JP7403966B2 - 薄膜エッチング液組成物、及びそれを利用した金属パターン形成方法 - Google Patents
薄膜エッチング液組成物、及びそれを利用した金属パターン形成方法 Download PDFInfo
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- JP7403966B2 JP7403966B2 JP2019065751A JP2019065751A JP7403966B2 JP 7403966 B2 JP7403966 B2 JP 7403966B2 JP 2019065751 A JP2019065751 A JP 2019065751A JP 2019065751 A JP2019065751 A JP 2019065751A JP 7403966 B2 JP7403966 B2 JP 7403966B2
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- weight
- thin film
- silver
- etching
- phosphate
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- 239000010409 thin film Substances 0.000 title claims description 125
- 238000005530 etching Methods 0.000 title claims description 124
- 239000000203 mixture Substances 0.000 title claims description 106
- 238000000034 method Methods 0.000 title claims description 30
- 229910052751 metal Inorganic materials 0.000 title description 13
- 239000002184 metal Substances 0.000 title description 13
- 229910052709 silver Inorganic materials 0.000 claims description 87
- 239000004332 silver Substances 0.000 claims description 87
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 81
- 239000010410 layer Substances 0.000 claims description 72
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 70
- 239000010408 film Substances 0.000 claims description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- 239000000758 substrate Substances 0.000 claims description 37
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 35
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 30
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- 235000021317 phosphate Nutrition 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 12
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 11
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 11
- 239000002356 single layer Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 claims description 5
- 229940061607 dibasic sodium phosphate Drugs 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229940116349 dibasic ammonium phosphate Drugs 0.000 claims description 3
- 229940111685 dibasic potassium phosphate Drugs 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229940111688 monobasic potassium phosphate Drugs 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 claims 1
- 239000000243 solution Substances 0.000 description 49
- -1 region Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000007547 defect Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910003437 indium oxide Inorganic materials 0.000 description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 7
- 239000001488 sodium phosphate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- CHIZIVLYKRJSQQ-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Fe+2].[N+](=O)([O-])[O-].[Fe+2] Chemical compound [N+](=O)([O-])[O-].[Fe+2].[N+](=O)([O-])[O-].[Fe+2] CHIZIVLYKRJSQQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AXFZAZQUMXZWJV-UHFFFAOYSA-N diazanium;phosphono phosphate Chemical compound [NH4+].[NH4+].OP(O)(=O)OP([O-])([O-])=O AXFZAZQUMXZWJV-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- DFIWJEVKLWMZBI-UHFFFAOYSA-M sodium;dihydrogen phosphate;phosphoric acid Chemical compound [Na+].OP(O)(O)=O.OP(O)([O-])=O DFIWJEVKLWMZBI-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Images
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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
- 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
- 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
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- 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
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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
-
- 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
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Description
タの電極、配線及び反射膜などに適用することが検討されている。すなわち、銀を含む膜を適用することで、フラットパネルディスプレイ装置の大型化、高解像度及び低電力消費などを実現するための努力が傾けられている。そして、そのような材料に適用するためのエッチング液が要求されている。
In2O3+6HNO3→2In(NO3)3+6H+
SnO2+4HNO3→Sn(NO3)4+4H+
In2O3+2H3PO4→2In(PO4)+6H+
3SnO2+4H3PO4→Sn3(PO4)4+12H+
2Ag+2HNO3→2Ag++2NO2+H2O
Ag++H2PO4 -→AgH2PO4
本発明の薄膜エッチング液組成物に含まれるリン酸(H3PO4)は、主解離剤として使用される成分であり、一例として、該リン酸は、硝酸によって酸化された金属酸化物(例えば、インジウム酸化膜/銀/インジウム酸化膜)を解離させる役割を行う。
本発明の薄膜エッチング液組成物に含まれる硝酸(HNO3)は、主酸化剤として使用される成分であり、一例としては、インジウム酸化膜/銀/インジウム酸化膜といった銀含有薄膜を酸化させ、湿式エッチングを行う役割を行う。
本発明の薄膜エッチング液組成物に含まれる酢酸(CH3COOH)は、補助酸化剤として使用される成分であり、一例として、インジウム酸化膜/銀/インジウム酸化膜などの銀含有薄膜を酸化させ、湿式エッチングを行う役割を行う。
本発明の薄膜エッチング液組成物に含まれる硝酸鉄は、エッチング後に発生する銀イオン(Ag+)、またはコロイド形態の銀が、所望しない位置に再吸着され、暗点不良、または配線間の不必要な連結を作り、電気的ショート(短絡)が生じるということを防止する役割を行う。例えば、本実施例による硝酸鉄は、硝酸第1鉄及び硝酸第2鉄のうちから選択される1種以上の物質が使用される。
本発明の薄膜エッチング液組成物に含まれるリン酸塩は、湿式エッチング時、薄膜のパターンに対する臨界寸法バイアス(CD bias;Critical Dimension bias、微小寸法の偏差)を低下させ、エッチングが均一に進められるようにエッチング速度を調節する。例えば、該リン酸塩は、第一リン酸ナトリウム(NaH2PO4;リン酸二水素ナトリウム)、第二リン酸ナトリウム(Na2HPO4;リン酸水素二ナトリウム)、第三リン酸ナトリウム(Na3PO4;リン酸三ナトリウム)、第一リン酸カリウム(KH2PO4;リン酸二水素カリウム)、第二リン酸カリウム(K2HPO4;リン酸水素二カリウム)、第一リン酸アンモニウム((NH4)H2PO4;リン酸水素二アンモニウム)、第二リン酸アンモニウム((NH4)2HPO4リン酸水素二アンモニウム)及び第三リン酸アンモニウム((NH4)3PO4リン酸三アンモニウム)から選択される1種以上の物質が使用される。
本発明の薄膜エッチング液組成物に含まれる脱イオン水は、特別に限定されるものではなく、半導体工程用としての、比抵抗値が18MΩ/cm以上であるものを使用することが
望ましい。そのような脱イオン水は、本発明の薄膜エッチング液組成物のトータル100重量%に対する残量として含まれうる。したがって、例えば、約20重量%以上または約25重量%以上であって、約40重量%以下または約35重量%以下の量で含まれうる。
Ag++H2PO4 -→AgH2PO4
Alエッチング時: Al+3AgH2PO4→3Ag+Al(H2PO4)3
特には、銀またはその合金による金属層の上下または上方に、これより薄いITOのキャッピング層を積層させることで、耐食性などを向上させる。
信号線、駆動電圧線、発光制御線などに用いる配線を周縁部に引き出すことで、外部機器との接続のための接続パッドを形成する。これらの配線及び接続パッドは、導電度及び延性に優れるアルミニウムを主体とする導電層により形成される。
特には、アルミニウムまたはその合金による金属層の上下または上方に、これより薄いチタン(Ti)のキャッピング層を積層させることで、耐食性などを向上させる。
銀を主体とする薄膜、特には、銀、及びITOなどの導電性金属酸化物からなる積層膜を高精度でパターニングするためには、このようなエッチング液を用いる必要がある。
これにより、図5に模式的に示すように、銀イオンの還元を抑制または防止する。
リン酸42~45%、硝酸5~8%、酢酸10~17%、硝酸第一鉄(硝酸鉄(II))1~3%、第一リン酸ナトリウム(りん酸二水素ナトリウム)1%。
粘度の測定は、例えば、二重円筒型のブルックフィールド式粘度計(英弘精機株式会社の精密回転粘度計RST-CC)、及び、その低粘度用の二重円筒スピンドル(CCT-DG)を用いて、温度を正確に40℃に制御しつつ行なうことができる。
エッチングは、本願図4に示す形式の湿式エッチング装置を用い、傾斜角度5゜、チャンバー内及びエッチング液の温度を40℃に制御して行なうことができる。本願のエッチング液を用いる際の、適した温度条件は、例えば30~45℃、特には35~42℃である。
図8に示すような、画素電極の縁の近傍を拡大した走査電子顕微鏡(SEM)写真から、画素電極を構成する積層膜中における銀層のサイドエッチングの量を、10箇所で測定し、その平均を求めた。0.1μm未満を非常に優秀(◎)、0.1μmと0.2μmとの間である場合に優秀(○)、0.2μmと0.3μmとの間である場合に良好(△)であるとした。
図7に示すように、接続パッド部を拡大した走査電子顕微鏡(SEM)写真から、それぞれの寸法が約150μm×900μmである6個の接続パッド上の銀粒子の総数を数えた。
図8に示すような、画素電極の縁の近傍を拡大した走査電子顕微鏡(SEM)写真から、上部ITO膜からのバリ状の突起(チップ)が、有意に存在するかどうかを目視判定した。
10’ 銀含有薄膜
11,21 第1導電層
12,22 第2導電層
13,23 第3導電層
20 パッド電極
30 PR層
S 基板
PD パッド部
PX 画素部
Claims (20)
- 銀を含む薄膜をエッチングする薄膜エッチング液組成物であって、
組成物の総重量に対して、
リン酸(A)43ないし46重量%と、
硝酸(B)5ないし8重量%と、
酢酸(C)10ないし17重量%と、
硝酸鉄(D)1ないし3重量%と、
リン酸塩(E)0.7ないし1.5重量%と、
脱イオン水(F)残量と、を含む薄膜エッチング液組成物。 - 前記薄膜エッチング液組成物は、銀または銀合金からなる単層膜、または前記単層膜とインジウム含有金属酸化物膜とから構成される積層膜をエッチングするためのものであることを特徴とする請求項1に記載の薄膜エッチング液組成物。
- 前記インジウム含有金属酸化物膜は、酸化スズインジウム(ITO)、酸化亜鉛インジウム(IZO)、酸化スズ亜鉛インジウム(ITZO)及び酸化ガリウム亜鉛インジウム(IGZO)から選択される1種以上を含むことを特徴とする請求項2に記載の薄膜エッチング液組成物。
- 前記銀合金は、銀、及びネオジム(Nd)、銅(Cu)、パラジウム(Pd)、ニオブ(Nb)、ニッケル(Ni)、モリブデン(Mo)、クロム(Cr)、マグネシウム(Mg)、タングステン(W)、プロトアクチニウム(Pa)及びチタン(Ti)から選択される1種以上を含むことを特徴とする請求項2に記載の薄膜エッチング液組成物。
- 前記硝酸鉄は、硝酸第一鉄及び硝酸第二鉄のうちから選択される1種以上であることを特徴とする請求項1に記載の薄膜エッチング液組成物。
- 前記リン酸塩は、第一リン酸ナトリウム(NaH2PO4)、第二リン酸ナトリウム(Na2HPO4)、第三リン酸ナトリウム(Na3PO4)、第一リン酸カリウム(KH2PO4)、第二リン酸カリウム(K2HPO4)、第1リン酸アンモニウム((NH4)H2PO4)、第二リン酸アンモニウム((NH4)2HPO4)及び第三リン酸アンモニウム((NH4)3PO4)から選択される1種以上であることを特徴とする請求項1に記載の薄膜エッチング液組成物。
- 40℃で、前記薄膜エッチング液組成物の粘度(cP)は、5.0ないし5.5であることを特徴とする請求項1に記載の薄膜エッチング液組成物。
- 前記薄膜エッチング液組成物は、組成物の総重量に対して、リン酸(A)45重量%と、硝酸(B)6.5重量%と、酢酸(C)15重量%と、硝酸鉄(D)2重量%と、リン酸塩(E)1重量%と、脱イオン水(F)残量と、を含むことを特徴とする請求項1に記載の薄膜エッチング液組成物 。
- 銀を含む導電膜が配置された基板を準備する段階と、
前記導電膜をエッチングしてパターンを形成する段階と、を含み、
前記パターンを形成する段階は、
組成物総重量に対して、リン酸(A)43ないし46重量%と、硝酸(B)5ないし8重量%と、酢酸(C)10ないし17重量%と、硝酸鉄(D)1ないし3重量%と、リン酸塩(E)0.7ないし1.5重量%と、脱イオン水(F)残量と、を含む薄膜エッチング液組成物でエッチングする段階を含む導電膜パターン形成方法。 - (a)基板上に半導体層を形成する段階と、
(b)前記半導体層の上方にゲート電極を形成する段階と、
(c)前記ゲート電極の上方に、ソース電極及びドレイン電極を形成する段階と、
(d)前記ソース電極または前記ドレイン電極と電気的に連結され、銀を含む薄膜を形成する段階と、
(e)前記薄膜をエッチングし、画素電極を形成する段階と、を含み、
前記(e)段階において、前記画素電極を形成する段階は、
組成物の総重量に対して、リン酸(A)43ないし46重量%と、硝酸(B)5ないし8重量%と、酢酸(C)10ないし17重量%と、硝酸鉄(D)1ないし3重量%と、リン酸塩(E)0.7ないし1.5重量%と、脱イオン水(F)残量と、を含む薄膜エッチング液組成物でエッチングする段階を含むディスプレイ装置用アレイ基板の製造方法。 - 前記ゲート電極、前記ソース電極及び前記ドレイン電極のうちの少なくとも一つは、アルミニウム(Al)を含むことを特徴とする請求項10に記載のディスプレイ装置用アレイ基板の製造方法。
- (f)前記基板の一方の縁の近傍にパッド部を形成する段階をさらに含み、前記パッド部は、アルミニウム(Al)を含むことを特徴とする請求項11に記載のディスプレイ装置用アレイ基板の製造方法。
- 前記(f)段階は、前記(b)段階または前記(c)段階と同時に遂行されることを特徴とする請求項12に記載のディスプレイ装置用アレイ基板の製造方法。
- 前記(e)段階を遂行する間、前記パッド部は、前記薄膜エッチング液組成物に露出されることを特徴とする請求項12に記載のディスプレイ装置用アレイ基板の製造方法。
- 銀を含む薄膜をエッチングする薄膜エッチング液組成物であり、
前記薄膜エッチング組成物は、
リン酸43ないし46重量%と、
硝酸5ないし8重量%と、
酢酸10ないし17重量%と、
硝酸第二鉄(Fe(NO3)3)1ないし3重量%と、
第一リン酸ナトリウム(NaH2PO4)0.7ないし1.5重量%と、
脱イオン水残量と、を含む薄膜エッチング液組成物。 - 銀または銀合金からなる単層膜、または前記単層膜を含む積層膜をエッチングするための薄膜エッチング液組成物であって、
前記薄膜エッチング液組成物は、
リン酸43ないし46重量%と、
硝酸5ないし8重量%と、
酢酸10ないし17重量%と、
硝酸第二鉄(Fe(NO3)3)1ないし3重量%と、
第一リン酸ナトリウム(NaH2PO4)0.7ないし1.5重量%と、
脱イオン水残量と、を含む薄膜エッチング液組成物。 - 40℃で、前記薄膜エッチング液組成物の粘度(cP)は、5.0ないし5.5であることを特徴とする請求項15または16に記載の薄膜エッチング液組成物。
- 前記積層膜は、前記単層膜とインジウム含有金属酸化物膜とから構成されることを特徴とする請求項16に記載の薄膜エッチング液組成物。
- 前記インジウム含有金属酸化物膜は、酸化スズインジウム(ITO)、酸化亜鉛インジウム(IZO)、酸化スズ亜鉛インジウム(ITZO)及び酸化ガリウム亜鉛インジウム(IGZO)から選択される1種以上を含むことを特徴とする請求項18に記載の薄膜エッチング液組成物。
- 銀合金は、銀、及びネオジム(Nd)、銅(Cu)、パラジウム(Pd)、ニオブ(Nb)、ニッケル(Ni)、モリブデン(Mo)、クロム(Cr)、マグネシウム(Mg)、タングステン(W)、プロトアクチニウム(Pa)及びチタン(Ti)から選択される1種以上を含むことを特徴とする請求項18に記載の薄膜エッチング液組成物。
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