KR101972630B1 - Etching solution composition for silver layer and an display substrate using the same - Google Patents
Etching solution composition for silver layer and an display substrate using the same Download PDFInfo
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- KR101972630B1 KR101972630B1 KR1020150116145A KR20150116145A KR101972630B1 KR 101972630 B1 KR101972630 B1 KR 101972630B1 KR 1020150116145 A KR1020150116145 A KR 1020150116145A KR 20150116145 A KR20150116145 A KR 20150116145A KR 101972630 B1 KR101972630 B1 KR 101972630B1
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- South Korea
- Prior art keywords
- silver
- indium
- film
- indium oxide
- wiring
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000004332 silver Substances 0.000 title claims abstract description 109
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 102
- 238000005530 etching Methods 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 104
- 229910003437 indium oxide Inorganic materials 0.000 claims description 59
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 6
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 239000008367 deionised water Substances 0.000 abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 abstract description 8
- 206010020710 Hyperphagia Diseases 0.000 abstract description 3
- 235000020830 overeating Nutrition 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 30
- 150000002739 metals Chemical class 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- LXFUCSMCVAEMCD-UHFFFAOYSA-N acetic acid;nitric acid;phosphoric acid Chemical compound CC(O)=O.O[N+]([O-])=O.OP(O)(O)=O LXFUCSMCVAEMCD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- 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
Abstract
The present invention relates to a silver etchant composition containing phosphoric acid, nitric acid, acetic acid, methyltetrazole and deionized water, and a display substrate using the silver etchant composition, which can prevent overeating of a silver or silver alloy film, It has the effect of facilitating the control on the process by controlling the etching rate, does not cause residue and re-adsorption, and has excellent stability over time.
Description
The present invention relates to a silver etchant composition and a display substrate using the silver etchant composition. More particularly, the silver etchant composition is a silver etchant composition comprising phosphoric acid, nitric acid, acetic acid, methyltetrazole and deionized water, and a display substrate using the same.
As the era of information technology becomes full-scale, the display field for processing and displaying a large amount of information has been rapidly developed, and various flat panel displays have been developed in response to this.
Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display panel (PDP), a field emission display (FED), an electroluminescence Display devices (ELD), organic light emitting diodes (OLED), and the like. These flat panel display devices are used for various applications such as computers and mobile phones as well as home appliances such as televisions and videos. These flat panel display devices are rapidly replacing the conventional cathode ray tube (NIT) due to their excellent performance such as reduction in thickness, weight, and power consumption.
In particular, since the OLED emits light by itself and can be driven at a low voltage, it is rapidly applied to a small display market such as a portable device. In addition, OLED is expected to commercialize large-sized TV beyond small-sized display.
On the other hand, conductive metals such as indium tin oxide (ITO) and indium zinc oxide (IZO) have relatively high transmittance to light and have conductivity. Therefore, the electrode of a color filter used in a flat panel display Is widely used. However, these metals also have a high resistance, which is an obstacle to the enlargement of the flat panel display device and the realization of high resolution through improvement of the response speed.
In the case of reflectors, past aluminum (Al) reflectors have been mainly used for products, but in order to realize low power consumption through improvement of luminance, materials are being sought for metal with higher reflectance. For this purpose, a silver (Ag: specific resistance: about 1.59 Ω · cm) film having a lower resistivity and a higher luminance than the metals applied to a flat panel display device, a silver alloy or a multilayer film containing the same, It is required to develop an etchant for application of this material in order to realize a large-sized flat panel display device and high resolution and low power consumption.
However, silver (Ag) is extremely poor in adhesion to an insulating substrate such as glass or a lower substrate such as a semiconductor substrate made of intrinsic amorphous silicon or doped amorphous silicon or the like, lifting or peeling is easily induced. Further, even when a silver (Ag) conductive layer is deposited on a substrate, an etchant is used to pattern the same. When a conventional etching solution is used as the etching solution, silver (Ag) is excessively etched or inhomogeneously etched to cause lifting or peeling of the wiring, resulting in poor lateral profile of the wiring.
The silver etching solution disclosed in Korean Patent No. 10-0579421 uses a small carbon-based surfactant together with an auxiliary oxide dissolving agent as an additive to phosphoric acid, nitric acid and acetic acid. However, the SO 4 2- compound used as a secondary oxide dissolving agent has a disadvantage that it reacts with silver (Ag) and remains as a residue in the form of silver sulfide (Ag 2 S). ClO 4 - There is a difficulty in specifying and using. Also, in the case of the Hambil small carbon surfactant, when the lower film of silver is an organic insulating film, the organic insulating film at the edge of the substrate is easily damaged by the etching solution, causing peeling.
An object of the present invention is to provide a silver etching composition capable of forming a wiring of a pixel electrode by preventing an overexposure angle of a metal film containing silver, thereby forming a fine pattern wiring.
It is another object of the present invention to provide a silver-based etchant composition which can control the etching rate of a metal film containing silver to facilitate process control, prevent re-adsorption of silver, prevent residue from being formed, .
It is another object of the present invention to provide a display substrate and a wiring using the silver etchant composition.
In order to achieve the above object,
The present invention relates to a silver etching composition comprising 30 to 70% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 0.5 to 30% by weight of acetic acid, 0.01 to 10% by weight of methyltetrazole and 100% And a remaining amount of deionized water.
The present invention also provides a display substrate comprising a metal film etched with the silver etchant composition.
The present invention also provides a wiring etched with the silver etchant composition.
The silver etching composition of the present invention prevents re-adsorption of silver and residue, and has an excellent stability over time.
In addition, the silver etching composition of the present invention can form a wiring of a pixel electrode by preventing the over-etching angle of a metal film containing silver, thereby forming a fine pattern wiring.
In addition, the silver etching composition of the present invention can facilitate process control by controlling the etching rate of the metal film containing silver.
Further, the display substrate including the metal film etched with the silver etching solution composition of the present invention has excellent driving characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a SEM photograph showing that no silver residue was formed during etching with the silver etching composition of the present invention. FIG.
FIG. 2 is a SEM photograph showing that a silver residue is generated when the conventional silver etching composition is etched. FIG.
FIG. 3 is a SEM photograph showing that no silver sorption occurs when the silver etching composition of the present invention is etched. FIG.
FIG. 4 is a SEM photograph showing that silver was adsorbed when etching with a conventional silver etching composition. FIG.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a silver etching composition comprising 30 to 70% by weight of phosphoric acid, 0.5 to 10% by weight of nitric acid, 0.5 to 30% by weight of acetic acid, 0.01 to 10% by weight of methyltetrazole and 100% Lt; RTI ID = 0.0 > deionized < / RTI > water.
The silver etching solution composition of the present invention is characterized by being capable of etching a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and the indium oxide film, and the multilayer film can be simultaneously etched.
The silver alloy contains silver as a main component and is in the form of an alloy containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti and a nitride of silver, silicide, carbide and oxide And the like, but the present invention is not limited thereto.
The indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), zinc indium tin oxide (ITZO) and gallium indium zinc oxide (IGZO).
The multilayered film may be a multilayer film formed of indium oxide / silver, indium oxide / silver alloy, indium oxide / silver / indium oxide, indium oxide / silver alloy / indium oxide, When the composition is used, it can exhibit etching uniformity without damaging the lower film and can be usefully used for wet etching.
Phosphoric acid ( H 3 PO 4 )
Phosphoric acid (H 3 PO 4 ) contained in the silver etching solution composition of the present invention is used as a stocking agent and performs a redox reaction with silver (Ag) or a silver alloy when a single film or a multilayer film is etched and dissolves the indium oxide film to perform wet etching .
The phosphoric acid is contained in an amount of 30 to 70% by weight, and preferably 40 to 60% by weight based on the total weight of the silver etching composition.
If the phosphoric acid is contained in an amount of less than 30 wt%, the etching ability is insufficient and sufficient etching may not be performed. In addition, as the process proceeds, when a certain amount of silver (Ag) is dissolved in the silver etching composition, silver (Ag) re-adsorption or silver (Ag) precipitate may be generated to cause electrical short in a subsequent process, .
When the phosphoric acid is contained in an amount of more than 70% by weight, the etching rate of the indium oxide film is lowered and the etching rate of the silver or silver alloy becomes too fast when the multilayer film is etched with the indium oxide film laminated on a single film of silver or silver alloy, May occur, which may result in an etching amount that can not function as a wiring. In addition, a tip due to the etching rate difference between the silver or silver alloy and the indium oxide film may be generated, which may cause problems in the subsequent process.
nitric acid( HNO 3 )
The nitric acid (HNO 3 ) contained in the silver etching solution composition of the present invention is a component serving as an auxiliary etchant. In the multi-layer etching process in which a single film of silver or silver alloy or an indium oxide film is laminated on a single film of silver or silver alloy , Silver (Ag) or a silver alloy and an indium oxide film to perform wet etching.
The silver nitrate is contained in an amount of 0.5 to 10% by weight, and preferably 2 to 10% by weight based on the total weight of the etchant composition.
When the content of the nitric acid is less than 0.5% by weight, the etch rate of the silver or silver alloy and the indium oxide film is lowered, and the electric shots and dark areas of the residues remain dark due to the silver residue, Can occur.
When the content of nitric acid is more than 10 wt%, it is difficult to control the etching in the process due to the excessive etching rate, and an overeating angle is generated, thereby failing to function as a wiring.
Acetic acid (CH 3 COOH)
Acetic acid (CH 3 COOH) contained in the silver etching composition of the present invention functions as a buffer to control the reaction rate and the like, thereby controlling the decomposition rate of nitric acid and generally reducing nitric acid decomposition rate.
The acetic acid is contained in an amount of 0.5 to 30% by weight, and preferably 1 to 20% by weight based on the total weight of the silver etching composition.
If the content of acetic acid is less than 0.5% by weight, the uniformity of the wiring substrate on the display substrate, more specifically, the TFT array substrate, may deteriorate and the wiring resistance may increase due to the decrease in linearity of the wiring, The etching speed becomes uneven and a problem arises that the substrate is stained.
Further, if the content of acetic acid is more than 30 wt%, the etching rate becomes very slow and it is difficult to control the maximum process time which is the maximum time applicable to the process.
Methyl tetrazole ( Methyltetrazole , MTZ )
Methyltetrazole (MTZ) contained in the silver etchant composition of the present invention acts as a corrosion inhibitor which slows down the etching rate of silver (Ag) or a silver alloy. When the multi-layer film is etched, It is possible to control the tip generation of the indium oxide film without slowing down the speed and to adjust the etching time in the process. In addition, it is possible to form wirings of a narrow pixel electrode by blocking the overexposure angle of silver (Ag), and it can be used as an additive to an etchant composition which forms a fine wiring.
Also, conventionally, when a single film of silver or silver alloy without a barrier film such as an indium oxide film is etched using an etching solution composition, an overexcitation angle occurs. In order to prevent this, a barrier film is applied to the upper and lower portions of the single film, but this causes a cost increase in the process.
However, the silver etchant composition of the present invention is advantageous in that the use of methyltetrazole prevents overeating and eliminates the need for the use of a barrier film, thereby reducing the processing time and reducing the raw materials, thereby reducing production costs.
The methyltetrazole is contained in an amount of 0.01 to 10% by weight based on the total weight of the silver etching composition.
If the content of the methyltetrazole is less than 0.01% by weight, the etching rate can not be slowed down. Therefore, when the wiring pattern is formed to have a fine pattern, the insufficient wiring loss may occur.
If it exceeds 10% by weight, the etching rate of the silver or silver alloy is remarkably reduced, and unnecessary portions are not completely etched and electrical short-circuiting may occur, which may cause defects. In addition, residues remain due to the lowering of the etching rate, which may lead to a bad phenomenon that a dark spot appears in some areas during production of the product after the subsequent process.
The deionized water contained in the silver etchant composition of the present invention is used for semiconductor processing, and preferably water of 18 M / cm or more is used.
The silver etchant composition of the present invention may further include at least one of an etch control agent and a pH adjuster conventionally used in this field in addition to the above-mentioned components.
The etch regulator that may be further included is a compound containing one nitrate of potassium or sodium acetate, and the pH adjuster that may be further included is a compound containing one organic acid such as glycolic acid, glutamic acid, or glycine.
Further, the present invention can provide a display substrate comprising a metal film etched with the silver etching solution composition of the present invention.
More specifically, the display device may be a liquid crystal display (LCD) or a thin film transistor (TFT) substrate of an organic light emitting diode (OLED).
In addition, the OLED can deposit a metal film on the top and bottom of the OLED, and can etch the metal film with the etchant composition of the present invention. By adjusting the thickness of the metal film on the upper and lower sides and stacking them, the metal film can serve as a reflective film and a transflective film.
The reflective film should have a thickness that does not allow transmission of light, and the transflective film should have a thickness such that light is substantially transmitted. Therefore, the thickness of the metal film is preferably 50 to 5000 angstroms.
The metal film is a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and the indium oxide film.
The silver alloy contains silver as a main component and is in the form of an alloy containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti and a nitride of silver, silicide, carbide and oxide And the like, but the present invention is not limited thereto.
The indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), zinc indium tin oxide (ITZO) and gallium indium zinc oxide (IGZO).
The multilayered film may be a multilayer film formed of indium oxide / silver, indium oxide / silver alloy, indium oxide / silver / indium oxide, indium oxide / silver alloy / indium oxide.
Further, the present invention can provide an etched wiring with the silver etchant composition of the present invention.
More specifically, the wiring may be a trace wiring for reading a signal mainly sensed in X, Y coordinates in a touch screen panel (TSP), or a nanowire wiring for flexible wiring.
The wiring is a single film made of silver (Ag) or a silver alloy, or a multilayer film made of the single film and the indium oxide film.
The silver alloy contains silver as a main component and is in the form of an alloy containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti and a nitride of silver, silicide, carbide and oxide And the like, but the present invention is not limited thereto.
The indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), zinc indium tin oxide (ITZO) and gallium indium zinc oxide (IGZO).
The multilayered film may be a multilayer film formed of indium oxide / silver, indium oxide / silver alloy, indium oxide / silver / indium oxide, indium oxide / silver alloy / indium oxide.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
< Etchant Composition Preparation>
Example 1 to 7 and Comparative Example 1 to 11.
The ingredients shown in Table 1 below were mixed in the respective amounts to prepare silver etching composition.
MTZ: methyl tetrazole
ATZ: Aminotetrazole
BTZ: benzotriazole
Experimental Example 1. Silver Etchant Performance testing of the composition
An organic insulating film was deposited on the substrate, and ITO / Ag / ITO triplet deposited thereon was cut into 500 × 600 mm using a diamond knife to prepare a specimen.
Using the silver etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11, performance tests were carried out as follows.
One. The reflection film (or wiring) One side Etching Measure distance (S / E, Side Etch)
Each of the silver etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11 was placed in an experimental equipment (model name: ETCHER (TFT), manufactured by KC Tech) of a spray type etching system, and the temperature was set to 40 DEG C, When the temperature reached 40 + - 0.1 [deg.] C, the etching process of the specimen was performed. The total etching time was 60 seconds.
After the substrate was injected and spraying was started, when the etching time was reached for 60 seconds, the substrate was taken out and washed with deionized water, and then dried using a hot air drying apparatus. After cleaning and drying, the substrate was cut and its cross-section was measured using an electron microscope (SEM; model: SU-8010, manufactured by Hitachi). As a standard for measuring the unilateral etching distance, the width of the inside of the photoresist was measured from the end of the photoresist. The results are shown in Table 2 below.
<Evaluation Criteria of Unilateral Etching Distance Measurement>
Excellent: 0.5㎛ or less
Good: more than 0.5 mu m to 1.0 mu m or less
Defective: exceeding 1.0 탆
2. Residue Measure
Each of the silver etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11 was placed in an experimental equipment (model name: ETCHER (TFT), manufactured by KC Tech) of a spray type etching system, and the temperature was set to 40 DEG C, When the temperature reached 40 + - 0.1 [deg.] C, the etching process of the specimen was performed. The total etching time was 60 seconds.
After the substrate was injected and spraying was started, when the etching time of 60 seconds had elapsed, the substrate was taken out, washed with deionized water, dried using a hot air drier, and photoresist was removed using a photoresist stripper. After cleaning and drying, residual silver halide (Ag) was left unetched in a portion not covered with photoresist using an electron microscope (SEM; model name: SU-8010, manufactured by Hitachi) The results are shown in Table 2 below.
<Evaluation Criteria of Residue Measurement>
Excellent: No residue (Fig. 1)
Bad: Residual (residue is an incomplete etch, present amorphous over the entire substrate. Figure 2)
3. Etching Speed measurement
Each of the silver etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11 was placed in an experimental equipment (model name: ETCHER (TFT), manufactured by KC Tech) of a spray type etching system, and the temperature was set to 40 DEG C, When the temperature reached 40 + - 0.1 [deg.] C, the etching process of the specimen was performed. The total etching time was 60 seconds.
The etch rate (E / R, Etch Rate) with time was obtained by measuring End Point Detection (EPD) with the naked eye. The etch rate of the Å (thickness) (Å / sec) per second (hour) can be obtained by dividing the thickness of the etched metal film by the EPD. The etch rate was evaluated according to the following criteria, and the results are shown in Table 2 below.
<Evaluation Criteria of Etching Rate>
Excellent: 100 Å / sec or less
Good: more than 100 Å / sec to less than 200 Å / sec
Defective: exceeding 200 Å / sec
4. Measurement stability over time
The reference etch test was performed using the silver etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 11, and the remaining silver etchant composition was stored at 25 占 폚 for the planned date (one month basis). Thereafter, the deposited silver etching composition was again etched under the same conditions as in the above etching rate test, and the results were compared with those in the reference etching test. The evaluation criteria are as follows, and the results are shown in Table 2 below.
<Evaluation Criteria for Time Stability>
Excellent: Good etching profile up to 180 days
Good: Good etch profile up to 30 days
Bad: Within 30 days Bad etching profile
5. Re-adsorption measurement
Each of the silver etching compositions of Examples 1 to 7 and Comparative Examples 1 to 11 was placed in an experimental equipment (model name: ETCHER (TFT), manufactured by KC Tech) of a spray type etching system, and the temperature was set to 40 DEG C, When the temperature reached 40 + - 0.1 [deg.] C, the etching process of the specimen was performed. The total etching time was 60 seconds.
After the substrate was injected and spraying was started, when the etching time of 60 seconds had elapsed, the substrate was taken out, washed with deionized water, dried using a hot air drier, and photoresist was removed using a photoresist stripper. After being cleaned and dried, it is etched using a scanning electron microscope (SEM; model: SU-8010, manufactured by HITACHI), and then exposed to a part of different metals such as data lines or a specific region where friction may occur due to bending (Ag) adsorbed on the surface of the substrate was observed through a full observation. The results are shown in Table 2 below.
≪ Criteria for re-adsorption measurement >
Excellent: No resorption (Fig. 3)
Bad: Re-adsorption (Silver adsorption is adsorption by reduction, and is observed as spherical at the specific site. Figure 4)
Etching distance
In the results of Table 2 above, the silver etching compositions of Examples 1 to 7 of the present invention including methyltetrazole showed excellent or good overall results of the above five evaluations.
On the other hand, the silver etching solution compositions of Comparative Examples 1 to 11, which contain different kinds of azole compounds instead of methyltetrazole, or which contain phosphoric acid, nitric acid, acetic acid and methyltetrazole in the content range of the present invention, All items showed no excellent or good results, and more than one item showed poor results.
Therefore, the silver etching solution composition of the present invention can be etched by controlling the etching rate without any residue and re-adsorption when the metal film containing silver is etched.
Claims (17)
Silver or silver alloy, or a multilayer film composed of the single film and the indium oxide film can be simultaneously etched.
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| KR102421116B1 (en) | 2017-06-22 | 2022-07-15 | 삼성디스플레이 주식회사 | Etchant composition and method for forming wiring using etchant composition |
| KR102368026B1 (en) * | 2018-02-06 | 2022-02-24 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and method of forming conductive pattern using the same |
| KR102478164B1 (en) * | 2020-06-05 | 2022-12-14 | 한국항공대학교산학협력단 | Etchant composition for silver containning layer, method of patterning metal using the same and manufacturing method of array substrate for disaplay device |
| CN116200749A (en) * | 2023-02-28 | 2023-06-02 | 深圳新宙邦科技股份有限公司 | Etching solution for multi-layer film containing indium oxide or alloy/silver or alloy thereof |
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| KR101302827B1 (en) * | 2013-03-20 | 2013-09-02 | 동우 화인켐 주식회사 | Silver ＆ silver alloy etchant for metal electrode ＆ reflection layer |
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