KR20150004971A - Manufacturing method of an array substrate for liquid crystal display - Google Patents
Manufacturing method of an array substrate for liquid crystal display Download PDFInfo
- Publication number
- KR20150004971A KR20150004971A KR20130077823A KR20130077823A KR20150004971A KR 20150004971 A KR20150004971 A KR 20150004971A KR 20130077823 A KR20130077823 A KR 20130077823A KR 20130077823 A KR20130077823 A KR 20130077823A KR 20150004971 A KR20150004971 A KR 20150004971A
- Authority
- KR
- South Korea
- Prior art keywords
- film
- copper
- group
- forming
- based metal
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 56
- 238000005530 etching Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 18
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 25
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 18
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- -1 azole compound Chemical class 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 claims description 2
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 2
- 239000010408 film Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 229910016027 MoTi Inorganic materials 0.000 description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Nonlinear Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Weting (AREA)
Abstract
A) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer (n + a-Si: H and a-Si: H) on the gate insulating layer; d) forming a source / drain electrode on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, wherein in the step a) or d), the copper-based metal film is etched to form each electrode Wherein the etchant composition for use in the etching comprises polyalcohol type surfactant and citric acid as a treatment amount improving agent. The present invention also relates to a method for producing an array substrate for a liquid crystal display device.
Description
The present invention relates to a method of manufacturing an array substrate for a liquid crystal display.
A typical example of an electronic circuit for driving a semiconductor device and a flat panel display device is a thin film transistor (TFT). The manufacturing process of a TFT is generally composed of forming a metal film as a gate and a data wiring material on a substrate, forming a photoresist in a selective region of the metal film, and etching the upper metal film using the photoresist as a mask.
Typically, as the gate and data wiring material, a copper single film or a copper alloy film containing copper having good electrical conductivity and low resistance and a metal oxide film having excellent interfacial adhesion to these films are used. In recent years, a film containing indium oxide, zinc oxide, or a mixture thereof together with gallium oxide has been used as a metal oxide film in order to improve the performance of a TFT.
Korean Patent Laid-Open Publication No. 10-2006-0064881 discloses a composition containing an aqueous solution of hydrogen peroxide, an organic acid, an azole compound, a fluorine compound and an IDA-type compound as a chelate by etching an etching solution of copper molybdenum film. When the copper molybdenum film is etched with the etching solution, a tape profile having excellent linearity is formed, and the residue of the molybdenum alloy is not left after the etching. However, since the number of the etching treatment after 30 days is remarkably reduced, There is a problem that the heat stability is extremely low.
It is an object of the present invention to provide a method of manufacturing an array substrate for a liquid crystal display, which comprises a copper-based metal film.
It is also an object of the present invention to provide a copper-based metal film etchant composition exhibiting an excellent etching profile as well as an improved storage stability.
In order to achieve the above object,
a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer (n + a-Si: H and a-Si: H) on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The etchant composition used in the etching includes a polyhydric alcohol type surfactant and citric acid as a treatment amount improving agent, and the step (a) or (d) includes forming each electrode by etching a copper-based metal film. The present invention also provides a method of manufacturing an array substrate for a liquid crystal display.
The present invention also provides an etchant composition for a copper-based metal film, which comprises a polyhydric alcohol-type surfactant and citric acid as a treatment amount-improving agent.
The etchant composition of the copper-based metal film according to the present invention has remarkably improved the number of etched treatments by using citric acid as a process enhancing agent, and particularly shows excellent effects in terms of the number of etched treatments even after storage for 30 days or longer, . Furthermore, the heat stability is also greatly improved.
The present invention relates to a batch etching solution composition of a copper-based metal film containing a polyhydric alcohol-type surfactant and citric acid as a treatment amount improving agent.
In the present invention, the copper-based metal film is a single film of copper or a copper alloy in which copper is contained in the constituent components of the film; And a multilayer film comprising at least one film selected from a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film.
Here, the alloy film is a concept including a nitride film or an oxide film.
Examples of the multilayer film include a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, a double film such as a copper / titanium film, or a triple film. The copper / molybdenum film means that the copper / molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, Means that the alloy / molybdenum alloy film includes a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper / titanium film includes a titanium layer and a copper layer formed on the titanium layer.
The molybdenum alloy layer may be at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium Means a layer made of an alloy of metal and molybdenum.
In particular, the etchant composition of the present invention can be preferably applied to a multilayer film made of a copper or copper alloy film and a molybdenum or molybdenum alloy film.
1. Etchant composition
The polyhydric alcohol type surfactant (A) contained in the etchant composition of the present invention serves to lower the surface tension and increase the uniformity of the etching. In addition, the polyhydric alcohol type surfactant (A) encapsulates copper ions dissolved in the etching solution after etching the copper film, thereby suppressing the activity of copper ions and inhibiting the decomposition reaction of hydrogen peroxide. Thus, lowering the activity of the copper ion allows the process to proceed stably while using the etchant. The content of the A) polyhydric alcohol type surfactant is in the range of 0.001 to 5.0% by weight based on the total weight of the composition, and particularly preferably in the range of 0.1 to 3.0% by weight. When the content of the A) polyhydric alcohol surfactant is less than the above range, the etching uniformity is lowered and the decomposition of hydrogen peroxide accelerates, so that a heat generation phenomenon may occur when a certain amount of copper is treated. If the content of the polyhydric alcohol type surfactant (A) is in the above range, there is a disadvantage that much foam is generated.
Examples of the polyhydric alcohol type surfactant (A) include glycerol, triethylene glycol, and polyethylene glycol. Of these, triethylene glycol is preferable.
B) citric acid contained in the etchant composition of the present invention serves to increase the number of treatments of the copper-based metal film as a treatment quantity improving agent. In the case of IDA (iminodiacetic acid) as a process improvement agent used in the past, it was indispensable factor for improving the number of treatments in the etching of the copper-based metal film, but there was a phenomenon in which the number of treatments do. In addition, there are many examples of the use of organic acid used in the etching of a copper-based metal film, but not all organic acids contribute to the improvement of the number of treatments, and only citric acid serves to increase the number of treatments in etching the copper-based metal film. The B) citric acid is contained in an amount of 1.0 to 10.0% by weight, preferably 3.0 to 7.0% by weight based on the total weight of the composition. The etching rate of the copper-based metal film becomes slower than the range described above, and etch residues may be generated. If it is contained in excess of the above-mentioned range, it may lead to over etching of the copper-based metal film.
The etchant composition may further comprise hydrogen peroxide, a fluorinated compound, an azole compound, and a residual amount of water.
The C) hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is a main component for etching the copper-based metal film, and it also enhances the activity of the D) fluorine compound which may be further included.
The C) hydrogen peroxide (H 2 O 2 ) is contained in an amount of 15.0 to 25.0% by weight, preferably 18.0 to 23.0% by weight, based on the total weight of the composition. If it is contained below the above-mentioned range, the copper-based metal film is not etched or the etching rate is very slow. If it exceeds the above-mentioned range, it is difficult to control the process because the etching rate is accelerated as a whole.
The fluorine-containing compound (D) contained in the etchant composition of the present invention means a compound capable of releasing fluorine ions by being dissolved in water. The D) fluorine compound is a main component for etching a copper-based metal film and removes residues that are inevitably generated in molybdenum and molybdenum alloy films.
The D) fluorine compound is contained in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.20% by weight based on the total weight of the composition. If it is contained below the above-mentioned range, the etching rate of the molybdenum or molybdenum alloy film may be slowed, and etch residues may be generated. If it exceeds the above range, there is a problem that the etching rate of the glass substrate becomes large.
The D) fluorine compound is not particularly limited as long as it can be dissociated into a fluorine ion or a polyatomic fluorine ion in a solution used in this field. However, the D) fluorine compound may be a fluorine compound such as ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF ), Sodium bifluoride (NaF 占 HF), and potassium bifluoride (KF 占 HF).
The E) azole compound contained in the etchant composition of the present invention controls the etch rate of the copper-based metal film and reduces the CD loss of the pattern, thereby enhancing the process margin.
The E) azole compound is contained in an amount of 0.1 to 5.0% by weight, preferably 0.3 to 1.0% by weight, based on the total weight of the composition. If it is included below the above-mentioned range, the etching rate becomes high and the seed loss can be caused to be too large. If contained in excess of the above-mentioned range, the etching rate of the copper-based metal film becomes too slow, and etching residues may be generated. The E) azole compound may be selected from the group consisting of 5-aminotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4- triazole, aminotetrazole ), Benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole , 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole.
F) water contained in the etchant composition of the present invention is not particularly limited, but deionized water is preferred. More preferably, it is preferable to use deionized water having a resistivity value of water (i.e., the degree of removal of ions in water) of 18 M OMEGA .cm or more. The F) water is contained in such an amount that the total weight of the etchant composition of the present invention is 100% by weight.
Each component used in the present invention can be manufactured by a conventionally known method, and the etchant composition of the present invention preferably has purity for semiconductor processing.
2. Manufacturing Method of Array Substrate for Liquid Crystal Display
In the method for manufacturing an array substrate for a liquid crystal display of the present invention,
a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer (n + a-Si: H and a-Si: H) on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The step a) or d) comprises forming a copper-based metal film on the substrate and etching the copper-based metal film with the etching solution composition of the present invention to form a gate wiring or a source and a drain electrode. And may be a manufacturing method of an array substrate for a display device.
The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.
Examples 1 to 4, Comparative Example 1 to Comparative Example 3: Etchant Preparation of composition
180 kg of the etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared according to the compositions shown in Table 1 below.
(H 2 O 2 )
compound
compound
(TEG)
(Unit: wt%)
- Fluorine compounds: Ammonium bifluoride (NH 4 F · HF)
3-amino-1,2,4-triazole < / RTI >
- TEG: triethylene glycol
- IDA: Iminodiacetic acid
Test Example
:
Etchant
Evaluation of composition characteristics
<Cu / MoTi etching>
MoTi was deposited on a glass substrate (100 mm x 100 mm), a copper film was deposited on the MoTi, and then a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. Thereafter, etching processes were performed on Cu / MoTi using the etching composition compositions of Examples 1 to 4 and Comparative Examples 1 to 3, respectively.
(ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 30 캜 in the etching process. The etching time was about 100 ~ 300 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, model name S-4700), and the results are shown in Table 2 below.
≪ Evaluation of processing number &
15 solutions of the chemical solutions of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared in an amount of 10 liters each. Add 10 g of copper powder to 80 g of 5 g unit to each prepared chemical liquid, and observe the temperature change of the chemical liquid for a certain period of time. The maximum concentration of the chemical solution, which does not generate heat even after a lapse of a predetermined time, is the number of treatments of the chemical solution.
The evaluation results are shown in Table 2.
<30 days post-storage processing evaluation>
15 solutions of the chemical solutions of Examples 1 to 4 and Comparative Examples 1 to 3 were prepared in an amount of 10 liters each. Each of the prepared solutions is stored at room temperature for 30 days, and then 10 g of copper powder is added to 80 g in 5 g increments to observe the temperature change of the solution for a certain period of time. The maximum concentration of the chemical solution that does not generate heat even after a certain period of time is the number of treatments after 30 days of storage of the chemical solution.
The evaluation results are shown in Table 2.
<Storage stability evaluation>
10 liters of the chemical solutions of Examples 1 to 4 and Comparative Examples 1 to 3 are prepared. After storing the chemical solution for 30 days at room temperature, add 50 g of copper powder to observe the temperature change of the chemical solution.
The evaluation results are shown in Table 2.
<Evaluation Criteria of Etching Profile>
?: A taper angle of not less than 35 ° and less than 60 °,
DELTA: The taper angle was 30 DEG or more to less than 35 DEG or 60 DEG or more to 65 DEG or less,
Х: The taper angle is less than 30 ° or more than 65 °,
Unetch: not etched
<Etching straightness evaluation standard>
&Amp; cir &: The pattern was formed as a straight line,
[Delta]: The shape of the curve in the pattern is 20% or less,
Х: Pattern has more than 20% curved shape,
Unetch: not etched
Referring to Table 2, all of the etching liquid compositions of Examples 1 to 4 exhibited good etching characteristics. Also, when the contents of the polyhydric alcohol type surfactant are compared with those of the examples 1, 2, and 3, it can be understood that the number of the processed products is improved. In particular, the polyalcohol type surfactant has an excellent number of treatments during the etching of the copper-based metal film.
On the other hand, in the case of Comparative Example 1, a composition containing glycolic acid instead of citric acid has good basic etching properties in etching a copper-based metal film, but does not contribute to the number of treatments.
Also, in the case of Comparative Example 2, the IDA type used for improving the number of treatments has good basic etching characteristics, but it can be seen that the number of treatments is decreased due to self-decomposition with time after 30 days storage.
In Comparative Example 3, when the polyhydric alcohol type surfactant was not included, it was found that there was no effect of improving the number of treatments, and it was found that the polyhydric alcohol type surfactant was effective in increasing the number of treated Cu have.
In the case of the etchant compositions of Examples 1 to 4, it was confirmed that the heat stability was excellent by maintaining the initial 28 to 31 ° C at a temperature (° C) when 5000 ppm of copper (Cu) was added after storage for 30 days have.
On the other hand, in the case of Comparative Example 1, since the etching capacity of the chemical solution does not become 700 ppm as shown in the number of treatments after 30 days storage, it can be seen that when more than 5000 ppm is added, the copper does not dissolve more than a certain amount.
In the case of Comparative Example 2, IDA is decomposed in the chemical solution although IDA is present. Because of this, there is no separate compound to capture the copper ion, so the added copper ion reacts with the fruit juice to cause fever.
In the case of Comparative Example 3, storage stability was deteriorated because citric acid was contained but no polyhydric alcohol type surfactant was included.
Claims (13)
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer (n + a-Si: H and a-Si: H) on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The etchant composition used in the etching includes a polyhydric alcohol type surfactant and citric acid as a treatment amount improving agent, and the step (a) or (d) includes forming each electrode by etching a copper-based metal film. Wherein the method comprises the steps of:
Wherein the etchant composition further comprises hydrogen peroxide.
Wherein the etchant composition further comprises at least one compound selected from the group consisting of fluorine compounds and azole compounds.
The copper-based metal film may be a single film of copper or a copper alloy; And at least one film selected from the group consisting of a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film. / RTI >
Wherein the etchant composition further comprises hydrogen peroxide.
Wherein the etchant composition further comprises at least one compound selected from the group consisting of fluorine compounds and azole compounds.
The copper-based metal film may be a single film of copper or a copper alloy; And at least one film selected from the group consisting of a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film, Composition.
A) 0.001 to 5.0% by weight of a polyhydric alcohol type surfactant; And
B) citric acid 1.0 to 10.0 wt%
C) 15.0 to 25.0% by weight of water (H 2 O 2 );
D) 0.01 to 1.0% by weight of a fluorine compound;
E) 0.1 to 5.0% by weight of an azole compound; And
F) residual water.
Wherein the A) polyhydric alcohol surfactant is at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol.
The D) fluorinated compound may be selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF) Wherein the copper-based metal film is at least one selected from the group consisting of sodium bifluoride (NaF.HF) and potassium bifluoride (KF.HF).
The E) azole compound may be selected from the group consisting of 5-aminotriazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4- triazole, aminotetrazole ), Benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole , 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole. The copper-based metal film etchant composition
The copper-based metal film may be a single film of copper or a copper alloy; And at least one film selected from the group consisting of a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film, Composition.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130077823A KR20150004971A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
| CN201910330615.3A CN110147008B (en) | 2013-07-03 | 2014-06-04 | Method for manufacturing array substrate for liquid crystal display |
| CN201410246018.XA CN104280916A (en) | 2013-07-03 | 2014-06-04 | Method for manufacturing array substrate of liquid crystal display |
| TW103121389A TWI632670B (en) | 2013-07-03 | 2014-06-20 | Method of manufacturing array substrate for liquid crystal display |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130077823A KR20150004971A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150004971A true KR20150004971A (en) | 2015-01-14 |
Family
ID=52476930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR20130077823A KR20150004971A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150004971A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190106475A (en) * | 2018-03-09 | 2019-09-18 | 동우 화인켐 주식회사 | Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display |
| KR20200114895A (en) | 2019-03-29 | 2020-10-07 | 동우 화인켐 주식회사 | A manufacturing method of an array substrate for liquid crystal display |
-
2013
- 2013-07-03 KR KR20130077823A patent/KR20150004971A/en active Search and Examination
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190106475A (en) * | 2018-03-09 | 2019-09-18 | 동우 화인켐 주식회사 | Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display |
| KR20200114895A (en) | 2019-03-29 | 2020-10-07 | 동우 화인켐 주식회사 | A manufacturing method of an array substrate for liquid crystal display |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102160286B1 (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR101608873B1 (en) | Etchant for metal wire and method for manufacturing metal wire using the same | |
| CN110147008B (en) | Method for manufacturing array substrate for liquid crystal display | |
| KR102209423B1 (en) | Etching solution composition for metal layer and manufacturing method of an array substrate for liquid crystal display using the same | |
| KR20150124540A (en) | Echtant and method for manufacturing display device using the same | |
| KR102660286B1 (en) | Etching solution composition for copper-based metal layer and metal oxide layer and method of etching using the same | |
| KR102269327B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR20150004972A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR20150004971A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR102282958B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR20170047921A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR101934863B1 (en) | Etchant composition for etching double layer of metal layer and indium oxide layer and method for etching using the same | |
| KR102362555B1 (en) | Composition for Etching Copper-Containing Metal Layer | |
| KR20170089315A (en) | Manufacturing method of an array substrate for crystal display | |
| KR102281191B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR102282957B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR102265898B1 (en) | Etching solution composition for cupper-based metal layer and method for etching cupper-based metal layer using the same | |
| KR20150004970A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR102639571B1 (en) | A manufacturing method of an array substrate for liquid crystal display | |
| KR20130018531A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR102204219B1 (en) | Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same | |
| KR102148879B1 (en) | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same | |
| KR102677476B1 (en) | Etching solution composition and method of manufacturing metal pattern | |
| KR20160107763A (en) | Etching solution composition and manufacturing method of an array substrate for Liquid crystal display using the same | |
| KR102423633B1 (en) | Manufacturing method of an array substrate for liquid crystal display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment |