KR101409638B1 - Etching solution composition - Google Patents
Etching solution composition Download PDFInfo
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- KR101409638B1 KR101409638B1 KR1020097003619A KR20097003619A KR101409638B1 KR 101409638 B1 KR101409638 B1 KR 101409638B1 KR 1020097003619 A KR1020097003619 A KR 1020097003619A KR 20097003619 A KR20097003619 A KR 20097003619A KR 101409638 B1 KR101409638 B1 KR 101409638B1
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- acid
- water
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- etching
- soluble amine
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- 238000005530 etching Methods 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims description 18
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 6
- 150000004649 carbonic acid derivatives Chemical group 0.000 claims 1
- 150000003840 hydrochlorides Chemical group 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 23
- 238000005187 foaming Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000002253 acid Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 phosphoric acid ester salt Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- Liquid Crystal (AREA)
- ing And Chemical Polishing (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
옥살산, 나프탈렌술폰산 축합물 또는 그 염, 염산, 황산 및 수용성 아민 중 적어도 1종류, 및 물을 함유하는 산화인듐주석 투명 도전막용 에칭액 조성물이다. 이 에칭조성물은, 기판상에 바탕막 없이 형성된 투명 도전막뿐만 아니라, 기판상의 바탕막상에 형성된 투명 도전막에 대해서도 에칭 찌꺼기 제거성능이 우수하고, 발포를 억제할 수 있으며, 또한 고형물의 석출이 없고, 따라서 종래품보다 액 수명이 길다.An etchant composition for an indium tin oxide transparent conductive film containing oxalic acid, a condensate of naphthalenesulfonic acid or a salt thereof, at least one of hydrochloric acid, sulfuric acid and water-soluble amine, and water. This etching composition is excellent in not only the transparent conductive film formed on the substrate but also the transparent conductive film formed on the base film on the substrate, the etching residue removal performance is excellent, the foaming can be suppressed, Therefore, the liquid life is longer than that of the conventional product.
Description
본 발명은 액정디스플레이(LCD)나 일렉트로루미네센스(EL)디스플레이 등의 표시장치에 사용되는 투명 도전막을 위한 에칭액에 관한 것이다.The present invention relates to an etching solution for a transparent conductive film used in a display device such as a liquid crystal display (LCD) or an electroluminescence (EL) display.
LCD나 EL 디스플레이 등의 표시장치에 있어서, 화소의 표시전극 등에 투명 도전막이 사용되고 있다. 이 투명 도전막으로서 산화인듐계 투명 도전막, 예를 들면 산화인듐주석(ITO)막이 널리 사용되고 있다. ITO막은, 예를 들면 스퍼터링법 등의 막 형성 프로세스를 사용하여 유리 등의 기판상에 형성된다. 레지스트 등을 마스크로 하여 ITO막을 에칭함으로써 전극패턴이 기판상에 형성된다. 이 에칭공정에는 습식과 건식이 있는데, 습식에서는 에칭액이 사용된다.BACKGROUND ART In a display device such as an LCD or an EL display, a transparent conductive film is used for a display electrode of a pixel or the like. As this transparent conductive film, an indium oxide-based transparent conductive film such as an indium tin oxide (ITO) film is widely used. The ITO film is formed on a substrate such as glass using a film forming process such as sputtering. An electrode pattern is formed on the substrate by etching the ITO film using a resist or the like as a mask. The etching process includes wet etching and dry etching. In wet etching, an etchant is used.
종래, 다결정 ITO막의 습식 에칭에는 통상 염산계의 강산이 사용되고 있는데, 에칭시 알루미늄배선 등의 부식이 생기고 또한 ITO의 결정립계로부터 선택적으로 에칭이 진행되기 때문에, 가공 정밀도 좋게 패터닝하는 것이 곤란하였다. Conventionally, a hydrochloric acid-based strong acid is generally used for wet etching of a polycrystalline ITO film, which causes corrosion such as aluminum wiring during etching and selective etching from the crystal grain boundary of ITO, so that it is difficult to pattern with high precision.
따라서, 근래, 비정질 ITO막을 투명 도전막으로 사용하고, 약산, 특히 옥살산수용액을 이용하여 에칭하는 방법이 시도되고 있다. 그러나, 옥살산 수용액을 이 용하여 ITO막을 에칭한 경우에는, 에칭 찌꺼기가 기판상에 남는다는 문제가 있었다. 이러한 문제를 해결하기 위하여, 옥살산 수용액에 알킬벤젠술폰산을 첨가하는 것이 검토되어, 예를 들면 일본국 특개 평7(1995)-141932호 공보에는 옥살산과 도데실벤젠술폰산과 물을 배합하여 이루어지는 에칭액이 개시되어 있다.Thus, in recent years, attempts have been made to use an amorphous ITO film as a transparent conductive film and to etch using a weak acid, particularly an oxalic acid aqueous solution. However, when the ITO film is etched using the oxalic acid aqueous solution, there is a problem that the etching residue remains on the substrate. In order to solve such a problem, it has been investigated to add an alkylbenzenesulfonic acid to an oxalic acid aqueous solution. For example, Japanese Patent Application Laid-Open No. 7-1141932 discloses an etching solution comprising oxalic acid, dodecylbenzenesulfonic acid, Lt; / RTI >
그러나, 에칭액에 도데실벤젠술폰산 등의 계면활성제를 첨가하면 에칭 찌꺼기는 생기지 않게 되지만, 에칭액의 발포가 현저해진다. 발포가 현저하면 거품이 기판을 밀어 올리는 경우가 있고, 또한 거품이 기판상에 발생하면 에칭액과의 접촉에 지장을 주어 에칭을 방해하게 되므로, 어떤 경우에도 에칭이 정확히 실시되지 않게 되어 배선 패턴에 결함이 생기는 원인이 된다. However, when a surfactant such as dodecylbenzenesulfonic acid is added to the etching solution, no etching residue occurs, but the foaming of the etching solution becomes remarkable. If the foaming is significant, the foam may push up the substrate. If bubbles are generated on the substrate, contact with the etching liquid may be hindered and the etching may be interrupted. In any case, the etching is not performed correctly, .
옥살산 수용액에 퍼플루오로알킬기함유인산에스테르염을 첨가한 에칭액도 알려져 있다(예를 들면, 일본국 특개 2005-11654호 공보 참조). 이 기술에 의하면, 발포는 억제되어 있지만, 그러나 찌꺼기 제거능력이 반드시 충분하다고는 할 수 없는 경우가 있다.An etchant in which a perfluoroalkyl group-containing phosphoric acid ester salt is added to an aqueous oxalic acid solution is also known (see, for example, Japanese Patent Application Laid-Open No. 2005-11654). According to this technique, foaming is suppressed, but there are cases in which it is not necessarily sufficient to remove the residue.
다른 방면에 있어서, 특히 LCD 분야에 있어서는, 유리기판으로부터의 금속불순물의 혼입을 방지하기 위하여, 기판상에 질화규소막 등의 바탕막을 형성하고 그 위에 비결정 ITO막 형성이 실시되고 있다. 또한, 개구부의 개구율을 향상시키기 위하여 평탄화 막을 형성하고 그 위에 비결정 ITO막 형성이 실시되고 있다. 그러나, 이러한 바탕막상에 형성된 ITO막을 에칭하는 경우에는, 기판상에 바탕막을 사용하지 않고 ITO막을 형성하는 경우에 비하여 에칭 찌꺼기가 생기기 쉽고, 종래의 에칭액으로는 충분한 찌꺼기 제거가 곤란한 경우가 있다. In another aspect, particularly in the LCD field, a base film such as a silicon nitride film is formed on a substrate and an amorphous ITO film is formed thereon in order to prevent incorporation of metal impurities from the glass substrate. Further, in order to improve the aperture ratio of the openings, a planarization film is formed and an amorphous ITO film is formed thereon. However, when the ITO film formed on such a base film is etched, etching residues tend to occur more easily than when an ITO film is formed on a substrate without using a backing film, and it is difficult to remove a sufficient residue by a conventional etching solution.
예를 들면, 일본국 특개 2002-164332호 공보는 옥살산 수용액과 폴리술폰산화합물과 폴리옥시에틸렌-폴리옥시프로필렌블록코폴리머를 조합한 것으로, 바탕막상에 형성된 ITO막도 양호하게 에칭할 수 있고, 또한 발포도 적다. 그러나 이러한 에칭액을 사용하여 비정질 ITO를 에칭하면, 에칭의 진행에 따라 옥살산과 인듐과의 염이 고형물로서 석출된다는 문제가 있다. 이 석출물의 출현은 일반적인 옥살산계 에칭액에서는 인듐의 가용농도가 200ppm정도이므로, 그 과잉분이 석출물로서 나타나기 때문이라고 생각된다. For example, Japanese Patent Application Laid-Open No. 2002-164332 discloses a combination of an oxalic acid aqueous solution, a polysulfonic acid compound and a polyoxyethylene-polyoxypropylene block copolymer, which can well etch an ITO film formed on a base film, Foam is also low. However, when the amorphous ITO is etched using such an etching solution, there is a problem that the salt of oxalic acid and indium precipitates as a solid material as the etching progresses. The appearance of this precipitate is presumably because the concentration of indium in the general oxalic acid-based etching solution is about 200 ppm, and the excess portion appears as a precipitate.
1㎛보다도 작은 파티클조차 문제가 되는 전자부품의 제조공정에 있어서, 이러한 고형물의 석출은 치명적이다. 또한, 이 염의 석출에 의해 처리액의 순환용으로 설치된 필터가 막혀 그 교환비용이 고액이 될 우려도 있다. 따라서, 비록 에칭액으로서의 성능이 충분히 남아 있어도 이 염이 석출되기 전에 액을 교환해야하므로, 액 수명이 짧아지게 되어버린다.Precipitation of such solids is fatal in the manufacturing process of electronic parts, which is problematic even for particles smaller than 1 mu m. In addition, due to the precipitation of the salt, the filter installed for circulation of the treatment liquid may be clogged and the exchange cost may become high. Therefore, even if the performance as an etchant is sufficiently retained, the solution must be exchanged before the salt is precipitated, so that the solution life is shortened.
또한, 일본국 특개 2000-309888호 공보에는 염산 0.5~15중량%, 인산 및 칼본산, 계면활성제, 및 폴리아민을 함유하는 ITO막 제거액이 기재되어 있다. 그러나, 이 ITO막 제거액은 메탈마스크 상의 ITO막 제거가 주목적이며, 패터닝 형성이 목적인 에칭에 있어서 중요시되는 찌꺼기 제거성은 불충분하다.Japanese Patent Application Laid-Open No. 2000-309888 discloses an ITO film removing liquid containing 0.5 to 15% by weight of hydrochloric acid, phosphoric acid, and carboxylic acid, a surfactant, and a polyamine. However, this ITO film removing liquid is mainly used for removing the ITO film on the metal mask, and there is insufficient remnant removing property which is important in etching for the purpose of pattern formation.
발명의 개시DISCLOSURE OF INVENTION
발명이 해결하고자 하는 과제Problems to be solved by the invention
상술한 현상을 감안하여, 본 발명은 기판상에 바탕막 없이 형성된 투명 도전막뿐만 아니라 기판상의 바탕막상에 형성된 투명 도전막에 대해서도 에칭 찌꺼기 제거성능이 우수하고 발포를 억제할 수 있으며, 또한 고형물의 석출이 없어 종래품보다 액 수명이 긴 에칭액 조성물을 제공하는 것을 목적으로 한다.In view of the above-described phenomenon, the present invention can provide a transparent conductive film formed on a substrate not only as a transparent conductive film but also as a transparent conductive film formed on a base film on a substrate, which has excellent etching residue removal performance and can suppress foaming, And an object of the present invention is to provide an etchant composition which has a longer lifetime than that of conventional products.
과제를 해결하기 위한 수단Means for solving the problem
본 발명은, (a)옥살산, (b)나프탈렌술폰산축합물 또는 그 염, (c)염산, 황산, 수용성 아민 및 이들의 염 중 적어도 1종류, 및 (d)물을 함유하는 것을 특징으로 하는 투명 도전막용 에칭액 조성물이다.The present invention relates to a process for producing a naphthalenesulfonic acid, which comprises (a) a condensate of oxalic acid, (b) a naphthalenesulfonic acid condensate or salt thereof, (c) at least one of hydrochloric acid, sulfuric acid, Is an etchant composition for a transparent conductive film.
발명의 효과Effects of the Invention
본 발명은 상술한 구성에 의해, 계면활성제를 함유하면서도 거품이 일어나는 것이 억제되기 때문에 투명 도전막이 붙는 기판의 제조프로세스에서의 에칭공정에 적합하게 적용할 수 있다.The present invention can be suitably applied to the etching process in the production process of a substrate to which a transparent conductive film is attached since the above-described structure suppresses foaming while containing a surfactant.
본 발명은 또한, 상술한 구성에 의해 유리기판상에 성막된 ITO막에 적용해도, 또 질화규소막 등의 바탕막상에 성막된 ITO막에 적용해도 양호한 찌꺼기 제거능력을 발휘할 수 있으므로, 종래 비교적 곤란하였던 바탕막상의 ITO막의 고품위 에칭이 가능하다. The present invention is also applicable to an ITO film formed on a glass substrate or a ITO film formed on a base film such as a silicon nitride film by the above-described constitution, so that it is possible to exhibit a good debris removal capability, High-quality etching of a film-like ITO film is possible.
또한 본 발명은, 종래의 에칭액이 에칭성능을 유지한 채 액 교환의 원인이 되었던 옥살산과 인듐과의 염 석출을 억제하므로, 종래품보다도 액 교환의 빈도가 낮아 긴 수명의 에칭액을 제공하는 것이 가능하다.Further, the present invention suppresses precipitation of salts of oxalic acid and indium, which has caused the liquid exchange while maintaining the etching performance of the conventional etchant, and it is possible to provide an etchant with a long service life because the frequency of liquid exchange is lower than that of the conventional product. Do.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
발명을 실시하기 위한 최선의 형태BEST MODE FOR CARRYING OUT THE INVENTION
본 발명의 에칭액 조성물은, (a)옥살산(이하 (a)성분이라고도 함), (b)나프탈렌술폰산축합물 또는 그 염(이하 (b)성분이라고도 함), (c)염산, 황산, 수용성 아민 및 이들의 염 중 적어도 1종류(이하 (c)성분이라고도 함), 및 (d)물(이하 (d)성분이라고도 함)을 필수성분으로서 함유한다.The etching solution composition of the present invention can be produced by a process comprising the steps of: (a) adding an oxalic acid (hereinafter also referred to as (a) component), (b) a naphthalenesulfonic acid condensate or salt thereof (Hereinafter also referred to as component (c)), and (d) water (hereinafter also referred to as component (d)).
본 발명에 사용되는 옥살산(a)의 배합량은, 에칭액 조성물 중, 물에 대한 용해도 이내이면 좋고, 바람직하게는 15중량% 이하이며, 하한은 에칭 속도의 관점에서 상기 (a)~(d)성분의 합계배합량을 100중량%로 했을 경우에, 바람직하게는 0.5중량% 이상이다. 0.5중량% 미만이면 에칭 속도가 느려지게 될 우려가 있다. 보다 바람직하게는 1~5중량%이다.The amount of the oxalic acid (a) to be used in the present invention may be within the range of the solubility in water of the etchant composition, preferably 15% by weight or less, Is preferably 0.5% by weight or more based on 100% by weight of the total amount of the composition. If it is less than 0.5% by weight, the etching rate may be slowed down. More preferably 1 to 5% by weight.
본 발명에 사용되는 나프탈렌술폰산축합물 또는 그 염(b)은, β-나프탈렌술폰산 또는 그 염을, 예를 들면 포름알데히드로 축합시킨 형태의 축합체로, 분자량은 1000~5000 정도이다. 술폰산의 부분은, 예를 들면 산, 나트륨염, 칼륨염, 암모늄염, 모노에탄올아민염, 트리에탄올아민염 등, 어떠한 형태라도 무방하다. 시판되고 있는 것을 사용하는 것도 가능하며, 예를 들면 다이이치코교세이야쿠 가부시키가이샤 제품 라벨린FM-P, 라벨린FH-P, 카오 가부시키가이샤 제품 MX-2045L, 라이온 가부시키가이샤 제품 폴리티N-100K 등이 있다. 상기 (b)성분은 1종류를 사용해도 되고 또는 2종류 이상을 조합해도 된다.The naphthalenesulfonic acid condensate or its salt (b) used in the present invention is a condensate obtained by condensing? -Naphthalenesulfonic acid or its salt with, for example, formaldehyde, and has a molecular weight of about 1,000 to 5,000. The sulfonic acid moiety may be in any form such as, for example, an acid, a sodium salt, a potassium salt, an ammonium salt, a monoethanolamine salt, and a triethanolamine salt. For example, Labelin FM-P, Labelin FH-P, Kao Corporation MX-2045L, manufactured by Daicel Chemical Industries, Ltd., polytetrafluoroethylene available from Lion Corporation, N-100K and the like. The component (b) may be used alone or in combination of two or more.
상기 (b) 성분의 배합량으로서는, 상기 (a)~(d) 성분의 합계배합량을 100중량%로 했을 경우에, 바람직하게는 0.005~5중량%이다. 이 범위 미만이면 찌꺼기 제거능력이 불충분한 경우가 있고, 한편 이 범위를 초과해서 배합해도 찌꺼기 제거능력은 그다지 향상되지 않고, 과잉으로 배합하면 에칭비율 저하의 문제가 생긴다. 보다 바람직하게는 0.01~1중량%이다.The blending amount of the component (b) is preferably 0.005 to 5% by weight based on 100% by weight of the total of the components (a) to (d). If the amount is less than this range, the residue removing ability may be insufficient. On the other hand, when the amount exceeds the above range, the residue removing ability is not improved so much. More preferably, it is 0.01 to 1% by weight.
본 발명에 있어서 상기 (c)성분으로서는 염산, 황산, 수용성 아민, 또는 이들의 염이다. 이들은 각각 단독으로 사용해도 되고, 또는 각각을 조합하여, 예를 들면 염산과 황산, 염산과 수용성 아민, 황산과 수용성 아민, 또는 염산과 황산과 수용성 아민, 또는 수용성 아민염 등 이들의 임의 성분의 염을 사용해도 된다. 산을 사용하는 경우는 아민 등을 첨가함으로써 염을 형성하여 산의 휘발을 방지하는 효과도 얻을 수 있다. 또한, 상기 산이나 아민 이외에도 인듐과 수용성 염을 형성하는 것(예를 들면 염화암모늄 등)을 첨가하면, 옥살산과 인듐의 염이 석출되는 것을 방지하는 효과를 기대할 수 있다.In the present invention, the component (c) is hydrochloric acid, sulfuric acid, a water-soluble amine, or a salt thereof. These may be used alone or in combination of two or more of them, for example, hydrochloric acid and sulfuric acid, hydrochloric acid and water-soluble amine, sulfuric acid and water-soluble amine, hydrochloric acid and sulfuric acid and water-soluble amine, May be used. When an acid is used, an amine or the like may be added to form a salt to prevent the volatilization of the acid. In addition to the above acid or amine, addition of indium and a water-soluble salt (for example, ammonium chloride or the like) may be added to prevent precipitation of oxalic acid and indium salts.
상기 수용성 아민으로서는, 알카놀아민, 4급알킬암모늄, 암모니아, 알킬아민 및 이들의 염 중 적어도 1종류인 것이 바람직하고, 구체적으로는 모노에탄올아민, 모노이소프로판올아민, N-프로판올아민, 모노메틸에탄올아민, 디에탄올아민, 트리에탄올아민 등의 알카놀아민; 암모니아; 메틸아민, 에틸아민, 프로필아민, 디메틸아민, 디에틸아민, 디프로필아민, 트리메틸아민, 트리에틸아민, 트리프로필아민 등의 알킬아민; 테트라메틸암모늄하이드로옥사이드 등의 4급알킬암모늄; 또는 이들의 염(예를 들면 아민의 염산염, 황산염, 탄산염 등, 암모늄의 염산염, 황산염, 탄산염 등) 등으로, 이들 중 1종류를 사용해도 되고 또는 2종류 이상을 조합하여도 된다. 이들 중 모노에탄올아민이 바람직하다.As the water-soluble amine, at least one of alkanolamine, quaternary alkylammonium, ammonia, alkylamine and salts thereof is preferable, and specifically, monoethanolamine, monoisopropanolamine, N-propanolamine, monomethylethanol Alkanolamines such as amine, diethanolamine and triethanolamine; ammonia; Alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, dipropylamine, trimethylamine, triethylamine and tripropylamine; Quaternary alkylammonium such as tetramethylammonium hydroxide; Or a salt thereof (for example, a hydrochloride, a sulfate or a carbonate of an amine, a hydrochloride, a sulfate or a carbonate of ammonium, etc.), or a combination of two or more of them may be used. Of these, monoethanolamine is preferred.
상기 (c)성분 중, 염산을 함유하는 경우의 배합량으로서는, 상기(a)~(d) 성분을 포함하는 합계배합량을 100중량%로 했을 경우, 바람직하게는 0.01~0.3중량%이다. 이 범위 미만이면 옥살산과 인듐과의 염이 석출되는 것을 방지하는 능력이 불충분한 경우가 있고, 한편 이 범위를 초과하여 과잉으로 배합하면 찌꺼기 제거성에 문제가 생긴다. 보다 바람직하게는 0.05~0.1중량%이다. The amount of the component (c) containing hydrochloric acid is preferably 0.01 to 0.3% by weight based on 100% by weight of the total of the components (a) to (d). If the amount is less than this range, the ability to prevent precipitation of salts of oxalic acid and indium may be insufficient. On the other hand, if the amount exceeds the above range, excessive removal may cause problems in removing the residue. More preferably, it is 0.05 to 0.1% by weight.
상기 (c)성분 중, 황산 또는 수용성 아민을 함유하는 경우의 배합량으로서는, 각각 상기 (a)~(d)성분의 합계배합량을 100중량%로 했을 경우, 바람직하게는 0.5~20중량%이다. 이 범위 미만이면 옥살산과 인듐과의 염이 석출하는 것을 방지하는 능력이 불충분한 경우가 있고, 한편 이 범위를 초과하여 과잉으로 배합하면 찌꺼기 제거성에 문제가 생기거나 에칭비율의 저하를 초래할 우려가 있다. 보다 바람직하게는 1~10중량%이다.When the total amount of the components (a) to (d) is 100% by weight, the amount of the sulfuric acid or the water-soluble amine to be contained in the component (c) is preferably 0.5 to 20% by weight. If it is less than this range, the ability to prevent the precipitation of salts of oxalic acid and indium may be inadequate. On the other hand, if it exceeds this range and excessively blended, there is a fear of causing a problem in the removal of the residue and a decrease in the etching rate . More preferably 1 to 10% by weight.
본 발명에 사용되는 물(d)의 배합량은, 상기 (a)~(d)성분의 합계배합량을 100중량%로 했을 경우에 상기 (a)~(c)성분의 배합량의 잔부이다.The amount of the water (d) to be used in the present invention is the balance of the amounts of the components (a) to (c) when the total amount of the components (a) to (d) is 100 wt%.
본 발명의 에칭액 조성물은, 본 발명의 목적을 방해하지 않는 범위에서 그 외의 성분(예를 들면 플루오로화알킬기 함유 인산계 계면활성제나 알킬알킬렌계 계면활성제 등)을 필요에 따라 적절히 배합할 수 있다.The etching solution composition of the present invention can be appropriately compounded with other components (for example, a fluorinated alkyl group-containing phosphoric acid surfactant, an alkyl alkylene surfactant, and the like) within a range not hindering the object of the present invention .
본 발명의 에칭액 조성물은, 상기 각 성분의 소요량을 통상의 방법으로 혼합(상온에서 교반혼합)함으로써 조제할 수 있다.The etching solution composition of the present invention can be prepared by mixing the required amounts of the respective components in a usual manner (stirring and mixing at room temperature).
본 발명의 에칭액 조성물은, 기판(예를 들면, 유리 등)상에 형성된 투명 도전막(산화인듐계 막 등)의 에칭에 사용된다. 예를 들면, 기판상에 스퍼터링 등의 수법으로 형성된 ITO막의 에칭에 의한 패터닝에 사용할 수 있다. 또한, 기판상에 바탕막을 형성한 후에 형성된 ITO막의 에칭에도 적합하게 사용할 수 있다. 또한, 본 명세서 중, 바탕막이란 기판 위에, ITO막의 아래에, ITO막의 형성에 앞서 형성되고 그 위에 ITO막이 형성된 막을 말하며, 예를 들면 질화규소(SiN)막 등이다.The etching solution composition of the present invention is used for etching a transparent conductive film (such as an indium oxide-based film) formed on a substrate (for example, glass or the like). For example, it can be used for patterning by etching an ITO film formed by a technique such as sputtering on a substrate. It can also be suitably used for etching an ITO film formed after a base film is formed on a substrate. In the present specification, the background film refers to a film formed on the substrate before the formation of the ITO film and below the ITO film, and on which an ITO film is formed, such as a silicon nitride (SiN) film.
에칭공정에 있어서는, 본 발명의 에칭액 조성물은 실온에서 또는 가열(예를 들면 25~50℃)하여 사용할 수 있다. 에칭에 필요한 시간은 ITO막의 막 두께 등에 따라 다르지만, 일반적으로는 예를 들면 1~30분 정도이다. 에칭 후 필요에 따라 린스공정에서 세정할 수 있다.In the etching process, the etching solution composition of the present invention can be used at room temperature or by heating (for example, at 25 to 50 DEG C). The time required for the etching depends on the thickness of the ITO film or the like, but is generally about 1 to 30 minutes, for example. After the etching, it can be cleaned in a rinsing process as necessary.
이하에 실시예를 나타내어 본 발명을 더욱 상세히 설명하는데, 본 발명은 이들에 한정되는 것은 아니다. 또한 이하의 표 중의 약호는 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The abbreviations in the following table are as follows.
MEA : 모노에탄올아민MEA: Monoethanolamine
MIPA : 모노이소프로판올아민MIPA: Monoisopropanolamine
NPA: N-프로판올아민NPA: N-propanolamine
TMAH : 테트라메틸암모늄하이드로옥사이드TMAH: tetramethylammonium hydroxide
MMA : 모노메틸에탄올아민MMA: Monomethylethanolamine
DEA : 디에탄올아민DEA: diethanolamine
TEA : 트리에탄올아민TEA: triethanolamine
NSFM : 나프탈렌술폰산포름알데히드 축합물 MEA염 50%수용액NSFM: Naphthalenesulfonic acid formaldehyde condensate MEA salt 50% aqueous solution
PFP : 퍼플루오로알킬기 함유인산 에스테르계 계면활성제PFP: Perfluoroalkyl group-containing phosphate ester surfactant
DBS : 도데실벤젠술폰산DBS: Dodecylbenzenesulfonic acid
실시예 1~16 및 비교예 1~7Examples 1 to 16 and Comparative Examples 1 to 7
표 1의 배합으로 에칭액을 조제하였다. 이들 에칭액을 사용하여 다음과 같이 평가하였다. 결과를 표 2에 나타내었다.An etching solution was prepared from the formulation shown in Table 1. These etchants were evaluated as follows. The results are shown in Table 2.
1. 찌꺼기 제거능력1. Dust removal ability
유리기판상Glass plate
유리기판상에 ITO막을 형성한 기판을 에칭속도로부터 산출되는 에칭시간의 정확히 1.4배의 시간동안 에칭처리하였다. 수세, 질소블로 처리후의 샘플을 전자현미경으로 관찰하여 에칭후의 찌꺼기를 평가하였다.The substrate on which the ITO film was formed on the glass substrate was subjected to etching treatment for exactly 1.4 times the etching time calculated from the etching rate. A sample after washing with water and nitrogen blowing was observed with an electron microscope to evaluate the residue after etching.
바탕막상Background
유리기판상에 질화규소막을 형성하고, 또한 ITO막을 형성한 기판을 에칭속도로부터 산출되는 에칭시간의 정확히 1.4배의 시간동안 에칭처리하였다. 수세, 질소블로 처리후의 샘플을 전자현미경으로 관찰하여 에칭 후의 찌꺼기를 평가하고, 이하의 기준으로 표기하였다. 이 평가에서 찌꺼기 제거성에 대하여 불합격된 것은 이하의 거품 및 인듐용해도 평가는 실시하지 않았다. 또한, 합격은 ◎ 및 ○이다.A silicon nitride film was formed on a glass substrate and the substrate on which the ITO film was formed was etched for exactly 1.4 times the etching time calculated from the etching rate. A sample after washing with water and nitrogen blowing was observed with an electron microscope to evaluate the residue after etching, and the following criteria were used. In this evaluation, the following bubbles and indium solubility evaluations which failed to remove the residue were not carried out. The acceptance is ⊚ and ◯.
◎ : 찌꺼기 없음◎: No residue
○ : 근소하게 찌꺼기 있음○: Slight residue
△ : 다수는 아니지만 많은 찌꺼기 있음△: Many but not many residues
× : 다수의 찌꺼기 있음X: many residues
2. 거품이 일어남2. Foaming occurs
100㎖의 비색관에 에칭액을 30㎖ 넣고, TS식 쉐이커에 셋트하여, 2분간 진탕하였다. 진탕정지후 1분 후에 거품의 높이(㎜)를 측정하여 발포성을 평가하였다. 또한, 거품높이 5㎜ 미만의 경우에는 거품의 발생이 실질적으로 없어 에칭장치의 운전에 지장이 없고, 5~15㎜의 경우에는 다소의 거품 발생이 있지만 에칭장치의 운전에 실질적 지장은 생기지 않는다. 그러나, 15㎜를 초과하는 경우에는 거품의 발생에 의해 장치의 운전에 지장이 생길 우려가 크다. 따라서, 이하의 기준을 설정하여 표기하였다. 또한, 합격은 ◎ 및 ○이다.30 ml of the etching solution was placed in a 100 ml colorimetric tube, set in a TS shaker, and shaken for 2 minutes. The foam height (mm) was measured one minute after the shaking was stopped to evaluate the foamability. When the foam height is less than 5 mm, bubbles are not generated substantially and the operation of the etching apparatus is not affected. In the case of 5 to 15 mm, bubbles are generated somewhat, but there is no substantial problem in operation of the etching apparatus. However, if it exceeds 15 mm, there is a possibility that the operation of the apparatus may be hindered by the generation of bubbles. Therefore, the following criteria are set and indicated. The acceptance is ⊚ and ◯.
◎ : 거품높이 5㎜ 미만◎: Foam height less than 5 mm
○ : 거품높이 5~15㎜ ○: Bubble height 5 to 15 mm
× : 거품높이 15㎜ 초과X: Bubble height exceeded 15 mm
3. 인듐 용해도3. Indium solubility
삼각 플라스크에 각 에칭액을 넣고 그 안에 산화인듐을 투입하여 환류관을 장착하여 교반하면서 4시간 끓였다. 끓인 후 25℃로 48시간 냉각하고, 과포화 인듐화합물이 석출되어 있는 것을 확인한 후, 구멍 사이즈가 0.2㎛인 필터로 여과하였다. 여과액을 채취하고 여과액 중에 용해되어 있는 인듐 농도를 ICP발광으로 측정하여 평가결과를 이하의 기준으로 표기하였다. 또한 여기에서의 합격은 △ 이상이다.Each of the etching solutions was placed in an Erlenmeyer flask, and indium oxide was added thereto. Then, a reflux tube was attached and the mixture was boiled for 4 hours while stirring. After boiling, it was cooled at 25 DEG C for 48 hours. After confirming that the supersaturated indium compound precipitated, it was filtered with a filter having a pore size of 0.2 mu m. The filtrate was sampled, the indium concentration dissolved in the filtrate was measured by ICP emission, and the evaluation results were expressed by the following criteria. Also, the acceptance here is △ or better.
◎ : 인듐 용해량 2000ppm 이상?: Indium dissolution amount of 2000 ppm or more
○ : 인듐 용해량 1000~1999ppm ?: Indium dissolution amount 1000 to 1999 ppm
□ : 인듐 용해량 500~999ppm □: Indium dissolution amount 500 to 999 ppm
△ : 인듐 용해량 300~499ppm DELTA: Indium dissolution amount 300 to 499 ppm
× : 인듐 용해량 299ppm 이하X: Indium dissolution amount: 299 ppm or less
상기 실시예 1~16으로부터, 본 발명의 에칭액 조성물에 의하면 유리기판상 뿐만 아니라 바탕막상에도 찌꺼기 제거능력이 우수하며, 거품도 매우 적고, 또한 인듐의 용해량도 높은 것을 알 수 있었다. 한편, 옥살산과 NSFM과 물을 함유한 비교예 2는 찌꺼기 제거능력은 있지만 인듐의 용해량은 200ppm정도로 낮았다. 또한, 옥살산과 계면활성제와 물을 함유하는 비교예 6, 7은 찌꺼기 제거능력은 있지만 인듐의 용해량은 낮고, 더욱이 비교예 7은 거품도 많았다. 옥살산과 염산 및/또는 수용성아민과 물을 함유하는 비교예 3~5는 찌꺼기 제거능력에 문제가 있었다. 이와 같이, 상기 (a)~(d)의 성분을 함유함으로써 본 발명의 효과를 발휘할 수 있는 것을 확인할 수 있었다.From the above Examples 1 to 16, it was found that the etching solution composition of the present invention has excellent scum removing ability on not only the glass substrate but also the base film, has very few bubbles, and has a high dissolution amount of indium. On the other hand, in Comparative Example 2 containing oxalic acid, NSFM and water, the amount of indium dissolved was as low as about 200 ppm although it was capable of removing residues. In Comparative Examples 6 and 7 containing oxalic acid, a surfactant and water, the dissolution amount of indium was low and the amount of bubbles in Comparative Example 7 was large even though it had the ability to remove residues. In Comparative Examples 3 to 5 containing oxalic acid, hydrochloric acid and / or water-soluble amine and water, there was a problem in the debris removal ability. Thus, it was confirmed that the effect of the present invention can be exhibited by containing the components (a) to (d).
본 발명은 종래 기술에 비하여 찌꺼기 제거능력, 저포성(低泡性)이 향상되고, 패터닝의 수률, 정밀도 향상에 기여할 수 있으므로 전자부품의 제조에 매우 유용하다. 또한 에칭액을 종래품보다 오래 사용할 수 있으므로, 약액의 사용량 저감이 가능하여 비용면, 환경면으로도 메리트가 높은 것이다. Compared with the prior art, the present invention is effective for the production of electronic parts because it can improve the residue removal ability and the low foaming property (low foam property) and contributes to the improvement of the patterning yield and precision. In addition, since the etchant can be used for a longer time than the conventional products, it is possible to reduce the amount of the chemical solution, which is advantageous in cost and environment.
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| JP5354989B2 (en) | 2008-08-14 | 2013-11-27 | 関東化学株式会社 | Etching composition for transparent conductive film |
| JP5431014B2 (en) * | 2009-05-01 | 2014-03-05 | 関東化学株式会社 | Indium oxalate solubilizer composition |
| WO2014010471A1 (en) * | 2012-07-09 | 2014-01-16 | 攝津製油株式会社 | Etching fluid, etching force recovery agent, method for manufacturing semiconductor substrate for solar cell, and semiconductor substrate for solar cell |
| JP6044337B2 (en) * | 2012-12-28 | 2016-12-14 | 三菱瓦斯化学株式会社 | Etching solution and etching method for oxide of indium and gallium and oxygen or indium and gallium, zinc and oxygen |
| JP6261926B2 (en) | 2013-09-18 | 2018-01-17 | 関東化學株式会社 | Metal oxide etchant composition and etching method |
| CN105659365B (en) | 2013-10-30 | 2020-07-31 | 三菱瓦斯化学株式会社 | Etching solution and etching method for oxide substantially composed of zinc, tin and oxygen |
| KR102148851B1 (en) | 2014-01-07 | 2020-08-27 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Etching liquid for oxide containing zinc and tin, and etching method |
| KR102128276B1 (en) | 2014-02-17 | 2020-06-30 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Liquid composition for etching oxides comprising indium, zinc, tin, and oxygen and etching method |
| CN105087008B (en) * | 2014-04-30 | 2017-09-26 | 重庆市中光电显示技术有限公司 | The etching liquid etched for ito film |
| WO2016028454A1 (en) * | 2014-08-18 | 2016-02-25 | 3M Innovative Properties Company | Conductive layered structure and methods of making same |
| KR102203444B1 (en) * | 2016-03-24 | 2021-01-15 | 가부시키가이샤 아데카 | Etching solution composition and etching method |
| JP2017216444A (en) * | 2016-05-31 | 2017-12-07 | ナガセケムテックス株式会社 | Etchant |
| CN106701085A (en) * | 2016-12-28 | 2017-05-24 | 杭州格林达化学有限公司 | ITO (Indium Tin Oxide) reworking etching solution and preparation method of ITO reworking etching solution |
| JP7252712B2 (en) * | 2017-03-31 | 2023-04-05 | ナガセケムテックス株式会社 | etching solution |
| JP6795543B2 (en) * | 2018-04-27 | 2020-12-02 | 株式会社Ｊｏｌｅｄ | Manufacturing method of semiconductor devices |
| CN109233837A (en) * | 2018-10-29 | 2019-01-18 | 苏州博洋化学股份有限公司 | The novel oxalic acid system ITO etching solution of Display panel array process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164332A (en) | 2000-09-08 | 2002-06-07 | Kanto Chem Co Inc | Etchant composition |
| JP2003124203A (en) | 2001-10-19 | 2003-04-25 | Mitsubishi Gas Chem Co Inc | Etchant composition for transparent conductive film |
| JP2005197397A (en) | 2004-01-06 | 2005-07-21 | Mitsubishi Gas Chem Co Inc | Etching liquid composition and etching method |
| JP2005243901A (en) | 2004-02-26 | 2005-09-08 | Mitsubishi Gas Chem Co Inc | Etchant composition and etching method |
-
2007
- 2007-09-03 TW TW096132711A patent/TWI421937B/en not_active IP Right Cessation
- 2007-09-12 KR KR1020097003619A patent/KR101409638B1/en active IP Right Grant
- 2007-09-12 JP JP2008534357A patent/JP4674704B2/en active Active
- 2007-09-12 WO PCT/JP2007/067710 patent/WO2008032728A1/en active Application Filing
- 2007-09-12 CN CNA2007800340139A patent/CN101517712A/en active Pending
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- 2010-12-03 JP JP2010270711A patent/JP4678559B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164332A (en) | 2000-09-08 | 2002-06-07 | Kanto Chem Co Inc | Etchant composition |
| JP2003124203A (en) | 2001-10-19 | 2003-04-25 | Mitsubishi Gas Chem Co Inc | Etchant composition for transparent conductive film |
| JP2005197397A (en) | 2004-01-06 | 2005-07-21 | Mitsubishi Gas Chem Co Inc | Etching liquid composition and etching method |
| JP2005243901A (en) | 2004-02-26 | 2005-09-08 | Mitsubishi Gas Chem Co Inc | Etchant composition and etching method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4678559B2 (en) | 2011-04-27 |
| TW200826193A (en) | 2008-06-16 |
| JPWO2008032728A1 (en) | 2010-01-28 |
| TWI421937B (en) | 2014-01-01 |
| KR20090064367A (en) | 2009-06-18 |
| CN101517712A (en) | 2009-08-26 |
| WO2008032728A1 (en) | 2008-03-20 |
| JP4674704B2 (en) | 2011-04-20 |
| JP2011049602A (en) | 2011-03-10 |
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