TW201704537A - Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same - Google Patents
Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same Download PDFInfo
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- TW201704537A TW201704537A TW105104270A TW105104270A TW201704537A TW 201704537 A TW201704537 A TW 201704537A TW 105104270 A TW105104270 A TW 105104270A TW 105104270 A TW105104270 A TW 105104270A TW 201704537 A TW201704537 A TW 201704537A
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- Prior art keywords
- silver
- film
- etching
- transparent conductive
- weight
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 118
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 106
- 239000004332 silver Substances 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000000758 substrate Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 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
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims 1
- 229910001195 gallium oxide Inorganic materials 0.000 claims 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 239000004323 potassium nitrate Substances 0.000 claims 1
- 235000010333 potassium nitrate Nutrition 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 26
- 239000010408 film Substances 0.000 description 129
- 238000000034 method Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- GHIQFHXMXDVBQS-UHFFFAOYSA-N [In].[Sn]=O.[In] Chemical compound [In].[Sn]=O.[In] GHIQFHXMXDVBQS-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 239000002042 Silver nanowire Substances 0.000 description 1
- YRXWPCFZBSHSAU-UHFFFAOYSA-N [Ag].[Ag].[Te] Chemical compound [Ag].[Ag].[Te] YRXWPCFZBSHSAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Liquid Crystal (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
本發明涉及含銀(Ag)薄膜的蝕刻液組合物和使用了其的顯示裝置用陣列基板的製造方法。 The present invention relates to an etching liquid composition containing a silver (Ag) film and a method of manufacturing an array substrate for a display device using the same.
隨著進入真正的資訊化時代，對大量的資訊進行處理和顯示的顯示器領域急速地發展，相應地開發了多種平板顯示器而受到關注。 With the entry into the real information age, the field of displays that process and display a large amount of information has rapidly developed, and various flat panel displays have been developed accordingly.
作為這樣的平板顯示裝置的例子，可列舉液晶顯示裝置(Liquid Crystal Display device：LCD)、等離子體顯示裝置(Plasma Display Panel device：PDP)、場致發射顯示裝置(Field Emission Display device：FED)、有機發光元件(Organic Light Emitting Diodes：OLED)等。 Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display panel device (PDP), and a field emission display device (FED). Organic Light Emitting Diodes (OLED) and the like.
特別地，OLED由於由元件自身發光，同時即使用低電壓也能夠驅動，因此不僅已迅速地應用於可攜式裝置等的小型顯示器市場，而且根據向顯示器的大畫面化的 趨勢，目前正在進行向大型電視機等的商用化。伴隨顯示器的大畫面化，配線等延長，配線電阻增加，因此要求降低電阻、可以實現顯示裝置的大型化和高解析度的方法。 In particular, since the OLED is driven by the element itself and can be driven using a low voltage, it has not only been rapidly applied to a small display market such as a portable device, but also according to a large screen to the display. Trends are currently being commercialized for large TV sets and the like. With the increase in the size of the display, the wiring and the like are prolonged, and the wiring resistance is increased. Therefore, it is required to reduce the electric resistance and to increase the size and high resolution of the display device.
為了解決電阻的增加引起的信號延遲等的問題，有必要用具有盡可能低的比電阻的材料形成所述配線。作為這樣的努力的一環，致力於將具有比其他金屬低的比電阻和高的亮度、電導率的銀(Ag：比電阻約1.59μΩcm)膜、銀合金膜、或包含銀膜、銀合金膜的多層膜應用於濾色器的電極、配線和反射膜等、用於實現平板顯示裝置的大型化以及高解析度和低電力消耗等的努力，要求用於應用於這樣的材料的蝕刻液。 In order to solve the problem of signal delay or the like caused by an increase in resistance, it is necessary to form the wiring with a material having a specific resistance as low as possible. As part of such an effort, we are working on a silver (Ag: specific resistance of about 1.59 μΩcm) film, a silver alloy film, or a silver film or a silver alloy film having a specific resistance lower than that of other metals and a high luminance and electrical conductivity. The multilayer film is applied to an electrode, a wiring, a reflection film, and the like of a color filter, an operation for increasing the size of a flat panel display device, high resolution, and low power consumption, and an etching liquid for use in such a material is required.
將含銀(Ag)薄膜蒸鍍於基板的情況下，為了將其形成圖案、蝕刻，使用以往的蝕刻液的情況下，有時產生蝕刻不良、殘渣產生、工序時間延長等問題。另外，與其相反，將銀(Ag)過度地蝕刻，不均一地蝕刻，發生配線浮起或剝離現象，配線的側面輪廓可變得不良。因此，要求開發能夠解決這樣的問題的新的蝕刻液。 When a silver (Ag)-containing thin film is deposited on a substrate, in order to form a pattern and etch it, when a conventional etching liquid is used, problems such as etching failure, residue generation, and prolonged process time may occur. On the contrary, silver (Ag) is excessively etched, unevenly etched, and wiring floating or peeling occurs, and the side profile of the wiring can be deteriorated. Therefore, it is required to develop a new etching liquid capable of solving such a problem.
本發明為了解決所述的問題而完成，目的在於提供將銀(Ag)或銀合金的單一膜、或者包含所述單一膜和透明導電膜的多層膜蝕刻時極限尺寸偏差(CD bias)優異、不存在下部資料配線的損傷和殘渣的產生、顯示均一的蝕 刻特性的蝕刻液組合物。 The present invention has been made to solve the above problems, and an object thereof is to provide an excellent film thickness limit (CD bias) when etching a single film of silver (Ag) or a silver alloy or a multilayer film including the single film and the transparent conductive film. There is no damage to the underlying data wiring and the generation of residue, showing uniform etch An etching solution composition of the characteristics.
另外，本發明的目的在於提供使用所述蝕刻液組合物製造OLED、LCD等的顯示裝置用陣列基板的方法。 Further, an object of the present invention is to provide a method for producing an array substrate for a display device such as an OLED or an LCD using the etching liquid composition.
為了實現所述的目的，本發明提供含銀(Ag)薄膜的蝕刻液組合物，其特徵在於，相對於組合物的總重量，包含：磷酸(A)40~60重量%；硝酸(B)3~8重量%；醋酸(C)5~20重量%；磷酸鹽(D)0.1~3重量%；選自硝酸鹽(E)0.1~3重量%和醋酸鹽(F)0.1~3重量%中的1種以上的鹽；和脫離子水(G)餘量。 In order to achieve the object, the present invention provides an etchant composition containing a silver (Ag) film, characterized in that it comprises: 40 to 60% by weight of phosphoric acid (A), and nitric acid (B), based on the total weight of the composition. 3~8 wt%; acetic acid (C) 5-20 wt%; phosphate (D) 0.1-3 wt%; selected from nitrate (E) 0.1-3 wt% and acetate (F) 0.1-3 wt% One or more salts in the middle; and the balance of deionized water (G).
另外，本發明提供顯示裝置用陣列基板的製造方法，該顯示裝置用陣列基板的製造方法包括：a)在基板上形成柵極配線的步驟、b)在包含所述柵極配線的基板上形成柵極絕緣層的步驟、c)在所述柵極絕緣層上形成半導體層的步驟、d)在所述半導體層上形成源電極和漏電極的步驟、e)形成與所述漏電極連接的像素電極或反射膜的步驟，其特徵在於，所述e)步驟包含在基板上形成含銀(Ag) 薄膜，用本發明的含銀薄膜的蝕刻液組合物蝕刻，形成像素電極或反射膜的步驟。 Further, the present invention provides a method of manufacturing an array substrate for a display device, comprising: a) a step of forming a gate wiring on a substrate; b) forming a substrate on the substrate including the gate wiring a step of forming a gate insulating layer, c) a step of forming a semiconductor layer on the gate insulating layer, d) a step of forming a source electrode and a drain electrode on the semiconductor layer, and e) forming a connection with the drain electrode a step of a pixel electrode or a reflective film, wherein the step e) comprises forming silver (Ag) on the substrate The film is etched by the etchant composition containing the silver film of the present invention to form a pixel electrode or a reflective film.
進而，本發明提供用所述含銀(Ag)薄膜的蝕刻液組合物蝕刻了的配線。 Further, the present invention provides a wiring etched using the etchant composition containing the silver (Ag) film.
本發明的含銀(Ag)薄膜的蝕刻液組合物通過包含磷酸、硝酸、醋酸、磷酸鹽、硝酸鹽和/或醋酸鹽、和脫離子水，能夠提供在將含銀(Ag)薄膜蝕刻時極限尺寸偏差(CD bias)優異、不存在下部配線的損傷和蝕刻殘渣的產生、具有均一的蝕刻特性、蝕刻速度的控制容易的蝕刻液組合物。 The silver (Ag) film-containing etchant composition of the present invention can provide a silver (Ag) film during etching by containing phosphoric acid, nitric acid, acetic acid, phosphate, nitrate and/or acetate, and deionized water. An etchant composition which is excellent in limit deviation (CD bias), which does not cause damage of the lower wiring and generation of etching residue, and which has uniform etching characteristics and easy control of etching rate.
另外，本發明能夠提供使用所述蝕刻液組合物製造顯示裝置用陣列基板的方法。 Further, the present invention can provide a method of manufacturing an array substrate for a display device using the etching liquid composition.
圖1為用蝕刻液蝕刻時用於說明極限尺寸偏差(CD bias：光致抗蝕劑寬度-配線寬度、寬度差)的SEM照片。 Fig. 1 is a SEM photograph for explaining the limit dimensional deviation (CD bias: photoresist width - wiring width, width difference) when etching with an etching solution.
圖2為用蝕刻液蝕刻後測定了銀(Ag)殘渣產生的有/無的SEM照片。 Fig. 2 is a SEM photograph of the presence/absence of silver (Ag) residue measured after etching with an etching solution.
圖3為用蝕刻液蝕刻後測定了銀(Ag)再吸附發生的有/無的SEM照片。 Fig. 3 is a SEM photograph of the presence/absence of silver (Ag) re-adsorption after etching with an etching solution.
圖4為蝕刻液的蝕刻速度的評價中為了說明縱向的蝕刻速度而示出的圖。 FIG. 4 is a view for explaining the etching rate in the vertical direction in the evaluation of the etching rate of the etching solution.
本發明人為了提供對於含銀(Ag)薄膜具有優異的蝕刻特性、不產生殘渣和再吸附、蝕刻控制優異、不發生過剩的蝕刻的蝕刻液組合物，反復銳意努力，結果作為包含磷酸、硝酸、醋酸作為酸、包含磷酸鹽、硝酸鹽和/或醋酸鹽等的蝕刻液組合物完成了本發明。 The inventors of the present invention have made an effort to provide an etching liquid composition which has excellent etching characteristics, does not cause residue and re-adsorption, has excellent etching control, and does not cause excessive etching. The present invention has been completed by an acetic acid as an acid, an etching solution composition containing a phosphate, a nitrate, and/or an acetate.
本發明涉及含銀(Ag)薄膜的蝕刻液組合物，其特徵在於，相對於組合物的總重量，包含：磷酸(A)40~60重量%；硝酸(B)3~8重量%；醋酸(C)5~20重量%；磷酸鹽(D)0.1~3重量%；選自硝酸鹽(E)0.1~3重量%和醋酸鹽(F)0.1~3重量%中的1種以上的鹽；和脫離子水(G)餘量。 The present invention relates to an etchant composition containing a silver (Ag) film, characterized in that it comprises: 40 to 60% by weight of phosphoric acid (A); 3 to 8% by weight of nitric acid (B); acetic acid, based on the total weight of the composition (C) 5 to 20% by weight; phosphate (D) 0.1 to 3% by weight; one or more salts selected from the group consisting of nitrate (E) 0.1 to 3% by weight and acetate (F) 0.1 to 3% by weight ; and the deionized water (G) balance.
所述含銀(Ag)薄膜是在膜的構成成分中包含銀(Ag)、包括單一膜和二重膜以上的多層膜的概念。所述含銀(Ag)薄膜可列舉由銀(Ag)或銀合金構成的單一膜、或者由所述單一膜和透明導電膜構成的多層膜等，但並不限定於此。 The silver (Ag)-containing film is a concept in which silver (Ag) is included in a constituent component of the film, and a multilayer film including a single film or a double film or more is included. The silver (Ag)-containing thin film may be a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and the transparent conductive film, but is not limited thereto.
所述透明導電膜一般地是指如IZO和a-ITO那樣具有在可見光區域中透射率為約90%以上、電阻率為1×10-4Ωcm以下的特性的透明導電膜。為了透明導電膜為透明，一般地傳導電子必須少，為了電導率變大，傳導電子 必須多。即，透明導電膜的情況下，必須滿足這樣相反的2個條件。 The transparent conductive film generally has a transparent conductive film having a transmittance of about 90% or more and a specific resistance of 1 × 10 -4 Ωcm or less in the visible light region, such as IZO and a-ITO. In order for the transparent conductive film to be transparent, generally, electron conduction must be small, and in order to increase the electrical conductivity, it is necessary to conduct a large amount of electrons. That is, in the case of a transparent conductive film, it is necessary to satisfy the two conditions which are opposite.
在將IZO和ITO蒸鍍的方法中，一般地使用濺射(Sputtering)方法，與CVD(Chemical Vapor Deposition)方法相比，調節蒸鍍條件容易。另外，使用大型的基板製造的情況下，具有實現薄膜的厚度和薄膜特性的均一化容易的優點。採用濺射方法製造的情況下，存在使用氧化物靶或合金靶(alloy target)的2種方法，使用合金靶的情況下，具有蒸鍍速度快、靶壽命也長得很、可以實現靶製造的容易性和再利用的優點，但具有顯示對於工序變數敏感的特性變化的缺點。如果使用氧化物靶，能夠具有再現性地控制薄膜的化學計量比，但與合金靶相比，具有蒸鍍速度慢、蒸鍍中途可在靶中產生物理的龜裂、在靶中產生電弧的缺點。 In the method of depositing IZO and ITO, a sputtering method is generally used, and the vapor deposition conditions are easier to adjust than the CVD (Chemical Vapor Deposition) method. Further, in the case of using a large-sized substrate, it is advantageous in that the thickness of the film and the film characteristics are easily uniformized. In the case of production by a sputtering method, there are two methods using an oxide target or an alloy target. When an alloy target is used, the vapor deposition rate is fast, the target life is also long, and target production can be achieved. The ease of use and the advantages of reuse, but have the disadvantage of showing a change in characteristics that are sensitive to process variables. If an oxide target is used, the stoichiometric ratio of the film can be reproducibly controlled, but the vapor deposition rate is slower than that of the alloy target, physical cracking can occur in the target during vapor deposition, and an arc is generated in the target. Disadvantages.
採用濺射方法蒸鍍銦-主成分系氧化物的情況下，與O2反應，具有In2O3的形態，為了提高電導率，作為摻雜劑，能夠使用Ga、Ge、Si、Ti、Sb、Zr、Sn、和Zn等。本發明中的IZO和ITO分別意味著將In2O3與ZnO、In2O3與SnO2以適當比率混合的透明導電膜氧化物。 When the indium-main component oxide is deposited by a sputtering method, it reacts with O 2 to have a form of In 2 O 3 , and in order to increase the electrical conductivity, Ga, Ge, Si, Ti, and the dopant can be used. Sb, Zr, Sn, and Zn, and the like. The present invention is meant to IZO and ITO, respectively, In 2 O 3 and ZnO, In 2 O 3 and SnO in a suitable mixing ratio of the oxide transparent conductive film 2.
以下對構成本發明的含銀(Ag)薄膜的蝕刻液組合物的各成分進行說明。但是，本發明並不限定於這些成分。 Hereinafter, each component of the etching liquid composition constituting the silver (Ag) film of the present invention will be described. However, the present invention is not limited to these components.
(A)磷酸(A) phosphoric acid
本發明的含銀(Ag)薄膜的蝕刻液組合物中所 含的磷酸(H3PO4)是作為主氧化劑使用的成分，作為一例，起到將透明導電膜/銀(Ag)/透明導電膜等這樣的含銀薄膜氧化而濕式蝕刻的作用。 Phosphoric acid (H 3 PO 4 ) contained in the etching solution composition containing a silver (Ag) film of the present invention is a component used as a main oxidizing agent, and as an example, a transparent conductive film/silver (Ag)/transparent conductive is used. A silver-containing thin film such as a film is oxidized and wet-etched.
所述磷酸相對於本發明的含銀(Ag)薄膜的蝕刻液組合物的總重量，可含有40~60重量%，更優選地可含有50~60重量%。以不到40重量%含有所述磷酸的情況下，有時引起銀的蝕刻速度的下降和銀殘渣的產生導致的不良。相反，超過60重量%含有的情況下，有時帶來透明導電膜的蝕刻速度的下降，而銀的蝕刻速度過度地加速。因此，將其應用於銀或銀合金和透明導電膜的多層膜的情況下，由於上下部透明導電膜的尖端(Tip)的產生或過剩的蝕刻現象的產生，在後續工序中可誘發問題而不希望。 The phosphoric acid may be contained in an amount of 40 to 60% by weight, and more preferably 50 to 60% by weight based on the total weight of the etching solution composition containing the silver (Ag) film of the present invention. When the phosphoric acid is contained in an amount of less than 40% by weight, the etching rate of silver may be lowered and the silver residue may be defective. On the other hand, when it exceeds 60% by weight, the etching rate of the transparent conductive film may be lowered, and the etching rate of silver may be excessively accelerated. Therefore, in the case of applying it to a multilayer film of silver or a silver alloy and a transparent conductive film, problems may be induced in a subsequent process due to generation of a tip (Tip) of the upper and lower transparent conductive film or generation of an excessive etching phenomenon. do not wish.
(B)硝酸(B) nitric acid
本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的硝酸(HNO3)是作為輔助氧化劑使用的成分，作為一例，起到將透明導電膜/銀(Ag)/透明導電膜等這樣的含銀薄膜氧化而濕式蝕刻的作用。 The nitric acid (HNO 3 ) contained in the etching solution composition containing the silver (Ag) film of the present invention is a component used as an auxiliary oxidizing agent, and as an example, a transparent conductive film/silver (Ag)/transparent conductive film or the like is used. Such a silver-containing thin film is oxidized and wet-etched.
所述硝酸(B)相對於本發明的含銀(Ag)薄膜的蝕刻液組合物的總重量，可含有3~8重量%，更優選地可含有5~7重量%。所述硝酸的含量不到3重量%的情況下，發生銀(Ag)、銀合金(silver alloy)、或透明導電膜的蝕刻速度的下降，由此基板內的蝕刻均一性(uniformity)變得不良，因此發生洇滲。所述硝酸的含量超過8重量%的情況下，使上下部透明導電膜的蝕刻速度加速化，由於過 剩的蝕刻的發生，有時在後續工序中產生問題。 The nitric acid (B) may be contained in an amount of 3 to 8% by weight, and more preferably 5 to 7% by weight, based on the total weight of the etching solution composition containing the silver (Ag) film of the present invention. When the content of the nitric acid is less than 3% by weight, the etching rate of silver (Ag), a silver alloy, or a transparent conductive film is lowered, whereby the uniformity of etching in the substrate becomes Poor, so bleeding occurs. When the content of the nitric acid exceeds 8% by weight, the etching rate of the upper and lower transparent conductive films is accelerated, The occurrence of residual etching sometimes causes problems in subsequent processes.
(C)醋酸(C) Acetic acid
本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的醋酸(CH3COOH)是作為輔助氧化劑使用的成分，作為一例，起到將透明導電膜/銀(Ag)/透明導電膜等含銀薄膜氧化而濕式蝕刻的作用。 Acetic acid (CH 3 COOH) contained in the etching solution composition containing a silver (Ag) film of the present invention is a component used as an auxiliary oxidizing agent, and as an example, a transparent conductive film/silver (Ag)/transparent conductive film is used. The effect of the wet etching of the silver-containing thin film.
所述醋酸相對於本發明的含銀(Ag)薄膜的蝕刻液組合物的總重量，可以含有5~20重量%，更優選地可含有5~15重量%。所述醋酸的含量不到5重量%的情況下，存在由於基板內的蝕刻速度的不均一而發生洇滲的問題。相反，含量超過20重量%的情況下，發生泡的產生，這樣的泡在基板內存在的情況下，有時無法進行完全的蝕刻，在後續工序中引起問題。 The acetic acid may contain 5 to 20% by weight, and more preferably 5 to 15% by weight, based on the total weight of the etching solution composition containing the silver (Ag) film of the present invention. When the content of the acetic acid is less than 5% by weight, there is a problem that bleeding occurs due to unevenness in the etching rate in the substrate. On the other hand, when the content exceeds 20% by weight, generation of bubbles occurs, and when such bubbles are present in the substrate, complete etching may not be performed, which may cause problems in the subsequent steps.
(D)磷酸鹽(D) phosphate
本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的磷酸鹽使濕式蝕刻時對於薄膜的極限尺寸偏差(CD Bias)減小，調整蝕刻速度以致蝕刻均一地進行。作為所述磷酸鹽的具體例，可列舉磷酸二氫鈉(NaH2PO4)、磷酸氫二鈉(Na2HPO4)、磷酸三鈉(Na3PO4)、磷酸二氫鉀(KH2PO4)、磷酸氫二鉀(K2HPO4)、磷酸二氫銨((NH4)H2PO4)、磷酸氫二銨((NH4)2HPO4)、和磷酸銨((NH4)3PO4)等，但並不限定於這些，能夠使用從這些中選擇的1種以上。 The phosphate contained in the etching solution composition containing the silver (Ag) film of the present invention reduces the limit dimensional deviation (CD Bias) of the film during wet etching, and adjusts the etching rate so that etching proceeds uniformly. Specific examples of the phosphate include sodium dihydrogen phosphate (NaH 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), trisodium phosphate (Na 3 PO 4 ), and potassium dihydrogen phosphate (KH 2 ). PO 4 ), dipotassium hydrogen phosphate (K 2 HPO 4 ), ammonium dihydrogen phosphate ((NH 4 )H 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ), and ammonium phosphate ((NH) 4 ) 3 PO 4 ), etc., but it is not limited to these, and one or more types selected from these can be used.
所述磷酸鹽相對於本發明的含銀(Ag)薄膜的 蝕刻液組合物的總重量，可以含有0.1~3重量%，更優選地可以含有0.5~2重量%。所述磷酸鹽的含量不到0.1重量%的情況下，有時基板內的蝕刻均一性(uniformity)降低，銀殘渣產生。相反，含量超過3重量%的情況下，蝕刻速度降低，不能實現所期望的蝕刻速度，由此有時工序時間延長等工序效率降低。 The phosphate is relative to the silver (Ag) containing film of the present invention The total weight of the etching solution composition may be 0.1 to 3% by weight, and more preferably 0.5 to 2% by weight. When the content of the phosphate is less than 0.1% by weight, the uniformity of etching in the substrate may be lowered, and silver residue may be generated. On the other hand, when the content exceeds 3% by weight, the etching rate is lowered, and the desired etching rate cannot be achieved, and the process efficiency such as the extension of the process time may be lowered.
(E)硝酸鹽(E) nitrate
本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的硝酸鹽起到如下的作用：防止蝕刻後產生的銀離子(Ag+)或膠體形態的銀在不希望的位置再吸附、產生暗點不良或配線間的不必要的連接而發生電氣短路(短路)。作為所述硝酸鹽的具體例，可列舉硝酸鉀(KNO3)、硝酸鈉(NaNO3)、和硝酸銨(NH4NO3)等，但並不限定於這些，能夠使用從這些中選擇的1種以上。 The nitrate contained in the etching solution composition containing a silver (Ag) film of the present invention functions to prevent silver ions (Ag + ) generated in the etching or colloidal form of silver from being adsorbed again at an undesired position. An electrical short (short circuit) occurs due to poor dark spots or unnecessary connections between wirings. Specific examples of the nitrate salt include potassium nitrate (KNO 3 ), sodium nitrate (NaNO 3 ), and ammonium nitrate (NH 4 NO 3 ). However, the present invention is not limited thereto, and those selected from these can be used. More than one type.
所述硝酸鹽，相對於本發明的含銀(Ag)薄膜的蝕刻液組合物的總重量，可含有0.1~3重量%，更優選地可含有0.5~2重量%。所述硝酸鹽的含量不到0.1重量%的情況下，不能很好地發揮防止基板內的銀的再吸附的作用，超過3重量%的情況下，蝕刻速度降低，不能實現所期望的蝕刻速度，有時由於銀殘渣的產生在後續工序中誘發問題。 The nitrate may be contained in an amount of 0.1 to 3% by weight, and more preferably 0.5 to 2% by weight based on the total weight of the etchant composition containing the silver (Ag) film of the present invention. When the content of the nitrate is less than 0.1% by weight, the effect of preventing re-adsorption of silver in the substrate is not well exhibited. When the content exceeds 3% by weight, the etching rate is lowered, and the desired etching rate cannot be achieved. Sometimes, problems arise in subsequent processes due to the generation of silver residue.
(F)醋酸鹽(F) Acetate
本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的醋酸鹽(F)發揮如下的作用：在與顯示裝置的高解析度相伴的配線、像素電極或反射膜的微細圖案化時(為了 在同一區域中納入大量的像素，配線的寬度和大小變小的現象)，由於蝕刻量的減少，防止配線的流失。所述醋酸鹽通過不僅使銀或銀合金的蝕刻量減少，而且使透明導電膜的蝕刻量減少，從而在多重膜中能夠獲得更優異的蝕刻減少效果。 The acetate (F) contained in the etching solution composition containing a silver (Ag) film of the present invention functions to finely pattern wiring, a pixel electrode, or a reflective film associated with high resolution of a display device. (in order to In the same area, a large number of pixels are incorporated, and the width and size of the wiring become small, and the loss of wiring is prevented due to the reduction in the amount of etching. The acetate can obtain a more excellent etching reduction effect in the multiple film by reducing not only the etching amount of the silver or the silver alloy but also the etching amount of the transparent conductive film.
另外，發揮如下的作用：隨著由於蝕刻液組合物的使用時間的經過而使磷酸(A)濃縮，相對於蝕刻液組合物的總重量的磷酸的重量%可增加，防止因此而發生的配線、像素電極或反射膜的流失。 Further, as the phosphoric acid (A) is concentrated due to the passage of the etching liquid composition, the weight % of phosphoric acid with respect to the total weight of the etching liquid composition can be increased, and the wiring thus occurring can be prevented. , the loss of the pixel electrode or the reflective film.
本發明的含銀薄膜的蝕刻液組合物中所含的醋酸鹽，作為具體例，可列舉醋酸鉀(CH3COOK)、醋酸鈉(CH3COONa)和醋酸銨(CH3COONH4)等，但並不限定於這些，可以從這些中選擇1種以上而使用。 The acetate contained in the etching solution composition containing the silver thin film of the present invention may, for example, be potassium acetate (CH 3 COOK), sodium acetate (CH 3 COONa) or ammonium acetate (CH 3 COONH 4 ). However, it is not limited to these, and one or more types can be selected and used.
所述醋酸鹽(F)，相對於本發明的含銀(Ag)薄膜的蝕刻液組合物的總重量，可以含有0.1~3重量%，更優選地可含有0.5~2重量%。所述醋酸鹽的含量不到0.1重量%的情況下，蝕刻效果很小，不能很好地起到使蝕刻量減少的作用，超過3重量%的情況下，蝕刻速度降低，不能實現所期望的蝕刻速度，由於銀殘渣的產生，有時在後續工序中誘發問題。 The acetate (F) may be contained in an amount of 0.1 to 3% by weight, and more preferably 0.5 to 2% by weight based on the total weight of the etchant composition containing the silver (Ag) film of the present invention. When the content of the acetate is less than 0.1% by weight, the etching effect is small, and the effect of reducing the etching amount is not well performed. When the content exceeds 3% by weight, the etching rate is lowered, and the desired effect cannot be achieved. The etching rate, due to the generation of silver residue, sometimes causes problems in subsequent processes.
(G)脫離子水(G) deionized water
對本發明的含銀(Ag)薄膜的蝕刻液組合物中所含的脫離子水並無特別限定，作為半導體工序用，優選使用比電阻值為18MΩ/cm以上的脫離子水。 The deionized water contained in the etching liquid composition containing the silver (Ag) film of the present invention is not particularly limited, and as the semiconductor step, deionized water having a specific resistance value of 18 MΩ/cm or more is preferably used.
所述脫離子水，相對於本發明的含銀(Ag)薄膜的蝕刻液組合物合計100重量%，作為餘量含有。 The deionized water is contained in an amount of 100% by weight based on the total of the etching liquid composition containing the silver (Ag) film of the present invention, and is contained as the balance.
本發明的含銀(Ag)薄膜的蝕刻液組合物除了所述提及的成分以外，可以追加地包含選自蝕刻調節劑、表面活性劑、金屬離子封閉劑、防腐蝕劑、pH調節劑、和並不限於此的其他的添加劑中的1種以上。所述添加劑為了在本發明的範圍內使本發明的效果更為良好，能夠從本領域中通常使用的添加劑中選擇使用。 The silver (Ag) film-containing etching liquid composition of the present invention may additionally include, in addition to the components mentioned above, an etching regulator, a surfactant, a metal ion blocking agent, an anticorrosive agent, a pH adjuster, and It is not limited to one or more of the other additives described above. The additive can be selected from the additives generally used in the art in order to further improve the effects of the present invention within the scope of the present invention.
另外，構成本發明的含銀(Ag)薄膜的蝕刻液組合物的成分優選具有半導體工序用的純度。 Further, the components of the etching liquid composition constituting the silver (Ag) film of the present invention preferably have a purity for a semiconductor process.
應用本發明的含銀(Ag)薄膜的蝕刻液組合物的含銀(Ag)薄膜在膜的構成成分中含有銀(Ag)，可列舉銀(Ag)或銀合金的單一膜、或者由所述單一膜和透明導電膜構成的多層膜等，但並不限定於此。 The silver (Ag)-containing film of the etchant composition containing the silver (Ag) film of the present invention contains silver (Ag) in the constituent components of the film, and a single film of silver (Ag) or a silver alloy, or a A multilayer film composed of a single film and a transparent conductive film is described, but is not limited thereto.
對所述含銀薄膜並無特別限定，作為具體例，可列舉銀(Ag)膜、以銀作為主成分、包含選自釹(Nd)、銅(Cu)、鈀(Pd)、鈮(Nb)、鎳(Ni)、鉬(Mo)、鉻(Cr)、鎂(Mg)、鎢(W)、鏷(Pa)、和鈦(Ti)等中的1種以上的金屬的銀合金膜、銀的氮化物、銀的矽化物、銀的碳化物、或銀的氧化物等的單一膜；由所述單一膜和透明導電膜構成的多層膜；等。 The silver-containing thin film is not particularly limited, and specific examples thereof include a silver (Ag) film containing silver as a main component and a material selected from the group consisting of niobium (Nd), copper (Cu), palladium (Pd), and niobium (Nb). a silver alloy film of one or more kinds of metals such as nickel (Ni), molybdenum (Mo), chromium (Cr), magnesium (Mg), tungsten (W), lanthanum (Pa), and titanium (Ti), a single film of silver nitride, silver halide, silver carbide, or silver oxide; a multilayer film composed of the single film and a transparent conductive film;
作為所述透明導電膜的具體例，可列舉氧化錫銦(ITO)、氧化鋅銦(IZO)、氧化錫鋅銦(ITZO)、或氧化鎵鋅銦(IGZO)等，但並不限定於這些。 Specific examples of the transparent conductive film include indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide indium (ITZO), or indium gallium zinc oxide (IGZO), but are not limited thereto. .
作為所述多層膜的更具體的例子，可列舉透明導電膜/銀(Ag)或透明導電膜/銀合金(silver alloy)等的二重膜、透明導電膜/銀(Ag)/透明導電膜或透明導電膜/銀合金/透明導電膜等的三重膜等，但並不限定於此。 More specific examples of the multilayer film include a double film of a transparent conductive film/silver (Ag) or a transparent conductive film/silver alloy, a transparent conductive film/silver (Ag)/transparent conductive film. Or a triple film such as a transparent conductive film/silver alloy/transparent conductive film, etc., but is not limited thereto.
另外，本發明涉及含銀薄膜的蝕刻方法，其包括：(1)在基板上形成含銀(Ag)薄膜的步驟、(2)在所述含銀薄膜上選擇性地使光反應物質殘留的步驟、和(3)使用所述本發明的含銀薄膜的蝕刻液組合物將所述含銀薄膜蝕刻的步驟。 Further, the present invention relates to an etching method for a silver-containing film, comprising: (1) a step of forming a silver (Ag)-containing film on a substrate, and (2) selectively removing a photoreactive substance on the silver-containing film. Step, and (3) a step of etching the silver-containing film using the etchant composition of the silver-containing film of the present invention.
本發明的蝕刻方法中，所述光反應物質優選為通常的光致抗蝕劑物質，可通過通常的曝光和顯影工序選擇性地使其殘留。 In the etching method of the present invention, the photoreactive substance is preferably a usual photoresist material, and can be selectively left to remain by a usual exposure and development process.
進而，本發明提供顯示裝置用陣列基板的製造方法，該顯示裝置用陣列基板的製造方法包括：a)在基板上形成柵極配線的步驟、b)在包含所述柵極配線的基板上形成柵極絕緣層的步驟、c)在所述柵極絕緣層上形成氧化物半導體層的步驟、d)在所述氧化物半導體層上形成源電極和漏電極的步驟、e)形成與所述漏電極連接的像素電極或反射膜的步驟，其特徵在於，所述e)步驟包含在基板上形成含銀(Ag) 薄膜，用本發明的含銀薄膜的蝕刻液組合物蝕刻，形成像素電極或反射膜的步驟。 Furthermore, the present invention provides a method of manufacturing an array substrate for a display device comprising: a) a step of forming a gate wiring on a substrate; b) forming a substrate on the substrate including the gate wiring a step of forming a gate insulating layer, c) a step of forming an oxide semiconductor layer on the gate insulating layer, d) a step of forming a source electrode and a drain electrode on the oxide semiconductor layer, e) forming and The step of draining the pixel electrode or the reflective film connected to the electrode, wherein the step e) comprises forming silver (Ag) on the substrate The film is etched by the etchant composition containing the silver film of the present invention to form a pixel electrode or a reflective film.
所述顯示裝置可以是有機發光元件(OLED)或液晶顯示裝置(LCD)，所述顯示裝置用陣列基板可以是薄膜電晶體(TFT)陣列基板。 The display device may be an organic light emitting element (OLED) or a liquid crystal display device (LCD), and the array substrate for the display device may be a thin film transistor (TFT) array substrate.
所述含銀薄膜可以是銀(Ag)或銀合金的單一膜、或者由所述單一膜和透明導電膜構成的多層膜，所述銀合金為以銀(Ag)作為主成分、包含釹(Nd)、銅(Cu)、鈀(Pd)、鈮(Nb)、鎳(Ni)、鉬(Mo)、鉻(Cr)、鎂(Mg)、鎢(W)、鏷(Pa)、或鈦(Ti)等其他金屬的合金形態，或者可以是銀的氮化物、銀的矽化物、銀的碳化物、或銀的氧化物等的形態。 The silver-containing film may be a single film of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film containing silver (Ag) as a main component and containing ruthenium ( Nd), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), molybdenum (Mo), chromium (Cr), magnesium (Mg), tungsten (W), lanthanum (Pa), or titanium The alloy form of other metals such as (Ti) may be in the form of a silver nitride, a silver telluride, a silver carbide, or a silver oxide.
所述透明導電膜可列舉氧化錫銦(ITO)、氧化鋅銦(IZO)、氧化錫鋅銦(ITZO)、或氧化鎵鋅銦(IGZO)等，但並不限定於這些。 Examples of the transparent conductive film include indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide indium (ITZO), or indium gallium zinc oxide (IGZO), but are not limited thereto.
即，用所述顯示裝置用陣列基板的製造方法製造的顯示裝置用陣列基板也包含在本發明的範圍內。此時，所述顯示裝置可以是有機發光元件(OLED)或液晶顯示裝置(LCD)，但並不限定於此。 That is, the array substrate for a display device manufactured by the method for manufacturing an array substrate for a display device is also included in the scope of the present invention. At this time, the display device may be an organic light emitting element (OLED) or a liquid crystal display device (LCD), but is not limited thereto.
另外，本發明能夠提供使用本發明的含銀(Ag)薄膜的蝕刻液組合物蝕刻的配線。 Further, the present invention can provide wiring which is etched using the etching solution composition containing the silver (Ag) film of the present invention.
更詳細地說，所述配線可以是觸控式螢幕面板(Touch Screen Panel、TSP)中讀取主要在X、Y座標傳感的信號的示蹤(Trace)配線或柔性用銀納米線配線。 In more detail, the wiring may be a trace wiring or a flexible silver nanowire wiring for reading signals mainly detected at X and Y coordinates in a touch screen panel (TSP).
所述配線可以是由銀(Ag)或銀合金構成的單一膜、或者由所述單一膜和透明導電膜構成的多層膜。關於所述銀合金的單一膜、由所述單一膜和透明導電膜構成的多層膜的內容，可同樣地應用對於含銀(Ag)薄膜所述的內容。 The wiring may be a single film composed of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and the transparent conductive film. Regarding the content of the single film of the silver alloy and the multilayer film composed of the single film and the transparent conductive film, the contents described for the silver-containing (Ag) film can be similarly applied.
本發明的含銀薄膜的蝕刻液組合物能夠在顯示裝置(OLED、LCD等)的製造時在作為配線和反射膜使用的由銀(Ag)或銀合金構成的單一膜、和由所述單一膜和透明導電膜構成的多層膜的蝕刻中使用。另外，觸控式螢幕面板的配線形成時，能夠在蝕刻中使用。即，本發明的含銀薄膜的蝕刻液組合物可以多樣地應用於OLED、LCD、TSP等的製造。 The etchant composition containing a silver thin film of the present invention can be used as a single film made of silver (Ag) or a silver alloy as a wiring and a reflective film at the time of manufacture of a display device (OLED, LCD, etc.), and by the single It is used for etching of a multilayer film composed of a film and a transparent conductive film. In addition, when the wiring of the touch panel is formed, it can be used for etching. That is, the etching liquid composition containing a silver thin film of the present invention can be variously applied to the production of OLED, LCD, TSP, and the like.
以下使用實施例對本發明更詳細地說明。但是，下述的實施例用於對本發明進行例示，本發明並不受下述的實施例限定，可以進行各種修正和變形。本發明的範圍由後述的申請專利範圍的技術思想確定。 The invention will now be described in more detail using examples. However, the following examples are intended to exemplify the invention, and the invention is not limited by the following examples, and various modifications and changes can be made. The scope of the invention is determined by the technical idea of the scope of the patent application described later.
<實施例和比較例>蝕刻液組合物的製造<Examples and Comparative Examples> Manufacture of Etching Liquid Composition
以下述表1中所示的組成和含量製造了實施例1~14和比較例1~12的蝕刻液組合物。 The etching liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 12 were produced in the compositions and contents shown in Table 1 below.
<實驗例>蝕刻液組合物的性能試驗<Experimental Example> Performance Test of Etching Liquid Composition
在基板上蒸鍍有機絕緣膜，在其上蒸鍍ITO/Ag/ITO的三重膜，將其使用金剛石刀切割為500X600mm，準備試驗片。 An organic insulating film was deposited on the substrate, and a triple film of ITO/Ag/ITO was deposited thereon, and this was cut into 500×600 mm using a diamond knife to prepare a test piece.
使用所述實施例1~14和比較例1~12的蝕刻液組合物，進行了下述的性能試驗。 Using the etching liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 12, the following performance tests were carried out.
實驗例1.極限尺寸偏差(CD bias)的測定Experimental Example 1. Determination of Limit Dimensionality (CD bias)
在噴射式蝕刻方式的實驗裝備(模型名：ETCHER、K.C.Tech社)內分別裝入所述實施例1~14和比較例1~12的銀蝕刻液組合物，將溫度設定為40℃，加熱後，溫度到達40±0.1℃時，進行了所述試驗片的蝕刻工序。總蝕刻時間設為100秒而實施。 The silver etching liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 12 were placed in the experimental equipment of the spray etching method (model name: ETCHER, KCTech), and the temperature was set to 40 ° C and heated. Thereafter, when the temperature reached 40 ± 0.1 ° C, the etching step of the test piece was performed. The total etching time was set to 100 seconds.
裝入基板，開始噴射，成為100秒的蝕刻時間，則取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥。清洗和乾燥後，將基板切斷，對斷面使用電子掃描顯微鏡(SEM；模型名：SU-8010、HITACHI社製造)測定。作為極限尺寸偏差的測定標準，由光致抗蝕劑兩端部分的寬度測定配線的寬度之差(圖1)，用下述的標準評價，將結果示於下述表2中。 The substrate was placed and the ejection was started, and the etching time was 100 seconds. Then, it was taken out, washed with deionized water, and then dried using a hot air drying device. After washing and drying, the substrate was cut, and the cross section was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI Co., Ltd.). As a measurement standard of the limit dimensional deviation, the difference in width of the wiring was measured from the width of both ends of the photoresist (Fig. 1), and the results were evaluated by the following criteria, and the results are shown in Table 2 below.
<評價標準> <Evaluation criteria>
不到0.5μm：優秀 Less than 0.5μm: excellent
0.5~1.0μm：良好 0.5~1.0μm: good
超過1.0μm：不良 More than 1.0μm: bad
實驗例2.殘渣的測定Experimental Example 2. Determination of residue
在噴射式蝕刻方式的實驗裝備(模型名：ETCHER、K.C.Tech社)內分別裝入所述實施例1~14和比較例1~12的銀蝕刻液組合物，將溫度設定為40℃，加熱後，溫度到達40±0.1℃時，進行了所述試驗片的蝕刻工序。總蝕刻時間設為100秒而實施。 The silver etching liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 12 were placed in the experimental equipment of the spray etching method (model name: ETCHER, KCTech), and the temperature was set to 40 ° C and heated. Thereafter, when the temperature reached 40 ± 0.1 ° C, the etching step of the test piece was performed. The total etching time was set to 100 seconds.
裝入基板，開始噴射，成為100秒的蝕刻時間，則取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥，使用光致抗蝕劑剝離機(PR stripper)將光致抗蝕劑除去。清洗和乾燥後，使用電子掃描顯微鏡(SEM；模型名：SU-8010、HITACHI社製造)測定在沒有被光致抗蝕劑覆蓋的部分中銀(Ag)沒有被蝕刻而殘留的現象即殘渣，用下述的標準評價，將結果示於下述表2中。 The substrate was placed and sprayed, and the etching time was 100 seconds. Then, it was taken out, washed with deionized water, dried by a hot air drying device, and the photoresist was removed using a PR stripper. After washing and drying, an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI Co., Ltd.) was used to measure a phenomenon in which silver (Ag) was not etched and remained as a residue in a portion not covered with a photoresist. The following standard evaluations are shown in Table 2 below.
<殘渣的評價標準> <Evaluation criteria of residue>
無殘渣：無 No residue: no
殘渣產生：有 Residue generation: yes
實驗例3.銀再吸附的測定Experimental Example 3. Determination of Silver Resorption
在噴射式蝕刻方式的實驗裝備(模型名：ETCHER、K.C.Tech社)內分別裝入所述實施例1~14和比較例1~12的銀蝕刻液組合物，將溫度設定為40℃，加熱後，溫度到達40±0.1℃時，進行了所述試驗片的蝕刻工序。總蝕刻時間設為100秒而實施。 The silver etching liquid compositions of Examples 1 to 14 and Comparative Examples 1 to 12 were placed in the experimental equipment of the spray etching method (model name: ETCHER, KCTech), and the temperature was set to 40 ° C and heated. Thereafter, when the temperature reached 40 ± 0.1 ° C, the etching step of the test piece was performed. The total etching time was set to 100 seconds.
裝入基板，開始噴射，成為100秒的蝕刻時間，則取出，用脫離子水清洗後，使用熱風乾燥裝置乾燥，使用光致抗蝕劑剝離機(PR stripper)將光致抗蝕劑除去。清 洗和乾燥後，使用電子掃描顯微鏡(SEM；模型名：SU-8010、HITACHI社製造)，對於進行了蝕刻後主要在資料配線等的異種金屬露出的部分、由於彎曲現象而可產生摩擦的特定部位被蝕刻的銀(Ag)吸附的現象通過全面觀察進行分析，用下述的標準評價，將其結果示於下述表2中。 The substrate was placed and sprayed, and the etching time was 100 seconds. Then, it was taken out, washed with deionized water, dried by a hot air drying device, and the photoresist was removed using a PR stripper. clear After washing and drying, a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI Co., Ltd.) was used, and the portion where the dissimilar metal such as the data wiring was exposed after the etching was performed, and the friction was generated due to the bending phenomenon. The phenomenon of silver (Ag) adsorption in which the portion was etched was analyzed by comprehensive observation, and evaluated by the following criteria, and the results are shown in Table 2 below.
<再吸附的評價標準> <Evaluation criteria for resorption>
無再吸附：無 No re-adsorption: no
再吸附發生：有 Resorption occurs: there is
實驗例4.蝕刻速度的測定Experimental Example 4. Measurement of etching rate
在噴射式蝕刻方式的實驗裝備(模型名：ETCHER(TFT)、K.C.Tech社)內分別裝入所述實施例1~14和比較例1~12的銀蝕刻液組合物，將溫度設定為40℃，加熱後，溫度到達40±0.1℃時，進行了所述試驗片的蝕刻工序。總蝕刻時間設為100秒而實施。 The silver etching solution compositions of Examples 1 to 14 and Comparative Examples 1 to 12 were placed in the experimental equipment of the spray etching method (model name: ETCHER (TFT), KCTech), and the temperature was set to 40. °C, after heating, when the temperature reached 40 ± 0.1 ° C, the etching process of the test piece was performed. The total etching time was set to 100 seconds.
用肉眼測定端點檢測(End Point Detection、EPD)，得到了對應於時間的蝕刻速度(E/R、Etch Rate)，蝕刻速度只用縱向的蝕刻速度評價(圖4)。將進行了蝕刻的金屬膜的厚度除以EPD，能夠求出每秒(時間)的Å(厚度)(Å/sec)的蝕刻速度，用下述的標準評價，將結果示於下述表2中。 End point detection (EPD) was measured with the naked eye to obtain an etching rate (E/R, Etch Rate) corresponding to time, and the etching rate was evaluated only by the longitudinal etching speed (Fig. 4). By dividing the thickness of the etched metal film by EPD, the etching rate of Å (thickness) (Å/sec) per second (time) can be obtained and evaluated by the following criteria. The results are shown in Table 2 below. in.
<蝕刻速度的評價標準> <Evaluation criteria for etching speed>
不到20Å/sec：不良 Less than 20Å/sec: bad
20Å/sec~不到50Å/sec：良好 20Å/sec~ less than 50Å/sec: good
50Å/sec以上：優秀 50Å/sec or more: excellent
如通過所述表2的結果可知那樣，作為本發明的含銀(Ag)薄膜的蝕刻液組合物的實施例1~14在極限尺寸偏差(CD bias)、蝕刻速度的評價結果中顯示優秀或良好的結果，確認了沒有發生銀殘渣和再吸附現象。 As can be seen from the results of the above Table 2, Examples 1 to 14 which are the etching liquid compositions containing the silver (Ag) film of the present invention showed excellent results in the evaluation results of the limit deviation (CD bias) and the etching rate. Good results confirmed that no silver residue and re-adsorption occurred.
相反，比較例1~12在極限尺寸偏差、蝕刻速度、銀殘渣產生、再吸附發生的評價結果中，確認了在1個以上的評價中顯示不良或不適合的評價結果。 On the other hand, in Comparative Examples 1 to 12, in the evaluation results of the limit size deviation, the etching rate, the silver residue generation, and the re-adsorption, it was confirmed that the evaluation results were unfavorable or unsuitable in one or more evaluations.
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| KR102546803B1 (en) * | 2016-05-23 | 2023-06-22 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and an display substrate using the same |
| KR101718460B1 (en) * | 2016-11-14 | 2017-03-22 | 길기환 | Etchant composition for gold thin films |
| KR101935131B1 (en) * | 2017-02-02 | 2019-01-03 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method for an array substrate for display device using the same |
| KR102400258B1 (en) * | 2017-03-28 | 2022-05-19 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and manufacturing method of forming conductive pattern using the same |
| KR102457171B1 (en) * | 2017-03-30 | 2022-10-19 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and manufacturing method of forming conductive pattern using the same |
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| KR102263693B1 (en) * | 2017-11-02 | 2021-06-10 | 동우 화인켐 주식회사 | Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same |
| KR102218937B1 (en) * | 2017-11-16 | 2021-02-23 | 동우 화인켐 주식회사 | Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same |
| KR102368026B1 (en) * | 2018-02-06 | 2022-02-24 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and method of forming conductive pattern using the same |
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| TWI378989B (en) * | 2006-09-01 | 2012-12-11 | Taiwan Tft Lcd Ass | Etchant for patterning composite layer and method of fabricating thin film transistor using the same |
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