KR102639626B1 - An etchant composition for silver thin layer and an ehting method and a mehtod for fabrication metal pattern using the same - Google Patents
An etchant composition for silver thin layer and an ehting method and a mehtod for fabrication metal pattern using the same Download PDFInfo
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- KR102639626B1 KR102639626B1 KR1020180132371A KR20180132371A KR102639626B1 KR 102639626 B1 KR102639626 B1 KR 102639626B1 KR 1020180132371 A KR1020180132371 A KR 1020180132371A KR 20180132371 A KR20180132371 A KR 20180132371A KR 102639626 B1 KR102639626 B1 KR 102639626B1
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- acid
- silver
- film
- etchant composition
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004332 silver Substances 0.000 title claims abstract description 87
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 31
- 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 50
- 239000010409 thin film Substances 0.000 claims abstract description 39
- 150000002978 peroxides Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- -1 triazole compound Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 98
- 239000000758 substrate Substances 0.000 claims description 20
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 16
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229960003330 pentetic acid Drugs 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012964 benzotriazole Substances 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229960003767 alanine Drugs 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- 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 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- WFYASTPQDOUBSW-UHFFFAOYSA-N 1h-1,2,4-triazole Chemical compound C=1N=CNN=1.C1=NN=CN1 WFYASTPQDOUBSW-UHFFFAOYSA-N 0.000 claims 1
- ULMNNWOODRUGCA-UHFFFAOYSA-N 2H-triazole Chemical compound C=1C=NNN=1.C=1C=NNN=1 ULMNNWOODRUGCA-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 31
- 229910003437 indium oxide Inorganic materials 0.000 description 18
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 7
- 238000001039 wet etching Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- IZQZNLBFNMTRMF-UHFFFAOYSA-N acetic acid;phosphoric acid Chemical compound CC(O)=O.OP(O)(O)=O IZQZNLBFNMTRMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition 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
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002310 reflectometry 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
Abstract
본 발명은 조성물은 총 중량에 대해, (A) 무기산 1 내지 10 중량%; (B) 유기산 30 내지 70 중량%; (C) 과산화물 0.1 내지 10 중량%; (D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물 0.01 내지 1 중량%; (E) 트리아졸 화합물 0.01 내지 1 중량%; 및 (F) 잔량의 물을 포함하는 것을 특징으로 하는 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법을 제공한다.The present invention includes, based on the total weight, (A) 1 to 10% by weight of inorganic acid; (B) 30 to 70% by weight of organic acid; (C) 0.1 to 10% by weight of peroxide; (D) 0.01 to 1% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule; (E) 0.01 to 1% by weight of a triazole compound; and (F) a residual amount of water. A silver thin film etchant composition, an etching method using the same, and a method of forming a metal pattern are provided.
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 for 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.As we enter the full-fledged information age, the display field that processes and displays large amounts of information has developed rapidly, and in response to this, various flat panel displays have been developed and are in the spotlight.
이러한 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 가전분야뿐만 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: NIT)을 빠르게 대체하고 있는 실정이다. Examples of such flat panel display devices include Liquid crystal display device (LCD), Plasma Display Panel device (PDP), Field Emission Display device (FED), and Electroluminescence display device. Display devices (ELD), Organic Light Emitting Diodes (OLED), etc. These flat display devices are used for a variety of purposes, not only in home appliances such as televisions and videos, but also in computers such as laptops and mobile phones. These flat panel display devices are rapidly replacing previously used cathode ray tubes (NITs) due to their excellent performance such as thinness, weight reduction, 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 at low voltage, so it has recently been rapidly applied to the small display market such as mobile devices. In addition, OLED is going beyond small displays and is about to be commercialized for large-sized TVs.
한편, 산화주석인듐(Indium Tin Oxide, ITO)과 산화아연인듐(Indium Zinc Oxide, IZO)과 같은 도전성 금속은 빛에 대한 투과율이 비교적 뛰어나고, 도전성을 가지므로 평판디스플레이장치에 사용되는 칼라필터의 전극으로 널리 쓰이고 있다. 그러나 이들 금속들 또한 높은 저항을 가져 응답속도의 개선을 통한 평판표시장치의 대형화 및 고해상도 실현에 장애가 되고 있다.Meanwhile, conductive metals such as indium tin oxide (ITO) and indium zinc oxide (IZO) have relatively excellent light transmittance and conductivity, so they are used as electrodes for color filters in flat panel display devices. It is widely used. However, these metals also have high resistance, which is an obstacle to realizing larger and higher resolution flat panel displays through improved response speed.
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 reflectors, aluminum (Al) reflectors have been mainly used in products in the past, but in order to realize low power consumption through improved brightness, changes to metals with higher reflectivity are being explored. For this purpose, silver (Ag: resistivity about 1.59μΩcm) film, silver alloy, or multilayer film containing it, which has low resistivity and high luminance compared to metals used in flat display devices, is used as electrodes of color filters, LCD or OLED wiring, and In order to apply it to a reflector and realize larger flat panel displays, higher resolution and lower power consumption, the development of an etchant for the application of this material was 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) has extremely poor adhesion to lower substrates such as insulating substrates such as glass or semiconductor substrates made of intrinsic amorphous silicon or doped amorphous silicon, so deposition is not easy, and wiring may be lifted. Lifting or peeling is easily caused. Additionally, 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 such an etchant, silver (Ag) is excessively etched or etched unevenly, causing 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, there are difficulties in implementing low skew for high-resolution implementation.
특히, 은(Ag)은 쉽게 환원이 되는 금속으로 식각 속도가 빨라야 잔사 유발 없이 식각이 되게 되는데 이때 식각 속도가 빨라 상하부 간 식각 속도의 차이가 발생하지 않아 식각 후 테이퍼 각(taper angle) 형성이 어렵고 식각 패턴의 직진성 확보에 어려움이 있어서, 배선 및 패턴 형성 시 많은 한계점을 가지고 있다. In particular, silver (Ag) is a metal that is easily reduced, so the etching speed must be fast to be etched without causing residue. In this case, the etching speed is fast, so there is no difference in etching speed between the upper and lower parts, making it difficult to form a taper angle after etching. Because it is difficult to ensure the straightness of the etch pattern, there are many limitations when forming wiring and patterns.
금속막이 테이퍼 각(taper angle) 없이 수직으로 서 있는 경우, 후속 공정에서 절연막 또는 후속 배선 형성 시 은(Ag)과 절연막 또는 배선 사이에 공극이 발생 할 수 있으며, 이러한 공극 발생은 전기적 쇼트 등 불량 발생의 원인이 된다.If the metal film stands vertically without a taper angle, voids may occur between the silver (Ag) and the insulating layer or wiring when forming the insulating layer or subsequent wiring in the subsequent process. Such voids may cause defects such as electrical shorts. It becomes the cause of.
대한민국 등록특허 제10-1323458호는 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 산화인듐막으로 구성된 다층막 식각액 조성물을 개시하고 있으나, 당해 기술분야의 주요한 문제점인 잔사 및 은 재흡착 문제를 완전히 해결하고 있지 못한 실정이다.Republic of Korea Patent No. 10-1323458 discloses a single film made of silver (Ag) or a silver alloy and a multilayer etchant composition composed of the single film and an indium oxide film, but residue and silver re-adsorption are major problems in the art. The problem is not being completely resolved.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용되며, 은 재흡착 문제가 발생하지 않으며, 단일막 및 다층막 성분의 석출 문제가 발생하지 않는 것을 특징으로 하는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is intended to improve the problems of the prior art described above, and is used for etching a single film made of silver (Ag) or a silver alloy and a multilayer film composed of the single film and a transparent conductive film, and silver re-adsorption problems occur. The purpose is to provide a silver thin film etchant composition that does not cause precipitation problems of single-layer and multi-layer components.
또한, 본 발명은 상기 단일막 및 상기 다층막을 동시에 식각할 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a silver thin film etchant composition that can simultaneously etch the single film and the multilayer film.
또한, 본 발명은 식각 속도의 제어를 통해 side etch를 조절할 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.Additionally, the purpose of the present invention is to provide a silver thin film etchant composition that can control side etch through control of the etching rate.
또한, 본 발명은 하부막의 손상 없이 식각 균일성을 나타내는 습식 식각에 유용하게 사용될 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a silver thin film etchant composition that can be usefully used in wet etching that exhibits etching uniformity without damaging the underlying film.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.Additionally, the present invention aims to provide an etching method using the silver thin film etchant composition.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.Additionally, the present invention aims to provide a method of forming a metal pattern using the silver thin film etchant composition.
상기 목적을 달성하기 위해, 본 발명은 조성물은 총 중량에 대해, (A) 무기산 1 내지 10 중량%; (B) 유기산 30 내지 70 중량%; (C) 과산화물 0.1 내지 10 중량%; (D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물 0.01 내지 1 중량%; (E) 트리아졸 화합물 0.01 내지 1 중량%; 및 (F) 잔량의 물을 포함하는 것을 특징으로 하는 은 박막 식각액 조성물을 제공한다.In order to achieve the above object, the present invention provides a composition comprising, based on the total weight, (A) 1 to 10% by weight of an inorganic acid; (B) 30 to 70% by weight of organic acid; (C) 0.1 to 10% by weight of peroxide; (D) 0.01 to 1% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule; (E) 0.01 to 1% by weight of a triazole compound; and (F) a residual amount of water.
또한, 본 발명은, 상기 은 박막 식각액 조성물을 사용하는 식각 방법을 제공한다.Additionally, 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.Additionally, 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, 은 재흡착, 단일막 및 다층막 성분의 석출 문제가 발생하지 않는 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 multilayer film composed of the single film and a transparent conductive film, so that there are problems with silver re-adsorption and precipitation of single film and multilayer film components. Provides an effect that does not occur.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막을 동시에 식각하여, 식각 효율을 향상시키는 효과를 제공한다.In addition, the silver thin film etchant composition of the present invention provides the effect of improving etching efficiency by simultaneously etching the single film and the multilayer film.
또한, 본 발명의 은 박막 식각액 조성물은 etch stop 현상을 발생시켜, 식각 속도를 제어하고, side etch를 조절할 수 있는 효과를 제공한다.In addition, the silver thin film etchant composition of the present invention generates an etch stop phenomenon, providing the effect of controlling the etch rate and side etch.
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 in wet etching that exhibits etching uniformity without damaging the underlying film.
본 발명은 (A) 무기산, (B) 유기산, (C) 과산화물, (D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물, (E) 트리아졸 화합물 및 (F) 물을 포함하는 것을 특징으로 하는 은 박막 식각액 조성물에 대한 것으로, (C) 과산화물 및 (D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물을 함께 사용하는 경우 은 흡착방지제로써 매우 우수한 효과를 나타냄을 실험적으로 확인하여 완성되었다. The present invention is characterized by comprising (A) an inorganic acid, (B) an organic acid, (C) a peroxide, (D) a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, (E) a triazole compound, and (F) water. This is a silver thin film etchant composition, and was completed by experimentally confirming that (C) peroxide and (D) a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule are used together to show a very excellent effect as a silver adsorption prevention agent.
본 발명의 은 박막 식각액 조성물은 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용될 수 있으며, 은 재흡착, 단일막 및 다층막 성분의 석출 문제가 발생하지 않는 것을 특징으로 한다.The silver thin film etchant composition of the present invention can be used for etching a single film made of silver (Ag) or a silver alloy and a multilayer film composed of the single film and a transparent conductive film, and solves problems of silver re-adsorption and precipitation of single film and multilayer film components. It is characterized by not occurring.
본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막을 동시에 식각할 수 있다.The silver thin film etchant composition of the present invention can simultaneously etch the single film and the multilayer film.
본 발명의 은 박막 식각액 조성물은 etch stop 현상을 발생시켜, 식각 속도를 제어하고, side etch를 조절할 수 있는 효과를 제공할 수 있다.The silver thin film etchant composition of the present invention can generate an etch stop phenomenon, control the etch rate, and provide the effect of controlling side etch.
본 발명의 은 박막 식각액 조성물은 하부막 손상이 없어 식각 균일성을 나타내는 습식 식각에 유용하게 사용될 수 있다.The silver thin film etchant composition of the present invention can be usefully used in wet etching to show etching uniformity without damaging the underlying film.
상기 은 합금은 은을 주성분으로 하여 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa 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 containing silver as a main component and other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, and Ti; It may include silver nitride, silicide, carbide, oxide, etc., but is not limited thereto.
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 one or more types selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc 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 multilayer 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 조성물은 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 can be used for forming OLED TFT array substrates for reflective films, trace wiring for touch screen panels, or nanowire wiring, but is not limited to this, and electronic components including the single film and the multilayer film. Can be used for materials.
(A) 무기산(A) Inorganic acid
상기 무기산은 주 산화제로 사용되는 성분으로서, 산화인듐막/Ag/산화인듐막에서 은(Ag)과 산화인듐막을 산화시켜 습식 식각하는 역할을 수행한다.The inorganic acid is a component used as a main oxidizing agent, and performs a wet etching function by oxidizing silver (Ag) and indium oxide film in the indium oxide film/Ag/indium oxide film.
상기 무기산은 조성물 총 중량에 대하여 1 내지 10 중량%, 바람직하게는3 내지 9 중량%로 포함될 수 있다. 상기 무기산의 함량이 1 중량% 미만인 경우에는 은의 식각 속도 저하와 은 잔사 발생에 따른 불량을 야기시킬 수 있으며, 10 중량%를 초과하는 경우에는 은 및 산화인듐막의 식각 속도가 빨라져 과식각 현상 발생으로 후속공정에 문제가 되는 불리한 점이 있다.The inorganic acid may be included in an amount of 1 to 10% by weight, preferably 3 to 9% by weight, based on the total weight of the composition. If the content of the inorganic acid is less than 1% by weight, it may cause defects due to a decrease in the etching speed of silver and the generation of silver residues. If it exceeds 10% by weight, the etching speed of the silver and indium oxide films increases, resulting in overetching. There are disadvantages that cause problems in subsequent processes.
상기 무기산의 구체적인 예로는 질산 및 염산 및 등을 들 수 있으며, 질산을 사용하는 것이 바람직하다.Specific examples of the inorganic acid include nitric acid and hydrochloric acid, and nitric acid is preferably used.
(B) 유기산(B) Organic acid
상기 유기산은 보조 산화제로 사용되는 성분으로서, 산화인듐막/Ag/산화인듐막에서 은(Ag)과 산화인듐막을 산화시켜 습식 식각하는 역할을 수행한다.The organic acid is a component used as an auxiliary oxidizing agent, and plays a role in wet etching by oxidizing silver (Ag) and indium oxide film in the indium oxide film/Ag/indium oxide film.
상기 유기산은 조성물 총 중량에 대하여 30 내지 70 중량%, 바람직하게는 40 내지 60 중량%로 포함될 수 있다. 상기 유기산의 함량이 30 중량% 미만인 경우에는 은(Ag)과 인듐산화막의 식각 속도 저하가 발생하여 기판 내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 70 중량%를 초과하는 경우에는 은 및 산화인듐막의 식각 속도가 빨라져 과식각 현상 발생으로 후속공정에 문제가 되는 불리한 점이 있다.The organic acid may be included in an amount of 30 to 70% by weight, preferably 40 to 60% by weight, based on the total weight of the composition. If the content of the organic acid is less than 30% by weight, the etching speed of the silver (Ag) and indium oxide films decreases, and the etching uniformity within the substrate becomes poor, causing stains. If the content exceeds 70% by weight, the silver Additionally, there is a disadvantage in that the etching speed of the indium oxide film becomes faster, causing problems in subsequent processes due to overetching.
상기 유기산의 구체적인 예로는 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 펜탄산(pentanoic acid) 및 옥살산(oxalic acid) 등을 들 수 있으며, 글리콜산(glycolic acid)을 사용하는 것이 바람직하다.Specific examples of the organic acids include acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, and malonic acid. ), pentanoic acid, and oxalic acid, etc., and it is preferable to use glycolic acid.
(C) 과산화물(C) peroxide
상기 과산화물은 보조 산화제로 사용되는 성분으로서, 산화인듐막/Ag/산화인듐막에서 은(Ag)을 산화시켜 습식 식각하는 역할 및 Ag 재흡착을 방지 시켜주는 역할을 수행한다.The peroxide is a component used as an auxiliary oxidizing agent, and serves to oxidize silver (Ag) in the indium oxide film/Ag/indium oxide film for wet etching and to prevent Ag re-adsorption.
상기 과산화물은 조성물 총 중량에 대하여 0.1 내지 10 중량%, 바람직하게는 3 내지 8 중량%로 포함될 수 있다. 상기 과산화물의 함량이 0.1 중량% 미만인 경우에는 은(Ag)과 인듐산화막의 식각 속도 저하가 발생하여 기판 내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 10 중량%를 초과하는 경우에는 은(Ag)및 산화인듐막의 식각 속도가 빨라져 과식각 현상 발생으로 후속공정에 문제가 되는 불리한 점이 있다.The peroxide may be included in an amount of 0.1 to 10% by weight, preferably 3 to 8% by weight, based on the total weight of the composition. If the content of the peroxide is less than 0.1% by weight, the etching speed of the silver (Ag) and indium oxide film decreases, and the etching uniformity within the substrate becomes poor, causing stains. If the content of the peroxide exceeds 10% by weight, the silver There is a disadvantage in that the etching speed of (Ag) and indium oxide films becomes faster, causing problems in subsequent processes due to overetching.
상기 과산화물의 구체적인 예로는 Oxone, SPS(Sodium persulfate) 및 APS(Ammonium persulfate) 등을 들 수 있으며, Oxone을 사용하는 것이 바람직하다.Specific examples of the peroxide include Oxone, SPS (Sodium persulfate), and APS (Ammonium persulfate), and Oxone is preferably used.
(D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물(D) Water-soluble compound having a nitrogen atom and a carboxyl group in one molecule
상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 처리매수 진행 시 side etch 변화량을 유지 및 Ag 재흡착을 방지 시켜 주는 역할을 한다.The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule plays a role in maintaining the change in side etch and preventing re-adsorption of Ag during treatment.
상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 조성물 총 중량에 대하여 0.01 내지 1 중량%, 바람직하게는 0.1 내지 0.8 중량%로 포함될 수 있다. 상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물의 함량이 0.01 중량% 미만인 경우에는 처리매수 진행 시 side etch 변화량을 유지 시켜주지 못하며, 1 중량%를 초과하는 경우에는 기판 내의 식각 균일성이 저하되고 또한 기판 내에 부분적으로 잔사가 발생할 수 있다.The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule may be included in an amount of 0.01 to 1% by weight, preferably 0.1 to 0.8% by weight, based on the total weight of the composition. If the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is less than 0.01% by weight, the change in side etch cannot be maintained during the treatment process, and if it exceeds 1% by weight, the etch uniformity within the substrate is reduced. Additionally, residue may occur partially within the substrate.
상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물의 구체적인 예로는 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 디에틸렌트리아민 펜타아세트산(diethylenetriamine pentaacetic acid), 에틸렌다이아민테트라아세트산(Ethylenediaminetetraacetic acid), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine) 등을 들 수 있으며, 디에틸렌트리아민 펜타아세트산을 사용하는 것이 바람직하다.Specific examples of water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule include alanine, aminobutyric acid, glutamic acid, glycine, and diethylenetriamine pentaacetic acid. , ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, and sarcosine, etc., and it is preferable to use diethylenetriamine pentaacetic acid. .
(E) 트리아졸 화합물(E) Triazole compound
상기 트리아졸 화합물은 Ag의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주어 공정상의 마진을 높이는 역할을 한다.The triazole compound controls the etching rate of Ag and reduces CD loss of the pattern, thereby increasing process margins.
상기 트리아졸 화합물은 조성물 총 중량에 대하여 0.01 내지 1 중량%, 바람직하게는 0.1 내지 0.8 중량%로 포함될 수 있다. 상기 트리아졸 화합물의 함량이 0.01 중량% 미만인 경우에는 식각 속도가 빠르게 되어 시디로스가 너무 크게 발생될 수 있고, 1 중량%를 초과하여 포함되면, Ag의 식각 속도가 너무 느려지게 되어 식각 잔사가 발생될 수 있다.The triazole compound may be included in an amount of 0.01 to 1% by weight, preferably 0.1 to 0.8% by weight, based on the total weight of the composition. If the content of the triazole compound is less than 0.01% by weight, the etching rate may become fast and excessively large sid loss may be generated, and if it is included in excess of 1% by weight, the etching rate of Ag may become too slow, resulting in etching residues. It can be.
상기 트리아졸 화합물의 구체적인 예로는 1, 2, 3 트리아졸(1, 2, 3 triazole), 1, 2, 4 트리아졸(1, 2, 4 triazole) 벤조트리아졸 (benzotriazole) 및 톨리트리아졸(Tolyltriazole) 등을 들 수 있으며, 벤조트리아졸을 사용하는 것이 바람직하다.Specific examples of the triazole compounds include 1, 2, 3 triazole, 1, 2, 4 triazole, benzotriazole, and tolytriazole. (Tolyltriazole), etc., and it is preferable to use benzotriazole.
식각액 조성물 내에 상기 트리아졸 화합물이 아닌, 아졸 화합물을 포함하는 경우, 식각 공정에서 ITO 석출물이 발생할 수 있다.If the etchant composition contains an azole compound rather than the triazole compound, ITO precipitates may occur during the etching process.
(F) 물(F) water
상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water may be deionized water for semiconductor processing, and preferably, deionized water of 18 MΩ/cm or higher can be used.
상기 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The water content may be included in a residual amount such that the total weight of the composition is 100% by weight.
본 발명에 따른 은 박막 식각액 조성물은 표시 장치(OLED, LCD 등)의 제조 시, 배선 및 반사막으로 사용되는 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 산화인듐막으로 구성된 다층막, 바람직하게는 산화인듐막/은 또는 산화인듐막/은/산화인듐막으로 형성된 다층막의 습식 식각에 유용하게 사용할 수 있다.The silver thin film etchant composition according to the present invention is a single film made of silver (Ag) or a silver alloy used as a wiring and reflective film when manufacturing display devices (OLED, LCD, etc.), and a multilayer film made of the single film and an indium oxide film, Preferably, it can be usefully used for wet etching of a multilayer film formed of an indium oxide film/silver or an indium oxide film/silver/indium oxide film.
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 식각 방법을 제공한다.Additionally, the present invention provides an etching method using the silver thin film etchant composition according to the present invention.
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.The etching method includes the steps of i) forming a single film made of silver or a silver alloy, or a multilayer film made of the single film and a transparent conductive film, on a substrate; ii) selectively leaving a photo-reactive material on the single layer or the multilayer layer; and iii) etching the single film or the multilayer film using the silver thin film etchant composition according to the present invention.
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공한다.Additionally, the present invention provides a method of forming a metal pattern using the silver thin film etchant composition according to the present invention.
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.The method of forming the metal pattern includes the steps of i) forming a single film made of silver or a silver alloy, or a multilayer film made of the single film and a transparent conductive film, on a substrate; and ii) etching the single film or the multilayer film using the silver thin film etchant composition according to the present invention.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 질량 기준이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and further includes all changes within the scope and meaning equivalent to the record of the claims. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.
실시예 및 비교예에 따른 은 박막 식각액 조성물의 제조Preparation of silver thin film etchant composition according to Examples and Comparative Examples
하기 [표 1] (단위: 중량%)을 참조하여, 실시예 1 내지 9 및 비교예 1 내지 12에 따른 은 박막 식각액 조성물을 제조하였다. 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함하도록 하였다. Referring to Table 1 below (unit: weight %), silver thin film etchant compositions according to Examples 1 to 9 and Comparative Examples 1 to 12 were prepared. The water content was included in a residual amount so that the total weight of the composition was 100% by weight.
(A) 무기산: HNO3 (A) Inorganic acid: HNO 3
(B) 유기산: GA(Glycolic acid)(B) Organic acid: GA (Glycolic acid)
(C) 과산화물: Oxone(2KHSO5·KHSO4·K2SO4), APS(Ammonium persulfate)(C) Peroxide: Oxone (2KHSO 5 ·KHSO 4 ·K 2 SO 4 ), APS (Ammonium persulfate)
(D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물: DTPA (Diethylenetriamine pentaacetic acid), IDA(Iminodiacetic acid)(D) Water-soluble compounds with a nitrogen atom and a carboxyl group in one molecule: DTPA (Diethylenetriamine pentaacetic acid), IDA (Iminodacetic acid)
(E) 트리아졸 화합물: BTA(Benzotriazole)(E) Triazole compound: BTA (Benzotriazole)
ATZ : AminotetrazoleATZ: Aminotrazole
시험예 1: Side Etch(S/E) 측정Test Example 1: Side Etch (S/E) measurement
기판 상에 ITO(산화주석인듐)/은/ITO 삼중막 시편을 형성하고 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 9 및 비교예 1 내지 12의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 승온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였으며, 기판을 넣고 분사를 시작하여 식각 시간이 80초가 되면, 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하였다.An ITO (indium tin oxide)/silver/ITO triple film specimen was formed on a substrate, and the samples of Examples 1 to 9 and Comparative Examples 1 to 12 were formed in a spray-etched experimental equipment (model name: ETCHER (TFT), SEMES). Each silver etchant composition was added, the temperature was set to 40°C, and the temperature was raised. When the temperature reached 40±0.1°C, the etching process for the specimen was performed. The substrate was placed and spraying began, and the etching time reached 80 seconds. , took it out, washed it with deionized water, and dried it using a hot air dryer.
세정 및 건조 후 기판을 절단하고 단면을 전자주사현미경(SEM; 모델명:SU-8010, HITACHI사 제조)을 이용하여 측정하였다. 편측 식각 거리 측정 기준으로는 포토레지스트 끝 부분부터 금속이 식각 되어 안쪽까지 들어간 너비를 측정하였으며, 하기의 기준으로 평가하여 하기 [표 2]에 나타내었다.After cleaning and drying, the substrate was cut and the cross section was measured using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI). As a standard for measuring the one-sided etching distance, the width of the metal etched from the end of the photoresist to the inside was measured. It was evaluated based on the following criteria and is shown in [Table 2] below.
<평가 기준><Evaluation criteria>
O : 양호 (S/E : 0.50㎛ 미만)O: Good (S/E: less than 0.50㎛)
X : 불량 (S/E : 0.50㎛ 이상 및 unetch)X: Defective (S/E: 0.50㎛ or more and unetch)
시험예 2: 은(Ag) 재흡착 측정Test Example 2: Silver (Ag) re-adsorption measurement
기판 상에 ITO(산화주석인듐)/은/ITO 삼중막 시편을 형성하고 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 9 및 비교예 1 내지 12의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 승온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였으며, 기판을 넣고 분사를 시작하여 식각 시간이 80초가 되면, 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하였다.An ITO (indium tin oxide)/silver/ITO triple film specimen was formed on a substrate, and the samples of Examples 1 to 9 and Comparative Examples 1 to 12 were formed in a spray-etched experimental equipment (model name: ETCHER (TFT), SEMES). Each silver etchant composition was added, the temperature was set to 40°C, and the temperature was raised. When the temperature reached 40±0.1°C, the etching process for the specimen was performed. The substrate was placed and spraying began, and the etching time reached 80 seconds. , took it out, washed it with deionized water, and dried it using a hot air dryer.
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, 하기 [표 2]에 나타내었다.After cleaning and drying, the substrate was cut and the cross section was measured using a scanning electron 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 layer of the exposed S/D portion in the substrate was measured, evaluated based on the following criteria, and is shown in [Table 2] below. .
< 평가 기준><Evaluation criteria>
O : 양호 (50개 미만)O: Good (less than 50)
X : 불량 (50개 이상)X: Defective (more than 50)
시험예 3: ITO 석출물 측정Test Example 3: ITO precipitate measurement
실시예 1 내지 9 및 비교예 1 내지 12의 은 식각액 조성물에 ITO를 0ppm 용해 시킨 조성물과 500ppm 용해 시킨 조성물을 24시간 방치 하고 이때 생기는 석출물의 성분을 분석하였고, 하기의 기준으로 평가하여 하기 [표 2]에 나타내었다.The compositions in which 0 ppm of ITO was dissolved in the silver etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 12 and the compositions in which 500 ppm of ITO was dissolved were left for 24 hours, and the components of the precipitates formed at this time were analyzed, and evaluated based on the following criteria. 2] is shown.
ITO를 500ppm 용해 시킨 조성물의 경우, 식각 공정이 진행됨에 따라 ITO 석출물이 석출된 것을 가정한 용액이다.In the case of a composition in which 500 ppm of ITO is dissolved, the solution assumes that ITO precipitates are deposited as the etching process progresses.
< 평가 기준><Evaluation criteria>
O : 석출물 미발생O: No precipitates
X : 석출물 발생X: Precipitate generation
실시예에 따른 은 박막 식각액 조성물을 사용하여 식각 공정을 수행하는 경우, side etch가 0.25 내지 0.4 μm로 측정되고, 은 재흡착 및 ITO 석출 문제가 발생하지 않는 것을 알 수 있다.When an etching process is performed using the silver thin film etchant composition according to the example, the side etch is measured to be 0.25 to 0.4 μm, and it can be seen that silver re-adsorption and ITO precipitation problems do not occur.
반면, 비교예에 따른 은 박막 식각액 조성물을 사용하여 식각 공정을 수행하는 경우, 식각 공정이 진행됨에 따라 너무 많이 식각되는 등 side etch의 조절이 용이하지 않고, 은 재흡착 및 ITO 석출 문제가 발생하는 것을 알 수 있다.On the other hand, when the etching process is performed using the silver thin film etchant composition according to the comparative example, it is not easy to control the side etch, such as too much etching as the etching process progresses, and silver re-adsorption and ITO precipitation problems occur. You can see that
이와 같이, 본 발명에 따른 은 박막 식각액 조성물을 사용하여 식각 공정을 수행하는 경우, side etch 조절이 용이하고, 은 재흡착 및 ITO 석출 문제가 발생하지 않는다는 것을 알 수 있다.As such, it can be seen that when an etching process is performed using the silver thin film etchant composition according to the present invention, side etch control is easy and silver re-adsorption and ITO precipitation problems do not occur.
Claims (11)
(A) 무기산 1 내지 10 중량%;
(B) 유기산 30 내지 70 중량%;
(C) 과산화물 0.1 내지 10 중량%;
(D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물 0.01 내지 1 중량%;
(E) 트리아졸 화합물 0.01 내지 1 중량%; 및
(F) 잔량의 물을 포함하며,
인산을 포함하지 않는 것을 특징으로 하는 은 박막 식각액 조성물.
The composition, in terms of total weight,
(A) 1 to 10% by weight of inorganic acid;
(B) 30 to 70% by weight of organic acid;
(C) 0.1 to 10% by weight of peroxide;
(D) 0.01 to 1% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule;
(E) 0.01 to 1% by weight of a triazole compound; and
(F) contains a residual amount of water;
A silver thin film etchant composition comprising no phosphoric acid.
상기 (A) 무기산은 질산 및 염산으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 1,
(A) A silver thin film etchant composition, wherein the inorganic acid is at least one selected from the group consisting of nitric acid and hydrochloric acid.
상기 (B) 유기산은 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 펜탄산(pentanoic acid) 및 옥살산(oxalic acid)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 1,
The (B) organic acids include acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, and malonic acid. ), a silver thin film etchant composition comprising at least one selected from the group consisting of pentanoic acid and oxalic acid.
상기 (C) 과산화물은 Oxone, SPS(Sodium persulfate) 및 APS(Ammonium persulfate)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 1,
(C) A silver thin film etchant composition, wherein the peroxide is at least one selected from the group consisting of Oxone, SPS (Sodium persulfate), and APS (Ammonium persulfate).
상기 (D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물은 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 디에틸렌트리아민 펜타아세트산(diethylenetriamine pentaacetic acid), 에틸렌다이아민테트라아세트산(Ethylenediaminetetraacetic acid), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 1,
The water-soluble compounds (D) having a nitrogen atom and a carboxyl group in one molecule include alanine, aminobutyric acid, glutamic acid, glycine, and diethylenetriamine pentaacetic acid. , Ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, and sarcosine. A silver thin film etchant composition, characterized in that at least one selected from the group consisting of.
상기 (E) 트리아졸 화합물은 1, 2, 3 트리아졸(1, 2, 3 triazole), 1, 2, 4 트리아졸(1, 2, 4 triazole), 벤조트리아졸 (benzotriazole) 및 톨리트리아졸(Tolyltriazole)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 1,
The (E) triazole compounds include 1, 2, 3 triazole (1, 2, 3 triazole), 1, 2, 4 triazole (1, 2, 4 triazole), benzotriazole and tolytria. A silver thin film etchant composition comprising at least one selected from the group consisting of tolyltriazole.
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.
In claim 1,
The silver thin film etchant composition is capable of simultaneously etching a single film made of silver or a silver alloy, or a multilayer film made of the single film and a transparent conductive film.
상기 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
In claim 7,
The transparent conductive film is a silver thin film etchant composition, characterized in that at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc 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 포함하는 은 박막 식각액 조성물.
In claim 7,
A silver thin film etchant composition comprising the multilayer film being formed of 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.
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, or a multilayer film made of the single film and a transparent conductive film, on a substrate;
selectively leaving a photo-reactive material on the single layer or the multilayer layer; and
An etching method comprising etching the single layer or the multilayer layer using the composition of claim 1.
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, or a multilayer film made of the single film and a transparent conductive film, on a substrate; and
A method of forming a metal pattern comprising etching the single layer or the multilayer layer using the composition of claim 1.
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