KR102623991B1 - An etching solution composition for silver-containing layer, an array substrate for display device using the same and a manufacturing method for the array substrate for display device - Google Patents
An etching solution composition for silver-containing layer, an array substrate for display device using the same and a manufacturing method for the array substrate for display device Download PDFInfo
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- KR102623991B1 KR102623991B1 KR1020180136131A KR20180136131A KR102623991B1 KR 102623991 B1 KR102623991 B1 KR 102623991B1 KR 1020180136131 A KR1020180136131 A KR 1020180136131A KR 20180136131 A KR20180136131 A KR 20180136131A KR 102623991 B1 KR102623991 B1 KR 102623991B1
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- silver
- film
- transparent conductive
- display device
- conductive film
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000005530 etching Methods 0.000 title claims description 43
- 239000010409 thin film Substances 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 68
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000004973 liquid crystal related substance Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
- H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
Abstract
본 발명은, 조성물 총 중량에 대하여, 인산 40.0 내지 60.0 중량%; 질산 5.0 내지 9.0 중량 %; 질산제이철 0.1 내지 4.0 중량%; 무기산염 0.5 내지 5.0 중량%; 및 잔량의 물을 포함하는 은 함유 박막의 식각액 조성물 및 이를 이용하여 제조된 표시장치용 어레이기판 및 이의 제조방법을 제공한다.The present invention, based on the total weight of the composition, 40.0 to 60.0% by weight of phosphoric acid; 5.0 to 9.0% by weight of nitric acid; 0.1 to 4.0% by weight of ferric nitrate; 0.5 to 5.0% by weight of inorganic acid salt; and an etchant composition for a silver-containing thin film containing a residual amount of water, an array substrate for a display device manufactured using the same, and a method for manufacturing the same.
Description
본 발명은 은 함유 박막 식각액 조성물, 이를 이용하여 제조된 표시장치용 어레이기판 및 이의 제조방법에 관한 것이다.The present invention relates to a silver-containing thin film etchant composition, an array substrate for a display device manufactured using the same, and a method for manufacturing the same.
본격적인 정보화시대로 접어들게 됨에 따라 대량의 정보를 처리 및 표시하는 표시장치 분야가 급속도로 발전해 왔으며, 이에 부응하여 다양한 평판 디스플레이가 개발되어 각광받고 있다. 이러한 평판 표시장치 장치의 예로는 액정디스플레이장치(Liquid Crystal Display device: LCD), 플라즈마 디스플레이장치(Plasma Display Panel device:PDP), 전계방출디스플레이장치(Field Emission Display device: FED), 유기발광소자(Organic Light Emitting Diodes: OLED) 등을 들 수 있다.As we enter the information age, the field of display devices that process and display large amounts of information has developed rapidly, and in response to this, various flat panel displays have been developed and are in the spotlight. Examples of such flat panel display devices include Liquid Crystal Display device (LCD), Plasma Display Panel device (PDP), Field Emission Display device (FED), and Organic Light Emitting Device (Organic Light Emitting Device). Light Emitting Diodes (OLED), etc.
일례로서, OLED는 소자 자체적으로 빛을 발광하면서 저전압에서도 구동될 수있기 때문에 휴대기기 등의 소형 표시장치 시장에 빠르게 적용되고 있을 뿐만 아니라, 표시장치의 대화면화에 대한 트랜드에 따라 대형 TV 등에의 상용화를 목전에 둔 상황이다. 표시장치가 대화면화 되면서, 배선 등이 길어지게 되어 배선 저항이 증가하게 됨에 따라, 저항을 낮추어 표시장치의 대형화 및 고해상도 실현을 가능하게 하는 방법이 요구되고 있다.As an example, OLED is not only rapidly being applied to the small display device market such as portable devices because the device itself emits light and can be driven at low voltage, but is also being commercialized for large-sized TVs according to the trend toward larger screens in display devices. The situation is at hand. As display devices become larger screens, wiring becomes longer and wiring resistance increases. As a result, there is a need for a method of lowering resistance to enable display devices to become larger and have higher resolution.
저항 증가에 의한 신호 지연 등의 문제를 해결하기 위해서는, 상기 배선을 최대한 낮은 비저항을 가지는 재료로 형성할 필요가 있다. 그러한 노력의 일환으로 다른 금속들에 비해 낮은 비저항과 높은 휘도, 전도도를 가지고 있는 은(Ag: 비저항 약 1.59μΩ㎝)막, 은합금막 또는 은막이나 은합금막을 포함한 다층막을 컬러필터의 전극, 배선 및 반사막 등에 적용하여 평판 표시장치장치의 대형화와 고해상도 및 저전력 소비 등을 실현하기 위한 노력이 경주되고 있으며, 이러한 재료에 적용하기 위한 식각액이 요구되고 있다.In order to solve problems such as signal delay due to increased resistance, it is necessary to form the wiring with a material having the lowest specific resistance as possible. As part of such efforts, silver (Ag: resistivity approx. 1.59μΩcm) film, silver alloy film, or multilayer film including silver film or silver alloy film, which has low resistivity, high brightness, and conductivity compared to other metals, was used for color filter electrodes, wiring, and other materials. Efforts are being made to realize larger flat panel displays, higher resolution, and lower power consumption by applying reflective membranes, etc., and etchants for application to these materials are required.
은(Ag) 포함 박막을 이용하는 경우, 저해상도 표시장치에서 은의 재흡착의 발생이 문제되지 않았지만, 고해상도 표시장치 기술에서는 은의 재흡착 이 문제로 대두되고 있는 실정이다. 이와 관련하여 기존에 인산, 초산, 질산을 포함하는 식각액 조성물(한국 등록공보 제 10-0579421호)등으로 은을 포함하는 박막을 식각하는 방법이 개발되었지만, 초산을 포함할 경우 초산의 강한 휘발성에 의해 경시 안정성이 떨어지는 문제가 있었으며, 직진성 제어 효과가 떨어지는 문제 등이 발생하였다.When using a thin film containing silver (Ag), silver re-adsorption is not a problem in low-resolution display devices, but silver re-adsorption is emerging as a problem in high-resolution display technology. In relation to this, a method of etching a thin film containing silver has been developed using an etchant composition containing phosphoric acid, acetic acid, and nitric acid (Korean Registration Publication No. 10-0579421). However, when acetic acid is included, it is difficult to etch due to the strong volatility of acetic acid. As a result, there were problems with poor stability over time and poor straight-line control effectiveness.
본 발명은, 상기 종래 기술의 문제를 해결하기 위하여 안출된 것으로, 은을 포함하는 금속막의 식각시 경시 안정성 문제가 개선되며, 은 잔사 및 재흡착이 거의 없어 우수한 효과를 나타내며, 직진성이 우수한 은 함유 박막의 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention was developed to solve the problems of the prior art, and improves the problem of stability over time when etching a metal film containing silver, exhibits excellent effects with almost no silver residue and re-adsorption, and contains silver with excellent straightness. The purpose is to provide a thin film etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하여 제조된 표시 장치용 어레이기판 및 이의 제조 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an array substrate for a display device manufactured using the etchant composition and a method for manufacturing the same.
본 발명은, 조성물 총 중량에 대하여, 인산 40.0 내지 60.0 중량%; 질산 5.0 내지 9.0 중량 %; 질산제이철 0.1 내지 4.0 중량%; 무기산염 0.5 내지 5.0 중량%; 및 잔량의 물을 포함하는 은 함유 박막의 식각액 조성물을 제공한다.The present invention, based on the total weight of the composition, 40.0 to 60.0% by weight of phosphoric acid; 5.0 to 9.0% by weight of nitric acid; 0.1 to 4.0% by weight of ferric nitrate; 0.5 to 5.0% by weight of inorganic acid salt; and a residual amount of water. It provides an etchant composition for a silver-containing thin film.
또한, 본 발명은 a) 기판 상에 게이트 배선을 형성하는 단계;In addition, the present invention includes the steps of a) forming a gate wiring on a substrate;
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;c) forming an oxide semiconductor layer on the gate insulating layer;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the oxide semiconductor layer; and
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a display device comprising:
상기 e) 단계는 기판 상에 은(Ag) 함유 박막을 형성하고, 청구항 1 의 은 함유 박막의 식각액 조성물로 식각하여 화소전극 또는 반사막을 형성하는 단계를 포함하는 것을 특징으로 하는 표시장치용 어레이기판의 제조방법을 제공한다. Step e) includes forming a silver (Ag)-containing thin film on a substrate and etching it with the etchant composition for the silver-containing thin film of claim 1 to form a pixel electrode or a reflective film. Provides a manufacturing method.
또한, 본 발명은 상술한 식각액 조성물을 사용하여 식각된 표시장치용 어레이기판을 제공한다.Additionally, the present invention provides an array substrate for a display device etched using the above-described etchant composition.
본 발명은, 상기 종래 기술의 문제를 해결하기 위하여 안출된 것으로, 은을 포함하는 금속막의 식각시 경시 안정성 문제가 개선되며, 은 잔사 및 재흡착이 거의 없어 우수한 효과를 나타내며, 직진성이 우수한 은 함유 박막의 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention was developed to solve the problems of the prior art. It improves the problem of stability over time when etching a metal film containing silver, shows excellent effects due to little silver residue and re-adsorption, and contains silver with excellent straightness. The purpose is to provide a thin film etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하는 표시 장치용 어레이기판의 제조 방법을 제공한다.Additionally, the present invention provides a method of manufacturing an array substrate for a display device using the etchant composition.
도 1은 직진성이 양호함을 보여주는 사진으로, 실시예 1의 조성물을 사용하여 실험예의 시편을 식각할 경우의 SEM 사진이다.
도 2는 직진성이 불량함을 보여주는 사진으로, 비교예 1의 조성물을 사용하여 실험예의 시편을 식각할 경우의 SEM 사진이다.Figure 1 is a photograph showing good straightness, and is an SEM photograph when the specimen of the experimental example was etched using the composition of Example 1.
Figure 2 is a photograph showing poor straightness, and is an SEM photograph when the specimen of the experimental example was etched using the composition of Comparative Example 1.
본 발명은, 조성물 총 중량에 대하여, 인산 40.0 내지 60.0 중량%; 질산 5.0 내지 9.0 중량 %; 질산제이철 0.1 내지 4.0 중량%; 무기산염 0.5 내지 5.0 중량%; 및 잔량의 물을 포함하는 은 함유 박막의 식각액 조성물에 대한 것으로, 은을 금속막의 식각시 경시 안정성 문제가 개선되며, 은 잔사 및 재흡착이 거의 없어 우수한 효과를 나타내며, 직진성이 우수한 은 함유 박막의 식각액 조성물을 제공한다.The present invention, based on the total weight of the composition, 40.0 to 60.0% by weight of phosphoric acid; 5.0 to 9.0% by weight of nitric acid; 0.1 to 4.0% by weight of ferric nitrate; 0.5 to 5.0% by weight of inorganic acid salt; and an etchant composition for silver-containing thin films containing a residual amount of water, which improves the problem of stability over time when etching silver metal films, exhibits excellent effects with almost no silver residue and re-adsorption, and provides excellent straightness for silver-containing thin films with excellent straightness. An etchant composition is provided.
본 발명에서, 은 함유 박막은 은 또는 은합금의 단일막 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 포함할 수 있으며, 이에 제한되지 않는다.In the present invention, the silver-containing thin film may include a single film of silver or a silver alloy or a multilayer film composed of the single film and a transparent conductive film, but is not limited thereto.
본 발명에서, 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및/또는 산화갈륨아연인듐(IGZO)등으로 구성된 군에서 선택되는 1종 이상일 수 있으며, 이에 제한되지 않는다.In the present invention, the transparent conductive film may be one or more types selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), and/or gallium zinc indium oxide (IGZO). , but is not limited to this.
본 발명에서, 은합금은 은(Ag) 및, 니켈(Ni), 구리(Cu), 아연(Zn), 망간(Mn), 크롬(Cr), 주석(Sn), 팔라듐(Pd), 네오디늄(Nd), 니오븀(Nb), 몰리브덴(Mo), 마그네슘(Mg), 텅스텐(W), 프로트악티늄(Pa), 알루미늄(Al) 및 티타늄(Ti)으로부터 선택되는 1종 이상을 포함할 수 있으며, 이에 제한되지 않는다. In the present invention, the silver alloy is silver (Ag), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), chromium (Cr), tin (Sn), palladium (Pd), and neodymium. (Nd), niobium (Nb), molybdenum (Mo), magnesium (Mg), tungsten (W), protactinium (Pa), aluminum (Al), and titanium (Ti). , but is not limited to this.
본 발명에서, 단일막과 투명전도막으로 구성되는 다층막은 투명전도막/은, 투명전도막/은 합금, 투명전도막/은/투명전도막 또는 투명전도막/은 합금/투명전도막일 수 있으며, 이에 제한되지 않는다. 상기 투명전도막/은/투명전도막은 a-ITO/AgX/a-ITO 일 수 있으며, 이에 제한되지 않는다. In the present invention, the multilayer film consisting of a single film and a transparent conductive film may be a transparent conductive film/silver, a transparent conductive film/silver alloy, a transparent conductive film/silver/transparent conductive film, or a transparent conductive film/silver alloy/transparent conductive film. , but is not limited to this. The transparent conductive film/silver/transparent conductive film may be a-ITO/AgX/a-ITO, but is not limited thereto.
본 발명의 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)인 것을 특징으로 한다.The transparent conductive film of the present invention is characterized by indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), and gallium zinc indium oxide (IGZO).
본 발명의 식각액에 포함되는 인산(H3PO4)은 주 해리제로 사용되는 성분으로서, 은(Ag)과 투명전도막을 산화시켜 습식 식각하는 역할을 수행한다. 그 함량은 식각액 조성물 총중량에 대하여 40.0 내지 60.0 중량% 포함 될 수 있다. 인산의 함량이 40 중량% 미만인 경우에는 은의 식각 속도 저하와 식각 프로파일의 불량을 야기시킬 수 있으며 Ag 재흡착이 증가하게 되고, 60 중량%를 초과하는 경우에는 투명전도막의 식각 속도는 저하되고, 은의 식각 속도는 너무 빨라져 상하부 투명전도막의 팁(Tip)이 발생하게 되어 후속공정에 문제가 되는 불리한 점이 있다. Phosphoric acid (H 3 PO 4 ) included in the etching solution of the present invention is a component used as a main dissociation agent and performs a wet etching function by oxidizing silver (Ag) and a transparent conductive film. The content may be 40.0 to 60.0% by weight based on the total weight of the etchant composition. If the phosphoric acid content is less than 40% by weight, it may cause a decrease in the etching rate of silver and a defective etching profile, and Ag re-adsorption increases. If the content exceeds 60% by weight, the etching rate of the transparent conductive film decreases and the silver etch rate decreases. The etching speed becomes too fast, causing tips on the upper and lower transparent conductive films, which has the disadvantage of causing problems in subsequent processes.
본 발명의 식각액에 포함되는 질산(HNO3)은 산화제로 사용되는 성분으로서, 은(Ag)과 투명전도막을 산화시켜 습식 식각하는 역할을 수행한다. 그 함량은 식각액 조성물 총중량에 대하여 5.0 내지 9.0 중량% 포함될 수 있다. 질산의 함량이 5.0 중량% 미만인 경우에는 은(Ag)과 ITO의 식각 속도 저하가 발생하며 이로써 기판내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 9.0 중량%을 초과하는 경우에는 상하부 투명전도막의 식각 속도가 가속화 되어 상하부 투명전도막의 언더컷 발생으로 후속 공정에 문제가 발생되는 불리한 점이 있다.Nitric acid (HNO 3 ) contained in the etching solution of the present invention is an ingredient used as an oxidizing agent, and performs a wet etching function by oxidizing silver (Ag) and a transparent conductive film. The content may be 5.0 to 9.0% by weight based on the total weight of the etchant composition. If the nitric acid content is less than 5.0% by weight, the etching speed of silver (Ag) and ITO decreases, and as a result, the etching uniformity within the substrate becomes poor and stains occur. If the nitric acid content exceeds 9.0% by weight, the top and bottom are transparent. There is a disadvantage in that the etching speed of the conductive film is accelerated and undercuts occur in the upper and lower transparent conductive films, causing problems in subsequent processes.
본 발명의 식각액 중의 질산제이철은 보조 산화제 및 Ag 리간드로 사용되는 성분으로서, 습식 식각 시 박막에 대한 Ag 재흡착을 감소시키고 또한 균일하게 식각되도록 식각 속도를 조절한다. 그 함량은 식각액 조성물 총중량에 대하여 0.1 내지 4.0 중량%으로 포함될 수 있다. 질산제이철 함량이 0.1 중량% 미만인 경우에는 기판 내의 식각 균일성(Uniformity)이 저하되고 또한 기판 내에 부분적으로 은 잔사가 생길 수 있으며, 4.0 중량%를 초과하는 경우에는 식각 속도가 저하되어 원하는 식각 속도를 구현할 수 없다.Ferric nitrate in the etching solution of the present invention is used as an auxiliary oxidizing agent and Ag ligand, and reduces Ag re-adsorption to the thin film during wet etching and also controls the etching rate to ensure uniform etching. The content may be 0.1 to 4.0% by weight based on the total weight of the etchant composition. If the ferric nitrate content is less than 0.1% by weight, the etching uniformity within the substrate may deteriorate and silver residues may partially form within the substrate, and if it exceeds 4.0% by weight, the etching rate decreases, making it difficult to achieve the desired etching rate. It cannot be implemented.
본 발명의 식각액 중의 무기산염은 에칭 후 직진성을 제어하는 성분으로서, 그 함량은 식각액 조성물 총중량에 대하여 0.5~5.0 중량%으로 포함될 수 있다. 상기 무기산염 함량이 0.5중량% 미만인 경우에는 직진성이 불량이 되어 전기적 특성이 저하되고 또한 기판 내에 부분적으로 잔사가 생길 수 있으며, 5.0 중량%를 초과하는 경우에는 과식각이 발생하여 원하는 식각 속도를 구현할 수 없는 문제가 발생할 수 있다.The inorganic acid salt in the etchant of the present invention is a component that controls straightness after etching, and its content may be 0.5 to 5.0% by weight based on the total weight of the etchant composition. If the inorganic acid salt content is less than 0.5% by weight, straightness may be poor, electrical properties may deteriorate, and residues may partially form within the substrate. If it exceeds 5.0% by weight, overetching may occur, making it impossible to achieve the desired etching speed. Uncontrollable problems may arise.
본 발명에서 무기산염은 질산, 황산 및/또는 인산의 칼륨염, 나트륨염 및/또는 암모늄염등이 사용될 수 있으며, 질산 칼륨 또는 황산암모늄이 바람직하며, 질산 칼륨이 보다 바람직 할 수 있다. 상기 무기산을 포함할 경우 직진성 및 잔사 문제의 개선이 가능하다. In the present invention, the inorganic acid salt may be potassium, sodium, and/or ammonium salts of nitric acid, sulfuric acid, and/or phosphoric acid, preferably potassium nitrate or ammonium sulfate, and more preferably potassium nitrate. When the inorganic acid is included, straightness and residue problems can be improved.
본 발명에서, 본 발명에서 사용되는 물은 탈이온수를 의미하며 반도체 공정용을 사용하며, 바람직하게는 18㏁/㎝ 이상의 물을 사용할 수 있다. 잔량의 물은 전체 조성물 총중량이 100 중량%가 되도록 포함된다.In the present invention, the water used in the present invention refers to deionized water and is used for semiconductor processing. Preferably, water of 18 MΩ/cm or more can be used. The remaining amount of water is included so that the total weight of the entire composition is 100% by weight.
본 발명은 초산을 포함하지 않음에도 우수한 직진성 효과를 가지며, 은 재흡착 문제가 개선될 뿐만 아니라, 초산을 포함함으로써 발생되는 문제인 경시 안정성이 저하되는 문제가 현저히 개선된 식각액 조성물을 제공할 수 있다.The present invention can provide an etchant composition that has an excellent straightness effect even though it does not contain acetic acid, not only improves the silver re-adsorption problem, but also significantly improves the problem of decreased stability over time, which is a problem caused by containing acetic acid.
본 발명의 식각액은 은 또는 은 합금의 단일막 뿐만 아니라, 투명전도막/ 은, 투명전도막/은 합금의 이중막, 투명전도막/은/투명전도막으로 구성되는 3중막에 대해서도 일괄 에칭도 가능하며, 2 단계 에칭 상부 투명전도막을 다른 식각액으로 에칭 후 본 식각액으로 은(은합금) 및 하부 투명전도막을 에칭 가능하며, 3 단계 에칭 즉 상부 투명전도막을 다른 식각액으로 에칭 후 본 식각액으로 은(은합금) 에칭 후 다른 식각액으로 하부 투명전도막을 에칭하는 공정에서도 사용 가능하다.The etchant of the present invention can collectively etch not only a single film of silver or silver alloy, but also a triple layer consisting of a transparent conductive film/silver, a transparent conductive film/silver alloy double film, and a transparent conductive film/silver/transparent conductive film. This is possible, in 2-step etching, the upper transparent conductive film is etched with another etchant, and then the silver (silver alloy) and the lower transparent conductive film are etched with this etchant. In 3-step etching, that is, the upper transparent conductive film is etched with another etchant, and then the silver (silver alloy) is etched with this etchant. It can also be used in the process of etching the lower transparent conductive film with another etchant after etching (silver alloy).
표시 장치의 제조 시, 배선 및 반사막으로 사용되는 은(Ag) 또는 은합금으로 이루어진 단일막 및 기 단일막과 투명전도막으로 구성된 다층막 대해 본 발명의 식각액 조성물을 사용하는 경우, 패턴부의 배선 및 반사막에 대한 미세 식각 균일성을 나타내고 Pad부 Data배선의 손상으로부터 발생하는 Ag 재흡착 문제도 개선할 수 있다. When manufacturing a display device, when the etchant composition of the present invention is used for a single film made of silver (Ag) or a silver alloy used as a wiring and reflective film and a multilayer film made of a basic single film and a transparent conductive film, the wiring and reflective film of the pattern portion are used. It shows fine etching uniformity and can also improve the Ag re-adsorption problem that occurs from damage to the pad data wiring.
본 발명은, a) 기판 상에 게이트 배선을 형성하는 단계; b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계; d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소전극 또는 반사막을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서, 상기 e) 단계는 기판 상에 은(Ag) 함유 박막을 형성하고, 상술한 본 발명의 은 함유 박막의 식각액 조성물로 식각하여 화소전극 또는 반사막을 형성하는 단계를 포함하는 것을 특징으로 하는 표시장치용 어레이기판의 제조방법을 제공한다. The present invention includes the steps of a) forming gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming an oxide semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the oxide semiconductor layer; and e) forming a pixel electrode or a reflective film connected to the drain electrode; In the method of manufacturing an array substrate for a display device comprising, step e) forms a silver (Ag)-containing thin film on the substrate, and etches it with the etchant composition for the silver-containing thin film of the present invention described above to form a pixel electrode or a reflective film. It provides a method of manufacturing an array substrate for a display device, comprising the step of forming a.
또한, 본 발명은 상술한 식각액 조성물을 이용하여 제조된 표시장치용 어레이기판을 제공한다.Additionally, the present invention provides an array substrate for a display device manufactured using the above-described etchant composition.
본 발명에서, 상술한 제조방법 및 상술한 식각액 조성물을 이용하여 제조되는 표시장치용 어레이기판은 유기발광소자용(OLED) 및/또는 액정표시장치(LCD)용으로 사용될 수 있으며, 이에 제한 되지 않는다.In the present invention, the array substrate for a display device manufactured using the above-described manufacturing method and the above-described etchant composition may be used for an organic light emitting device (OLED) and/or a liquid crystal display (LCD), but is not limited thereto. .
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않으며, 다양하게 수정 및 변경될 수 있다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples and may be modified and changed in various ways. The scope of the present invention will be determined by the technical spirit of the claims described later.
<실시예 및 비교예> 은 식각액 조성물 제조<Examples and Comparative Examples> Preparation of silver etchant composition
하기 표 1에 나타낸 조성 및 함량에 따라 실시예1 내지 실시예10 및 비교예1 내지 비교예9 각각의 식각액 조성물 10㎏을 제조하였으며, 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하였다.10 kg of each etchant composition of Examples 1 to 10 and Comparative Examples 1 to 9 was prepared according to the composition and content shown in Table 1 below, and the remaining amount of water was included so that the total weight of the etchant composition was 100% by weight. did.
[표 1][Table 1]
[표 2][Table 2]
<실험 예> <Experiment example>
기판 상에 유기 절연막을 증착하고, 그 위에 ITO/Ag/ITO 삼층막을 75 ÅA / 1000 ÅA / 50 ÅA 의 두께로 증착한 것을 다이아몬드 칼을 이용하여 500×600mm로 절단하여 시편 준비를 하였다. An organic insulating film was deposited on the substrate, and an ITO/Ag/ITO trilayer film was deposited on it to a thickness of 75 ÅA / 1000 ÅA / 50 ÅA and cut to 500 × 600 mm using a diamond knife to prepare a specimen.
상기 실시예 1 내지 10 및 비교예 1 내지 9의 식각액 조성물을 사용하여 하기와 같이 성능 테스트를 진행하였다.A performance test was conducted using the etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 9 as follows.
실험 예 1: Ag Side etch 평가Experimental Example 1: Ag Side etch evaluation
분사식 식각 방식의 실험장비(모델명: 5.5 ETCHER, 프로웨트 사) 내에 상기 실시예 1 내지 10 및 비교예 1 내지 9의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온 한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조하고, 각각 6시간 및 12시간 후 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 분석을 진행하였고, 하기의 기준으로 평가하였으며, 그 결과를 하기 표 3 및 4에 나타내었다. The silver etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were placed in a spray-etching experiment equipment (model name: 5.5 ETCHER, Prowet Co., Ltd.), and the temperature was set to 40°C and heated. When the temperature reached 40±0.1°C, the etching process of the specimen was performed. The total etching time was 85 seconds. The substrate was put in and spraying started. When the etching time of 85 seconds was over, it was taken out, washed with deionized water, dried using a hot air dryer, and the photoresist was removed using a photoresist stripper (PR stripper). Washed and dried, and analyzed using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI) after 6 and 12 hours, respectively, and evaluated based on the following criteria. The results are shown in Table 3 and It is shown in 4.
[Ag 식각량 평가 기준][Ag etch amount evaluation criteria]
◎ : 매우 우수 (Side Etch : ≤0.2㎛)◎: Very good (Side Etch: ≤0.2㎛)
○ : 우수 (Side Etch : >0.2㎛,≤ 0.3㎛)○: Excellent (Side Etch: >0.2㎛,≤ 0.3㎛)
△ : 양호 (Side Etch :>0.3㎛, ≤ 0.4㎛)△: Good (Side Etch:>0.3㎛, ≤ 0.4㎛)
Ⅹ : 불량 (Side Etch : > 0.4㎛)Ⅹ: Defective (Side Etch: > 0.4㎛)
실험예 2: 직진성 평가Experimental Example 2: Straightness evaluation
분사식 식각 방식의 실험장비(모델명: 5.5 ETCHER, 프로웨트 사) 내에 상기 실시예 1 내지 10 및 비교예 1 내지 9의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온 한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 하고, 각각 6시간 및 12시간 후 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 SEM 30K 배율에서 금속배선의 프로파일을 관찰하였고, 이를 하기의 기준으로 평가하여 그 결과를 하기 표 3 및 4에 나타내었다. 직진성이 양호한 경우 anode 전극 크기에 의한 수율에 영향이 거의 발생하지 않으며, 직진성이 불량할 경우 후속 공정에서 anode 전극의 크기가 작은 문제가 발생하여 수율에 부정적인 영향을 미칠 수 있다. The silver etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were placed in a spray-etching experiment equipment (model name: 5.5 ETCHER, Prowet Co., Ltd.), and the temperature was set to 40°C and heated. When the temperature reached 40±0.1°C, the etching process of the specimen was performed. The total etching time was 85 seconds. The substrate was placed and spraying was started, and when the etching time of 85 seconds was over, it was taken out, washed with deionized water, dried using a hot air dryer, and the photoresist was removed using a photoresist stripper (PR stripper). After washing and drying, 6 hours and 12 hours respectively, the profile of the metal wiring was observed at SEM 30K magnification using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), and was evaluated based on the following criteria. The results are shown in Tables 3 and 4 below. If straightness is good, there is little effect on the yield due to the size of the anode electrode. If straightness is poor, problems with the small size of the anode electrode may occur in the subsequent process, which may have a negative impact on yield.
◎ : 우수 ±0.1μm 미만◎: Excellent, less than ±0.1μm
○ : 양호 ±0.1μm 이상 ±0.3μm 미만○: Good ±0.1μm or more, less than ±0.3μm
△ : 보통 ±0.3μm 이상 ±0.5μm 미만△: Usually ±0.3μm or more and less than ±0.5μm
Ⅹ : 불량 ±0.5μm 이상Ⅹ: Defect ±0.5μm or more
실험 예 3: Ag 재흡착 평가 (패드 부 분석)Experimental Example 3: Ag resorption evaluation (pad analysis)
분사식 식각 방식의 실험장비(모델명: 5.5 ETCHER, 프로웨트 사) 내에 상기 실시예 1 내지 10 및 비교예 1 내지 9의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온 한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 하고, 각각 6시간 및 12시간 후 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여, 주로 데이터 배선 등 이종 금속이 노출 된 부분이나 굴곡 현상에 의해 마찰이 발생할 수 있는 특정 부위에 식각된 은(Ag)이 흡착되어 있는 현상을 전면 관찰을 통해 분석을 진행하였다. 하기의 기준으로 평가하였으며, 그 결과를 하기 표 3 및 4에 나타내었다.The silver etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were placed in a spray-etching experiment equipment (model name: 5.5 ETCHER, Prowet Co., Ltd.), and the temperature was set to 40°C and heated. When the temperature reached 40 ± 0.1°C, the etching process of the specimen was performed. The total etching time was 85 seconds. The substrate was placed and spraying was started, and when the etching time of 85 seconds was over, it was taken out, washed with deionized water, dried using a hot air dryer, and the photoresist was removed using a photoresist stripper (PR stripper). Washed and dried, and after 6 and 12 hours, respectively, using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), friction occurred mainly in exposed areas of dissimilar metals, such as data wiring, or due to bending. Analysis was conducted through full-scale observation of the phenomenon of etched silver (Ag) being adsorbed to specific visible areas. It was evaluated based on the following criteria, and the results are shown in Tables 3 and 4 below.
[Ag 재흡착 평가 기준][Ag resorption evaluation criteria]
◎ : 매우 우수 (50개 이하)◎: Very good (50 or less)
○ : 우수 (80개 이하)○: Excellent (80 or less)
△ : 양호 (100개 이하)△: Good (100 or less)
Ⅹ : 불량 (100개 초과)Ⅹ: Defective (exceeding 100)
[표 3][Table 3]
[표 4][Table 4]
본원발명의 구성 및 함량을 전부 포함하는 실시예 1 내지 10의 경우, side etch 값이 우수하였고, 직진성이 양호하였으며, Ag 재흡착 문제가 우수하거나 매우 우수하여 개선된 효과를 보였으며, 경시변화에 따른 식각액 조성물의 효과가 거의 변하지 않음을 확인 하였다. 한편, 본원발명의 구성 및 함량을 만족하지 않는 비교예 1 내지 9는 side etch, 얼룩, 재흡착 효과가 떨어짐을 확인하였다.In the case of Examples 1 to 10, which include all the composition and content of the present invention, the side etch value was excellent, the straightness was good, the Ag re-adsorption problem was excellent or very excellent, showing an improved effect, and the effect was improved with respect to changes over time. It was confirmed that the effect of the etchant composition was almost unchanged. On the other hand, it was confirmed that Comparative Examples 1 to 9, which did not satisfy the composition and content of the present invention, had poor side etching, staining, and resorption effects.
Claims (9)
인산 40.0 내지 60.0 중량%;
질산 5.0 내지 9.0 중량 %;
질산제이철 0.1 내지 4.0 중량%;
무기산염 0.5 내지 5.0 중량%; 및
잔량의 물을 포함하고, 초산을 포함하지 않는,
은 함유 박막의 식각액 조성물.
With respect to the total weight of the composition,
40.0 to 60.0% by weight of phosphoric acid;
5.0 to 9.0% by weight of nitric acid;
0.1 to 4.0% by weight of ferric nitrate;
0.5 to 5.0% by weight of inorganic acid salt; and
Contains a residual amount of water and does not contain acetic acid,
Etching solution composition for silver-containing thin films.
The etchant composition for a silver-containing thin film according to claim 1, wherein the inorganic acid salt is at least one selected from the group consisting of potassium salts, sodium salts, and ammonium salts of nitric acid, sulfuric acid, or phosphoric acid.
The silver-containing thin film etchant composition according to claim 1, wherein the silver-containing thin film comprises a single film of silver or a silver alloy or a multilayer film composed of the single film and a transparent conductive film.
The silver-containing thin film etchant composition according to claim 3, wherein the transparent conductive film is at least one selected from the group consisting of indium tin oxide, indium zinc oxide, indium tin oxide, and indium gallium zinc oxide.
The method of claim 3, wherein the silver alloy is silver and one selected from the group consisting of nickel, copper, zinc, manganese, chromium, tin, palladium, neodymium, niobium, molybdenum, magnesium, tungsten, protactinium, aluminum, and titanium. An etchant composition for a silver-containing thin film, characterized in that it contains more than one species.
The method of claim 3, wherein the multilayer film consisting of a single film and a transparent conductive film is a transparent conductive film/silver, a transparent conductive film/silver alloy, a transparent conductive film/silver/transparent conductive film, or a transparent conductive film/silver alloy/transparent conductive film. An etchant composition for a silver-containing thin film, characterized in that:
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소전극 또는 반사막을 형성하는 단계; 를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,
상기 e) 단계는 기판 상에 은 함유 박막을 형성하고, 청구항 1의 은 함유 박막의 식각액 조성물로 식각하여 화소전극 또는 반사막을 형성하는 단계를 포함하는 것을 특징으로 하는 표시장치용 어레이기판의 제조방법.
a) forming gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming an oxide semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the oxide semiconductor layer; and
e) forming a pixel electrode or a reflective film connected to the drain electrode; In the method of manufacturing an array substrate for a display device comprising:
Step e) is a method of manufacturing an array substrate for a display device, comprising forming a silver-containing thin film on a substrate and etching it with the etchant composition for the silver-containing thin film of claim 1 to form a pixel electrode or a reflective film. .
상기 표시장치용 어레이기판은 액정표시장치용 또는 유기발광소자용인 것을 특징으로 하는 표시장치용 어레이기판의 제조방법.
In claim 7,
A method of manufacturing an array substrate for a display device, wherein the array substrate for a display device is for a liquid crystal display device or an organic light emitting device.
An array substrate for a display device etched using the etchant composition of any one of claims 1 to 6.
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| US6630433B2 (en) * | 1999-07-19 | 2003-10-07 | Honeywell International Inc. | Composition for chemical mechanical planarization of copper, tantalum and tantalum nitride |
| JP2004076103A (en) * | 2002-08-19 | 2004-03-11 | Kobe Steel Ltd | Etchant for thin silver alloy film and pattern formation method using the same |
| KR100579421B1 (en) | 2004-11-20 | 2006-05-12 | 테크노세미켐 주식회사 | Etching composition for ag |
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| KR20140086669A (en) * | 2012-12-28 | 2014-07-08 | 동우 화인켐 주식회사 | Etchant composition for metal oxide layer |
| KR102245565B1 (en) * | 2015-02-10 | 2021-04-28 | 동우 화인켐 주식회사 | Etching solution composition for silver layer and an display substrate using the same |
| KR102121805B1 (en) * | 2015-02-16 | 2020-06-11 | 동우 화인켐 주식회사 | Etchant composition for ag thin layer and method for fabricating metal pattern using the same |
| KR20160108944A (en) * | 2015-03-09 | 2016-09-21 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
| KR102259145B1 (en) * | 2015-03-26 | 2021-06-01 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
| 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 |
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