CN103824808A - Etchant composition, method for forming LED wiring, array substrate, and method for manufacturing array substrate - Google Patents
Etchant composition, method for forming LED wiring, array substrate, and method for manufacturing array substrate Download PDFInfo
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- CN103824808A CN103824808A CN201310471239.2A CN201310471239A CN103824808A CN 103824808 A CN103824808 A CN 103824808A CN 201310471239 A CN201310471239 A CN 201310471239A CN 103824808 A CN103824808 A CN 103824808A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 71
- 239000002184 metal Substances 0.000 claims abstract description 71
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 16
- 239000010408 film Substances 0.000 claims description 101
- 238000005530 etching Methods 0.000 claims description 84
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 239000002131 composite material Substances 0.000 claims description 51
- 150000004706 metal oxides Chemical class 0.000 claims description 36
- 238000009413 insulation Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 235000019262 disodium citrate Nutrition 0.000 claims description 2
- 239000002526 disodium citrate Substances 0.000 claims description 2
- 229940079896 disodium hydrogen citrate Drugs 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- -1 phosphate salt compounds Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
-
- 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
-
- 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
-
- 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
- G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66742—Thin film unipolar transistors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
Abstract
The invention relates to a method for manufacturing an array substrate for a liquid crystal display. The method comprises steps of (a) forming a gate on a substrate, (b) forming a gate insulating layer on the substrate having the gate, (c) forming a metallic oxide film (active layer) on the gate insulating layer, and (d) forming a Mo metal film (source/drain) on the metallic oxide film. The (d) includes forming the Mo metal film on the metallic oxide film and using an etchant composition to etch the Mo metal film. Based on the total weight of the composition, the etchant composition contains (A) hydrogen peroxide (H2O2), (B) pH modifier and (c) the balance being water. The invention further relates to the etchant composition, a method for forming LED wiring, and the array susbtrate for an LCD display.
Description
The cross reference of related application
The application requires the rights and interests of the korean patent application 10-2012-0130686 submitting on November 19th, 2012, thereby is incorporated to by quoting in full.
Technical field
The present invention relates to etching agent composite, form the method for wiring and manufacture the method for the array base palte of liquid crystal display (LCD) with it, wherein, in the bilayer that comprises Mo metal film/metal oxide film of wiring that is used to form thin-film transistor (TFT), this etching agent composite can make to the erosion of lower metal oxidation film minimize, for top Mo metal film can form have excellent linear tapered profiles and can be optionally etching top Mo metal film only.
Background technology
According to the kind of substrate and desired properties, comprise various metals or their alloy for the metal line material of the semiconductor device such as TFT-LCD, the example of these metal or alloy can comprise Al, Al-Cu, Ti-W, Ti-N etc.Particularly, there is go between/leakage of the source class level lead-in wire that low-resistance Al or its alloy are mainly used in TFT-LCD.
But, recently because should improve electrical property according to the manufacture of process simplification, cost and large substrates, replacing traditional Cr individual layer, or the single or multiple lift of Al or Al alloy (for example, tri-layers of Mp/Al-Nd bilayer or Mp/Al-Nd/Mo) and use the trial of the individual layer that formed by Mo.
Meanwhile, mainly formed by amorphous silicon or polysilicon for the semiconductor layer of the TFT that drives flat-panel monitor.With regard to film forming process, amorphous silicon is simple, and production cost is low, but its electric reliability is not guaranteed; And polysilicon is because high processing temperature is very difficult to be applied to large-area formation, and can not guarantee to depend on the uniformity of crystallization process.
But, in the situation that semiconductor layer is made up of oxide, even, in the time that it forms at low temperatures, also can obtain high mobility, and the change of resistance is large, proportional with oxygen content, thus be highly susceptible to obtaining required character.Therefore, it is applied to TFT and receives great concern.
For example, attempt using a kind of method of manufacturing following TFT to form the wiring of tft array, this TFT uses the bilayer that comprises Mo metal film/metal oxide film.For this reason, need can be optionally etching Mo metal film and do not corrode the technology of lower metal oxide only.
Thus, Korean patent application publication 10-2010-0082094 discloses etching agent composite, and this etching agent composite is used for Cu film, Cu alloy film, Ti film, Ti alloy film, Mo metal film, Mo alloy film or comprises their stacked multilayer film.This etching agent composite comprises the peroxide, oxidant, fluorochemical, additive and the deionized water that are selected from sodium peroxydisulfate, potassium peroxydisulfate and their mixture.In addition, Korean patent application publication 10-2007-0005275 discloses wet etchant composition, this wet etchant composition is applicable to comprise the single or multiple lift of Mo, Al, Mo alloy or Al alloy, the water (H2O) that this etching agent composite comprises phosphoric acid, nitric acid, inorganic phosphate salt compounds or inorganic nitrate compounds and surplus.
But, because use and comprise in the method for double-deck TFT of Mo metal film/metal oxide film in manufacture, in the time of etching Mo metal film, there is the worry of the erosion to lower metal oxide, so these etching agent composites are problematic.
[quoted passage list]
[patent document]
Korean patent application publication 10-2010-0082094
Korean patent application publication 10-2007-0005275
Summary of the invention
Therefore, the present invention keeps in mind the problems referred to above that run in correlation technique, and the object of this invention is to provide etching agent composite, use described etching agent composite form the method for wiring and manufacture the method for the array base palte of liquid crystal display, wherein, in the bilayer that comprises Mo metal film/metal oxide film of wiring that is used to form tft array, described etching agent composite can make the erosion of lower metal oxidation film minimize, for top Mo metal film can form have excellent linear tapered profiles and can be optionally etching top Mo metal film only.
To achieve these goals, the invention provides etching agent composite, comprise: (A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt%; And (C) water of surplus, wherein, comprising in the bilayer of Mo metal film/metal oxide film, etching agent composite etching described in the Mo metal membrane-coating of top.
In addition, the invention provides the method for the wiring that forms liquid crystal display, described method comprises: (I) on substrate, form metal oxide film; (II) on described metal oxide film, form Mo metal film; (III) optionally light-sensitive material is stayed on described Mo metal film; And (IV) use Mo metal film described in etching agent composite etching, wherein, based on the total weight of described composition, described etching agent composite comprises: (A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
In addition, the invention provides the method for manufacturing for the array base palte of liquid crystal display, described method comprises: (a) on substrate, form grid; (b) on the substrate with described grid, form gate insulation layer; (c) on described gate insulation layer, form the metal oxide semiconductor layer (active layer) as metal oxide film; And (d) on described metal oxide semiconductor layer, form Mo metal film (source/drain), wherein, (d) be included in and on described metal oxide semiconductor layer, form described Mo metal film and carry out Mo metal film described in etching with etching agent composite, based on the total weight of described composition, described etching agent composite comprises: (A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
Accompanying drawing explanation
In detailed description below in conjunction with accompanying drawing, above-mentioned and other object, the Characteristics and advantages of the present invention will be more clearly understood, wherein:
Fig. 1 illustrate use embodiment 1 etching agent composite scanning electron microscopy (SEM) image of etched Mo metal film and metal oxide film;
Fig. 2 illustrate use embodiment 3 etching agent composite the SEM image of etched Mo metal film and metal oxide film;
Fig. 3 illustrate use embodiment 4 etching agent composite the SEM image of etched Mo metal film and metal oxide film;
Fig. 4 illustrate use comparative example 2 etching agent composite the SEM image of etched Mo metal film and metal oxide film.
Embodiment
Hereinafter, the invention will now be more particularly described.
The present invention proposes etching agent composite, and described etching agent composite comprises: A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt%; And (C) water of surplus, wherein, comprising in the bilayer of Mo metal film/metal oxide film, etching agent composite etching described in the Mo metal membrane-coating of top.
As used herein, term " metal oxide film " refers to and contains AxByCzO(A, B, C=Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; X, y, z >=0, wherein two or more in x, y and z are not zero) ternary oxide or the film of quaternary oxide, and can refer to oxide semiconductor layer or the film for oxide semiconductor layer.
In etching agent composite according to the present invention, (A) hydrogen peroxide (H
2o
2) as the primary oxidant of etching top Mo metal film.In addition, based on the total weight of composition, with the amount of 5.0～25.0wt%, and preferably use (A) hydrogen peroxide (H with the amount of 8.0～16.0wt%
2o
2).If its amount is less than above-mentioned lower limit, the etching performance variation of the composition of gained, thus can not carry out abundant etching.In contrast, if its amount exceedes 25.0wt%, total etch-rate may increase, and makes to be difficult to control this process.
In etching agent composite according to the present invention, (B) pH adjusting agent refers to the compound that dissociates the pH that improves etchant in hydrogen peroxide and water.(B) pH adjusting agent plays increases the etch-rate of top Mo metal film, remove the residue mainly being produced by etchant solutions and make the minimized effect of the erosion of lower metal oxidation film.
Based on the total weight of composition, use (B) pH adjusting agent with the amount of 1.0～5.0wt%.If its amount is less than above-mentioned lower limit, the etch-rate of top Mo metal film may decline, thus part not etching maybe may produce residue, and may become serious to the erosion of lower metal oxidation film.In contrast, if its amount exceedes 5.0wt%, top Mo metal film may be by over etching, thereby this metal film may be peeled off from substrate (lift-off).
(B) pH adjusting agent is for activating the etching behavior of hydrogen peroxide, and its example can comprise Sodium citrate/DisodiumHydrogen Citrate, sodium hydrogen phosphate/trisodium citrate, or ammonium acetate.In addition, this conditioning agent is the additive conventionally using in etchant solutions, and can comprise another kind of additive and be not particularly limited, and the example of another kind of additive can comprise surfactant, chelating agent etc.Thereby add surfactant and improve etch uniformity with the viscosity that reduces etching solution, and can use any anion surfactant, cationic surfactant, amphoteric surfactant or non-ionic surface active agent, preferred fluorinated surfactant, as long as its etch resistant solution compatible with it.
In etching agent composite according to the present invention, (C) water is not particularly limited, but preferably includes deionized water (DIW).Useful especially is the deionized water that resistivity (, removing the degree of ion from water) is at least 18M Ω cm.In addition, use (C) with surplus it is 100wt% that thus water makes according to the total weight of etching agent composite of the present invention.
Except said components, can also use common additive, and can comprise such as chelating agent, corrosion inhibitor etc.
In the present invention, prepare (A) hydrogen peroxide (H by common known method
2o
2), (B) pH adjusting agent and (C) water, and preferably there is the purity of the semiconductor processes of being applicable to according to etching agent composite of the present invention.
In addition, the present invention proposes the method for the wiring that forms liquid crystal display, and described method comprises: (I) on substrate, form metal oxide film; (II) on described metal oxide film, form Mo metal film; (III) optionally light-sensitive material is stayed on described Mo metal film; And (IV) use Mo metal film described in etching agent composite etching, wherein, based on the total weight of composition, described etching agent composite comprises: (A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
In the method for formation according to the present invention wiring, light-sensitive material is common photoresist preferably, and can use common exposure and development and optionally stay.
In addition, the present invention proposes to manufacture the method for the array base palte of liquid crystal display, and described method comprises: (a) on substrate, form grid; (b) on the substrate with described grid, form gate insulation layer; (c) on described gate insulation layer, form the metal oxide semiconductor layer (active layer) as metal oxide film; And (d) on described metal oxide semiconductor layer, form Mo metal film (source/drain), wherein, (d) be included in and on described metal oxide semiconductor layer, form described Mo metal film and carry out Mo metal film described in etching with etching agent composite, based on the total weight of composition, described etching agent composite comprises: (A) hydrogen peroxide (H of 5.0～25.0wt%
2o
2); (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
Allow to form for the method for the array base palte of liquid crystal display the bilayer that comprises Mo metal film/metal oxide film according to manufacture of the present invention.
The above-mentioned array base palte for liquid crystal display can be tft array substrate.This array base palte that is used for liquid crystal display comprises to be used according to the next etched Mo metal film of etching agent composite of the present invention.
Can use this area of comprising such as submergence, spilling (spill) etc. conventionally known technique use etching agent composite etching Mo metal film.Can, at the temperature of 20～50 ℃, preferably at the temperature of 30～45 ℃, carry out etching process; If need, can determine suitable processing temperature according to other processing conditions and processing factors.
According to the thickness of temperature and film, carrying out the required time of etching Mo metal film with etching agent composite may change, but is conventionally set to several seconds to the scope between dozens of minutes.
In addition, the present invention proposes the array base palte for liquid crystal display, and this array base palte comprises that use is according to the etching agent composite etched source electrode of institute of the present invention and drain electrode.
The more detailed description of the present invention by the following examples and comparative example below.
< embodiment >
the preparation of etching agent composite
Carry out the etching agent composite of Preparation Example 1～4 and comparative example 1 and 2 with the composition shown in table 1 below.
[table 1]
| Unit: wt%H 2O 2PH adjusting agent DIWMo etching character | To the erosion of metal oxide film |
| Embodiment 112187 ◎ | Nothing |
| Embodiment 215184 ◎ | Nothing |
| Embodiment 315,580 0 | Nothing |
| Embodiment 425174 △ | Nothing |
| Comparative example 13097x | Have |
| Comparative example 212088 ◎ | Have |
◎: excellent (CD skew (Skew) :≤1 μ m, cone angle: 40 °～60 °)
Zero: good (CD skew :≤1.5 μ m, cone angle: 30 °～60 °)
△: general (CD skew :≤2 μ m, cone angle: 20 °～60 °)
X: poor (metal film loss and generation residue)
test case: the Performance Evaluation of etching agent composite
Come etching top Mo metal film and lower metal oxidation film with the each composition in embodiment 1～4 and comparative example 1 and 2.For this reason, used atomizing etching machine (etching machine (ETCHER) obtaining from SEMES (TFT)), and the temperature setting of etching agent composite has been set to approximately 40 ℃ in the time of etching.But if needed, according to other processing conditions and processing factors, suitable temperature can change.According to etch temperature, etching period can change, but is conventionally set to approximately 100 seconds.Use the S-4700 that obtains from HITACHI of SEM() observe etching process the image of etched Mo metal film and metal oxide film.
From table 1 and Fig. 1～3, obviously, all etchants in embodiment 1～4 show to the proportional good etching performance of growth of the amount of hydrogen peroxide and do not produce residue.Particularly, the etchant of the embodiment 4 that contains a large amount of hydrogen peroxide demonstrates the high etch rates to Mo metal film.
And, as seen in Figure 2, in the time that the amount of pH adjusting agent increases, the increase with regard to the etch-rate of Mo metal film of the etchant of embodiment 3.
The amount that the etchant of comparative example 1 contains hydrogen peroxide is far below above-mentioned scope, and therefore Mo metal film part is etched and produce residue.As seen in Figure 4, the etchant of comparative example 2 shows the excellent etching performance to top Mo metal film, but because not using pH adjusting agent to demonstrate the erosion to lower metal oxidation film.
As described above, the invention provides the method for manufacturing for the array base palte of liquid crystal display.According to the present invention, in the bilayer that comprises Mo metal film/metal oxide film of wiring that is used to form tft array, etching agent composite can make to the erosion of lower metal oxidation film minimize, for top Mo metal film can form have excellent linear tapered profiles and can be optionally etching top Mo metal film only.
Can carry out various modifications, increase and replace and not deviate from as disclosed scope and spirit of the present invention in the appended claims although the preferred embodiment of the present invention, for illustration purpose is disclosed, it will be appreciated by those skilled in the art that.
Claims (8)
1. manufacture, for a method for the array base palte of liquid crystal display, comprising:
(a) on substrate, form grid;
(b) on the described substrate with described grid, form gate insulation layer;
(c) on described gate insulation layer, form the metal oxide film as active layer; And
(d) on described metal oxide film, form the Mo metal film as source/drain,
Wherein, (d) be included in and on described metal oxide film, form described Mo metal film and carry out Mo metal film described in etching with etching agent composite, based on the total weight of described composition, described etching agent composite comprises: (A) hydrogen peroxide of 5.0～25.0wt%; (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
2. method according to claim 1, wherein, the described array base palte for liquid crystal display is thin-film transistor array base-plate.
3. method according to claim 1, wherein, described metal oxide film is the ternary oxide that contains AxByCzO or the film of quaternary oxide, A, B, C=Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; X, y, z >=0, wherein two or more in x, y and z are not zero.
4. an etching agent composite, comprises:
(A) hydrogen peroxide of 5.0～25.0wt%;
(B) pH adjusting agent of 1.0～5.0wt%; And
(C) water of surplus,
Wherein, comprising in the bilayer of Mo metal film/metal oxide film, etching agent composite etching described in the Mo metal membrane-coating of top.
5. etching agent composite according to claim 4, wherein, (B) pH adjusting agent is Sodium citrate/DisodiumHydrogen Citrate, sodium hydrogen phosphate/trisodium citrate, or ammonium acetate.
6. etching agent composite according to claim 4, also comprises chelating agent or anticorrosive.
7. form a method for the wiring of liquid crystal display, described method comprises:
(I) on substrate, form metal oxide film;
(II) on described metal oxide film, form Mo metal film;
(III) optionally light-sensitive material is stayed on described Mo metal film; And
(IV) Mo metal film described in the etching of use etching agent composite,
Wherein, based on the total weight of described composition, described etching agent composite comprises: (A) hydrogen peroxide of 5.0～25.0wt%; (B) pH adjusting agent of 1.0～5.0wt% and (C) water of surplus.
8. for an array base palte for liquid crystal display, described array base palte comprises the use etching agent composite etched source electrode of institute according to claim 4 and drain electrode.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120130686A KR20140065616A (en) | 2012-11-19 | 2012-11-19 | Manufacturing method of an array substrate for liquid crystal display |
| KR10-2012-0130686 | 2012-11-19 |
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| Publication Number | Publication Date |
|---|---|
| CN103824808A true CN103824808A (en) | 2014-05-28 |
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|---|---|---|---|
| CN201310471239.2A Pending CN103824808A (en) | 2012-11-19 | 2013-10-10 | Etchant composition, method for forming LED wiring, array substrate, and method for manufacturing array substrate |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20140065616A (en) |
| CN (1) | CN103824808A (en) |
| TW (1) | TWI608125B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107475716A (en) * | 2016-06-08 | 2017-12-15 | 东友精细化工有限公司 | The etchant of copper system metal film and its application |
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|---|---|---|---|---|
| US20080318368A1 (en) * | 2007-06-20 | 2008-12-25 | Samsung Electronics Co., Ltd. | Method of manufacturing ZnO-based this film transistor |
| CN101952485A (en) * | 2007-11-22 | 2011-01-19 | 出光兴产株式会社 | Etching liquid composition |
| CN102637591A (en) * | 2012-05-03 | 2012-08-15 | 华南理工大学 | Method for etching electrode layer on oxide semiconductor |
| CN102648269A (en) * | 2009-11-16 | 2012-08-22 | 东友Fine-Chem股份有限公司 | Etchant composition for a single molybdenum film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY152247A (en) * | 2007-12-21 | 2014-09-15 | Wako Pure Chem Ind Ltd | Etching agent, etching method and liquid for preparing etching agent |
| KR101619380B1 (en) * | 2009-05-14 | 2016-05-11 | 삼성디스플레이 주식회사 | Etchant and method of array substrate using the same |
-
2012
- 2012-11-19 KR KR1020120130686A patent/KR20140065616A/en not_active Application Discontinuation
-
2013
- 2013-10-10 CN CN201310471239.2A patent/CN103824808A/en active Pending
- 2013-11-04 TW TW102139895A patent/TWI608125B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080318368A1 (en) * | 2007-06-20 | 2008-12-25 | Samsung Electronics Co., Ltd. | Method of manufacturing ZnO-based this film transistor |
| CN101952485A (en) * | 2007-11-22 | 2011-01-19 | 出光兴产株式会社 | Etching liquid composition |
| CN102648269A (en) * | 2009-11-16 | 2012-08-22 | 东友Fine-Chem股份有限公司 | Etchant composition for a single molybdenum film |
| CN102637591A (en) * | 2012-05-03 | 2012-08-15 | 华南理工大学 | Method for etching electrode layer on oxide semiconductor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107475716A (en) * | 2016-06-08 | 2017-12-15 | 东友精细化工有限公司 | The etchant of copper system metal film and its application |
| CN107475716B (en) * | 2016-06-08 | 2021-07-09 | 东友精细化工有限公司 | Etching solution composition for copper-based metal film and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201420811A (en) | 2014-06-01 |
| KR20140065616A (en) | 2014-05-30 |
| TWI608125B (en) | 2017-12-11 |
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