JP4674704B2 - Etching solution composition - Google Patents
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- JP4674704B2 JP4674704B2 JP2008534357A JP2008534357A JP4674704B2 JP 4674704 B2 JP4674704 B2 JP 4674704B2 JP 2008534357 A JP2008534357 A JP 2008534357A JP 2008534357 A JP2008534357 A JP 2008534357A JP 4674704 B2 JP4674704 B2 JP 4674704B2
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- 238000005530 etching Methods 0.000 title claims description 60
- 239000000203 mixture Substances 0.000 title claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 29
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 description 28
- 239000000758 substrate Substances 0.000 description 22
- 229910052738 indium Inorganic materials 0.000 description 18
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 18
- 238000005187 foaming Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 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
- 238000000034 method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- -1 phosphate ester salt Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-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
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 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
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 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
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 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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- 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
- H01L21/04—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
-
- 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)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
Description
本発明は、液晶ディスプレイ（ＬＣＤ）やエレクトロルミネッセンス（ＥＬ）ディスプレイなどの表示装置に使用される透明導電膜のためのエッチング液に関する。 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.
ＬＣＤやＥＬディスプレイ等の表示装置において、画素の表示電極等に透明導電膜が用いられている。この透明導電膜として、酸化インジウム系透明導電膜、例えば、酸化インジウム錫(ＩＴＯ)膜、が広く使用されている。ＩＴＯ膜は、例えば、スパッタリング法等の成膜プロセスを用いて、ガラス等の基板上に形成される。レジスト等をマスクにしてＩＴＯ膜をエッチングすることで電極パターンが基板上に形成される。このエッチング工程には湿式と乾式があるが、湿式ではエッチング液が使用される。 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. As this transparent conductive film, an indium oxide-based transparent conductive film, for example, an indium tin oxide (ITO) film is widely used. The ITO film is formed on a substrate such as glass by using a film forming process such as sputtering. By etching the ITO film using a resist or the like as a mask, an electrode pattern is formed on the substrate. There are wet and dry etching processes. In the wet process, an etchant is used.
従来、多結晶ＩＴＯ膜の湿式エッチングには、通常、塩酸系の強酸が用いられているが、エッチングの際にアルミニウム配線等の腐食が生じ、さらに、ＩＴＯの結晶粒界から選択的にエッチングが進行するために、加工精度よくパターニングすることが困難であった。 Conventionally, hydrochloric acid-based strong acid is usually used for wet etching of a polycrystalline ITO film. However, corrosion of aluminum wiring or the like occurs during etching, and etching is selectively performed from the crystal grain boundary of ITO. Because of the progress, it is difficult to pattern with high processing accuracy.
そこで、近年、非晶質ＩＴＯ膜を透明導電膜として使用し、弱酸、特に、シュウ酸水溶液を用いてエッチングする方法が試みられている。しかしながら、シュウ酸水溶液を用いてＩＴＯ膜をエッチングした場合には、エッチング残渣が基板上に残るという問題があった。この問題を解決するために、シュウ酸水溶液にアルキルベンゼンスルホン酸を添加することが検討され、例えば、特許文献１には、シュウ酸とドデシルベンゼンスルホン酸と水を配合してなるエッチング液が開示されている。 Therefore, in recent years, an attempt has been made to perform etching using a weak acid, in particular, an oxalic acid aqueous solution, using an amorphous ITO film as a transparent conductive film. However, when the ITO film is etched using an aqueous oxalic acid solution, there is a problem that etching residues remain on the substrate. In order to solve this problem, it has been studied to add alkylbenzene sulfonic acid to an oxalic acid aqueous solution. For example, Patent Document 1 discloses an etching solution comprising oxalic acid, dodecylbenzene sulfonic acid and water. ing.
しかし、エッチング液にドデシルベンゼンスルホン酸等の界面活性剤を添加すると、エッチング残渣は生じにくくなるものの、エッチング液の発泡が著しくなる。発泡が著しいと泡が基板を押し上げることがあり、また、泡が基板上に発生するとエッチング液との接触を妨げてエッチングを妨害することになり、いずれの場合もエッチングが正確に行われなくなり、配線パターンに欠陥が生じる原因となる。 However, when a surfactant such as dodecylbenzenesulfonic acid is added to the etching solution, the etching residue is less likely to be produced, but the foaming of the etching solution becomes remarkable. If foaming is significant, bubbles may push up the substrate, and if bubbles are generated on the substrate, it will interfere with etching by preventing contact with the etchant, and in either case, etching will not be performed accurately, This causes a defect in the wiring pattern.
シュウ酸水溶液にパーフルオロアルキル基含有リン酸エステル塩を添加したエッチング液も知られている（例えば、特許文献２参照。）。この技術によれば、発泡は抑制されているのであるが、しかしながら、残渣除去能力が必ずしも充分ではない場合がある。 An etching solution in which a perfluoroalkyl group-containing phosphate ester salt is added to an oxalic acid aqueous solution is also known (for example, see Patent Document 2). According to this technique, foaming is suppressed, however, there are cases where the residue removing ability is not always sufficient.
他方において、特にＬＣＤの分野においては、ガラス基板からの金属不純物の混入を防ぐために、基板上に窒化ケイ素膜等の下地膜を形成して、その上に非結晶ＩＴＯ膜を形成することが行われている。また、開口部の開口率を向上させるために、平坦化膜を形成してその上に非結晶ＩＴＯ膜を形成する事が行われている。しかし、これらの下地膜上に形成されたＩＴＯ膜をエッチングする場合には、基板上に下地膜を使用せずにＩＴＯ膜を形成する場合と比べてエッチング残渣が生じやすく、従来のエッチング液では充分な残渣除去が困難な場合がある。 On the other hand, in the LCD field in particular, in order to prevent the mixing of metal impurities from the glass substrate, a base film such as a silicon nitride film is formed on the substrate and an amorphous ITO film is formed thereon. It has been broken. In order to improve the aperture ratio of the opening, a planarization film is formed and an amorphous ITO film is formed thereon. However, when etching the ITO film formed on these base films, etching residues are more likely to occur than when forming an ITO film on the substrate without using the base film. Sufficient residue removal may be difficult.
例えば、特許文献３は、シュウ酸水溶液とポリスルホン酸化合物とポリオキシエチレン−ポリオキシプロピレンブロックコポリマーを組み合わせたもので、下地膜上に形成されたＩＴＯ膜も良好にエッチングでき、且つ発泡も少ない。しかし、このようなエッチング液を用いて非晶質ＩＴＯをエッチングすると、エッチングの進行に伴いシュウ酸とインジウムとの塩が固形物として析出してくるという問題がある。この析出物の出現は、一般的なシュウ酸系エッチング液ではインジウムの可溶濃度が２００ｐｐｍ程度であるため、その過剰分が析出物として現れるからであると考えられる。 For example, Patent Document 3 is a combination of an oxalic acid aqueous solution, a polysulfonic acid compound, and a polyoxyethylene-polyoxypropylene block copolymer, and an ITO film formed on a base film can be satisfactorily etched and foaming is small. However, when amorphous ITO is etched using such an etching solution, there is a problem that a salt of oxalic acid and indium precipitates as a solid as the etching progresses. The appearance of this precipitate is thought to be because a soluble concentration of indium is about 200 ppm in a general oxalic acid-based etching solution, and an excess thereof appears as a precipitate.
１μｍよりも小さなパーティクルですら問題となる電子部品の製造工程において、このような固形物の析出は致命的である。また、この塩の析出により、処理液の循環用に設けられたフィルターが詰まり、その交換コストが高額になる虞もある。そのため、たとえエッチング液としての性能が十分に残っていても、この塩が析出してくる前に液を交換せねばならず、液寿命が短いものとなってしまっている。 In the manufacturing process of electronic parts, which is a problem even with particles smaller than 1 μm, such solid deposition is fatal. Further, the precipitation of the salt may clog a filter provided for the circulation of the treatment liquid, which may increase the replacement cost. Therefore, even if sufficient performance as an etching solution remains, the solution must be replaced before the salt is deposited, resulting in a short solution life.
また、特許文献４には塩酸０．５〜１５重量％、燐酸及びカルボン酸、界面活性剤、並びに、ポリアミンを含有するＩＴＯ膜除去液が記載されている。しかし、このＩＴＯ膜除去液はメタルマスク上のＩＴＯ膜除去が主目的であり、パターニング形成が目的のエッチングにおいて重要視される残渣除去性は不十分である。
上述の現状に鑑みて、本発明は、基板上に下地膜なしに形成された透明導電膜のみならず基板上の下地膜上に形成された透明導電膜についても、エッチング残渣除去性能に優れ、発泡を抑制することができ、しかも、固形物の析出がなく従来品より液寿命が長い、エッチング液組成物を提供することを目的とする。 In view of the above-mentioned present situation, the present invention has excellent etching residue removal performance not only for a transparent conductive film formed on a substrate without a base film but also for a transparent conductive film formed on a base film on the substrate, An object of the present invention is to provide an etching solution composition that can suppress foaming and that has no solid precipitation and has a longer liquid life than conventional products.
本発明は、（ａ）シュウ酸、（ｂ）ナフタレンスルホン酸縮合物又はその塩、（ｃ）塩酸、硫酸、水溶性アミン及びこれらの塩のうち少なくとも１種、並びに、（ｄ）水を含有することを特徴とする酸化インジウム系透明導電膜用のエッチング液組成物である。
The present invention contains (a) oxalic acid, (b) naphthalenesulfonic acid condensate or salt thereof, (c) at least one of hydrochloric acid, sulfuric acid, water-soluble amine and salts thereof, and (d) water. An etching solution composition for an indium oxide-based transparent conductive film.
本発明は上述の構成により、界面活性剤を含有しながら、泡立ちが抑制されているので、透明導電膜付き基板の製造プロセスにおけるエッチング工程に好適に適用することができる。
本発明はまた、上述の構成により、ガラス基板上に成膜されたＩＴＯ膜に適用しても、また、窒化ケイ素膜等の下地膜上に成膜されたＩＴＯ膜に適用しても、良好な残渣除去能力を発揮することができるので、従来、比較的困難であった下地膜上のＩＴＯ膜の高品位エッチングが可能である。
さらに本発明は、従来のエッチング液がエッチング性能を保持したまま液交換される原因である、シュウ酸とインジウムとの塩の析出を抑制するので、従来品よりも液交換の頻度が少なくて済む長寿命のエッチング液を提供することが可能である。
以下、本発明を詳細に説明する。The present invention can be suitably applied to an etching step in a manufacturing process of a substrate with a transparent conductive film because foaming is suppressed while containing a surfactant by the above-described configuration.
The present invention can also be applied to an ITO film formed on a glass substrate or to an ITO film formed on a base film such as a silicon nitride film by the above-described configuration. Therefore, it is possible to perform high-quality etching of the ITO film on the base film, which has been comparatively difficult in the past.
Furthermore, the present invention suppresses the precipitation of a salt of oxalic acid and indium, which is a cause for the conventional etching liquid to be exchanged while maintaining the etching performance, so that the frequency of liquid exchange is less than that of the conventional product. It is possible to provide a long-life etching solution.
Hereinafter, the present invention will be described in detail.
本発明のエッチング液組成物は、（ａ）シュウ酸（以下、（ａ）成分ともいう）、（ｂ）ナフタレンスルホン酸縮合物又はその塩（以下、（ｂ）成分ともいう）、（ｃ）塩酸、硫酸、水溶性アミン及びこれらの塩のうち少なくとも１種（以下、（ｃ）成分ともいう）、並びに（ｄ）水（以下、（ｄ）成分ともいう）を必須成分として含有する。 The etching solution composition of the present invention comprises (a) oxalic acid (hereinafter also referred to as (a) component), (b) naphthalenesulfonic acid condensate or salt thereof (hereinafter also referred to as (b) component), (c) It contains at least one of hydrochloric acid, sulfuric acid, water-soluble amine and salts thereof (hereinafter also referred to as (c) component) and (d) water (hereinafter also referred to as (d) component) as essential components.
本発明に使用されるシュウ酸（ａ）の配合量は、エッチング液組成物中、水に対する溶解度以内であればよく、好ましくは１５重量％以下であり、下限は、エッチング速度の観点から、上記（ａ）〜（ｄ）成分の合計配合量を１００重量％とした場合に好ましくは０．５重量％以上である。０．５重量％未満であるとエッチング速度が遅くなる虞がある。より好ましくは１〜５重量％である。 The blending amount of oxalic acid (a) used in the present invention may be within the solubility in water in the etching solution composition, preferably 15% by weight or less, and the lower limit is the above from the viewpoint of etching rate. When the total amount of the components (a) to (d) is 100% by weight, it is preferably 0.5% by weight or more. If it is less than 0.5% by weight, the etching rate may be slow. More preferably, it is 1 to 5% by weight.
本発明に使用されるナフタレンスルホン酸縮合物又はその塩（ｂ）は、β−ナフタレンスルホン酸またはその塩を、例えばホルムアルデヒドで、縮合させた形の縮合体で、分子量は１０００〜５０００程度である。スルホン酸の部分は、例えば、酸、ナトリウム塩、カリウム塩、アンモニウム塩、モノエタノールアミン塩、トリエタノールアミン塩等、どのような形でも構わない。上市されているものを使用することもでき、例えば第一工業製薬株式会社製ラベリンＦＭ−Ｐ、ラベリンＦＨ−Ｐ、花王株式会社製ＭＸ−２０４５Ｌ、ライオン株式会社製ポリティＮ−１００Ｋなどがある。上記（ｂ）成分は、１種を使用してもよく又は２種以上を組み合わせてもよい。 The naphthalene sulfonic acid condensate or salt (b) used in the present invention is a condensate obtained by condensing β-naphthalene sulfonic acid or a salt thereof with, for example, formaldehyde, and has a molecular weight of about 1000 to 5000. . The sulfonic acid moiety may be in any form such as acid, sodium salt, potassium salt, ammonium salt, monoethanolamine salt, triethanolamine salt, and the like. What is marketed can also be used, for example, Daiichi Kogyo Seiyaku Co., Ltd. Labelin FM-P, Labelin FH-P, Kao Corporation MX-2045L, Lion Corporation Politi N-100K etc., etc. As the component (b), one type may be used, or two or more types may be combined.
上記（ｂ）成分の配合量としては、上記（ａ）〜（ｄ）成分の合計配合量を１００重量％とした場合に、好ましくは０．００５〜５重量％である。この範囲未満であると、残渣除去能力が不充分の場合があり、一方、この範囲を超えて配合しても残渣除去能力はあまり向上せず、過剰に配合するとエッチングレート低下の不都合が生じる。より好ましくは０．０１〜１重量％である。 The amount of the component (b) is preferably 0.005 to 5% by weight when the total amount of the components (a) to (d) is 100% by weight. If the amount is less than this range, the residue removal ability may be insufficient. On the other hand, the residue removal ability is not improved even if the amount exceeds this range. More preferably, it is 0.01 to 1 weight%.
本発明において上記（ｃ）成分としては、塩酸、硫酸、水溶性アミン、又は、これらの塩である。これらは、それぞれ単独で用いても構わず、又はそれぞれを組み合わせて、例えば、塩酸と硫酸、塩酸と水溶性アミン、硫酸と水溶性アミン、若しくは、塩酸と硫酸と水溶性アミン、又は、水溶性アミン塩等これらの任意の成分の塩、を用いてよい。酸を用いる場合は、アミン等を加えることにより塩を形成し、酸の揮発を防ぐ効果も得られる。さらに、上記酸やアミン以外でも、インジウムと水溶性の塩を形成するもの（例えば、塩化アンモニウム等）を添加すれば、シュウ酸とインジウムの塩が析出してくる事を防ぐ効果は期待できる。 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, for example, hydrochloric acid and sulfuric acid, hydrochloric acid and water-soluble amine, sulfuric acid and water-soluble amine, or hydrochloric acid and sulfuric acid and water-soluble amine, or water-soluble You may use the salt of these arbitrary components, such as an amine salt. In the case of using an acid, an effect of preventing the volatilization of the acid can be obtained by forming a salt by adding an amine or the like. Furthermore, the addition of an acid or amine that forms a water-soluble salt with indium (for example, ammonium chloride) can be expected to prevent the precipitation of the salt of oxalic acid and indium.
上記水溶性アミンとしては、アルカノールアミン、四級アルキルアンモニウム、アンモニア、アルキルアミン及びそれらの塩のうち少なくとも１種であることが好ましく、具体的にはモノエタノールアミン、モノイソプロパノールアミン、Ｎ−プロパノールアミン、モノメチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン；アンモニア；メチルアミン、エチルアミン、プロピルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン等のアルキルアミン；テトラメチルアンモニウムハイドロオキサイド等の四級アルキルアンモニウム；またはそれらの塩（例えば、アミンの塩酸塩、硫酸塩、炭酸塩等、アンモニウムの塩酸塩、硫酸塩、炭酸塩等）などであり、これらのうち１種を使用してもよく又は２種以上を組み合わせてもよい。これらのうち、モノエタノールアミンが好ましい。 The water-soluble amine is preferably at least one of alkanolamine, quaternary alkylammonium, ammonia, alkylamine and salts thereof, specifically, monoethanolamine, monoisopropanolamine, N-propanolamine. Alkanolamines such as monomethylethanolamine, diethanolamine and triethanolamine; ammonia; alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, dipropylamine, trimethylamine, triethylamine and tripropylamine; tetramethylammonium hydro Quaternary alkyl ammoniums such as oxides; or salts thereof (eg, ammonium hydrochlorides, sulfates, carbonates, ammonium hydrochlorides, Salts, and the like carbonates, etc.), may be combined with well or two or more even when using one of these. Of these, monoethanolamine is preferred.
上記（ｃ）成分のうち、塩酸を含有する場合の配合量としては、上記（ａ）〜（ｄ）成分を含む合計配合量を１００重量％とした場合に、好ましくは０．０１〜０．３重量％である。この範囲未満であると、シュウ酸とインジウムとの塩が析出するのを防ぐ能力が不充分の場合があり、一方、この範囲を超えて過剰に配合すると残渣除去性に不都合が生じる。より好ましくは０．０５〜０．１重量％である。 Among the components (c), the amount of hydrochloric acid is preferably 0.01 to 0.00 when the total amount including the components (a) to (d) is 100% by weight. 3% by weight. If the amount is less than this range, the ability to prevent the salt of oxalic acid and indium from precipitating may be insufficient. On the other hand, if the amount exceeds this range, the residue removal performance will be inconvenient. More preferably, it is 0.05 to 0.1% by weight.
上記（ｃ）成分のうち、硫酸又は水溶性アミンを含有する場合の配合量としては、それぞれ、上記（ａ）〜（ｄ）成分の合計配合量を１００重量％とした場合に、好ましくは０．５〜２０重量％である。この範囲未満であると、シュウ酸とインジウムとの塩が析出するのを防ぐ能力が不充分の場合があり、一方、この範囲を超えて過剰に配合すると残渣除去性に不都合が生じたりエッチングレートの低下を招く恐れがある。より好ましくは１〜１０重量％である。 Of the above component (c), the amount of sulfuric acid or a water-soluble amine is preferably 0 when the total amount of components (a) to (d) is 100% by weight. 0.5 to 20% by weight. If it is below this range, the ability to prevent the salt of oxalic acid and indium from precipitating may be insufficient. On the other hand, if it exceeds this range, the residue removal performance may be inconvenient or the etching rate may be reduced. There is a risk of lowering. More preferably, it is 1 to 10% by weight.
本発明に使用される水（ｄ）の配合量は、上記（ａ）〜（ｄ）成分の合計配合量を１００重量％とした場合に上記（ａ）〜（ｃ）成分の配合量の残部である。 The blending amount of water (d) used in the present invention is the balance of the blending amounts of the components (a) to (c) when the total blending amount of the components (a) to (d) is 100% by weight. It is.
本発明のエッチング液組成物は、本発明の目的を妨げない範囲で、その他の成分（例えば、フッ化アルキル基含有燐酸系界面活性剤やアルキルアルキレン系界面活性剤など）を必要に応じて適宜配合することができる。 In the etching solution composition of the present invention, other components (for example, fluorinated alkyl group-containing phosphoric acid-based surfactants and alkylalkylene-based surfactants) are appropriately added as necessary within the range not impeding the object of the present invention. Can be blended.
本発明のエッチング液組成物は、上記各成分の所要量を常法により混合（常温で攪拌混合）することにより調製することができる。 The etching solution composition of the present invention can be prepared by mixing the required amounts of the above components by a conventional method (stirring and mixing at room temperature).
本発明のエッチング液組成物は、基板（例えば、ガラス等）上に形成された透明導電膜（酸化インジウム系膜等）のエッチングに使用される。例えば、基板上にスパッタリング等の手法で形成されたＩＴＯ膜のエッチングによるパターニングに使用することができる。また、基板上に、下地膜を形成した上に形成されたＩＴＯ膜のエッチングにも好適に使用することができる。なお、本明細書中、下地膜とは、基板上に、ＩＴＯ膜の下に、ＩＴＯ膜の形成に先立って形成され、その上にＩＴＯ膜が形成される膜をいい、例えば、窒化ケイ素（ＳｉＮ）膜等であってよい。 The etching solution composition of the present invention is used for etching a transparent conductive film (such as an indium oxide film) formed on a substrate (such as glass). For example, it can be used for patterning by etching an ITO film formed on the substrate by a technique such as sputtering. Moreover, it can be used suitably also for the etching of the ITO film | membrane formed after forming a base film on a board | substrate. In this specification, the base film refers to a film formed on a substrate, below the ITO film, prior to the formation of the ITO film, and on which the ITO film is formed. For example, silicon nitride ( SiN) film or the like.
エッチング工程においては、本発明のエッチング液組成物は、室温で、又は、加熱（例えば、２５〜５０℃）して、使用することができる。エッチングに要する時間は、ＩＴＯ膜の膜厚等により異なるが、一般には、例えば、１〜３０分程度である。エッチングの後、必要に応じて、リンス工程で洗浄することができる。 In the etching step, the etching solution composition of the present invention can be used at room temperature or by heating (for example, 25 to 50 ° C.). The time required for etching varies depending on the film thickness of the ITO film, but is generally about 1 to 30 minutes, for example. After the etching, it can be cleaned in a rinsing step if necessary.
以下に実施例を示して本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。なお、以下の表中の略号は下記のとおり。
ＭＥＡ：モノエタノールアミン
ＭＩＰＡ：モノイソプロパノールアミン
ＮＰＡ：Ｎ−プロパノールアミン
ＴＭＡＨ：テトラメチルアンモニウムハイドロオキサイド
ＭＭＡ：モノメチルエタノールアミン
ＤＥＡ：ジエタノールアミン
ＴＥＡ：トリエタノールアミン
ＮＳＦＭ：ナフタレンスルホン酸ホルムアルデヒド縮合物ＭＥＡ塩５０％水溶液
ＰＦＰ：パーフルオロアルキル基含有リン酸エステル系界面活性剤
ＤＢＳ：ドデシルベンゼンスルホン酸The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The abbreviations in the table below are as follows.
MEA: monoethanolamine MIPA: monoisopropanolamine NPA: N-propanolamine TMAH: tetramethylammonium hydroxide MMA: monomethylethanolamine DEA: diethanolamine TEA: triethanolamine NSFM: naphthalenesulfonic acid formaldehyde condensate MEA salt 50% aqueous solution PFP : Perfluoroalkyl group-containing phosphate ester surfactant DBS: Dodecylbenzenesulfonic acid
実施例１〜１４、参考例１〜２及び比較例１〜７
表１の配合でエッチング液を調製した。これらのエッチング液を用いて、以下の評価をした。結果を表２に示した。
Examples 1 to 14, Reference Examples 1 to 2 and Comparative Examples 1 to 7
An etching solution was prepared according to the formulation shown in Table 1. The following evaluation was performed using these etching solutions. The results are shown in Table 2.
１．残渣除去能力
ガラス基板上
ガラス基板上にＩＴＯ膜を形成した基板を、エッチング速度から算出されるジャストエッチング時間の１．４倍の時間、エッチング処理した。水洗、窒素ブロー後、処理後のサンプルを電子顕微鏡観察をおこない、エッチング後の残渣を評価した。
下地膜上
ガラス基板上に窒化ケイ素膜を形成し、さらに、ＩＴＯ膜を形成した基板を、エッチング速度から算出されるジャストエッチッグ時間の１．４倍の時間、エッチング処理した。水洗、窒素ブロー後、処理後のサンプルの電子顕微鏡観察をおこない、エッチング後の残渣を評価し、以下の基準で表記した。この評価で残渣除去性について不合格となったものは、以下の泡立ち及びインジウム溶解度の評価は行わなかった。なお、合格は◎及び○である。
◎：残渣なし
○：ごくわずかに残渣あり
△：多数ではないがかなり残渣あり
×：多数の残渣あり1. Residue removal capability On glass substrate The substrate on which the ITO film was formed on the glass substrate was etched for 1.4 times the just etching time calculated from the etching rate. After washing with water and blowing with nitrogen, the treated sample was observed with an electron microscope to evaluate the residue after etching.
On the base film A silicon nitride film was formed on a glass substrate, and the substrate on which the ITO film was further formed was etched for 1.4 times the just etch time calculated from the etching rate. After washing with water and nitrogen blowing, the treated sample was observed with an electron microscope, the residue after etching was evaluated, and the following criteria were used. The evaluation of the following foaming and indium solubility was not performed for those that failed the residue removability in this evaluation. In addition, a pass is (double-circle) and (circle).
◎: No residue ○: Very little residue △: Not many but quite residue ×: Many residues
２．泡立ち
１００ｍｌの比色管にエッチング液を３０ｍｌ入れ、ＴＳ式シェーカーにセットし、２分間震盪した。震盪停止後、１分後に、泡高さ（ｍｍ）を測定し、発泡性を評価した。なお、泡高さ５ｍｍ未満の場合には、泡の発生が実質的になくエッチング装置の運転に支障はなく、５〜１５ｍｍの場合には多少の泡の発生があるもののエッチング装置の運転に実質的支障は生じない。しかし、１５ｍｍを超える場合には泡の発生により装置の運転に支障が生じるおそれが大きい。そこで、以下の基準を設けて表記した。なお、合格は◎及び○である。
◎：泡高さ５ｍｍ未満
○：泡高さ５〜１５ｍｍ
×：泡高さ１５ｍｍを超える2. Foaming 30 ml of the etching solution was put into a 100 ml colorimetric tube, set on a TS type shaker, and shaken for 2 minutes. One minute after shaking was stopped, the foam height (mm) was measured to evaluate foamability. In addition, when the bubble height is less than 5 mm, there is substantially no generation of bubbles and there is no problem in the operation of the etching apparatus. There will be no disruption. However, if it exceeds 15 mm, the operation of the apparatus is likely to be hindered due to the generation of bubbles. Therefore, the following criteria are provided. In addition, a pass is (double-circle) and (circle).
◎: Bubble height less than 5 mm ○: Bubble height 5-15 mm
×: Bubble height exceeds 15 mm
３．インジウム溶解度
三角フラスコに各エッチング液を入れその中に酸化インジウムを投入し、還流管を取り付け攪拌しながら４時間煮沸した。煮沸終了後２５℃で４８時間冷却し、過飽和のインジウム化合物が析出していることを確認した後、ポアサイズ０．２μｍのフィルターでろ過した。ろ液を採取し、ろ液中に溶解しているインジウム濃度をＩＣＰ発光にて測定し、評価結果を以下の基準で表記した。なお、ここでの合格は△以上である。
◎：インジウム溶解量２０００ｐｐｍ以上
○：インジウム溶解量１０００〜１９９９ｐｐｍ
□：インジウム溶解量５００〜９９９ｐｐｍ
△：インジウム溶解量３００〜４９９ｐｐｍ
×：インジウム溶解量２９９ｐｐｍ以下3. Indium Solubility Each etching solution was put into an Erlenmeyer flask, indium oxide was put therein, and a reflux tube was attached and boiled for 4 hours while stirring. After completion of boiling, the mixture was cooled at 25 ° C. for 48 hours, and it was confirmed that a supersaturated indium compound was deposited, followed by filtration with a filter having a pore size of 0.2 μm. The filtrate was collected, the concentration of indium dissolved in the filtrate was measured by ICP emission, and the evaluation results were expressed according to the following criteria. In addition, the pass here is more than (triangle | delta).
◎: Indium dissolution amount 2000 ppm or more ○: Indium dissolution amount 1000 to 1999 ppm
□: Indium dissolution amount 500 to 999 ppm
Δ: Indium dissolution amount 300 to 499 ppm
X: Indium dissolution amount 299 ppm or less
上記実施例１〜１４から、本発明のエッチング液組成物によると、ガラス基板上のみならず下地膜上でも残渣除去能力に優れており、泡立ちも非常に少なく、更にインジウムの溶解量も高いことがわかった。一方、シュウ酸とＮＳＦＭと水を含有する比較例２は、残渣除去能力はあるもののインジウムの溶解量は２００ｐｐｍ程度と低かった。また、シュウ酸と界面活性剤と水を含有する比較例６、７は残渣除去能力はあるもののインジウムの溶解量は低く、更に比較例７は泡立ちも高かった。シュウ酸と塩酸及び／又は水溶性アミンと水を含有する比較例３〜５は、残渣除去能力に問題があった。このように、上記（ａ）〜（ｄ）の成分を含有することにより、本発明の効果を発揮することができることが確認できた。 From Examples 1 to 14 above, according to the etching solution composition of the present invention, the residue removal ability is excellent not only on the glass substrate but also on the underlying film, the foaming is very small, and the dissolution amount of indium is also high. I understood. 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 had a residue removal capability. Further, Comparative Examples 6 and 7 containing oxalic acid, surfactant and water had a residue removing ability, but the amount of dissolved indium was low, and Comparative Example 7 was also highly foamed. Comparative Examples 3 to 5 containing oxalic acid and hydrochloric acid and / or water-soluble amine and water had a problem in the ability to remove residues. Thus, it has confirmed that the effect of this invention can be exhibited by containing the said component (a)-(d).
本発明は、従来技術に比べて残渣除去能力、低泡性が向上しており、パターニングの歩留り、精度向上に寄与することができ、電子部品の製造に極めて有用である。またエッチング液を従来品よりも長く使用することができるため、薬液の使用量低減が可能であり、コスト面、環境面ともにメリットの高いものである。 The present invention has improved residue removal capability and low foamability compared to the prior art, can contribute to patterning yield and accuracy improvement, and is extremely useful in the manufacture of electronic components. In addition, since the etching solution can be used longer than the conventional product, the amount of the chemical solution used can be reduced, and the cost and the environment are highly advantageous.
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| JP2006247697 | 2006-09-13 | ||
| JP2006247697 | 2006-09-13 | ||
| PCT/JP2007/067710 WO2008032728A1 (en) | 2006-09-13 | 2007-09-12 | Etching solution composition |
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| JP2010270711A Division JP4678559B2 (en) | 2006-09-13 | 2010-12-03 | Etching solution composition |
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| 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 |
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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 |
| JPWO2014010471A1 (en) * | 2012-07-09 | 2016-06-23 | 攝津製油株式会社 | Etching solution, etching power recovery agent, method for producing 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 |
| KR102077506B1 (en) | 2013-10-30 | 2020-02-14 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Etching liquid and etching method for oxide consisting essentially of zinc, tin and oxygen |
| CN105874570B (en) * | 2014-01-07 | 2020-07-28 | 三菱瓦斯化学株式会社 | Etching solution containing zinc and tin oxide and etching method |
| WO2015122250A1 (en) * | 2014-02-17 | 2015-08-20 | 三菱瓦斯化学株式会社 | Liquid composition for etching oxides comprising indium, zinc, tin, and oxygen and etching method |
| CN105087009B (en) * | 2014-04-30 | 2017-06-30 | 东莞市钜升金属科技有限公司 | A kind of technique for ito film etching |
| US10168805B2 (en) | 2014-08-18 | 2019-01-01 | 3M Innovative Properties Company | Conductive layered structure and methods of making same |
| WO2017164090A1 (en) * | 2016-03-24 | 2017-09-28 | 株式会社Adeka | Etching liquid 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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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| CN101517712A (en) | 2009-08-26 |
| JPWO2008032728A1 (en) | 2010-01-28 |
| JP4678559B2 (en) | 2011-04-27 |
| TW200826193A (en) | 2008-06-16 |
| KR101409638B1 (en) | 2014-06-18 |
| WO2008032728A1 (en) | 2008-03-20 |
| TWI421937B (en) | 2014-01-01 |
| JP2011049602A (en) | 2011-03-10 |
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