비 변화율이 낮아 처리 매수가 향상되고, 물에 대한 용해도가 우수하여 식각 후 린스 공정에서 입자가 발생 및 잔류하지 않음을 알 수 있다.Referring to Table 3, when using the etchant composition according to the embodiment, the selection ratio is easy to adjust, the selection ratio change rate is low, the number of treatments is improved, the solubility in water is excellent, the particles in the rinse process after etching It can be seen that it does not occur and does not remain.
반면, 비교예 1에 따른 식각액 조성물의 경우, 식각 처리 횟수를 5회까지 수행한 경우(평가 2), 실리콘 산화막의 Etch rate이 -0.03Å으로 측정되었다. 이는 실리콘 산화막 표면에 실리카가 흡착되어 막 두께가 초기보다 더 증가한다는 것을 의미하며, 처리 매수 측면에서 매우 좋지 않은 양상으로, 실리콘 산화막 표면에 입자 발생을 유발할 수 있음을 의미한다고 볼 수 있으며, 이로 인해 선택비 변화율이 매우 큰 것을 확인할 수 있다. 또한, 물에 대한 용해도가 낮아 육안으로 입자가 관찰되며 침전이 발생하고, 이는 식각 후 린스 공정에서 입자가 발생되어 및 기판 표면에 입자가 잔류(흡착)되는 문제를 유발할 수 있다고 볼 수 있다.On the other hand, in the case of the etching solution composition according to Comparative Example 1, when the number of etching treatments was performed up to 5 times (evaluation 2), the etching rate of the silicon oxide film was measured to be -0.03 Hz. This means that the silica is adsorbed on the surface of the silicon oxide film, which means that the film thickness is increased more than the initial one, and it is a very poor aspect in terms of the number of treatments. It can be seen that the selection ratio change rate is very large. In addition, since the solubility in water is low, particles are observed with the naked eye and precipitation occurs, which can be seen to cause particles to be generated in the rinsing process after etching and residual (adsorption) particles on the substrate surface.
비교예 2에 따른 식각액 조성물의 경우, 실리콘 질화막 및 실리콘 산화막에 대해 모두 식각 효과를 나타내어, 실리콘 산화막에 대한 보호 효과가 제공되지 않는 것을 확인 할 수 있으며, 이에 따라 선택비 또한 매우 낮은 것을 확인 할 수 있다. 또한 물에 대한 용해도가 낮아 육안으로 입자가 관찰되며 침전이 발생하는 것을 확인할 수 있다.In the case of the etchant composition according to Comparative Example 2, it was confirmed that both the silicon nitride film and the silicon oxide film exhibited an etch effect, so that a protective effect for the silicon oxide film was not provided, and accordingly, the selectivity was also very low. have. In addition, the solubility in water is low, and particles can be observed with the naked eye, and it can be confirmed that precipitation occurs.
Claims (6)
(A) A silicon nitride film etchant composition comprising phosphoric acid, (B) silicone resin, and (C) water.
상기 실리콘 레진은 하기 화학식 1 또는 2로 표시되는 화합물 1종 이상을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물:
[화학식 1]
상기 화학식 1에서,
R11 내지 R16은 각각 독립적으로 수소, 할로겐, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 4의 알콕시기 및 아세톡시기로 이루어진 군에서 선택되며, n은 1 내지 5의 정수이다.
[화학식 2]
상기 화학식 2에서,
R2는 수소, 할로겐, 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 4의 알콕시기 및 아세톡시기로 이루어진 군에서 선택되며,
R은 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기 및 탄소수 2 내지 10의 알키닐로 이루어진 군에서 선택되며,
X는 수소, 할로겐, 하이드록시기, 에테르기, 에스테르기, 아민기, 포스포네이트기, 포스페이트기, 설포네이트기 및 설페이트기로 이루어진 군에서 선택되는 작용기를 포함하며,
n은 1 내지 4의 정수이다.
The method according to claim 1,
The silicone resin is a silicon nitride film etchant composition, characterized in that it comprises at least one compound represented by the following formula (1) or (2):
[Formula 1]
In Chemical Formula 1,
R11 to R16 are each independently selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 4 carbon atoms and acetoxy group, n is an integer of 1 to 5.
[Formula 2]
In Chemical Formula 2,
R2 is selected from the group consisting of hydrogen, halogen, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 4 carbon atoms and acetoxy group,
R is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms,
X includes a functional group selected from the group consisting of hydrogen, halogen, hydroxy group, ether group, ester group, amine group, phosphonate group, phosphate group, sulfonate group and sulfate group,
n is an integer from 1 to 4.
상기 화학식 2에서, X는 하기 화학식 2-1 내지 2-9로 표시되는 화합물로 이루어진 군에서 선택되는 것을 특징으로 하는 실리콘 질화막 식각액 조성물:
[화학식 2-1]
[화학식 2-2]
[화학식 2-3]
[화학식 2-4]
[화학식 2-5]
[화학식 2-6]
[화학식 2-7]
[화학식 2-8]
[화학식 2-9]
상기 화학식 2-1 내지 2-9에서,
Rx는 각각 독립적으로 수소, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기, 탄소수 2 내지 10의 알키닐기 및 하이드록시기로 치환된 상기 알킬기, 상기 알케닐기, 상기 알키닐기로 이루어진 군에서 선택된다.
The method according to claim 2,
In Formula 2, X is a silicon nitride film etchant composition, characterized in that is selected from the group consisting of compounds represented by the following formulas 2-1 to 2-9:
[Formula 2-1]
[Formula 2-2]
[Formula 2-3]
[Formula 2-4]
[Formula 2-5]
[Formula 2-6]
[Formula 2-7]
[Formula 2-8]
[Formula 2-9]
In Chemical Formulas 2-1 to 2-9,
Rx is each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and the alkyl group substituted with a hydroxy group, the alkenyl group, and the alkynyl group do.
상기 식각액 조성물은 산화물막 및 질화물막을 포함하는 다층막에서, 상기 질화물막만을 선택적으로 식각하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물.
The method according to claim 1,
The etchant composition is a silicon nitride film etchant composition, characterized in that selectively etching only the nitride film in a multilayer film including an oxide film and a nitride film.
상기 산화물막은 SiO2을 포함하고,
상기 질화물막은 SiN을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물.
The method according to claim 4,
The oxide film includes SiO 2 ,
The nitride film is a silicon nitride film etchant composition comprising SiN.
조성물 총 중량에 대하여,
인산 60 내지 95 중량%;
실리콘 레진 0.001 내지 2.0 중량%; 및
물 잔량을 포함하는 것을 특징으로 하는 실리콘 질화막 식각액 조성물.
The method according to claim 1,
With respect to the total weight of the composition,
Phosphoric acid 60 to 95% by weight;
0.001 to 2.0% by weight of silicone resin; And
A silicon nitride film etchant composition comprising the remaining amount of water.
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| KR20180106144A (en) * | 2017-03-17 | 2018-10-01 | 동우 화인켐 주식회사 | Etchant composition for etching nitride layer and methods of forming nitride pattern |
| KR101769349B1 (en) | 2017-04-06 | 2017-08-18 | (주)제이씨아이 | A Composition for Wet Etching to Silicon Nitride |
| KR101828437B1 (en) * | 2017-04-06 | 2018-03-29 | 주식회사 디엔에스 | A Composition for Wet Etching to Silicon Nitride |
| KR102346832B1 (en) * | 2018-05-23 | 2022-01-03 | 삼성에스디아이 주식회사 | Etching composition for silicon nitride layer and etching process using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111471462B (en) | 2022-03-25 |
| SG10202000680TA (en) | 2020-08-28 |
| CN111471462A (en) | 2020-07-31 |
| KR102654224B1 (en) | 2024-04-04 |
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