CN101076869A - Transparent electrode and method for manufacturing same - Google Patents
Transparent electrode and method for manufacturing same Download PDFInfo
- Publication number
- CN101076869A CN101076869A CN200580042675.1A CN200580042675A CN101076869A CN 101076869 A CN101076869 A CN 101076869A CN 200580042675 A CN200580042675 A CN 200580042675A CN 101076869 A CN101076869 A CN 101076869A
- Authority
- CN
- China
- Prior art keywords
- nesa coating
- transparency electrode
- aqueous solution
- etching
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 91
- 238000000034 method Methods 0.000 title claims description 47
- 238000005530 etching Methods 0.000 claims abstract description 89
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011701 zinc Substances 0.000 claims abstract description 59
- 239000011787 zinc oxide Substances 0.000 claims abstract description 33
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 90
- 238000000576 coating method Methods 0.000 claims description 90
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 70
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 63
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 34
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 34
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- 235000006408 oxalic acid Nutrition 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- -1 halogen acids Chemical class 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000003384 imaging method Methods 0.000 claims description 9
- JZDJWEKMXXNNIM-UHFFFAOYSA-N nitric acid hydrate hydrochloride Chemical compound O.[N+](=O)(O)[O-].Cl JZDJWEKMXXNNIM-UHFFFAOYSA-N 0.000 claims description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 79
- 239000000758 substrate Substances 0.000 description 47
- 229960001296 zinc oxide Drugs 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 238000005477 sputtering target Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- KKEYTLVFLSCKDE-UHFFFAOYSA-N [Sn+2]=O.[O-2].[Zn+2].[O-2] Chemical compound [Sn+2]=O.[O-2].[Zn+2].[O-2] KKEYTLVFLSCKDE-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000036647 reaction Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910007717 ZnSnO Inorganic materials 0.000 description 2
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 description 2
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Landscapes
- Liquid Crystal (AREA)
- Weting (AREA)
- Electroluminescent Light Sources (AREA)
- Gas-Filled Discharge Tubes (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention provides a transparent electrode which does not use indium, has excellent alkali resistance or damp-heat stability, and has excellent etching performance. The transparent electrode comprises zinc oxide and tin oxide as main components, and the taper angle of the end part of the electrode is 30-89 degrees. The ratio of zinc atoms to the total amount of zinc atoms and tin atoms (Zn/(Zn + Sn), atomic ratio) in the transparent electrode is 0.5 to 0.9.
Description
Technical field
The present invention relates to a kind of transparency electrode that is used for thin display etc.More particularly, relating to a kind of is to be the transparency electrode of main component and the electrode that electrode tip is subjected to tapering and the manufacture method of this electrode with zinc oxide and tin oxide.
Background technology
With regard to liquid crystal indicator, owing to have features such as low power consumption, easy panchromaticization, in thin display, come into one's own, the exploitation that relevant in recent years display frame is maximized is active.Wherein, be arranged as active matrix mode liquid crystal flat panel display rectangular and that drive with α-Si type thin-film transistor (TFT) or p-Si type TFT as switch element in each pixel, even carrying out the above height of 800 * 600 pixels becomes more meticulous, contrast compares also not deterioration, therefore shows as high-performance color and is gazed at flat-panel screens.
For such active matrix mode liquid crystal flat panel display, use indium oxide-tin oxide transparency electrodes such as (ITO) as pixel electrode more, use Al class alloy firm as gate electrode, source-drain electrode.This be because, the sheet resistance of ITO is low, transmitance height, and Al forms pattern easily, resistance is low, the adhesiveness height.
Here, the configuration example to the TFT substrate describes.Fig. 4 is illustrated in the manufacturing process of liquid crystal flat panel display, and the pattern of pixel electrode forms near the cross section of α-SiTFT of ending phase.
In Fig. 4; on translucent glass substrate 21, form gate electrode pattern 22; use plasma CVD method to form SiN gate insulating film 23, α-Si:H (i) film 24, path protection film 25 and α-Si:H (n) film 26 continuously then, form the pattern of required form.And then adopt vacuum vapour deposition or sputtering method accumulation based on the metal film of Al, and adopt photoetching technique to form source electrode pattern 27 and drain electrode pattern 28, finish α-SiTFT componentry.Moreover, be formed with diaphragm 30 in this example.
Adopt sputtering method to pile up the ITO film thereon, adopt photoetching technique to form the pixel electrode pattern 29 that is electrically connected with source electrode 27.Why piling up the ITO film behind the Al film, is because can not make the contact characteristics deterioration of α-Si:H film and source and drain electrode.
The price of Al is low, resistivity is low, is necessary material on the display performance reduction aspect of the LCD that the resistance increase that prevents grid and source-drain electrode distribution produces.
In above-mentioned manufacturing process,, use HCl-HNO if behind the source-drain electrode pattern that forms based on Al
3-H
2O class etching solution is processed the ITO pixel electrode pattern, the problem of Al pattern stripping when then frequently being created in process finishing.
This results from originally, and Al also has the HCl-HNO that is dissolved in as the ITO etching solution
3-H
2Character in the O class etching solution.HNO in the etching solution
3Form thin Al oxide-film on Al surface, on the aspect that prevents the Al stripping, add, if but the etching period of ITO film is long, there are defect parts such as the impurity that is blended in the Al film of Al in piling up, foreign matter, because of local cell reacts, think above-mentioned HNO
3The oxidation effectiveness of the Al that produces can't play one's part to the full.In addition, under Al and ITO electricity engagement state, impregnated in as in the 2.38wt% aqueous solution of the tetramethylammonium hydroxide (TMAH) of resist imaging liquid the time, also have the problem that makes the Al stripping because of cell reaction.
In order to prevent the stripping of such Al, having developed by making the ITO film is noncrystalline, makes ITO/Al with respect to HCl-HNO
3-H
2The etching speed of O class etching solution is than increasing (for example, with reference to patent documentation 1).
But, be noncrystalline even make the ITO film, owing to use HCl-HNO
3-H
2Therefore the etching solution of O class can not prevent the stripping of Al fully, can not realize high meticulous LCD.
About this problem, proposed to carry out the transparency electrode that forms by indium oxide-zinc oxide on Al grid, the source-drain electrode pattern, the patterning of pixel electrode by etching solution with the oxalic acid class, make patterning become easily (for example, with reference to patent documentation 2).
But, as the normally used indium oxide-tin oxide of transparency electrode (ITO), indium oxide-zinc oxide (IZO), all be to be principal component with the indium oxide.In recent years, the demand of indium in thin display purposes etc. sharply increases, and its price is surging.Therefore, the problem that exists the price of the sputtering target be used to make transparency electrode also to rise.
Therefore, the Zinc-oxide-based nesa coating of indium oxide, the nesa coating of tin oxide class (for example, with reference to non-patent literature 1, patent documentation 3,4) have been proposed not use.
But, known for Zinc oxide film owing to not acidproof in nature and aqueous slkali at it, therefore do not have durability, can not be practical.In addition, in the film forming of zinc oxide, has the character that the crystallinity on crystallinity step-down, the nesa coating surface of near the zinc oxide the substrate increases, therefore in etching work procedure, near the substrate film is etched from the surface easily, exists etched electrode to form the problem of trapezoidal (undercut).
On the other hand, tin oxide even therefore there is the chloroazotic acid (mixed liquor of nitric acid hydrochloric acid) of strong acid, also is difficult to etched problem because chemical stability is strong excessively.
Patent documentation 1: the spy opens clear 63-184726 communique
Patent documentation 2: the spy opens flat 11-264995 communique
Patent documentation 3: the spy opens flat 6-293956 communique
Patent documentation 4: the spy opens flat 9-35535 communique
Non-patent literature 1: JSPS transparent oxide photoelectron material the 166th committee compiles: the technology of nesa coating, ohm (オ one system) company (1999)
Summary of the invention
The present invention proposes just in view of the above problems, and its purpose is, provides and does not use indium and alkali resistance or hydrothermal stability excellence and the also excellent transparency electrode of etching.
In addition, its purpose also is, provides electrode tip to be difficult to the manufacture method of the transparency electrode of formation trapezoidal (can easily form taper).
The inventor etc. have carried out research with keen determination in order to solve above-mentioned problem, found that: by using with the sputtering target formation transparency electrode of zinc oxide tin oxide as main component, and the etching solution that use is stipulated when using this sputtering target to form transparency electrode, can easily electrode tip be formed taper, thereby finish the present invention.
According to the present invention, can provide following transparency electrode and manufacture method thereof etc.
1. transparency electrode, it is a main component with zinc oxide and tin oxide, the cone angle of electrode tip is 30～89 degree.
2. above-mentioned 1 described transparency electrode, wherein, with respect to the total amount of zinc atom and tin atom in the above-mentioned transparency electrode, the ratio of zinc atom (Zn/ (Zn+Sn), atomic ratio) is 0.5～0.9.
3. the manufacture method of transparency electrode, wherein, so that the cone angle of electrode tip is the modes of 30～89 degree, to being that the nesa coating of main component carries out etching with zinc oxide and tin oxide.
4. the manufacture method of above-mentioned 3 described transparency electrodes, wherein, with respect to the total amount of zinc atom and tin atom in the above-mentioned transparency electrode, the ratio of zinc atom (Zn/ (Zn+Sn), atomic ratio) is 0.5～0.9.
5. above-mentioned 3 or the manufacture method of 4 described transparency electrodes, wherein, in above-mentioned etching, used the aqueous solution of halogen acid of concentration as 1wt%～40wt%.
6. the manufacture method of each described transparency electrode of above-mentioned 3～5, it comprises: form first operation of nesa coating, zinc atom is 0.5～0.9 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom and is main component with zinc oxide and tin oxide in the described nesa coating;
On described nesa coating, form second operation of resist film;
1～5wt% the aqueous solution that uses tetramethylammonium hydroxide is as the resist imaging liquid, in the temperature of this aqueous solution is to make described resist film form the 3rd operation of pattern under 20～50 ℃ the scope;
The concentration of using halogen acids is carried out etching as the aqueous solution of 1wt%～40wt% to described nesa coating, and forming cone angle is the 4th operation of the transparency electrodes of 30～89 degree; With
The anticorrosive additive stripping liquid controlling that use contains monoethanolamine will remain in the 5th operation that the resist film on the described transparency electrode is peeled off.
7. the manufacture method of above-mentioned 3 described transparency electrodes, it has: form the operation of nesa coating, zinc atom is 0.5～0.85 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom and is main component with zinc oxide and tin oxide in the described nesa coating; With
Use concentration of oxalic acid as the aqueous solution of 1wt%～10wt% as etching solution, be under 20～50 ℃ the scope described nesa coating to be carried out etching in the temperature of etching solution, form the operation of pattern.
8. above-mentioned 3 or the manufacture method of 4 described transparency electrodes, it comprises: forming with zinc oxide and tin oxide is first operation of the nesa coating of main component; On above-mentioned nesa coating, form second operation of resist film; Make above-mentioned resist film form the 3rd operation of pattern; Use the mixed solution of nitric acid, hydrochloric acid and water that above-mentioned nesa coating is carried out etching, forming cone angle is the 4th operation of the transparency electrode of 30～89 degree; The 5th operation of peeling off with the resist film that will remain on the above-mentioned transparency electrode.
9. the manufacture method of above-mentioned 8 described transparency electrodes, wherein, the composition of above-mentioned mixed solution is in three composition systems of nitric acid-hydrochloric acid-water, with nitric acid: hydrochloric acid: the ratio of water represents, is in (A) 2: 2: 96, (B) 2: 2: 96, (C) 78: 2: 20 and (D) in the tetragonal zone that 78: 20: 2 composition point surrounds.
10. above-mentioned 8 or the manufacture method of 9 described transparency electrodes, wherein, nitric acid in above-mentioned the 4th operation: hydrochloric acid: the temperature of the mixed solution of water is 20～50 ℃.
11. the manufacture method of each described transparency electrode of above-mentioned 8～10, wherein, the resist imaging liquid that uses in above-mentioned the 3rd operation contains monoethanolamine as 1～5wt% aqueous solution of tetramethylammonium hydroxide, the anticorrosive additive stripping liquid controlling that uses in above-mentioned the 5th operation.
12. use oxalic acid aqueous solution to carrying out etching method as the nesa coating of main component with zinc oxide and tin oxide.
13. above-mentioned 12 described engraving methods, wherein, the concentration of above-mentioned oxalic acid aqueous solution mesoxalic acid is 1wt%～10wt%.
14. the mixed solution that uses nitric acid, hydrochloric acid and water is to carrying out etching method with zinc oxide and tin oxide as the ELD of main component.
15. above-mentioned 14 described engraving methods, wherein, the composition of the mixed solution of above-mentioned nitric acid, hydrochloric acid and water is in three composition systems of nitric acid-hydrochloric acid-water, with nitric acid: hydrochloric acid: the ratio of water represents, is in (A) 2: 2: 96, (B) 2: 2: 96, (C) 78: 2: 20 and (D) in the tetragonal zone that 78: 20: 2 composition point surrounds.
Transparency electrode of the present invention, owing to do not use indium, irrelevant with the price movement of indium, low price.By using zinc oxide and tin oxide, make alkali resistance, the humidity resistance excellence of electrode as main component.
In addition, by using the etching solution of regulation, it is trapezoidal to prevent that electrode tip from forming, and can controlledly be the electrode of certain cone angle.
Description of drawings
Fig. 1 is the sectional view of transparency electrode.
Fig. 2 is the figure of the manufacturing process of expression transparency electrode of the present invention.
Fig. 3 is preferred nitric acid among expression the present invention: hydrochloric acid: the figure of the compositing area of the mixed liquor of water.
Fig. 4 is the figure of an example of expression TFT substrate.
Embodiment
Below transparency electrode of the present invention is specifically described.
Fig. 1 is the sectional view of transparency electrode of the present invention.
So-called " is main component with zinc oxide and tin oxide " is meant that oxide shared ratio (atomic ratio) in transparency electrode of zinc and tin is more than 51%.Moreover in the present invention, the shared ratio of above-mentioned oxide is preferably more than 75%, is preferably more than 90% especially.
As the form of the oxide of zinc and tin, comprise the form of zinc oxide such as ZnO, SnO
2, tin oxide such as SnO form, ZnSnO
3, Zn
2SnO
4Deng the form of the composite oxides between zinc oxide-tin oxide, preferred amorphous form.
This noncrystalline nesa coating, the etching characteristic with excellence that nesa coating did not have of Zinc-oxide-based nesa coating and tin oxide class.That is, different with Zinc-oxide-based nesa coating, the electrode tip after the etching is difficult for forming trapezoidal, and can be as the tin oxide class, and etching characteristic is poor.
Transparency electrode of the present invention, the cone angle of electrode tip are 30～89 degree.Than 30 degree hour, the distance of electrode edge part is elongated at cone angle, and when driving liquid crystal or organic EL, contrast can be different sometimes with inside at the pixel periphery.If cone angle, is easy to generate the electrode cracking of marginal portion above 89 degree or peels off, and under the situation that is liquid crystal, produces the bad of alignment films sometimes, under the situation that is organic EL, produce the broken string of counter electrode sometimes.
Preferred 5～the 300nm of thickness of this nesa coating (transparency electrode), more preferably 20～150nm, preferred especially 30～80nm.During less than 5nm, resistance value might be too high at thickness, if surpass 300nm, the cone angle of the electrode tip after the etching might be not in the scopes of 30～89 degree.
In the present invention, owing to uses above-mentionedly, so can control the cone angle of transparency electrode with zinc oxide and tin oxide nesa coating as main component.
The cooperation of the etching solution that uses when the control of cone angle is carried out etching and processing by adjusting to nesa coating, concentration, temperature etc. are carried out.Specifically, can use the mixed solution, aqueous solution of halogen acid of oxalic acid aqueous solution, nitric acid-hydrochloric acid-water as etching solution.
When using oxalic acid aqueous solution, cone angle can be controlled with the concentration of oxalic acid aqueous solution.Specifically, reduce, the concentration of oxalic acid aqueous solution can be turned down, for cone angle is increased, the concentration of oxalic acid aqueous solution can be heightened on the contrary in order to make cone angle.
Moreover in this case, zinc atom is preferably 0.5～0.85 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom in the transparency electrode.Zn/ (Zn+Sn) if bigger than 0.85, the control difficulty that becomes then, cone angle that might electrode tip be 90 spend more than, the edge etching is excessive, the possibility that exists electrode to attenuate or break.In addition, also might increase with the contact resistance of the anisotropic conductive film that is connected transparency electrode and external circuit (ACF), the contact resistance with ACF in long duration test (high temperature, high humidity) increases.
On the other hand, when Zn/ (Zn+Sn) less than 0.5 the time, etching speed reduces, sometimes can not etching.Zn/ (Zn+Sn) is preferably 0.5～0.8, and more preferably 0.7～0.8.
During as etching solution, cone angle can be controlled by the ratio of components of regulating mixed solution at the mixed solution that uses nitric acid-hydrochloric acid-water.Specifically, reduce, can increase the ratio of hydrochloric acid, in order to increase cone angle, can reduce the ratio of hydrochloric acid on the contrary in order to make cone angle.
Moreover when the mixed solution with nitric acid-hydrochloric acid-water carried out etching, zinc atom was 0.5～0.9 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom in the transparency electrode.Its reason is identical during with above-mentioned oxalic acid.More preferably Zn/ (Zn+Sn) is 0.55～0.85, more preferably 0.57～0.8.Preferred especially 0.60～0.77, further preferred 0.64～0.74, most preferably 0.64～0.69.
When using aqueous solution of halogen acid as etching solution, cone angle can be controlled by the concentration of halogen acids or the temperature of aqueous solution of halogen acid.Specifically, reduce, can reduce the concentration of halogen acids or the temperature of the reduction aqueous solution,, can improve the concentration of halogen acids or the temperature of the raising aqueous solution on the contrary in order to increase cone angle in order to make cone angle.
Moreover when carrying out etching with aqueous solution of halogen acid, zinc atom is preferably 0.5～0.9 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom in the transparency electrode.Its reason is identical during with above-mentioned oxalic acid.More preferably Zn/ (Zn+Sn) is 0.52～0.7, more preferably 0.55～0.67, preferred especially 0.55～0.63.
Moreover, be that the nesa coating of main component is preferably noncrystalline with zinc oxide tin oxide among the present invention.When not being the noncrystalline film, cone angle is difficult to control, can not reach the scope of 30～89 degree sometimes.
In addition, the ratio of atom (Zn/ (Zn+Sn), atomic ratio) is to adopt the value of ICP (high-frequency induction is in conjunction with plasma) assay.Moreover the ratio of the atom of the ratio of atom and the actual nesa coating that obtains about equally in the raw material of the sputtering target that uses in the formation of nesa coating (transparency electrode).Therefore, the ratio of the atom of nesa coating [Zn/ (Zn+Sn)] can be controlled by the ratio of the atom in the raw material of regulating sputtering target.
Transparency electrode of the present invention is by to being that the nesa coating that the noncrystalline electroconductive oxide of main component forms carries out etching, patterning is made with zinc oxide and tin oxide.Followingly describe with reference to accompanying drawing.
Fig. 2 is the figure of the manufacturing process of expression transparency electrode of the present invention.Manufacturing process mainly is made up of the etching (the 4th operation, Fig. 2 (d)) of the patterning that forms (second operation, Fig. 2 (b)), resist film (the 3rd operation, Fig. 2 (c)) that forms (first operation, Fig. 2 (a)), resist film of nesa coating, nesa coating, peel off (the 5th operation, Fig. 2 (e)) of resist film on the transparency electrode.
(1) formation of nesa coating
On the substrate 10 that forms transparency electrode, form nesa coating 11 '.
As substrate 10, can use transparent resin plates such as glass plate as transparency carrier, polysulfones, Merlon etc.
As the film build method of nesa coating 11 ', can enumerate vapour deposition method, sputtering method, CVD method, gunite, infusion process etc.Wherein preferably use sputtering method.
Specifically, can use with zinc oxide and tin oxide as primary raw material be prepared, the sputtering target of sintering.Moreover, becoming the noncrystalline nesa coating in order to make formed nesa coating 11 ', the substrate temperature in the sputter can be adjusted to below 300 ℃, perhaps can add hydrogen (below the 10vol%) in the sputter gas in sputter.
Like this, be noncrystalline, can easily carry out etching with above-mentioned etching solution by making nesa coating 11 '.
(2) formation of transparency electrode
Then, nesa coating is carried out etching, form required electrode pattern.Patterning can adopt normally used in the art method, for example adopts photoengraving to carry out.That is, go up at nesa coating 11 ' and to form resist film 12 (Fig. 2 (b)), expose, video picture, resist film 12 patternings (Fig. 2 (c)).Then, use etching solution, nesa coating 11 ' is carried out etching, form required pattern.At last, use stripper resist film remaining on the transparency electrode 11 12 to be removed (Fig. 2 (d)), thereby form transparency electrode (Fig. 2 (e)).
In the present invention, as etching solution, preferably use the mixed solution or the aqueous solution of halogen acid of oxalic acid aqueous solution, nitric acid-hydrochloric acid-water.
When using oxalic acid aqueous solution as etching solution, the concentration of oxalic acid aqueous solution mesoxalic acid is preferably 1wt%～10wt%.During less than 1wt%, etching speed is slow, and is impracticable at concentration of oxalic acid, if surpass 10wt%, the crystallization of oxalates might be separated out.More preferably 2wt%～7wt% is preferably 2wt%～5wt% especially.
At the mixed solution that uses nitric acid-hydrochloric acid-water during as etching solution, the composition of preferred this mixed solution is in nitric acid: hydrochloric acid: the ratio of water (volume ratio), and by (A) 2: 96: 2, (B) 2: 2: 96, (C) 78: 2: 20 and (D) 78: 20: 2 form in the tetragonal zone that point surrounds.
Fig. 3 represents the compositing area of the mixed liquor of preferred nitric acid, hydrochloric acid and water among the present invention.In Fig. 3, the tetragonal zone (imposing the zone of oblique line) that is formed by the point of point (A)～(D) is a preferred range.Beyond this scope, possible etching speed is too fast, perhaps slow excessively, and the cone angle of electrode might be in 30～89 scopes of spending.
The composition of this mixed solution, with nitric acid: hydrochloric acid: the ratiometer of water, more preferably in forming in the tetragonal zone that point surrounds by (A ') 4: 48: 48, (B ') 4: 8: 88, (C ') 78: 8: 14 and (D ') 78: 11: 11, the composition of this mixed solution, with nitric acid: hydrochloric acid: the ratiometer of water, particularly preferably in forming in the tetragonal zone that point surrounds by (A ") 6: 47: 47, (B ") 6: 8: 86, (C ") 50: 8: 42 and (D ") 50: 25: 25.
Moreover so-called nitric acid is common red fuming nitric acid (RFNA) (concentration 60%, proportion 1.40), and so-called hydrochloric acid is common concentrated hydrochloric acid (concentration 35%, proportion 1.18).
When using aqueous solution of halogen acid,, can use for example HI, HBr, HCl or HF as halogen acids as etching solution.Be preferably HCl, HI or HF.
The concentration of halogen acids is preferably 1wt%～40wt% in the aqueous solution of halogen acid.If halogen acids concentration is less than 1wt%, etching speed is slow, and is impracticable, if surpass 40wt%, the crystallization of hydrogen halogen might be separated out.More preferably 2wt%～35wt% is preferably 3wt%～15wt% especially.
In the present invention, the serviceability temperature of etching solution during etching is preferably 20～50 ℃.If less than 20 ℃, etching speed is slow, and is impracticable, if surpass 50 ℃, because of the evaporation of moisture or hydrochloric acid etc. makes the concentration change of etching solution, the concentration of the liquid management sometimes difficulty that becomes.Be preferably 25 ℃～45 ℃, more preferably 30 ℃～45 ℃.
The resist imaging liquid preferably uses the aqueous solution of tetramethylammonium hydroxide (TMAH).If use the alkali composition beyond the TMAH, the deviation or the dissolving that might produce the resist pattern can produce great problem in etching.In addition, when Al engages with the nesa coating electricity, when contacting, cause cell reaction sometimes, should be noted that sometimes with electrolyte solution.
Preferred 1～the 5wt% of the concentration of TMAH.If not enough 1wt% causes that sometimes the resist video picture is bad, the easy short circuit of the transparency electrode of formation.In addition, if surpass the concentration of 5wt%, attenuate or peel off owing to produce the line of resist pattern, the line that produces electrode pattern sometimes attenuates or breaks.Be preferably 2～4wt%.
Anticorrosive additive stripping liquid controlling preferably uses ethanolamines amine.As ethanolamines amine, comprise monoethanolamine, diethanol amine, triethanolamine etc., preferably use diethanol amine.In addition, can use the aqueous solution, also can use mixed liquor with polar solvent.As such polar solvent, can enumerate DMF, DMSO, NMP etc.
The concentration of ethanolamines amine is preferably 10wt%～60wt% in the anticorrosive additive stripping liquid controlling, is preferably 20wt%～40wt% especially.
Moreover, if use inorganic bases such as NaOH or KOH, form the electrode surface dissolving concavo-convex, therefore not preferred sometimes as stripper.
The carrier mobility of the transparency electrode of Xing Chenging is preferably 10cm like this
2More than/the VSEC.20cm more preferably
2More than/the VSEC.Drive at TFT under the situation of LCD, if less than 10cm
2/ VSEC, answer speed is slack-off sometimes, and the image quality of liquid crystal is reduced.Resistivity is low more good more, but under the situation that TFT drives, since very short from the TFT element to the distance of LCD drive electrode end, if be 10 therefore
-2No problem then about Ω cm.
Moreover carrier mobility adopts hole determination method (micro through hole method: Off ア Application デ イ ア Port one method) measure.
For transparency electrode of the present invention, in the scope that carrier mobility is not exerted an influence, can add the 3rd metal.As the 3rd metal, for example,, can add the little metal oxide of refractive index in order to improve transmitance.As their typical example, can enumerate MgO, B
2O
3, Ga
2O
3, GeO
2Deng.
In addition, in order to reduce the resistivity of transparency electrode, can add the little oxide of resistivity.As their typical example, can enumerate rheium oxide, yttrium oxide, ruthenium-oxide etc.But, these heavy metallic oxides might be painted, must be noted that its addition, therefore adds in the scope that does not influence transmitance.
[embodiment]
Below, by embodiment the present invention is further specified.
[sputtering target and the making that has the substrate of nesa coating]
Production Example 1
(1) making of sputtering target
Zinc oxide powder below the average grain diameter 1 μ m (plain boiled water テ Star Network corporate system) and the following stannic oxide powder (Mitsubishi Materials corporate system) of average grain diameter 1 μ m are in harmonious proportion, make it to become the ratio of Zn/ (Zn+Sn)=0.79 (atomic ratio), the resin system of packing into crucible, add pure water again, use hard ZrO
2The ball mill by wet process of ball mill mixes.Incorporation time is 20 hours.
The slurry that taking-up makes filters, drying and granulation.
This granulation thing is applied 294MPa (3t/cm
2) pressure, with calm hydraulic pressure extrusion forming.
As described below this formed body is carried out sintering.
In sintering furnace, with every 0.1m
3The ratio of furnace volume 5L/min imports under the atmosphere of oxygen, carries out 5 hours sintering under 1500 ℃.At this moment, be warmed up to 1000 ℃, be warmed up to 1000～1500 ℃ with 3 ℃/min with 1 ℃/min.Then, stop to import oxygen, cool to 1500 ℃～1300 ℃ with 10 ℃/min.Then, with every 0.1m
3The ratio of furnace volume 10L/min imports under the atmosphere of argon gas, after 3 hours, puts cold 1300 ℃ of maintenances.Obtain the sintered body that contain zinc oxide tin oxide of relative density more than 90% like this.
With cup-shaped grinding stone the sputter face of the sintered body that obtains is ground, be processed into diameter 100mm, thick 5mm, use indium class alloy applying backing plate, make sputtering target (sintered body target 1).The density of this target is 5.72g/cm
3
Moreover, in target, preferably be dispersed with tin oxide, especially preferably replace the zinc side of solid solution in zinc oxide.That is, to be included in the form in the target can be with SnO to Sn
2, tin oxide such as SnO the form form of disperseing, but preferably with ZnSnO
3, Zn
2SnO
4Be scattered in form in the zinc oxide sintered body Deng the form of the composite oxides between zinc oxide-tin oxide.This be because, Sn is dispersed in the zinc oxide sintered body with atomic level, makes discharge stability in the sputter, making the transparent conducting film that obtains is low resistance.
The diameter of being handled the average crystalline particle of trying to achieve by the changing image of the Sn atom of the EPMA (the miniature analyzer of X ray) of sintered body target 1 is 3.87 μ m.In addition, the volume resistance of target 1 (resistivity) is 360 Ω cm, obtains carrying out the target of stable RF sputter.
The proterties of sintered body target is shown in table 1.
Table 1
| Zn/ (Zn+Sn) [atomic ratio] | Density [g/cm 3] | The average grain diameter of crystalline particle [μ m] | Resistivity [Ω cm] | |
| Production Example 1 | 0.79 | 5.72 | 3.87 | 360 |
| Production Example 2 | 0.75 | 5.86 | 3.32 | 350 |
| Production Example 3 | 0.70 | 5.83 | 3.4 | 370 |
| Production Example 4 | 0.67 | 5.92 | 3.5 | 420 |
| Production Example 5 | 0.55 | 6.10 | - | 480 |
| Production Example 6 | 0.97 | 5.42 | - | 280 |
| Production Example 7 | 0.40 | 6.34 | - | 4400 |
(2) making of nesa coating
Sintered body target 1 is installed in the sputter equipment.(thick 1mm or 1.1mm) moves in the device with glass substrate, in final vacuum: 5 * 10
-4Pa, one-tenth film pressure: 0.1Pa, substrate temperature: on substrate, form nesa coating (thick 100nm) under 200 ℃.
Ratio [Zn/ (Zn+Sn)], resistivity, carrier mobility and light penetration to the atom of this nesa coating are estimated.Moreover resistivity and charge carrier (electric charge) mobility adopts the hole to measure and tries to achieve.In addition, light penetration adopts spectrophotometer that the light of wavelength 550nm is measured.In addition, the ratio of atom (Zn/ (Zn+Sn), atomic ratio) adopts ICP (high-frequency induction is in conjunction with plasma) analytic approach to measure.
Measurement result is shown in table 2.
Table 2
| Zn/ (Zn+Sn) [atomic ratio] | Resistivity [Ω cm] | Charge mobility [cm 2/V·sec] | Light penetration [%] | |
| Production Example 1 | 0.79 | 0.25 | 25 | 87.8 |
| Production Example 2 | 0.75 | 0.04 | 45 | 86.3 |
| Production Example 3 | 0.70 | 0.009 | 48 | 86.5 |
| Production Example 4 | 0.67 | 0.006 | 46 | 86.3 |
| Production Example 5 | 0.55 | 0.03 | 35 | 85.9 |
| Production Example 6 | 0.97 | 0.86 | 15 | 79.8 |
| Production Example 7 | 0.40 | 0.08 | 8 | 78.8 |
Light transmission rate: the light penetration of wavelength 550nm.
Production Example 2-7
Make the following stannic oxide powder of following Zinc oxide powder of average grain diameter 1 μ m and average grain diameter 1 μ m as material powder, the ratio that makes zinc atom and tin atom is that ratio is prepared shown in the table 1, in addition, similarly make sputtering target (sintered body target 2-7) with Production Example 1, make the substrate that has formed nesa coating.
Moreover the diameter of sputtering target is 152mm, and thickness is 5mm.
The proterties of sputtering target, the evaluation result of nesa coating are shown in table 1 and 2.
[making of transparency electrode]
Embodiment 1
On the nesa coating of the substrate of in Production Example 1, making that has nesa coating, use resist liquid (FUJI HUNT corporate system, HPR204), adopt spin-coating method to form resist film.
Then, use the resist mask of predetermined pattern, carry out exposure, the video picture of resist film.Imaging liquid uses the 2.8wt% aqueous solution of tetramethylammonium hydroxide (TMAH).
Then, adopt and this substrate is handled, carry out the etching of nesa coating, transparency electrode is formed pattern as the oxalic acid aqueous solution of etching solution.The condition of this moment is: the concentration of oxalic acid aqueous solution is 3.5wt%, and temperature is 30 ℃, adopts dipping to carry out etching.Etching speed under this condition is estimated.
When in addition, the serviceability temperature that makes oxalic acid aqueous solution being 40 ℃ and make the concentration of oxalic acid aqueous solution be 5.0wt%, the etching speed when making serviceability temperature be 35 ℃ also estimates.
Show the result in table 3.
At last, the DMSO solution (30wt%) that uses diethanol amine is removed resist film remaining on the transparency electrode as stripper.The condition of this moment is 40 ℃, 1 minute a dipping.
Make the substrate that has formed transparency electrode (wide 90 μ m, spacing 110 μ m) as mentioned above.
Observe by SEM the cone angle of the electrode tip of the transparency electrode that obtains is measured.Show the result in table 3.
Table 3
| The substrate that has nesa coating that uses | Etching speed [/min] (following hurdle: the concentration of oxalic acid aqueous solution and serviceability temperature) | Cone angle [degree] | |||
| 3.5 | 3.5wt％ 40℃ | 5.0wt％ 35℃ | |||
| Embodiment 1 | Production Example 1 | 105000 | 220000 | 180000 | 86 |
| | Production Example 2 | 65000 | 132000 | 96000 | 75 |
| Embodiment 3 | Production Example 3 | 500 | 1100 | 950 | 48 |
| Embodiment 4 | Production Example 4 | 30 | 71 | 55 | 42 |
| Embodiment 5 | Production Example 5 | 10 | 25 | 22 | 38 |
| Comparative example 1 | Production Example 6 | 3560000 | 7210000 | 6800000 | 134 |
| Comparative example 2 | Production Example 7 | - | - | - | - |
*Cone angle represents that the concentration of oxalic acid aqueous solution is 3.5wt%, the angle when serviceability temperature is 30 ℃.
*Comparative example 2 is cannot etching.
Embodiment 2-5, comparative example 1-2
The substrate of the band nesa coating of in using Production Example 2-7, making, make transparent electrode substrate similarly to Example 1, estimate.Show the result in table 3.
Embodiment 6
On the nesa coating of the substrate of in Production Example 1, making that has nesa coating, use resist liquid (FUJI HUNT corporate system, HPR204), adopt spin-coating method to form resist film.
Then, use the resist mask of predetermined pattern, carry out exposure, the video picture of resist film.Imaging liquid uses the 2.8wt% aqueous solution of tetramethylammonium hydroxide (TMAH).
Then, adopt nitric acid: hydrochloric acid: the mixed solution of water (nitric acid: hydrochloric acid: water=25: 13: 62) this substrate is handled, carried out the etching of nesa coating, transparency electrode is formed pattern as etching solution.The serviceability temperature of this liquid is 30 ℃, adopts dipping to carry out etching.
Under this condition, estimate etching speed.
Moreover, water=25: 25: 50), the etching speed when making serviceability temperature be 35 ℃ also estimates when the serviceability temperature that makes above-mentioned etching solution is 40 ℃ and the mixed solution (nitric acid: hydrochloric acid: that uses nitric acid, hydrochloric acid and water.
Show the result in table 4.
At last, the DMSO solution (30wt%) that uses diethanol amine is removed resist film remaining on the transparency electrode as stripper.The condition of this moment is 40 ℃, 1 minute a dipping.
Make the substrate that has formed transparency electrode (wide 90 μ m, spacing 110 μ m) as mentioned above.
Observe by SEM the cone angle of the electrode tip of the transparency electrode that obtains is measured.Show the result in table 4.
Table 4
| The substrate that has nesa coating that uses | Etching speed [/min] (following hurdle: the ratio (HNO of mixed solution 3∶HCl∶ H 2O) and serviceability temperature) | Cone angle [degree] | |||
| 25∶13∶6230 | 25∶13∶6240 | 25∶25∶5035℃ | |||
| Embodiment 6 | Production Example 1 | 15000 | 30000 | 25000 | 85 |
| Embodiment 7 | Production Example 2 | 2500 | 5000 | 4000 | 70 |
| Embodiment 8 | Production Example 3 | 1200 | 2100 | 1800 | 50 |
| Embodiment 9 | Production Example 4 | 450 | 1050 | 900 | 45 |
| | Production Example 5 | 50 | 100 | 90 | 40 |
| Comparative example 3 | Production Example 6 | 200000 | 400000 | 350000 | 140 |
| Comparative example 4 | Production Example 7 | - | - | - | - |
*Cone angle is represented the ratio (HNO of mixed solution
3: HCl: H
2O) be 25: 13: 62, the angle when serviceability temperature is 30 ℃.
*Comparative example 4 is cannot etching.
Embodiment 7-10, comparative example 3-4
The substrate of the band nesa coating of in using Production Example 2-7, making, make transparent electrode substrate similarly to Example 6, estimate.Show the result in table 4.
On the nesa coating of the substrate of in Production Example 1, making that has nesa coating, use resist liquid (FUJI HUNT corporate system, HPR204), adopt spin-coating method to form resist film.
Then, use the resist mask of predetermined pattern, carry out exposure, the video picture of resist film.Imaging liquid uses the 2.8wt% aqueous solution of tetramethylammonium hydroxide (TMAH).
Then, adopt and this substrate is handled, carry out the etching of nesa coating, transparency electrode is formed pattern as hydrogen chloride (HCl) the 35wt% aqueous solution of etching solution.The temperature of this moment is 30 ℃, adopts dipping to carry out etching.
Under this condition, estimate etching speed.
Moreover, when the serviceability temperature that makes above-mentioned aqueous hydrochloric acid solution is 40 ℃ and the concentration of using the acid iodide aqueous solution also estimate as 5wt%, etching speed when making serviceability temperature be 35 ℃.
Show the result in table 5.
At last, the DMSO solution (30wt%) that uses diethanol amine is removed resist film remaining on the transparency electrode as stripper.The condition of this moment is 40 ℃, 1 minute a dipping.
Make the substrate that has formed transparency electrode (wide 90 μ m, spacing 110 μ m) as mentioned above.
Observe by SEM the cone angle of the electrode tip of the transparency electrode that obtains is measured.Show the result in table 5.
Table 5
| The substrate that has nesa coating that uses | Etching speed [/min] (following hurdle: the kind of the etching solution of use and serviceability temperature) | Cone angle [degree] | |||
| HCl：35wt％ 30℃ | HCl：35wt％ 40℃ | HCl：5wt％ 35 | |||
| Embodiment | |||||
| 11 | Production Example 1 | 30000 | 60000 | 50000 | 88 |
| | Production Example 2 | 5000 | 10000 | 9000 | 75 |
| Embodiment 13 | Production Example 3 | 2500 | 4000 | 3600 | 58 |
| Embodiment 14 | Production Example 4 | 900 | 2000 | 1900 | 51 |
| Embodiment 15 | Production Example 5 | 100 | 200 | 180 | 42 |
| Comparative example 5 | Production Example 6 | 400000 | 800000 | 700000 | 141 |
| Comparative example 6 | Production Example 7 | - | - | - | - |
*Cone angle represents to use the HCl:35wt% aqueous solution, the angle when serviceability temperature is 30 ℃.
*Comparative example 6 is cannot etching.
Embodiment 12-15, comparative example 5-6
The substrate of the band nesa coating of in using Production Example 2-7, making, make transparent electrode substrate similarly to Example 11, estimate.Show the result in table 5.
Estimate 1
For the substrate of the band transparency electrode of making among the foregoing description 1-15 and the comparative example 1-6, adopt the connection test of TCP method (Tape Carrier Package), estimate connective stability.
Connect substrate for TCP, under 60 ℃, the environment of 90%RH, preserve, observe connect resistance through the time change.Show the result in table 6～table 8.
Moreover, in comparative example 2,4,6, do not obtain having the substrate of transparency electrode, but, connect resistance for the substrate evaluation after the above-mentioned processing for reference.
Table 6
| Zn/ (Zn+Sn) [atomic ratio] | TCP connects resistance [Ω] | ||||
| After just having connected | After 240 hours | After 480 hours | After 960 hours | ||
| Embodiment 1 | 0.79 | 4.2 | 5.6 | 6.2 | 6.5 |
| | 0.75 | 4.3 | 5.0 | 5.4 | 5.4 |
| Embodiment 3 | 0.70 | 4.5 | 4.9 | 5.3 | 5.3 |
| Embodiment 4 | 0.67 | 4.8 | 5.3 | 5.5 | 5.7 |
| Embodiment 5 | 0.55 | 5.1 | 5.4 | 5.6 | 5.6 |
| Comparative example 1 | 0.97 | 6.5 | 15.6 | 31.4 | 125 |
| Comparative example 2 | 0.40 | 5.2 | 5.8 | 6.3 | 6.4 |
Table 7
| Zn/ (Zn+Sn) [atomic ratio] | TCP connects resistance [Ω] | ||||
| After just having connected | After 240 hours | After 480 hours | After 960 hours | ||
| Embodiment 6 | 0.79 | 4.5 | 4.9 | 5.7 | 6.6 |
| Embodiment 7 | 0.75 | 4.4 | 4.8 | 5.8 | 5.8 |
| Embodiment 8 | 0.70 | 4.7 | 5.2 | 5.3 | 5.4 |
| Embodiment 9 | 0.67 | 4.6 | 4.8 | 5.0 | 5.1 |
| | 0.55 | 4.8 | 5.2 | 5.5 | 5.7 |
| Comparative example 3 | 0.97 | 7.1 | 20.5 | 36.5 | 130 |
| Comparative example 4 | 0.40 | 5.5 | 6.2 | 6.8 | 6.7 |
Table 8
| Zn/ (Zn+Sn) [atomic ratio] | TCP connects resistance [Ω] | ||||
| After just having connected | After 240 hours | After 480 hours | After 960 | ||
| Embodiment | |||||
| 11 | 0.79 | 4.6 | 5.3 | 5.9 | 6.8 |
| | 0.75 | 4.5 | 5.1 | 5.5 | 6.0 |
| Embodiment 13 | 0.70 | 4.8 | 5.1 | 5.4 | 5.6 |
| Embodiment 14 | 0.67 | 4.7 | 4.9 | 5.1 | 5.3 |
| Embodiment 15 | 0.55 | 4.9 | 5.3 | 5.6 | 5.9 |
| Comparative example 5 | 0.97 | 7.3 | 21.2 | 37.1 | 135 |
| Comparative example 6 | 0.40 | 5.7 | 6.3 | 6.9 | 6.9 |
The sputtering target of pure Al is installed in the sputter equipment.On glass substrate, in final vacuum: 5 * 10
-4Pa, one-tenth film pressure: 0.1Pa, substrate temperature: the film (thick 200nm) that on glass substrate, forms Al under the room temperature.
With of 1/10 sealing of kapton (Kapton) adhesive tape with the area of the glass substrate that obtains.On this substrate, use the target 1-7 that makes among the Production Example 1-7, at room temperature form the film of thick 100nm.Then, with the kapton tape stripping, the glass substrate of the band laminate film that the part of making Al film is exposed.
Moreover, as a reference example, also be produced on the glass substrate of the band laminate film that has formed ito thin film on the Al film.
The glass substrate of these band laminate films was flooded 2 minutes in the 2.4wt% of the TMAH aqueous solution (20 ℃), observe the dissolving of Al film.Show the result in table 9.
Table 9
| Laminate structures | The variation of film |
| The nesa coating of Al film/Production Example 1 | No change |
| The nesa coating of Al film/Production Example 2 | No change |
| The nesa coating of Al film/Production Example 3 | No change |
| The nesa coating of Al film/Production Example 4 | No change |
| The nesa coating of Al film/Production Example 5 | No change |
| The nesa coating of Al film/Production Example 6 | Conducting film dissolves |
| The nesa coating of Al film/Production Example 7 | Conducting film takes place painted |
| Reference example: Al film/ITO film | The Al film dissolves fully |
Moreover, impregnated in this aqueous solution even will only be formed with the glass substrate of pure Al film, do not observe the dissolving of Al layer yet.Therefore, in this evaluation, observed the dissolving of Al, confirmed to cause cell reaction owing to the laminate structures of Al/ nesa coating.
Estimate 3
In as the mixed liquor of diethanol amine 30vol%, dimethyl sulfoxide (DMSO) (DMSO) 70vol% of corrosion inhibitor stripper, add the water of 10vol%, under 45 ℃ with the glass-impregnated of the band 100nm film that obtains in the Production Example 15 minutes.Then, with scanning electron microscope (SEM) surface of film is observed.Its result does not observe convex-concave and rough surface.
On the other hand, use the glass of the band 100nm film that obtains in the Production Example 6, carry out same operation, the result at the surface observation of film to convex-concave and rough surface, confirm to be not suitable for as liquid crystal with or organic EL electrode.
Estimate 4
Use is laminated on glass substrate the nesa coating of Production Example 1-7 and a substrate of Al film, and nesa coating and Al film are formed the thin-line-shaped of live width 50 μ m respectively, makes Al fine rule and electrically conducting transparent fine rule quadrature (two fine rule intersection points partly become stacked state).Measure the contact resistance at this stacked interface with the Kelvin probe method.Show the result in table 10.
Table 10
| Laminate structures | Contact resistance value (Ω) |
| The nesa coating of Al film/Production Example 1 | 0.4 |
| The nesa coating of Al film/Production Example 2 | 0.6 |
| The nesa coating of Al film/Production Example 3 | 0.7 |
| The nesa coating of Al film/Production Example 4 | 0.8 |
| The nesa coating of Al film/Production Example 5 | 1.2 |
| The nesa coating of Al film/Production Example 6 | 0.4 |
| The nesa coating of Al film/Production Example 7 | 12 |
| Reference example: Al film/ITO film | 130 |
Industrial utilizability
Transparency electrode of the present invention is owing to not using indium to make low price. In addition, etching characteristic is good, electrode tip can be formed taper. Therefore, suitable to the transparency electrode of using in the thin displays such as liquid crystal indicator, organic electroluminescence display device and method of manufacturing same, plasma display.
Claims (15)
1. transparency electrode, it is a main component with zinc oxide and tin oxide, the cone angle of electrode tip is 30～89 degree.
2. transparency electrode as claimed in claim 1, wherein,
With respect to the total amount of zinc atom and tin atom in the described transparency electrode, the ratio of zinc atom (Zn/ (Zn+Sn), atomic ratio) is 0.5～0.9.
3. the manufacture method of a transparency electrode, wherein,
So that the cone angle of electrode tip is the modes of 30～89 degree, to being that the nesa coating of main component carries out etching with zinc oxide and tin oxide.
4. the manufacture method of transparency electrode as claimed in claim 3, wherein,
With respect to the total amount of zinc atom and tin atom in the described transparency electrode, the ratio of zinc atom (Zn/ (Zn+Sn), atomic ratio) is 0.5～0.9.
5. as the manufacture method of claim 3 or 4 described transparency electrodes, wherein,
Working concentration is the aqueous solution of halogen acid of 1wt%～40wt% in described etching.
6. as the manufacture method of each described transparency electrode of claim 3～5, it comprises:
Form first operation of nesa coating, zinc atom is 0.5～0.9 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom and is main component with zinc oxide and tin oxide in the described nesa coating;
On described nesa coating, form second operation of resist film;
1～5wt% the aqueous solution that uses tetramethylammonium hydroxide is as the resist imaging liquid, in the temperature of this aqueous solution is to make described resist film form the 3rd operation of pattern under 20～50 ℃ the scope;
The concentration of using halogen acids is carried out etching as the aqueous solution of 1wt%～40wt% to described nesa coating, and forming cone angle is the 4th operation of the transparency electrodes of 30～89 degree; With
The anticorrosive additive stripping liquid controlling that use contains monoethanolamine will remain in the 5th operation that the resist film on the described transparency electrode is peeled off.
7. the manufacture method of transparency electrode as claimed in claim 3, it has:
Form the operation of nesa coating, zinc atom is 0.5～0.85 with respect to the ratio (Zn/ (Zn+Sn), atomic ratio) of the total amount of zinc atom and tin atom and is main component with zinc oxide and tin oxide in the described nesa coating; With
Use concentration of oxalic acid as the aqueous solution of 1wt%～10wt% as etching solution, be under 20～50 ℃ the scope described nesa coating to be carried out etching in the temperature of etching solution, form the operation of pattern.
8. as the manufacture method of claim 3 or 4 described transparency electrodes, it comprises:
Formation is first operation of the nesa coating of main component with zinc oxide and tin oxide;
On described nesa coating, form second operation of resist film;
Make described resist film form the 3rd operation of pattern;
Use the mixed solution of nitric acid, hydrochloric acid and water that described nesa coating is carried out etching, forming cone angle is the 4th operation of the transparency electrode of 30～89 degree; With
The 5th operation that the resist film that remains on the described transparency electrode is peeled off.
9. the manufacture method of transparency electrode as claimed in claim 8, wherein,
The composition of described mixed solution, in three composition systems of nitric acid-hydrochloric acid-water, with nitric acid: hydrochloric acid: the ratio of water represents, is in (A) 2: 2: 96, (B) 2: 2: 96, (C) 78: 2: 20 and (D) in the tetragonal zone that 78: 20: 2 composition point surrounds.
10. the manufacture method of transparency electrode as claimed in claim 8 or 9, wherein,
Nitric acid in described the 4th operation: hydrochloric acid: the temperature of the mixed solution of water is 20～50 ℃.
11. as the manufacture method of each described transparency electrode of claim 8～10, wherein,
The resist imaging liquid that uses in described the 3rd operation contains monoethanolamine as 1～5wt% aqueous solution of tetramethylammonium hydroxide, the anticorrosive additive stripping liquid controlling that uses in described the 5th operation.
12 1 kinds are used oxalic acid aqueous solution to carrying out etching method with zinc oxide and tin oxide as the nesa coating of main component.
13. engraving method as claimed in claim 12, wherein,
The concentration of described oxalic acid aqueous solution mesoxalic acid is 1wt%～10wt%.
14. a mixed solution that uses nitric acid, hydrochloric acid and water is to carrying out etching method with zinc oxide and tin oxide as the ELD of main component.
15. engraving method as claimed in claim 14, wherein,
The composition of the mixed solution of described nitric acid, hydrochloric acid and water, in three composition systems of nitric acid-hydrochloric acid-water, with nitric acid: hydrochloric acid: the ratio of water represents, is in (A) 2: 2: 96, (B) 2: 2: 96, (C) 78: 2: 20 and (D) in the tetragonal zone that 78: 20: 2 composition point surrounds.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005003473A JP2006194926A (en) | 2005-01-11 | 2005-01-11 | Method for manufacturing transparent electrode |
| JP003477/2005 | 2005-01-11 | ||
| JP003473/2005 | 2005-01-11 | ||
| JP2005003487A JP2006196201A (en) | 2005-01-11 | 2005-01-11 | Clear electrode and its manufacturing method |
| JP003487/2005 | 2005-01-11 | ||
| JP2005003477A JP2006196200A (en) | 2005-01-11 | 2005-01-11 | Transparent electrode and its manufacturing method |
| PCT/JP2005/023700 WO2006075506A1 (en) | 2005-01-11 | 2005-12-26 | Transparent electrode and method for fabricating same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101076869A true CN101076869A (en) | 2007-11-21 |
| CN101076869B CN101076869B (en) | 2010-05-05 |
Family
ID=36802113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580042675.1A Expired - Fee Related CN101076869B (en) | 2005-01-11 | 2005-12-26 | Transparent electrode and method for manufacturing same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006196200A (en) |
| CN (1) | CN101076869B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7875155B2 (en) | 2006-03-16 | 2011-01-25 | Sumitomo Chemical Company, Limited | Transparent electrically conductive film and method for production thereof |
| CN102253562A (en) * | 2011-07-13 | 2011-11-23 | 深圳超多维光电子有限公司 | Stereo display device and liquid crystal lens thereof |
| CN101038796B (en) * | 2006-03-15 | 2012-02-08 | 住友金属矿山株式会社 | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| CN103911156A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN103911157A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN103911158A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN105449116A (en) * | 2015-11-18 | 2016-03-30 | Tcl集团股份有限公司 | ITO substrate and manufacturing method, OLED device and manufacturing method |
| CN105511176A (en) * | 2016-01-29 | 2016-04-20 | 京东方科技集团股份有限公司 | Preparation method of array substrate |
| WO2016206203A1 (en) * | 2015-06-26 | 2016-12-29 | 京东方科技集团股份有限公司 | Conductive structure and manufacturing method thereof, array substrate and display device |
| CN108539036A (en) * | 2017-03-06 | 2018-09-14 | Tcl集团股份有限公司 | A kind of electrode structure, QLED and preparation method that light extraction efficiency can be improved |
| WO2018210040A1 (en) * | 2017-05-15 | 2018-11-22 | 京东方科技集团股份有限公司 | Organic light emitting diode and preparation method therefor |
| CN108878370A (en) * | 2018-06-27 | 2018-11-23 | 深圳市华星光电技术有限公司 | A kind of transparent conductive electrode and preparation method thereof, display device |
| CN108885922A (en) * | 2016-03-23 | 2018-11-23 | 三菱综合材料株式会社 | Laminating transparent conductive film, stacking wiring membrane and the manufacturing method that wiring membrane is laminated |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4730204B2 (en) * | 2006-05-24 | 2011-07-20 | 住友金属鉱山株式会社 | Oxide sintered compact target and method for producing oxide transparent conductive film using the same |
| JP2010034032A (en) * | 2008-06-25 | 2010-02-12 | Sumitomo Chemical Co Ltd | Method of manufacturing transparent conductive film |
| JP2010031364A (en) * | 2008-06-25 | 2010-02-12 | Sumitomo Chemical Co Ltd | Transparent conductive film and method for producing the same |
| JP5024226B2 (en) * | 2008-08-06 | 2012-09-12 | 日立金属株式会社 | Oxide sintered body and manufacturing method thereof, sputtering target, semiconductor thin film |
| JP5724157B2 (en) * | 2009-04-13 | 2015-05-27 | 日立金属株式会社 | Oxide semiconductor target and method of manufacturing oxide semiconductor device using the same |
| JP5686067B2 (en) * | 2011-08-05 | 2015-03-18 | 住友金属鉱山株式会社 | Zn-Sn-O-based oxide sintered body and method for producing the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3616128B2 (en) * | 1994-03-27 | 2005-02-02 | グンゼ株式会社 | Method for producing transparent conductive film |
| JP4354019B2 (en) * | 1997-04-18 | 2009-10-28 | 出光興産株式会社 | Organic electroluminescence device |
| JP3313306B2 (en) * | 1997-05-30 | 2002-08-12 | 住友ベークライト株式会社 | Antistatic film |
| JP2000067657A (en) * | 1998-08-26 | 2000-03-03 | Internatl Business Mach Corp <Ibm> | Transparent conductive film excellent in infrared transmission and its manufacture |
| JP4559554B2 (en) * | 1999-03-05 | 2010-10-06 | 出光興産株式会社 | Sintered body for sputtering, electron beam and ion plating, and sputtering target |
| JP3366864B2 (en) * | 1998-09-11 | 2003-01-14 | グンゼ株式会社 | Transparent conductive film |
| JP2004240091A (en) * | 2003-02-05 | 2004-08-26 | Idemitsu Kosan Co Ltd | Method for manufacturing transflective type electrode substrate |
-
2005
- 2005-01-11 JP JP2005003477A patent/JP2006196200A/en active Pending
- 2005-12-26 CN CN200580042675.1A patent/CN101076869B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101038796B (en) * | 2006-03-15 | 2012-02-08 | 住友金属矿山株式会社 | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| US7875155B2 (en) | 2006-03-16 | 2011-01-25 | Sumitomo Chemical Company, Limited | Transparent electrically conductive film and method for production thereof |
| CN102253562A (en) * | 2011-07-13 | 2011-11-23 | 深圳超多维光电子有限公司 | Stereo display device and liquid crystal lens thereof |
| CN103911156A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN103911157A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN103911158A (en) * | 2012-12-28 | 2014-07-09 | 东友精细化工有限公司 | Etchant composition for metallic oxide layer |
| CN103911156B (en) * | 2012-12-28 | 2018-07-20 | 东友精细化工有限公司 | Etching agent composite for metal oxide layer |
| WO2016206203A1 (en) * | 2015-06-26 | 2016-12-29 | 京东方科技集团股份有限公司 | Conductive structure and manufacturing method thereof, array substrate and display device |
| US10204931B2 (en) | 2015-06-26 | 2019-02-12 | Boe Technology Group Co., Ltd. | Electrically conductive structure and manufacturing method thereof, array substrate, display device |
| CN105449116A (en) * | 2015-11-18 | 2016-03-30 | Tcl集团股份有限公司 | ITO substrate and manufacturing method, OLED device and manufacturing method |
| CN105511176A (en) * | 2016-01-29 | 2016-04-20 | 京东方科技集团股份有限公司 | Preparation method of array substrate |
| CN108885922A (en) * | 2016-03-23 | 2018-11-23 | 三菱综合材料株式会社 | Laminating transparent conductive film, stacking wiring membrane and the manufacturing method that wiring membrane is laminated |
| CN108885922B (en) * | 2016-03-23 | 2021-10-08 | 三菱综合材料株式会社 | Laminated transparent conductive film, laminated wiring film, and method for producing laminated wiring film |
| CN108539036A (en) * | 2017-03-06 | 2018-09-14 | Tcl集团股份有限公司 | A kind of electrode structure, QLED and preparation method that light extraction efficiency can be improved |
| WO2018210040A1 (en) * | 2017-05-15 | 2018-11-22 | 京东方科技集团股份有限公司 | Organic light emitting diode and preparation method therefor |
| US11171301B2 (en) | 2017-05-15 | 2021-11-09 | Boe Technology Group Co., Ltd. | Organic light emitting diode and method for fabricating the same |
| CN108878370A (en) * | 2018-06-27 | 2018-11-23 | 深圳市华星光电技术有限公司 | A kind of transparent conductive electrode and preparation method thereof, display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101076869B (en) | 2010-05-05 |
| JP2006196200A (en) | 2006-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101076869A (en) | Transparent electrode and method for manufacturing same | |
| CN1294656C (en) | Semiconductor device and producing method thereof | |
| CN1170321C (en) | Patterns of electrically conducting polymers and their application as electrodes or electrical contacts | |
| CN1229655C (en) | Color filter and electro-optical device | |
| CN1930318A (en) | Indium oxide-cerium oxide sputtering target, transparent conductive film, and method for producing transparent conductive film | |
| CN1315003C (en) | Electronic device and its making method, spattering target | |
| CN1940688A (en) | Display apparatus and manufacturing method thereof | |
| CN1917218A (en) | Source/drain electrodes, transistor substrates and manufacture methods, thereof, and display devices | |
| CN1168076A (en) | Transparent conductive laminate and electroluminescence light-emitting element using same | |
| CN1690011A (en) | Oxide sintered body, sputtering target, transparent conductive thin film and manufacturing method therefor | |
| CN1769528A (en) | Etchant for conductive materials and method of manufacturing a thin film transistor array panel using the same | |
| CN1599056A (en) | Light emitting device and method of manufacturing thereof | |
| JP2017092439A (en) | Silver etchant composition and display substrate using the same | |
| CN1533561A (en) | Display device and method for manufacturing the same | |
| CN1869796A (en) | Liquid crystal display device | |
| CN1967803A (en) | Display device and manufacturing method of the same | |
| CN1258209C (en) | Conductive thin film for semiconductor device, and method for manufacturing the same | |
| CN1678145A (en) | Mask, method for manufacturing a mask, method for manufacturing an electro-optical device, and electronic equipment | |
| CN1743935A (en) | The substrate of display device and have its liquid crystal display device and a manufacture method thereof | |
| CN1685767A (en) | Laminate, substrate with wiring, organic EL display element, connecting terminal of the element, and their manufacturing method | |
| JP2006194926A (en) | Method for manufacturing transparent electrode | |
| TWI608127B (en) | Etchant composition, method of forming metal pattern and method of manufacturing an array substrate | |
| CN1822372A (en) | Display device and sputtering target for producing the same | |
| CN1959980A (en) | Conductive structure, manufacturing method for conductive structure, element substrate, and manufacturing method for element substrate | |
| TWI636157B (en) | Etching solution composition for silver layer and display substrate using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100505 Termination date: 20151226 |
|
| EXPY | Termination of patent right or utility model |