KR20190080289A - Silicon nitride film etching method and manufacturing method of semiconductor device using the same - Google Patents
Silicon nitride film etching method and manufacturing method of semiconductor device using the same Download PDFInfo
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- KR20190080289A KR20190080289A KR1020170182660A KR20170182660A KR20190080289A KR 20190080289 A KR20190080289 A KR 20190080289A KR 1020170182660 A KR1020170182660 A KR 1020170182660A KR 20170182660 A KR20170182660 A KR 20170182660A KR 20190080289 A KR20190080289 A KR 20190080289A
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- etching
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- silicon nitride
- phosphoric acid
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- 238000005530 etching Methods 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 41
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000009835 boiling Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000004767 nitrides Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000126 substance Substances 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
-
- 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
- H01L21/31—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
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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
- H01L21/31—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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
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- Weting (AREA)
Abstract
Description
본 발명은 실리콘 질화막 식각방법 및 이를 이용한 반도체 소자의 제조 방법에 관한 것이며, 보다 상세하게는 인산 및 C1~C5의 알칸올을 포함하는 식각 조성물을 이용하여 빠른 시간내에 적은 에너지를 이용해 효율적으로 식각할 수 있는 실리콘 질화막 식각방법에 관한 것이다.The present invention relates to a silicon nitride film etching method and a method of manufacturing a semiconductor device using the same, and more particularly, to a method of manufacturing a silicon nitride film using an etching composition containing phosphoric acid and a C 1 to C 5 alkanol, And more particularly, to a silicon nitride film etching method capable of etching.
반도체 제조 공정에 있어서, 실리콘 산화막(SiO2) 등의 산화막 및 실리콘 질화막(SiNx) 등의 질화막은 대표적인 절연막으로 각각 단독으로, 또는 1층 이상의 막들이 교대로 적층되어 사용된다. 상기 실리콘 질화막은 실리콘 산화막, 폴리 실리콘막, 실리콘 웨이퍼 표면 등과 접촉하는 구조로CVD (Chemical vapor deposition) 공정을 통해서 증착되며, 이는 건식 식각 및 습식 식각을 통해서 제거되는데, 인산(phosphoric acid)을 이용한 습식 식각이 널리 이용되고 있다. In the semiconductor manufacturing process, an oxide film such as a silicon oxide film (SiO 2 ) and a nitride film such as a silicon nitride film (SiN x ) are used as representative insulating films, respectively, or one or more films are alternately laminated. The silicon nitride film is deposited through a CVD (Chemical Vapor Deposition) process in a structure in contact with a silicon oxide film, a polysilicon film, or a silicon wafer surface. The silicon nitride film is removed by dry etching and wet etching. Etching is widely used.
상기 실리콘 질화막을 제거하기 위한 습식 식각 공정에서는 일반적으로 인산과 탈이온수(deionized water)의 혼합물이 사용되고 있다. 상기 탈이온수는 식각율 감소 및 산화막에 대한 식각 선택성의 변화를 방지하기 위하여 첨가되는 것이나, 공급되는 탈이온수의 양의 미세한 변화에도 질화막 식각 제거 공정에 불량이 발생하는 문제가 있다. 또한, 인산은 강산으로서 부식성을 가지고 있어 취급에 어려움이 있다.In the wet etching process for removing the silicon nitride film, a mixture of phosphoric acid and deionized water is generally used. The deionized water is added in order to prevent the decrease of the etching rate and the change of the etching selectivity to the oxide film, but there is also a problem that the nitriding film etching process is defective even when the amount of the supplied deionized water is changed. In addition, phosphoric acid is corrosive as a strong acid, which makes handling difficult.
대한민국 등록특허 제1623654호(플라즈마 가스를 사용한 실리콘 기판 식각방법)은 실리콘 기판의 원하는 부분을 식각하는 실리콘 기판 식각방법에 있어서, 실리콘 기판 상에 식각 마스크를 형성하는 단계; 할로겐 기초가스, 불화탄소 가스 및 산소를 포함하는 제1 가스를 준비하는 단계; 및 상기 제1 가스를 상기 기판 상에 플라즈마 처리하여 상기 기판을 식각하는 단계를 포함한 실리콘 기판의 식각방법에 대하여 개시하고 있다.Korean Patent No. 1623654 (method of etching silicon substrate using plasma gas) is a method of etching a desired portion of a silicon substrate, comprising the steps of: forming an etching mask on a silicon substrate; Preparing a first gas comprising a halogen-based gas, a fluorocarbon gas, and oxygen; And etching the substrate by plasma-treating the first gas on the substrate.
대한민국 등록특허 제1576286호(실리콘 웨이퍼의 이방성 식각방법 및 그 장치)은 수용성 암모니아계 용액 및 첨가제를 포함하는 것을 특징으로 하는 실리콘 웨이퍼의 이방성 식각액, 식각방법 및 장치에 관한 것으로 수용성 암모니아계 용액 및 첨가제를 포함하는 식각액을 제조하여 식각 장치에 투입하는 단계; 상기 식각 장치에 실리콘 웨이퍼를 그 피식각면이 상부를 향하도록 로딩하여 상기 식각액에 침지시키는 단계; 회전식 교반기를 피식각면과 근접하게 이격되도록 상기 식각 장치의 위쪽으로부터 상기 식각액에 침지시키는 단계; 및 상기 회전식 교반기를 작동시켜 상기 식각액의 흐름이 피식각면과 평행을 이루도록 교반하는 단계를 포함하고, 상기 첨가제는 피라진(pyrazin), AP(ammonium persulfate) 또는 AHS(ammonium hydrogen sulfate)인 것을 특징으로 하는 실리콘 웨이퍼의 이방성 식각방법에 대하여 개시하고 있다.Korean Patent No. 1576286 (an anisotropic etching method and apparatus for a silicon wafer) is characterized by including a water-soluble ammonia-based solution and an additive. The present invention relates to an anisotropic etching solution, an etching method and an apparatus for a silicon wafer, And then introducing the etchant into the etching apparatus; Loading the silicon wafer on the etch apparatus such that the corrugated surface faces upward, and dipping the silicon wafer in the etchant; Immersing the rotary stirrer in the etchant from above the etch apparatus such that the rotary agitator is spaced apart from the etching facet; And agitating the rotary agitator so that the flow of the etchant is in parallel with the corrugated surface, wherein the additive is pyrazin, ammonium persulfate (AP), or ammonium hydrogen sulfate (AHS) Discloses an anisotropic etching method of a silicon wafer.
본 발명은 고온에서 수행되는 식각 공정에서 빠른 시간내에 적은 에너지를 이용해 효율적으로 식각하며, 식각 공정 동안 실리콘 질화막/산화막의 선택비가 저하되지 않는 실리콘 질화막 식각방법을 제공하고자 한다.The present invention provides a method of etching a silicon nitride film that efficiently etches using a small amount of energy in an etching process performed at a high temperature, and does not lower the selectivity of the silicon nitride / oxide film during the etching process.
본 발명은 상기 식각방법에 이용되는 식각 조성물을 제공하고자 한다.The present invention seeks to provide an etching composition for use in the etching method.
본 발명은 상기 식각방법을 이용한 반도체 소자의 제조방법을 제공하고자 한다.The present invention provides a method of manufacturing a semiconductor device using the etching method.
본 발명은 a) 인산 80 내지 85 중량% 및 C1~C5의 알칸올 10,000 내지 1,000,000 ppm을 포함하는 식각 조성물을 준비하는 단계; b) 상기 식각 조성물을 110℃ 내지 200℃으로 가열하는 단계; 및 c) 상기 가열된 식각 조성물이 실리콘 질화막을 식각하는 단계를 포함하는, 실리콘 질화막 식각방법을 제공한다.The present invention provides a process for preparing an etching composition comprising: a) preparing an etching composition comprising 80 to 85% by weight of phosphoric acid and 10,000 to 1,000,000 ppm of an alkanol of C 1 to C 5 ; b) heating the etch composition to a temperature of from 110 캜 to 200 캜; And c) etching the silicon nitride film by the heated etching composition.
본 발명은 상기 식각방법에 이용되는 식각 조성물을 제공한다.The present invention provides an etching composition used in the etching method.
본 발명은 상기 식각방법을 이용한 반도체 소자의 제조방법을 제공한다.The present invention provides a method of manufacturing a semiconductor device using the etching method.
본 발명은 인산 및 C1~C5의 알칸올을 포함하는 식각 조성물을 가열하여 인산의 농도를 쉽게 높이는 방법 및 상기 가열된 식각 조성물을 이용하여 실리콘 질화막을 식각하는 질화막 식각 방법을 제공함으로써, 빠른 시간내에 적은 에너지를 이용해 효율적으로 공정을 진행할 수 있게 한다. The present invention provides a method of easily increasing the concentration of phosphoric acid by heating an etching composition containing phosphoric acid and a C 1 to C 5 alkanol and a nitriding film etching method of etching a silicon nitride film using the heated etching composition, The process can be efficiently carried out using less energy in a short period of time.
또한 본 발명은 상기 실리콘 질화막 식각방법을 제공함으로써, 고온에서 수행되는 식각 공정에서도 식각 속도가 안정적으로 유지되고 질화막/산화막 선택비가 높고, 질화막의 빠른 식각과 산화막의 식각 억제 효율이 뛰어난 실리콘 질화막 식각방법을 제공한다.The present invention also provides a silicon nitride film etching method which is capable of stably maintaining the etching rate at a high temperature, high selectivity of the nitride film / oxide film, high etching rate of the nitride film, and excellent etching- .
현재 상업적으로 통용되는 고농도 인산 수용액 내 인산의 농도는 85%로, 반도체 제조공정에서는 보다 높은 실리콘 질화막/산화막의 선택비를 얻기 위해, 인산 수용액을 일정시간 가열하여 인산의 농도를 89 내지 93%로 만든 후 식각 공정을 진행한다.The concentration of phosphoric acid in commercially available high concentration aqueous phosphoric acid solution is 85%. In order to obtain a higher selectivity ratio of silicon nitride film / oxide film in the semiconductor manufacturing process, the aqueous phosphoric acid solution is heated for a predetermined time to adjust the concentration of phosphoric acid to 89 to 93% After etching, the etching process is carried out.
이때 대용량의 인산을 가열만으로 원하는 농도로 만들기 위해서는 매우 많은 열과 에너지가 필요하고, 장시간이 소요되어 매우 비효율적이다. At this time, it takes a lot of heat and energy to make a large amount of phosphoric acid to a desired concentration only by heating, and it takes a long time and is very inefficient.
따라서, 이러한 문제점을 극복하여 실리콘 산화막에 대해 실리콘 질화막을 선택적으로 식각하면서도, 빠른 시간내에 적은 에너지를 이용해 효율적으로 식각 할 수 있는 새로운 식각방법의 개발이 요구되고 있다.Therefore, there is a need to develop a new etching method capable of efficiently etching a silicon nitride film by using a small amount of energy while selectively etching a silicon nitride film on the silicon oxide film.
본 발명에서는 '함께 끓는 혼합물'에 관한 물리적인 특성을 식각 조성물에 적용한 것이 특징인데, 2성분 이상의 혼합액에 평형한 증기의 조성이 액의 조성과 같을 때 그 액을 '함께 끓는 혼합물'[-混合物, constant boiling mixture, azeotropic mixture]이라 하며, 대상이 되는 혼합액의 조성을 함께 끓는 혼합물의 조성에 가까운 범위에서 여러 가지로 변화시켜 일정 압력의 기체-액체 평형 관계를 측정해 보면 함께 끓는 혼합물의 끓는점이 극대 또는 극소를 취하는 것을 알 수 있다. 끓는점이 극대로 될 경우를 최고 끓는점 함께 끓는 혼합물이라 하는데 질산-물의 2성분계 등의 예는 잘 알려져 있다. 또한 끓는점이 극소가 되는 경우는 최저 끓는점 함께 끓는 혼합물이라 하는데 에탄올-물계 등 대단히 많은 예가 알려져 있다. The present invention is characterized in that the physical properties of the 'boiling mixture' are applied to the etching composition. When the composition of the vapor equilibrated to the mixture of two or more components is equal to the composition of the solution, the solution is called a 'boiling mixture' , the constant boiling mixture, and the azeotropic mixture], and the gas-liquid equilibrium relationship at a constant pressure is measured by varying the composition of the target mixture in various ranges close to the composition of the boiling mixture. When the boiling point of the boiling mixture is maximized Or to take a minimum. When the boiling point is maximized, it is the boiling mixture with the highest boiling point. Examples of the two-component system of nitric acid-water are well known. In addition, when the boiling point becomes the minimum, the boiling mixture with the lowest boiling point is called an ethanol-water system.
본 발명의 발명자는 이러한 함께 끓는 혼합물의 원리를 이용한 실리콘 질화막의 효율적인 식각방법을 연구하였고, 인산과 C1~C5의 알칸올을 포함하고, 각 성분의 최적의 조합을 적용한 본 발명을 완성하였다. The inventors of the present invention have studied a method of efficiently etching a silicon nitride film using the principle of this boiling mixture and have completed the present invention in which an optimal combination of phosphoric acid and C 1 to C 5 alkanols is applied .
이하, 본 발명에 대하여 상세하게 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현 가능하다.The present invention is not limited to the embodiments described below, but can be embodied in various other forms.
아래 열거된 정의는 본 발명을 기술하기 위해 사용된 다양한 용어들의 정의이다. 이들 정의는 달리 제한되지 않는 한, 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다.The definitions listed below are definitions of various terms used to describe the present invention. These definitions are used to describe only specific embodiments, unless otherwise limited, and are not intended to limit the invention.
본 발명에서의 용어 “알칸올”은 특별한 언급이 없는 한 탄소수 1 내지 5개의 직쇄 또는 측쇄의 알킬기로 치환된 알코올을 가리킨다. 예를 들면 메탄올, 에탄올, 프로판-1-올, 부탄-2-올 등이 있으나, 이에 한정되지 않는다.The term " alkanol " in the present invention refers to an alcohol substituted with a linear or branched alkyl group having 1 to 5 carbon atoms unless otherwise specified. For example, methanol, ethanol, propan-1-ol, butan-2-ol, and the like, but are not limited thereto.
본 발명은 The present invention
a) 인산 80 내지 85 중량% 및 C1~C5의 알칸올 10,000 내지 1,000,000 ppm을 포함하는 식각 조성물을 준비하는 단계;a) preparing an etching composition comprising 80 to 85% by weight of phosphoric acid and 10,000 to 1,000,000 ppm of an alkanol of C 1 to C 5 ;
b) 상기 식각 조성물을 110℃ 내지 200℃으로 가열하는 단계; 및b) heating the etch composition to a temperature of from 110 캜 to 200 캜; And
c) 상기 가열된 식각 조성물이 실리콘 질화막을 식각하는 단계를 포함하는, 실리콘 질화막 식각방법을 제공한다.c) etching the silicon nitride film by the heated etching composition.
인산 및 C1~C5의 알칸올을 포함하는 식각 조성물을 제조한 후, 이를 가열하면 보다 빠른 시간에 원하는 인산의 농도에 도달한다. 또한 C1~C5의 알칸올을 포함하는 식각 조성물을 이용하여 식각을 진행하는 경우, 식각 조성물 내의 알칸올의 농도가 증가할수록 실리콘 산화막의 식각 속도가 감소하는데, 이는 알칸올이 실리콘 산화막의 보호에 기여하기 때문이다.After the etching composition comprising phosphoric acid and a C 1 to C 5 alkanol is prepared, it is heated to reach the desired phosphoric acid concentration more rapidly. Also, when the etching is carried out using the etching composition containing C 1 to C 5 alkanol, the etching rate of the silicon oxide film decreases as the concentration of the alkanol in the etching composition increases, .
따라서 인산 및 알칸올의 최적의 농도를 이용하여 실리콘 질화막의 식각을 진행하면, 높은 실리콘 질화막/산화막의 선택비를 가지는 동시에, 빠른 시간내에 적은 에너지를 이용해 실리콘 질화막을 효율적으로 식각할 수 있다.Therefore, when the silicon nitride film is etched using the optimum concentration of phosphoric acid and alkanol, the silicon nitride film can be efficiently etched by using a high selectivity of silicon nitride film / oxide film and using less energy in a short time.
본 발명의 일 구현예에 따르면, 상기 a) 단계의 식각 조성물은 인산을 80 내지 85 중량%, 더욱 바람직하게는 상기 인산을 83 내지 85 중량% 포함할 수 있다. According to an embodiment of the present invention, the etching composition of step a) may contain 80 to 85% by weight of phosphoric acid, and more preferably 83 to 85% by weight of phosphoric acid.
상기 식각 조성물 내 인산을 80 중량% 미만으로 포함하는 경우, 이물질이 발생하거나 실리콘 질화막 식각 속도가 저하되어 질화막이 용이하게 제거되지 않을 우려가 있으며, 인산을 85 중량%를 초과하여 포함하는 경우, 점도 등에 영향을 끼치며, 본 발명에 의한 에너지 절약 등의 효과가 미미하다.When the etching composition contains phosphoric acid in an amount of less than 80% by weight, there is a fear that a foreign substance is generated or the etching rate of the silicon nitride film is lowered and the nitrided film is not easily removed. In the case of containing more than 85% by weight of phosphoric acid, And the effect of energy saving and the like according to the present invention is insignificant.
본 발명의 바람직한 구현예에 따르면, 상기 a) 단계의 식각 조성물은 상기 식각 조성물 전체에 대하여, 상기 C1~C5의 알칸올을 10,000 내지 1,000,000 ppm, 바람직하게는 20,000 내지 80,000 ppm, 보다 바람직하게는 30,000 내지 60,000 ppm 으로 포함할 수 있다.According to a preferred embodiment of the present invention, the etching composition of step a) comprises, in the range of 10,000 to 1,000,000 ppm, preferably 20,000 to 80,000 ppm, of the C 1 to C 5 alkanol, Can be included in the range of 30,000 to 60,000 ppm.
상기 C1~C5의 알칸올의 함량이 10,000ppm 미만인 경우, 실리콘 질화막 식각 과정에서 C1~C5의 알칸올이 실리콘 산화막을 보호하는 효과가 미미할 수 있고, 1,000,000 ppm을 초과하여 투입되는 경우, 인산의 농도가 상대적으로 부족하여 실리콘 질화막이 효율적으로 식각되지 않을 우려가 있다.When the content of C 1 to C 5 alkanol is less than 10,000 ppm, the C 1 to C 5 alkanol may have little effect on protecting the silicon oxide film during the silicon nitride film etching process, and when the content is more than 1,000,000 ppm , There is a fear that the concentration of phosphoric acid is relatively insufficient and the silicon nitride film is not efficiently etched.
따라서, 본 발명에 따른 중량%와 ppm 범위로 인산 및 C1~C5의 알칸올을 포함하는 식각 조성물을 이용하면 알칸올이 실리콘 산화막을 보호하는 효과가 충분하여, 빠른 시간내에 적은 에너지를 이용해 실리콘 질화막을 효율적으로 식각할 수 있다.Therefore, the use of the etching composition containing phosphoric acid and C 1 to C 5 alkanol in the range of weight% and ppm according to the present invention is sufficient for the alkanol to protect the silicon oxide film, The silicon nitride film can be efficiently etched.
또한 본 발명에 따른 실리콘 질화막 식각방법을 이용하는 경우, 반도체 공정시 적정 수준의 안정성을 유지하면서도 높은 실리콘 산화막/질화막 선택비 및 향상된 실리콘 질화막 식각 속도를 구현할 수 있어 안정적인 식각 공정이 가능하다.Further, when the silicon nitride film etching method according to the present invention is used, it is possible to realize a high silicon oxide / nitride film selectivity and an improved silicon nitride film etching rate while maintaining an appropriate level of stability in a semiconductor process, thereby enabling a stable etching process.
본 발명의 일 구현예에 따르면, 상기 b) 단계의 식각 조성물의 가열 온도는 110℃ 내지 200℃, 바람직하게는 160℃ 내지 180℃이며, 상기 온도 내의 범위에서 실리콘 질화막이 가장 효율적으로 식각된다.According to an embodiment of the present invention, the heating temperature of the etching composition in step b) is 110 ° C to 200 ° C, preferably 160 ° C to 180 ° C, and the silicon nitride film is most efficiently etched in the temperature range.
본 발명의 일 구현예에 따르면, 상기 b) 단계는 식각 조성물을 가열하여, 식각 조성물 내의 인산 농도를 89 내지 93%로 조절하는 단계일 수 있다.According to an embodiment of the present invention, the step b) may be a step of heating the etching composition to adjust the concentration of phosphoric acid in the etching composition to 89 to 93%.
또한 본 발명의 바람직한 일 구현예에 따르면, 상기 b) 단계에서 식각 조성물 내의 인산 농도를 89 내지 93%로 조절하는데 소요되는 시간은 상압의 조건에서 10분 미만일 수 있다.According to a preferred embodiment of the present invention, the time required to adjust the phosphoric acid concentration in the etching composition to 89 to 93% in the step b) may be less than 10 minutes under atmospheric pressure.
이는 C1~C5의 알칸올을 포함하지 않는 식각 조성물을 가열하는 경우에 비해 현저히 적은 시간이 소요되므로, 에너지를 절약하여 효율적으로 식각을 진행 가능하게 한다.This is because it takes a considerably less time than in the case of heating an etching composition containing no C 1 to C 5 alkanol, so that the etching can be efficiently performed by saving energy.
본 발명의 일 구현예에 따라, 인산에 C1~C5의 알칸올을 첨가한 식각 조성물은 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있다. According to an embodiment of the present invention, the etching composition to which C 1 -C 5 alkanol is added to phosphoric acid can selectively remove the nitride film while minimizing the etching rate of the oxide film.
더욱 구체적으로, 본 발명의 일 구현예 따르면, 상기 식각 조성물의 실리콘 산화막의 식각 속도는 1 내지 20 Å/min이고, 실리콘 질화막/산화막 선택비는 6 이상을 가지게 되어, 산화막의 식각율을 최소화하면서 질화막을 선택적으로 제거할 수 있게 한다.More specifically, according to one embodiment of the present invention, the etching rate of the silicon oxide film of the etching composition is 1 to 20 Å / min, and the silicon nitride film / oxide film selection ratio is 6 or more, so that the etching rate of the oxide film is minimized Thereby making it possible to selectively remove the nitride film.
본 발명의 일 구현예에서, 상기 a) 단계의 식각 조성물은 식각 속도 향상을 위한 첨가제가 추가로 포함될 수 있다.In one embodiment of the present invention, the etching composition of step a) may further include an additive for improving the etching rate.
상기 첨가제는 식각 성능을 향상시키기 위하여 당업계에서 통상적으로 사용되는 임의의 첨가제를 말하는데, 계면활성제, pH조절제, 부식 방지제, 금속 이온 봉쇄제, 산화방지제 및 유기용제 등이 있으며, 본 발명의 특징에 어긋나지 않는 범위 내에서 추가로 포함할 수 있다.The additive is an additive commonly used in the art to improve the etching performance. Examples of the additive include a surfactant, a pH adjuster, a corrosion inhibitor, a sequestering agent, an antioxidant and an organic solvent. But can be additionally included within a range that does not deviate.
상기 계면활성제는 식각의 균일성을 증가시키는 역할을 하며, 이때 사용되는 계면활성제의 구체적인 종류는 특별하게 한정할 것은 아니며, 글리세롤, 폴리에틸렌글리콜, 폴리프로필렌글리콜 등을 사용할 수 있다.The surfactant has a role of increasing the uniformity of the etching. The specific kind of the surfactant used herein is not particularly limited, and glycerol, polyethylene glycol, polypropylene glycol and the like can be used.
상기 pH 조절제는 pH를 낮추는 유기산 및 무기산, pH를 높일 수 있는 염기 및 중성염 등을 의미하며, 이때 사용되는 pH조절제의 구체적인 종류는 특별하게 한정할 것은 아니다.The pH adjuster refers to an organic acid or inorganic acid which lowers the pH, a base or a neutral salt which can increase the pH, and the specific kind of the pH adjuster to be used at this time is not particularly limited.
본 발명의 또 다른 구현예는 상기 실리콘 질화막 식각방법에서 사용되는 식각 조성물을 제공한다. Another embodiment of the present invention provides an etching composition for use in the silicon nitride film etching method.
본 발명의 일 구현예는 상기 식각 조성물을 이용하여 수행되는 식각 공정을 포함하는 반도체 소자의 제조 방법을 제공한다. One embodiment of the present invention provides a method of manufacturing a semiconductor device including an etching process performed using the etching composition.
본 발명에 따른 상기 식각 공정은 실리콘 산화막에 대하여 실리콘 질화막을 선택적으로 식각하는 것이며, 140 내지 195 의 온도에서 수행되는 것인 반도체 소자의 제조 방법 일 수 있으며, 그 외 공정은 통상 알려진 방법을 사용할 수 있으므로 자세한 설명은 생락하도록 한다. The etching process according to the present invention is a process for selectively etching a silicon nitride film on a silicon oxide film and is performed at a temperature of 140 to 195. In other processes, Therefore, the detailed explanation should be omitted.
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, specific embodiments of the present invention will be described. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
실시예Example
(1) (One) 식각Etching 조성물의 제조 Preparation of composition
다음 표 1에 기재된 성분 배합으로 통상적인 제조방법을 이용하여 식각 조성물을 제조하였다.Etching compositions were prepared using conventional manufacturing methods with the ingredients shown in Table 1 below.
(2) (2) 식각Etching 조성물의 가열 및 인산의 농도 측정 Heating the composition and measuring the concentration of phosphoric acid
실시예 1 내지 3 및 비교예 1의 식각 조성물을 175가 될 때까지 가열하고, 175에 도달하는데 소요되는 시간을 측정하였다.The etching compositions of Examples 1 to 3 and Comparative Example 1 were heated to 175 and the time required to reach 175 was measured.
상기 가열된 식각 조성물을 적정한 뒤, 인산의 농도를 측정하였다.After the heated etching composition was titrated, the concentration of phosphoric acid was measured.
상기 표 2에 따르면, 실시예 1 내지 3의 식각 조성물은 비교예 1에 비해 빠른 시간내에 원하는 온도에 도달하는 것을 확인할 수 있었다.According to the above Table 2, it was confirmed that the etching compositions of Examples 1 to 3 reach the desired temperature within a short time as compared with Comparative Example 1.
또한 175에서 실시예 1 내지 3의 인산의 농도는 89 내지 93%로 비교예 1에 비해 인산의 농도가 높아, 빠른 시간내에 적은 에너지를 이용해 원하는 농도로 제조할 수 있음을 확인할 수 있었다.In addition, the concentration of phosphoric acid in Examples 1 to 3 was from 89 to 93% at 175, which is higher than that of Comparative Example 1, and it can be confirmed that the phosphoric acid can be prepared at a desired concentration using less energy in a short time.
(3) (3) 식각Etching 속도 측정 Speed measurement
실시예 4, 5 및 비교예 1에 따라 제조된 식각 조성물을 공정온도를 달리하면서 실리콘 질화막 기판을 넣어 식각을 진행하였다.The etching compositions prepared according to Examples 4 and 5 and Comparative Example 1 were etched by inserting a silicon nitride film substrate at different process temperatures.
실리콘 질화막은 식각 조성물에 넣기 전 평탄화 작업을 진행하였으며, 평탄화작업은 50질량% 불산을 200:1로 희석한 후 희석 불산에 30초간 담가 진행하였다.The silicon nitride film was planarized before being put into the etching composition, and the planarization process was performed by immersing the substrate in a diluted hydrofluoric acid for 30 seconds after diluting 50% by mass of hydrofluoric acid with 200: 1.
식각 속도는 엘립소미트리(Nano-View, SE MG-1000; Ellipsometery)를 이용하여 실리콘 질화막을 300초 동안 식각한 후, 양 막의 식각 전의 두께와 식각 후의 두께의 차이를 식각 시간(분)으로 나누어 산출하였다.The etching rate was determined by etching the silicon nitride film for 300 seconds using a Nano-View (SE MG-1000; Ellipsometry), dividing the difference between the thickness before etching and the thickness after etching by the etching time Respectively.
하기 [표 3]에 공정온도에 따른 식각 속도의 결과값을 나타내었다.Table 3 shows the results of the etching rate according to the process temperature.
(Å/min)Nitride film etch rate
(Å / min)
(Å/min)Oxide etch rate
(Å / min)
(질화막/ 산화막)Selection ratio
(Nitride film / oxide film)
상기 [표 3]에 나타난 바와 같이 실시예 4및 5의 식각 조성물을 이용하여 실리콘 질화막/산화막을 식각하는 경우, 실리콘 질화막의 식각 속도는 유지되는 반면에 산화막의 식각 속도는 억제되는 것을 확인 할 수 있었다.As shown in Table 3, when the silicon nitride film / oxide film was etched using the etching compositions of Examples 4 and 5, it was found that the etching rate of the silicon nitride film was maintained, while the etching rate of the oxide film was suppressed there was.
또한 식각 조성물 내의 알칸올의 농도가 증가할수록 산화막의 식각 속도가 보다 억제되는 것을 확인 할 수 있었다.Also, it was confirmed that as the concentration of alkanol in the etching composition increases, the etching rate of the oxide film is further suppressed.
이는 본 발명에 따른 식각 조성물의 높은 선택비를 나타내는 것으로, 실리콘 식각 공정에서 본 발명의 효과를 확인할 수 있었다.This represents a high selectivity of the etching composition according to the present invention, and the effect of the present invention can be confirmed in the silicon etching process.
Claims (8)
b) 상기 식각 조성물을 110℃ 내지 200℃으로 가열하는 단계; 및
c) 상기 가열된 식각 조성물이 실리콘 질화막을 식각하는 단계를 포함하는, 실리콘 질화막 식각방법.
a) preparing an etching composition comprising 80 to 85% by weight of phosphoric acid and 10,000 to 1,000,000 ppm of an alkanol of C 1 to C 5 ;
b) heating the etch composition to a temperature of from 110 캜 to 200 캜; And
c) etching the silicon nitride film by the heated etch composition.
상기 a) 단계의 식각 조성물은 상기 식각 조성물 전체에 대하여,
상기 C1~C5의 알칸올을 20,000 내지 80,000 ppm의 농도로 포함하는 인산 용액인 것을 특징으로 하는, 실리콘 질화막 식각방법.
The method according to claim 1,
The etching composition of step a) may be applied to the entire etching composition,
Wherein the etching solution is a phosphoric acid solution containing the C 1 to C 5 alkanol in a concentration of 20,000 to 80,000 ppm.
상기 b) 단계의 식각 조성물을 160℃ 내지 180℃으로 가열하는 것을 특징으로 하는, 실리콘 질화막 식각방법.
The method according to claim 1,
Wherein the etching composition of step b) is heated to 160 to 180 占 폚.
상기 b) 단계는 식각 조성물을 가열하여, 식각 조성물 내의 인산 농도를 89 내지 93%로 조절하는 것을 특징으로 하는, 실리콘 질화막 식각방법.
The method according to claim 1,
Wherein step b) comprises heating the etching composition to adjust the phosphoric acid concentration in the etching composition to 89 to 93%.
상기 b) 단계에서 식각 조성물 내의 인산 농도를 89 내지 93%로 조절하는데 소요되는 시간은 상압의 조건에서 10분 미만인 것을 특징으로 하는, 실리콘 질화막 식각방법.
5. The method of claim 4,
Wherein the time required for adjusting the phosphoric acid concentration in the etching composition to 89 to 93% in the step b) is less than 10 minutes under atmospheric pressure.
상기 a) 단계의 식각 조성물은 식각 속도 향상을 위한 첨가제가 추가로 포함하는 것을 특징으로 하는, 실리콘 질화막 식각방법.
The method according to claim 1,
Wherein the etching composition of step a) further comprises an additive for improving the etching rate.
인산 80 내지 85 중량% 및 C1~C5의 알칸올 10,000 내지 1,000,000 ppm을 포함하는 식각 조성물.
7. An etching composition for use in any one of claims 1 to 6,
From 80 to 85% by weight of phosphoric acid and from 10,000 to 1,000,000 ppm of C 1 to C 5 alkanols.
A method for fabricating a semiconductor device using the silicon nitride film etching method according to any one of claims 1 to 6.
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