CN110359050A - Argentiferous film etching liquid composition, the array substrate and its manufacturing method for display device manufactured with it - Google Patents
Argentiferous film etching liquid composition, the array substrate and its manufacturing method for display device manufactured with it Download PDFInfo
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- CN110359050A CN110359050A CN201811267385.2A CN201811267385A CN110359050A CN 110359050 A CN110359050 A CN 110359050A CN 201811267385 A CN201811267385 A CN 201811267385A CN 110359050 A CN110359050 A CN 110359050A
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- weight
- transparent conductive
- film
- silver
- display device
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- 238000005530 etching Methods 0.000 title claims abstract description 65
- 239000000758 substrate Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- -1 inorganic acid salt Chemical class 0.000 claims abstract description 10
- 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 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-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
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 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
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 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
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- 239000004411 aluminium Substances 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
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 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
- 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 claims description 2
- 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
- 238000009738 saturating Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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 potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Geometry (AREA)
- Weting (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The array substrate and its manufacturing method for display device that the present invention provides a kind of argentiferous film etching liquid composition, it is utilized to manufacture, relative to the total weight of composition, which includes ferric nitrate, the inorganic acid salt of 0.5 to 5.0 weight % and the water of surplus of the phosphoric acid of 40.0 to 60.0 weight %, the nitric acid of 5.0 to 9.0 weight %, 0.1 to 4.0 weight %.
Description
Technical field
The present invention relates to a kind of argentiferous film etching liquid compositions, the array substrate for display device manufactured using it
And its manufacturing method.
Background technique
With the real information age is stepped into, for handling and showing that the field of display of bulk information rapidly develops,
It correspondingly develops a variety of flat-panel monitors and attracts attention.As the example of this panel display apparatus, liquid can be enumerated
Crystal display device (Liquid crystal display device:LCD), plasm display device (Plasma
Display Panel device:PDP), field-emission display device (Field Emission Display device:
FED), organic illuminating element (Organic Light Emitting Diodes:OLED) etc..
As an example, since OLED element itself issues light and can also be driven at low voltage, OLED mesh
It is preceding not only to be applied rapidly in the compact display apparatus such as portable equipment market, but also with the large screen trend of display device,
Commercialization is obtained in large-scale TV etc..With the large screen for realizing display device, wiring etc. is lengthened out and leads to routing resistance
Increase, it is therefore desirable to can reduce resistance to realize the enlarged and high-resolution method of display device.
Caused by order to solve because of resistance increase the problems such as signal delay, it is necessary to utilize the material with minimum specific resistance
Material is to form above-mentioned wiring.As a link of this effort, it is being dedicated to lower by that will have with other metal phase ratios
Specific resistance, higher brightness and conductivity silver (Ag: specific resistance is about 1.59 μ Ω cm) film, silver alloy film or comprising silverskin
Or the multilayer film of silver alloy film is applied in electrode, wiring and reflectance coating of colour filter etc. the large size for realizing panel display apparatus
Change, high-resolution and low power consumption etc., it is therefore desirable to for being applied to the etching solution of this material.
Using argentiferous (Ag) film, although adsorption phenomena will not be made silver again in low-resolution display device
It is problematic, but adsorption phenomena significantly throws into question silver again in high-definition display device technology.Related to thisly, it opens in the past
Sent out using etchant (Korean Patent Publication No. 10-0579421) comprising phosphoric acid, acetic acid or nitric acid etc. come
To the method being etched containing Ag films, but comprising acetic acid, there are ageing stabilities due to the strong volatility of acetic acid
The problem of decline, and the problem of rectilinear propagation control effect reduces occurs etc..
Existing technical literature
Patent document
Patent document 1: Korean Patent Publication No. 10-0579421
Summary of the invention
Technical problem
The present invention is proposed to solve above-mentioned problem of the prior art, a kind of containing Ag films erosion the purpose is to provide
Liquid composition is carved, which improves ageing stability problem when etching argentiferous metal film, and due to hardly
Excellent effect is showed there are silver-colored residue and silver-colored adsorption phenomena again, and there is excellent rectilinear propagation.
Moreover, it is an object that a kind of battle array for display device manufactured using the etchant
Column substrate and its manufacturing method.
Technological means
The present invention provides a kind of argentiferous film etching liquid composition, gross weight of the etchant relative to composition
Amount, the phosphoric acid comprising 40.0 to 60.0 weight %, the nitric acid of 5.0 to 9.0 weight %, the ferric nitrate of 0.1 to 4.0 weight %, 0.5
To the inorganic acid salt of 5.0 weight % and the water of surplus.
In addition, the present invention provides a kind of method for manufacturing the array substrate for display device, comprising:
A) grid wiring step: is formed on substrate；
B) step: gate insulating layer is formed on the substrate comprising the grid wiring；
C) step: oxide semiconductor layer is formed on the gate insulating layer；
D) step: source electrode and drain electrode are formed on the oxide semiconductor layer；And
E) step: forming the pixel electrode connecting with the drain electrode,
It is characterized in that, e) the step on substrate the following steps are included: form argentiferous (Ag) film, and utilize upper
Argentiferous film etching liquid composition is stated to be etched and form pixel electrode or reflectance coating.
In addition, the present invention provide it is a kind of made of being etched using above-mentioned etchant for display device
Array substrate.
Invention effect
The present invention provides a kind of argentiferous film etching liquid composition, which changes when etching argentiferous metal film
Kind ageing stability problem, and excellent effect is showed due to there's almost no silver-colored residue and silver-colored adsorption phenomena again, and
And there is excellent rectilinear propagation.
In addition, the present invention provides a kind of side of array substrate using the manufacture of above-mentioned etchant for display device
Method.
Detailed description of the invention
Fig. 1 is the photo for indicating that rectilinear propagation is excellent, is the test film that experimental example is etched using the composition of embodiment 1
When SEM photograph.
Fig. 2 is to indicate the undesirable photo of rectilinear propagation, is the test film that experimental example is etched using the composition of comparative example 1
When SEM photograph.
Specific embodiment
The present invention provides a kind of argentiferous film etching liquid composition, gross weight of the etchant relative to composition
Amount, the phosphoric acid comprising 40.0 to 60.0 weight %, the nitric acid of 5.0 to 9.0 weight %, the ferric nitrate of 0.1 to 4.0 weight %, 0.5
To the inorganic acid salt of 5.0 weight % and the water of surplus, which improves ageing stability when etching silver metal film
Problem, and there's almost no silver-colored residue and silver again adsorption phenomena and show excellent effect, and with excellent straight
Property.
In the present invention, containing Ag films may include silver or silver alloy monofilm or by the monofilm and transparent conductive
The multilayer film that film is constituted, but it is not limited to this.
In the present invention, transparent conductive film can be selected from by tin indium oxide (ITO), indium zinc oxide (IZO), tin indium oxide
One or more of group of compositions such as zinc (ITZO) and/or indium gallium zinc (IGZO), but it is not limited to this.
In the present invention, silver alloy may include silver-colored (Ag) and be selected from, nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), chromium
(Cr), in tin (Sn), palladium (Pd), neodymium (Nd), niobium (Nb), molybdenum (Mo), magnesium (Mg), tungsten (W), protactinium (Pa), aluminium (Al) and titanium (Ti)
More than one, but it is not limited to this.
In the present invention, transparent conductive film/silver, transparent biography can be by the multilayer film that monofilm and transparent conductive film are constituted
Guided membrane/silver alloy, transparent conductive film/silver/transparent conductive film or transparent conductive film/silver alloy/transparent conductive film, but and it is unlimited
In this.Transparent conductive film/silver/transparent conductive the film can be a-ITO/AgX/a-ITO, and but it is not limited to this.
Transparent conductive film of the invention is characterized as tin indium oxide (ITO), indium zinc oxide (IZO), tin indium oxide
Zinc (ITZO) and indium gallium zinc (IGZO).
Phosphoric acid (the H included in etching solution of the invention3PO4) it is ingredient as principal solution from agent, it executes by making silver
(Ag) and the oxidation of transparent conductive film and carry out the effect of wet etching.Relative to the total weight of etchant, phosphorus acid content
It can be 40.0 to 60.0 weight %.In the case where phosphorus acid content is less than 40 weight %, it is possible to the etching speed of silver can be caused
Degree reduces and etching outline is bad, and increases Ag and adsorb again；In the case where phosphorus acid content is greater than 60 weight %, transparent biography is reduced
The etching speed of guided membrane, and the etching speed of silver is too fast, generates the tip (Tip) of top and the bottom transparent conductive film, thus have
The drawback to throw into question in subsequent handling.
Nitric acid (the HNO included in etching solution of the invention3) it is the ingredient as oxidant, it executes by making silver
(Ag) and the oxidation of transparent conductive film and carry out the effect of wet etching.Relative to the total weight of etchant, nitric acid content
It can be 5.0 to 9.0 weight %.In the case where nitric acid content is less than 5.0 weight %, cause the etching of silver-colored (Ag) and ITO speed
Degree reduces, and causes the etch uniformity (Uniformity) in substrate bad, thus speckle occurs；It is greater than 9.0 in nitric acid content
In the case where weight %, the undercutting of top and the bottom transparent conductive film occurs because of the acceleration of the etching speed of top and the bottom transparent conductive film,
Thus have and throws into question in subsequent handling.
Ferric nitrate in etching solution of the invention is the ingredient as auxiliary oxidizing agent and Ag ligand, in wet etching
Reduce film adsorbing again and adjust etching speed to equably etch to Ag.Gross weight relative to etchant
Amount, nitric acid iron content can be 0.1 to 4.0 weight %.In the case where nitric acid iron content is less than 0.1 weight %, substrate is reduced
It interior etch uniformity (Uniformity) and is possible to that silver-colored residue can be locally generated in substrate；It is greater than in nitric acid iron content
In the case where 4.0 weight %, it is possible to cannot achieve required etching speed because etching speed reduces.
Inorganic acid salt in etching solution of the invention is the ingredient for controlling rectilinear propagation after the etching, relative to etching solution group
The total weight of object is closed, inorganic acid salt content can be 0.5~5 weight %.In the inorganic acid salt content less than 0.5 weight %'s
In the case of, cause electrical characteristics to decline and be possible to be locally generated residue in substrate because rectilinear propagation is bad；In the nothing
In the case that machine phosphate content is greater than 5.0 weight %, it is possible to generate because overetch occurs and cannot achieve required etching
The problem of speed.
In the present invention, the sylvite, sodium salt and/or ammonium salt of nitric acid, sulfuric acid and/or phosphoric acid can be used as inorganic acid salt
Deng preferable potassium nitrate or ammonium sulfate, it may be more preferable to potassium nitrate.Comprising the inorganic acid, rectilinear propagation can be improved
And scrap problems.
The water being used in the present invention refers to deionized water and for semiconductor process, preferably uses 18M Ω/cm or more
Water.So that the total weight of overall composition includes the water of surplus as the content of 100 weight %.
The present invention can provide a kind of following etchants: even if also having in the case where not including acetic acid excellent
Rectilinear propagation, not only improve silver absorption problem again, but also significantly improve the problem of occurring because including acetic acid i.e. ageing stability
The problem of decline.
Etching solution of the invention can not only be etched the monofilm of silver or silver alloy, but also can be to transparent biography
Guided membrane/silver or transparent conductive film/silver alloy duplex film and the triple films being made of transparent conductive film/silver/transparent conductive film into
Row etches together, and can be used in the etching of two steps, i.e., is etched it to upper transparent conductive membranes using other etching solutions
The process that silver-colored (silver alloy) and lower transparent conductive membranes are etched using etching solution of the invention afterwards, additionally it is possible to be used for three steps
Rapid etching, i.e., carry out silver using etching solution of the invention after being etched using other etching solutions to upper transparent conductive membranes
The process that lower transparent conductive membranes are etched using other etching solutions after (silver alloy) etching.
When manufacturing display device, to the monofilm being made of silver-colored (Ag) or silver alloy for being used as wiring and reflectance coating and by
In the case that the multilayer film that the monofilm and transparent conductive film are constituted uses etchant of the invention, to the cloth of drafting department
Line and reflectance coating show Micro etching uniformity, and can also improve because the pad portion (Pad) and data wiring damage due to
The Ag of generation absorption problem again.
The present invention provides a kind of method for manufacturing the array substrate for display device, this method comprises: a) step: in base
Grid wiring is formed on plate；B) step: gate insulating layer is formed on the substrate comprising the grid wiring；C) step: in institute
It states and forms oxide semiconductor layer on gate insulating layer；D) step: on the oxide semiconductor layer formed source electrode and
Drain electrode；And e) step: the pixel electrode or reflectance coating connecting with the drain electrode are formed, wherein e) the step packet
It includes following steps: forming argentiferous (Ag) film on substrate, and utilize the argentiferous film etching liquid composition of aforementioned present invention
It is etched and forms pixel electrode or reflectance coating.
In addition, the present invention provides a kind of array base for display device manufactured using above-mentioned etchant
Plate.
In the present invention, the battle array for display device manufactured using above-mentioned manufacturing method and above-mentioned etchant
Column substrate can be used for organic illuminating element (OLED) and/or liquid crystal display device (LCD) to use, and but it is not limited to this.
In the following, the present invention is described in more detail using Examples and Comparative Examples.But following embodiments are for illustrating
Illustrate that the present invention, the present invention are not limited by following embodiments, can modify and change in many ways.Of the invention
Range is defined by the technical concept of appended claims.
<Examples and Comparative Examples>prepare silver-colored etchant
Embodiment 1 is prepared according to composition shown in following table 1 and content to embodiment 10 and comparative example 1 to comparative example 9
Respective etchant 10kg, and so that the content that the total weight of etchant becomes 100 weight % includes remaining
The water of amount.
[table 1]
[table 2]
<experimental example>
Organic insulating film is deposited on substrate, and on the insulating film withThickness deposition
Then ITO/Ag/ITO trilamellar membrane prepares test film and being cut to 500 × 600mm using diamond tool.
Performance test is proceeded as follows using the etchant of above-described embodiment 1 to 10 and comparative example 1 to 9.
Experimental example 1: the side etching of Ag is evaluated
On being added respectively into the experimental facilities (model name: 5.5ETCHER, prowet company) of injecting type etching mode
The silver-colored etchant of embodiment 1 to 10 and comparative example 1 to 9 is stated, and temperature is set as heating after 40 DEG C, then
When temperature reaches 40 ± 0.1 DEG C, the etching work procedure of above-mentioned test film is executed.Total etching period is set as 85 seconds and is implemented.It will
Substrate starts to spray after being put into the experimental facilities, when 85 seconds etching periods then, it is simultaneously clear with deionized water to take out substrate
It after washing, is dried using hot-air drying device, and removes light using photoresist stripping machine (PR stripper)
Cause resist.Electronic scanner microscope (SEM is utilized after being respectively washed and drying 6 hours and 12 hours；Model name: SU-
8010, manufactured by Hitachi, Ltd) to be analyzed, and evaluated using following standards, the results are shown in following Table 3 and
In table 4.
[Ag etch quantity evaluation criterion]
◎: very excellent (side etching≤0.2 μm)
Zero: excellent (side etching: > 0.2 μm and≤0.3 μm)
△: good (side etching: > 0.3 μm and≤0.4 μm)
×: bad (side etching: > 0.4 μm)
Experimental example 2: evaluation rectilinear propagation
On being added respectively into the experimental facilities (model name: 5.5ETCHER, prowet company) of injecting type etching mode
The silver-colored etchant of embodiment 1 to 10 and comparative example 1 to 9 is stated, and temperature is set as heating after 40 DEG C, then
When temperature reaches 40 ± 0.1 DEG C, the etching work procedure of above-mentioned test film is executed.Total etching period is set as 85 seconds and is implemented.It will
Substrate starts to spray after being put into the experimental facilities, when 85 seconds etching periods then, it is simultaneously clear with deionized water to take out substrate
It after washing, is dried using hot-air drying device, and is removed using photoresist stripping machine (PR stripper)
Photoresist.Electronic scanner microscope (SEM is utilized after being respectively washed and drying 6 hours and 12 hours；Model name:
SU-8010 is manufactured by Hitachi, Ltd) profile of metal line is observed under SEM 30K multiplying power, and commented using following standards
The valence profile, the results are shown in following Table 3 and table 4.In the good situation of rectilinear propagation, to output capacity almost without generation
Due to being influenced caused by anode (anode) electrode size, in the undesirable situation of rectilinear propagation, it is possible to because being sent out in subsequent handling
The lesser problem of green anode electrode size and output capacity is brought a negative impact.
◎: excellent (being less than ± 0.1 μm)
Zero: good (± 0.1 μm more than and less than ± 0.3 μm)
△: common (± 0.3 μm more than and less than ± 0.5 μm)
×: bad (± 0.5 μm or more)
Embodiment 3: evaluation Ag adsorbs (analysis welding disk) again
On being added respectively into the experimental facilities (model name: 5.5ETCHER, prowet company) of injecting type etching mode
The silver-colored etchant of embodiment 1 to 10 and comparative example 1 to 9 is stated, and temperature is set as heating after 40 DEG C, then
When temperature reaches 40 ± 0.1 DEG C, the etching work procedure of above-mentioned test film is executed.Total etching period is set as 85 seconds and is implemented.It will
Substrate starts to spray after being put into the experimental facilities, when 85 seconds etching periods then, it is simultaneously clear with deionized water to take out substrate
It after washing, is dried using hot-air drying device, and is removed using photoresist stripping machine (PR stripper)
Photoresist.After being respectively washed and drying 6 hours and 12 hours, by utilizing electronic scanner microscope (SEM；Model
Title: SU-8010 is manufactured by Hitachi, Ltd) complete observation mainly data wiring etc. dissimilar metals expose part or because curved
The privileged site that Qu Xianxiang is likely to occur friction is adsorbed with the phenomenon that silver (Ag) etched to be analyzed.Utilize following marks
Standard is evaluated, and the results are shown in following Table 3 and table 4.
[Ag again adsorption assessment standard]
◎: very excellent (50 or less)
Zero: excellent (80 or less)
△: good (100 or less)
×: bad (being greater than 100)
[table 3]
[table 4]
Comprising the embodiment 1 to 10 of all the components and content of the invention, confirm because of side etching value
Excellent, rectilinear propagation is good and Ag absorption problem is excellent or very excellent and show improved effect again, and based on through when
The effect of the etchant of variation hardly changes.In addition, confirming be unsatisfactory for ingredient of the invention and containing
Side etching, speckle and adsorption effect reduction again in the comparative example 1 to 9 of amount.
Claims (9)
1. a kind of argentiferous film etching liquid composition includes 40.0 weight % to 60.0 weights relative to the total weight of composition
Measure ferric nitrate, the 0.5 weight % of the phosphoric acid of %, the nitric acid of 5.0 weight % to 9.0 weight %, 0.1 weight % to 4.0 weight %
To the inorganic acid salt of 5.0 weight % and the water of surplus.
2. argentiferous film etching liquid composition according to claim 1, wherein
The inorganic acid salt is selected from one or more of the group being made of the sylvite, sodium salt and ammonium salt of nitric acid, sulfuric acid or phosphoric acid.
3. argentiferous film etching liquid composition according to claim 1, which is characterized in that
The multilayer for including the monofilm of silver or silver alloy containing Ag films or being made of the monofilm and transparent conductive film
Film.
4. argentiferous film etching liquid composition according to claim 3, which is characterized in that
The transparent conductive film is in the group being made of tin indium oxide, indium zinc oxide, indium tin zinc oxide and indium gallium zinc
More than one.
5. argentiferous film etching liquid composition according to claim 3, which is characterized in that
The silver alloy includes silver and is selected from by nickel, copper, zinc, manganese, chromium, tin, palladium, neodymium, niobium, molybdenum, magnesium, tungsten, protactinium, aluminium and titanium
One or more of group of composition.
6. argentiferous film etching liquid composition according to claim 3, which is characterized in that
The multilayer film being made of the monofilm and transparent conductive film is transparent conductive film/silver, transparent conductive film/silver alloy, saturating
Bright conductive membranes/silver/transparent conductive film or transparent conductive film/silver alloy/transparent conductive film.
7. a kind of method of array substrate of manufacture for display device, comprising:
A) grid wiring step: is formed on substrate；
B) step: gate insulating layer is formed on the substrate for including the grid wiring；
C) step: oxide semiconductor layer is formed on the gate insulating layer；
D) step: source electrode and drain electrode are formed on the oxide semiconductor layer；And
E) step: forming the pixel electrode connecting with the drain electrode,
It is characterized in that, e) the step contains Ag films the following steps are included: being formed on substrate, and utilize claim 1
The argentiferous film etching liquid composition is etched and forms pixel electrode or reflectance coating.
8. the method for array substrate of the manufacture according to claim 7 for display device, which is characterized in that
The array substrate for display device is for liquid crystal display device or is used for organic illuminating element.
9. a kind of array substrate for display device, the array substrate is used described in any one of claim 1 to 6
Etchant is etched.
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| KR102245565B1 (en) * | 2015-02-10 | 2021-04-28 | 동우 화인켐 주식회사 | Etching solution composition for silver layer and an display substrate 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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| KR102623991B1 (en) | 2024-01-12 |
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