CN103820784A - Etchant composition, method for fabricating metal pattern, and method for manufacturing array substrate - Google Patents
Etchant composition, method for fabricating metal pattern, and method for manufacturing array substrate Download PDFInfo
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- CN103820784A CN103820784A CN201310445629.2A CN201310445629A CN103820784A CN 103820784 A CN103820784 A CN 103820784A CN 201310445629 A CN201310445629 A CN 201310445629A CN 103820784 A CN103820784 A CN 103820784A
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004332 silver Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims description 120
- 239000010408 film Substances 0.000 claims description 118
- 239000003795 chemical substances by application Substances 0.000 claims description 83
- 229910003437 indium oxide Inorganic materials 0.000 claims description 34
- 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 34
- 238000009413 insulation Methods 0.000 claims description 15
- 150000002505 iron Chemical class 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Thin Film Transistor (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses an etchant composition, a method for fabricating a metal pattern, and a method for manufacturing an array substrate of a liquid crystal display. The etchant composition for a silver (Ag) or silver alloy single film or multilayer film includes a nitric acid, a sulfuric acid, a trivalent molysite and water.
Description
The cross reference of related application
The application requires the rights and interests of the korean patent application 10-2012-0130463 submitting on November 16th, 2012, and therefore, this application by reference and entirety is incorporated to the application.
Technical field
The application relates to a kind of etching agent composition, and this etching agent composition is for silver (Ag) or the unitary film of silver alloys or the multilayer film being made up of described unitary film and indium oxide film; The application also relates to a kind of method of utilizing described etching agent composition to form metal pattern; And a kind of method of described etching agent composition manufacture for the array substrate of liquid-crystal display of utilizing.
Background technology
Liquid-crystal display is one of the most widely used flat-panel monitor, and it comprises: two substrates, and each substrate is provided with electrode; And be placed on two liquid crystal layers between substrate.Liquid-crystal display is to make thus the liquid crystal molecule in liquid crystal layer rearrange to control the display device that light is propagated by voltage being applied on electrode.
At present, in liquid-crystal display, conventionally use liquid-crystal display, wherein, each liquid-crystal display disposes two substrates that are provided with separately electric field generating electrodes.In addition the liquid-crystal display generally using, is: multiple pixel electrodes are arranged on a substrate with matrix array, and another substrate entirety is coated with ordinary electrode.In this liquid-crystal display, by voltage is applied on each pixel electrode and shows image.For this reason, configure this liquid-crystal display, thereby make thin film transistor be connected to each pixel electrode, and on substrate, form grid line and data line, wherein, thin film transistor is the three terminal device that is applied to the voltage on each pixel electrode for changing, and grid line is used for transmitting the signal of controlling thin film transistor, and data line is used for transmitting the voltage that will be applied on each pixel electrode.
Meanwhile, along with the increase of liquid-crystal display display area, elongated with grid line and data line that thin film transistor (TFT) is connected, thus increase the resistance connecting up.For this reason, in the time that chromium (Cr), molybdenum (Mo), aluminium (Al) or their alloy are used in grid line and data line, the high resolving power that is difficult to increase the size of flat-panel monitor and is difficult to realize flat-panel monitor.Therefore, the problem of the signal delay of bringing in order to solve resistance increase, need to manufacture grid line and data line with the material with low-resistance coefficient.
For this object, carried out increasing flat-panel monitor size, realize the high resolving power of flat-panel monitor and reduce the effort of energy consumption, this effort is by by silver-colored (Ag) film, silver alloy film or comprise silverskin and the multilayer film of silver alloy film (these films have specific resistance (specific resistance: approximately 1.59 μ Ω cm) lower than other metallic membranes and the brightness higher than other metallic membranes) is applied to the electrode of coloured filter, wiring and the reflector of LCD carries out.As a part for above-mentioned effort, develop and be applicable to the etching agent that uses in these materials.
At present, by the etching agent that comprises phosphoric acid and hydrogen peroxide for this object.For example, korean patent application 2011-0077734 discloses a kind of etching agent composition that comprises sulfuric acid, phosphoric acid, weak acid and hydrogen peroxide.But this etching agent composition at room temperature stores one month or probably lost efficacy after the longer time.This is because of hydrogen peroxide and persulphate can not stably continue one month or the longer time.
Therefore, need to develop a kind of etching agent that there is no this standing storage problem.
Summary of the invention
Therefore, the present invention is proposed to address the above problem, and the object of this invention is to provide a kind of etching agent composition, even if this etching agent composition also can show the good etching performance for the unitary film of silver (Ag) or silver alloys or the multilayer film that is made up of described unitary film and indium oxide film after long-time storage; The present invention also aims to provide a kind of utilizes method and a kind of this etching agent composition that utilizes that this etching composition forms metal pattern to manufacture the method for the array substrate of liquid-crystal display.
To achieve these goals, one aspect of the invention is a kind of etching agent composition is provided, described etching agent composition is for silver (Ag) or the unitary film of silver alloys or the multilayer film being made up of described unitary film and indium oxide film, and described etching agent composition comprises nitric acid, sulfuric acid, trivalent iron salt and water.
Another aspect of the invention is a kind of method that forms metal pattern is provided, said method comprising the steps of: (i) at least one film that forms the multilayer film that is selected from the unitary film of silver or silver alloys and formed by described unitary film and indium oxide on substrate; And (ii) utilize at least one film described in described etching agent composition etching.
Another aspect of the present invention, for the method for a kind of manufacture for the array substrate of liquid-crystal display is provided, said method comprising the steps of: a) on substrate, form grid; B) on the substrate that comprises described grid, form gate insulation layer; C) on described gate insulation layer, form semiconductor layer; D) on described semiconductor layer, form source electrode and drain electrode; And e) form and treat the pixel electrode that is connected with described drain electrode, wherein, described step a), at least one step d) and e) comprise the following steps: at least one film that forms the multilayer film that is selected from the unitary film of silver or silver alloys and be made up of described unitary film and indium oxide film; And utilize described in described etching agent composition etching at least one film to form each electrode.
Accompanying drawing explanation
From the detailed description below in conjunction with accompanying drawing, will more clearly understand above and other object of the present invention, feature and advantage, wherein:
Fig. 1 is the SEM photo that shows a-ITO-Ag-ITO trilamellar membrane, and this trilamellar membrane utilizes the etching agent composition of embodiment 1 to carry out etching, and wherein this etching agent composition has stored 1 day after preparation;
Fig. 2 is the surperficial SEM photo that shows substrate, on this substrate, utilizes the etching agent composition of embodiment 1 to carry out etching a-ITO-Ag-ITO trilamellar membrane, and has peeled off photoresist material, and wherein this etching agent composition has stored 1 day after preparation;
Fig. 3 is the SEM photo that shows a-ITO-Ag-ITO trilamellar membrane, and this trilamellar membrane utilizes the etching agent composition of embodiment 1 to carry out etching, and wherein this etching agent composition has stored 30 days after preparation;
Fig. 4 is the surperficial SEM photo that shows substrate, on this substrate, utilizes the etching agent composition of embodiment 1 to carry out etching a-ITO-Ag-ITO trilamellar membrane, and has peeled off photoresist material, and wherein this etching agent composition has stored 30 days after preparation;
Fig. 5 is the SEM photo that shows a-ITO-Ag-ITO trilamellar membrane, and this trilamellar membrane utilizes the etching agent composition of comparative example 1 to carry out etching, and wherein this etching agent composition has stored 1 day after preparation;
Fig. 6 is the surperficial SEM photo that shows substrate, on this substrate, utilizes the etching agent composition of comparative example 1 to carry out etching a-ITO-Ag-ITO trilamellar membrane, and has peeled off photoresist material, and wherein this etching agent composition has stored 1 day after preparation;
Fig. 7 is the SEM photo that shows a-ITO-Ag-ITO trilamellar membrane, and this trilamellar membrane utilizes the etching agent composition of comparative example 1 to carry out etching, and wherein this etching agent composition has stored 30 days after preparation; And
Fig. 8 is the surperficial SEM photo that shows substrate, on this substrate, utilizes the etching agent composition of comparative example 1 to carry out etching a-ITO-Ag-ITO trilamellar membrane, and has peeled off photoresist material, and wherein this etching agent composition has stored 30 days after preparation.
Embodiment
Below, will describe the present invention in detail.
The invention provides a kind of etching agent composition, described etching agent composition is for silver or the unitary film of silver alloys or the multilayer film being made up of described unitary film and indium oxide film, and described erosion agent composition comprises nitric acid, sulfuric acid, trivalent iron salt and water.
Being characterized as of etching agent composition of the present invention: this etching agent composition is etching silver or silver-colored alloy unitary film or the multilayer film being made up of described unitary film and indium oxide film simultaneously.
In the present invention, the multilayer film being made up of unitary film and the indium oxide film of silver or silver alloys can be the duplicature of indium oxide film/silverskin, trilamellar membrane of indium oxide film/silverskin/indium oxide film etc.In addition, indium oxide can be tin indium oxide (ITO), indium zinc oxide (IZO) etc.
In etching agent composition of the present invention, the nitric acid that is used as primary oxidant composition loses silverskin and indium oxide film by making silverskin and the oxidation of indium oxide film for wet etching.Based on the gross weight of this etching agent composition, the amount of nitric acid is 2.0～4.0wt%.In the time that the amount of nitric acid is less than 2.0wt%, the etch rate of silverskin can reduce, and the et ch profiles of silverskin can variation.In addition, in the time that the amount of nitric acid exceedes 4.0wt%, in the situation of the trilamellar membrane of etching indium oxide film/silverskin/indium oxide film, due to the overetch of indium oxide film, the upper layer of silverskin is exposed, thereby cause that silver separates and be adsorbed to by the thermal treatment of subsequent technique subsequently again the problem on substrate with substrate surface.
In etching agent composition of the present invention, based on the gross weight of this etching agent composition, add the sulfuric acid as assisted oxidation thing solvent of 4.0～6.0wt%.In the time adding the amount of sulfuric acid to exceed 6.0wt%, increase because high etch rate makes etching length, thereby hinder this technique.In addition,, in the time that the amount of the sulfuric acid adding is less than 4.0wt%, be not easy etching silverskin.
In etching agent composition of the present invention, lose silverskin and indium oxide film by making silverskin and the oxidation of indium oxide film for wet etching as the trivalent iron salt of primary oxidant composition.Based on the gross weight of this etching agent composition, the amount of trivalent iron salt is 0.1～2.0wt%, and preferred 0.1～0.4wt%.In the time that the amount of trivalent iron salt is less than 0.1wt%, the etch rate of silverskin can reduce, and the et ch profiles of silverskin can variation.In addition, in the time that the amount of trivalent iron salt exceedes 2.0wt%, in the situation of the trilamellar membrane of etching indium oxide film/silverskin/indium oxide film, due to the overetch of indium oxide film, the upper layer of silverskin is exposed, thereby cause that silver separates and be adsorbed to by the thermal treatment of subsequent technique subsequently again the problem on substrate with substrate surface.
In etching agent composition of the present invention, water is not particularly limited, but preferred deionized water.Particularly, more preferably there is 18M Ω/cm or be greater than the deionized water of the specific resistance (, removing the degree of ion from water) of 18M Ω/cm.
Except mentioned component, above-mentioned etching agent composition can further comprise conventional additives.Can use tensio-active agent, sequestrant or corrosion inhibitor as additive.
In etching agent composition of the present invention, nitric acid, sulfuric acid and trivalent iron salt can be prepared by the known method of routine.Particularly, preferably they have the purity for semiconductor technology.
In addition, the invention provides a kind of method that forms metal pattern, said method comprising the steps of: (i) at least one film that forms the multilayer film that is selected from the unitary film of silver or silver alloys and formed by this unitary film and indium oxide film on substrate; And (ii) utilize at least one film described in etching agent composition etching of the present invention.
In the method for formation metal pattern according to the present invention, step (i) comprises the following steps: substrate is provided; And on described substrate, form and be selected from the unitary film of silver or silver alloys and at least one film of the multilayer film that formed by this unitary film and indium oxide film.
For substrate, can use wafer, glass substrate, stainless steel substrate, plastic base or the quartz base plate that can clean by ordinary method.Can be undertaken on this substrate, forming the unitary film of silver or silver alloys or the technique of the multilayer film that formed by described unitary film and indium oxide film by several different methods well known by persons skilled in the art.Preferably form these films by vacuum moulding machine or sputter.
Step (ii) in, step (i) in form at least one film on form photoresist material, utilize mask optionally to make the resist exposure of this formation; After bake and bank up with earth through exposure photoresist material; Then make through after the photoresist developing of baking and banking up with earth to form photoetching agent pattern.
Utilize etching agent composition etching of the present invention to provide at least one film of photoetching agent pattern, thereby complete metal pattern.
In addition, the invention provides the method for a kind of manufacture for the array substrate of liquid-crystal display, said method comprising the steps of: a) on substrate, form grid; B) on the substrate that comprises described grid, form gate insulation layer; C) on described gate insulation layer, form semiconductor layer; D) on described semiconductor layer, form source electrode and drain electrode; And e) form and treat the pixel electrode that is connected with described drain electrode, wherein, step a), at least one step d) and e) comprise the following steps: at least one film that forms the multilayer film that is selected from the unitary film of silver or silver alloys and be made up of described unitary film and indium oxide film; And utilize described in etching agent composition etching of the present invention at least one film to form each electrode.
Array substrate for liquid-crystal display can be the array substrate for thin film transistor.
Method in manufacture according to the present invention for the array substrate of liquid-crystal display, step a) comprises the following steps: a1) utilize vapour deposition or sputter, on substrate, deposit at least one film in the multilayer film that is selected from the unitary film of silver or silver alloys and formed by described unitary film and indium oxide film; And a2) utilize described in etching agent composition etching of the present invention at least one film to form grid.In this article, the technique of described at least one film of formation is not limited to this.
Method in manufacture according to the present invention for the array substrate of liquid-crystal display, in step b), by silicon nitride (SiN
x) be deposited on the grid being formed on substrate to form gate insulation layer.In this article, form the material using in gate insulation layer and be not limited to silicon nitride (SiN
x), gate insulation layer can utilize and be selected from the multiple silicon-dioxide (SiO that contains
2) inorganic insulating material in any formation.
Method in manufacture according to the present invention for the array substrate of liquid-crystal display, in step c), utilizes chemical Vapor deposition process (CVD) on gate insulation layer, to form semiconductor layer.That is, form successively active layer (active layer) and ohmic contact layer, then by dry etching, active layer and ohmic contact layer are carried out to patterning.In this article, active layer is formed by pure amorphous silicon (a-Si:H) conventionally, and ohmic contact layer is conventionally by impure amorphous silicon (n
+a-Si:H) form.These active layers and ohmic contact layer can utilize chemical Vapor deposition process and form, but the method that forms these layers is not limited to this.
Method in manufacture according to the present invention for the array substrate of liquid-crystal display, step d) comprises the following steps: d1) on semiconductor layer, form source electrode and drain electrode; And d2) in described source electrode and drain electrode, form insulation layer.In steps d 1) in, utilize sputter that at least one film in the multilayer film that is selected from the unitary film of silver or silver alloys and be made up of described unitary film and indium oxide film is deposited on ohmic contact layer, then utilize described in etching agent composition etching of the present invention at least one film to form source electrode and drain electrode.In this article, the method that forms at least one film on substrate is not limited to aforesaid method.In steps d 2) in, utilize and contain silicon nitride (SiN
x) and silicon-dioxide (SiO
2) inorganic insulating material or the organic insulation that contains benzocyclobutene (BCB) and acrylic resin in source electrode and drain electrode, form insulation layer or double-deck insulation layer of individual layer.In this article, the starting material of insulation layer are not limited to above-mentioned starting material.
Method in manufacture according to the present invention for the array substrate of liquid-crystal display, in step e), forms and treats and the pixel electrode that drains and be connected.For example, deposit at least one film in the multilayer film that is selected from the unitary film of silver or silver alloys and formed by described unitary film and indium oxide film by sputter, then utilize etching agent composition of the present invention to carry out described in etching at least one film to form pixel electrode.The method of deposition indium oxide film is not limited to sputter.
Below, with reference to the following example, the present invention is described in further detail.But these embodiment are used for explaining the present invention, and scope of the present invention is not limited to this.
the preparation of etching agent composition
Recently prepare by the composition shown in following table 1 the etching agent composition that weight is 10kg.
[table 1]
the assessment of etching characteristic
On substrate, form a-ITO/Ag/a-ITO trilamellar membrane, then utilize diamond cutting cutter to cut into 10 × 10mm size with preparation test sample.
To after preparation, store the embodiment 1～3 of 1 day and the etching agent composition of comparative example 1～3 is introduced into injection-type etching test set (manufacture of SEMES company), then the design temperature based on 38 ℃ is heated to 38 ± 0.1 ℃, the etching process of then testing sample.Etching process is performed such: based on end-point detection (EPD), total etching time comprises for 50% over etching time.In addition, utilize the etching agent composition that has stored the embodiment 1～3 of 30 days and comparative example 1～3 after preparation to carry out in the same manner described above the etching process of test sample.
Test sample through etching is taken out from test set, by washed with de-ionized water, then utilize air flow dryer dry, and utilize subsequently photoresist material (PR) stripper to get on except photoresist material from test sample.After this, utilize scanning electronic microscope (SEM) (S-4700, Hitachi company manufactures) to assess the etching characteristic of test sample, for example side etch rate.
The test result of its etching characteristic is shown in following table 2.
[table 2]
| (μ m) for etch rate | After 1 day | After 30 | Change |
| Embodiment | |||
| 1 | 0.64 | 0.47 | Reduce by 26% |
| Embodiment 2 | 0.64 | 0.46 | Reduce by 28% |
| Embodiment 3 | 0.63 | 0.46 | Reduce by 27% |
| Comparative example 1 | 4.36 | 2.29 | Reduce by 47% |
| Comparative example 2 | 2.14 | 0.41 | Reduce by 81% |
| Comparative example 3 | 5.56 | 1.28 | Reduce by 77% |
As above shown in table 2, in the time utilizing the etching agent composition etching a-ITO/Ag/a-ITO substrate of embodiment 1, compared with storing the etch rate of etching agent composition of the embodiment 1 after 1 day, stores the etch rate reduction by 26% of the etching agent composition of the embodiment 1 after 30 days.By contrast, in the time utilizing the etching agent composition etching a-ITO/Ag/a-ITO substrate of comparative example 1, compared with storing the etch rate of etching agent composition of the comparative example 1 after 1 day, stores the etch rate reduction by 47% of the etching agent composition of the comparative example 1 after 30 days.Therefore, can determine, compared with the standing storage of conventional etching agent composition, the standing storage of etching agent composition of the present invention improves greatly.
Further, with reference to figure 1～Fig. 8, can determine, compared with the etching characteristic of the etching agent composition of comparative example 1, the etching characteristic of the etching agent composition of embodiment 1 is good.
Beneficial effect
As mentioned above, even if etching agent composition of the present invention also can show the good etching characteristic for the unitary film of silver (Ag) or silver alloys or the multilayer film that is made up of described unitary film and indium oxide film after long-time storage.Therefore, this etching agent composition can use and there is no the problem of standing storage in etching process.
Although disclose the preferred embodiment of the present invention for task of explanation, those skilled in the art will know, in the situation that not deviating from the disclosed scope and spirit of the present invention of appended claim, and multiple change, increase and to substitute be possible.
Claims (8)
1. an etching agent composition, described etching agent composition is for silver or the unitary film of silver alloys or the multilayer film being made up of described unitary film and indium oxide film, and described etching agent composition comprises nitric acid, sulfuric acid, trivalent iron salt and water.
2. etching agent composition according to claim 1, wherein, based on the gross weight of described etching agent composition, described etching agent composition comprises:
The nitric acid of 2～4.0wt%;
The sulfuric acid of 4.0～6.0wt%;
The trivalent iron salt of 0.1～2.0wt%; And
The water of surplus.
3. etching agent composition according to claim 1, wherein, described water is deionized water.
4. etching agent composition according to claim 1, also comprises at least one additive in the group of selecting free tensio-active agent, sequestrant and corrosion inhibitor composition.
5. a method that forms metal pattern, said method comprising the steps of:
(i) on substrate, form at least one film of the multilayer film that is selected from the unitary film of silver or silver alloys and formed by described unitary film and indium oxide film; And
(ii) utilize in claim 1～4 at least one film described in the etching agent composition etching described in any one.
6. method according to claim 5, is also included in the step that forms photoetching agent pattern on described at least one film.
7. manufacture, for a method for the array substrate of liquid-crystal display, said method comprising the steps of:
A) on substrate, form grid;
B) on the substrate that comprises described grid, form gate insulation layer;
C) on described gate insulation layer, form semiconductor layer;
D) on described semiconductor layer, form source electrode and drain electrode;
E) form the pixel electrode being connected with described drain electrode,
Wherein, described step a), at least one step d) and e) comprise the following steps: at least one film that forms the multilayer film that is selected from the unitary film of silver or silver alloys and be made up of described unitary film and indium oxide film; And utilize in claim 1～4 described in the etching agent composition etching described in any one at least one film to form each electrode.
8. method according to claim 7, wherein, the described array substrate for liquid-crystal display is the array substrate for thin film transistor.
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| KR1020120130463A KR20140063284A (en) | 2012-11-16 | 2012-11-16 | Etchant composition for ag thin layer and method for fabricating metal pattern using the same |
| KR10-2012-0130463 | 2012-11-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105887091A (en) * | 2015-02-16 | 2016-08-24 | 东友精细化工有限公司 | Etchant Composition For Ag Thin Layer And Method For Fabricating Metal Pattern Using The Same And Method For Fabricating Array Substrate By Using The Same |
| CN106011861A (en) * | 2015-03-26 | 2016-10-12 | 东友精细化工有限公司 | Etching solution composition for silver-containing layer and manufacturing method of array substrate for display device using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190058758A (en) | 2017-11-21 | 2019-05-30 | 삼성디스플레이 주식회사 | Etchant and manufacturing method of display device using the same |
| KR102661845B1 (en) | 2018-10-11 | 2024-04-30 | 삼성디스플레이 주식회사 | Echtant and method for manufacturing display device using the same |
| KR102676044B1 (en) | 2020-04-29 | 2024-06-20 | 삼성디스플레이 주식회사 | Etchant and manufacturing method of display device using the same |
| KR102659176B1 (en) | 2020-12-28 | 2024-04-23 | 삼성디스플레이 주식회사 | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
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| JP2000008184A (en) * | 1998-06-24 | 2000-01-11 | Toppan Printing Co Ltd | Etching of multilayer electrically conductive film |
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| TW201420812A (en) | 2014-06-01 |
| CN103820784B (en) | 2017-12-08 |
| KR20140063284A (en) | 2014-05-27 |
| TWI586838B (en) | 2017-06-11 |
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