KR20200105221A - 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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- KR20200105221A KR20200105221A KR1020190024095A KR20190024095A KR20200105221A KR 20200105221 A KR20200105221 A KR 20200105221A KR 1020190024095 A KR1020190024095 A KR 1020190024095A KR 20190024095 A KR20190024095 A KR 20190024095A KR 20200105221 A KR20200105221 A KR 20200105221A
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- Prior art keywords
- etchant composition
- etching
- film
- ammonium
- tungsten
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000005530 etching Methods 0.000 claims abstract description 70
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 56
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 47
- 239000010937 tungsten Substances 0.000 claims abstract description 47
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 29
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 2
- IGMBKNUVZFAHJM-UHFFFAOYSA-I hydrogen sulfate;oxido hydrogen sulfate;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC IGMBKNUVZFAHJM-UHFFFAOYSA-I 0.000 claims description 2
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical group COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- -1 (A) phosphoric acid Chemical compound 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 235000013399 edible fruits Nutrition 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- 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 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
- H01L21/3205—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01074—Tungsten [W]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/049—Nitrides composed of metals from groups of the periodic table
- H01L2924/0494—4th Group
- H01L2924/04941—TiN
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
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 of forming a metal pattern.
반도체 제조 공정에서 게이트(gate) 또는 배선 형성을 위해, 텅스텐막과 티타늄질화막이 증착되고 증착된 텅스텐막과 티타늄질화막을 동시에 식각하거나, 다른 하나의 막질에 대해서는 손상을 주지 않는, 선택적 식각 공정이 요구될 수 있다.To form a gate or wiring in a semiconductor manufacturing process, a tungsten film and a titanium nitride film are deposited, and the deposited tungsten film and titanium nitride film are etched at the same time, or a selective etching process that does not damage the other film quality is required. Can be.
일반적으로 텅스텐막과 티타늄질화막의 식각을 위한 식각액 조성물은 동시 식각 또는 선택적 식각을 위해 과산화수소, 인산, 초산, 질산, 황산 등을 포함하고 있으며, 이와 관련하여, 대한민국 등록특허 제10-1154762호 및 대한민국 공개특허 제10-2015-0050278호 등, 텅스텐막과 티타늄질화물막 식각 시 식각 비율 조절이 가능한 식각액 조성물이 개발되고 왔으나, 식각 속도가 느린 질산을 주산화제로 사용하고 있어, 빠른 식각 속도를 요구하는 식각 공정을 수행하는 경우에는 적용할 수 없으며, 질산과 IPA의 반응으로 인해 식각 공정 후 IPA로 세정을 수행할 수 없어 텅스텐막 잔류물이 잔존할 수 있으며, 황산을 포함하는 식각액 조성물의 경우 폭발 위험성이 높이 취급이 용이하지 않다는 문제점 등이 있다.In general, the etchant composition for etching the tungsten film and the titanium nitride film contains hydrogen peroxide, phosphoric acid, acetic acid, nitric acid, sulfuric acid, etc. for simultaneous etching or selective etching, and in this regard, Korean Patent Registration No. 10-1154762 and Korea Although etchant compositions capable of controlling the etch rate when etching tungsten and titanium nitride films, such as Korean Patent Publication No. 10-2015-0050278, have been developed, nitric acid having a slow etch rate is used as the main oxidizing agent, which requires a fast etching rate. This is not applicable in the case of performing the etching process, and tungsten film residue may remain as it cannot be cleaned with IPA after the etching process due to the reaction of nitric acid and IPA, and there is a risk of explosion in the case of an etchant composition containing sulfuric acid. There is a problem that this height handling is not easy.
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 to improve the above-described problems of the prior art, and is used for etching at least one of a tungsten (W) layer and a titanium nitride (TiN) layer, so that the etching rate and the etching rate can be easily adjusted, and the etching uniformity is excellent. It is an object of the present invention 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.In addition, an object of the present invention is to provide an etchant composition that does not damage an oxide layer when at least one of a tungsten layer and a titanium nitride layer is etched.
또한, 본 발명은 식각 공정 후, IPA 세정 시 문제점이 개선된 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etchant composition with improved problems during IPA cleaning after the etching process.
또한, 본 발명은 상기 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching method using the etchant composition.
또한, 본 발명은 상기 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method of forming a metal pattern using the etchant composition.
상기 목적을 달성하기 위해, 본 발명은, 질산 및 황산을 포함하지 않으며, (A) 인산, (B) 과산화물 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 and sulfuric acid, contains (A) phosphoric acid, (B) peroxide and (C) water, and includes a tungsten (W) film and a titanium nitride (TiN) film. It is for etching one or more, it provides an etchant composition.
또한, 본 발명은, 상기 식각액 조성물을 사용하는 식각 방법을 제공한다.In addition, the present invention provides an etching method using the etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하는 금속 패턴의 형성 방법을 제공한다.In addition, 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 to etch at least one of a tungsten (W) film and a titanium nitride (TiN) film, so that it is easy to control an etch rate and an etch rate, and provides an effect of 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 an effect of not damaging the oxide layer when at least one of the tungsten layer and the titanium nitride layer is etched.
또한, 본 발명의 식각액 조성물은 식각 공정 후, IPA 세정 시 문제점이 발생되지 않는 효과를 제공한다.In addition, the etchant composition of the present invention provides an effect that does not cause problems during IPA cleaning after the etching process.
본 발명은, 질산 및 황산을 포함하지 않으며, (A) 인산, (B) 과산화물 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 and sulfuric acid, contains (A) phosphoric acid, (B) peroxide, and (C) water, and is for etching at least one of a tungsten (W) film and a titanium nitride (TiN) film Phosphorus, an etchant composition, an etching method using the same, and a method of forming a metal pattern, wherein the etchant composition may etch the tungsten film or the titanium nitride film, and preferably, the tungsten film and the titanium nitride film are simultaneously etched. I can.
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 : 0.7~1.8인 것이 바람직하다.In the etchant composition of the present invention, the etch rate of the tungsten film and the titanium nitride film may be adjusted 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 1:0.7 to 1.8.
<식각액 조성물> <Etching liquid 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 may be used to etch the tungsten layer.
상기 인산의 함량은 식각액 조성물 총 중량에 대하여, 48 내지 81 중량%로 포함되며, 55 내지 75 중량%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 included in 48 to 81% by weight, and preferably 55 to 75% by weight, based on the total weight of the etchant composition. When the phosphoric acid is included in the content range, the tungsten layer may be uniformly etched by adjusting the dissociation rate of the tungsten layer to an appropriate level.
(B) 과산화물(B) peroxide
본 발명의 식각액 조성물에 포함되는 상기 과산화물은 상기 텅스텐막 및 상기 티타늄 질화물막을 식각하는 데 사용될 수 있다.The peroxide contained in the etchant composition of the present invention may be used to etch the tungsten layer and the titanium nitride layer.
상기 과산화물은, 예를 들어, 과산화수소, 테트라부틸하이드로퍼옥사이드, 메틸에틸케톤퍼옥사이드, 암모늄 퍼옥소모노설페이트, 과황산암모늄, 테트라메틸암모늄 퍼설페이트, 테트라뷰틸암모늄 퍼옥소모노설페이트, 퍼옥소모노황산 및 과아세트산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하고, 바람직하게는 과산화수소, 테트라부틸하이드로퍼옥사이드, 메틸에틸케톤퍼옥사이드 중 1종 이상을 포함할 수 있다The peroxide is, for example, hydrogen peroxide, tetrabutyl hydroperoxide, methyl ethyl ketone peroxide, ammonium peroxomonosulfate, ammonium persulfate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfate And at least one selected from the group consisting of peracetic acid, and preferably at least one of hydrogen peroxide, tetrabutyl hydroperoxide, and methyl ethyl ketone peroxide.
상기 과산화물의 함량은 식각액 조성물 총 중량에 대하여, 1 내지 15 중량%로 포함되며, 5 내지 10 중량%가 바람직하다. 상기 과산화물이, 상기 함량 범위 미만으로 포함될 경우, 식각 속도가 너무 느리고, 상기 함량 범위 초과로 포함될 경우, 식각 속도가 너무 빨라, 상기 텅스텐막 및 상기 티타늄 질화물막 표면의 식각 균일성(uniformity)이 저하될 수 있다.The content of the peroxide is included in 1 to 15% by weight, preferably 5 to 10% by weight, based on the total weight of the etchant composition. When the peroxide is contained within the content range, the etching rate is too slow, and when the peroxide content exceeds the content range, the etching rate is too fast, so that the etching uniformity of the surface of the tungsten layer and the titanium nitride layer decreases. Can be.
(C) 물(C) water
본 발명의 식각액 조성물에 포함되는 상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water contained in the etchant composition of the present invention may be deionized water for a semiconductor process, and preferably, deionized water of 18㏁/cm or more may be used.
상기 물의 함량은 식각액 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The amount of water may be included in a residual amount such that the total weight of the etchant composition is 100% by weight.
(D) 암모늄염(D) ammonium salt
본 발명의 식각액 조성물은 상기 암모늄염을 더 포함할 수 있으며, 상기 암모늄염은 상기 텅스텐막의 식각 균일성을 개선시키는 데 사용될 수 있다. 구체적으로, 상기 암모늄염의 암모늄 양이온에 의해, 식각된 상기 텅스텐막의 식각 균일성이 개선될 수 있다.The etchant composition of the present invention may further include the ammonium salt, and the ammonium salt may be used to improve the etching uniformity of the tungsten layer. Specifically, the etching uniformity of the etched tungsten layer may be improved by the ammonium cation of the ammonium salt.
상기 암모늄염은, 예를 들어, 암모늄 설페이트, 암모늄 바이설페이트, 암모늄 나이트레이트, 암모늄 포스페이트, 암모늄아세테이트, 암모늄시트레이트 및 암모늄 퍼설페이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하고, 바람직하게는 암모늄 설페이트, 암모늄 나이트레이트, 암모늄 포스페이트 및 암모늄 퍼설페이트 중 1종 이상을 포함할 수 있다The ammonium salt includes, for example, at least one selected from the group consisting of ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium citrate and ammonium persulfate, and preferably ammonium sulfate , Ammonium nitrate, ammonium phosphate and ammonium persulfate.
상기 암모늄염의 함량은 식각액 조성물 총 중량에 대하여, 0.001 내지 1 중량%로 포함되며, 0.1 내지 1 중량%가 바람직하다. 상기 암모늄염이, 상기 함량 범위 미만으로 포함될 경우, 상기 텅스텐막의 식각 균일성 개선 효과가 미미하고, 상기 함량 범위 초과로 포함될 경우, 식각 대상 웨이퍼(wafer)를 한 장씩 처리하는 매엽식 세정 장치(single tool)로 식각 공정을 수행하는 경우, 상기 암모늄염이 재결정화되어 입자를 생성하고, 생성된 암모늄염 입자가 금속 패턴 내에 결함을 발생시킬 수 있다.The content of the ammonium salt is included in an amount of 0.001 to 1% by weight, preferably 0.1 to 1% by weight, based on the total weight of the etchant composition. When the ammonium salt is contained within the content range, the effect of improving the etching uniformity of the tungsten film is insignificant, and when the ammonium salt is included in the content exceeding the content range, a single tool that processes wafers to be etched one by one. ), the ammonium salt is recrystallized to generate particles, and the generated ammonium salt particles may cause defects in the metal pattern.
(E) 계면활성제(E) surfactant
본 발명의 식각액 조성물은 계면활성제를 더 포함할 수 있으며, 상기 계면활성제는 상기 암모늄염과 함께 상기 텅스텐막의 식각 균일성을 개선시키는데 사용될 수 있다. 구체적으로, 상기 계면활성제는 식각액 조성물의 점도 및 젖음(wetting)성을 개선시켜, 상기 텅스텐막의 식각 균일성을 개선시킬 수 있다.The etchant composition of the present invention may further include a surfactant, and the surfactant may be used together with the ammonium salt to improve the etching uniformity of the tungsten layer. Specifically, the surfactant may improve the viscosity and wettability of the etchant composition, thereby improving the etching uniformity of the tungsten layer.
상기 계면활성제는 고온 및 강산에 반응성이 없는 음이온성 계면활성제인 것이 바람직하며, 술폰산계 계면활성제가 더욱 바람직하고, 상기 술폰산계 계면활성제는 불소를 함유한 것일 수 있다.The surfactant is preferably an anionic surfactant that is not reactive to high temperatures and strong acids, more preferably a sulfonic acid surfactant, and the sulfonic acid surfactant may contain fluorine.
상기 계면활성제의 함량은 식각액 조성물 총 중량에 대하여, 0.001 내지 1 중량%로 포함되며, 0.01 내지 0.1 중량%가 바람직하다. 상기 계면활성제가, 상기 함량 범위 미만으로 포함될 경우, 상기 텅스텐막의 식각 균일성 개선 효과가 미미하고, 상기 함량 범위 초과로 포함될 경우, 다량의 거품이 발생되고, 미세 거품들이 금속 패턴 표면에 잔류하여, 식각 공정 후 증착 공정에서의 불균일한 증착을 야기하여 결함을 발생시킬 수 있다.The content of the surfactant is included in an amount of 0.001 to 1% by weight, and preferably 0.01 to 0.1% by weight, based on the total weight of the etchant composition. When the surfactant is contained in an amount less than the content range, the effect of improving the etching uniformity of the tungsten film is insignificant, and when it is included in an amount exceeding the content range, a large amount of bubbles is generated, and fine bubbles remain on the surface of the metal pattern, Defects may be generated by causing non-uniform deposition in the deposition process after the etching process.
본 발명의 식각액 조성물은 질산 및 황산을 포함하지 않는다. 식각액 조성물이 질산을 포함할 경우, 경시안정성이 저하되며, 황산을 포함할 경우, 폭발 위험성이 높아 취급이 용이하지 않으므로 바람직하지 않다. 또한 금속 패턴 형성 시, 텅스텐 잔류물 제거, 패턴 손상(pattern collapse) 및 워터마크(water mark) 방지를 위해 IPA 세정이 요구되나, 질산 및 황산은 IPA와의 반응성이 높아 IPA 세정이 어렵다는 문제가 있다. 따라서 본 발명의 식각액 조성물은 질산 및 황산을 포함하지 않는 것이 바람직하다.The etchant composition of the present invention does not contain nitric acid and sulfuric acid. When the etchant composition contains nitric acid, the stability over time is deteriorated, and when sulfuric acid is included, it is not preferable because handling is not easy due to high risk of explosion. In addition, when forming a metal pattern, IPA cleaning is required to remove tungsten residues, prevent pattern collapse and water mark, but nitric acid and sulfuric acid have a problem that IPA cleaning is difficult due to high reactivity with IPA. Therefore, it is preferable that the etchant composition of the present invention does not contain nitric acid and sulfuric acid.
<식각액 조성물을 이용한 식각 방법><Etching method using an 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. In addition, the present invention provides an etching method using the etchant composition according to the present invention. The etching method of the present invention may form a pattern according to a known metal etching method, except that the etching solution 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.For example, the etching method may include i) forming a single layer made of tungsten (W) or titanium nitride (TiN) on a substrate, or a multilayer layer including the single layer of tungsten and the single layer of titanium nitride; ii) selectively leaving a photoreactive 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 of 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. In addition, 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 may form a pattern according to a known method of forming a metal pattern, 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.For example, the method of forming the metal pattern may include: i) forming a single layer made of tungsten (W) or titanium nitride (TiN) or a multilayered layer including the single layer of tungsten and the single layer of titanium nitride 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 for explaining 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 furthermore, it contains the meanings equivalent to the claims recorded and all modifications within the scope. In addition, "%" and "parts" indicating content in the following examples and comparative examples are based on mass unless otherwise noted.
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.Referring to Table 1 below, an etchant composition according to Examples and Comparative Examples was prepared.
과수: 과산화수소Fruit tree: hydrogen peroxide
TBHP: tetrabutyl hydroperoxideTBHP: tetrabutyl hydroperoxide
MEKP: Methyl ethyl ketone peroxideMEKP: Methyl ethyl ketone peroxide
AS: Ammonium SulfateAS: Ammonium Sulfate
AP: Ammonium Phosphate AP: Ammonium Phosphate
AN: Ammonium NitrateAN: Ammonium Nitrate
APS: Ammonium persulfateAPS: Ammonium persulfate
S4300: 3M Novec-4300 Electronic Surfactant(술폰산계 계면활성제)S4300: 3M Novec-4300 Electronic Surfactant (sulfonic acid-based surfactant)
시험예 1: 식각 속도 측정Test Example 1: Etch 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 the titanium nitride (TiN) film by immersing in the etchant composition according to Examples and Comparative Examples, the etch rate (Å/min) was measured using SEM, and the tungsten film and titanium The etching 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, a silicon oxide (SiOx) film and an aluminum oxide (AlOx) film were immersed in the etchant composition according to Examples and Comparative Examples, and the degree of etching was determined according to the following evaluation criteria, and then shown in Table 2 below.
<실리콘산화물막 및 알루미늄 산화물막에 대한 식각 정도 평가 기준><Criteria 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 speed 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.With respect to the tungsten film etched through Test Example 1, the etching uniformity of the surface of the tungsten film was measured using AFM, and then numerically expressed in RMS (root mean square) and shown in Table 2 below. 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, 7 및 8을 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 means the roughness of the surface of the film, and the closer it is to 0, the more uniformly it is etched. However, it is preferable to understand it as a relative value compared to the initial etch rate in consideration of the etch amount of the tungsten film. For example, in Table 1 and Table 2 below, in Examples 1, 7 and 8, it was confirmed that even when etching was performed using a composition having the same composition, when the temperature was high, the amount of etching increased and the RMS value increased. I can.
시험예 3Test Example 3
시험예 1을 통해 텅스텐막을 식각한 뒤, 잔존하는 식각액 조성물과 텅스텐 잔류물을 IPA(isopropyl alcohol)로 세정(rinse)하고, 세정이 가능한 경우 ○, 세정이 불가능한 경우 X로 평가하여, 하기 표 2에 나타내었다.After etching the tungsten film through Test Example 1, the remaining etchant composition and tungsten residue were rinsed with IPA (isopropyl alcohol) and evaluated as ○ when cleaning was possible, and evaluated as X when cleaning was impossible, and Table 2 below. Shown in.
또한, 식각 처리 과정 중에서 식각액 조성물의 구성 성분이 석출되어 나오는 지, 식각액 조성물의 용해도를 아래 평가 기준에 따라 판단한 뒤, 하기 표 2에 나타내었다.In addition, after determining whether constituents of the etchant composition are precipitated during the etching process and the solubility of the etchant composition is determined according to the following evaluation criteria, it is shown in Table 2 below.
<용해도 평가 기준><Solubility evaluation criteria>
○: 탁도측정결과 NTU가 1 이하○: As a result of turbidity measurement, NTU is less than 1
△: 탁도측정결과 NTU가 1 초과 내지 5 이하△: As a result of turbidity measurement, NTU exceeds 1 to 5
X: 탁도측정결과 NTU가 5 초과X: As a result of turbidity measurement, NTU exceeds 5
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, IPA 세정 시 문제가 발생하지 않으며, 실리콘 산화물막 및 알루미늄 산화물막의 식각 시 식각 속도가 1 Å/min 이하로, 실질적으로 손상을 주지 않는 것을 확인할 수 있다. Referring to Table 2, when the etching process is performed using the etchant composition according to the embodiment, an appropriate level of etch rate is provided for the tungsten film and the titanium nitride film, and thus the etching uniformity is excellent, and IPA cleaning When the silicon oxide layer and the aluminum oxide layer are etched, the etching rate is less than 1 Å/min, and it can be seen that there is no damage.
또한, 실시예 1 및 4 내지 6의 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 and 4 to 6, it can be seen that the etch rate for the tungsten film and the titanium nitride film can be easily adjusted by adjusting the components constituting the etchant composition and the content of each component. have.
또한, 실시예 9 내지 15의 결과를 통해, 식각액 조성물이 암모늄염을 포함하는 경우, 텅스텐막 표면의 식각 균일성이 개선됨을 알 수 있다.In addition, from the results of Examples 9 to 15, it can be seen that when the etchant composition contains an ammonium salt, the etching uniformity of the tungsten film surface is improved.
반면, 비교예에 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. 특히, 질산 또는 황산을 포함하는 경우, IPA와의 반응에 의해 IPA 세정 시 문제가 발생하며 따라서 식각 후 발생되는 텅스텐 잔류물을 제거하기 어려울 뿐만 아니라, pattern collapse, water mark 등의 문제점이 발생될 수 있다. 또한, 불산을 포함하는 경우, 실리콘 산화물막 및 알루미늄 산화물막에는 손상이 발생되므로, 텅스텐막 및 티타늄 질화물막 하부의 산화물막을 포함하는 경우 사용에 제한이 따른다.On the other hand, when the etching process is performed using the etchant composition according to the comparative example, it can be seen that the tungsten film and the titanium nitride film cannot be provided with an appropriate level of etch rate, and thus, the etch uniformity is lowered. In particular, in the case of containing nitric acid or sulfuric acid, a problem occurs during IPA cleaning due to reaction with IPA, and thus it is difficult to remove tungsten residues generated after etching, and problems such as pattern collapse and water mark may occur. . In addition, when hydrofluoric acid is included, damage is caused to the silicon oxide film and the aluminum oxide film, and therefore, the use of the oxide film under the tungsten film and the titanium nitride film is limited.
Claims (9)
(A) 인산, (B) 과산화물 및 (C) 물을 포함하고, 텅스텐(W)막 및 티타늄 질화물(TiN)막 중 하나 이상을 식각하기 위한 것인, 식각액 조성물.
Does not contain nitric acid and sulfuric acid,
Including (A) phosphoric acid, (B) peroxide, and (C) water, and for etching at least one of a tungsten (W) film and a titanium nitride (TiN) film.
상기 (B) 과산화물은 과산화수소, 테트라부틸하이드로퍼옥사이드, 메틸에틸케톤퍼옥사이드, 암모늄 퍼옥소모노설페이트, 과황산암모늄, 테트라메틸암모늄 퍼설페이트, 테트라뷰틸암모늄 퍼옥소모노설페이트, 퍼옥소모노황산 및 과아세트산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
The (B) peroxide is hydrogen peroxide, tetrabutyl hydroperoxide, methyl ethyl ketone peroxide, ammonium peroxomonosulfate, ammonium persulfate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfate and peroxomonosulfate. An etching solution composition comprising at least one selected from the group consisting of acetic acid.
식각액 조성물 총 중량에 대하여,
상기 (A) 인산 48 내지 81 중량%;
상기 (B) 과산화물 1 내지 15 중량%; 및
상기 (C) 물 잔량을 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
Based on the total weight of the etchant composition,
48 to 81% by weight of the (A) phosphoric acid;
1 to 15% by weight of the (B) peroxide; And
An etching solution composition comprising the remaining amount of (C) water.
식각액 조성물 총 중량에 대하여,
상기 (A) 인산 55 내지 75 중량%;
상기 (B) 과산화물 5 내지 10 중량%; 및
상기 (C) 물 잔량을 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
Based on the total weight of the etchant composition,
55 to 75% by weight of the (A) phosphoric acid;
5 to 10% by weight of the (B) peroxide; And
An etching solution composition comprising the remaining amount of (C) water.
상기 식각액 조성물은 (D) 암모늄염을 더 포함하는 것을 특징으로 하는 식각액 조성물.
The method according to claim 1,
The etching solution composition (D) an etching solution composition, characterized in that it further comprises an ammonium salt.
상기 (D) 암모늄염은 암모늄 설페이트, 암모늄 바이설페이트, 암모늄 나이트레이트, 암모늄 포스페이트, 암모늄아세테이트, 암모늄시트레이트 및 암모늄 퍼설페이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 식각액 조성물.
The method of claim 5,
The (D) ammonium salt is an etchant composition comprising at least one selected from the group consisting of ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, ammonium citrate and ammonium persulfate.
식각액 조성물 총 중량에 대하여, 상기 암모늄염은 0.001 내지 1 중량%로 포함되는 것을 특징으로 하는 식각액 조성물.
The method of claim 5,
An etchant composition, characterized in that the ammonium salt is contained in an amount of 0.001 to 1% by weight based on the total weight of the etchant composition.
상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및
청구항 1의 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 식각 방법.
Forming a single film made of tungsten (W) or titanium nitride (TiN) or a multilayer film including the single tungsten film and the single titanium nitride film on a substrate;
Selectively leaving a photoreactive material on the single layer or the multilayer layer; And
An etching method comprising the step of etching the single layer or the multilayer layer using the etchant composition of claim 1.
청구항 1의 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 금속 패턴의 형성 방법.Forming a single film made of tungsten (W) or titanium nitride (TiN) or a multilayer film including the single tungsten film and the single titanium nitride film on a substrate; And
A method of forming a metal pattern comprising the step of etching the single layer or the multilayer layer using the etchant composition of claim 1.
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| KR101154762B1 (en) | 2004-05-11 | 2012-06-18 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching solution for titanium or titanium alloy |
| KR20150050278A (en) | 2013-10-31 | 2015-05-08 | 솔브레인 주식회사 | Composition for etching titanium nitrate layer-tungsten layer containing laminate, method for etching using the same and semiconductor device manufactured by using the same |
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| KR101154762B1 (en) | 2004-05-11 | 2012-06-18 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching solution for titanium or titanium alloy |
| KR20150050278A (en) | 2013-10-31 | 2015-05-08 | 솔브레인 주식회사 | Composition for etching titanium nitrate layer-tungsten layer containing laminate, method for etching using the same and semiconductor device manufactured by using the same |
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| CN114369462A (en) * | 2021-12-16 | 2022-04-19 | 湖北兴福电子材料有限公司 | Etching solution for selectively etching titanium nitride and tungsten |
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