KR20200054866A - Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same - Google Patents
Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same Download PDFInfo
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- KR20200054866A KR20200054866A KR1020190129433A KR20190129433A KR20200054866A KR 20200054866 A KR20200054866 A KR 20200054866A KR 1020190129433 A KR1020190129433 A KR 1020190129433A KR 20190129433 A KR20190129433 A KR 20190129433A KR 20200054866 A KR20200054866 A KR 20200054866A
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- Prior art keywords
- silver
- film
- etchant composition
- thin film
- etching
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000004332 silver Substances 0.000 title claims abstract description 117
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000005530 etching Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000010409 thin film Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 79
- 239000010410 layer Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 18
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 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
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- WGCXSIWGFOQDEG-UHFFFAOYSA-N [Zn].[Sn].[In] Chemical compound [Zn].[Sn].[In] WGCXSIWGFOQDEG-UHFFFAOYSA-N 0.000 claims 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 1
- 238000001039 wet etching Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000011282 treatment Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- -1 Hydrogen peroxide nitric acid Potassium bisulfate Chemical compound 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229940100688 oral solution Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
Abstract
Description
본 발명은 은 박막 식각액 조성물, 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 관한 것이다.The present invention relates to a silver thin film etchant composition, an etching method using the same, and a method of forming a metal pattern.
본격적인 정보화 시대로 접어들게 됨에 따라 대량의 정보를 처리 및 표시하는 디스플레이 분야가 급속도로 발전해 왔으며, 이에 부응하여 다양한 평판 디스플레이가 개발되어 각광받고 있다.With the advent of the full-fledged information age, the display field for processing and displaying a large amount of information has rapidly developed, and in response, various flat panel displays have been developed and attracting attention.
평판디스플레이 장치의 예로는 액정디스플레이장치(Liquid crystal display device: LCD), 플라즈마디스플레이장치(Plasma Display Panel device: PDP), 전계방출디스플레이장치(Field Emission Display device: FED), 전기발광디스플레이장치(Electroluminescence Display device: ELD), 유기발광디스플레이(Organic Light Emitting Diodes: OLED) 등을 들 수 있으며, 이러한 평판디스플레이 장치는 텔레비전이나 비디오 등의 가전분야 뿐만 아니라 노트북과 같은 컴퓨터 및 핸드폰 등에 다양한 용도로 사용되고 있다. 이들 평판디스플레이 장치는 박형화, 경량화, 및 저소비전력화 등의 우수한 성능으로 인하여 기존에 사용되었던 브라운관(Cathode Ray Tube: CRT)을 빠르게 대체하고 있는 실정이다. Examples of flat panel display devices include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescence display device. device: ELD), Organic Light Emitting Diodes (OLED), and the like. These flat panel display devices are used for various purposes, such as home appliances such as televisions and videos, as well as computers and mobile phones such as laptops. These flat panel display devices are rapidly replacing the conventionally used cathode ray tube (CRT) due to excellent performance such as thinning, lightening, and low power consumption.
특히 OLED는 소자 자체적으로 빛을 발광하며 저전압에서도 구동될 수 있기 때문에 최근 휴대기기 등의 소형 디스플레이 시장에 빠르게 적용되고 있다. 또한 OLED는 소형 디스플레이를 넘어서 대형 TV의 상용화를 목전에 둔 상태이다.In particular, OLED emits light on its own and can be driven even at low voltage, so it has been rapidly applied to small display markets such as portable devices. In addition, OLED is in the midst of commercialization of large TVs beyond small displays.
또한, 반사판의 경우 과거 알루미늄(Al) 반사판을 주로 제품에 이용해왔으나, 휘도 향상을 통한 저전력 소비실현을 위해서는 반사율이 더 높은 금속으로의 재료변경을 모색하고 있는 상태이다. 이를 위해 평판디스플레이장치에 적용되고 있는 금속들에 비해 낮은 비저항과 높은 휘도를 가지고 있는 은(Ag: 비저항 약 1.59μΩ㎝)막, 은합금 또는 이를 포함한 다층막을 칼라필터의 전극, LCD 또는 OLED 배선 및 반사판에 적용, 평판표시장치의 대형화와 고 해상도 및 저전력 소비 등을 실현하고자 하여, 이 재료의 적용을 위한 식각액의 개발이 요구되었다.In addition, in the case of the reflector, aluminum (Al) reflector has been mainly used in the past, but in order to realize low power consumption through improvement in luminance, a material change to a metal having a higher reflectance is being sought. To this end, a silver (Ag: resistivity of about 1.59 μΩcm) film, silver alloy, or a multi-layer film including the same, which has a low specific resistance and high brightness compared to metals applied to a flat panel display device, is used as a color filter electrode, LCD or OLED wiring, and In order to realize the application to the reflector, the enlargement of the flat panel display, and the realization of high resolution and low power consumption, development of an etchant for application of this material has been required.
그러나, 은(Ag)은 유리 등의 절연 기판 또는 진성 비정질 규소나 도핑된 비정질 규소 등으로 이루어진 반도체 기판 등의 하부 기판에 대해 접착성(adhesion)이 극히 불량하여 증착이 용이하지 않고, 배선의 들뜸(lifting) 또는 벗겨짐(Peeling)이 쉽게 유발된다. 또한, 은(Ag)도전층이 기판에 증착된 경우에도 이를 패터닝하기 위해 식각액을 사용하게 된다. 이러한 식각액으로서 종래의 식각액을 사용하는 경우 은(Ag)이 과도하게 식각되거나, 불균일하게 식각되어 배선의 들뜸 또는 벗겨짐 현상이 발생하고, 배선의 측면 프로파일이 불량하게 된다.However, silver (Ag) is extremely poor in adhesion to an insulating substrate such as glass or a semiconductor substrate made of intrinsic amorphous silicon or doped amorphous silicon, so that deposition is not easy and the wiring is lifted. (lifting) or peeling is easily caused. Further, even when a silver (Ag) conductive layer is deposited on the substrate, an etchant is used to pattern it. When a conventional etchant is used as the etchant, silver (Ag) is excessively etched or non-uniformly etched, resulting in the lifting or peeling of the wiring, and the side profile of the wiring is poor.
또한 고해상도 구현을 위한 낮은 스큐(LOW Skew)구현이 공정을 하는데 있어 어려움이 있다.In addition, the implementation of low skew for realizing high resolution has difficulties in the process.
특히, 은(Ag)은 쉽게 환원이 되는 금속으로 식각 속도가 빨라야 잔사 유발 없이 식각이 되게 되는데 식각 후 테이퍼 각(taper angle) 형성이 어렵고 식각 패턴의 직진성 확보에 어려움이 있어서, 배선 및 패턴 형성 시 많은 한계점을 가지고 있다. 또한, 은 식각액 조성물을 사용하여 은 박막 식각시, 기판 내 노출된 S/D 부의 금속막에 식각된 은 입자가 다시 흡착되는 문제가 발생하며, 이 경우 후속 공정에서 전기적 쇼트가 발생할 수 있어 불량 발생의 원인이 될 수 있다 점에서 문제가 있다. Particularly, silver (Ag) is a metal that is easily reduced, and the etching rate must be fast to etch without inducing residue. It has many limitations. In addition, when the silver thin film is etched using the silver etchant composition, there is a problem that the etched silver particles are adsorbed again on the metal film of the S / D part exposed in the substrate, and in this case, electrical short may occur in a subsequent process, resulting in defects. There is a problem in that it can be the cause of.
이와 관련하여, 대한민국 공개특허 제 2008-0009866호 등, 주 산화제로써 인산이 필수적으로 사용되는 인산계 은 식각액 조성물이 주로 개발되어 왔으나, 인산에 의한 하부막 손상 등 인산계 식각액 조성물의 문제점 발생하고 있다. 따라서, 인산이 포함되지 않으면서도 은 식각 특성이 우수한 식각액 조성물의 개발이 필요하며, 특히, 당해 기술분야의 주요한 문제점인 잔사 및 은 재흡착 문제 및 처리매수 증가에 따른 식각액 조성물의 성능 저하 문제를 완전히 해결할 수 있는 비인산계 은 식각액 조성물의 개발이 필요한 실정이다.In this regard, Korea Patent Publication No. 2008-0009866, etc., phosphoric acid-based silver etchant composition, which is essentially used as a main oxidant, has been mainly developed, but there is a problem with the phosphoric acid-based etchant composition, such as damage to the underlying film due to phosphoric acid. . Therefore, it is necessary to develop an etchant composition having excellent silver etching properties without phosphoric acid, and in particular, the problem of deterioration in the performance of the etchant composition due to residue and silver re-adsorption problems and increase in the number of treatments, which are the main problems in the art, is required. Non-phosphate-based silver etchant compositions that can be solved are needed.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용할 수 있으며, 편측 식각(Side etch)량을 감소시킬 수 있고, 은 잔사 및 은 재흡착의 발생을 억제하면서 장기적으로 반복 사용할 수 있는, 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is to improve the above-mentioned problems of the prior art, and can be used for etching a single film made of silver (Ag) or a silver alloy, and a multi-layer film composed of the single film and the transparent conductive film, and side etching It is an object of the present invention to provide a silver thin film etchant composition that can reduce the amount and can be used repeatedly in the long term while suppressing the occurrence of silver residue and silver resorption.
또한, 본 발명은 상기 단일막 및 상기 다층막을 동시에 식각할 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a silver thin film etchant composition capable of simultaneously etching the single film and the multilayer film.
또한, 본 발명은 하부막의 손상 없이 식각 균일성을 나타내는 습식 식각에 유용하게 사용될 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a silver thin film etchant composition that can be effectively used for wet etching that exhibits etching uniformity without damaging the underlying film.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 식각 방법 및 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching method using the silver thin film etchant composition and a method of forming a metal pattern.
상기 목적을 달성하기 위해, 본 발명은, (A) 은식각촉진제; (B) 무기산; (C) 중황산염; 및 (D) 물을 포함하는, 은 박막 식각액 조성물을 제공한다.In order to achieve the above object, the present invention, (A) silver etch promoter; (B) inorganic acids; (C) bisulfate; And (D) water.
또한, 본 발명은, 상기 은 박막 식각액 조성물을 사용하는 식각 방법을 제공한다.In addition, the present invention provides an etching method using the silver thin film etchant composition.
또한, 본 발명은 상기 은 박막 식각액 조성물을 사용하는 금속 패턴의 형성 방법을 제공한다.In addition, the present invention provides a method of forming a metal pattern using the silver thin film etchant composition.
본 발명의 은 박막 식각액 조성물은 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용되어, 잔사(예를 들어, 은 잔사 및/또는 투명전도막 잔사 등)및 은 재흡착을 억제하는 효과를 제공한다.The silver thin film etchant composition of the present invention is used for etching a single film made of silver (Ag) or a silver alloy and a multi-layer film composed of the single film and a transparent conductive film, such that residues (eg, silver residue and / or transparent conductivity) Membrane residue, etc.) and silver provide an effect of suppressing resorption.
또한, 본 발명의 은 박막 식각액 조성물은 처리 매수가 누적된 후에도 신액 특성을 유지할 수 있어 장기적으로 반복 사용할 수 있다.In addition, the silver thin film etchant composition of the present invention can maintain the new liquid properties even after the number of treatments is accumulated, and thus can be repeatedly used in the long term.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막을 동시에 식각하여, 식각 효율을 향상시킬 수 있다.In addition, the silver thin film etchant composition of the present invention can improve the etching efficiency by simultaneously etching the single layer and the multilayer layer.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막의 과식각을 방지하여 편측 식각(Side etch)량을 감소시킬 수 있어 미세패턴을 형성할 수 있다.In addition, the silver thin film etchant composition of the present invention can prevent over-etching of the single layer and the multi-layer layer, thereby reducing a side etch amount, thereby forming a fine pattern.
또한, 본 발명의 은 박막 식각액 조성물은 하부막의 손상 없이 식각 균일성을 나타내는 습식 식각에 유용하게 사용될 수 있다.In addition, the silver thin film etchant composition of the present invention can be usefully used for wet etching that exhibits etching uniformity without damaging the underlying film.
본 발명은, (A) 은식각촉진제, (B) 무기산 및 (C) 중황산염을 포함하며, 용제로써 (D) 물을 포함하는 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 관한 것이다.The present invention, (A) a silver etching accelerator, (B) inorganic acid and (C) bisulfate, and as a solvent (D) a silver thin film etchant composition containing water and etching method using the same and a method of forming a metal pattern It is about.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용될 수 있으며, 특히 중황산염을 포함함으로, 잔사(예를 들어, 은 잔사 및/또는 투명전도막 잔사 등) 및 은 재흡착 문제가 발생하지 않는 것을 특징으로 한다. 상기 재흡착은 기판 내 노출된 S/D(소스/드레인) 부의 금속막에, 식각된 은 입자가 부착되는 현상을 의미하는 것일 수 있으며, 상기 기판 내 노출된 S/D 부의 금속막은 Mo, Cu, 및 이들의 합금으로 구성된 단일막 또는 다층막일 수 있고, 삼중막 상부 Ti, 중앙의 Al, 하부의 Ti 의 일부 또는 모든 부분에서 은의 재흡착 일 수 있다.The silver thin film etchant composition of the present invention, and an etching method using the same and a method of forming a metal pattern may be used for etching a single film made of silver (Ag) or a silver alloy, and a multi-layer film composed of the single film and the transparent conductive film. By containing bisulfate, it is characterized in that the residue (eg, silver residue and / or transparent conductive film residue, etc.) and silver re-adsorption problems do not occur. The re-adsorption may mean a phenomenon in which etched silver particles are attached to the metal film of the S / D (source / drain) part exposed in the substrate, and the metal film of the S / D part exposed in the substrate is Mo, Cu , And may be a single film or a multi-layer film made of an alloy of these, it may be the re-adsorption of silver in some or all of the upper portion of the triple layer Ti, Al in the middle, Ti in the lower portion.
또한, 본 발명의 은 박막 식각액 조성물은 처리 매수가 누적된 후에도 신액 특성을 유지할 수 있어 장기적으로 반복 사용할 수 있는 것으로, 식각 공정 초반에도 잔사 및 은 재흡착 문제가 발생하지 않을 뿐만 아니라, 장시간 식각공정을 진행하여 처리매수 높은 시점에도 잔사가 발생하지 않으며 은 재흡착 방지 효과가 우수하게 유지될 수 있다. In addition, the silver thin film etchant composition of the present invention can maintain a new liquid property even after the number of treatments is accumulated, so that it can be repeatedly used for a long time. In addition, a problem of residue and silver re-adsorption does not occur at the beginning of the etching process, but also a long etching process By proceeding, no residue is generated even when the number of treatments is high, and the effect of preventing silver re-adsorption can be maintained excellently.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 상기 단일막 및 상기 다층막을 동시에 식각에 사용될 수 있다.The silver thin film etchant composition of the present invention, the etching method using the same, and a method of forming a metal pattern may be used for etching the single layer and the multilayer layer simultaneously.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막의 과식각을 방지하여 편측 식각(Side etch)량을 감소시킬 수 있어 미세패턴을 형성할 수 있다.In addition, the silver thin film etchant composition of the present invention can prevent over-etching of the single layer and the multi-layer layer, thereby reducing a side etch amount, thereby forming a fine pattern.
상기 은 합금은 은을 주성분으로 하여 하여 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, In, Zn, Sn, Al 및 Ti 등의 다른 금속을 포함하는 합금 형태와; 은의 질화물, 규화물, 탄화물, 산화물 등을 포함할 수 있으며, 이에 한정되지 않는다.The silver alloy is an alloy form containing silver and other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, In, Zn, Sn, Al, and Ti as a main component. Wow; Silver nitride, silicide, carbide, oxide, and the like.
상기 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다.The transparent conductive film may include at least one selected from the group consisting of tin indium oxide (ITO), zinc indium oxide (IZO), tin zinc indium oxide (ITZO) and gallium zinc indium oxide (IGZO).
상기 다층막은 투명전도막/은, 투명전도막/은 합금, 투명전도막/은/투명전도막 또는 투명전도막/은 합금/투명전도막으로 형성되는 것을 포함할 수 있다.The multi-layer film may include a transparent conductive film / silver, a transparent conductive film / silver alloy, a transparent conductive film / silver / transparent conductive film or a transparent conductive film / silver alloy / transparent conductive film.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 반사막용 OLED TFT 어레이 기판, 터치스크린 패널용 trace 배선 또는 나노와이어(nanowire) 배선의 형성에 사용될 수 있으며, 이에 한정되지 않고 상기 단일막 및 상기 다층막을 포함하는 전자 부품 소재에 사용될 수 있다. The silver thin film etchant composition of the present invention, and an etching method using the same and a method of forming a metal pattern may be used for forming an OLED TFT array substrate for a reflective film, a trace wiring for a touch screen panel, or a nanowire wiring, but are not limited thereto. It may be used for electronic component materials including the single layer and the multilayer layer.
이하에서, 본 발명의 은 박막 식각액 조성물에 포함되는 구성성분들에 대하여 설명한다. Hereinafter, the components included in the silver thin film etchant composition of the present invention will be described.
<은 박막 식각액 조성물> <Silver thin film etchant composition>
본 발명의 식각액 조성물은, (A) 은식각촉진제, (B) 무기산 및 (C) 중황산염을 포함하며, 용제로써 (D) 물을 포함할 수 있다. The etching solution composition of the present invention includes (A) a silver etching accelerator, (B) an inorganic acid and (C) bisulfate, and may include (D) water as a solvent.
(A) 은식각촉진제(A) Silver etching promoter
본 발명의 은 박막 식각액 조성물에 포함되는 은식각촉진제는 주산화제로서, 은 박막 및/또는 투명전도막을 산화시켜 습식 식각하는 역할을 수행한다.The silver etch accelerator included in the silver thin film etchant composition of the present invention is a main oxidizer, and serves to wet etch by oxidizing the silver thin film and / or the transparent conductive film.
본 발명의 은식각촉진제는 과산화수소 및 철염으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. The silver etching accelerator of the present invention may include one or more selected from the group consisting of hydrogen peroxide and iron salt.
상기 철염으로는, 예를 들면, 질산철, 질산 제이철, 황산철 및 황산 제이철 등을 들 수 있고, 질산제이철이 가장 바람직하다.Examples of the iron salts include iron nitrate, ferric nitrate, iron sulfate and ferric sulfate, and ferric nitrate is most preferred.
다만, 상기 철염이 FeCl3와 같이 염소화합물(즉, 염소이온)을 포함하는 경우, 이를 사용하는 본 발명의 인 박막 식각액 조성물로 은 박막을 식각하게 되면 은 석출이 발생하는 문제점을 야기 시킨다. 따라서, 본 발명에서 철염은 FeCl3 등의 염소화합물을 포함하지 않는 것이 바람직하다However, when the iron salt contains a chlorine compound (ie, chlorine ion), such as FeCl 3 , when the silver thin film is etched with the phosphorus thin film etchant composition of the present invention, silver precipitation occurs. Therefore, in the present invention, it is preferable that the iron salt does not contain chlorine compounds such as FeCl 3 .
상기 은식각촉진제의 함량은 조성물 총 중량에 대하여, 0.01 내지 20 중량%로 포함되며, 바람직하게는 1 내지 5 중량%로 포함될 수 있다. 은식각촉진제의 함량이 상기 함량범위 내로 포함되는 경우, 은의 식각 속도와 은 잔사 발생 방지 효과가 우수하고, 다층막 식각 시 은 박막과 투명전도막에 대한 식각 밸런스가 양호한 이점이 있다.The content of the silver etching accelerator is included in an amount of 0.01 to 20% by weight based on the total weight of the composition, and preferably 1 to 5% by weight. When the content of the silver etching accelerator is included within the above content range, the etching rate of silver and the effect of preventing the generation of silver residue are excellent, and the etching balance of the silver thin film and the transparent conductive film is good when the multilayer film is etched.
(B) 무기산(B) inorganic acid
본 발명의 식각액 조성물에 포함되는 무기산은 식각개선제로 사용되는 성분으로서, 은 박막 및/또는 투명전도막을 산화시켜 습식 식각하는 역할을 수행한다.The inorganic acid contained in the etching solution composition of the present invention is a component used as an etching improving agent, and serves to wet etch by oxidizing a silver thin film and / or a transparent conductive film.
상기 무기산은 보다 구체적으로, 질산 및 황산 등으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있으며, 바람직하게는 2종 이상을 포함하고, 가장 바람직하게는 질산 및 황산을 포함할 수 있다. More specifically, the inorganic acid may include one or more types selected from the group consisting of nitric acid and sulfuric acid, and more preferably two or more types, and most preferably nitric acid and sulfuric acid.
상기 무기산의 함량은 조성물 총 중량에 대하여, 0.1 내지 20 중량%로 포함되며, 바람직하게는 3 내지 8 중량%로 포함될 수 있다. The content of the inorganic acid is contained in 0.1 to 20% by weight, based on the total weight of the composition, preferably 3 to 8% by weight.
무기산의 함량이 상기 함량범위 내로 포함되는 경우, 식각 속도 및 식각 균일성(Uniformity)이 우수하여 미세패턴을 형성할 수 있다.When the content of the inorganic acid is included within the content range, the etching rate and the etching uniformity are excellent, thereby forming a fine pattern.
(C) 중황산염 (C) bisulfate
본 발명의 식각액 조성물에 포함되는 중황산염은 처리매수 향상제로 사용되는 성분으로서, 은 박막 식각시 Ag+ 이온이 증가됨에 따른 Etch 특성 변화를 억제하는 역할을 수행한다.The bisulfate contained in the etchant composition of the present invention is a component used as an agent for improving the number of treatments, and serves to suppress the change in the etching characteristic as the Ag + ion increases during the etching of the silver thin film.
상기 중황산염은 양이온이 암모늄, 칼륨, 나트륨으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것으로, 예를 들면, 중황산칼륨, 중황산나트륨, 중황산암모늄 등을 들 수 있다. The bisulfite is a cation containing at least one selected from the group consisting of ammonium, potassium, and sodium, and examples thereof include potassium bisulfate, sodium bisulfate, and ammonium bisulfate.
상기 중황산염의 함량은 조성물 총 중량에 대하여, 0.1 내지 30 중량%로 포함되며, 바람직하게는 3 내지 8 중량%로 포함될 수 있다. 본 발명에서 중황산염의 함량이 상기 함량범위 내인 경우, Ag+ 이온을 킬레이팅(Chelating)하는 효과가 우수하고, 은 박막 식각 속도 증가에 의한 과식각을 방지할 수 있다. The content of the bisulfate is contained in 0.1 to 30% by weight relative to the total weight of the composition, preferably 3 to 8% by weight. In the present invention, when the content of the bisulfate is within the above-mentioned content range, the effect of chelating Ag + ions is excellent, and over-etching due to an increase in the etching rate of the silver thin film can be prevented.
(D) 물(D) water
본 발명의 은 박막 식각액 조성물에 포함되는 상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water contained in the silver thin film etchant composition of the present invention may be deionized water for semiconductor processing, and preferably, the deionized water of 18 kPa / cm or more may be used.
본 발명에서 물은 잔량으로 포함될 수 있으며, 상기 잔량은, 본 발명의 필수 성분 및 그 외 다른 성분들을 더 포함한 총 조성물의 중량이 100중량%가 되도록 하는 잔량을 의미한다. In the present invention, water may be included as a residual amount, and the residual amount means a residual amount such that the weight of the total composition including the essential components and other components of the present invention is 100% by weight.
예를 들면, 본 발명은 조성물의 총 중량대비 30 내지 99 중량 %로 포함될 수 있다. For example, the present invention may be included in an amount of 30 to 99% by weight based on the total weight of the composition.
본 발명의 은 박막 식각액 조성물은 유발시키는 인산을 포함하지 않는 것을 특징으로 하여, 은(Ag) 또는 은합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성된 다층막 식각시에 하부막을 손상시키지 않으면서 우수한 식각 균일성을 나타낼 수 있다.The silver thin film etchant composition of the present invention is characterized in that it does not contain phosphoric acid to induce, and does not damage the lower film when etching a single film made of silver (Ag) or silver alloy and a multilayer film composed of the single film and the transparent conductive film. Therefore, it can exhibit excellent etching uniformity.
<은 박막 식각액 조성물을 이용한 식각 방법><Etching method using silver thin film etchant composition>
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 식각 방법을 제공한다. 본 발명의 식각 방법은, 본 발명의 상기 은 박막 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 silver thin film 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 silver thin film etchant composition of the present invention is used.
일 예로, 상기 식각 방법은, i) 기판 상에, 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 형성하는 단계; ii) 상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및 iii) 본 발명에 따른 은 박막 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.For example, the etching method may include: i) forming a single film made of silver or a silver alloy on a substrate, or a multilayer film made of the single film and a transparent conductive film; ii) selectively leaving a photoreactive material on the single layer or the multilayer layer; And iii) using the silver thin film etchant composition according to the present invention, etching the single layer or the multilayer layer.
<< 은 박막 식각액 조성물을 이용한 금속 패턴의 형성 방법>Method of forming metal pattern using silver thin film etchant composition>
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공한다. 본 발명의 금속 패턴의 형성 방법은, 본 발명의 상기 은 박막 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 silver thin film etchant composition according to the present invention. The method of forming the metal pattern of the present invention can form a pattern according to a known metal pattern forming method, except that the silver thin film etchant composition of the present invention is used.
일 예로, 상기 금속 패턴의 형성 방법은, i) 기판 상에, 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 형성하는 단계; 및 ii) 본 발명에 따른 은 박막 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.For example, the method of forming the metal pattern includes: i) forming a single film made of silver or a silver alloy on a substrate, or a multilayer film made of the single film and a transparent conductive film; And ii) using the silver thin film etchant composition according to the present invention, etching the single layer or the multilayer layer.
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 more specifically, but the scope of the present invention is not limited by the following examples. The scope of the invention is indicated in the claims, and furthermore, includes all changes within the meaning and scope equivalent to the claims of the claims. In addition, "%" and "part" showing content in the following Examples and Comparative Examples are based on mass unless otherwise specified.
실시예 및 비교예: 은 박막 식각액 조성물의 제조Examples and Comparative Examples: Preparation of silver thin film etchant composition
하기 표 1에 나타난 조성에 따라 실시예 1 내지 12 및 비교예 1 내지 4의 은 박막 식각액 조성물을 제조하였으며, 100 중량%가 되도록 잔량의 물을 포함하였다 (단위: 중량%).Silver thin film etchant compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were prepared according to the composition shown in Table 1 below, and the residual amount of water was included to be 100% by weight (unit:% by weight).
(Ferric Nitrate)Ferric nitrate
(Ferric Nitrate)
(Potassium Bisufate)Potassium bisulfate
(Potassium Bisufate)
시험예Test example
1. 처리매수 평가1. Evaluation of the number of treatments
상기 실시예 1 내지 12 및 비교예 1 내지 4의 은 식각액 조성물이 제조 직후의 상태를 신액이라 하고, 상기 실시예들 및 비교예들의 식각액이 장시간 식각공정을 했다는 가정으로 인위적으로 은 파우더 1000ppm 을 녹여준 상태(처리매수 평가)를 구액이라 하였다.The silver etchant compositions of Examples 1 to 12 and Comparative Examples 1 to 4 are referred to as a new liquid immediately after preparation, and artificially melt 1000 ppm of silver powder under the assumption that the etchant of Examples and Comparative Examples has been subjected to a long etching process. The quasi-state (evaluation of the number of treatments) was referred to as an oral solution.
각각의 신액 및 구액을 사용하여 아래의 방법으로 Side Etch, 은 잔사 및 은 재흡착을 평가하였다.Side Etch, silver residue, and silver re-adsorption were evaluated in the following manner using each new solution and old solution.
2. Side Etch 측정2. Side Etch Measurement
기판 상에 ITO(산화주석인듐)/은/ITO 삼중막을 형성한 뒤, 상기 삼중막 상에 포토레지스트를 패터닝하였다. 상기 기판을 실시예 및 비교예에 따른 은 박막 식각액 조성물을 이용하여 식각 공정을 수행하였다.After forming a triple layer of ITO (indium oxide) / silver / ITO on a substrate, a photoresist was patterned on the triple layer. The substrate was etched using a silver thin film etchant composition according to Examples and Comparative Examples.
포토레지스트가 안덮혀 있는 부분의 투명전도막/은/투명전도막 삼중막의 에치가 끝난 시점으로부터 추가적으로 Etch Time를 100sec 진행하여 패터닝 된 포토레지스트 끝단으로부터 식각 된 은(Ag)막까지의 거리를 전자주사현미경 (SEM; 모델명: SU-8010, HITACHI)을 이용하여 측정하여 그 결과를 표 2에 나타내었다. Etching time is additionally 100 sec. From the time when the etch of the transparent conductive film / silver / transparent conductive film of the photoresist is not covered, and the distance from the patterned photoresist end to the etched silver (Ag) film is injected. It was measured using a microscope (SEM; model name: SU-8010, HITACHI) and the results are shown in Table 2.
[편측식각 차이(즉, skew 차이) 기준][Based on unilateral etch difference (ie skew difference)]
○ : 양호 (편측식각 Side Etch : Side etch ≤ 0.25㎛)○: Good (Side Etch: Side etch ≤ 0.25㎛)
△ : 보통 (편측식각 Side Etch : 0.25㎛ ＜ Side etch ≤ 0.50㎛)△: Normal (Side Etch: 0.25㎛ <Side etch ≤ 0.50㎛)
Ⅹ : 불량 (편측식각 Side Etch : 0.50㎛ ≤ side Etch)Ⅹ: Poor (Side Etch: 0.50㎛ ≤ side Etch)
3. 은 잔사 측정3. Silver residue measurement
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 12 및 비교예 1 내지 4의 은 박막 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 포토레지스트가 덮여 있지 않은 부분에 은(Ag)이 식각 되지 않고 남아 있는 현상인 잔사를 측정하였으며, 하기의 기준으로 평가하여, 결과를 표 2 에 나타내었다. After inserting each of the silver thin film etchant compositions of Examples 1 to 12 and Comparative Examples 1 to 4 into the spray-etching test equipment (model name: ETCHER (TFT), SEMES), heat the temperature by setting the temperature to 40 ° C, When the temperature reached 40 ± 0.1 ° C, the etching process of the specimen was performed. The total etching time was 85 seconds. After inserting the substrate and starting spraying, when the etching time of 85 seconds was reached, it was taken out, washed with deionized water, dried using a hot air drying device, and the photoresist was removed using a photoresist stripper. After washing and drying, the residue, which is a phenomenon in which silver (Ag) is not etched and remains in the portion not covered with the photoresist, was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI). It evaluated by reference, and the result is shown in Table 2.
<잔사 측정 평가 기준><Residential measurement evaluation criteria>
양호: 잔사 미발생Good: No residue
불량: 잔사 발생Poor: residue
4. 은 재흡착 평가4. Silver resorption evaluation
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 12 및 비교예 1 내지 4의 은 박막 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 승온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하였다. 세정 및 건조 후 기판을 절단하고 단면을 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 측정하였다. 상기 식각 공정으로 인해, 상기 기판 내 노출된 S/D 부의 Ti/Al/Ti 삼중막의 상부 Ti에 흡착된 은 입자의 개수를 측정하고, 하기의 기준으로 평가하여, 결과를 표 2 에 나타내었다.After inserting each of the silver thin film etchant compositions of Examples 1 to 12 and Comparative Examples 1 to 4 into the spray-etching type experimental equipment (model name: ETCHER (TFT), SEMES), after raising the temperature by setting the temperature to 40 ° C, When the temperature reached 40 ± 0.1 ° C, the etching process of the specimen was performed. The total etching time was 85 seconds. After inserting the substrate and starting spraying, when the etching time of 85 seconds was reached, the substrate was taken out, washed with deionized water, and dried using a hot air drying device. After washing and drying, the substrate was cut and the cross section was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI). Due to the etching process, the number of silver particles adsorbed on the upper Ti of the Ti / Al / Ti triple film of the S / D portion exposed in the substrate was measured and evaluated based on the following criteria, and the results are shown in Table 2.
<은 재흡착 평가 기준><Silver resorption evaluation criteria>
양호: 5개 미만Good: less than 5
보통: 5개 이상 50개 미만Normal: 5 or more and less than 50
불량: 50개 이상Poor: 50 or more
상기 표에서 나타나듯이, 실시예 1 내지 12의 식각액 조성물은 신액 및 구액 모두 Side Etch 특성이 양호/우수 할 뿐만 아니라, 은 잔사 및 은 재흡착 효과가 우수하여, 처리매수 능력이 우수함을 확인하였다. As shown in the above table, it was confirmed that the etchant compositions of Examples 1 to 12 had good / excellent side etch properties in both new and old solutions, as well as excellent silver residue and silver re-adsorption effects, and excellent treatment capacity.
반면, 본 발명의 식각액 조성물에 포함되는 성분 중 일부를 포함하지 않은 비교예 1 내지 3 및 은식각촉진제로 염소이온을 포함하는 화합물을 사용한 비교예 4의 경우, 신액의 식각액 조성물의 Side Etch, 은 잔사 및 은 재흡착 효과가 불량할 뿐만 아니라 구액의 식각액 조성물 효과 또한 불량함을 확인하였다.On the other hand, in Comparative Examples 1 to 3, which do not include some of the components included in the etchant composition of the present invention, and Comparative Example 4 using a compound containing chlorine ion as a silver etch promoter, Side Etch, silver It was confirmed that not only the resorption effect of the residue and silver was poor, but also the effect of the composition of the etchant composition in the oral fluid was poor.
Claims (12)
(B) 무기산;
(C) 중황산염; 및
(D) 물을 포함하는, 은 박막 식각액 조성물.(A) Silver etching promoter;
(B) inorganic acids;
(C) bisulfate; And
(D) A silver thin film etchant composition containing water.
조성물 총 중량에 대하여,
(A) 0.01 내지 20 중량%의 은식각촉진제;
(B) 0.1 내지 20 중량%의 무기산;
(C) 0.1 내지 30 중량%의 중황산염; 및
(D) 잔량의 물을 포함하는, 은 박막 식각액 조성물.The method according to claim 1,
With respect to the total weight of the composition,
(A) 0.01 to 20% by weight of silver etch promoter;
(B) 0.1 to 20% by weight of an inorganic acid;
(C) 0.1 to 30% by weight of bisulfate; And
(D) A silver thin film etchant composition containing the remaining amount of water.
상기 은 박막 식각액 조성물은 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 동시에 식각할 수 있는 것을 특징으로 하는 은 박막 식각액 조성물.The method according to claim 1,
The silver thin film etchant composition is a silver thin film etchant composition characterized in that it can etch a single film made of silver or a silver alloy, or a multilayer film made of the single film and a transparent conductive film at the same time.
상기 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.The method according to claim 8,
The transparent conductive film is a silver thin film etchant composition, characterized in that at least one selected from the group consisting of tin indium oxide (ITO), zinc indium oxide (IZO), tin zinc indium (ITZO) and gallium zinc indium (IGZO) .
상기 다층막은 투명전도막/은, 투명전도막/은 합금, 투명전도막/은/투명전도막 또는 투명전도막/은 합금/투명전도막으로 형성되는 것을 포함하는 은 박막 식각액 조성물.The method according to claim 8,
The multi-layer film is a transparent conductive film / silver, a transparent conductive film / silver alloy, a transparent conductive film / silver / transparent conductive film or a transparent conductive film / silver alloy / transparent conductive film comprising a thin film etchant composition.
상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및
청구항 1의 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 식각 방법.Forming a single film made of silver or a silver alloy on the substrate, or a multi-layer film made of the single film and the transparent conductive film;
Selectively leaving a photoreactive material on the single layer or the multilayer layer; And
Using the composition of claim 1, the etching method comprising the step of etching the single film or the multilayer film.
청구항 1의 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 금속 패턴의 형성 방법.Forming a single film made of silver or a silver alloy on the substrate, or a multi-layer film made of the single film and the transparent conductive film; And
Using the composition of claim 1, the method of forming a metal pattern comprising the step of etching the single film or the multilayer film.
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