KR20100119728A - Indium oxalate dissolving agent composition - Google Patents
Indium oxalate dissolving agent composition Download PDFInfo
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- KR20100119728A KR20100119728A KR1020100040745A KR20100040745A KR20100119728A KR 20100119728 A KR20100119728 A KR 20100119728A KR 1020100040745 A KR1020100040745 A KR 1020100040745A KR 20100040745 A KR20100040745 A KR 20100040745A KR 20100119728 A KR20100119728 A KR 20100119728A
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- acid
- indium oxalate
- indium
- composition
- aminopolycarboxylic
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- LKEDUJPRSZGTHZ-UHFFFAOYSA-H indium(3+);oxalate Chemical compound [In+3].[In+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LKEDUJPRSZGTHZ-UHFFFAOYSA-H 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 46
- -1 acids amine salt Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 150000007513 acids Chemical class 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 229960001484 edetic acid Drugs 0.000 claims description 26
- 238000004090 dissolution Methods 0.000 claims description 21
- 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 20
- 238000005530 etching Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000001039 wet etching Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-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 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 13
- 239000013522 chelant Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- OTZKODYMSSYHRQ-UHFFFAOYSA-N acetic acid;azane;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid Chemical compound N.CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O OTZKODYMSSYHRQ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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- 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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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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- 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
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
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- 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
- C23F1/32—Alkaline compositions
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- 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
- C23F17/00—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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Abstract
Description
본 발명은 ITO(산화 인듐주석), IZO(산화 인듐 아연) 등의 에칭 장치 내부에서 석출한 인듐 옥살레이트를 용해 제거하는 것이 가능한 용해제에 관한 것이다.
The present invention relates to a dissolving agent capable of dissolving and removing indium oxalate precipitated inside an etching apparatus such as ITO (indium tin oxide) or IZO (indium zinc oxide).
LCD(액정 디스플레이)나 ELD(전계 발광 디스플레이)등의 FPD(플랫 패널 디스플레이) 표시장치와 관련하여, 화소의 표시 전극 등에 투명 도전막이 사용되고 있다. 이와 같은 투명 도전막의 재료로서 ITO(산화 인듐주석), IZO(산화 인듐 아연)등이 넓게 사용되고 있다. 통상적으로, ITO, IZO를 이용한 표시 전극의 가공은 옥살산을 주성분으로 한 에칭액이 이용되고(예를 들면 특허 문헌 1), 포토리소그래피(photolithography)에 의해 패터닝 된 레지스터를 마스크로 사용하여 ITO, IZO를 습식 에칭하는 방법으로, 목적하는 ITO, IZO 표시 전극 패턴이 형성된다.
BACKGROUND ART In connection with flat panel display (FPD) display devices such as LCD (liquid crystal display) and ELD (electroluminescent display), transparent conductive films are used for display electrodes of pixels and the like. As a material of such a transparent conductive film, ITO (indium tin oxide), IZO (indium zinc oxide), etc. are widely used. Usually, the processing of the display electrode using ITO and IZO uses an etching solution containing oxalic acid as a main component (for example, Patent Document 1), and uses ITO and IZO by using a patterned resistor as a mask as a photolithography. By wet etching, a desired ITO or IZO display electrode pattern is formed.
옥살산을 주성분으로 한 에칭액에 의한 ITO막 또는 IZO막의 습식 에칭은 옥살산의 킬레이트 효과에 의해 ITO, IZO의 주성분인 인듐을 착체화하는 것으로, 인듐 옥살레이트로 용해됨으로써 에칭이 진행되고 있다. 이와 같은 옥살산을 주성분으로 한 에칭액은 장기간에 걸치는 연속 사용에 의해, 인듐 옥살레이트가 에칭액중에 모두 용해되지 않고 습식 에칭 장치 내부에 석출되는 문제가 있다(예를 들면 특허 문헌 2).The wet etching of an ITO film or an IZO film by the etching liquid containing oxalic acid as a main component complexes indium which is a main component of ITO and IZO by the chelating effect of oxalic acid, and is etching by dissolving with indium oxalate. The etching liquid containing such oxalic acid as a main component has a problem in that indium oxalate does not dissolve in the etching liquid but is precipitated inside the wet etching apparatus due to continuous use for a long time (for example, Patent Document 2).
이와 같은 인듐 옥살레이트는, 배관, 밸브, 필터, 펌프, 스프레이 노즐, 기판 반송 롤러, 습식 에칭 실내벽, 버퍼 탱크내 등, 습식 에칭 장치계의 내부에 석출되어 이하와 같은 문제를 일으키고 있다.
Such indium oxalate precipitates inside the wet etching apparatus system, such as a pipe, a valve, a filter, a pump, a spray nozzle, a substrate conveying roller, a wet etching room wall, and a buffer tank, causing the following problems.
예를 들면, 배관 내경의 감소, 밸브 개폐나 펌프 동작의 불량, 필터나 스프레이 노즐의 로딩 등의 이상이 발생한다. 이러한 이상이 에칭 처리 공정 중에 발생했을 경우, 면내 균일성의 저하나 에칭 형상 불량 등의 에칭 특성에의 영향이 지극히 크고, 제품의 완성도를 저하시키는 치명적인 문제가 된다.
For example, abnormalities such as a decrease in the pipe inner diameter, a valve opening and closing, a poor pump operation, and a loading of a filter or a spray nozzle occur. When such an abnormality occurs during the etching treatment step, the influence on etching characteristics such as lowering of in-plane uniformity or poor etching shape is extremely large, which is a fatal problem of lowering the completeness of the product.
종래, 상기 문제점에 대해서, 정기적으로 습식 에칭 장치계 내부에 석출하는 인듐 옥살레이트를 물리적으로 회수하는 방법이 대책으로서 행해지고 있다. 즉, 물 또는 온수를 이용하여 높은 유속으로 순환 세정을 실시하는 방법으로 장치 내부에 석출하는 인듐 옥살레이트를 박리 제거하고 있다. 또한, 순환 세정에 의해 제거되지 않은 인듐 옥살레이트에 대해서는 습식 에칭 장치계 내부로부터 완전하게 에칭액을 배출한 후, 사람의 수작업에 의해 인듐 옥살레이트를 긁어내 제거하고 있다.
Conventionally, the method of physically recovering the indium oxalate which precipitates inside a wet etching apparatus system regularly is performed as a countermeasure against the said problem. That is, the indium oxalate which precipitates in the inside of the apparatus is peeled off by the method of carrying out circulation washing at high flow velocity using water or hot water. In addition, about the indium oxalate which was not removed by circulation washing, the etching liquid was completely discharged from the inside of the wet etching apparatus system, and the indium oxalate was scraped off by manual labor.
<선행 기술 문헌>Prior art literature
(특허 문헌 1) 특개 2005－244083호 공보(Patent Document 1) JP 2005-244083 A
(특허 문헌 2) 특개 2006－77241호 공보
(Patent Document 2) JP 2006-77241 A
본 발명의 목적은 상기 종래의 문제점을 해결해, 산화 인듐주석(ITO) 막 또는 산화 인듐 아연(IZO)으로 구성되는 투명 도전막의 습식 에칭 장치 내부에 석출되는 인듐 옥살레이트를 화학적으로 용해 제거하기 위한 인듐 옥살레이트 용해제를 제공하는 것이다.
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to solve the above problem, indium for chemically dissolving and removing indium oxalate deposited inside a wet etching apparatus of a transparent conductive film composed of an indium tin oxide (ITO) film or indium zinc oxide (IZO). It is to provide an oxalate dissolving agent.
본 발명자들은 상기 과제를 해결하기 위하여 열심히 검토를 거듭한 결과, 아미노폴리카르본산을 함유하는 알칼리 수용액이 인듐 옥살레이트를 효율적으로 용해 제거한다는 것을 알게 되었다. 한층 더 연구를 진행시킨 결과, 아미노폴리카르본산아민염으로부터 유래하는 화합물을 추가적으로 함유시킴에 의하여 인듐 옥살레이트의 최대 용해량을 높이는 것이 가능한 것을 찾아내, 본 발명을 완성하기에 이르렀다.
MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it turned out that the aqueous alkali solution containing amino polycarboxylic acid dissolves and removes indium oxalate efficiently. As a result of further studies, the inventors have found that it is possible to increase the maximum dissolved amount of indium oxalate by additionally containing a compound derived from an aminopolycarboxylic acid amine salt, thereby completing the present invention.
즉, 본 발명은 에칭 장치계 내부에 석출된 인듐 옥살레이트를 용해 제거하기 위하여 사용되는 용해제 조성물에 관한 것이며, 알칼리 성분과 아미노폴리카르본산 및 그 염으로부터 선택되는 1종 또는 2종 이상을 함유하는 수용액인 것을 특징으로 하는 상기 용해제 조성물에 관한 것이다.
That is, the present invention relates to a dissolving agent composition used to dissolve and remove indium oxalate precipitated in the etching apparatus system, and contains one or two or more kinds selected from alkali components, aminopolycarboxylic acids and salts thereof. It is related with the said solubilizer composition characterized by the above-mentioned.
또한 본 발명은 pH가 9 ~ 11의 범위인 상기의 용해제 조성물에 관한 것이다.
The present invention also relates to the above-mentioned dissolving agent composition having a pH in the range of 9-11.
나아가 본 발명은 아미노폴리카르본산 및 그 염으로부터 선택되는 1종 또는 2종 이상의 화합물의 농도가 합계로 1 ~ 40 중량%인 상기의 용해제 조성물에 관한 것이다.The present invention further relates to the above-mentioned dissolving agent composition wherein the concentration of one or two or more compounds selected from aminopolycarboxylic acids and salts thereof is 1 to 40% by weight in total.
더 나아가 본 발명은 아미노폴리카르본산으로부터 선택되는 화합물을 적어도 1종 또는 2종 이상 함유하는 상기의 용해제 조성물에 관한 것이다.
Furthermore, this invention relates to the said solubilizer composition containing at least 1 type, or 2 or more types of compounds chosen from aminopolycarboxylic acid.
더 나아가 본 발명은 아미노폴리카르본산으로부터 선택되는 화합물 및 아미노폴리카르본산아민염으로부터 선택되는 화합물을 각각 적어도 1종 함유하는 상기의 용해제 조성물에 관한 것이다.
Furthermore, this invention relates to the said solubilizer composition containing at least 1 sort (s) each of the compound chosen from amino polycarboxylic acid, and the compound chosen from aminopolycarboxylic acid amine salt.
더 나아가 본 발명은 아미노폴리카르본산으로부터 선택되는 화합물의 농도가 1 ~ 20 중량%, 아미노폴리카르본산아민염으로부터 유래하는 군으로부터 선택되는 화합물의 농도가 1 ~ 20 중량%인 상기의 용해제 조성물에 관한 것이다.
Furthermore, the present invention relates to the above-mentioned dissolving agent composition wherein the concentration of the compound selected from the aminopolycarboxylic acid is 1 to 20% by weight, and the concentration of the compound selected from the group derived from the aminopolycarboxylic acid amine salt is 1 to 20% by weight. It is about.
더 나아가 본 발명은 아미노폴리카르본산이 에틸렌 디아민2아세트산, 에틸렌 디아민4아세트산, 디에틸렌 트리아민5아세트산, 트리에틸렌 테트라 아민6아세트산, 트렌스－1,2－시클로 헥산 디아민4아세트산으로부터 선택되는 것을 특징으로 하는 상기의 용해제 조성물에 관한 것이다.
Furthermore, the present invention is characterized in that the aminopolycarboxylic acid is selected from ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, triethylene tetra amine hexaacetic acid, trans-1,2-cyclohexanediamine tetraacetic acid. It relates to the above-mentioned dissolving agent composition.
더 나아가 본 발명은 아미노폴리카르본산의 염이 에틸렌 디아민2아세트산, 에틸렌 디아민4아세트산, 디에틸렌 트리아민5아세트산, 트리에틸렌 테트라 아민6아세트산, 트렌스－1, 2－시클로 헥산 디아민4아세트산의 아민염인 것을 특징으로 하는 상기의 용해제 조성물에 관한 것이다.
Furthermore, in the present invention, the salt of aminopolycarboxylic acid is an amine salt of ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, triethylene tetra amine tereacetic acid, trans-1, 2-cyclohexanediamine tetraacetic acid. It is related with the said solubilizer composition characterized by the above-mentioned.
더 나아가 본 발명은 알칼리 성분이 암모니아, 수산화 나트륨, 수산화 칼륨, 수산화 테트라 메틸 암모늄 중 어느 하나인 것을 특징으로 하는 상기의 용해제 조성물에 관한 것이다.
The present invention further relates to the above-mentioned dissolving agent composition, wherein the alkali component is any one of ammonia, sodium hydroxide, potassium hydroxide and tetramethyl ammonium hydroxide.
더 나아가 본 발명은 에칭 장치계 내부의 세정 방법에 있어서,Furthermore, the present invention provides a cleaning method in an etching apparatus system.
(1) 계 내부로부터 에칭액을 배출한 후, pH가 중성이 될 때까지 물로 세정하는 공정,(1) removing the etching solution from the inside of the system and then washing with water until the pH becomes neutral,
(2) 상기의 용해제를 이용해, 장치 내부에 석출하는 인듐 옥살레이트를 화학적으로 용해 제거하는 공정,(2) Process of chemically dissolving and removing indium oxalate which precipitates in apparatus inside using said solubilizer,
(3) 용해제를 제거한 후, pH가 중성이 될 때까지 물로 세정하는 공정(3) After removing the solvent, washing with water until the pH is neutral
을 포함하는 상기 세정 방법에 관한 것이다.
It relates to the cleaning method comprising a.
더 나아가 본 발명은 용해 제거에 이용한 후의 상기의 용해제 조성물을 회수하는 공정을 더 포함하는 것을 특징으로 하는 상기의 세정 방법에 관한 것이다.
Furthermore, this invention relates to the said washing | cleaning method further including the process of collect | recovering the said solvent composition after using for dissolution removal.
더 나아가 본 발명은 에칭 장치가 ITO막 또는 IZO막으로 구성되는 투명 도전막의 습식 에칭의 장치인 것을 특징으로 하는 상기의 세정 방법에 관한 것이다.
Furthermore, this invention relates to the said washing | cleaning method characterized by the etching apparatus being the apparatus of the wet etching of the transparent conductive film comprised from an ITO film or an IZO film.
더 나아가 본 발명은 배관, 밸브, 필터, 펌프, 스프레이 노즐, 기판 반송 롤러, 습식 에칭 실내벽, 버퍼 탱크내로부터 선택되는 1 또는 2 이상의 개소에서 석출되는 인듐 옥살레이트를 용해 제거하는 것을 특징으로 하는 상기의 세정 방법에 관한 것이다.
Furthermore, the present invention is characterized by dissolving and removing indium oxalate precipitated at one or two or more points selected from a pipe, a valve, a filter, a pump, a spray nozzle, a substrate conveying roller, a wet etching interior wall, and a buffer tank. It relates to the above washing method.
본 발명에 따르면, 아미노폴리카르본산이 그 킬레이트 효과에 의하여, 인듐 옥살레이트를 수용액중에 효율적으로 용해하는 작용이 있는 것을 알게 되었다. 또한, 아미노폴리카르본산과 아미노폴리카르본산아민염의 조합에 의해, 수용액 중 인듐 옥살레이트의 최대 용해량을 증가시키는 일도 가능하다는 것을 알게 되었다.
According to the present invention, it has been found that aminopolycarboxylic acid has an effect of efficiently dissolving indium oxalate in an aqueous solution due to its chelate effect. It has also been found that it is also possible to increase the maximum dissolved amount of indium oxalate in aqueous solution by the combination of aminopolycarboxylic acid and aminopolycarboxylic acid amine salt.
이하에 본 발명의 실시 형태에 대해 상술한다.
EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.
본 발명에 따른 인듐 옥살레이트 용해제는 아미노폴리카르본산 및 그 염으로부터 선택되는 1종 또는 2종 이상의 킬레이트제와 알칼리 성분을 포함한 조성물이다. 킬레이트제란 금속 이온에 배위결합하는 능력을 가진 전자 공여체(배위자)를 복수로 가지는 화합물이며, 2자리 배위자 이상을 가지는 화합물을 총칭해 다좌배위자(킬레이트제)라고 부른다. 킬레이트제는 용액중의 금속 이온을 자신의 배위자에 의해 감싸는 형태로 수용성의 금속 킬레이트 화합물을 생성하는 특징이 있다.
Indium oxalate solubilizer according to the present invention is a composition comprising one or two or more chelating agents selected from aminopolycarboxylic acids and salts thereof and an alkali component. A chelating agent is a compound which has a plurality of electron donors (ligands) which have the ability to coordinate to a metal ion, and the compound which has a bidentate ligand or more is collectively called a polydentate ligand (chelating agent). Chelating agents are characterized by producing a water-soluble metal chelate compound in the form of surrounding the metal ions in solution by its ligand.
본 발명의 인듐 옥살레이트 용해제로 사용되는 아미노폴리카르본산은 예를 들어 에틸렌 디아민2아세트산, 에틸렌 디아민4아세트산, 디에틸렌 트리아민5아세트산, 트리에틸렌 테트라 아민6아세트산, 트렌스－1,2－시클로 헥산 디아민4아세트산 등을 들 수 있다. 구입비용이나 킬레이트 능력의 관점에서, 바람직한 것은 에틸렌 디아민4아세트산이다.
The aminopolycarboxylic acid used as the indium oxalate dissolving agent of the present invention is, for example, ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine acetic acid, triethylene tetra amine 6 acetic acid, trans-1,2-cyclohexane Diamine tetraacetic acid etc. are mentioned. From the viewpoint of purchase cost and chelating ability, preferred is ethylene diamine tetraacetic acid.
본 발명의 인듐 옥살레이트 용해제로 바람직하게 사용되는 아미노폴리카르본산염은 예를 들어 암모늄염, 아민염, 나트륨염, 칼륨염, 칼슘염 등을 들 수 있다. 전자 공업용으로서 사용하는 경우에는, 나트륨, 칼륨 등의 알칼리 금속을 함유하는 것은 디바이스의 전기적 특성의 열화 인자가 될 수 있기 때문에, 암모늄염, 아민염인 것이 바람직하다.
The aminopolycarboxylic acid salts preferably used as the indium oxalate dissolving agent of the present invention include, for example, ammonium salts, amine salts, sodium salts, potassium salts, calcium salts and the like. In the case of use for the electronics industry, containing an alkali metal such as sodium or potassium may be a deterioration factor of the electrical characteristics of the device, and therefore, an ammonium salt or an amine salt is preferable.
본 발명의 인듐 옥살레이트 용해제로 사용되는 알칼리 성분은 예를 들어, 암모니아, 수산화 나트륨, 수산화 칼륨, 수산화 테트라 메틸 암모늄 등을 들 수 있다. 전자 공업용으로서 사용하는 경우에는, 나트륨, 칼륨 등의 알칼리 금속을 함유하는 것은 디바이스의 전기적 특성의 열화 인자가 될 수 있기 때문에, 암모니아, 수산화 테트라 메틸 암모늄인 것이 바람직하고, 구입비용 등의 관점에서, 암모니아가 가장 바람직하다.
Examples of the alkali component used as the indium oxalate dissolving agent of the present invention include ammonia, sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide and the like. When used for the electronics industry, since containing alkali metals such as sodium and potassium can be a deterioration factor of the electrical characteristics of the device, it is preferable that they are ammonia and tetramethyl ammonium hydroxide, and from the viewpoint of purchase cost and the like, Most preferred is ammonia.
본 발명의 아미노폴리카르본산 및 그 염의 농도는 바람직하게는 합계로 1 ~ 40 중량%이며, 더욱 바람직하게는 1 ~ 20 중량%, 가장 바람직하게는 1 ~ 10 중량%이다. 1 중량%미만에서는 충분한 킬레이트 효과를 얻지 못하고 인듐 옥살레이트 용해량은 극히 적다. 또한, 40 중량%를 넘는 첨가량에서는 첨가량에 따르는 효과를 얻을 수 없기 때문에 경제적이지 못하다.
The concentration of the aminopolycarboxylic acid and salts thereof of the present invention is preferably 1 to 40% by weight in total, more preferably 1 to 20% by weight, most preferably 1 to 10% by weight. Below 1% by weight, sufficient chelate effect is not obtained and indium oxalate dissolution is extremely small. In addition, the addition amount of more than 40% by weight is not economical because the effect according to the addition amount is not obtained.
본 발명의 인듐 옥살레이트 용해제는 킬레이트 능력의 관점에서, 바람직하게는 적어도 아미노폴리카르본산으로부터 유래하는 군으로부터 선택되는 화합물을 포함한다.
Indium oxalate solubilizers of the present invention include compounds selected from the group preferably derived from at least aminopolycarboxylic acids, in view of chelating ability.
더욱 바람직하게는 추가의 킬레이트제로서 아미노폴리카르본산아민염을 더 포함한다. 본 발명자들은 아미노폴리카르본산 및 그 염으로부터 유래하는 군으로부터 선택되는 킬레이트제에 아미노폴리카르본산아민염으로부터 유래하는 군으로부터 선택되는 추가의 킬레이트제를 첨가하는 것을 통하여, 킬레이트제 단독으로 사용하는 것보다도 높은 킬레이트 효과를 발휘할 수 있다는 것을 알게 되었다.
More preferably, it further comprises an aminopolycarboxylic acid amine salt as an additional chelating agent. The present inventors use the chelating agent alone by adding an additional chelating agent selected from the group derived from the aminopolycarboxylic acid amine salt to the chelating agent selected from the group derived from the aminopolycarboxylic acid and salts thereof. It has been found that higher chelate effects can be achieved.
아미노폴리카르본산아민염으로는 예를 들어, 에틸렌 디아민2아세트산, 에틸렌 디아민4아세트산, 디에틸렌 트리아민5아세트산, 트리에틸렌 테트라 아민6아세트산, 트렌스－1,2－시클로 헥산 디아민4아세트산, 이의 아민염을 들 수 있다. 그 중에서도, 구입비용이나 킬레이트 능력의 관점에서 에틸렌 디아민4아세트산 아민염이 바람직하다.
As aminopolycarboxylic acid amine salt, For example, ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, triethylene tetra amine hexaacetic acid, trans- 1, 2- cyclohexane diamine tetraacetic acid, its amine Salts. Especially, an ethylene diamine tetraacetic acid amine salt is preferable from a viewpoint of a purchase cost and a chelate ability.
이와 같은 아미노폴리카르본산아민염에 이용되고 있는 아민류에는 모노에탄올 아민, 디에탄올 아민, 트리에탄올 아민, 모노이소 프로파놀 아민, 디이소프로파놀아민, 트리이소프로파놀아민 등으로 대표되는 알칸올 아민류나, 모노메틸 아민, 모노에틸아민, 이소프로필 아민, 모노-n－부틸 아민 등으로 대표되는 알킬 아민류가 있다. 특히 알칸올 아민류는 배위자를 복수로 가져, 금속 킬레이트를 생성하는 능력이 있어 인듐과 안정된 킬레이트 화합물을 생성하기가 용이하다고 생각된다.
The amines used for such aminopolycarboxylic acid amine salts include alkanols represented by monoethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanolamine, triisopropanolamine, and the like. Amines and alkyl amines represented by monomethyl amine, monoethylamine, isopropyl amine, mono-n-butyl amine and the like. In particular, alkanol amines have a plurality of ligands and have the ability to generate metal chelates, which makes it easy to produce indium and stable chelate compounds.
아미노폴리카르본산아민염과 함께 사용되는 아미노폴리카르본산의 농도는 바람직하게는 1 ~ 20 중량%, 더욱 바람직하게는 1 ~ 10 중량%이다. 아미노폴리카르본산의 농도가 1 중량%미만인 경우에는 충분한 킬레이트 효과를 얻지 못하고 인듐 옥살레이트 용해량은 극히 작다. 또한, 20 중량%를 넘는 첨가량에서는 첨가량에 따르는 효과를 얻을 수 없어 경제적이지 못하다.
The concentration of the aminopolycarboxylic acid used with the aminopolycarboxylic acid amine salt is preferably 1 to 20% by weight, more preferably 1 to 10% by weight. If the concentration of aminopolycarboxylic acid is less than 1% by weight, sufficient chelate effect is not obtained and the amount of dissolved indium oxalate is extremely small. In addition, the addition amount of more than 20% by weight can not obtain the effect according to the addition amount is not economical.
추가의 킬레이트제로서 사용되는 아미노폴리카르본산아민염의 농도는 1 ~ 20 중량%, 바람직한 농도는 1 ~ 10 중량%이다. 아미노폴리카르본산아민염의 농도가 1 중량%미만에서는 충분한 킬레이트 효과를 얻지 못하고 인듐 옥살레이트 용해량의 향상은 작다. 또한, 20 중량%를 넘는 첨가량에서는 첨가량에 따르는 효과를 얻을 수 없으므로 경제적이지 못하다.
The concentration of the aminopolycarboxylic acid amine salt used as further chelating agent is 1 to 20% by weight, and the preferred concentration is 1 to 10% by weight. If the concentration of the amino polycarboxylic acid amine salt is less than 1% by weight, a sufficient chelate effect is not obtained and the improvement of the indium oxalate dissolution amount is small. In addition, the addition amount of more than 20% by weight is not economical because the effect according to the addition amount is not obtained.
본 발명의 인듐 옥살레이트 용해제로 사용되는 알칼리 수용액의 농도는 아미노폴리카르본산의 킬레이트제가 가장 효과적으로 작용하는 pH영역으로 조정할 필요가 있다. 아미노폴리카르본산아민염을 포함하는 본 발명의 인듐 옥살레이트 용해제에 있어서도, 킬레이트제가 가장 효과적으로 작용하는 pH영역으로 조정할 필요가 있다. 알칼리 수용액은 pH가 9 ~ 11의 범위내에 들어가는 첨가량이 바람직하고, 더욱 바람직하게는, pH가 10 ~ 11의 범위내이다. pH가 9 미만의 경우, 충분한 킬레이트 효과를 얻지 못하고 인듐 옥살레이트 용해량은 극히 작다. 더욱이 pH가 1에 가까워짐에 따라, 킬레이트제 자신의 용해량이 저하되어 용액중에 석출된다. pH가 11을 넘는 첨가량에서는 충분한 킬레이트 효과를 얻지 못하고 인듐 옥살레이트 용해량은 극히 작아 경제적이지 않다.
The concentration of the aqueous alkali solution used as the indium oxalate dissolving agent of the present invention needs to be adjusted to the pH range where the chelating agent of aminopolycarboxylic acid acts most effectively. Also in the indium oxalate dissolving agent of this invention containing an amino polycarboxylic acid amine salt, it is necessary to adjust to the pH range in which a chelating agent acts most effectively. The amount of addition of the aqueous alkali solution is preferably in the range of 9 to 11, and more preferably in the range of 10 to 11. If the pH is less than 9, sufficient chelate effect is not obtained and indium oxalate dissolution is extremely small. Furthermore, as the pH approaches 1, the amount of dissolution of the chelating agent itself decreases and precipitates in the solution. If the pH is more than 11, sufficient chelating effect is not obtained and indium oxalate dissolution is extremely small and not economical.
본 발명에 따른 인듐 옥살레이트 용해제의 바람직한 사용 방법과 관련하여, 산화 인듐주석(ITO) 막 또는 산화 인듐 아연(IZO) 막에서 유래하는 투명 도전막의 습식 에칭 장치계 내부를 세정하는 방법이 있다. 우선 산화 인듐주석(ITO) 막 또는 산화 인듐 아연(IZO) 막에서 유래하는 투명 도전막의 습식 에칭 장치계 내부로부터 완전하게 ITO 에칭액을 배출해, pH가 중성이 될 때까지, 물 또는 온수에 의한 순환 세정을 반복 수행하여 배출한다. 다음에, 본 발명의 인듐 옥살레이트 용해제를 에칭 장치계 내부에 투입해, 순환 세정을 4시간 이상 실시한다. 세정 완료 후에는 인듐 옥살레이트 용해제를 배출해, 최종적으로 물 또는 온수에 의한 순환 세정을 실시한다.
In connection with a preferred method of using the indium oxalate dissolving agent according to the present invention, there is a method for cleaning the inside of a wet etching apparatus system of a transparent conductive film derived from an indium tin oxide (ITO) film or an indium zinc oxide (IZO) film. First, the ITO etching solution is completely discharged from the inside of the wet etching apparatus system of the transparent conductive film derived from the indium tin oxide (ITO) film or the indium zinc oxide (IZO) film, and circulated and washed with water or hot water until the pH becomes neutral. Repeatedly discharge. Next, the indium oxalate dissolving agent of this invention is thrown into the inside of an etching apparatus system, and circulation washing is performed for 4 hours or more. After the washing is completed, the indium oxalate dissolving agent is discharged and finally circulated washing with water or hot water is performed.
세정하는 온도는 인듐 옥살레이트가 용해되는 온도면 어떠한 온도도 상관없지만, 용해도의 관점에서, 바람직하게는 30 ~ 50 ℃, 더욱 바람직하게는 약 40 ℃이다.
The temperature to be washed may be any temperature as long as the temperature at which the indium oxalate is dissolved, but from the viewpoint of solubility, it is preferably 30 to 50 ° C, more preferably about 40 ° C.
본 발명의 세정 방법에 의해, 배관, 밸브, 필터, 펌프, 스프레이 노즐, 기판 반송 롤러, 습식 에칭 실내벽, 버퍼 탱크내로부터 선택되는 1 또는 2 이상의 개소에 석출하는 인듐 옥살레이트를 용해 제거하는 것이 가능하다.
According to the cleaning method of the present invention, it is possible to dissolve and remove indium oxalate deposited at one or two or more locations selected from a pipe, a valve, a filter, a pump, a spray nozzle, a substrate conveying roller, a wet etching chamber wall, and a buffer tank. It is possible.
본 발명에 따른 용해제는 충분히 높은 인듐 옥살레이트의 용해도를 가지기 때문에, 본 발명에 따른 사용이 끝난 세정액으로부터 레어 메탈인 인듐을 용이하게 회수하는 것이 가능하다.
Since the solvent according to the present invention has a sufficiently high solubility of indium oxalate, it is possible to easily recover indium which is rare metal from the used cleaning liquid according to the present invention.
이하의 실시예 및 비교예를 들어 본 발명을 보다 구체적으로 설명하지만, 본 발명은 이와 같은 실시예로 한정되는 것은 아니다.
Although an Example and a comparative example are the following, this invention is demonstrated more concretely, but this invention is not limited to such an Example.
<실시예><Examples>
알칼리 성분 농도와 인듐 Alkali Component Concentration and Indium 옥살레이트Oxalate 용해량의 관계 Relationship between dissolution amount
표 1에 에틸렌 디아민4아세트산과 암모니아에 의한 pH 및 인듐 옥살레이트 용해량과의 관계를 나타내었다. 인듐 옥살레이트 용해제는 표 1의 비율이 되도록 원료 및 물을 더하고 킬레이트제가 완전하게 용해할 때까지 교반해 제조한다. 인듐 옥살레이트 용해량은 제조된 인듐 옥살레이트 용해제를 40 ℃로 가온하고, 그 용해제중에 인듐 옥살레이트를 투입 후 4 시간동안 교반을 실시해, 그 용해성을 검토하였다.Table 1 shows the relationship between the pH and indium oxalate dissolved by ethylene diamine tetraacetic acid and ammonia. Indium oxalate solubilizer is prepared by adding the raw material and water to the ratio of Table 1 and stirring until the chelating agent is completely dissolved. The indium oxalate dissolution amount heated the prepared indium oxalate dissolving agent at 40 degreeC, stirred in 4 hours after adding indium oxalate to the dissolving agent, and examined the solubility.
(%)Ethylene Diamine Tetraacetic Acid
(%)
(%)ammonia
(%)
(%)Indium Oxalate Dissolution
(%)
*: 에틸렌 디아민4아세트산이 용해되지 않았다.
*: Ethylenediaminetetraacetic acid was not dissolved.
표 1로부터, 암모니아 농도 증가에 수반해 pH도 상승 경향이 있음을 알 수 있다. 한편, 인듐 옥살레이트 용해량은 pH가 10.0 ~ 11.0 부근이 되는 암모니아 농도가 5.0 ~ 10.0 중량% 영역에서 최대치를 나타내었다.
From Table 1, it turns out that pH also tends to increase with increasing ammonia concentration. On the other hand, the indium oxalate dissolved amount showed the maximum value in the range of 5.0-10.0 weight% of the ammonia concentration which becomes pH 10.0-11.0 vicinity.
(비교예 1)(Comparative Example 1)
표 1 및, 비교예 1로부터 암모니아를 함유하지 않는 조성으로서, 에틸렌 디아민4아세트산 5.0 중량%가 되도록 원료 및 물을 더하고 제조를 시도했지만, 킬레이트제 자체의 물에 대한 용해성이 낮아 용해시킬 수가 없었다.
As a composition containing no ammonia from Table 1 and Comparative Example 1, raw materials and water were added so as to be 5.0% by weight of ethylene diamine tetraacetic acid, and production was attempted, but the chelating agent itself was not soluble in water and could not be dissolved.
비교예 1로부터 에틸렌 디아민4아세트산을 용해하려면 암모니아수 등의 알칼리 용액이 필요하다는 것을 알 수 있었다.
It was found from Comparative Example 1 that an alkaline solution such as ammonia water is required to dissolve ethylene diamine tetraacetic acid.
킬레이트제Chelating agents 농도와 인듐 Concentration and indium 옥살레이트Oxalate 용해량의 관계 Relationship between dissolution amount
표 2는 암모니아 첨가 농도를 표 1의 실시예 2에 대해 인듐 옥살레이트 용해량이 최대치를 나타낸 5.0 중량%로 고정해, 에틸렌 디아민4아세트산 첨가량을 증감했을 경우의 pH 및 인듐 옥살레이트 용해량의 변화를 나타낸다.Table 2 shows the change in pH and indium oxalate dissolved when the ammonia addition concentration was fixed at 5.0 wt%, showing the maximum value of indium oxalate dissolved relative to Example 2 of Table 1. Indicates.
(%)Ethylene Diamine Tetraacetic Acid
(%)
(%)ammonia
(%)
(%)Indium Oxalate Dissolution
(%)
표 2로부터 킬레이트제인 에틸렌 디아민4아세트산 첨가량이 증가하는 만큼, 인듐 옥살레이트 용해량이 증대하는 경향이 있음을 알 수 있다.
It can be seen from Table 2 that the amount of dissolved indium oxalate tends to increase as the amount of ethylene diamine tetraacetic acid added as a chelating agent increases.
에틸렌 Ethylene 디아민4아세트산염의Of diamine tetraacetate 킬레이트제Chelating agents
표 3은 암모니아를 5.0 중량%에 고정하고 에틸렌 디아민4아세트산 암모늄염 첨가량을 증감했을 경우의 pH 및 인듐 옥살레이트 용해량의 변화를 나타낸다. 인듐 옥살레이트 용해제는 표 3의 비율이 되도록 원료 및 물을 더하고 킬레이트제가 완전하게 용해할 때까지 교반하여 제조한다. 인듐 옥살레이트 용해량에 대해서는 제조된 인듐 옥살레이트 용해제를 40℃로 가온하고, 그 용해제중에 인듐 옥살레이트를 투입 후 4시간동안 교반을 실시하여 그 용해성에 대해 검토하였다.Table 3 shows the change of pH and indium oxalate dissolved amount when ammonia is fixed at 5.0 wt% and the amount of ethylene diamine tetraacetic acid ammonium acetate added is increased or decreased. Indium oxalate dissolving agent is prepared by adding the raw material and water to the ratio of Table 3 and stirring until the chelating agent is completely dissolved. About the indium oxalate dissolution amount, the prepared indium oxalate dissolving agent was heated to 40 degreeC, the indium oxalate was thrown in, and stirring was performed for 4 hours, and the solubility was examined.
(%)Ethylene Diamine Tetraacetic Acid
(%)
(%)ammonia
(%)
(%)Indium Oxalate Dissolution
(%)
표 3으로부터, 에틸렌 디아민4아세트산 암모늄염을 사용했을 경우에도 인듐 옥살레이트 용해 효과가 있음을 알 수 있다. 또한, 킬레이트제인 에틸렌 디아민4아세트산 암모늄염 첨가량이 증가하는 만큼 인듐 옥살레이트 용해량이 증대하는 경향이 있음을 알 수 있다.
From Table 3, it turns out that there is an indium oxalate dissolution effect even when an ethylene diamine tetraacetic acid ammonium salt is used. In addition, it can be seen that the amount of dissolved indium oxalate tends to increase as the amount of ethylene diamine tetraacetic acid ammonium acetate added as a chelating agent increases.
표 4는 에틸렌 디아민4아세트산 아민염과 암모니아에 의한 pH 및 인듐 옥살레이트 용해량과의 관계를 나타낸다. 에틸렌 디아민4아세트산 아민염은 킬레이트제 제조사에서 많이 시판되고 있다. 예를 들면, 키레스토 주식회사에서 키레스토 M, 키레스토 M－50, 키레스토 OH 등의 상품명으로 시판되고 있다. 그 중에서도 키레스토 M－50은 킬레이트 효과가 크고, 한편 용액상태이므로 용이하게 용해제를 제조할 수가 있어 특히 바람직하다.
Table 4 shows the relationship between the ethylene diamine tetraacetic acid amine salt and the pH and indium oxalate dissolved amount by ammonia. Ethylenediaminetetraacetic acid amine salts are commercially available from chelating agent manufacturers. For example, it is marketed by Kiresto Co., Ltd. under brand names, such as Kiresto M, Kiresto M-50, and Kiresto OH. Among them, Kiresto M-50 is particularly preferred because it has a high chelating effect and can be easily dissolved in a solution state.
인듐 옥살레이트 용해제는 표 4의 비율이 되도록 원료 및 물을 더하고 킬레이트제가 완전하게 용해할 때까지 교반하여 제조한다. 인듐 옥살레이트 용해량에 대해서는 제조된 인듐 옥살레이트 용해제를 40 ℃로 가온하고, 그 용해제중에 인듐 옥살레이트를 투입 후 4시간동안 교반을 실시하여 그 용해성에 대해 검토하였다.Indium oxalate dissolving agent is prepared by adding the raw material and water to the ratio of Table 4 and stirring until the chelating agent is completely dissolved. About the indium oxalate dissolution amount, the prepared indium oxalate dissolving agent was heated to 40 degreeC, the indium oxalate was thrown in, and stirring was performed for 4 hours, and the solubility was examined.
(%)Kiresto M-50
(%)
(%)ammonia
(%)
(%)Indium Oxalate Dissolution
(%)
표 4를 통하여, 에틸렌 디아민4아세트산 아민염을 사용했을 경우에도 인듐 옥살레이트 용해 효과가 있음을 알 수 있다. 또한, 킬레이트제인 키레스토 M－50 첨가량이 증가하는 만큼, 인듐 옥살레이트 용해량이 증대하는 경향이 있음을 알 수 있다.
It can be seen from Table 4 that even when an ethylene diamine tetraacetic acid amine salt is used, there is an indium oxalate dissolution effect. Moreover, it turns out that there exists a tendency for the indium oxalate melt | dissolution amount to increase as the addition amount of the chelating agent Kiresto M-50 increases.
에틸렌 Ethylene 디아민4아세트산계Diamine tetraacetic acid system 이외의 Other than 킬레이트제Chelating agents
트렌스－1,2－시클로 헥산 디아민4아세트산 5.0 중량%, 암모니아 7.0 중량%를 물에 용해시켜 용해제를 제조하였다. 용액의 pH는 10.1이었다.
A dissolving agent was prepared by dissolving 5.0 wt% of trans-1,2-cyclohexanediaminetetraacetic acid and 7.0 wt% of ammonia in water. The pH of the solution was 10.1.
제조한 용해제를 40 ℃로 가온하고, 그 용해제중에 인듐 옥살레이트를 투입 후 4시간동안 교반하여 그 용해성에 대해 조사하였다. 그 결과, 인듐 옥살레이트는 최대 2.9 중량%까지 용해시키는 것이 가능하였다.
The prepared solubilizer was warmed to 40 ° C., and indium oxalate was added to the solubilizer, followed by stirring for 4 hours to investigate its solubility. As a result, indium oxalate was able to dissolve up to 2.9% by weight.
이 결과를 통하여, 에틸렌 디아민4아세트산 이외의 킬레이트제를 사용했을 경우에도 인듐 옥살레이트 용해 효과가 있음을 알 수 있다.
These results show that indium oxalate dissolution effects are obtained even when chelating agents other than ethylene diamine tetraacetic acid are used.
추가적 Additional 킬레이트제로서의As a chelating agent 아민염의Amine salt 효과 effect
킬레이트제로서 에틸렌 디아민4아세트산을 이용한 조성에, 추가의 킬레이트제로서 에틸렌 디아민4아세트산 아민염인 키레스토 M－50을 추가하였다. 에틸렌 디아민4아세트산이 5.0 중량%, 키레스토 M－50이 5.0 중량%, 암모니아가 5.0 중량%가 되도록 물에 용해시켰다. 용액의 pH는 10.2가 되었다.
To the composition using ethylene diamine tetraacetic acid as a chelating agent, Kiresto M-50, which is an ethylene diamine tetraacetic acid amine salt, was added as a further chelating agent. It was dissolved in water so that ethylene diamine tetraacetic acid was 5.0 weight%, Kirsto M-50 was 5.0 weight%, and ammonia was 5.0 weight%. The pH of the solution was 10.2.
제조한 용해제를 40 ℃로 가온하고, 그 용해제중에 인듐 옥살레이트를 투입 후 4시간동안 교반하여, 그 용해성에 대해 조사하였다. 그 결과, 인듐 옥살레이트는 최대 6. 5 중량%까지 용해시키는 것이 가능하였다.
The prepared dissolving agent was warmed to 40 degreeC, the indium oxalate was added to the dissolving agent, and it stirred for 4 hours, and investigated the solubility. As a result, indium oxalate was able to dissolve up to 6. 5% by weight.
에틸렌 디아민4아세트산과 에틸렌 디아민4아세트산 아민염과의 병용에 의해, 인듐 옥살레이트의 최대 용해량이 증가하는 것을 알 수 있었다.
By using together ethylene diamine tetraacetic acid and ethylene diamine tetraacetic acid amine salt, it turned out that the maximum melt | dissolution amount of indium oxalate increases.
이상과 같이, 종래는 물 또는 온수의 강한 흐름에 의한 물리적인 힘을 이용한 순환 세정에 의해 인듐 옥살레이트를 박리 제거하였지만, 본 발명에 따르는 용해제 조성물은 인듐 옥살레이트를 화학적으로 용해 제거하는 것이 가능한 뛰어난 세정 효과를 나타낸다.
As mentioned above, although indium oxalate was peeled off by cyclic cleaning using a physical force by a strong flow of water or hot water, the dissolving agent composition which concerns on this invention is excellent in that it can chemically dissolve and remove indium oxalate. It shows a cleaning effect.
Claims (13)
A solubilizer composition used to dissolve and remove precipitated indium oxalate in an etching apparatus system, wherein the solvent composition is an aqueous solution containing one or two or more selected from an alkali component, aminopolycarboxylic acid, and salts thereof. .
The solubility composition of claim 1 wherein the pH is in the range of 9-11.
The solubility composition according to claim 1 or 2, wherein the concentration of one or two or more compounds selected from aminopolycarboxylic acids and salts thereof is 1 to 40% by weight in total.
The solubility composition of Claim 1 containing 1 type (s) or 2 or more types of compounds chosen from at least an amino polycarboxylic acid.
The dissolving agent composition of Claim 1 containing at least 1 sort (s) of the compound chosen from amino polycarboxylic acid, and the compound chosen from amino polycarboxylic acid amine salt, respectively.
The concentration of the compound selected from aminopolycarboxylic acid is 1 to 20% by weight, and the concentration of the compound selected from the group derived from aminopolycarboxylic acid amine salt is 1 to 20% by weight. Solvent composition
The group of claim 1 wherein the aminopolycarboxylic acid is composed of ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, triethylene tetra amine hexaacetic acid, and trans-1,2-cyclohexanediamine tetraacetic acid. Soluble composition, characterized in that selected from.
The salt of aminopolycarboxylic acid according to claim 1, wherein the salt of the aminopolycarboxylic acid consists of ethylene diamine diacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, triethylene tetra amine hexaacetic acid, trans-1,2-cyclohexanediamine tetraacetic acid. It is an amine salt of what is chosen from the group, The solubilizer composition characterized by the above-mentioned.
The solubility composition according to claim 1, wherein the alkaline component is selected from the group consisting of ammonia, sodium hydroxide, potassium hydroxide, and tetramethyl ammonium hydroxide.
(1) 계 내부로부터 에칭액을 배출한 후, pH가 중성이 될 때까지 물로 세정하는 공정,
(2) 제1항에 따른 용해제 조성물을 이용해 장치 내부에 석출하는 인듐 옥살레이트를 화학적으로 용해 제거하는 공정,
(3) 용해제를 제거한 후, pH가 중성이 될 때까지 물로 세정하는 공정
을 포함하는 것을 특징으로 하는 세정 방법.
In the cleaning method inside the etching apparatus system,
(1) removing the etching solution from the inside of the system and then washing with water until the pH becomes neutral,
(2) chemically dissolving and removing the indium oxalate precipitated inside the apparatus using the dissolving agent composition according to item 1,
(3) After removing the solvent, washing with water until the pH is neutral
Cleaning method comprising a.
The cleaning method according to claim 10, further comprising the step of recovering the solvent composition according to claim 1 after being used in the dissolution removal step.
The cleaning method according to claim 10, wherein the etching apparatus is an apparatus for wet etching a transparent conductive film derived from an ITO film or an IZO film.
The method of claim 10, wherein the indium oxalate precipitated at one or two or more points selected from the group consisting of a pipe, a valve, a filter, a pump, a spray nozzle, a substrate conveying roller, a wet etching chamber wall, and a buffer tank is dissolved and removed. The cleaning method characterized by the above-mentioned.
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| Application Number | Priority Date | Filing Date | Title |
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| JPJP-P-2009-112330 | 2009-05-01 | ||
| JP2009112330A JP5431014B2 (en) | 2009-05-01 | 2009-05-01 | Indium oxalate solubilizer composition |
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| JP (1) | JP5431014B2 (en) |
| KR (1) | KR101686007B1 (en) |
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| CN109234072A (en) * | 2018-11-02 | 2019-01-18 | 江阴江化微电子材料股份有限公司 | A kind of cleaning process of indium oxalate dissolving agent composition and etching machines |
| CN113025333B (en) * | 2021-03-01 | 2022-04-08 | 四川江化微电子材料有限公司 | Improved indium oxalate dissolving agent composition and etching equipment cleaning process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181686A (en) * | 1999-12-27 | 2001-07-03 | Lion Corp | Detergent composition for liquid crystal glass substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6465403B1 (en) * | 1998-05-18 | 2002-10-15 | David C. Skee | Silicate-containing alkaline compositions for cleaning microelectronic substrates |
| KR20030021249A (en) * | 2000-07-14 | 2003-03-12 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching compositions |
| JP2002033304A (en) * | 2000-07-14 | 2002-01-31 | Mitsubishi Gas Chem Co Inc | Composition for etching |
| US6599370B2 (en) * | 2000-10-16 | 2003-07-29 | Mallinckrodt Inc. | Stabilized alkaline compositions for cleaning microelectronic substrates |
| JP2003282520A (en) * | 2002-03-22 | 2003-10-03 | Sanyo Electric Co Ltd | Cleaning method of vessel and method for manufacturing solar battery |
| JP2005244083A (en) * | 2004-02-27 | 2005-09-08 | Hayashi Junyaku Kogyo Kk | Etchant composition for conductive film |
| US20050205835A1 (en) * | 2004-03-19 | 2005-09-22 | Tamboli Dnyanesh C | Alkaline post-chemical mechanical planarization cleaning compositions |
| JP2005314786A (en) * | 2004-03-31 | 2005-11-10 | Mitsui Mining & Smelting Co Ltd | Method for collecting indium |
| KR101337263B1 (en) * | 2004-08-25 | 2013-12-05 | 동우 화인켐 주식회사 | Etchant composition for indium oxide layer and etching method using the same |
| JP4586628B2 (en) * | 2005-05-19 | 2010-11-24 | 和光純薬工業株式会社 | Semiconductor substrate surface treatment agent and treatment method |
| TWI421937B (en) * | 2006-09-13 | 2014-01-01 | Nagase Chemtex Corp | Etchant composition |
| JP5354989B2 (en) * | 2008-08-14 | 2013-11-27 | 関東化学株式会社 | Etching composition for transparent conductive film |
| JP2010103214A (en) * | 2008-10-22 | 2010-05-06 | Hayashi Junyaku Kogyo Kk | Composition of etching liquid for conductor film |
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| KR101686007B1 (en) | 2016-12-13 |
| CN101876076A (en) | 2010-11-03 |
| TW201042033A (en) | 2010-12-01 |
| JP2010261070A (en) | 2010-11-18 |
| TWI493030B (en) | 2015-07-21 |
| JP5431014B2 (en) | 2014-03-05 |
| CN101876076B (en) | 2014-11-12 |
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