CN108493299A - Azo transparent conductive film and its preparation method and application - Google Patents
Azo transparent conductive film and its preparation method and application Download PDFInfo
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- CN108493299A CN108493299A CN201810319725.5A CN201810319725A CN108493299A CN 108493299 A CN108493299 A CN 108493299A CN 201810319725 A CN201810319725 A CN 201810319725A CN 108493299 A CN108493299 A CN 108493299A
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- zinc oxide
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- transparent conductive
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 372
- 239000011787 zinc oxide Substances 0.000 claims abstract description 185
- 239000010408 film Substances 0.000 claims abstract description 128
- 230000008021 deposition Effects 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 239000010409 thin film Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000012545 processing Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000001464 adherent effect Effects 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- -1 aluminum ions Chemical class 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229960001296 zinc oxide Drugs 0.000 description 138
- 239000000243 solution Substances 0.000 description 71
- 238000000151 deposition Methods 0.000 description 67
- 239000010410 layer Substances 0.000 description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 22
- 229910052725 zinc Inorganic materials 0.000 description 22
- 239000011701 zinc Substances 0.000 description 22
- 238000000137 annealing Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- SMFFOCYRDBWPIA-UHFFFAOYSA-N N.[O-2].[Zn+2] Chemical compound N.[O-2].[Zn+2] SMFFOCYRDBWPIA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 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
- 239000008187 granular material Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- 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
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The present invention provides a kind of preparation methods of AZO transparent conductive film, include the following steps：Substrate is provided, surface cleaning processing is carried out to the substrate；Zinc oxide seed solution is provided, deposits the zinc oxide seed solution over the substrate, prepares the zinc oxide seed layer for being incorporated in the substrate surface；Deposition of zinc oxide solution is provided, the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide solution, the deposition of zinc oxide solution is set to submerge the substrate, and deposition has the surface of zinc oxide seed layer not adherent in the substrate, under heating conditions, it is continually introduced into aluminium ion and stir process in the deposition of zinc oxide solution, is grown in the zinc oxide seed layer surface and prepares AZO performed thin films；Ultraviolet irradiation processing is carried out to the AZO performed thin films, AZO transparent conductive film is prepared.
Description
Technical field
The invention belongs to new energy fields more particularly to a kind of AZO transparent conductive film and its preparation method and application.
Background technology
Photovoltaic solar cell has many advantages, such as clean energy, renewable and nexhaustible, its industrialized manufacture is got in addition
Come more ripe, cost is lower and lower, it is made to be increasingly becoming one of the effective way for solving energy crisis and environmental crisis.Currently,
The research of solar cell is concentrated mainly on the transfer efficiency for improving battery and saves manufacturing cost, and raising battery has
It imitates in usage time.There are two the main paths for improving photovoltaic solar cell efficiency：First, to make the solar spectrum of each wave band
Energy is fully utilized；Second is that improve the collection efficiency of photo-generated carrier.Wherein, transparent conductive film is solar-electricity
One of critical material in pond.By increasing the transmitance of transparent conductive film, more sunlights can be made to reach battery
Absorbed layer, and then generate more photo-generated carriers；By reducing the resistivity of transparent conductive film, can make more
Photo-generated carrier effectively improves energy conversion efficiency by film；By optimizing structure of transparent conductive film, can improve
The chemistry and mechanical stability of solar cell.Therefore, the development of transparent conductive film material must, transmission lower towards cost
Rate higher, resistivity are lower, the better direction of chemical stability carries out.
Currently, commercial transparent conductive film is based on indium doping tin oxide (ITO), but due to its production cost compared with
Reason high, raw material is limited and toxic, therefore be badly in need of developing novel transparent conductive film alternative materials.Aluminium mixes zinc oxide
(AZO) film raw material derive from a wealth of sources, be nontoxic, good photoelectric properties, the ideal for being increasingly becoming transparent conductive film material replaces
Dai Zhe.The excellent AZO transparent conductive film of photoelectric properties can all be prepared using vacuum method and solwution method at present, and successfully realized
Its extensive use.But the area of the AZO films of vacuum method preparation will be limited by vacuum-chamber dimensions, and complexity is true
Null device significantly increases film production cost.And the AZO films prepared by solwution method, it need to be in 600 DEG C or more of high temperature
Long term annealing then carries out after annealing processing under 550 DEG C of hydrogen atmosphere, can just obtain resistivity 1.7 × 10-3~
7.2×10-3AZO films between Ω cm.For thin-film solar cells, such as copper indium gallium selenide (CIGS) or copper zinc-tin
Sulphur (CZTS) thin-film solar cells, AZO transparent conductive film will be deposited on the top of battery, and excessively high annealing temperature can cause
Excessive cadmium or zinc are diffused into the absorbed layer of battery (the excessive elements diffusion in pn-junction interface, to destroy pn-junction), cause
Battery obsorbing layer forms number of drawbacks, increases Carrier recombination chance, deteriorates battery performance, to reduce cell photoelectric conversion effect
Rate.Therefore, the annealing temperature of Window layer, a kind of antivacuum, low temperature of development, low cost, and transparent lead that can be mass-produced are reduced
The method of electrolemma becomes current development trend.
Invention content
The purpose of the present invention is to provide a kind of AZO transparent conductive films and preparation method thereof, it is intended to it is thin to solve existing AZO
The preparation method of film is of high cost, and because annealing temperature height causes the metallic atom in the film deposited to spread, influences device
The problem of part especially thin-film solar cells performance (especially electricity conversion).
Another object of the present invention is to provide a kind of thin-film solar cells containing AZO transparent conductive film.
For achieving the above object, the technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of preparation method of AZO transparent conductive film, includes the following steps：
Substrate is provided, surface cleaning processing is carried out to the substrate；
Zinc oxide seed solution is provided, deposits the zinc oxide seed solution over the substrate, preparation is incorporated in described
The zinc oxide seed layer of substrate surface；
Deposition of zinc oxide solution is provided, the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide solution
In, so that the deposition of zinc oxide solution is submerged the substrate, and deposition has the surface of zinc oxide seed layer not paste in the substrate
Wall is continually introduced into aluminium ion and stir process, in the zinc oxide in the deposition of zinc oxide solution under heating conditions
The growth of seed layer surface prepares AZO performed thin films；
Ultraviolet irradiation processing is carried out to the AZO performed thin films, AZO transparent conductive film is prepared.
Another aspect of the present invention provides a kind of AZO transparent conductive film, including zinc oxide seed layer, and is incorporated in described
The array-like AZO films of zinc oxide seed layer surface.
Further aspect of the present invention provides a kind of thin-film solar cells, including above-mentioned AZO transparent conductive film, or as above
State the AZO transparent conductive film of method preparation.
The preparation method of AZO transparent conductive film provided by the invention first prepares oxidation on substrate using aqua-solution method
Zinc seed layer, the zinc oxide that then deposition of aluminum is adulterated in the zinc oxide seed layer, is handled finally by ultraviolet irradiation, is prepared
Obtain AZO transparent conductive film.
First, this method whole process uses aqueous process deposition film, does not need the high temperature anneal, therefore, can keep away
Exempt from the metallic atom diffusion in the functional layer deposited in high-temperature annealing process, the influence to other functional layers.Particularly, when
It, can be to avoid the cadmium in the functional layer in high-temperature annealing process when the AZO transparent conductive film is used for thin-film solar cells
Or zinc is diffused into the absorbed layer of thin-film solar cells, to improve cell photoelectric transformation efficiency.It leads the described AZO is transparent
Conducting window layer of the conductive film as copper-zinc-tin-sulfur (CZTS) thin-film solar cells, cell photoelectric transformation efficiency can reach
5.47%.
Secondly, AZO transparent conductive film provided by the invention, by being carried out at ultraviolet irradiation to the AZO performed thin films
Reason, can remove carbon impurity extra in film, improve the carrier concentration and electric conductivity of film, and it is excellent to obtain electric conductivity
AZO transparent conductive film.
Again, in the present invention, the mild condition of AZO transparent conductive film is prepared, the equipment that complex and expensive need not be used,
Advantageously reduce the production cost of AZO transparent conductive film.
AZO transparent conductive film electric conductivity provided by the invention is excellent, and manufacturing cost is cheap, is transparent conductive thin
The ideal replacer of film can be widely used for CIGS and CZTS thin-film solar cells, and with preferable cell photoelectric conversion effect
Rate.
Thin-film solar cells provided by the invention can not only be reduced into due to containing above-mentioned AZO transparent conductive film
This, and cell photoelectric transformation efficiency can be improved.
Zinc oxide seed layer aqueous solution was prepared before this, in glass surface depositing homogeneous depositing zinc oxide seed layer, was then made
The aqueous solution of standby aluminium-doped zinc oxide growth, in the aluminium-doped zinc oxide nanometer battle array of seed layer surface deposition compact Cylindrical Homogeneous
Row then use UV lamp to radiate, you can to obtain the excellent preparing aluminum-doped zinc oxide transparent conducting films of photoelectric properties.
Description of the drawings
Fig. 1 is the preparation technology flow chart of AZO transparent conductive film provided in an embodiment of the present invention；
Fig. 2 is the plan view for the AZO transparent conductive film that the embodiment of the present invention 1 provides；
Fig. 3 is the sectional view for the AZO transparent conductive film that the embodiment of the present invention 1 provides；
Fig. 4 is the translucency detection result figure for the AZO transparent conductive film that the embodiment of the present invention 1 provides；
Fig. 5 is the CZTA film solar battery structure schematic diagrames that the embodiment of the present invention 2 provides；
Fig. 6 is the sectional view for the CZTA film solar battery structures that the embodiment of the present invention 2 provides；
Fig. 7 is the i-v curve figure for the CZTA film solar battery structures that the embodiment of the present invention 2 provides.
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indicating or implies relative importance or implicitly indicate the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more this feature.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In conjunction with Fig. 1, an embodiment of the present invention provides a kind of preparation methods of AZO transparent conductive film, include the following steps：
S01., substrate is provided, surface cleaning processing is carried out to the substrate；
S02., zinc oxide seed solution is provided, deposits the zinc oxide seed solution over the substrate, preparation is incorporated in
The zinc oxide seed layer of the substrate surface；
S03., deposition of zinc oxide solution is provided, it is molten that the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide
In liquid, the deposition of zinc oxide solution is set to submerge the substrate, and deposition has the surface of zinc oxide seed layer not in the substrate
It is adherent, under heating conditions, aluminium ion and stir process are continually introduced into the deposition of zinc oxide solution, in the oxidation
The growth of zinc seed layer surface prepares AZO performed thin films；
S04. ultraviolet irradiation processing is carried out to the AZO performed thin films, AZO transparent conductive film is prepared.
The preparation method of AZO transparent conductive film provided in an embodiment of the present invention is first made on substrate using aqua-solution method
Standby zinc oxide seed layer, the zinc oxide that then deposition of aluminum is adulterated in the zinc oxide seed layer, at ultraviolet irradiation
Reason, is prepared AZO transparent conductive film.
First, this method whole process uses aqueous process deposition film, does not need the high temperature anneal, therefore, can keep away
Exempt from the metallic atom diffusion in the functional layer deposited in high-temperature annealing process, the influence to other functional layers.Particularly, when
It, can be to avoid the cadmium in the functional layer in high-temperature annealing process when the AZO transparent conductive film is used for thin-film solar cells
Or zinc is diffused into the absorbed layer of thin-film solar cells, to improve cell photoelectric transformation efficiency.It leads the described AZO is transparent
Conducting window layer of the conductive film as copper-zinc-tin-sulfur (CZTS) thin-film solar cells, cell photoelectric transformation efficiency can reach
5.47%.
Secondly, AZO transparent conductive film provided in an embodiment of the present invention, it is ultraviolet by being carried out to the AZO performed thin films
Treatment with irradiation can remove carbon impurity extra in film, improve the carrier concentration and electric conductivity of film, obtain electric conductivity
Excellent AZO transparent conductive film.
Again, in the embodiment of the present invention, the mild condition of AZO transparent conductive film is prepared, complex and expensive need not be used
Equipment, advantageously reduce the production cost of AZO transparent conductive film.
Specifically, in above-mentioned steps S01, it is used as the substrate of AZO transparent conductive film, without considered critical, this can be selected
The common substrate in field, such as ultra-clear glasses.It is molten in depositing zinc oxide seed in order to improve the adhesive force of material over the substrate
Before liquid, need to carry out surface cleaning processing to the substrate.
The method of the surface cleaning processing is as follows as a preferred implementation manner,：
After tentatively cleaning substrate surface spot with cleanser, the glass cleaner (alkali that preferably volumetric concentration is 5% is used
Property water-detergent solution, alkaline detergent and deionized water are 5 by volume:95 prepare) it is cleaned, remove glass surface hardly possible
With the greasy dirt of removal.
Then, it after the substrate being rinsed in clean deionized water, is put into acetone, removes the organic of glass surface
Impurity, then it is cleaned by ultrasonic 10min in isopropanol.
Then, the substrate is put into low concentration glass cleaner and is cleaned, remove the substrate surface granule foreign, then
It is secondary to be rinsed using deionized water, it is finally putting into absolute ethyl alcohol for use after being cleaned by ultrasonic 10min.
Carrying out surface cleaning using the above method, treated that the substrate surface is clean as new, and it is water-soluble to be conducive to zinc oxide
The deposition of liquid.
In the embodiment of the present invention, large stretch of substrate can be cut according to the specification of the AZO transparent conductive film of formation
It cuts, to obtain the substrate dimension met the requirements, such as 25mm × 25mm.It should be understood that can first be cut to large stretch of substrate
Cutting is cut, surface cleaning processing is then carried out；It can also be first to row cutting is cut again after the progress surface cleaning processing of large stretch of substrate.
Preferably, in order to avoid introducing impurity or dirt in cutting cutting process, the side of cutting is cut after preferably first surface cleaning processing
Formula.
In above-mentioned steps S02, since the binding force of Al-Doped ZnO and the substrate especially glass substrate surface is not strong,
It in conjunction with insecure, or even is difficult in the substrate surface forming core, therefore, before depositing Al-Doped ZnO, first in the substrate
One layer of zinc oxide seed layer of upper deposition is used for the formation and growth of follow-up yield zinc oxide nano array.Specifically, utilizing oxidation
Zinc seed solution forms transition zone i.e. zinc oxide seed layer in the substrate surface forming core, deposition.Further, with the oxidation
Zinc seed layer deposits Al-Doped ZnO over the substrate as medium.
In the embodiment of the present invention, the zinc oxide seed solution is the zinc oxide aqueous solution added with excessive ammonia, is passed through
The ammonium hydroxide of excessive addition is conducive to the solubility for improving zinc oxide.As a specific embodiment, the zinc oxide seed solution
Preparation method be：Zinc oxide powder is scattered in deionized water, ammonium hydroxide is then added and is sufficiently stirred, promotes oxidisability powder
Dissolving.Further, dissolved solution is filtered processing, removes excessive zinc oxide impurities, clear solution is retained.
Specifically, filtration treatment is filtered using a diameter of 0.45 μm of filter.
Specifically, the zinc oxide seed solution is deposited over the substrate, with ammonia in the zinc oxide seed solution
The solubility property of the volatilization of water, zinc oxide reduces, and then is attached to the substrate surface and forms film layer.Preferably, the oxidation
A concentration of 20-50mmol/L of zinc oxide in zinc seed solution, to form the zinc oxide seed layer of dense uniform.If the oxygen
Oxidation zinc concentration is too low in change zinc seed solution, then the film layer formed is not fine and close.If being aoxidized in the zinc oxide seed solution
Zinc concentration is excessively high, then the Zinc oxide particles deposited over the substrate are uneven, and obtained superficial film is in uneven thickness, shadow
The caliper uniformity of the yield zinc-oxide film of subsequent deposition is rung, the stability of film performance is further influenced.In addition, the oxygen
Change the excessive concentration of zinc oxide in zinc seed solution, the thickness for the zinc oxide seed layer that will also result in is blocked up, and it is saturating to influence AZO
The performance of bright conductive film.It is further preferred that in the zinc oxide seed solution zinc oxide a concentration of 30-40mmol/L.
The zinc oxide seed solution is deposited over the substrate, prepares the zinc oxide seed for being incorporated in the substrate surface
The method of layer, it is preferred to use spin-coating method.As a specific embodiment, the method that zinc oxide seed layer is prepared using spin-coating method
For：
The substrate cleaned up is taken out, puts it under stream of nitrogen gas after drying up and is placed on the sample stage of sol evenning machine.Setting
The prerotation revolution of good sol evenning machine and prerotation time, rotation revolution and rotational time draw zinc oxide ammonia spirit and by its drop coating
It is on the to described, it is ensured that sample surfaces are completely covered in zinc oxide seed layer solution, then open vacuum pump and sol evenning machine is true
Sky control switch, spin coating is carried out by start button.Substrate after spin coating is placed on thermostatic platform, heated at constant temperature exists after a certain period of time
It is cooling in air, that is, form zinc oxide seed layer.
In above-mentioned steps S03, the embodiment of the present invention prepares AZO transparent conductive film by solwution method.Specifically, first providing
Deposition of zinc oxide solution for deposition.Contain zinc oxide, ammonium hydroxide and deionized water in the deposition of zinc oxide solution, wherein
The ammonium hydroxide is used to improve the solubility of the zinc oxide, meanwhile, it is real by the volatilization of ammonium hydroxide when preparing AZO performed thin films
The deposition of existing zinc oxide.Preferably, the additive amount of the ammonium hydroxide meets：It is 9-12 to make the pH value of the deposition of zinc oxide solution.
Within the scope of the pH, the solubility property of zinc oxide in deionized water can be improved, is conducive to the deposition rate for controlling zinc oxide,
And improve the compactness of obtained film layer.Meanwhile the present invention reduces the solubility of zinc oxide by the volatilization of ammonium hydroxide, and then mix
The growth of zinc oxide after aluminium in zinc oxide seed layer surface.
It is further preferred that also containing ammonium citrate, ammonium nitrate in the deposition of zinc oxide solution.The ammonium citrate,
Ammonium nitrate can control crystal structure and pattern of the zinc oxide for mixing aluminium when zinc oxide seed layer surface is grown, to obtain battle array
The AZO transparent conductive film of array structure, specifically, array structure is column structure.It is saturating compared to the AZO for not having array structure
Bright conductive film, in charge such as electronic transmission process, electronics directly passes the AZO transparent conductive film of array structure along array
It is defeated, it is possible to reduce the inhibition of crystal boundary, to improve photoelectricity effect.
Further, in the deposition of zinc oxide solution, the concentration of each component is preferably：
20~60mmol/L of zinc oxide；
0.01~4mmol/L of ammonium citrate；
0.01~2mmol/L of ammonium nitrate concn.
The concentration of suitable above-mentioned substance, can Al-Doped ZnO nano-array, and Al-Doped ZnO nano-array is uniform
It is fine and close.If specifically, the excessive concentration of the zinc oxide, the speed of growth of zinc oxide is fast, and the doping speed of aluminium does not catch up with oxidation
The speed of growth of zinc causes aluminium doping content in finally obtained AZO transparent conductive film to be unsatisfactory for requiring.In addition, zinc oxide
Excessive concentration, the Zinc oxide particles formed in deposition process are coarse, hole formed between Zinc oxide particles, reduction finally obtains
AZO transparent conductive film performance.If the oxidation zinc concentration is too low, the speed of growth of zinc oxide is slow.And the lemon
Whether formation of the content about Al-Doped ZnO nano-array of sour ammonium, ammonium nitrate, i.e. AZO transparent conductive film have array
Structure.The ammonium citrate, ammonium nitrate as a kind of additive, in aqueous solution with citrate ion, nitrate ion and
The form of ammonium ion occurs, and since electrostatic attraction acts on, what citrate ion, nitrate ion can be strong is adsorbed in oxidation
The crystal face of zinc, to occupy the growth position of most of zinc and oxygen so that growth of the zinc oxide nano rod along c-axis direction is pressed down
System, and the growth of nanometer rods transverse direction is affected smaller, therefore the trend of the oriented cross growth of nanometer rods, draw ratio reduction is received
It can be in contact with each other to form dense film between rice stick.And simultaneously, the ammonium ion of introducing is due to inherently existing in the solution,
Therefore solution chemistry will not be had an impact.If the excessive concentration of the lemon acid ammonium and the ammonium nitrate, zinc-oxide nano
The growth limitation of stick longitudinal direction is serious, and rodlike zinc oxide president slabbing is thus unfavorable for the raising of carrier mobility, causes
The reduction of Electrical performance.
As a specific embodiment, the preparation method of the deposition of zinc oxide solution is：Clean container such as beaker is taken,
A certain amount of deionized water is weighed, required ammonium citrate, ammonium nitrate, Zinc oxide powder and ammonium hydroxide is added into the beaker respectively
Reagent.It stirs at room temperature for 24 hours, then excessive zinc oxide impurities in solution is filtered to remove using a diameter of 0.45 μm of filter,
Stay clear solution for use.
In the embodiment of the present invention, the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide solution, is made
The deposition of zinc oxide solution submerges the substrate, and deposition has the surface of zinc oxide seed layer not adherent in the substrate, with
Just Al-Doped ZnO is grown in the zinc oxide seed layer surface.Preferably, it is heavy to be placed on the zinc oxide vertically for the substrate
In product solution.When the substrate is placed on the deposition of zinc oxide solution vertically, it can prevent impurity from falling into institute in infall process
Zinc oxide seed layer surface is stated, and is conducive to save space, while realizing the deposition of multiple substrates.It is further preferred that by more
Part substrate is placed in the deposition of zinc oxide solution simultaneously, prepares AZO transparent conductive film.The substrate is placed on vertically
The deposition of zinc oxide solution, can realize by mold, the no specific requirement of selection of mold.
During the embodiment of the present invention prepares AZO transparent conductive film using aqua-solution method, oxidation is realized by heating
The deposition of zinc (volatilization ammonium hydroxide makes the zinc oxide in solution supersaturation occur)；Meanwhile it being continually introduced into deposition of zinc oxide solution
Aluminium ion is realized with the zinc oxide of deposition and is adulterated.It is specific preferred, connected into the deposition of zinc oxide solution using peristaltic pump
The continuous mode that nine water aluminum nitrates are added or immerse aluminium flake, is continually introduced into aluminium ion, to real in the deposition of zinc oxide solution
Existing Uniform Doped.As a particular preferred embodiment, nine are continuously added in the deposition of zinc oxide solution using peristaltic pump
Water aluminum nitrate is introduced into aluminum ions step, and aluminum ions introducing condition meets：The rotating speed of the peristaltic pump is >=0.1rpm, institute
It is 10~300mmol/L to state nine water aluminum nitrate concentrations in deposition of zinc oxide solution.As another particular preferred embodiment, adopt
Aluminium flake is continuously immersed with peristaltic pump in the deposition of zinc oxide solution to be introduced into aluminum ions step, aluminum ions introducing condition
Meet：The rotating speed of the peristaltic pump is >=0.1rpm, and the immersion area of the aluminium flake is 1~10cm2.Zinc oxide columnar grain is given birth to
In growth process, the cylindrical face of zinc oxide carries positive electricity, and top surface carries negative electricity, therefore can make not under the action of Electrostatic Absorption
Same surface is different to the attraction power of effects of ion.And aluminium ion can be with [Al (OH) in alkaline solution4]-Form exists,
Therefore most of crystal face that will be adsorbed in zinc oxide column crystal, will result in cylindrical face and can receive the position of zinc and largely subtract in this way
It is few, to inhibit the growth of column crystal transverse direction, the reduction of crystallite dimension, draw ratio is caused to increase.Therefore, if the nine water nitric acid
Aluminum concentration it is excessively high or immerse aluminium flake area it is excessive, zinc oxide columnar grain growth is restricted, then film cannot be in substrate
Upper growth；If the nine water aluminum nitrate concentration it is too low or immerse aluminium flake area it is too small, in zinc oxide aluminium doping concentration decline, oxygen
Change zinc Thin film conductive performance to decline.
In the embodiment of the present invention, the purpose of the heating is to volatilize the ammonium hydroxide in the deposition of zinc oxide solution, and adds
The temperature of heat prepares AZO performed thin films to the embodiment of the present invention and is affected.Preferably, contain in the deposition of zinc oxide solution
There are zinc oxide, ammonium hydroxide and deionized water, the pH value of the deposition of zinc oxide solution is 9-12, and the temperature of the heating is 60-90
℃.Again in temperature range, ammonium hydroxide can ensure suitable rate of volatilization, preferable to advantageously form crystal structure pattern
AZO performed thin films.If the temperature of the heating is too low, evaporation rate is slow；If the temperature of the heating is excessively high, ammonium hydroxide volatilization
Too fast, the speed of growth of zinc oxide is fast, and the doping speed of aluminium does not catch up with the speed of growth of zinc oxide, leads to finally obtained AZO
Aluminium doping content is unsatisfactory for requiring in transparent conductive film.In addition, deposition formed Zinc oxide particles it is coarse, Zinc oxide particles it
Between form hole, reduce the performance of finally obtained AZO transparent conductive film.
The deposition of zinc oxide solution is added in heating container as a preferred implementation manner, aerobicization will be deposited
The substrate of zinc seed layer is placed in the deposition of zinc oxide solution, and the deposition of zinc oxide solution is made to submerge the substrate, and institute
Stating deposition in substrate has the surface of zinc oxide seed layer not adherent；The heating container is placed in water-bath, in the item of heating
Under part, it is continually introduced into aluminium ion and stir process in the deposition of zinc oxide solution, is given birth in the zinc oxide seed layer surface
It is long to prepare AZO performed thin films.By deposition of zinc oxide solution described in heating water bath, can preferably controlling reaction temperature, make to sink
Product at the uniform velocity occurs.
The sample for having grown AZO performed thin films is taken out from aqueous solution, after being rinsed with a large amount of deionized water, is then existed
It is dried up under nitrogen stream.
In above-mentioned steps S04, ultraviolet irradiation processing is carried out to the AZO performed thin films, then, using UV irradiation lights to sample
Product surface is irradiated 5~10min of processing, completes the preparation of AZO film samples.Carbon impurity extra in film is removed, is improved
The carrier concentration and electric conductivity of film.Preferably, the condition of the ultraviolet irradiation processing is：UV lamp radiates effective area
100cm2, 1~20min of radiated time.
The embodiment of the present invention provides a kind of AZO transparent conductive film, including zinc oxide seed layer, and is incorporated in the oxygen
Change the array-like AZO films of zinc seed layer surface.
AZO transparent conductive film electric conductivity provided in an embodiment of the present invention is excellent, and manufacturing cost is cheap, is transparent
The ideal replacer of conductive film can be widely used for CIGS and CZTS thin-film solar cells, and have preferable cell photoelectric
Transformation efficiency.AZO transparent conductive film provided in an embodiment of the present invention can be prepared by the above method.
Compared to the AZO transparent conductive film for not having array structure, the AZO transparent conductive film of array structure is in charge
In electronic transmission process, electronics is directly transmitted along array, it is possible to reduce the inhibition of crystal boundary is beneficial to the receipts of carrier
Collection, to improve the electricity conversion of solar cell.Preferably, the array of the array-like AZO films is columnar nanometer battle array
Row.
Further aspect of the present invention provides a kind of thin-film solar cells, including above-mentioned AZO transparent conductive film, or as above
State the AZO transparent conductive film of method preparation.
Thin-film solar cells provided in an embodiment of the present invention not only can be with due to containing above-mentioned AZO transparent conductive film
Cost is reduced, and cell photoelectric transformation efficiency can be improved.
The thin-film solar cells can be copper indium gallium selenide (CIGS) or copper-zinc-tin-sulfur (CZTS) thin-film solar cells.
As a particular preferred embodiment, the thin-film solar cells is CZTA thin-film solar cells, including glass substrate, with
And Mo layer, CATS light absorbing layers, cadmium sulfide buffer layer, the AZO electrically conducting transparents being successively set in the glass substrate are thin
Film and silver electrode.The CZTA thin-film solar cells may be used following methods and prepare：
Cleaning deposition has the soda-lime glass of metal Mo, cleaning method to can refer to the side of the surface cleaning processing of the substrate
Method then continuously prepares CZTS light absorbing layers, using chemical bath deposition sulphur using sol-gel technique and high tempering two-step method
Cadmium buffer layer, 200 DEG C of temper 10min are then continued using the preparation method of the AZO transparent conductive film in sample
Surface prepares AZO transparent conductive film, and top electrode (link electrode) is prepared using conductive silver glue, completes CZTS thin film solar electricity
It is prepared by pond.
It is illustrated with reference to specific embodiment.
Embodiment 1
A kind of preparation method of AZO transparent conductive film, includes the following steps：
S11., substrate is provided, surface cleaning processing is carried out to the substrate；
S12. zinc oxide seed solution is provided, over the substrate zinc oxide seed solution described in spin-on deposition, prepares knot
Close the zinc oxide seed layer in the substrate surface, wherein the solution composition of the zinc oxide seed solution is：Zinc-oxide nano
Particle, high purity water, excessive ammonium hydroxide, wherein a concentration of 20~50mmol/L of zinc oxide；
S13., deposition of zinc oxide solution is provided, it is molten that the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide
In liquid, the deposition of zinc oxide solution is set to submerge the substrate, and deposition has the surface of zinc oxide seed layer not in the substrate
It is adherent, under conditions of 60 DEG C -90 DEG C, aluminium ion and stir process, deposition are continually introduced into the deposition of zinc oxide solution
40~80min grows in the zinc oxide seed layer surface and prepares AZO performed thin films, wherein the deposition of zinc oxide solution
PH is 9~12, and solution composition is：Aoxidize 20~60mmol/L of zinc concentration, 0~4mmol/L of ammonium citrate concentration, ammonium nitrate concn
0~2mmol/L, excessive ammonia；
S14. ultraviolet irradiation processing is carried out to the AZO performed thin films, treatment conditions are：UV lamp radiates effective area
100cm2, AZO transparent conductive film is prepared in 1~20min of radiated time.
The plan view and sectional view of AZO transparent conductive film prepared by the embodiment of the present invention 1 are as shown in Figure 2,3, this is sent out
AZO transparent conductive film prepared by bright embodiment 1 carries out translucency detection, and the results are shown in Figure 4, the big 85%-95% of light transmittance.
Embodiment 2
A kind of preparation method of CZTA thin-film solar cells, includes the following steps：
Cleaning deposition has the soda-lime glass of metal Mo, then continuously using sol-gel technique and high tempering two-step method system
Standby CZTS light absorbing layers, using chemical bath deposition cadmium sulfide buffer layer, 200 DEG C of temper 10min, then according to embodiment 1
Method prepare AZO transparent conductive film in sample surfaces, prepare top electrode (link electrode) using conductive silver glue, complete CZTS
It is prepared by thin-film solar cells.
CZTA film solar battery structures prepared by embodiment 2 are as shown in figure 5, CZTA film solar battery structures
Sectional view is as shown in Figure 6.
To embodiment 2 prepare CZTA thin-film solar cells and high annealing prepare AZO films (use 600 DEG C with
On high temperature long term annealing, then under 550 DEG C of hydrogen atmosphere carry out after annealing processing, obtain resistivity 1.7 × 10-3
~7.2 × 10-3AZO films between Ω cm, other layer methods are identical) obtained CZTS thin-film solar cells carries out photoelectricity
Performance test, the i-v curve figure tested are as shown in Figure 7.Because AZO films prepared by high annealing deposit to
CZTS thin-film solar cells surface leads to the excessive elements diffusion in pn-junction interface, to destroy pn-junction, therefore cells convert
Efficiency degradation.Compared to the CZTS thin-film solar cells that AZO films prepared by high annealing obtain, prepared by embodiment 2
CZTA thin-film solar cell photoelectric transformation efficiencies significantly improve.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of AZO transparent conductive film, which is characterized in that include the following steps：
Substrate is provided, surface cleaning processing is carried out to the substrate；
Zinc oxide seed solution is provided, deposits the zinc oxide seed solution over the substrate, preparation is incorporated in the substrate
The zinc oxide seed layer on surface；
Deposition of zinc oxide solution is provided, the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide solution, is made
The deposition of zinc oxide solution submerges the substrate, and deposition has the surface of zinc oxide seed layer not adherent in the substrate,
Under conditions of heating, aluminium ion and stir process are continually introduced into the deposition of zinc oxide solution, in the zinc oxide seed
Layer surface growth prepares AZO performed thin films；
Ultraviolet irradiation processing is carried out to the AZO performed thin films, AZO transparent conductive film is prepared.
2. the preparation method of AZO transparent conductive film as described in claim 1, which is characterized in that the deposition of zinc oxide is molten
Contain zinc oxide, ammonium hydroxide and deionized water in liquid, the pH value of the deposition of zinc oxide solution is 9-12, and the temperature of the heating
It is 60-90 DEG C.
3. the preparation method of AZO transparent conductive film as claimed in claim 2, which is characterized in that the deposition of zinc oxide is molten
Also contain ammonium citrate, ammonium nitrate in liquid.
4. the preparation method of AZO transparent conductive film as claimed in claim 3, which is characterized in that the deposition of zinc oxide is molten
In liquid, each component it is a concentration of：
20~60mmol/L of zinc oxide；
0.01~4mmol/L of ammonium citrate；
0.01~2mmol/L of ammonium nitrate concn.
5. the preparation method of AZO transparent conductive film according to any one of claims 1-4, which is characterized in that using wriggling
The mode for being continuously added to nine water aluminum nitrates into the deposition of zinc oxide solution or immersing aluminium flake is pumped, it is molten in the deposition of zinc oxide
Aluminium ion is continually introduced into liquid.
6. the preparation method of AZO transparent conductive film as claimed in claim 5, which is characterized in that using peristaltic pump described
It is continuously added to nine water aluminum nitrates in deposition of zinc oxide solution to be introduced into aluminum ions step, aluminum ions introducing condition meets：Institute
The rotating speed for stating peristaltic pump is >=0.1rpm, and nine water aluminum nitrate concentrations in the deposition of zinc oxide solution are 10~300mmol/L；
Or
Aluminium flake is continuously immersed using peristaltic pump in the deposition of zinc oxide solution to be introduced into aluminum ions step, it is aluminum ions to draw
Enter condition satisfaction：The rotating speed of the peristaltic pump is >=0.1rpm, and the immersion area of the aluminium flake is 1~10cm2。
7. the preparation method of AZO transparent conductive film according to any one of claims 1-4, which is characterized in that hold in heating
The deposition of zinc oxide solution is added in device, the substrate for having deposited zinc oxide seed layer is placed in the deposition of zinc oxide solution
In, so that the deposition of zinc oxide solution is submerged the substrate, and deposition has the surface of zinc oxide seed layer not paste in the substrate
Wall；The heating container is placed in water-bath, under heating conditions, aluminium is continually introduced into the deposition of zinc oxide solution
Ion and stir process grow in the zinc oxide seed layer surface and prepare AZO performed thin films.
8. a kind of AZO transparent conductive film, which is characterized in that including zinc oxide seed layer, and be incorporated in the zinc oxide kind
The array-like AZO films of sub-layer surface.
9. AZO transparent conductive film as claimed in claim 8, which is characterized in that the array of the array-like AZO films is column
Shape nano-array.
10. a kind of thin-film solar cells, which is characterized in that including such as claim 8-9 any one of them AZO electrically conducting transparents
Film, or the AZO transparent conductive film such as any the method preparations of claim 1-7.
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Application publication date: 20180904 |
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