KR20190066424A - Composition for Etching Copper-Containing Metal Layer - Google Patents
Composition for Etching Copper-Containing Metal Layer Download PDFInfo
- Publication number
- KR20190066424A KR20190066424A KR1020170166130A KR20170166130A KR20190066424A KR 20190066424 A KR20190066424 A KR 20190066424A KR 1020170166130 A KR1020170166130 A KR 1020170166130A KR 20170166130 A KR20170166130 A KR 20170166130A KR 20190066424 A KR20190066424 A KR 20190066424A
- Authority
- KR
- South Korea
- Prior art keywords
- copper
- film
- etching
- based metal
- compound
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 claims abstract description 70
- -1 azole compound Chemical class 0.000 claims abstract description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 109
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 20
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims 1
- 239000004323 potassium nitrate Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 10
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 239000010955 niobium Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- BQCWHJGCJKUHAA-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.N.[K+].[Ca+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.N.[K+].[Ca+2] BQCWHJGCJKUHAA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000004279 alanine Nutrition 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940124277 aminobutyric acid Drugs 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
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
-
- G02F2001/136295—
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명은 구리계 금속막용 식각 조성물에 관한 것으로, 보다 상세하게는 하부에 위치하는 산화물층에 데미지를 주지 않으면서도 구리계 금속막의 식각 특성이 우수한 식각 조성물에 관한 것이다.The present invention relates to a etching composition for a copper-based metal film, and more particularly, to an etching composition having excellent etching properties of a copper-based metal film without damaging the underlying oxide layer.
액정표시장치(LCD) 및 유기발광다이오드(OLED) 표시장치의 박막 트랜지스터(Thin film transistor, TFT) 기판에는 액정층 및 OLED 소자에 신호를 전달하기 위해 배선이 형성되어 있다. 박막 트랜지스터 기판의 배선은 게이트 배선과 데이터 배선을 포함한다. 상기 게이트 배선은 게이트 신호가 인가되는 게이트 라인과 박막 트랜지스터의 게이트 전극을 포함하며, 데이터 배선은 게이트 배선과 절연되어 데이터 신호를 인가하는 데이터 라인과 박막 트랜지스터의 데이터 전극을 구성하는 소스 전극과 드레인 전극을 포함한다.Wiring is formed on a thin film transistor (TFT) substrate of a liquid crystal display (LCD) and an organic light emitting diode (OLED) display to transmit signals to the liquid crystal layer and the OLED elements. The wiring of the thin film transistor substrate includes a gate wiring and a data wiring. The gate line includes a gate line to which a gate signal is applied and a gate electrode of the thin film transistor. The data line is insulated from the gate line to form a data line for applying a data signal, a source electrode and a drain electrode .
이러한 배선으로는 통상적으로 저항이 낮고 환경적으로 문제가 없는 구리 금속이 사용되고 있다. 그러나, 구리는 유리 기판과의 접착력이 낮고 하부 막으로 확산되는 문제점이 있어 몰리브덴을 하부 배리어 금속으로 함께 사용하고 있다.Such wiring typically uses copper metal, which has low resistance and is environmentally benign. However, since copper has a low adhesion to glass substrate and diffuses into a lower film, molybdenum is used as a lower barrier metal.
이러한 금속 배선은 식각 공정을 통하여 배선으로 패터닝된다. 기존에 구리/몰리브덴(합금)막으로 이루어진 다중 금속막을 식각하기 위해 사용되는 식각 조성물은 몰리브덴(합금)막의 식각을 위해 불소 함유 화합물을 포함한다[대한민국 공개특허 제10-2017-0068328호 참조].These metal wirings are patterned into wirings through an etching process. An etch composition used to etch a multi-metal film conventionally made of a copper / molybdenum (alloy) film includes a fluorine-containing compound for etching a molybdenum (alloy) film (see Korean Patent Publication No. 10-2017-0068328).
한편, 최근 디스플레이의 고해상도화 및 대형화에 따라 TFT의 활성층(active layer), 즉 반도체층의 구성물질이 기존의 비정질 실리콘에서 산화물로 대체되고 있다. 이러한 산화물 TFT는 비정질 실리콘 TFT에 비해 소스 전극에서 드레인 전극으로 가는 전자의 이동도가 우수하여 고해상도 및 저전력 구동이 필요한 대형 LCD나 OLED에 사용된다.On the other hand, as the display becomes higher in resolution and larger in size, the active layer of the TFT, that is, the constituent material of the semiconductor layer, is replaced with oxide in the conventional amorphous silicon. Such an oxide TFT has excellent mobility of electrons from the source electrode to the drain electrode as compared with the amorphous silicon TFT, and is used for a large-sized LCD or OLED requiring high resolution and low power driving.
그러나, 산화물 TFT 제조 시 구리/몰리브덴(합금)막으로 이루어진 다중 금속막을 식각하여 소스 전극과 드레인 전극을 형성시킬 때 식각액 중에 존재하는 불소 함유 화합물로 인해 하부에 위치하는 반도체층을 구성하는 산화물에 데미지를 줄 수 있는 문제점이 있다.However, when a multi-metal film made of a copper / molybdenum (alloy) film is etched to form a source electrode and a drain electrode in the manufacture of an oxide TFT, damage to an oxide constituting a semiconductor layer located at a lower portion due to a fluorine- There is a problem that it can give.
따라서, 하부에 위치하는 산화물층에 데미지를 주지 않으면서도 구리계 금속막의 식각 특성이 우수한 식각 조성물의 개발이 필요하다.Accordingly, it is necessary to develop an etching composition having excellent etching properties of the copper-based metal film without damaging the oxide layer located at the bottom.
본 발명의 한 목적은 하부에 위치하는 산화물층에 데미지를 주지 않으면서도 구리계 금속막의 식각 특성이 우수한 식각 조성물을 제공하는 것이다.It is an object of the present invention to provide an etching composition which is excellent in etching properties of a copper-based metal film without damaging the underlying oxide layer.
본 발명의 다른 목적은 상기 식각 조성물을 이용하여 형성된 구리계 금속 배선을 제공하는 것이다.Another object of the present invention is to provide a copper-based metal wiring formed using the etching composition.
본 발명의 또 다른 목적은 상기 구리계 금속 배선을 포함하는 박막 트랜지스터 어레이 기판을 제공하는 것이다.It is still another object of the present invention to provide a thin film transistor array substrate including the copper-based metal wiring.
한편으로, 본 발명은 과산화수소, 아졸 화합물, 질소 원자 및 카르복실기를 갖는 수용성 화합물, 인산염 화합물 및 질산염 화합물을 포함하며, 상기 질산염 화합물은 질산 금속염을 포함하는 구리계 금속막용 식각 조성물을 제공한다.On the other hand, the present invention provides an etching composition for a copper-based metal film comprising a water-soluble compound having a hydrogen peroxide, an azole compound, a nitrogen atom and a carboxyl group, a phosphate compound and a nitrate salt compound, and the nitrate salt compound includes a metal nitrate salt.
본 발명의 일 실시형태에서, 상기 구리계 금속막용 식각 조성물은 다가알코올형 계면활성제를 추가로 포함할 수 있다.In one embodiment of the present invention, the etching composition for a copper-based metal film may further comprise a polyhydric alcohol-type surfactant.
본 발명의 일 실시형태에서, 상기 구리계 금속막용 식각 조성물은 조성물 전체 중량에 대하여 과산화수소 5.0 내지 25.0 중량%, 아졸 화합물 0.1 내지 5.0 중량%, 질소 원자 및 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 인산염 화합물 0.1 내지 5.0 중량% 및 질산염 화합물 0.1 내지 5.0 중량%를 포함하며, 조성물의 전체 중량이 100 중량%가 되도록 잔량의 물을 포함할 수 있다.In one embodiment of the present invention, the etching composition for a copper-based metal film comprises 5.0 to 25.0% by weight of hydrogen peroxide, 0.1 to 5.0% by weight of an azole compound, 0.1 to 5.0% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group, 0.1 to 5.0% by weight of a phosphate compound and 0.1 to 5.0% by weight of a nitrate salt compound, and may contain residual water such that the total weight of the composition is 100% by weight.
다른 한편으로, 본 발명은 상기 구리계 금속막용 식각 조성물을 이용하여 형성된 구리계 금속 배선을 제공한다.On the other hand, the present invention provides a copper-based metal wiring formed using the etching composition for a copper-based metal film.
또 다른 한편으로, 본 발명은 상기 구리계 금속 배선을 포함하는 박막 트랜지스터 어레이 기판을 제공한다.On the other hand, the present invention provides a thin film transistor array substrate including the copper-based metal wiring.
본 발명에 따른 구리계 금속막용 식각 조성물은 구리계 금속막의 식각 시에 하부에 위치하는 산화물층에 데미지를 주지 않으면서도 양호한 식각 프로파일을 제공할 뿐만 아니라 식각 후 금속막의 잔사가 남지 않아 식각 특성을 개선할 수 있다.The etching composition for a copper-based metal film according to the present invention not only provides a good etching profile without damaging the underlying oxide layer during etching of the copper-based metal film, but also improves the etching property because no residue of the metal film remains after etching. can do.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 과산화수소(A), 아졸 화합물(B), 질소 원자 및 카르복실기를 갖는 수용성 화합물(C), 인산염 화합물(D) 및 질산염 화합물(E)을 포함하며, 상기 질산염 화합물(E)이 질산 금속염을 포함하는 구리계 금속막용 식각 조성물에 관한 것이다.An embodiment of the present invention includes a water-soluble compound (C), a phosphate compound (D), and a nitrate compound (E) having hydrogen peroxide (A), an azole compound (B), a nitrogen atom and a carboxyl group, ) Is a nitrate metal salt-containing etching composition for a copper-based metal film.
본 발명의 일 실시형태에서, 상기 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 구리 또는 구리 합금의 단일막; 및 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막과 몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 포함한다.In one embodiment of the present invention, the copper-based metal film is a single film of copper or a copper alloy, in which copper is included in the constituent components of the film; And a multilayer film comprising at least one film selected from a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film.
상기 구리 합금은 구리, 구리의 질화물 및 구리의 산화물 중에서 선택되는 하나 이상과 알루미늄(Al), 마그네슘(Mg), 칼슘(Ca), 티타늄(Ti), 은(Ag), 크롬(Cr), 망간(Mn), 철(Fe), 지르코늄(Zr), 나이오븀(Nb), 몰리브덴(Mo), 팔라듐(Pd), 하프늄(Hf), 탄탈륨(Ta) 및 텅스텐(W) 중에서 선택되는 하나 이상의 금속과의 합금을 의미한다.The copper alloy includes at least one selected from the group consisting of copper, a nitride of copper and an oxide of copper, and at least one selected from the group consisting of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag) At least one metal selected from Mn, Fe, Zr, Nb, Mo, Pd, Hf, Ta, ≪ / RTI >
상기 몰리브덴 합금은 몰리브덴, 몰리브덴의 질화물 및 몰리브덴의 산화물 중에서 선택되는 하나 이상과 나이오븀(Nb), 텅스텐(W), 티타늄(Ti) 및 니켈(Ni) 중에서 선택되는 하나 이상의 금속과의 합금을 의미한다.The molybdenum alloy means an alloy of at least one selected from the group consisting of molybdenum, molybdenum nitride and molybdenum oxide and at least one metal selected from niobium (Nb), tungsten (W), titanium (Ti) and nickel (Ni) do.
상기 다층막의 예로는, 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴 합금막 등의 2중막; 몰리브덴/구리/몰리브덴막, 몰리브덴 합금/구리/몰리브덴 합금막, 몰리브덴 합금/구리 합금/몰리브덴 합금막 등의 3중막 등을 들 수 있다. 상기 구리/몰리브덴막은 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 것을 의미하고, 상기 구리/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리 합금/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리 합금층을 포함하는 것을 의미하고, 상기 몰리브덴/구리/몰리브덴막은 몰리브덴층, 상기 몰리브덴층 상에 형성된 구리층 및 상기 구리층 상에 형성된 몰리브덴층을 포함하는 것을 의미하며, 상기 몰리브덴 합금/구리/몰리브덴 합금막은 몰리브덴 합금층, 상기 몰리브덴 합금층 상에 형성된 구리층 및 상기 구리층 상에 형성된 몰리브덴 합금층을 포함하는 것을 의미하고, 상기 몰리브덴 합금/구리 합금/몰리브덴 합금막은 몰리브덴 합금층, 상기 몰리브덴 합금층 상에 형성된 구리 합금층 및 상기 구리 합금층 상에 형성된 몰리브덴 합금층을 포함하는 것을 의미한다.Examples of the multilayer film include a double film such as a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, and the like; Molybdenum / copper / molybdenum film, molybdenum alloy / copper / molybdenum alloy film, molybdenum alloy / copper alloy / molybdenum alloy film and the like. The copper / molybdenum film means that the copper / molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, Wherein the molybdenum / copper / molybdenum film comprises a molybdenum layer, a copper layer formed on the molybdenum layer, and a copper layer on the molybdenum alloy layer, wherein the molybdenum / copper / molybdenum alloy film comprises a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, The molybdenum alloy / copper / molybdenum alloy film means that the molybdenum alloy layer includes a molybdenum alloy layer, a copper layer formed on the molybdenum alloy layer, and a molybdenum alloy layer formed on the copper layer, The molybdenum alloy / copper alloy / molybdenum alloy film is a molybdenum alloy Layer, said molybdenum alloy of copper formed on the alloy layer and the layer is meant to include a molybdenum alloy layer formed on the copper alloy layer.
특히, 본 발명의 식각액 조성물은 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막과 몰리브덴막 및 몰리브덴 합금막 중에서 선택되는 하나 이상의 막을 포함하는 다층막에 적용될 수 있다. In particular, the etchant composition of the present invention can be applied to a multilayer film including at least one film selected from a copper film and a copper alloy film, and at least one film selected from a molybdenum film and a molybdenum alloy film.
본 발명의 일 실시형태에서, 상기 구리계 금속막은 금속 산화물막 상에 형성된 것일 수 있다.In one embodiment of the present invention, the copper-based metal film may be formed on the metal oxide film.
상기 금속 산화물막은 AxByCzO(A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr 또는 Ta; x, y, z≥0; 단, x, y, z 중 적어도 둘은 0이 아님)의 삼성분계 또는 사성분계 산화물을 함유하는 막으로서, 산화물 반도체층을 구성하는 막일 수 있다.The metal oxide film may be formed of a material selected from the group consisting of A x B y C z O (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, or Ta; x, y, z? At least two of them are not 0) ternary or quaternary oxide, and may be a film constituting the oxide semiconductor layer.
상기 구리막 및 구리 합금막은 그 두께가 2,000 내지 10,000Å, 바람직하게는 2,500 내지 6,500Å의 범위일 수 있고, 상기 몰리브덴막 및 몰리브덴 합금막은 그 두께가 100 내지 450Å, 바람직하게는 100 내지 300Å의 범위일 수 있다.The copper film and the copper alloy film may have a thickness of 2,000 to 10,000 angstroms, preferably 2,500 to 6,500 angstroms, and the molybdenum film and the molybdenum alloy film may have a thickness of 100 to 450 angstroms, preferably 100 to 300 angstroms Lt; / RTI >
이하에서는 본 발명의 일 실시형태에 따른 식각 조성물의 구성성분들에 대해 보다 상세히 설명한다.Hereinafter, the constituents of the etching composition according to one embodiment of the present invention will be described in more detail.
과산화수소(A)Hydrogen peroxide (A)
본 발명의 일 실시형태에서, 상기 과산화수소(A)는 구리계 금속막의 식각에 영향을 미치는 주 산화제이다.In one embodiment of the present invention, the hydrogen peroxide (A) is a main oxidizing agent that affects the etching of the copper-based metal film.
상기 과산화수소는 조성물 전체 중량에 대하여 5.0 내지 25.0 중량%, 바람직하게는 15.0 내지 23.0 중량%로 포함될 수 있다. 상기 과산화수소의 함량이 5.0 중량% 미만인 경우 구리계 금속막의 식각력이 부족하여 충분한 식각이 이루어지지 않을 수 있으며, 25.0 중량%를 초과하는 경우에는 식각 속도가 전체적으로 빨라지기 때문에 공정 컨트롤이 어려울 수 있다.The hydrogen peroxide may be included in an amount of 5.0 to 25.0% by weight, preferably 15.0 to 23.0% by weight based on the total weight of the composition. If the content of hydrogen peroxide is less than 5.0 wt%, the etching performance of the copper-based metal film may be insufficient and sufficient etching may not be performed. If the content of hydrogen peroxide is more than 25.0 wt%, the etching speed may be accelerated.
아졸Azole 화합물(B) The compound (B)
본 발명의 일 실시형태에서, 상기 아졸 화합물(B)은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디 로스(CD loss), 즉 사이드 에치(side etch)를 줄여주어 공정 상의 마진을 높이는 역할을 한다.In one embodiment of the present invention, the azole compound (B) serves to control the etch rate of the copper-based metal film and to reduce the CD loss of the pattern, that is, the side etch, do.
상기 아졸 화합물로는 당해 기술분야에서 사용되는 것이라면 특별한 제한 없이 사용될 수 있으며, 예를 들면, 탄소수가 1 내지 30인 아졸 화합물인 것이 바람직하다. 구체적으로, 상기 아졸 화합물로는 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 티아졸(thiazole)계, 이소티아졸(isothiazole)계 등을 들 수 있다. 이들은 단독으로 또는 2종 이상의 혼합물로 사용될 수 있다.The azole compound is not particularly limited as long as it is used in the art. For example, it is preferably an azole compound having 1 to 30 carbon atoms. Specifically, examples of the azole compound include pyrrole, pyrazole, imidazole, triazole, tetrazole, pentazole, oxazole, Oxazole type, isoxazole type, thiazole type, isothiazole type, and the like. These may be used alone or as a mixture of two or more.
상기 아졸 화합물은 조성물 전체 중량에 대하여 0.1 내지 5.0중량%로 포함될 수 있다. 상기 아졸 화합물의 함량이 0.1 중량% 미만인 경우 식각 속도가 증가하여 시디 로스가 크게 발생될 수 있고, 5.0 중량%를 초과할 경우 식각 속도가 감소하여 공정시간이 손실될 수 있다. The azole compound may be contained in an amount of 0.1 to 5.0% by weight based on the total weight of the composition. If the content of the azole compound is less than 0.1% by weight, the etching rate may increase and the seeding loss may be increased. If the amount of the azole compound is more than 5.0% by weight, the etching rate may decrease and the process time may be lost.
질소 원자 및 카르복실기를 갖는 수용성 화합물(C)The water-soluble compound (C) having a nitrogen atom and a carboxyl group
본 발명의 일 실시형태에서, 상기 질소원자 및 카르복실기를 갖는 수용성 화합물(C)은 식각 조성물의 보관시 발생할 수 있는 과산화수소의 자체 분해 반응을 막아주고 많은 수의 기판을 식각할 시에 식각 특성이 변하는 것을 방지한다. 일반적으로 과산화수소를 사용하는 식각 조성물의 경우 보관시 과산화수소가 자체 분해하여 그 보관기간이 길지가 못하고 폭발이 일어날 수 있다. 반면, 상기 질소 원자와 카르복실기를 갖는 수용성 화합물이 포함될 경우 과산화수소의 분해 속도가 10배 가까이 줄어들어 보관기간 및 안정성 확보에 유리하다. 특히, 구리층의 경우 식각 조성물 내에 구리 이온이 다량 잔존할 경우에 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 발생할 수 있으나, 상기 화합물(C)을 첨가하였을 경우 이런 현상을 막을 수 있다. In one embodiment of the present invention, the water-soluble compound (C) having a nitrogen atom and a carboxyl group prevents the self-decomposition reaction of hydrogen peroxide that may occur during the storage of the etching composition and changes the etching property when a large number of substrates are etched ≪ / RTI > Generally, in the case of an etching composition using hydrogen peroxide, the hydrogen peroxide self-decomposes during storage, so that the storage period of the hydrogen peroxide may not be long and an explosion may occur. On the other hand, when a water-soluble compound having a nitrogen atom and a carboxyl group is included, the decomposition rate of hydrogen peroxide is reduced to about 10 times, which is advantageous for securing the storage period and stability. Particularly, in the case of the copper layer, when a large amount of copper ions remain in the etching composition, a passivation film may be formed to be oxidized to black and not further etched. However, when the compound (C) .
상기 질소 원자 및 카르복실기를 갖는 수용성 화합물의 예로는 알라닌(alanine), 아미노부티르산(aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상의 혼합물로 사용될 수 있다.Examples of the water-soluble compound having a nitrogen atom and a carboxyl group include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid, And sarcosine, which may be used alone or as a mixture of two or more.
상기 질소 원자 및 카르복실기를 갖는 수용성 화합물은 조성물의 전체 중량에 대해서 0.1 내지 5.0 중량%의 범위로 포함될 수 있다. 상기 화합물의 함량이 0.1 중량% 미만인 경우 다량의 기판(약 500매)의 식각 후에 패시베이션 막이 형성되어 충분한 공정 마진을 얻기가 어려워지며, 5.0 중량%를 초과할 경우 몰리브덴 함유 막의 식각속도가 느려지므로 공정시간의 손실이 발생할 수 있다.The water-soluble compound having a nitrogen atom and a carboxyl group may be contained in an amount of 0.1 to 5.0% by weight based on the total weight of the composition. When the content of the compound is less than 0.1% by weight, a passivation film is formed after etching a large amount of substrate (about 500), and it becomes difficult to obtain a sufficient process margin. If the content exceeds 5.0% by weight, the etching rate of the molybdenum- Loss of time can occur.
인산염 화합물(D)The phosphate compound (D)
본 발명의 일 실시형태에서, 상기 인산염 화합물(D)은 식각 프로파일을 양호하게 만들어주는 성분으로, 식각 조성물의 부분적 과침식 현상을 억제할 수 있다.In an embodiment of the present invention, The phosphate compound (D) is a component that makes the etching profile good, and can suppress the partial and erosion phenomenon of the etching composition.
상기 인산염 화합물은 인산의 하나 또는 2개의 수소 이온이 알칼리 금속 이온, 알칼리 토금속 이온 또는 암모늄 이온으로 치환된 염에서 선택되는 것이면 특별히 한정하지 않는다. 그 예로는 제1인산암모늄(ammonium dihydrogenphosphate), 제1인산나트륨(sodium dihydrogenphosphate), 제1인산칼륨(potassium dihydrogenphosphate), 제2인산암모늄(diammonium hydrogenphosphate), 제2인산나트륨(disodium hydrogenphosphate), 제2인산칼륨(dipotassium hydrogenphosphate) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상의 혼합물로 사용될 수 있다.The phosphate compound is not particularly limited as long as it is selected from salts in which one or two hydrogen ions of phosphoric acid are substituted with an alkali metal ion, an alkaline earth metal ion or an ammonium ion. Examples thereof include ammonium dihydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, diammonium hydrogenphosphate, disodium hydrogenphosphate, Dipotassium hydrogenphosphate, etc. These may be used alone or in a mixture of two or more.
상기 인산염 화합물은 조성물의 전체 중량에 대하여 0.1 내지 5.0 중량%의 범위로 포함될 수 있다. 상기 인산염 화합물의 함량이 0.1 중량% 미만인 경우 식각 프로파일이 불량하게 될 수 있고, 5.0 중량%를 초과할 경우 구리계 금속막의 식각 속도가 빨라질 수 있다.The phosphate compound may be contained in an amount of 0.1 to 5.0% by weight based on the total weight of the composition. If the content of the phosphate compound is less than 0.1% by weight, the etching profile may be poor, and if it is more than 5.0% by weight, the etching rate of the copper-based metal film may be accelerated.
질산염 화합물(E)The nitrate compound (E)
본 발명의 일 실시형태에서, 상기 질산염 화합물(E)은 몰리브덴막 및 몰리브덴 합금막의 보조산화제인 동시에 잔사가 발생하지 않도록 만들어주는 성분으로서, 질산 금속염을 포함한다.In an embodiment of the present invention, The nitrate compound (E) is a co-oxidant of the molybdenum film and the molybdenum alloy film and at the same time, contains a metal nitrate as a component which prevents the residue from being generated.
상기 질산 금속염은 질산의 수소 이온이 알칼리 금속 이온 또는 알칼리 토금속 이온으로 치환된 염이다. 그 예로는 질산칼륨(KNO3), 질산나트륨(NaNO3), 질산칼슘(Ca(NO3)2) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상의 혼합물로 사용될 수 있다.remind The nitrate metal salt is a salt in which the hydrogen ion of nitric acid is substituted with an alkali metal ion or an alkaline earth metal ion. Examples thereof include potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ) and calcium nitrate (Ca (NO 3 ) 2 ), which may be used alone or as a mixture of two or more.
상기 질산염 화합물은 조성물의 전체 중량에 대하여 0.1 내지 5.0 중량%의 범위로 포함될 수 있다. 상기 질산염 화합물의 함량이 0.1 중량% 미만인 경우 잔사가 발생할 수 있고, 5.0 중량%를 초과할 경우 식각 프로파일이 불량해질 우려가 있을 뿐만 아니라 언더컷(undercut)이 발생할 우려가 있다.The nitrate compound may be contained in an amount of 0.1 to 5.0% by weight based on the total weight of the composition. If the content of the nitrate compound is less than 0.1 wt%, residues may be formed. If the nitrate compound content is more than 5.0 wt%, the etching profile may be poor and undercuts may occur.
다가알코올형Polyhydric alcohol type 계면활성제(F) Surfactant (F)
본 발명의 일 실시형태에 따른 구리계 금속막용 식각 조성물은 표면장력을 저하시켜 식각의 균일성을 증가시키기 위하여 다가알코올형 계면활성제(F)를 추가로 포함할 수 있다. 또한, 상기 다가알코올형 계면활성제(F)는 구리막의 식각 후 식각액에 녹아져 나오는 구리 이온을 둘러 쌈으로써 구리 이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제시키는 역할을 할 수 있다. 이와 같이, 구리 이온의 활동도를 낮추게 되면 식각액을 사용하는 동안 발열 없이 안정적인 공정을 진행할 수 있게 된다.The etching composition for a copper-based metal film according to an embodiment of the present invention may further include a polyhydric alcohol-type surfactant (F) in order to lower the surface tension and increase the uniformity of the etching. In addition, the polyhydric alcohol surfactant (F) may act to suppress the decomposition reaction of hydrogen peroxide by suppressing the activity of copper ions by surrounding the copper ions dissolved in the etching solution after etching the copper film. Thus, lowering the activity of the copper ion makes it possible to carry out a stable process without heat generation while using the etching solution.
상기 다가알코올형 계면활성제의 예로는 글리세롤(glycerol), 에틸렌 글리콜(ethylene glycol), 디에틸렌 글리콜(diethylene glycol), 트리에틸렌 글리콜(triethylene glycol), 폴리에틸렌 글리콜(polyethylene glycol) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상의 혼합물로 사용될 수 있다.Examples of the polyhydric alcohol surfactant include glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and the like. They may be used alone or as a mixture of two or more.
상기 다가알코올형 계면활성제는 조성물의 전체 중량에 대하여 0.001 내지 5.0 중량%의 범위로 포함될 수 있다. 상기 다가알코올형 계면활성제의 함량이 0.001 중량% 미만인 경우, 식각 균일성이 저하되고 과산화수소의 분해가 가속화될 수 있고, 5.0 중량%를 초과할 경우 거품이 많이 발생될 수 있다.The polyhydric alcohol type surfactant may be contained in an amount of 0.001 to 5.0% by weight based on the total weight of the composition. If the content of the polyhydric alcohol surfactant is less than 0.001 wt%, the etching uniformity may be lowered and the decomposition of hydrogen peroxide may be accelerated. If the content of the polyhydric alcohol surfactant is more than 5.0 wt%, bubbles may be generated.
아울러, 본 발명의 일 실시형태에 따른 식각 조성물은 조성물의 전체 중량이 100 중량%가 되도록 잔량의 물을 포함할 수 있다. 본 발명에서, 상기 물은 특별히 한정하지 않으나, 탈이온수가 바람직하고, 물 속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·㎝ 이상인 탈이온수가 보다 바람직하다.In addition, the etching composition according to an embodiment of the present invention may contain a residual amount of water such that the total weight of the composition is 100% by weight. In the present invention, the water is not particularly limited, but deionized water is preferable, and deionized water having a specific resistance value of 18 M OMEGA. Or more is more preferable, showing the degree of removal of ions in water.
본 발명의 일 실시형태에 따른 식각 조성물은 상기한 성분들 이외에도, 당해 기술분야에서 일반적으로 사용되는 첨가제, 예를 들어 금속 이온 봉쇄제, 부식 방지제 등을 추가로 포함할 수 있다.In addition to the above-mentioned components, the etching composition according to an embodiment of the present invention may further include additives commonly used in the art, for example, sequestering agents, corrosion inhibitors, and the like.
본 발명의 일 실시형태에 따른 식각 조성물에 사용되는 상기 성분들은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 반도체 공정용의 순도를 가지는 것이 바람직하다.The components used in the etching composition according to one embodiment of the present invention can be prepared by a conventionally known method and preferably have purity for semiconductor processing.
본 발명의 일 실시형태에 따른 식각 조성물은 구리계 금속막의 식각 시에 하부에 위치하는 산화물층에 데미지를 주지 않으면서도 식각 균일성 및 직진성이 우수한 양호한 식각 프로파일을 제공할 수 있다. 또한, 본 발명의 일 실시형태에 따른 식각 조성물은 식각 후 금속막의 잔사가 남지 않아 전기적인 쇼트, 배선의 불량 및 휘도의 감소 등을 방지할 수 있다. 따라서, 본 발명의 일 실시형태에 따른 식각 조성물은 대화면 및/또는 고휘도의 회로가 구현되는 박막 트랜지스터 어레이 기판, 특히 산화물 반도체층을 포함하는 박막 트랜지스터 어레이 기판의 제조시에 매우 유용하게 사용될 수 있다.The etching composition according to one embodiment of the present invention can provide a good etching profile with excellent etching uniformity and straightness without damaging the underlying oxide layer when etching the copper based metal film. In addition, the etching composition according to an embodiment of the present invention can prevent electrical shorts, defective wiring, reduction in luminance, and the like because no residue of the metal film remains after the etching. Accordingly, the etching composition according to one embodiment of the present invention can be very usefully used in the manufacture of thin film transistor array substrates, in particular thin film transistor array substrates comprising oxide semiconductor layers, on which large-scale and / or high-brightness circuits are implemented.
본 발명의 일 실시형태는 상술한 식각 조성물을 이용하여 형성된 구리계 금속 배선에 관한 것이다.One embodiment of the present invention relates to a copper-based metal wiring formed using the above-described etching composition.
본 발명의 일 실시형태에 따른 구리계 금속 배선은 상술한 식각 조성물을 이용하여 당해 분야에 통상적으로 알려진 식각 공정, 예컨대 기판상에 금속 산화물막을 형성하는 단계; 상기 금속 산화물막 상에 구리계 금속막을 형성하는 단계; 상기 구리계 금속막 상에 포토레지스트 막을 형성한 후 패턴화하는 단계; 및 상술한 식각 조성물을 이용하여 상기 구리계 금속막을 식각하는 단계를 포함하는 식각 공정을 수행함으로써 제조될 수 있다.The copper-based metal wiring according to an embodiment of the present invention includes the steps of forming a metal oxide film on an etching process commonly known in the art, for example, using the above-described etching composition; Forming a copper-based metal film on the metal oxide film; Forming a photoresist film on the copper-based metal film and patterning the copper-based metal film; And etching the copper based metal film using the etching composition as described above.
본 발명의 일 실시형태는 상술한 구리계 금속 배선을 포함하는 표시장치용 어레이 기판에 관한 것이다. 일례로, 본 발명의 표시장치용 어레이 기판은 박막트랜지스터(thin film transistor) 어레이 기판일 수 있으며, 특히 산화물 반도체층을 포함하는 박막 트랜지스터 어레이 기판일 수 있다.One embodiment of the present invention relates to an array substrate for a display device including the copper-based metal interconnection described above. For example, the array substrate for a display device of the present invention may be a thin film transistor array substrate, and in particular, may be a thin film transistor array substrate including an oxide semiconductor layer.
본 발명의 일 실시형태에 따른 표시장치용 어레이 기판은 당해 분야의 통상적인 공정, 예컨대 a) 기판 상에 게이트 전극을 형성하는 단계; b) 상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 반도체층(금속 산화물막)을 형성하는 단계; d) 상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 공정에 있어서, 상기 d) 단계에서 반도체층 상에 구리계 금속막을 형성하고 상술한 식각 조성물로 상기 구리계 금속막을 식각하여 각각의 전극을 형성함으로써 제조될 수 있다.An array substrate for a display device according to an embodiment of the present invention may be manufactured by a conventional process in the art, for example, a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer (metal oxide film) on the gate insulating layer; d) forming a source / drain electrode on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode. In the step d), a copper-based metal film is formed on the semiconductor layer and the copper-based metal film is etched with the etching composition described above, Can be produced by forming an electrode.
상기 표시장치는 액정표시장치 또는 OLED 등일 수 있으나 이에 한정하지 않으며, 본 발명의 식각액 조성물은 식각 시 몰리브덴 잔사를 발생시키지 않으므로 전기적인 쇼트나 배선의 불량 문제가 없어 대화면, 고휘도의 회로가 구현되는 표시장치용 어레이 기판의 제조 시에 유용하게 사용될 수 있다.The display device may be a liquid crystal display device, an OLED or the like, but the present invention is not limited thereto. Since the etchant composition of the present invention does not generate molybdenum residue during etching, there is no problem of electrical shorts and wiring problems, It can be usefully used in manufacturing an array substrate for an apparatus.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
실시예Example 1 내지 3 및 1 to 3 and 비교예Comparative Example 1 내지 3: 1 to 3:
하기 표 1에 나타낸 바와 같이 각 성분들을 혼합하고, 전체 100 중량%가 되도록 잔량의 물을 추가하여 식각 조성물 6㎏을 제조하였다(단위: 중량%).As shown in Table 1 below, the components were mixed and the remaining amount of water was added to the total amount of 100 wt% to prepare 6 kg of the etching composition (unit: wt%).
(H2O2)Hydrogen peroxide
(H 2 O 2 )
(IDA)A compound having a nitrogen atom and a carboxyl group
(IDA)
(NHP)phosphate
(NHP)
ATZ: 5-아미노테트라졸(5-aminotetrazole)ATZ: 5-aminotetrazole
IDA: 이미노디아세트산(iminodiacetic acid)IDA: iminodiacetic acid
NHP: 제1인산나트륨(sodium dihydrogenphosphate)NHP: sodium dihydrogenphosphate
TEG: 트리에틸렌글리콜(triethyleneglycol)TEG: triethyleneglycol
실험예Experimental Example 1: One:
제조된 식각 조성물의 식각 성능을 평가하기 위하여, 유리기판(100mm×100mm) 상에 금속 산화물막(IGZO)을 증착시키고, 상기 막 상에 Cu/Mo-Nb 3500Å/300Å 이중막을 순차적으로 형성한 다음, 포토리소그래피 공정을 진행하여 패턴을 형성시켰다.In order to evaluate the etching performance of the etched composition, a metal oxide film (IGZO) was deposited on a glass substrate (100 mm x 100 mm), a Cu / Mo-Nb 3500 Å / 300 Å double film was sequentially formed on the film , A photolithography process was performed to form a pattern.
이때, 식각 공정은 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 식각 조성물의 온도는 약 30℃ 내외로 하였다. 식각 시간은 식각 온도에 따라서 다를 수 있으나, 통상 110초 정도로 진행하였다.At this time, an etching equipment (model name: ETCHER (TFT), manufactured by SEMES) was used for the etching process, and the temperature of the etching composition was about 30 캜 during the etching process. The etching time may vary depending on the etching temperature, but is usually about 110 seconds.
(1) (One) 식각Etching 프로파일 profile 및 직진성And straightness
식각 후, Cu/Mo-Nb 막의 식각 단면을 SEM(S-4700, Hitachi사)을 사용하여 관찰하고, 다음과 같은 평가 기준으로 식각 프로파일 및 직진성을 평가하였다.After the etching, the etching profile of the Cu / Mo-Nb film was observed using SEM (S-4700, Hitachi) and the etching profile and straightness were evaluated according to the following evaluation criteria.
<평가 기준><Evaluation Criteria>
○: 좋음○: Good
△: 보통△: Normal
×: 나쁨Poor: Poor
(2) 몰리브덴 (2) Molybdenum 합금막Alloy film 잔사Residue
식각 후, Mo-Nb 막의 잔사 발생 여부를 관찰하였다.After etching, the presence of Mo-Nb film residue was observed.
(3) 금속 (3) Metals 산화물막Oxide film 데미지damage
식각 후, 금속 산화물막(IGZO)의 표면을 관찰하여 데미지 발생 여부를 관찰하였다.After the etching, the surface of the metal oxide film (IGZO) was observed to observe whether or not the damage occurred.
(4) 발열 특성(4) Thermal properties
식각액에 Cu 이온을 4000ppm의 농도로 용해시킨 후 발열 발생 여부 및 발생 시간을 관찰하였다.After dissolving Cu ions in the etching solution at a concentration of 4000 ppm, the occurrence of fever and the occurrence time were observed.
<평가 기준><Evaluation Criteria>
○: 발열이 발생하지 않음○: No heat generated
△: 120 시간까지 발열 없음△: No heat up to 120 hours
×: 72 시간 이내 발열 발생×: Heat generated within 72 hours
측정된 식각 물성에 대한 결과를 하기 표 2에 나타내었다.The results of the measured etch properties are shown in Table 2 below.
상기 표 2에서 볼 수 있는 바와 같이, 질산 금속염을 포함하는 본 발명에 따른 실시예 1 내지 3의 식각 조성물은 산화물층에 데미지를 주지 않으면서도 양호한 식각 프로파일 및 직진성을 제공할 뿐만 아니라 식각 후 금속막의 잔사가 남지 않는 것을 확인하였다. 특히, 다가알코올형 계면활성제를 추가로 포함하는 실시예 1 및 3의 식각 조성물은 발열 특성도 우수하였다. 반면, 질산 금속염을 포함하지 않는 비교예 1 내지 3의 식각 조성물은 산화물층에 데미지를 주거나 식각 후 금속막의 잔사가 남는 것을 확인하였다.As can be seen in Table 2 above, the etching compositions of Examples 1 to 3 according to the present invention including metal nitrate not only provide a good etching profile and straightness without damaging the oxide layer, It was confirmed that no residue remained. In particular, the etching compositions of Examples 1 and 3, which further contained a polyhydric alcohol type surfactant, were excellent in heat generation characteristics. On the other hand, it was confirmed that the etching compositions of Comparative Examples 1 to 3, which did not contain a nitrate metal salt, gave damage to the oxide layer or remained a metal film residue after etching.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.
Claims (9)
상기 질산염 화합물은 질산 금속염을 포함하는 구리계 금속막용 식각 조성물.A water-soluble compound having a nitrogen atom and a carboxyl group, a phosphate compound and a nitrate compound,
Wherein the nitrate compound includes a nitrate metal salt.
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| KR20140108795A (en) * | 2013-02-28 | 2014-09-15 | 동우 화인켐 주식회사 | Echaing composition for copper-based metal layer and multiful layer of copper-based metal layer and metal oxide layer and method of preparing metal line |
| KR20170068328A (en) | 2015-12-09 | 2017-06-19 | 솔브레인 주식회사 | Etchant composition, and method for etching |
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| KR20140108795A (en) * | 2013-02-28 | 2014-09-15 | 동우 화인켐 주식회사 | Echaing composition for copper-based metal layer and multiful layer of copper-based metal layer and metal oxide layer and method of preparing metal line |
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