KR102653026B1 - An etchant composition and an ehting method and a mehtod for fabrication metal pattern using the same - Google Patents
An etchant composition and an ehting method and a mehtod for fabrication metal pattern using the same Download PDFInfo
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- KR102653026B1 KR102653026B1 KR1020190026082A KR20190026082A KR102653026B1 KR 102653026 B1 KR102653026 B1 KR 102653026B1 KR 1020190026082 A KR1020190026082 A KR 1020190026082A KR 20190026082 A KR20190026082 A KR 20190026082A KR 102653026 B1 KR102653026 B1 KR 102653026B1
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- etchant composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000005530 etching Methods 0.000 claims abstract description 63
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 38
- 239000010937 tungsten Substances 0.000 claims abstract description 38
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 32
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims description 11
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- LGCBVEQNSDSLIH-UHFFFAOYSA-N 4-pyridin-3-ylbutanal Chemical compound O=CCCCC1=CC=CN=C1 LGCBVEQNSDSLIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- PTIUDKQYXMFYAI-UHFFFAOYSA-N methylammonium nitrate Chemical compound NC.O[N+]([O-])=O PTIUDKQYXMFYAI-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229940015297 1-octanesulfonic acid Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LXFUCSMCVAEMCD-UHFFFAOYSA-N acetic acid;nitric acid;phosphoric acid Chemical compound CC(O)=O.O[N+]([O-])=O.OP(O)(O)=O LXFUCSMCVAEMCD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- WUOSYUHCXLQPQJ-UHFFFAOYSA-N n-(3-chlorophenyl)-n-methylacetamide Chemical compound CC(=O)N(C)C1=CC=CC(Cl)=C1 WUOSYUHCXLQPQJ-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
본 발명은, 질산을 포함하지 않으며, (A) 인산, (B) 질산암모늄 및 (C) 물을 포함하고, 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상을 식각하기 위한 것인, 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법을 제공한다.The present invention does not contain nitric acid, but includes (A) phosphoric acid, (B) ammonium nitrate, and (C) water, and is for etching one or more of a tungsten (W) film and a titanium nitride (TiN) film. , an etchant composition, an etching method using the same, and a method of forming a metal pattern are provided.
Description
본 발명은 식각액 조성물, 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 관한 것이다.The present invention relates to an etchant composition, an etching method using the same, and a method for forming a metal pattern.
실리콘산화막(SiO2)과 실리콘질화막(SiNx)은 반도체 제조 공정에서 사용되는 대표적인 절연막으로, 둘 중 하나의 단일막을 형성할 수도 있으나 교대로 적층되어 다층막을 형성하기도 한다. 실리콘산화막과 실리콘질화막은 금속 배선과 같은 도전성 패턴을 형성하기 위한 하드 마스크로도 이용될 수 있으나, 3D NAND 플래시 메모리의 게이트(gate) 형성에도 이용될 수 있다.Silicon oxide (SiO2) and silicon nitride (SiNx) are representative insulating films used in the semiconductor manufacturing process. They can form a single film, but they can also be alternately stacked to form a multilayer film. Silicon oxide and silicon nitride films can be used as hard masks to form conductive patterns such as metal wiring, but can also be used to form gates for 3D NAND flash memory.
실리콘 질화막을 식각하고, 이 때 식각된 실리콘질화막에 게이트(gate)를 형성하기 위하여 텅스텐막과 티타늄질화막을 증착할 수 있다. 이러한 게이트 소자 하나하나가 전기적인 특성을 갖고 구동될 수 있도록 증착된 텅스텐막과 티타늄질화막을 동시에 식각시키는 공정이 필수적이다. The silicon nitride film is etched, and at this time, a tungsten film and a titanium nitride film can be deposited to form a gate on the etched silicon nitride film. A process of simultaneously etching the deposited tungsten film and titanium nitride film is essential so that each of these gate devices can be driven with electrical characteristics.
이와 관련하여, 대한민국 등록특허 제10-1782329호 및 대한민국 공개특허 제10-2015-0050278호 등, 텅스텐막과 티타늄질화물막 식각 시 식각 비율 조절이 가능한 식각액 조성물이 개발되고 왔으나, 질산을 주산화제로 사용하고 있어, 질산의 빠른 분해로 인해 경시 안정성이 저하되는 등의 문제점이 있다.In this regard, etchant compositions capable of controlling the etching rate when etching tungsten films and titanium nitride films have been developed, such as Republic of Korea Patent No. 10-1782329 and Korea Patent Publication No. 10-2015-0050278, but use nitric acid as the main oxidizing agent. However, there are problems such as a decrease in stability over time due to rapid decomposition of nitric acid.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상의 식각에 사용되어, 식각 속도 및 식각 비율 조절이 용이하고, 식각 균일성이 우수한 것을 특징으로 하는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is intended to improve the problems of the prior art described above, and is used for etching at least one of a tungsten (W) film and a titanium nitride (TiN) film, so that the etch rate and etch rate can be easily adjusted and the etch uniformity is excellent. The purpose is to provide an etchant composition characterized in that.
또한, 본 발명은 텅스텐막 및 티타늄 질화물막 중 하나 이상의 식각 시, 산화물막에는 손상을 주지 않는 식각액 조성물을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an etchant composition that does not damage the oxide film when etching one or more of the tungsten film and the titanium nitride film.
또한, 본 발명은 경시안정성이 우수한 식각액 조성물을 제공하는 것을 목적으로 한다.Additionally, the present invention aims to provide an etchant composition with excellent aging stability.
또한, 본 발명은 상기 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.Additionally, the present invention aims to provide an etching method using the above etching liquid composition.
또한, 본 발명은 상기 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.Additionally, the present invention aims to provide a method of forming a metal pattern using the etchant composition.
상기 목적을 달성하기 위해, 본 발명은, 질산을 포함하지 않으며, (A) 인산, (B) 질산암모늄 및 (C) 물을 포함하고, 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상을 식각하기 위한 것인, 식각액 조성물을 제공한다.In order to achieve the above object, the present invention does not contain nitric acid, but includes (A) phosphoric acid, (B) ammonium nitrate, and (C) water, and one of a tungsten (W) film and a titanium nitride (TiN) film. An etchant composition for etching the above is provided.
또한, 본 발명은, 상기 식각액 조성물을 사용하는 식각 방법을 제공한다.Additionally, the present invention provides an etching method using the etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하는 금속 패턴의 형성 방법을 제공한다.Additionally, the present invention provides a method of forming a metal pattern using the etchant composition.
본 발명의 식각액 조성물은 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상의 식각에 사용되어, 식각 속도 및 식각 비율 조절이 용이하고, 식각 균일성이 우수한 효과를 제공한다.The etchant composition of the present invention is used for etching one or more of a tungsten (W) film and a titanium nitride (TiN) film, and provides the effect of easily controlling the etching speed and etching ratio and providing excellent etching uniformity.
또한, 본 발명의 식각액 조성물은 텅스텐막 및 티타늄 질화물막 중 하나 이상의 식각 시, 산화물막에는 손상을 주지 않는 효과를 제공한다.In addition, the etchant composition of the present invention provides the effect of not damaging the oxide film when etching one or more of the tungsten film and the titanium nitride film.
또한, 본 발명의 식각액 조성물은 경시안정성이 우수한 효과를 제공한다.In addition, the etchant composition of the present invention provides excellent stability over time.
도 1은 본 발명의 실시예 1 및 비교예 1에 따른 식각액 조성물의 경시안정성 평가 결과를 나타내는 도면이다.Figure 1 is a diagram showing the results of evaluating the aging stability of the etchant composition according to Example 1 and Comparative Example 1 of the present invention.
본 발명은, 질산을 포함하지 않으며, (A) 인산, (B) 질산암모늄 및 (C) 물을 포함하고, 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상을 식각하기 위한 것인, 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 대한 것으로, 상기 식각액 조성물은 상기 텅스텐막 또는 상기 티타늄 질화물막을 식각할 수 있으며, 바람직하게는 상기 텅스텐막 및 상기 티타늄 질화물막을 동시에 식각할 수 있다. The present invention does not contain nitric acid, but includes (A) phosphoric acid, (B) ammonium nitrate, and (C) water, and is for etching one or more of a tungsten (W) film and a titanium nitride (TiN) film. , an etchant composition, an etching method using the same, and a method of forming a metal pattern, wherein the etchant composition is capable of etching the tungsten film or the titanium nitride film, preferably etching the tungsten film and the titanium nitride film at the same time. there is.
본 발명의 식각액 조성물은, 식각액 조성물을 구성하는 구성 성분과 각 구성 성분의 함량을 조절하여, 상기 텅스텐막과 상기 티타늄 질화물막에 대한 식각 비율을 조절할 수 있다. 일 실시예를 들어, 상기 식각 비율(텅스텐막/티타늄 질화물막)은 1 : 1~20인 것이 바람직하며, 1 : 1~10인 것이 더욱 바람직하다.The etchant composition of the present invention can control the etching rate for the tungsten film and the titanium nitride film by adjusting the components constituting the etchant composition and the content of each component. For example, the etching ratio (tungsten film/titanium nitride film) is preferably 1:1 to 20, and more preferably 1:1 to 10.
<식각액 조성물> <Etching solution composition>
(A) 인산(A) Phosphoric acid
본 발명의 식각액 조성물에 포함되는 상기 인산(phosphoric acid)은 상기 텅스텐막을 식각하는 데 사용될 수 있다.The phosphoric acid included in the etchant composition of the present invention can be used to etch the tungsten film.
상기 인산의 함량은 식각액 조성물 총 중량에 대하여, 65 내지 85 중량%로 포함되며, 70 내지 85중량%가 바람직하다. 상기 인산이 상기 함량 범위 내로 포함되는 경우, 상기 텅스텐막의 해리 속도를 적절한 수준으로 조절하여, 상기 텅스텐막을 균일하게 식각할 수 있다.The content of phosphoric acid is 65 to 85% by weight, preferably 70 to 85% by weight, based on the total weight of the etchant composition. When the phosphoric acid is contained within the above content range, the tungsten film can be uniformly etched by controlling the dissociation rate of the tungsten film to an appropriate level.
(B) 질산암모늄(B) Ammonium nitrate
본 발명의 식각액 조성물에 포함되는 상기 질산암모늄은 상기 텅스텐막 및 상기 티타늄 질화물막을 식각하는 데 사용될 수 있다.The ammonium nitrate included in the etchant composition of the present invention can be used to etch the tungsten film and the titanium nitride film.
상기 질산암모늄은, 예를 들어, 질산암모늄, 메틸질산암모늄, 테트라에틸암모늄나이트레이트 및 테트라부틸암모늄나이트레이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하고, 바람직하게는 질산암모늄 및 질산 테트라부틸암모늄 중 1종 이상을 포함할 수 있다The ammonium nitrate includes, for example, at least one member selected from the group consisting of ammonium nitrate, methyl ammonium nitrate, tetraethylammonium nitrate, and tetrabutylammonium nitrate, and preferably ammonium nitrate and tetrabutylammonium nitrate. May include one or more of
상기 질산암모늄의 함량은 식각액 조성물 총 중량에 대하여, 0.1 내지 3 중량%로 포함되며, 0.5 내지 2 중량%가 바람직하다. 상기 질산암모늄이, 상기 함량 범위 미만으로 포함될 경우, 상기 텅스텐막 및 상기 티타늄 질화물막이 식각되지 않으며, 상기 함량 범위 초과로 포함될 경우, 용해도가 저하되어 상기 질산암모늄이 재결정화되어 입자를 생성하고, 생성된 질산암모늄 입자가 상기 텅스텐막 및 상기 티타늄 질화물막 표면에 손상을 줄 수 있다.The content of ammonium nitrate is 0.1 to 3% by weight, preferably 0.5 to 2% by weight, based on the total weight of the etchant composition. When the ammonium nitrate is contained in an amount less than the above range, the tungsten film and the titanium nitride film are not etched, and when the ammonium nitrate is contained in an amount exceeding the above range, the solubility is reduced and the ammonium nitrate is recrystallized to generate particles. Ammonium nitrate particles may damage the surfaces of the tungsten film and the titanium nitride film.
(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 included in the etchant composition of the present invention may be deionized water for semiconductor processing, and preferably, deionized water of 18 MΩ/cm or more may be used.
상기 물의 함량은 식각액 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The water content may be included in a residual amount such that the total weight of the etchant composition is 100% by weight.
(D) 유기산(D) Organic acid
본 발명의 식각액 조성물은 상기 유기산을 더 포함할 수 있으며, 상기 유기산은 식각액 조성물 내의 수분을 조절하여 상기 텅스텐막의 식각 속도를 조절 할 수 있고, 또한, 상기 텅스텐막의 식각 균일성을 개선시키는 데 사용될 수 있다. The etchant composition of the present invention may further include the organic acid, and the organic acid can control the etch rate of the tungsten film by controlling the moisture in the etchant composition, and can also be used to improve the etching uniformity of the tungsten film. there is.
상기 유기산은, 예를 들어, 카르복시산 및 술폰산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하고, 상기 카르복시산은 acetic acid, propionic acid, 2-hydroxyisobutyric acid, methoxyacetic acid 및 pyruvic acid를 포함하고, 상기 술폰산은 methane sulfonic acid, para-toluene sulfonic acid, ethane sulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid 및 benzene sulfonic acid를 포함할 수 있다. 상기 유기산은 acetic acid 및 methane sulfonic acid 중 1종 이상을 포함하는 것이 바람직하다.The organic acid includes, for example, at least one selected from the group consisting of carboxylic acid and sulfonic acid, the carboxylic acid includes acetic acid, propionic acid, 2-hydroxyisobutyric acid, methoxyacetic acid, and pyruvic acid, and the sulfonic acid is It may include methane sulfonic acid, para-toluene sulfonic acid, ethane sulfonic acid, 1-hexanesulfonic acid, 1-octanesulfonic acid, and benzene sulfonic acid. The organic acid preferably includes at least one of acetic acid and methane sulfonic acid.
상기 유기산의 함량은 식각액 조성물 총 중량에 대하여, 1 내지 15 중량%로 포함되며, 5 내지 10 중량%가 바람직하다. 상기 유기산이, 상기 함량 범위 미만으로 포함될 경우, 식각 균일성이 저하되며, 상기 함량 범위 초과로 포함될 경우, 식각 속도가 저하되거나 용해도 저하로 암모늄염이 석출될 수 있다.The content of the organic acid is 1 to 15% by weight, preferably 5 to 10% by weight, based on the total weight of the etchant composition. If the organic acid is included in an amount less than the above range, etching uniformity may deteriorate, and if it is contained in an amount exceeding the above range, the etching rate may decrease or ammonium salt may precipitate due to a decrease in solubility.
본 발명의 식각액 조성물은 질산을 포함하지 않는다. 식각액 조성물이 질산을 포함할 경우, 경시안정성이 저하되므로 바람직하지 않다.The etchant composition of the present invention does not contain nitric acid. If the etchant composition contains nitric acid, it is not preferable because aging stability is reduced.
<식각액 조성물을 이용한 식각 방법><Etching method using etchant composition>
또한, 본 발명은, 본 발명에 따른 식각액 조성물을 이용하는 식각 방법을 제공한다. 본 발명의 식각 방법은, 본 발명의 상기 식각액 조성물을 사용하는 점을 제외하고는, 공지의 금속 식각 방법에 따라 패턴을 형성 할 수 있다. Additionally, the present invention provides an etching method using the etchant composition according to the present invention. The etching method of the present invention can form a pattern according to a known metal etching method, except that the etchant composition of the present invention is used.
일 예로, 상기 식각 방법은, i) 기판 상에, 텅스텐(W) 또는 티타늄 질화물(TiN)로 이루어진 단일막 또는 상기 텅스텐 단일막과 상기 티타늄 질화물 단일막을 포함하는 다층막을 형성하는 단계; ii) 상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및 iii) 본 발명에 따른 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.As an example, the etching method includes the steps of i) forming a single layer of tungsten (W) or titanium nitride (TiN) or a multilayer layer including the tungsten single layer and the titanium nitride single layer on a substrate; ii) selectively leaving a photo-reactive material on the single layer or the multilayer layer; and iii) etching the single layer or the multilayer layer using the etchant composition according to the present invention.
<식각액 조성물을 이용한 금속 패턴의 형성 방법><Method for forming metal pattern using etchant composition>
또한, 본 발명은, 본 발명에 따른 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공한다. 본 발명의 금속 패턴의 형성 방법은, 본 발명의 상기 식각액 조성물을 사용하는 점을 제외하고는, 공지의 금속 패턴 형성 방법에 따라 패턴을 형성 할 수 있다. Additionally, the present invention provides a method of forming a metal pattern using the etchant composition according to the present invention. The method of forming a metal pattern of the present invention can form a pattern according to a known metal pattern forming method, except that the etchant composition of the present invention is used.
일 예로, 상기 금속 패턴의 형성 방법은, i) 기판 상에, 텅스텐(W) 또는 티타늄 질화물(TiN)로 이루어진 단일막 또는 상기 텅스텐 단일막과 상기 티타늄 질화물 단일막을 포함하는 다층막을 형성하는 단계; 및 ii) 본 발명에 따른 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.As an example, the method of forming the metal pattern includes the steps of: i) forming a single film made of tungsten (W) or titanium nitride (TiN) or a multilayer film including the tungsten single film and the titanium nitride single film on a substrate; and ii) etching the single layer or the multilayer layer using the etchant composition according to the present invention.
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. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 질량 기준이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and further includes all changes within the scope and meaning equivalent to the record of the claims. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.
실시예 및 비교예에 따른 식각액 조성물의 제조Preparation of etchant composition according to Examples and Comparative Examples
하기 표 1을 참조하여, 실시예 및 비교예에 따른 식각액 조성물을 제조하였다.With reference to Table 1 below, etchant compositions according to Examples and Comparative Examples were prepared.
MSA: methane sulfonic acid MSA: methane sulfonic acid
AN: ammonium nitrateAN: ammonium nitrate
TBAN: tetra-butyl ammonium nitrateTBAN: tetra-butyl ammonium nitrate
AS: ammonium sulfateAS: ammonium sulfate
AP: ammonium phosphateAP: ammonium phosphate
상기 표 1에서 처리 조건은, 실시예 및 비교예에 따른 식각액 조성물을 이용하여 후술되는 시험예 1 내지 3을 수행할 시, 식각 처리 조건을 의미하며, 식각은 60 내지 80℃에서 수행되는 것이 적절하다. 60℃ 미만의 온도 조건에서는 식각 속도가 저하될 수 있고, 80℃ 이상의 온도 조건에서는 수분이 증발되어 조성비가 변화하게 된다. The processing conditions in Table 1 refer to the etching treatment conditions when performing Test Examples 1 to 3 described below using the etchant compositions according to the Examples and Comparative Examples, and the etching is appropriately performed at 60 to 80°C. do. Under temperature conditions below 60°C, the etching rate may decrease, and under temperature conditions above 80°C, moisture evaporates and the composition ratio changes.
시험예 1: 식각 속도 측정Test Example 1: Etching rate measurement
텅스텐(W)막 및 티타늄 질화물(TiN)막을 실시예 및 비교예에 따른 식각액 조성물에 침지시켜 식각한 뒤, SEM을 이용하여 식각 속도(etch rate, Å/min)을 측정하고, 텅스텐막과 티타늄 질화물막에 대한 식각 비율(W/TiN)을 계산하여, 하기 표 2에 나타내었다.After etching the tungsten (W) film and titanium nitride (TiN) film by immersing them in the etchant composition according to the examples and comparative examples, the etch rate (Å/min) was measured using SEM, and the tungsten film and titanium film were etched. The etch ratio (W/TiN) for the nitride film was calculated and shown in Table 2 below.
또한, 실리콘 산화물(SiOx)막 및 알루미늄 산화물(AlOx)막을 실시예 및 비교예에 따른 식각액 조성물에 침지시켜, 식각 정도를 아래 평가 기준에 따라 판단한 뒤, 하기 표 2에 나타내었다.In addition, the silicon oxide (SiOx) film and the aluminum oxide (AlOx) film were immersed in the etchant composition according to the Examples and Comparative Examples, and the degree of etching was judged according to the evaluation criteria below, and is shown in Table 2 below.
<실리콘산화물막 및 알루미늄 산화물막에 대한 식각 정도 평가 기준><Standards for evaluating the degree of etching for silicon oxide film and aluminum oxide film>
○: 식각속도 1 Å/min 이하○: Etching speed 1 Å/min or less
X: 식각속도 1 Å/min 초과X: Etching rate exceeds 1 Å/min
시험예 2: 식각 균일성 측정Test Example 2: Etch uniformity measurement
시험예 1을 통해 식각된 텅스텐막에 대해, AFM을 이용하여 텅스텐막 표면의 식각 균일성을 측정한 뒤, RMS(root mean square)로 수치화하여 하기 표 2에 나타내었으며, RMS는 하기 수학식을 통해 연산될 수 있다.For the tungsten film etched through Test Example 1, the etching uniformity of the surface of the tungsten film was measured using AFM, and then quantified by RMS (root mean square), which is shown in Table 2 below, and RMS is expressed in the following equation: It can be calculated through
본 발명에서 RMS는 막질 표면의 거칠기를 의미하며, 0에 가까울수록 균일하게 식각된 것으로 볼 수 있으나, 텅스텐막의 식각량도 함께 고려하여 초기 식각 속도 대비 상대값으로 이해하는 것이 바람직하다. 예를 들어, 상기 표 1과 하기 표 2에서, 실시예 1 및 7을 보면, 동일 조성을 갖는 조성물을 사용하여 식각하는 경우에도, 온도가 높은 경우 식각량이 증가하여 RMS 값이 증가된 것을 확인할 수 있다.In the present invention, RMS refers to the roughness of the film surface, and the closer it is to 0, the more uniformly etched it can be considered. However, it is preferable to consider the etching amount of the tungsten film and understand it as a relative value compared to the initial etching speed. For example, looking at Examples 1 and 7 in Table 1 and Table 2 below, it can be seen that even when etching was performed using a composition having the same composition, the etching amount increased when the temperature was high, resulting in an increase in the RMS value. .
시험예 3: 용해도 평가Test Example 3: Solubility evaluation
식각 처리 과정 중에서 식각액 조성물의 구성 성분이 석출되어 나오는 지, 식각액 조성물의 용해도를 아래 평가 기준에 따라 판단한 뒤, 하기 표 2에 나타내었다.During the etching process, whether the components of the etchant composition precipitated out and the solubility of the etchant composition were judged according to the evaluation criteria below, and are shown in Table 2 below.
<용해도 평가 기준><Solubility evaluation criteria>
○: 탁도측정결과 NTU가 1 이하○: Turbidity measurement result NTU is 1 or less
△: 탁도측정결과 NTU가 1 초과 내지 5이하△: As a result of turbidity measurement, NTU is greater than 1 and less than 5.
X: 탁도측정결과 NTU가 5 초과X: Turbidity measurement result NTU exceeds 5
시험예 4: 경시안정성 평가Test Example 4: Evaluation of stability over time
실시예 및 비교예에 따른 식각액 조성물을 70℃에서 3시간 동안 방치 후, 경시안정성을 평가하여 그 결과를 하기 표 2에 나타내었다. 또한 시간 경과에 따른 질산암모늄(실시예 1) 또는 질산(비교예 1)의 함량 변화를 IC 분석을 통해 측정하여, 그 결과를 도 1에 나타내었다.After the etchant compositions according to Examples and Comparative Examples were left at 70°C for 3 hours, their stability over time was evaluated, and the results are shown in Table 2 below. In addition, the change in content of ammonium nitrate (Example 1) or nitric acid (Comparative Example 1) over time was measured through IC analysis, and the results are shown in Figure 1.
<경시안정성 평가 기준><Standards for evaluation of stability over time>
○: 3시간 방치 후 AN(ammonium nitrate) 또는 질산 함량분석 시 50% 이상 ○: More than 50% when analyzed for AN (ammonium nitrate) or nitric acid content after being left for 3 hours.
X: 3시간 방치 후 AN 또는 질산 함량분석 시 50% 미만 X: Less than 50% when analyzed for AN or nitric acid content after standing for 3 hours
상기 표 2를 참조하면, 실시예에 따른 식각액 조성물을 사용하여 식각 공정을 수행하는 경우, 텅스텐막 및 티타늄 질화물막에 대해 적절한 수준의 식각 속도를 제공하며, 따라서 식각 균일성이 우수하고, 실리콘 산화물막 및 알루미늄 산화물막의 식각 시 식각 속도가 1 Å/min 이하로, 실질적으로 손상을 주지 않으며, 경시안정성이 우수한 것을 확인할 수 있다. Referring to Table 2, when an etching process is performed using the etchant composition according to the example, an appropriate level of etch rate is provided for the tungsten film and titanium nitride film, and thus etch uniformity is excellent, and silicon oxide It can be seen that the etching rate when etching the film and aluminum oxide film is less than 1 Å/min, causing virtually no damage and having excellent aging stability.
또한, 실시예 1 내지 3 및 7 내지 11의 결과를 통해, 식각액 조성물을 구성하는 구성 성분과 각 구성 성분의 함량을 조절하여, 텅스텐막과 티타늄 질화물막에 대한 식각 비율을 용이하게 조절할 수 있음을 알 수 있다. In addition, through the results of Examples 1 to 3 and 7 to 11, it can be seen that the etching rate for the tungsten film and titanium nitride film can be easily adjusted by adjusting the components constituting the etchant composition and the content of each component. Able to know.
또한, 실시예 5 및 6의 결과를 통해, 식각액 조성물이 유기산을 포함하는 경우, 텅스텐막 표면의 식각 균일성이 개선됨을 알 수 있다.Additionally, the results of Examples 5 and 6 show that when the etchant composition contains an organic acid, the etching uniformity of the tungsten film surface is improved.
반면, 비교예 1 내지 5에 따른 식각액 조성물을 사용하여 식각 공정을 수행하는 경우, 텅스텐막 및 티타늄 질화물막에 대해 적절한 수준의 식각 속도를 제공하지 못하며, 따라서 식각 균일성이 저하됨을 알 수 있다. 구체적으로, 비교예 1, 2 및 5의 경우, 질산의 함유에 의해 경시안정성 저하가 확인되었으며, 비교예 3 및 4의 경우, 식각 속도가 너무 낮아 실질적으로 식각이 되지 않으므로, 경시안정성 평가의 진행이 어려웠다.On the other hand, when an etching process is performed using the etchant compositions according to Comparative Examples 1 to 5, it can be seen that an appropriate level of etching speed is not provided for the tungsten film and titanium nitride film, and thus the etching uniformity is deteriorated. Specifically, in the case of Comparative Examples 1, 2, and 5, a decrease in aging stability was confirmed due to the inclusion of nitric acid, and in the case of Comparative Examples 3 and 4, the etching rate was so low that it was not substantially etched, so the aging stability evaluation was conducted. This was difficult.
또한 상기 표 2 및 도 1을 참조하면, 질산을 포함하는 비교예 1에 따른식각액 조성물의 경우, 질산이 분해(4HNO3 → 2H2O + 4NO2 + O2)되어 NO2, O2 기포가 발생되고, 식각 대상의 표면에 흡착하여 균일한 식각을 저해할 수 있다.Also, referring to Table 2 and Figure 1, in the case of the etchant composition according to Comparative Example 1 containing nitric acid, nitric acid is decomposed (4HNO 3 → 2H 2 O + 4NO 2 + O 2 ) to form NO 2 and O 2 bubbles. It is generated and adsorbed to the surface of the object to be etched, which may inhibit uniform etching.
Claims (9)
식각액 조성물 총 중량에 대하여,
(A) 인산 65 내지 85 중량%;
(B) 질산암모늄 0.1 내지 3 중량%; 및
(C) 물 잔량을 포함하고,
텅스텐(W)막 및 티타늄 질화물(TiN)막을 식각하기 위한 것인, 식각액 조성물.
Does not contain nitric acid,
With respect to the total weight of the etchant composition,
(A) 65 to 85% by weight of phosphoric acid;
(B) 0.1 to 3% by weight of ammonium nitrate; and
(C) contains the remaining water volume,
An etchant composition for etching a tungsten (W) film and a titanium nitride (TiN) film.
상기 (B) 질산암모늄은 질산암모늄, 메틸질산암모늄, 테트라에틸암모늄나이트레이트 및 테트라부틸암모늄나이트레이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 식각액 조성물.
In claim 1,
The (B) ammonium nitrate is an etchant composition, characterized in that it contains at least one selected from the group consisting of ammonium nitrate, methyl ammonium nitrate, tetraethylammonium nitrate, and tetrabutylammonium nitrate.
식각액 조성물 총 중량에 대하여,
상기 (A) 인산 70 내지 85 중량%;
상기 (B) 질산암모늄 0.5 내지 2 중량%; 및
상기 (C) 물 잔량을 포함하는 것을 특징으로 하는 식각액 조성물.
In claim 1,
With respect to the total weight of the etchant composition,
(A) 70 to 85% by weight of phosphoric acid;
(B) 0.5 to 2% by weight of ammonium nitrate; and
An etchant composition comprising the remaining amount of water (C).
상기 식각액 조성물은 (D) 유기산을 더 포함하는 것을 특징으로 하는 식각액 조성물.
In claim 1,
The etchant composition further comprises (D) an organic acid.
상기 (D) 유기산은 카르복시산, 술폰산 및 포스폰산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 식각액 조성물.
In claim 5,
The (D) organic acid is an etchant composition, characterized in that it includes at least one selected from the group consisting of carboxylic acid, sulfonic acid, and phosphonic acid.
식각액 조성물 총 중량에 대하여, 상기 유기산은 1 내지 15 중량%로 포함되는 것을 특징으로 하는 식각액 조성물.
In claim 5,
An etchant composition, characterized in that the organic acid is contained in an amount of 1 to 15% by weight, based on the total weight of the etchant composition.
상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및
청구항 1의 식각액 조성물을 사용하여, 상기 다층막을 식각하는 단계를 포함하는 식각 방법.
forming a multilayer film including a tungsten (W) film and a titanium nitride (TiN) film on a substrate;
selectively leaving a photo-reactive material on the multilayer film; and
An etching method comprising etching the multilayer film using the etchant composition of claim 1.
청구항 1의 식각액 조성물을 사용하여, 상기 다층막을 식각하는 단계를 포함하는 금속 패턴의 형성 방법.
forming a multilayer film including a tungsten (W) film and a titanium nitride (TiN) film on a substrate; and
A method of forming a metal pattern comprising etching the multilayer film using the etchant composition of claim 1.
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| CA2603990A1 (en) * | 2005-04-08 | 2006-10-19 | Sachem, Inc. | Selective wet etching of metal nitrides |
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