KR101344541B1 - Composition of Selective Etching solutions For Silicon Oxide Film - Google Patents
Composition of Selective Etching solutions For Silicon Oxide Film Download PDFInfo
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- KR101344541B1 KR101344541B1 KR1020070010843A KR20070010843A KR101344541B1 KR 101344541 B1 KR101344541 B1 KR 101344541B1 KR 1020070010843 A KR1020070010843 A KR 1020070010843A KR 20070010843 A KR20070010843 A KR 20070010843A KR 101344541 B1 KR101344541 B1 KR 101344541B1
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- Prior art keywords
- etching
- acid
- oxide film
- silicon oxide
- composition
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- 238000005530 etching Methods 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims abstract description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001039 wet etching Methods 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
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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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- C11D2111/22—
Abstract
본 발명은 반도체 제조 공정에 있어서, 웨이퍼 상에 실리콘 산화막과 질화막 또는 티탄나이트라이드막이 동시에 노출되는 경우에 실리콘 산화막을 선택적으로 에칭하는 조성물로서, 조성물 총 중량에 대하여, 불화암모늄(NH4F) 1 내지 40중량%, 불산을 제외한 무기산 1 내지 20중량%, 및 잔량의 물을 포함하는 에칭액 조성물에 관한 것이다.The present invention provides a composition for selectively etching a silicon oxide film when a silicon oxide film and a nitride film or a titanium nitride film are simultaneously exposed on a wafer in a semiconductor manufacturing process, wherein the composition is ammonium fluoride (NH 4 F) 1. It is related with the etching liquid composition containing 40 to 40 weight%, 1 to 20 weight% of inorganic acids except hydrofluoric acid, and remainder of water.
불화암모늄, 에칭액, 식각, 무기산, 실리콘 산화막 Ammonium fluoride, etching solution, etching, inorganic acid, silicon oxide film
Description
본 발명은 반도체 제조 공정에 있어서, 웨이퍼 상에 실리콘 산화막과 질화막 또는 티탄나이트라이드막이 동시에 노출되는 경우에 실리콘 산화막을 선택적으로 에칭하는 조성물에 관한 것이다.The present invention relates to a composition for selectively etching a silicon oxide film when a silicon oxide film and a nitride film or a titanium nitride film are simultaneously exposed on a wafer in a semiconductor manufacturing process.
반도체 소자 제조 공정은 증착 공정, 사진공정, 식각 공정 및 이온주입 공정 등의 일련의 공정들을 수행하여 이루어지며, 이들 공정을 통하여 웨이퍼 위에 산화막, 질화막, 폴리실리콘막, 금속막 등 다양한 막들을 형성하고, 이들 막을 원하는 형상으로 패터닝하여 원하는 소자들을 완성한다. 반도체 소자 제조 공정 중 원하는 막을 선택적으로 습식 식각 하기 위해서는 식각 대상 막질을 높은 식각 선택비로 제거할 수 있는 식각액이 요구된다.The semiconductor device manufacturing process is performed by performing a series of processes such as a deposition process, a photo process, an etching process, and an ion implantation process. Through these processes, various films such as an oxide film, a nitride film, a polysilicon film, and a metal film are formed on a wafer. These films are then patterned into the desired shape to complete the desired devices. In order to selectively wet-etch a desired film during a semiconductor device manufacturing process, an etching solution capable of removing an etching target film quality with a high etching selectivity is required.
이러한 실리콘 산화막의 에칭액 조성물로는 지금까지는 BOE(buffered oxide etchant) 식각액이 주로 사용되어 왔으나, BOE의 경우는 불산(HF)과 불화암모 늄(NH4F) 및 물로 구성이 되어 있어 불산으로 인해 취급상 위험할 뿐 아니라, 실리콘 산화막과 함께 노출되어 있는 질화막 등에 대한 식각 선택비도 낮은 것이 문제점으로 인식되고 있다.BOE (buffered oxide etchant) etchant has been mainly used as an etching solution composition of the silicon oxide film, but BOE is treated with hydrofluoric acid (HF), ammonium fluoride (NH 4 F), and water. Not only is it dangerous, but a low etching selectivity for the nitride film exposed together with the silicon oxide film is recognized as a problem.
따라서, 산화막을 습식 식각 방법으로 제거하는데 있어서 보다 취급이 용이하고, 동시에 외부로 드러날 수 있는 다른 막질에 대한 에칭 선택비가 높은 새로운 식각액 조성물의 개발이 요구된다.Accordingly, there is a need for the development of a new etching liquid composition which is easier to handle and at the same time has a high etching selectivity to other films that may be exposed to the outside in the wet etching method.
본 발명은 상기에서 언급한 종래기술의 문제점을 해결함으로써 반도체 디바이스 가공에 있어서 실리콘 산화막의 습식 에칭에 유용한 에칭액을 제공하는 것을 목적으로 한다. 보다 구체적으로, 본 발명은 취급 및 사용상 안전하고, 산화막에 대한 식각 속도를 조절하여 적절한 공정 조건을 유지할 수 있으며, 식각시 산화막과 동시에 드러나는 다른 막질에 대한 식각 선택비가 높은 에칭액을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an etching solution useful for the wet etching of a silicon oxide film in semiconductor device processing by solving the above-mentioned problems of the prior art. More specifically, an object of the present invention is to provide an etching solution that is safe in handling and use, maintains an appropriate process condition by adjusting an etching rate with respect to an oxide film, and has a high etching selectivity for other films that are simultaneously exposed to the oxide film during etching. do.
본 발명은 반도체 제조 공정에 있어서, 웨이퍼 상에 실리콘 산화막과 질화막 또는 티탄나이트라이드막이 동시에 노출되는 경우에 실리콘 산화막을 선택적으로 에칭하는 조성물로서, 조성물 총 중량에 대하여, 불화암모늄(NH4F) 1 내지 40중량%, 불산을 제외한 무기산 1 내지 20중량%, 및 잔량의 물을 포함하는 에칭액 조성물에 관한 것이다.The present invention provides a composition for selectively etching a silicon oxide film when a silicon oxide film and a nitride film or a titanium nitride film are simultaneously exposed on a wafer in a semiconductor manufacturing process, wherein the composition is ammonium fluoride (NH 4 F) 1. It is related with the etching liquid composition containing 40 to 40 weight%, 1 to 20 weight% of inorganic acids except hydrofluoric acid, and remainder of water.
본 발명의 에칭액 조성물은 불화암모늄 5 내지 30중량%, 불산을 제외한 무기산 1 내지 15중량%, 및 잔량의 물을 포함하는 것이 더욱 바람직하다.It is more preferable that the etching liquid composition of this invention contains 5-30 weight% of ammonium fluorides, 1-15 weight% of inorganic acids except hydrofluoric acid, and remainder of water.
본 발명의 에칭액 조성물은 상기의 성분 외에, 용도에 따라, 계면활성제 또는 유기 용제를 추가로 더 포함할 수 있다.In addition to the above components, the etching solution composition of the present invention may further include a surfactant or an organic solvent, depending on the use.
본 발명의 에칭액 조성물은 기존의 산화막 에칭액과 달리 불산(HF)을 사용하지 않기 때문에 취급 및 사용상 안전할 뿐 아니라, 무기산의 농도를 조절함으로써 산화막에 대한 식각 속도를 조절하여 적절한 공정 조건을 유지할 수 있으며, 실리콘 산화막과 함께 노출되어 있는 티탄나이트라이드, 질화막 등에 대한 식각 선택비가 높아서 그러한 막에 대한 식각 손실을 줄일 수 있는 특징을 갖는다.Unlike the conventional oxide etching solution, the etching solution composition of the present invention does not use hydrofluoric acid (HF), and therefore is safe in handling and use, and by controlling the concentration of the inorganic acid, the etching rate for the oxide film can be adjusted to maintain appropriate process conditions. In addition, the etching selectivity of titanium nitride, nitride, and the like exposed together with the silicon oxide film is high, so that the etching loss of the film is reduced.
본 발명의 에칭액 조성물의 주성분인 불화암모늄은 실리콘 산화막을 식각할 수 있는 불소이온을 제공하며, 조성물 총 중량에 대하여, 1 내지 40중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 5 내지 30중량%로 포함되는 것이 좋다. 조성물에 포함되는 함량이 1중량% 미만일 경우, 공정에 맞는 식각 속도나 처리매수를 제공하지 못하며, 40중량%를 초과할 경우, 석출되는 문제가 발생한다.Ammonium fluoride, which is a main component of the etching solution composition of the present invention, provides fluorine ions capable of etching the silicon oxide film, and is preferably contained in an amount of 1 to 40% by weight, and more preferably 5 to 30% by weight, based on the total weight of the composition. It is good to be included in%. If the content is less than 1% by weight, the process does not provide an etching rate or the number of treatments for the process, if more than 40% by weight, the problem of precipitation occurs.
본 발명의 에칭액 조성물에 사용되는 무기산은 예를 들면, 인산, 염산, 질 산, 황산, 붕불화수소산, 과염소산, 요오드산, 브롬산 등을 들 수 있으며, 이들은 1종 단독 또는 2종 이상을 혼합하여 사용할 수 있다.Examples of the inorganic acid used in the etching solution composition of the present invention include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, perchloric acid, iodide, bromic acid, and the like. Can be used.
본 발명의 에칭액 조성물에서 무기산은 조성물 총 중량에 대하여, 1 내지 20 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 1 내지 15중량%로 포함되는 것이 좋다. 무기산이 1중량% 미만으로 포함되면 공정에 적합한 산화막 식각속도를 제공하지 못하며, 20중량%를 초과하면 질화막 등에 대한 식각 손실이 크게 발생하게 된다.In the etching solution composition of the present invention, the inorganic acid is preferably included in an amount of 1 to 20% by weight, and more preferably 1 to 15% by weight, based on the total weight of the composition. If the inorganic acid is included in less than 1% by weight does not provide a suitable oxide etching rate for the process, more than 20% by weight will cause a large etching loss for the nitride film.
본 발명에서 사용되는 불화암모늄, 각종 무기산 등은 통상적으로 공지된 방법에 따라 제조하는 것이 가능하며, 특히 반도체 공정용 순도를 가지는 것이 바람직하다.Ammonium fluoride used in the present invention, Various inorganic acids and the like can be produced by a conventionally known method, and it is particularly preferable to have a purity for semiconductor processing.
본 발명의 에칭액 조성물은 특히, 미세패턴용 식각액이나 낮은 표면장력을 요구하는 공정에 적용할 경우 등 용도에 따라 계면활성제가 0.001중량% 내지 1중량%까지 함유될 수 있으며, 용액내에서 계면활성제의 용해도가 떨어질 경우, 유기용제 1 내지 30중량%가 함유될 수 있다. The etching liquid composition of the present invention may contain from 0.001% to 1% by weight of the surfactant, depending on the application, especially when applied to an etching solution for a fine pattern or a process requiring low surface tension. When the solubility is lowered, it may contain 1 to 30% by weight of the organic solvent.
본 발명의 에칭액 조성물에 계면활성제를 첨가하면 미세패턴의 식각에 유리하며, 반도체의 수율 향상을 기대할 수도 있다. 상기 계면활성제로는 표면장력 개선에 유리한 불소계 비이온성 또는 음이온성 계면활성제 사용하는 것이 유리하다.When surfactant is added to the etching liquid composition of this invention, it is advantageous for the etching of a micropattern, and can also expect the yield improvement of a semiconductor. As the surfactant, it is advantageous to use a fluorine-based nonionic or anionic surfactant, which is advantageous for improving surface tension.
상기 유기용제의 경우 수용액에 잘 혼합되는 것이 선정될 수 있으나, 반드시 이들에 한정되는 것은 아니다. 유기용제의 바람직한 예로는 디메틸설프옥사이드, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노부틸에테르, N-메틸피롤리돈, 에탄올, 메탄올, 이소프로필알콜, 설포란, 테트라히드로푸란, 아세트알데히드 등을 들 수 있으며, 이들은 1종 단독 또는 2종 이상을 혼합하여 사용할 수 있다.In the case of the organic solvent may be selected to be well mixed in an aqueous solution, but is not necessarily limited to these. Preferred examples of the organic solvent include dimethyl sulfoxide, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, N-methylpyrrolidone, ethanol, methanol, isopropyl alcohol, sulfolane, tetrahydrofuran, acetaldehyde and the like. These can be used individually by 1 type or in mixture of 2 or more types.
이하, 본 발명을 실시예 및 시험예를 통하여 보다 상세하게 설명한다. 그러나 본 발명의 범위가 하기의 실시예에 의해서 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail through Examples and Test Examples. However, the scope of the present invention is not limited by the following examples.
실시예Example 1 내지 6 및 1 to 6 and 비교예Comparative Example 1 내지 3 : 에칭액 조성물 제조 1 to 3: etching solution composition preparation
불화암모늄, 질산, 계면활성제 및 잔량의 물을 하기 표 1에 나타낸 조성비로 혼합하여 실시예 1 내지 6 및 비교예 1 내지 3의 에칭액 조성물을 제조하였다.Ammonium fluoride, nitric acid, a surfactant, and the residual amount of water were mixed at the composition ratios shown in Table 1 to prepare the etching solution compositions of Examples 1 to 6 and Comparative Examples 1 to 3.
시험예Test Example ..
반도체 웨이퍼(Si)위에 13,000옹스트롱의 두께로 증착된 실리콘 산화막(PE TEOS)과 700옹스트롱 두께의 질화막(Si3N4)이 형성된 웨이퍼를 준비한 후, 이 웨이퍼를 실시예 1 내지 6 및 비교예 1 내지 3의 에칭용액에 23~26℃의 상온에서 10분간 침적시켜 식각한 후 탈이온수로 세정하고, 건조하여 막두께 측정장비(필름메트릭스)를 이용하여 각각에 대한 식각 속도를 측정하였고, 그 결과를 표1에 나타내었 다.After preparing a wafer on which a silicon oxide film (PE TEOS) deposited at a thickness of 13,000 angstroms and a nitride film (Si 3 N 4 ) having a thickness of 700 angstroms (Si 3 N 4 ) were prepared on a semiconductor wafer (Si), the wafers were compared with Examples 1 to 6 and compared. After etching for 10 minutes in the etching solution of Examples 1 to 3 at room temperature of 23 ~ 26 ℃, washed with deionized water, dried and measured the etch rate for each using a film thickness measurement equipment (film metrics), The results are shown in Table 1.
(PE TEOS) (Å/min)Oxide Etch Rate A
(PE TEOS) (Å / min)
(Å/min)Nitride Film (Si 3 N 4 ) Etching Speed B
(Å / min)
(A:B)Etch selectivity
(A: B)
상기의 시험결과 표 1에 나타낸 바와 같이, 본 발명의 에칭액 조성물인 실시예 1 내지 6의 에칭액 조성물은 불화암모늄과 질산의 함량에 따라 산화막 및 질화막의 식각 속도를 조절하는 것이 가능하며, 산화막의 식각 속도에 비해 질화막의 식각 속도가 현저하게 낮은 100:1 이상의 좋은 식각 선택비를 나타냄을 확인하였다. 그러나, 무기산을 넣지 않고 불화암모늄만을 넣은 비교예 1의 에칭액의 경우는 산화막이 거의 에칭되지 않아 공정 적용에 부적합함을 확인할 수 있었으며, 질산의 함량이 20중량%를 초과하는 비교예 2 및 3의 에칭액의 경우는 질화막의 식각 속도가 상대적으로 빨라져 목적하는 식각 선택비가 얻어지지 않음을 확인하였다. As shown in Table 1 above, the etching solution composition of Examples 1 to 6, which is the etching solution composition of the present invention, can control the etching rate of the oxide film and the nitride film according to the content of ammonium fluoride and nitric acid, and the etching of the oxide film. It was confirmed that the etching rate of the nitride film was significantly lower than that of the good etching selectivity of 100: 1 or more. However, in the case of the etching solution of Comparative Example 1 in which only the ammonium fluoride was added without the inorganic acid, the oxide film was hardly etched, and thus, it was confirmed that the etching solution was not suitable for the application of the process. In the case of the etching solution, it was confirmed that the etching rate of the nitride film was relatively fast, so that the desired etching selectivity was not obtained.
본 발명에 따른 식각 용액을 사용하면, 불산(HF)을 사용하지 않기 때문에 취급 및 사용상 안전할 뿐 아니라, 무기산의 농도를 조절하여 산화막에 대한 식각 속 도를 조절하여 적절한 공정 조건을 유지할 수 있으며, 질화막과 같은 막에는 식각 손실을 줄일 수 있는 효과를 얻을 수 있다. 또한 계면활성제를 첨가하는 경우는 미세패턴에 적용할 수 있을 뿐 아니라, 반도체의 수율 향상 효과를 얻을 수 있다.By using the etching solution according to the present invention, since hydrofluoric acid (HF) is not used, it is not only safe to handle and use, but also to control the concentration of the inorganic acid to control the etching rate of the oxide film to maintain appropriate process conditions. In a film such as a nitride film, an effect of reducing etching loss can be obtained. In addition, when the surfactant is added, not only can be applied to the fine pattern, but also the yield improvement effect of the semiconductor can be obtained.
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