TWI615508B - Etchant composition for a cu-based metal film, manufacturing method of an array substrate for liquid crystal display and array substrate for a liqouid crystal display - Google Patents
Etchant composition for a cu-based metal film, manufacturing method of an array substrate for liquid crystal display and array substrate for a liqouid crystal display Download PDFInfo
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- TWI615508B TWI615508B TW103135696A TW103135696A TWI615508B TW I615508 B TWI615508 B TW I615508B TW 103135696 A TW103135696 A TW 103135696A TW 103135696 A TW103135696 A TW 103135696A TW I615508 B TWI615508 B TW I615508B
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- 239000000203 mixture Substances 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 title 1
- 238000005530 etching Methods 0.000 claims abstract description 79
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 sulfate compound Chemical class 0.000 claims abstract description 23
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims description 108
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 claims 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 152
- 239000010410 layer Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 6
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 235000010599 Verbascum thapsus Nutrition 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
- G02F1/136277—Active matrix addressed cells formed on a semiconductor substrate, e.g. of silicon
-
- 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
-
- 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
-
- 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
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- 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
- H01L27/1259—Multistep manufacturing methods
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Thin Film Transistor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
一種製造液晶顯示器用陣列基板的方法，該方法包括：a)在基板上形成柵線；b)在具有柵線的基板上形成柵絕緣層；c)在柵絕緣層上形成半導體層；d)在半導體層上形成源極和漏極；以及e)形成與漏極連接的像素電極，其中，a)或d)步驟包括：在基板或半導體層上形成Cu基金屬膜，和藉由使用蝕刻劑組合物蝕刻Cu基金屬膜來形成柵線或源極和漏極，並且蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物，基於組合物的總重量，包括：5~25重量%的過氧化氫(H2O2)；0.1~5重量%的亞磷酸；0.01~1.0重量%的含氟化合物；0.1~5重量%的唑化合物；0.1~5重量%的在分子中具有N原子和羧基的水溶性化合物；0.1~5重量%的硫酸鹽化合物；以及餘量的水，以使得組合物的總重量為100重量%。 A method of manufacturing an array substrate for a liquid crystal display, the method comprising: a) forming a gate line on the substrate; b) forming a gate insulating layer on the substrate having the gate line; c) forming a semiconductor layer on the gate insulating layer; d) Forming a source electrode and a drain electrode on a semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein the steps a) or d) include: forming a Cu-based metal film on the substrate or the semiconductor layer, and by using etching The etchant composition etches a Cu-based metal film to form gate lines or source and drain electrodes, and the etchant composition is an etchant composition for a Cu-based metal film, based on the total weight of the composition, including: 5 to 25 weight % Hydrogen peroxide (H 2 O 2 ); 0.1 to 5% by weight of phosphorous acid; 0.01 to 1.0% by weight of fluorinated compounds; 0.1 to 5% by weight of azole compounds; 0.1 to 5% by weight in the molecule has A water-soluble compound of N atom and carboxyl group; a sulfate compound of 0.1 to 5% by weight; and the balance of water so that the total weight of the composition is 100% by weight.
Description
本申請主張2013年11月4日提交的韓國專利申請KR 10-2013-0132820的權益，在此將其全文藉由引用的方式併入本申請中。 This application claims the benefit of Korean Patent Application KR 10-2013-0132820 filed on November 4, 2013, the entire contents of which are hereby incorporated by reference into this application.
本發明係關於一種液晶顯示器用陣列基板的製造方法。 The present invention relates to a method for manufacturing an array substrate for a liquid crystal display.
在半導體裝置中，在基板上形成金屬佈線的步驟通常包括：使用濺射等形成金屬膜、塗覆光刻膠、進行曝光和顯影以便在選擇性區域上形成光刻膠，以及進行蝕刻，其中，在其每個單獨的步驟之前或之後進行清洗步驟。蝕刻步驟是使用光刻膠作為掩模來使得金屬膜能夠留在選擇性區域的步驟，並且蝕刻步驟通常包括：使用等離子體等的乾法蝕刻或者使用蝕刻劑組合物的濕法蝕刻。 In a semiconductor device, the steps of forming a metal wiring on a substrate generally include forming a metal film using sputtering or the like, coating a photoresist, performing exposure and development to form a photoresist on a selective area, and performing etching, wherein , Before or after each of its individual steps. The etching step is a step of using a photoresist as a mask to enable the metal film to remain in a selective region, and the etching step generally includes: dry etching using plasma or the like or wet etching using an etchant composition.
通常，對於柵線和資料線的材料，所使用的是包括導電性良好且電阻低的銅的銅膜層或銅合金膜層或者與上述層的介面黏合性良好的金屬氧化物層。 Generally, as the material of the gate line and the data line, a copper film layer or a copper alloy film layer including copper having good conductivity and low resistance, or a metal oxide layer having good interface adhesion with the above-mentioned layers is used.
在這點上，韓國專利申請公開10-2007-0055259公開 了一種用於Cu基金屬膜的蝕刻劑組合物，該組合物包括用於蝕刻銅-鉬合金膜層的過氧化氫、有機酸、磷酸鹽化合物等。 In this regard, Korean Patent Application Publication No. 10-2007-0055259 is published An etchant composition for a Cu-based metal film is provided. The composition includes hydrogen peroxide, an organic acid, a phosphate compound, and the like for etching a copper-molybdenum alloy film layer.
然而，如果蝕刻劑組合物被應用於Cu基金屬膜的厚膜，那麼該組合物因由磷酸二氫鹽(phosphate monobasic)引起的高錐度而可能在隨後的步驟中出現缺陷問題。 However, if the etchant composition is applied to a thick film of a Cu-based metal film, the composition may cause a defect problem in a subsequent step due to a high taper caused by a phosphate monobasic salt.
同時，韓國專利申請公開10-2010-0090538公開了一種用於Cu基金屬膜的蝕刻劑組合物，包括：過氧化氫(H2O2)、有機酸、磷酸鹽化合物等。 Meanwhile, Korean Patent Application Publication No. 10-2010-0090538 discloses an etchant composition for a Cu-based metal film, including: hydrogen peroxide (H 2 O 2 ), an organic acid, a phosphate compound, and the like.
當使用蝕刻劑組合物對銅-鉬膜層進行蝕刻時，形成了線性良好的錐形剖面。然而，當進行鉬-鈮(Mo-Nb)的鉬基金屬膜和Cu基金屬膜的批量蝕刻時，蝕刻速率變得緩慢，鉬-鈮(Mo-Nb)的鉬基金屬膜未被蝕刻，或者產生了殘留物，因而蝕刻性能不好。 When the copper-molybdenum film layer is etched using the etchant composition, a tapered cross section with good linearity is formed. However, when batch etching of a molybdenum-based metal film of Mo-Nb and a Cu-based metal film is performed, the etching rate becomes slow, and the molybdenum-based metal film of Mo-Nb is not etched. Or, a residue is generated, and thus the etching performance is not good.
(專利文獻1)韓國專利申請公開10-2007-0055259 A。 (Patent Document 1) Korean Patent Application Publication 10-2007-0055259 A.
(專利文獻2)韓國專利申請公開10-2010-0090538 A。 (Patent Document 2) Korean Patent Application Publication No. 10-2010-0090538 A.
為了解決上述問題，本發明的一個目的是提供一種製造由Cu基金屬膜組成的液晶顯示器用陣列基板的方法。 In order to solve the above problems, an object of the present invention is to provide a method for manufacturing an array substrate for a liquid crystal display composed of a Cu-based metal film.
為了解決上述問題，本發明的另一目的是使用本發明的用於Cu基金屬膜的蝕刻劑組合物來進行Cu基金屬膜的批量蝕刻。 In order to solve the above problems, another object of the present invention is to perform batch etching of a Cu-based metal film using the etchant composition for a Cu-based metal film of the present invention.
本發明的再一個目的是提供一種用於Cu基金屬膜的 蝕刻劑組合物以蝕刻多層膜而不產生殘留物。 It is still another object of the present invention to provide a Cu-based metal film. The etchant composition is used to etch a multilayer film without generating a residue.
為了達到上述目的，本發明提供了一種製造液晶顯示器用陣列基板的方法，該方法包括：a)在基板上形成柵線(gate wiring)；b)在具有該柵線的該基板上形成柵絕緣層；c)在該柵絕緣層上形成半導體層；d)在該半導體層上形成源極和漏極；以及e)形成與該漏極連接的像素電極，其中，a)或d)步驟包括：在該基板或該半導體層上形成Cu基金屬膜，以及藉由使用蝕刻劑組合物蝕刻該Cu基金屬膜來形成該柵線或該源極和該漏極，並且該蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物，基於該組合物的總重量，包括：5~25重量%的過氧化氫(H2O2)；0.1~5重量%的亞磷酸；0.01~1重量%的含氟化合物；0.1~5重量%的唑化合物；0.1~5重量%的在分子中具有N原子和羧基的水溶性化合物；0.1~5重量%的硫酸鹽化合物；以及餘量的水，以使得該組合物的總重量為100重量%。 In order to achieve the above object, the present invention provides a method for manufacturing an array substrate for a liquid crystal display, the method comprising: a) forming a gate wiring on a substrate; b) forming a gate insulation on the substrate having the gate line C) forming a semiconductor layer on the gate insulating layer; d) forming a source and a drain on the semiconductor layer; and e) forming a pixel electrode connected to the drain, wherein step a) or d) includes : Forming a Cu-based metal film on the substrate or the semiconductor layer, and forming the gate line or the source electrode and the drain electrode by etching the Cu-based metal film using an etchant composition, and the etchant composition is An etchant composition for a Cu-based metal film, based on the total weight of the composition, includes: 5 to 25% by weight of hydrogen peroxide (H 2 O 2 ); 0.1 to 5% by weight of phosphorous acid; 0.01 to 1 5% by weight of a fluorine-containing compound; 0.1 to 5% by weight of an azole compound; 0.1 to 5% by weight of a water-soluble compound having an N atom and a carboxyl group in a molecule; 0.1 to 5% by weight of a sulfate compound; and the balance of water So that the total weight of the composition is 100% by weight.
此外，本發明提供了一種用於Cu基金屬膜的蝕刻劑組合物，基於該組合物的總重量，包括：5~25重量%的過氧化氫(H2O2)；0.1~5重量%的亞磷酸；0.01~1重量%的 含氟化合物；0.1~5重量%的唑化合物；0.1~5重量%的在分子中具有N原子和羧基的水溶性化合物；0.1~5重量%的硫酸鹽化合物；以及餘量的水，以使得該組合物的總重量為100重量%。 In addition, the present invention provides an etchant composition for a Cu-based metal film, based on the total weight of the composition, including: 5-25% by weight of hydrogen peroxide (H 2 O 2 ); 0.1-5% by weight Phosphorous acid; 0.01 ~ 1% by weight of fluorinated compounds; 0.1 ~ 5% by weight of azole compounds; 0.1 ~ 5% by weight of water-soluble compounds having N atoms and carboxyl groups in the molecule; 0.1 ~ 5% by weight of sulfate Compound; and the balance of water so that the total weight of the composition is 100% by weight.
此外，本發明提供了一種液晶顯示器用陣列基板，該液晶顯示器用陣列基板包括：選自柵線、源極和漏極中的至少一個，藉由使用用於Cu基金屬膜的蝕刻劑組合物來蝕刻該柵線、該源極和該漏極。 In addition, the present invention provides an array substrate for a liquid crystal display, the array substrate for a liquid crystal display including at least one selected from a gate line, a source electrode, and a drain electrode by using an etchant composition for a Cu-based metal film. To etch the gate line, the source and the drain.
用於Cu基金屬膜的蝕刻劑組合物具有以下優點：提高蝕刻速率、蝕刻其它金屬膜的多層膜而不產生殘留物，並且不斷地保持側蝕的變化量。 The etchant composition for a Cu-based metal film has the advantages of increasing the etching rate, etching a multilayer film of other metal films without generating a residue, and continuously maintaining a change amount of side etching.
以下結合附圖進行詳細描述，將更清楚地理解本發明的上述和其它目的、特徵和優點。 The above and other objects, features, and advantages of the present invention will be more clearly understood in the following detailed description with reference to the accompanying drawings.
圖1顯示當在300ppm的銅的條件下使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像；圖2顯示當在3000ppm的銅的條件下使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像；以及圖3顯示當在5000ppm的銅的條件下使用實施例3的用於Cu基金屬膜的蝕刻劑組合物時，蝕刻剖面的掃描電子顯微鏡(SEM)圖像。 FIG. 1 shows a scanning electron microscope (SEM) image of an etching cross section when the etchant composition for a Cu-based metal film of Example 3 is used under conditions of 300 ppm copper; FIG. 2 shows when When using the etchant composition for a Cu-based metal film of Example 3 under conditions, a scanning electron microscope (SEM) image of the etching cross section; and FIG. 3 shows that when using the copper of 5000 ppm under the conditions of Example 3, In the case of an etchant composition for a Cu-based metal film, a scanning electron microscope (SEM) image of a cross section is etched.
在下文中，將對本發明進行詳細描述。 Hereinafter, the present invention will be described in detail.
本發明涉及一種使用用於Cu基金屬膜的蝕刻劑組合物來製造液晶顯示器用陣列基板的方法，並且製造的方法如下。 The present invention relates to a method for manufacturing an array substrate for a liquid crystal display using an etchant composition for a Cu-based metal film, and the manufacturing method is as follows.
製造的方法包括：a)在基板上形成柵線；b)在具有柵線的基板上形成柵絕緣層；c)在柵絕緣層上形成半導體層；d)在半導體層上形成源極和漏極；以及e)形成與漏極連接的像素電極，其中，a)或d)步驟包括：在基板或半導體層上形成Cu基金屬膜，以及藉由使用蝕刻劑組合物蝕刻Cu基金屬膜來形成柵線或源極和漏極。 The manufacturing method includes: a) forming a gate line on the substrate; b) forming a gate insulating layer on the substrate having the gate line; c) forming a semiconductor layer on the gate insulating layer; d) forming a source and a drain on the semiconductor layer And e) forming a pixel electrode connected to the drain, wherein the steps a) or d) include: forming a Cu-based metal film on a substrate or a semiconductor layer, and etching the Cu-based metal film using an etchant composition to Form a gate line or source and drain.
蝕刻劑組合物是用於Cu基金屬膜的蝕刻劑組合物，基於組合物的總重量，包括：5~25重量%的過氧化氫(H2O2)；0.1~5重量%的亞磷酸；0.01~1重量%的含氟化合物；0.1~5重量%的唑化合物；0.1~5重量%的在分子中具有N原子和羧基的水溶性化合物；0.1~5重量%的硫酸鹽化合物；以及餘量的水，以使得該組合物的總重量為100重量%。 The etchant composition is an etchant composition for a Cu-based metal film. Based on the total weight of the composition, it includes: 5 to 25% by weight of hydrogen peroxide (H 2 O 2 ); 0.1 to 5% by weight of phosphorous acid. 0.01 to 1% by weight of a fluorine-containing compound; 0.1 to 5% by weight of an azole compound; 0.1 to 5% by weight of a water-soluble compound having an N atom and a carboxyl group in a molecule; 0.1 to 5% by weight of a sulfate compound; and The balance of water so that the total weight of the composition is 100% by weight.
上述液晶顯示器用陣列基板是薄膜電晶體(TFT)陣列基板。 The array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate.
另外，本發明涉及一種用於Cu基金屬膜的蝕刻劑組合物，基於該組合物的總重量，包括： 5~25重量%的過氧化氫(H2O2)；0.1~5重量%的亞磷酸；0.01~1重量%的含氟化合物；0.1~5重量%的唑化合物；0.1~5重量%的在分子中具有N原子和羧基的水溶性化合物；0.1~5重量%的硫酸鹽化合物；以及餘量的水，以使得該組合物的總重量為100重量%。 In addition, the present invention relates to an etchant composition for a Cu-based metal film, based on the total weight of the composition, including: 5 to 25% by weight of hydrogen peroxide (H 2 O 2 ); 0.1 to 5% by weight Phosphorous acid; 0.01 ~ 1% by weight of fluorinated compounds; 0.1 ~ 5% by weight of azole compounds; 0.1 ~ 5% by weight of water-soluble compounds having N atoms and carboxyl groups in the molecule; 0.1 ~ 5% by weight of sulfate compounds And the balance of water so that the total weight of the composition is 100% by weight.
根據上述組成，本發明的用於Cu基金屬膜的蝕刻劑組合物可以提高蝕刻速率並且可以蝕刻由銅和其它金屬層(例如，鉬-鈮(Mo-Nb)合金)構成的多層膜，而不產生殘留物。 According to the above composition, the etchant composition for a Cu-based metal film of the present invention can increase an etching rate and can etch a multilayer film composed of copper and other metal layers (for example, a molybdenum-niobium (Mo-Nb) alloy), and No residue is produced.
Cu基金屬膜包括作為組成的銅，並且包括銅或銅合金的單層膜以及多層膜，多層膜包括：選自銅膜和銅合金膜中的至少一種膜，以及選自鉬膜和鉬合金膜、鈦膜和鈦合金膜中的至少一種膜。上述合金膜包括氮化物或氧化物。 The Cu-based metal film includes copper as a composition, and includes a single-layer film of copper or a copper alloy, and a multilayer film including at least one film selected from a copper film and a copper alloy film, and a film selected from a molybdenum film and a molybdenum alloy film. At least one of a titanium film, a titanium film, and a titanium alloy film. The alloy film includes a nitride or an oxide.
多層膜的實例包括雙層膜或三層膜，諸如：銅/鉬膜、銅/鉬合金膜、銅合金/鉬合金膜、銅/鈦膜等。 Examples of the multilayer film include a double-layer film or a triple-layer film, such as: a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, a copper / titanium film, and the like.
銅/鉬膜是指包括鉬膜和形成在鉬膜上的銅膜的膜；銅/鉬合金膜是指包括鉬合金膜和形成在鉬合金膜上的銅膜的膜；銅合金/鉬合金膜是指包括鉬合金膜和在鉬合金膜上的銅合金膜的膜；並且，銅/鈦膜是指包括鈦膜和形成在鈦膜上的銅膜的膜。 The copper / molybdenum film refers to a film including a molybdenum film and a copper film formed on the molybdenum film; the copper / molybdenum alloy film refers to a film including a molybdenum alloy film and a copper film formed on the molybdenum alloy film; a copper alloy / molybdenum alloy The film refers to a film including a molybdenum alloy film and a copper alloy film on the molybdenum alloy film; and the copper / titanium film refers to a film including a titanium film and a copper film formed on the titanium film.
本發明的用於Cu基金屬膜的蝕刻劑組合物的Cu基金屬膜較佳是多層膜，包括：選自銅膜和銅合金膜中的至少一種膜和選自鉬膜和鉬合金膜中的至少一種膜。 The Cu-based metal film of the etchant composition for a Cu-based metal film of the present invention is preferably a multilayer film including at least one film selected from a copper film and a copper alloy film and a copper film selected from a molybdenum film and a molybdenum alloy film. At least one film.
此外，鉬合金膜較佳由選自鈦(Ti)、鈮(Nb)和鎢 (W)中的至少一種金屬和鉬(Mo)組成。 In addition, the molybdenum alloy film is preferably selected from titanium (Ti), niobium (Nb), and tungsten (W) is composed of at least one metal and molybdenum (Mo).
此外，本發明的用於Cu基金屬膜的蝕刻劑組合物可另外包括多元醇表面活性劑。 In addition, the etchant composition for a Cu-based metal film of the present invention may further include a polyol surfactant.
在下文中，將對本發明的用於Cu基金屬膜的蝕刻劑組合物進行詳細描述。 Hereinafter, the etchant composition for a Cu-based metal film of the present invention will be described in detail.
(A)過氧化氫(H2O2) (A) Hydrogen peroxide (H 2 O 2 )
包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內的過氧化氫(H2O2)是對Cu基金屬膜的蝕刻具有影響的主要氧化劑，該Cu基金屬膜是：包括鉬膜和形成在鉬膜上的銅膜的銅-鉬膜，或者包括鉬合金膜和形成在鉬合金膜上的銅膜的銅-鉬合金膜。 Hydrogen peroxide (H 2 O 2 ) included in the etchant composition for a Cu-based metal film of the present invention is a main oxidant that has an effect on the etching of a Cu-based metal film. The Cu-based metal film is: including molybdenum A copper-molybdenum film including a film and a copper film formed on a molybdenum film, or a copper-molybdenum alloy film including a molybdenum alloy film and a copper film formed on a molybdenum alloy film.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，過氧化氫(H2O2)被設定為5~25重量%，較佳為15~23重量%。 Based on the total weight of the etchant composition for the Cu-based metal film, hydrogen peroxide (H 2 O 2 ) is set to 5 to 25% by weight, preferably 15 to 23% by weight.
在低於5重量%的上述量的範圍中，蝕刻因缺乏Cu基金屬膜的蝕刻能力而可能不足。 In the range of the above-mentioned amount of less than 5% by weight, the etching may be insufficient due to the lack of the etching ability of the Cu-based metal film.
另外，在高於25重量%的上述量的範圍中，熱穩定性隨著銅離子的增加而大幅降低。 In addition, in the range of the above-mentioned amount higher than 25% by weight, the thermal stability is greatly reduced as the copper ion increases.
(B)亞磷酸(H3PO3) (B) Phosphorous acid (H 3 PO 3 )
包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內的亞磷酸藉由調節pH來增強蝕刻速率。如果亞磷酸未包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內，那麼蝕刻速率非常緩慢並且蝕刻剖面因蝕刻速率非常緩慢而可能是差的。 Phosphorous acid included in the etchant composition for a Cu-based metal film of the present invention enhances the etching rate by adjusting the pH. If phosphorous acid is not included in the etchant composition for a Cu-based metal film of the present invention, the etching rate is very slow and the etching profile may be poor due to the very slow etching rate.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，亞磷酸被設定為0.1~5重量%，較佳為0.3~3重量%。 Based on the total weight of the etchant composition used for the Cu-based metal film, phosphorous acid is set to 0.1 to 5% by weight, preferably 0.3 to 3% by weight.
在低於0.1重量%的上述量的範圍中，蝕刻剖面可能是差的。 In the range of the above amount less than 0.1% by weight, the etching profile may be poor.
另外，在高於5重量%的上述量的範圍中，可能出現銅或銅合金膜的蝕刻速率變得太快或者鉬或鉬合金膜的蝕刻速率變得太慢的問題。 In addition, in the range of the above amount of more than 5% by weight, there may occur a problem that the etching rate of the copper or copper alloy film becomes too fast or the etching rate of the molybdenum or molybdenum alloy film becomes too slow.
(C)含氟化合物 (C) fluorinated compounds
含氟化合物是指在水中解離時可產生氟化物離子的化合物。含氟化合物是對鉬合金膜的蝕刻速率具有影響的輔助氧化劑，並且它調節鉬合金膜的蝕刻速率。 A fluorine-containing compound refers to a compound that can generate fluoride ions when dissociated in water. The fluorine-containing compound is an auxiliary oxidant having an influence on the etching rate of the molybdenum alloy film, and it regulates the etching rate of the molybdenum alloy film.
含氟化合物並不沒有特別限制，只要它被用於相關領域，但是較佳選自HF、NaF、NH4F、NH4BF4、NH4FHF、NH4F2、KF、KHF2、AlF3和HBF4中的至少一種，並且更佳為NH4F2。 The fluorine-containing compound is not particularly limited as long as it is used in related fields, but is preferably selected from HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, NH 4 F 2 , KF, KHF 2 , AlF At least one of 3 and HBF 4 and more preferably NH 4 F 2 .
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，含氟化合物被設定為0.01~1重量%，較佳為0.1~1重量%。 The fluorine-containing compound is set to 0.01 to 1% by weight, preferably 0.1 to 1% by weight, based on the total weight of the etchant composition used for the Cu-based metal film.
在低於0.01重量%的上述量的範圍中，鉬合金膜的蝕刻速率變慢。 In the range of the above amount less than 0.01% by weight, the etching rate of the molybdenum alloy film becomes slow.
另外，在高於1重量%的上述量的範圍中，蝕刻剖面得到改善，而總蝕刻速率也得到改善，並且下層(n+a-Si：H，a-Si：G)的下切或蝕刻所造成的損害因而過大。 In addition, in the range of the above-mentioned amount higher than 1% by weight, the etching profile is improved, and the total etching rate is also improved, and the undercutting or etching of the lower layer (n + a-Si: H, a-Si: G) is performed. The damage caused was therefore excessive.
(D)唑化合物 (D) azole compounds
包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內 的唑化合物用於調節Cu基金屬膜的蝕刻速率、降低圖案的CD損失並且藉由減少蝕刻剖面變化來提高步驟餘量。 Included in the etchant composition for a Cu-based metal film of the present invention The azole compound is used to adjust the etching rate of the Cu-based metal film, reduce the CD loss of the pattern, and increase the step margin by reducing the variation of the etching profile.
上述唑化合物可包括，例如，吡咯、吡唑(pyrazol)、咪唑、三唑、四唑、五唑、噁唑(oxazole)、異噁唑(isoxazole)、噻唑、異噻唑等，並且它可單獨使用或以兩種或更多種的組合使用。在該唑化合物中，較佳為三唑或四唑化合物，並且更佳是選自3-胺基三唑、4-胺基三唑、5-甲基四唑和5-胺基四唑中的至少一種。 The above-mentioned azole compound may include, for example, pyrrole, pyrazol, imidazole, triazole, tetrazole, pentaazole, oxazole, isoxazole, thiazole, isothiazole, and the like, and it may be alone Used or in combination of two or more. Among the azole compounds, triazole or tetrazole compounds are preferred, and more preferably selected from the group consisting of 3-aminotriazole, 4-aminotriazole, 5-methyltetrazole, and 5-aminotetrazole. At least one.
如果在本發明中可以混合並使用3-胺基三唑、4-胺基三唑、5-甲基四唑和5-胺基四唑，那麼較佳根據步驟條件進行計算和應用混合比，因為根據待處理的片材數調節蝕刻速率並減少蝕刻剖面變化的能力隨著化合物不同而不同。 If 3-aminotriazole, 4-aminotriazole, 5-methyltetrazole, and 5-aminotetrazole can be mixed and used in the present invention, it is preferable to calculate and apply the mixing ratio according to the step conditions, This is because the ability to adjust the etch rate and reduce changes in the etch profile according to the number of sheets to be processed varies from compound to compound.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，唑化合物被設定為0.1~5重量%，較佳為0.5~1.5重量%。 The azole compound is set to 0.1 to 5% by weight, and preferably 0.5 to 1.5% by weight based on the total weight of the etchant composition used for the Cu-based metal film.
在低於0.1重量%的上述量的範圍中，CD損失可能過大。 In the range of the above amount less than 0.1% by weight, the CD loss may be excessive.
另外，在高於5重量%的上述量的範圍中，用於Cu基金屬膜的蝕刻速率太慢並且步驟時間因而延長，並且因金屬氧化物層的蝕刻速率的相對加速而可能產生下切。 In addition, in the range of the above amount of more than 5% by weight, the etching rate for the Cu-based metal film is too slow and the step time is thus prolonged, and undercut may occur due to the relative acceleration of the etching rate of the metal oxide layer.
(E)在分子中具有N原子和羧基的水溶性化合物 (E) Water-soluble compound having N atom and carboxyl group in the molecule
包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內的在分子中具有N原子和羧基的水溶性化合物防止在貯存蝕刻劑組合物時可能出現的過氧化氫的自分解，並且也防 止當蝕刻大量的基板時蝕刻特性的變化。 The water-soluble compound having N atoms and carboxyl groups in the molecule included in the etchant composition for a Cu-based metal film of the present invention prevents the self-decomposition of hydrogen peroxide that may occur when the etchant composition is stored, and also Prevent Stop changes in etching characteristics when a large number of substrates are etched.
通常地，在使用過氧化氫的蝕刻劑組合物的情況中，貯藏期因過氧化氫在貯存時的自分解並且它具有容器可能爆炸的危險因素而不長。 Generally, in the case of an etchant composition using hydrogen peroxide, the storage period is not long due to the self-decomposition of hydrogen peroxide during storage and it has a risk factor that a container may explode.
然而，如果包含了在分子中具有N原子和羧基的水溶性化合物，那麼長的貯存期和穩定性因過氧化氫的分解率下降接近10倍而可以得到保證。 However, if a water-soluble compound having an N atom and a carboxyl group in the molecule is included, a long storage period and stability can be ensured because the decomposition rate of hydrogen peroxide is reduced by nearly 10 times.
具體地，在銅層的情況中，如果銅離子被大量地保留在蝕刻劑組合物中，那麼形成鈍化，並且在如燒焦的氧化後而不能進一步蝕刻。然而，這可藉由添加上述化合物進行防止。 Specifically, in the case of a copper layer, if copper ions are largely retained in the etchant composition, passivation is formed, and cannot be further etched after oxidation such as charring. However, this can be prevented by adding the aforementioned compounds.
在分子中具有N原子和羧基的水溶性化合物可選自丙胺酸、胺基丁酸、麩胺酸、甘胺酸、亞胺基二乙酸、乙二胺四乙酸、胺三乙酸(nitrilotriacetic acid)和肌胺酸。在這些中，較佳為亞胺基二乙酸。 The water-soluble compound having an N atom and a carboxyl group in the molecule may be selected from alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ethylenediaminetetraacetic acid, and nitrilotriacetic acid And creatine. Among these, imine diacetic acid is preferable.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，在分子中具有N原子和羧基的水溶性化合物被設定為0.1~5重量%，較佳為1.0~3重量%。 The water-soluble compound having N atoms and carboxyl groups in the molecule is set to 0.1 to 5% by weight, preferably 1.0 to 3% by weight, based on the total weight of the etchant composition used for the Cu-based metal film.
在低於0.1重量%的上述量的範圍中，因在蝕刻大量的基板(約500片)之後形成鈍化而難以得到足夠的步驟餘量。 In the range of less than 0.1% by weight, it is difficult to obtain a sufficient step margin because passivation is formed after etching a large number of substrates (about 500 pieces).
另外，在高於5重量%的上述量的範圍中，在銅-鉬膜或銅-鉬合金膜的情況中，因鉬膜或鉬合金膜的蝕刻速率緩慢而可能出現對鉬膜或鉬合金膜產生殘留物的問題。 In addition, in the range of the above amount of more than 5% by weight, in the case of a copper-molybdenum film or a copper-molybdenum alloy film, the molybdenum film or molybdenum alloy film may appear due to the slow etching rate of the molybdenum film or molybdenum alloy film. The problem of film residues.
(F)硫酸鹽化合物 (F) Sulfate compounds
包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內的硫酸鹽化合物調節上部Cu膜的錐度並調節包括Cu的膜的蝕刻速率，因而它可以調節所需的側蝕。 The sulfate compound included in the etchant composition for a Cu-based metal film of the present invention adjusts the taper of the upper Cu film and adjusts the etching rate of the film including Cu, so it can adjust the required side etching.
如果硫酸鹽化合物未包括在用於Cu基金屬膜的蝕刻劑組合物內，那麼因蝕刻速率緩慢而可能出現製造性能變差的問題。 If the sulfate compound is not included in the etchant composition for a Cu-based metal film, a problem that the manufacturing performance may deteriorate due to the slow etching rate may occur.
硫酸鹽化合物並沒有特別限制，只要它選自一個或兩個氫被銨、鹼金屬或鹼土金屬取代的硫酸鹽，並且較佳是選自硫酸氫銨、硫酸氫鈉、硫酸氫鉀、硫酸銨、硫酸鈉和硫酸鉀，並且更佳為硫酸鈉和硫酸銨。 The sulfate compound is not particularly limited as long as it is selected from sulfates in which one or two hydrogens are replaced by ammonium, alkali metal or alkaline earth metal, and is preferably selected from ammonium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium sulfate , Sodium sulfate and potassium sulfate, and more preferably sodium sulfate and ammonium sulfate.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，硫酸鹽化合物被設定為0.1~5重量%，較佳為0.5~3重量%。 Based on the total weight of the etchant composition for the Cu-based metal film, the sulfate compound is set to 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
在低於0.1重量%的上述量的範圍中，製造性能因蝕刻速率緩慢而變差。 In the range of the above-mentioned amount of less than 0.1% by weight, the manufacturing performance is deteriorated due to the slow etching rate.
另外，在高於5.0重量%的上述量的範圍中，因部分過度蝕刻而可能出現蝕刻剖面變差的問題。 In addition, in the range of the above-mentioned amount of more than 5.0% by weight, a problem that the etching cross section is deteriorated due to partial over-etching may occur.
(G)水 (G) Water
根據本發明的用於Cu基金屬膜的蝕刻劑組合物的水以餘量的方式使用，使得用於Cu基金屬膜的蝕刻劑組合物的總重量變為100重量%。 The water of the etchant composition for a Cu-based metal film according to the present invention is used in a balance manner so that the total weight of the etchant composition for a Cu-based metal film becomes 100% by weight.
水並沒有特別限制，但較佳包括去離子水(DIW)。特別有用的是電阻率(即，從水中除去離子的程度)為至少18MΩ．cm的去離子水。 Water is not particularly limited, but preferably includes deionized water (DIW). Particularly useful is a resistivity (ie, the extent to which ions are removed from water) of at least 18 MΩ. cm of deionized water.
(H)多元醇表面活性劑 (H) Polyol surfactant
可額外地包括在本發明的用於Cu基金屬膜的蝕刻劑組合物內的多元醇表面活性劑用於藉由降低表面張力來提高蝕刻的均勻性。 The polyol surfactant, which may be additionally included in the etchant composition for a Cu-based metal film of the present invention, is used to improve the uniformity of etching by reducing the surface tension.
另外，多元醇表面活性劑藉由在蝕刻Cu膜之後包封溶解在蝕刻劑組合物中的銅離子來抑制過氧化氫的分解反應，並且因而抑制銅離子的活性。 In addition, the polyol surfactant suppresses the decomposition reaction of hydrogen peroxide by encapsulating the copper ions dissolved in the etchant composition after etching the Cu film, and thus suppresses the activity of the copper ions.
當如上抑制銅離子的活性時，能夠在使用蝕刻劑組合物期間穩定地繼續進行步驟。 When the activity of the copper ion is suppressed as described above, it is possible to continue the step stably during the use of the etchant composition.
對於多元醇表面活性劑，可較佳選自甘油、三乙二醇和聚乙二醇中的至少一種。在這些中，較佳三乙二醇。 For the polyol surfactant, at least one selected from glycerin, triethylene glycol, and polyethylene glycol may be preferably used. Among these, triethylene glycol is preferred.
基於用於Cu基金屬膜的蝕刻劑組合物的總重量，多元醇表面活性劑被設定為0.001~5重量%，較佳為0.1~3重量%。 The polyol surfactant is set to 0.001 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the etchant composition used for the Cu-based metal film.
在低於0.001重量%的上述量的範圍中，可能出現蝕刻均勻度降低和過氧化氫的分解加速的問題。 In the range of the above-mentioned amount of less than 0.001% by weight, problems may occur in that etching uniformity is reduced and decomposition of hydrogen peroxide is accelerated.
另外，在高於5重量%的上述量的範圍中，可能出現生成大量氣泡的不利。 In addition, in the range of the above-mentioned amount of more than 5% by weight, the disadvantage of generating a large number of bubbles may occur.
本發明的用於Cu基金屬膜的蝕刻劑組合物可包括除了上述成分以外的添加劑，並且該添加劑可包括金屬離子封閉劑(metal ion containment)、腐蝕抑制劑等。 The etchant composition for a Cu-based metal film of the present invention may include additives other than the above-mentioned components, and the additives may include a metal ion containment, a corrosion inhibitor, and the like.
本發明中使用的用於Cu基金屬膜的蝕刻劑組合物的組成可藉由通常已知的方法製備，並且較佳用於Cu基金屬膜的蝕刻劑組合具有用於半導體加工的純度。 The composition of the etchant composition for a Cu-based metal film used in the present invention can be prepared by a generally known method, and the etchant combination preferably used for the Cu-based metal film has purity for semiconductor processing.
另外，本發明提供了一種液晶顯示器用陣列基板，液晶顯示器用陣列基板包括：柵線，源極和漏極中的至少一種，柵線，源極和漏極藉由使用上述用於Cu基金屬膜的蝕刻劑組合物進行蝕刻。 In addition, the present invention provides an array substrate for a liquid crystal display. The array substrate for a liquid crystal display includes at least one of a gate line, a source electrode, and a drain electrode. The gate line, the source electrode, and the drain electrode are used for the Cu-based metal. The film's etchant composition is etched.
在下面，藉由下面的實施例對本發明進行更詳細的描述，這些實施例用於說明而提出，並不應被理解為限制本發明。本發明的範圍已經示出在權利要求書中，並且，含有等同於權利要求書的記載和其範圍內的所有變型的含義。 In the following, the present invention is described in more detail by the following examples, which are provided for illustration and should not be construed as limiting the present invention. The scope of the present invention is set forth in the claims, and includes meanings equivalent to the description of the claims and all modifications within the scope.
<用於Cu基金屬膜的蝕刻劑組合物的製備> <Preparation of Etchant Composition for Cu-Based Metal Film>
實施例1至4和比較例1至4 Examples 1 to 4 and Comparative Examples 1 to 4
藉由使用下面的表1中所示的成分，製備180kg的實施例1至4和比較例1至4的用於Cu基金屬膜的蝕刻劑組合物。 By using the ingredients shown in Table 1 below, 180 kg of an etchant composition for a Cu-based metal film of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared.
ABF：二氟化銨 ABF: ammonium difluoride
5-ATZ：5-胺基四唑 5-ATZ: 5-aminotetrazole
IDA：亞胺基二乙酸 IDA: iminodiacetic acid
試驗例1：使用實施例1至4和比較例1至4的用於Cu基金屬膜的蝕刻劑組合物的蝕刻步驟 Test Example 1: Etching step using the etchant composition for a Cu-based metal film of Examples 1 to 4 and Comparative Examples 1 to 4
藉由使用實施例1至4和比較例1至4的用於Cu基金屬膜的各個蝕刻劑組合物來進行蝕刻步驟。使用噴霧型蝕刻機(ETCHER(TFT)，購自SEMES)，並且將蝕刻步驟中的用於Cu基金屬膜的蝕刻劑組合物的溫度設定為大約33℃。蝕刻的時間可隨著蝕刻的溫度不同而不同，並且LCD蝕刻步驟通常進行約30~80秒。使用SEM(S-4700，購自HITACHI)觀察蝕刻步驟中蝕刻的Cu基金屬膜的切割側和剖面。結果在下面的表2中給出。 The etching step is performed by using each of the etchant compositions for Cu-based metal films of Examples 1 to 4 and Comparative Examples 1 to 4. A spray type etching machine (ETCHER (TFT), available from SEMES) was used, and the temperature of the etchant composition for the Cu-based metal film in the etching step was set to about 33 ° C. The etching time may vary depending on the temperature of the etching, and the LCD etching step usually takes about 30 to 80 seconds. The cut side and cross section of the Cu-based metal film etched in the etching step were observed using an SEM (S-4700, available from HITACHI). The results are given in Table 2 below.
將Cu/Mo-Nb 3000/300Å薄膜基板用作蝕刻步驟中的Cu基金屬膜。 A Cu / Mo-Nb 3000 / 300Å thin film substrate was used as a Cu-based metal film in the etching step.
(○：良好，△：普通，X：不好，未蝕刻(Unetch)：不能蝕刻) (○: Good, △: Normal, X: Not good, Unetch: Unetchable)
實施例1至4中的用於Cu基金屬膜的蝕刻劑組合物都具有良好的蝕刻剖面和平直度，並且不產生鉬(Mo)和鈮(Nb)的殘留物。另外，待處理的片材數的變化量(側蝕的變化量)滿足±0.1μm的條件，並因而可以證實上述組合物具有優異的蝕刻性能。在實施例1至4中，實施例3的用於Cu基金屬膜的蝕刻劑組合物具有最好的蝕刻性能。 The etchant compositions for Cu-based metal films in Examples 1 to 4 all had good etching cross sections and flatness, and did not generate residues of molybdenum (Mo) and niobium (Nb). In addition, the amount of change in the number of sheets to be processed (amount of change in side etching) satisfies the condition of ± 0.1 μm, and thus it can be confirmed that the above composition has excellent etching performance. Among Examples 1 to 4, the etchant composition for a Cu-based metal film of Example 3 has the best etching performance.
然而，不包含亞磷酸的比較例1具有非常低的蝕刻速率，並因而引起未蝕刻。 However, Comparative Example 1 not containing phosphorous acid had a very low etching rate, and thus caused non-etching.
另外，在包含低於0.1重量%的亞磷酸的比較例3的情況中，待處理的片材的數量的變化量滿足0.1μm的條件，但蝕刻剖面和平直度因蝕刻速率非常緩慢而是正常的。 In addition, in the case of Comparative Example 3 containing less than 0.1% by weight of phosphorous acid, the amount of change in the number of sheets to be processed satisfies the condition of 0.1 μm, but the etching profile and flatness are normal because the etching rate is very slow. of.
在包含大於5重量%的亞磷酸的比較例4中，因過度的蝕刻速率而引起圖案出界。 In Comparative Example 4 containing more than 5% by weight of phosphorous acid, the pattern was out of boundary due to an excessive etching rate.
另外，在不包含硫酸鉀的比較例2的情況中，待處理的片材的數量的變化量滿足0.1μm的條件，但蝕刻剖面和平直度都正常，並因而比較例2的組合物不具有優異的蝕 刻性能。 In addition, in the case of Comparative Example 2 not containing potassium sulfate, the amount of change in the number of sheets to be treated satisfies the condition of 0.1 μm, but the etching profile and flatness are normal, and therefore the composition of Comparative Example 2 does not have Excellent eclipse Carved performance.
試驗例2：評價實施例3和比較例1至2的用於Cu基金屬膜的蝕刻劑組合物根據Cu濃度變化的蝕刻特性 Test Example 2: Evaluation of the etching characteristics of the etchant composition for a Cu-based metal film of Example 3 and Comparative Examples 1 to 2 according to a change in Cu concentration
使用實施例3和比較例1至2的用於Cu基金屬膜的蝕刻劑組合物評價根據Cu濃度的蝕刻特性。 The etchant composition for a Cu-based metal film of Example 3 and Comparative Examples 1 to 2 was used to evaluate the etching characteristics according to the Cu concentration.
將Cu/Mo-Nb 3000/300Å的薄膜基板用作蝕刻步驟中的Cu基金屬膜。 A thin film substrate of Cu / Mo-Nb 3000 / 300Å was used as the Cu-based metal film in the etching step.
測得根據Cu濃度變化的側蝕(μm)的變化量。側蝕是指蝕刻後測得的光刻膠的端部和下面金屬的端部之間的距離。如果側蝕的量變化，那麼因為當驅動TFT時信號傳輸速率變化而可能出現污點。因而，較佳最小化側蝕的變化量。 The amount of change in the side etch (μm) according to the change in Cu concentration was measured. Side etching is the distance between the end of the photoresist and the end of the underlying metal measured after etching. If the amount of side etching is changed, stains may occur because a signal transmission rate is changed when the TFT is driven. Therefore, it is preferable to minimize the amount of change in the side etch.
在此評價中，進行實驗以使得：具有±0.1μm的側蝕的變化量的蝕刻劑組合物能夠在蝕刻步驟中連續使用。 In this evaluation, an experiment was performed so that an etchant composition having a change amount of a side etch of ± 0.1 μm can be continuously used in the etching step.
結果在下面的表3中給出。 The results are given in Table 3 below.
實施例3，本發明的用於Cu基金屬膜的蝕刻劑組合物，即使在高的Cu濃度下也滿足±0.1μm的條件，因而具有優異的蝕刻性能。 In Example 3, the etchant composition for a Cu-based metal film of the present invention satisfies the condition of ± 0.1 μm even at a high Cu concentration, and thus has excellent etching performance.
然而，不包含亞磷酸的比較例1不能蝕刻。 However, Comparative Example 1 which does not contain phosphorous acid cannot be etched.
不包含硫酸鉀的比較例2能夠蝕刻，但是它隨著Cu濃度的增加而變得超過0.1μm的條件的範圍。 Comparative Example 2 not containing potassium sulfate was able to etch, but it became out of the range of the condition of 0.1 μm as the Cu concentration increased.
因此，本發明的用於Cu基金屬膜的蝕刻劑組合物具有優異的蝕刻剖面和平直度，並且也具有根據Cu濃度的變化而保持側蝕的變化量為恒定水準的優異性能。 Therefore, the etchant composition for a Cu-based metal film of the present invention has excellent etching cross-section and flatness, and also has excellent performance of maintaining a constant amount of change in the side etching according to a change in Cu concentration.
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| KR102310096B1 (en) * | 2015-12-03 | 2021-10-08 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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