CN106374010B - A kind of preparation method of nanometer of silver composite tin oxide transparent conductive film - Google Patents
A kind of preparation method of nanometer of silver composite tin oxide transparent conductive film Download PDFInfo
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- CN106374010B CN106374010B CN201610877043.7A CN201610877043A CN106374010B CN 106374010 B CN106374010 B CN 106374010B CN 201610877043 A CN201610877043 A CN 201610877043A CN 106374010 B CN106374010 B CN 106374010B
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- Prior art keywords
- tin oxide
- conductive film
- silver
- transparent conductive
- fluorine doped
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 99
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- 108010025899 gelatin film Proteins 0.000 claims abstract description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011049 filling Methods 0.000 claims abstract description 17
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 230000007704 transition Effects 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 76
- 238000002834 transmittance Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 241000370738 Chlorion Species 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- LMZURCXQQZLYNR-UHFFFAOYSA-N ethanol;silver Chemical compound [Ag].CCO LMZURCXQQZLYNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 organic acid tin salt Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- WPEOGXOIJDXEQY-UHFFFAOYSA-N silver;sulfamic acid Chemical compound [Ag].NS(O)(=O)=O WPEOGXOIJDXEQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- ZMQKZSQODJUBTO-UHFFFAOYSA-M silver ethanol acetate Chemical compound C(C)O.C(C)(=O)[O-].[Ag+] ZMQKZSQODJUBTO-UHFFFAOYSA-M 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to the preparation method of a kind of nanometer of silver composite tin oxide transparent conductive film, filling soluble silver salt and tin salt in tin oxide conductive film hole prepared by sol-gal process, in-situ reducing generates nano silver particles, high temperature sintering obtains a nanometer silver composite tin oxide transparent conductive film, and the chemical composition of nanometer silver composite tin oxide transparent conductive film is：AgxSnO2‑yFyIn molecular formula, x=0.01 0.1, y=0 0.6, the technical scheme taken is included in coating silicon dioxide transition zone on solar cell glass basis, the preparation of fluorine doped tin oxide Nano sol, the preparation of fluorine doped tin oxide gel film, five parts of porous oxidation tin gel film pore filling, nanometer silver composite tin oxide transparent conductive film formation.The present invention is reduction FTO conductive film resistance easy-to-use technical measures, with commercial application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer of silver composite tin oxide transparent conductive film, particularly one kind is molten
Tin oxide conductive film hole situ generation nano silver particles prepared by glue-gel method, obtain Nano Silver and are combined high transmission rate
The preparation method of low square resistance tin oxide transparent conductive film, belongs to new energy materialses and energy-conserving and environment-protective field.
Technical background
Transparent conductive oxide（TCO）It is that optical transparence and electric conductivity are compounded in integral photoelectric material, it is big at present
Transparency electrode of the amount as thin film solar cell, is also applied to the fields such as LCDs, photocatalysis and building energy conservation, and market is needed
Ask huge.TCO glass is uniformly to plate last layer TCO thin film by physics or chemical method in glass surface to be formed.It is common
TCO materials include indium oxide base, tin oxide base and the class of Zinc oxide-base three.FTO electro-conductive glass light transmittance more than 80%, raw material comes
Source is wide, and production cost is relatively low, and heat endurance and chemical stability are good, and laser ablation is easier to.Due to the sexual valence of FTO electro-conductive glass
Than advantage, turn into the important source material and commercial applications of thin film solar cell, calcium titanium as the substitute products of ITO electro-conductive glass
Ore deposit solar cell subversiveness technological break-through have stimulated FTO electro-conductive glass market developments.
FTO conductive films and electro-conductive glass have the transparency and the big fundamental characteristics of electric conductivity two, but its electric conductivity is still needed to
The technical requirements of thin film solar cell continuous improvement could be met by improving.It is domestic in addition to preparation process condition Optimal improvements
Outer research is main from three new way reduction FTO conductive film square resistances：（1）Multi-element doping increase FTO conductive films
Carrier concentration；（2）With low-resistance metal material formation composite transparent conductive film；（3）Form compound with low resistance transparent material
Nesa coating.
The metal such as silver, gold, nickel, copper has good electric conductivity, low two orders of magnitude of its resistivity ratio transparent oxide, but
Just only there is good light transmission when thickness of metal film is less than 20nm, and very thin metallic diaphragm is often with island
Form is present, and causes film to have very high resistance and reflectivity.It is a kind of reduction that FTO conductive films and metallic film, which are combined,
The effective way of FTO conductive film square resistances.Chinese patent CN103151394 (2013-06-12) discloses a kind of film sun
Energy battery and preparation method thereof, TCO conductive films are coated on the nano silver film of 10-20nm thickness, have obtained low-resistance
Silver-colored compound transparent electricity conductive film, improves thin film solar cell efficiency, but need the magnetic control using technical sophistication and high cost to splash
Penetrate technology and hot evaporation technology.Chinese patent CN101515602 (2009-08-26) discloses a kind of transparent conducting film glass,
Silver-colored gate electrode is printed on FTO conductive films, so that the ohmic loss of conductive substrates is reduced, but silver grating line prepared by printing is typically wide
Degree and thickness all block than the light of larger, wider silver grating line and reduce light transmittance, and thicker silver grating line is also unfavorable for subsequent optical
Absorbing material is uniformly coated.
The fluorine doped tin oxide transparent conductive film prepared using sol-gel process is loose high with porosity because of surface texture,
Film surface square resistance is caused to increase.If filling silver salt in FTO film holes, in-situ reducing generation Nano Silver cladding oxidation
Tin, will obtain Nano Silver and is combined the low square resistance tin oxide transparent conductive film of high transmission rate.
The content of the invention
It is an object of the invention to provide the preparation method of a kind of nanometer of silver composite tin oxide transparent conductive film, it is characterized in that
Filling soluble silver salt and tin salt in tin oxide conductive film hole prepared by sol-gel process, in-situ reducing generation are received
Rice silver particles, then high temperature sintering obtain Nano Silver and are combined the low square resistance tin oxide transparent conductive film of high transmission rate, Nano Silver
The chemical composition of composite tin oxide transparent conductive film is：AgxSnO2-yFy , wherein, x=0.01-0.1, y=0-0.6 take
Technical scheme be included in coating silicon dioxide transition zone on solar cell glass basis, fluorine doped tin oxide Nano sol prepare,
The preparation of fluorine doped tin oxide gel film, porous oxidation tin gel film pore filling, nanometer silver composite tin oxide electrically conducting transparent are thin
Five parts of film formation.
Coating silicon dioxide transition zone is in solar cell glass basis surface coating thickness on solar cell glass basis
50-100nm nano silicon transition zone, for blocking under high temperature, sodium calcium ion expands into conductive film in soda-lime glass
Dissipate, while increasing glass basis light transmittance as antireflection layer and improving fluorine doped tin oxide transparent conductive film on glass basis
Adhesive force.
Nano sol preparation method is：（1）Ammoniacal liquor is added into the butter of tin aqueous solution hydrolyzes pink salt, by the heavy of formation
Washing form sediment to without chlorion；（2）By aqua oxidation tin sediment suspend in deionized water, add ammonium fluoride containing fluorine dopant or
Hydrofluoric acid, adds the saturated oxalic acid aqueous solution, aqua oxidation tin is deposited at 50-60 DEG C complete peptization, generation fluorine doped oxidation
Tin Nano sol pH is 0.8-1.5, and the constitutive molar ratio of fluorine doped tin oxide Nano sol is Sn (OH)4：F： H2C2O4=1：0-
0.6：0.1-0.4；（3）Polyaminoester emulsion is added into fluorine doped tin oxide Nano sol, it is 0.01%- to make its mass percentage concentration
0.2%, to improve fluorine doped tin oxide collosol stability, coating homogeneity and ftracture when preventing that film layer from drying, fluorine doped tin oxide nanometer
Tin ash mass percentage concentration is 4%-5% in colloidal sol.
Gel film preparation method is fluorine doped tin oxide colloidal sol to be coated on solar cell glass transition zone 2-3 times, makes to coagulate
Glue film thickness 400-800nm, drying obtains fluorine doped tin oxide gel film at 150 DEG C, and fluorine doped tin oxide particle diameter is 10-
15nm, fluorine doped tin oxide gel film porosity is 20%-30%.
Porous oxidation tin gel film pore filling method is that solubility is coated with fluorine doped tin oxide porous gel film
Silver salt ethanol water 2-3 times, makes soluble silver salt dipping be filled into film hole, the ethanol for being coated tin salt is water-soluble
Liquid, it is nano silver particles to make soluble silver salt in-situ reducing, and the mol ratio for controlling raw material is (Sn4++ Sn2+)：F：Ag：Sn2+ =
1：0-0.6：0.01-0.1：0.01-0.1, at 150 DEG C dry, tin oxide gel film porosity be 10%-15%, it is described can
Soluble silver salt is silver nitrate, sulfamic acid silver, silver acetate and silver salicylate, the tin salt be stannous chloride, nitric acid stannous and
Organic acid tin salt.
Nanometer silver composite tin oxide transparent conductive film forming method is that coated glass matrix is heated into 300 DEG C,
Programming rate is reduced to 3-5 DEG C/min at 300-450 DEG C, the soluble silver salt high temperature of filling is completely decomposed into Nano Silver and is wrapped
Tin oxide is covered, is finally sintered 30 minutes under 500 DEG C of high temperature, organic matter is decomposed completely, fluorine atom doping is entered tin oxide
Fluorine doped tin oxide is formed in lattice, and makes fluorine doped tin oxide crystal growth formation transparent conductive film, Nano Silver is coated after filling
SnO 2 thin film porosity is 5%-10%, and electro-conductive glass visible light transmittance rate is 81%-85%, and square resistance is 1-5 Ω/.
The reason for present invention can reduce film rectangular resistance includes several aspects：（1）The Nano Silver of in-situ reducing generation
Cladding tin oxide itself connection forms low-resistance Nano Silver net, so as to reduce compound transparent electricity conductive film square resistance；（2）
The Nano Silver of in-situ reducing generation generates low resistance silver-tin alloy with tin oxide, so as to reduce compound transparent electricity conductive film square
Resistance（3）SnO 2 thin film pore filling and high temperature sintering reduce fluorine doped tin oxide gel film porosity, so as to reduce multiple
Close transparent conductive film square resistance.
Experimental raw silicon dioxide gel, butter of tin, stannous chloride, ammoniacal liquor, ammonium fluoride, oxalic acid used in the present invention,
Silver nitrate, ethanol, polyaminoester emulsion are commercially available chemically pure reagent；Solar cell glass is commercial goods.
The light transmittance type light splitting light of Lambda 920 of nanometer silver composite tin oxide transparent conductive film and electro-conductive glass
Degree measurement test agent is calculated in the transmitance of 400-760nm visible-ranges；Nanometer silver composite tin oxide transparent conductive film and
The square resistance of electro-conductive glass is measured with the probe sheet resistance of ST2258C types four and tried；The porosity of doped tin oxide transparent conductive film
Calculated by Sample Scan sem image section.
Beneficial effects of the present invention are embodied in：
（1）Nanometer silver composite tin oxide transparent conductive film and electro-conductive glass light transmittance of the present invention are high and square resistance is low,
It is suitable as large area film solar cell transparency electrode application；
（2）The present invention, in FTO conductive films situ formation Nano Silver net, is that reduction FTO conductive films resistance is easy easily
Capable technical measures, with commercial application prospect.
Embodiment
Embodiment 1
Silica transition zone is coated on glass basis:By 100mm × 100 mm × 1mm ultra-clear glasses matrix clear water
Rinse well, washes of absolute alcohol and dry, the nano silicon for being then 100nm with spreading rod coating thickness on its surface
Plate and the uniform coated glass transition zone in surface is formed after being dried in film sol, air, measure film front and rear visible in 400-760nm
The light transmittance of optical wavelength range is respectively 91.5% and 93.5%.
It is prepared by Nano sol:Anhydrous stannic chloride 26.1g (0.1mol) is dissolved in 500ml deionized waters, under agitation
Add 2mol/L ammoniacal liquor, until being 8-9 there is no Precipitation and pH value of solution, the precipitation hydrolyzed to form filtered, spend from
Sub- water washing is to without chlorion.Sediment is suspended in 200ml deionized waters, saturated oxalic acid aqueous solution 37g is added
(0.03mol), makes aqua oxidation tin be deposited at 50-60 DEG C complete peptization, adds ammonium fluoride 0.37g (0.01mol) and is used as and mixes
Miscellaneous Fluorine source, adds polyaminoester emulsion 0.5g, obtains the fluorine doped tin oxide Nano sol that tin ash mass percentage concentration is 5%, shape
PH into colloidal sol is 1.1.
It is prepared by gel film：Fluorine doped tin oxide colloidal sol is coated on solar cell glass transition zone 3 times, make gel film thick
Spend for 500-600nm, drying obtains fluorine doped tin oxide gel film at 150 DEG C, measure gel particle diameter for 10-15nm, gel
Film porosity is 27%.
Nano Silver is filled in porous oxidation tin gel film：The coating quality percentage on fluorine doped tin oxide porous gel film
The silver nitrate ethanol solution that concentration is 5% 3 times, makes its dipping be filled into film hole, and it is 5% to be coated mass percentage concentration
Stannous chloride ethanol water 2 times, makes silver nitrate in-situ reducing fill film hole for nano silver particles, is dried at 150 DEG C
Dry, it is 15% to measure film porosity.
Nanometer silver composite tin oxide is formed：Coated glass matrix is heated to 300 DEG C, the programming rate at 300-450 DEG C
3-5 DEG C/min is reduced to, the silver salt high temperature of filling is completely decomposed into Nano Silver and is coated tin oxide, finally in 500 DEG C of high temperature
Lower sintering 30 minutes, makes organic matter decompose completely, fluorine atom doping is entered in tin oxide lattice and forms fluorine doped tin oxide, and makes
Fluorine doped tin oxide crystal growth formation transparent conductive film, the porosity of Nano Silver cladding SnO 2 thin film is 8.5%, conductive glass
Glass visible light transmittance rate is 83.5%, and square resistance is 1.8 Ω/.
Embodiment 2
It is prepared by fluorine doped tin oxide Nano sol:Anhydrous stannic chloride 26.1g (0.1mol) is dissolved in 500ml deionized waters
In, 2mol/L ammoniacal liquor is added under agitation, until being 8-9 there is no Precipitation and pH value of solution, by the precipitation hydrolyzed to form
Filtering, is washed with deionized to without chlorion.Sediment is suspended in 200ml deionized waters, saturated oxalic acid is added water-soluble
Liquid 37g (0.03mol), makes aqua oxidation tin be deposited at 50-60 DEG C complete peptization, adds ammonium fluoride 0.37g (0.01mol) and makees
For doping Fluorine source, polyaminoester emulsion 0.5g is added, the fluorine doped tin oxide nanometer that tin ash mass percentage concentration is 5% is obtained molten
Glue, the pH for forming colloidal sol is 1.1.
It is prepared by gel film：Fluorine doped tin oxide colloidal sol is coated on solar cell glass transition zone 3 times, make gel film thick
Spend for 400-450nm, drying obtains fluorine doped tin oxide gel film at 150 DEG C, measure gel particle diameter for 10-15nm, gel
Film porosity is 28%.
Nano Silver is filled in porous oxidation tin gel film：The coating quality percentage on fluorine doped tin oxide porous gel film
The silver acetate ethanol solution that concentration is 1% 3 times, makes its dipping be filled into film hole, and it is 5% to be coated mass percentage concentration
Stannous chloride ethanol water 2 times, makes silver nitrate in-situ reducing fill film hole for nano silver particles, is dried at 150 DEG C
Dry, it is 17% to measure film porosity.
Nanometer silver composite tin oxide is formed：Coated glass matrix is heated to 300 DEG C, the programming rate at 300-450 DEG C
3-5 DEG C/min is reduced to, the silver salt high temperature of filling is completely decomposed into Nano Silver and is coated tin oxide, finally in 500 DEG C of high temperature
Lower sintering 30 minutes, makes organic matter decompose completely, fluoride-doped is entered in tin oxide lattice and forms fluorine doped tin oxide, and makes
Fluorine doped tin oxide crystal growth formation transparent conductive film, Nano Silver cladding SnO 2 thin film porosity 9.5%, electro-conductive glass can
It is 84.8% to see light light transmittance, and square resistance is 2.8 Ω/.
Embodiment 3
It is prepared by tin oxide nano colloidal sol:Anhydrous stannic chloride 26.1g (0.1mol) is dissolved in 500ml deionized waters,
The lower ammoniacal liquor for adding 2mol/L of stirring, until being 8-9 there is no Precipitation and pH value of solution, the precipitation hydrolyzed to form is filtered,
It is washed with deionized to without chlorion.Sediment is suspended in 200ml deionized waters, saturated oxalic acid aqueous solution 37g is added
(0.03mol), makes aqua oxidation tin be deposited at 50-60 DEG C complete peptization, doping Fluorine source is not added, only adds polyaminoester emulsion
0.5g, obtains the fluorine doped tin oxide Nano sol that tin ash mass percentage concentration is 5%, and it is 1.1 to form colloidal sol pH.
It is prepared by tin oxide gel film：Fluorine doped tin oxide colloidal sol is coated on solar cell glass transition zone 3 times, make gel
Film thickness is 500-600nm, and drying obtains fluorine doped tin oxide gel film at 150 DEG C, measures gel particle diameter for 10-
15nm, gel film porosity is 29%.
Nano Silver is filled in porous oxidation tin gel film：The coating quality percentage concentration on tin oxide porous gel film
For 5% silver nitrate ethanol solution 3 times, its dipping is filled into film hole, be coated the chlorination that mass percentage concentration is 5%
Stannous ethanol water 2 times, makes silver nitrate in-situ reducing fill film hole for nano silver particles, is dried at 150 DEG C, surveys
It is 18% to obtain film porosity.
Nanometer silver composite tin oxide is formed：Coated glass matrix is heated to 300 DEG C, the programming rate at 300-450 DEG C
3-5 DEG C/min is reduced to, the silver salt high temperature of filling is completely decomposed into Nano Silver and is coated tin oxide, finally in 500 DEG C of high temperature
Lower sintering 30 minutes, makes organic matter decompose completely, and makes tin oxide crystal growth formation transparent conductive film, Nano Silver cladding oxygen
The porosity for changing tin thin film is 9.6%, and electro-conductive glass visible light transmittance rate is 81.7%, and square resistance is 5.8 Ω/.
Reference examples 1
It is not both the ethanol water of filling silver salt in porous oxidation tin gel film, colloidal sol such as the process operation of embodiment 1
PH is 1.1, obtains tin oxide transparent conductive film, and it is 83.5% to measure visible light transmittance rate, and square resistance is 83 Ω/.
Reference examples 2
Such as the process operation of embodiment 2, it is the ethanol water that silver salt is filled in porous oxidation tin gel film not to be both, molten
Glue pH is 1.1, obtains tin oxide transparent conductive film, and it is 85.7% to measure visible light transmittance rate, and square resistance is 96 Ω/.
Reference examples 2
Such as process operation of embodiment 3, the difference is that the ethanol water of silver salt is filled in porous oxidation tin gel film, it is molten
Glue pH is 1.1, obtains tin oxide transparent conductive film, and it is 85.7%, 825 Ω of square resistance/ to measure visible light transmittance rate.
Claims (5)
1. the preparation method of a kind of nanometer of silver composite tin oxide transparent conductive film, it is characterized in that prepared in sol-gel process
Soluble silver salt and tin salt are filled in tin oxide conductive film hole, in-situ reducing generation nano silver particles, high temperature sintering is obtained
The low square resistance tin oxide transparent conductive film of high transmission rate, nanometer silver composite tin oxide transparent conductive film are combined to Nano Silver
Chemical composition be：AgxSnO2-yFy , wherein, x=0.01-0.1, y=0-0.6, the technical scheme taken are included in sun electricity
On the glass basis of pond prepared by coating silicon dioxide transition zone, fluorine doped tin oxide Nano sol, prepared by fluorine doped tin oxide gel film,
Porous oxidation tin gel film pore filling, five parts of nanometer silver composite tin oxide transparent conductive film formation.
2. the preparation method of as claimed in claim 1 nanometer of silver composite tin oxide transparent conductive film, it is characterized in that fluorine doped is aoxidized
Tin Nano sol preparation method is：
（1）Ammoniacal liquor is added into the butter of tin aqueous solution hydrolyzes pink salt, by the washing of precipitate of formation to without chlorion；
（2）Aqua oxidation tin sediment is suspended in deionized water, ammonium fluoride containing fluorine dopant or hydrofluoric acid is added, adds
The saturated oxalic acid aqueous solution, makes aqua oxidation tin be deposited at 50-60 DEG C complete peptization, generates the pH of fluorine doped tin oxide Nano sol
For 0.8-1.5, the constitutive molar ratio of fluorine doped tin oxide Nano sol is Sn (OH)4：F：H2C2O4=1：0-0.6：0.1-0.4；
（3）Polyaminoester emulsion is added into fluorine doped tin oxide Nano sol, it is 0.01%-0.2% to make its mass percentage concentration, to change
It is apt to fluorine doped tin oxide collosol stability, coating homogeneity and prevents from ftractureing when film layer from drying, two in fluorine doped tin oxide Nano sol
Tin oxide mass percentage concentration is 4%-5%.
3. the preparation method of as claimed in claim 1 nanometer of silver composite tin oxide transparent conductive film, it is characterized in that fluorine doped is aoxidized
Tin gel film preparation method is fluorine doped tin oxide colloidal sol to be coated on solar cell glass transition zone 2-3 times, makes gel film
Thickness is 400-800nm, and drying obtains fluorine doped tin oxide gel film at 150 DEG C, and fluorine doped tin oxide particle diameter is 10-15nm,
Fluorine doped tin oxide gel film porosity is 20%-30%.
4. the preparation method of as claimed in claim 1 nanometer of silver composite tin oxide transparent conductive film, it is characterized in that porous oxidation
Tin gel film pore filling method is that soluble silver salt ethanol water 2-3 is coated with fluorine doped tin oxide porous gel film
It is secondary, soluble silver salt dipping is filled into film hole, be coated the ethanol water of tin salt, make soluble silver salt in situ
Nano silver particles are reduced to, the mol ratio for controlling raw material is (Sn4++ Sn2+)：F：Ag：Sn2+=1：0-0.6：0.01-0.1：
0.01-0.1, at 150 DEG C dry, tin oxide gel film porosity be 10%-15%, the soluble silver salt be silver nitrate,
Sulfamic acid silver, silver acetate and silver salicylate, the tin salt is stannous chloride, nitric acid stannous and organic acid tin salt.
5. the preparation method of as claimed in claim 1 nanometer of silver composite tin oxide transparent conductive film, it is characterized in that Nano Silver is multiple
It is that coated glass matrix is heated into 300 DEG C to close tin oxide transparent conductive film forming method, the programming rate at 300-450 DEG C
3-5 DEG C/min is reduced to, the soluble silver salt high temperature of filling is completely decomposed into nano silver particles, finally under 500 DEG C of high temperature
Sintering 30 minutes, makes organic matter decompose completely and makes fluorine atom adulterate to form transparent conductive film, filling rear oxidation tin thin film hole
Gap rate is 5%-10%, and electro-conductive glass visible light transmittance rate is 81%-85%, and square resistance is 1-5 Ω/.
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