KR20190106645A - 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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- KR20190106645A KR20190106645A KR1020180132371A KR20180132371A KR20190106645A KR 20190106645 A KR20190106645 A KR 20190106645A KR 1020180132371 A KR1020180132371 A KR 1020180132371A KR 20180132371 A KR20180132371 A KR 20180132371A KR 20190106645 A KR20190106645 A KR 20190106645A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000004332 silver Substances 0.000 title claims abstract description 79
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 37
- 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 60
- 239000010409 thin film Substances 0.000 claims abstract description 40
- -1 triazole compound Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 150000002978 peroxides Chemical class 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 94
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- 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
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 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
- 239000000463 material 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
- 239000007788 liquid Substances 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
- 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 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-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
- 108010077895 Sarcosine Proteins 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229940043230 sarcosine Drugs 0.000 claims description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-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
- 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
- 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
- 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
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims description 2
- HUPQYPMULVBQDL-UHFFFAOYSA-N pentanoic acid Chemical compound CCCCC(O)=O.CCCCC(O)=O HUPQYPMULVBQDL-UHFFFAOYSA-N 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
- IOQLGFCIMRCCNA-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid Chemical compound OC(=O)CNCC(O)=O.OC(=O)CNCC(O)=O IOQLGFCIMRCCNA-UHFFFAOYSA-N 0.000 claims 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 29
- 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
- 239000002244 precipitate Substances 0.000 description 7
- 238000001039 wet etching Methods 0.000 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 description 5
- 230000000694 effects Effects 0.000 description 5
- 229960003330 pentetic acid Drugs 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000007423 decrease Effects 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
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- ZYVAQZSGKALVEU-UHFFFAOYSA-N 2-[2-[bis(2-hydroxy-2-oxoethyl)amino]ethyl-(2-hydroxy-2-oxoethyl)amino]ethanoic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O ZYVAQZSGKALVEU-UHFFFAOYSA-N 0.000 description 1
- OORRCVPWRPVJEK-UHFFFAOYSA-N 2-oxidanylethanoic acid Chemical compound OCC(O)=O.OCC(O)=O OORRCVPWRPVJEK-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-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
- 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 150000004767 nitrides Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 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
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
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.As the information age enters a full-fledged period, the display field for processing and displaying a large amount of information has been rapidly developed, and various flat panel displays have been developed and attracted 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 a flat panel display device include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescence display device (Electroluminescence). Display device (ELD), Organic Light Emitting Diodes (OLED), and the like, and such a flat panel display device is used for various purposes such as a computer and a mobile phone as well as a home appliance field such as a television or a video. These flat panel display devices are rapidly replacing conventional cathode ray tubes (NITs) due to their excellent performance such as thinning, 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, since OLEDs emit light by themselves and can be driven at low voltages, OLEDs are rapidly being applied to small display markets such as mobile devices. OLED is also expected to commercialize large TV beyond small display.
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.On the other hand, conductive metals such as indium tin oxide (ITO) and indium zinc oxide (IZO) have relatively high transmittance to light and have conductivity, so that the color filter electrodes used in flat panel display devices It is widely used. However, these metals also have high resistance, which hinders the enlargement of the flat panel display device and the high resolution.
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 products in the past, but in order to realize low power consumption through improved brightness, the state of seeking a material change to a metal having a higher reflectance is being sought. To this end, silver (Ag: 1.59 μΩcm resistivity) film, silver alloy, or a multilayer film including the same, which has a lower resistivity and higher brightness than metals applied to a flat panel display device, may be used as a color filter electrode, LCD or OLED wiring, In order to realize a large-sized flat panel display device, high resolution, and low power consumption, it is required to develop an etching solution for the application of the material.
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 lower substrate such as a semiconductor substrate made of intrinsic amorphous silicon, doped amorphous silicon, or the like, so that deposition is not easy and the wiring is lifted. Lifting or peeling is easily caused. In addition, even when a silver (Ag) conductive layer is deposited on a substrate, an etchant is used to pattern it. When a conventional etchant is used as such an etchant, silver (Ag) may be excessively etched or etched unevenly to cause lifting or peeling of the wiring, resulting in poor side profile of the wiring.
또한 고해상도 구현을 위한 낮은 스큐(LOW Skew)구현이 공정을 하는데 있어 어려움이 있다.In addition, a low skew for high resolution is difficult to process.
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. Particularly, silver (Ag) is a metal that can be easily reduced, so that the etching speed is faster without inducing residues. At this time, the etching speed is not high, so the difference between the upper and lower portions does not occur, and thus, it is difficult to form a taper angle after etching. Since it is difficult to secure the straightness of the etching pattern, there are many limitations in wiring and pattern formation.
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 is standing vertically without a taper angle, voids may occur between silver (Ag) and the insulating film or wiring during the formation of the insulating film or the subsequent wiring in a subsequent process, and such voids may cause defects such as an electrical short. Cause.
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.Korean Patent No. 10-1323458 discloses a single layer composed of silver (Ag) or a silver alloy and a multilayer film etchant composition composed of the single layer and an indium oxide layer, but the main problem in the art is residue and silver resorption. The situation is not completely solved.
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 to improve the above-mentioned problems of the prior art, 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 the transparent conductive film, a problem of silver resorption occurs It is not an object, and an object of the present invention is to provide a silver thin film etching liquid composition, characterized in that the problem of precipitation of single and multilayer film components does not occur.
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 capable of simultaneously etching 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.In addition, an object of the present invention is to provide a silver thin film etchant composition that can adjust the side etch through the 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.In addition, an object of the present invention is to provide a silver thin film etchant composition that can be usefully used for wet etching showing etching uniformity without damaging the underlying film.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching method using the silver thin film etchant composition.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method of forming a metal pattern using the 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 is a composition based on (A) 1 to 10% by weight of inorganic acid; (B) 30 to 70% by weight of organic acid; (C) 0.1 to 10 wt% 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 wt% triazole compound; And (F) provides a thin film etchant composition comprising a residual amount of 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, 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 the transparent conductive film, thereby preventing problems of silver resorption, deposition 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 an effect of improving the 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, thereby providing an effect of controlling the etching rate and adjusting the 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 may be usefully used for wet etching showing 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 comprises (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. The silver thin film etchant composition was completed by experimentally confirming that (C) a peroxide and (D) a water-soluble compound having a nitrogen atom and a carboxyl group together in one molecule exhibited a very excellent effect as a silver adsorption inhibitor.
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 the transparent conductive film, and problems of silver resorption and precipitation of single film and multilayer film components Characterized in that does not occur.
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 may simultaneously etch the single layer and the multilayer layer.
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 may generate an etch stop phenomenon, thereby providing an effect of controlling the etching rate and adjusting the 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 may be usefully used for wet etching because there is no damage to the lower layer and thus exhibits etching uniformity.
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 in the form of an alloy containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, and Ti, based on silver; It may include, but is not limited to, nitrides, silicides, carbides, oxides, and the like of silver.
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 indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), and indium 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 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 is not limited thereto. An electronic component including the single layer and the multilayer film. It 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 wet etching by oxidizing silver (Ag) and indium oxide film in an 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 1 to 10% by weight, preferably 3 to 9% by weight based on the total weight of the composition. When the content of the inorganic acid is less than 1% by weight, it may cause a decrease in the etching rate of silver and the occurrence of silver residue. When the content of the inorganic acid exceeds 10% by weight, the etching rate of the silver and the indium oxide film is increased, resulting in an overetching phenomenon. There are disadvantages that are problematic for 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 the like, 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 oxidant and performs wet etching by oxidizing silver (Ag) and indium oxide film in an 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 30 to 70% by weight, preferably 40 to 60% by weight based on the total weight of the composition. When the content of the organic acid is less than 30% by weight, the etching rate of silver (Ag) and the indium oxide film decreases, resulting in poor etching uniformity (uniformity) in the substrate, resulting in staining. And the etching rate of the indium oxide film is faster, there is a disadvantage that the problem occurs in the subsequent process due to the over-etching phenomenon.
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 acid include acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, and malonic acid. ), Pentanic acid (pentanoic acid) and oxalic acid (oxalic acid) and the like, it is preferable to use glycolic acid (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 oxidant, and serves to oxidize silver (Ag) in the indium oxide film / Ag / indium oxide film to wet etch and prevent Ag resorption.
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 rate of silver (Ag) and the indium oxide film decreases, resulting in poor etching uniformity (uniformity) in the substrate, resulting in staining. The etching rate of the Ag and the indium oxide film is increased, and there is a disadvantage in that an overetching phenomenon becomes a problem in the subsequent process.
상기 과산화물의 구체적인 예로는 Oxone, SPS(Sodium persulfate) 및 APS(Ammonium persulfate) 등을 들 수 있으며, Oxone을 사용하는 것이 바람직하다.Specific examples of the peroxides include Oxone, SPS (Sodium persulfate) and APS (Ammonium persulfate), and it is preferable to use Oxone.
(D) 한 분자 내에 질소 원자와 카르복실기를 갖는 수용성 화합물(D) a 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 the molecule serves to maintain the side etch change and prevent Ag resorption when the treatment sheet proceeds.
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 the one molecule may be included in 0.01 to 1% by weight, preferably 0.1 to 0.8% by weight relative to the total weight of the composition. When 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 amount of side etch cannot be maintained when the number of treatments proceeds, and when it exceeds 1% by weight, the etching uniformity in the substrate is lowered. Residue may also partially occur in 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 the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule include alanine, aminobutyric acid, glutamic acid, glycine, and diethylenetriamine pentaacetic acid. , Ethylenediaminetetraacetic acid (Ethylenediaminetetraacetic acid), iminodiacetic acid, nitrilotriacetic acid and sarcosine, and the like, and it is preferable to use diethylenetriamine pentaacetic acid. .
(E) 트리아졸 화합물(E) triazole compounds
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 the CD loss of the pattern, thereby increasing the process margin.
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. When the content of the triazole compound is less than 0.01% by weight, the etching rate may be increased so that the cisidose may be generated too large. When the triazole compound is included in an amount of more than 1% by weight, the etching rate of Ag may be too slow, resulting in etching residue. 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 compound include 1, 2, 3 triazole, 1, 2, 4 triazole, benzotriazole, and tolytriazole. (Tolyltriazole) etc. are mentioned, It is preferable to use benzotriazole.
식각액 조성물 내에 상기 트리아졸 화합물이 아닌, 아졸 화합물을 포함하는 경우, 식각 공정에서 ITO 석출물이 발생할 수 있다.When the etchant composition contains an azole compound other than the triazole compound, ITO precipitate may occur in 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 a semiconductor process, and preferably 18 deg./cm or more of the deionized water may be used.
상기 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다.The amount of water may be included in the remaining 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 comprises a single film made of silver (Ag) or a silver alloy used as a wiring and a reflective film in the manufacture of a display device (OLED, LCD, etc.) and a multilayer film composed of the single film and an indium oxide film, Preferably, it can be usefully used for the 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.In addition, 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 comprises the steps of: i) forming a single film made of silver or silver alloy or a multilayer film made of the single film and the transparent conductive film; ii) optionally leaving a photoreactive material over 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.The present invention also 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 comprises the steps of: i) forming a single film made of silver or silver alloy, or a multilayer film made of the single film and the transparent conductive film; And ii) etching the single layer or the multilayer layer 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 with reference to 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 invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.
실시예 및 비교예에 따른 은 박막 식각액 조성물의 제조Preparation of Silver Thin Film Etch Liquid Compositions 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 (unit: wt%), silver thin film etchant compositions according to Examples 1 to 9 and Comparative Examples 1 to 12 were prepared. The content of water was to be included in the balance so that the total weight of the composition is 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 having a nitrogen atom and a carboxyl group in one molecule: DTPA (Diethylenetriamine pentaacetic acid), IDA (Iminodiacetic acid)
(E) 트리아졸 화합물: BTA(Benzotriazole)(E) Triazole Compound: BTA (Benzotriazole)
ATZ : AminotetrazoleATZ: Aminotetrazole
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.Form ITO (Indium Tin Oxide) / Silver / ITO Triple Film Specimen on the substrate, and then in the Experimental Equipment (Model name: ETCHER (TFT), SEMES, Inc.) of the spray etching method, After the silver etchant composition was added to each other and the temperature was set to 40 ° C., the temperature was raised to 40 ± 0.1 ° C., and the etching process of the specimen was performed. It was taken out, washed with deionized water and dried 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 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). As a standard for measuring the one-side etching distance, the width of the metal is etched from the end of the photoresist to the inside was measured. The evaluation was performed based on the following criteria.
<평가 기준><Evaluation Criteria>
O : 양호 (S/E : 0.50㎛ 미만)O: good (S / E: less than 0.50 mu m)
X : 불량 (S/E : 0.50㎛ 이상 및 unetch)X: Poor (S / E: 0.50㎛ or more and unetch)
시험예 2: 은(Ag) 재흡착 측정Test Example 2: Determination of Silver (Ag) Resorption
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.Form ITO (Indium Tin Oxide) / Silver / ITO Triple Film Specimen on the substrate, and then in the Experimental Equipment (Model name: ETCHER (TFT), SEMES, Inc.) of the spray etching method, After the silver etchant composition was added to each other and the temperature was set to 40 ° C., the temperature was raised to 40 ± 0.1 ° C., and the etching process of the specimen was performed. It was taken out, washed with deionized water and dried 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 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 layer of the exposed S / D portion in the substrate was measured and evaluated according to the following criteria, and is shown in the following [Table 2]. .
< 평가 기준>Evaluation criteria
O : 양호 (50개 미만)O: good (less than 50)
X : 불량 (50개 이상)X: Poor (more than 50)
시험예 3: ITO 석출물 측정Test Example 3 Measurement of ITO Precipitate
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.In the silver etchant composition of Examples 1 to 9 and Comparative Examples 1 to 12, the composition of 0 ppm dissolved in ITO and the composition dissolved in 500 ppm were left to stand for 24 hours, and the components of precipitates produced at this time were analyzed and evaluated according to the following criteria. 2].
ITO를 500ppm 용해 시킨 조성물의 경우, 식각 공정이 진행됨에 따라 ITO 석출물이 석출된 것을 가정한 용액이다.In the case of 500 ppm dissolved ITO composition, it is assumed that ITO precipitates as the etching process proceeds.
< 평가 기준>Evaluation criteria
O : 석출물 미발생O: No precipitates generated
X : 석출물 발생X: precipitate occurrence
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 the etching process is performed using the silver thin film etchant composition according to the embodiment, the side etch is measured as 0.25 to 0.4 μm, it can be seen that the problems of silver resorption and ITO precipitation does 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, side etching is not easily controlled as the etching process proceeds, and silver resorption and ITO precipitation problems occur. It can be seen 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, when the etching process is performed using the silver thin film etchant composition according to the present invention, it can be seen that side etch control is easy and silver resorption 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 포함하는 것을 특징으로 하는 은 박막 식각액 조성물.
The composition is based on the total weight,
(A) 1 to 10 weight percent of inorganic acid;
(B) 30 to 70% by weight of organic acid;
(C) 0.1 to 10 wt% 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 wt% triazole compound; And
(F) A silver thin film etchant composition comprising a residual amount of water.
상기 (A) 무기산은 질산 및 염산으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
The method according to claim 1,
The (A) inorganic acid is a thin film etchant composition, characterized in that at least one member 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.
The method according to claim 1,
The organic acid (B) is acetic acid, butanoic acid, citric acid, formic acid, formic acid, gluconic acid, glycolic acid, malonic acid, and malonic acid. ), Pentanic acid (pentanoic acid) and oxalic acid (oxalic acid) is a thin film etching liquid composition, characterized in that at least one member selected from the group consisting of.
상기 (C) 과산화물은 Oxone, SPS(Sodium persulfate) 및 APS(Ammonium persulfate)로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.
The method according to claim 1,
The (C) peroxide is a silver thin film etchant composition, characterized in that 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.
The method according to claim 1,
The water-soluble compound having a nitrogen atom and a carboxyl group in the molecule (D) is alanine, aminobutyric acid, glutamic acid, glycine, diethylenetriamine pentaacetic acid Ethylenediaminetetraacetic acid (Ethylenediaminetetraacetic acid), iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid) and sarcosine (sarcosine) is a silver thin film etchant composition, characterized in that at least one.
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.
The method according to claim 1,
The (E) triazole compound is 1, 2, 3 triazole, 1, 2, 4 triazole, 1, 2, 4 triazole, benzotriazole and tolitria A silver thin film etchant composition, characterized in that at least one selected from the group consisting of sol (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.
The method according to 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 composed of the single film and the 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.
The method according to claim 7,
The transparent conductive film is at least one silver thin film etching liquid composition, characterized in that at least one selected from the group consisting of indium tin 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 포함하는 은 박막 식각액 조성물.
The method according to claim 7,
The multilayer film is a thin film etchant composition comprising a transparent conductive film / silver, transparent conductive film / silver alloy, transparent conductive film / silver / transparent conductive film or 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 silver alloy or a multilayer film made of the single film and the transparent conductive film on the substrate;
Selectively leaving a photoreactive material on the single layer or the multilayer layer; And
Etching method comprising etching the single layer or the multilayer film 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 silver alloy or a multilayer film made of the single film and the transparent conductive film on the substrate; 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101245462A (en) * | 2007-02-13 | 2008-08-20 | 峻科技有限公司 | Etching liquid composition and etching method |
| KR101323458B1 (en) | 2007-06-15 | 2013-10-29 | 동우 화인켐 주식회사 | Etchant composition for silver |
| KR20160115189A (en) * | 2015-03-26 | 2016-10-06 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
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