CN105914262A - Film solar cell buffer layer postprocessing technology - Google Patents
Film solar cell buffer layer postprocessing technology Download PDFInfo
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- CN105914262A CN105914262A CN201610390568.8A CN201610390568A CN105914262A CN 105914262 A CN105914262 A CN 105914262A CN 201610390568 A CN201610390568 A CN 201610390568A CN 105914262 A CN105914262 A CN 105914262A
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- cushion
- film solar
- thin
- solar cells
- aftertreatment technology
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- 238000005516 engineering process Methods 0.000 title claims abstract description 54
- 238000012805 post-processing Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 11
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 9
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000007654 immersion Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000005083 Zinc sulfide Substances 0.000 claims description 8
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 8
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 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 3
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 claims description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical group [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical group [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000000224 chemical solution deposition Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000012545 processing Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 105
- 238000000151 deposition Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 16
- 239000000758 substrate Substances 0.000 description 14
- 210000001142 back Anatomy 0.000 description 12
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 12
- 238000005457 optimization Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 238000001755 magnetron sputter deposition Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229940075417 cadmium iodide Drugs 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 4
- 229910000058 selane Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MRPMBDLQLPRQNM-UHFFFAOYSA-N [Cd].[I] Chemical compound [Cd].[I] MRPMBDLQLPRQNM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229960001939 zinc chloride Drugs 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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 invention provides a film solar cell buffer layer postprocessing technology. The technology comprises the following steps of providing a film solar cell whose surface is provided with an absorbed layer; configuring a reaction liquid; using a chemical bath deposition method to deposit the reaction liquid on an absorbed layer surface so as to form a buffer layer; and then placing the buffer layer in a water solution so as to carry out soaking processing; and finally taking out and using nitrogen to carry out drying. By using the buffer layer postprocessing technology, buffer layer surface flatness can be improved; buffer layer surface floccules can be reduced; a contact area with an upper layer window layer and lattice matching are increased; recombination of a carrier in a buffer layer/a window layer interface is reduced; a short-circuit current density of the film solar cell can increase 1.0-2.0mA/cm<2>; and a cell conversion efficiency absolute value can increase 1-3%. Because ammonia water, isopropanol, ammonium acetate and the like which are used for soaking treatment are conventional reagents and can be recycled, technological cost is low, equipment is simple and reliable and operation is safe, and the technology is suitable for industrial production.
Description
Technical field
The invention belongs to photovoltaic material technical field of new energies, be specifically related to a kind of thin-film solar cells cushion aftertreatment technology.
Background technology
CIGS (Cu (In, Ga) Se2: CIGS) thin-film solar cells is that laboratory conversion efficiency is the highest, the most promising
One of thin-film solar cells.It is adjustable that it has photonic band gap, is suitable for adjusting and optimizing energy gap；Have the highest
The absorption coefficient of light, the solaode of preparation only has a few micrometers, the weight reducing raw-material consumption with alleviating battery；Electricity
Pond is long for service life, and without Staebler-Wronski effect, under low light condition, performance is still good, also has the best in space is applied
Many advantages such as good anti-interference, capability of resistance to radiation.2014, Germany's solar energy was thin by CIGS with Hydrogen Energy research center
Film solar cell laboratory conversion efficiency brings up to 21.7%, surmounts the conversion efficiency of polysilicon 20.4%；Industrialization aspect,
Assembly conversion efficiency was brought up to 15.9% in 2015 by Manz group of Germany, and it is raw that power reaches 104.8W, Manz CIGSfab
Produce line production cost and have already decreased to every watt less than 2.5 yuan, it is shown that CIGS thin film solaode has vast potential for future development.
In CIGS thin film solaode, cushion is in the key position between absorbed layer and Window layer, can solve to inhale
Receive layer to mate with the lattice energy band of window interlayer with cushion, cushion, increase the width in running down of battery district, reduce tunnel-effect,
Improve contact berrier, cover CIGS absorbed layer surface, reduce interfacial state, protect absorbed layer surface, it is to avoid in sputtering Window layer
Time damage CIGS absorbed layer, the conversion efficiency of solar cell device is had very important impact.Cadmium sulfide, zinc sulfide,
The II-VI group compound-materials such as cadmium telluride are widely used as the cushion of thin-film solar cells.Laboratory obtains peak efficiency at present
CIGS thin film solaode cushioning layer material is cadmium sulfide prepared by chemical bath method.But cadmium sulfide prepared by chemical bath method,
Zinc sulfide buffer-layer surface floccule is more, surface irregularity, causes the lattice match between Window layer relatively low, and restriction is too
The photoelectric transformation efficiency of sun energy battery.
Summary of the invention
The shortcoming of prior art in view of the above, locates after it is an object of the invention to provide a kind of thin-film solar cells cushion
Science and engineering skill, more for solving the thin-film solar cells buffer-layer surface floccule of preparation in prior art, surface irregularity,
Cause the problem that the lattice match between Window layer is relatively low.
For achieving the above object and other relevant purposes, the present invention provides a kind of thin-film solar cells cushion aftertreatment technology,
Described aftertreatment technology at least includes:
There is provided surface to be formed with the thin-film solar cells of absorbed layer, configure reaction solution, use chemical bath method by described reaction
Solution deposition forms cushion in described absorbed layer surface, is placed in aqueous solution by described cushion afterwards and carries out immersion treatment,
Rear taking-up, dries up with nitrogen.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, described absorbed layer is copper and indium gallium
Selenium, CIS, Cu-In-Ga-Se-S, copper-zinc-tin-sulfur, copper-zinc-tin-selenium or copper zinc tin sulfur selenium.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, the described cushion of formation is
Cadmium sulfide or zinc sulfide.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, the reaction solution of described configuration
For cadmium source, sulfur source, the aqueous solution of chelating agent or zinc source, sulfur source, the aqueous solution of chelating agent, described reaction solution is mixed,
Use cushion described in chemical bath method formation of deposits.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, described cadmium source be cadmium iodide,
One or more in Caddy (Cleary) or cadmium sulfate, the concentration of cadmium source solution is 1.0～5.0umol/L.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, described zinc source be zinc chloride,
One or more in zinc hydroxide or zinc sulfate, the concentration of zinc source solution is 1.0～5.0umol/L.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, described sulfur source is thiourea, sulfur
Changing one or more in sodium or thioacetamide, the concentration of sulfur source solution is 20.0umol/L-0.1mol/L.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, described chelating agent be ammonia,
One or more in ammonium acetate, ammonium chloride, ammonium nitrate or ammonium sulfate, the concentration of enveloping agent solution is 0.1～3.0mol/L.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, the described reaction solution of configuration
Mixed pH value is 9.5～12.0.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, reaction temperature is 25～80 DEG C,
Response time is 5～40min, uses one or more combinations in electric stirring, magnetic agitation and sonic oscillation in deposition process
Alr mode be stirred.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, the described cushion of formation
Thickness is 20～200nm.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, carry out described immersion treatment
Aqueous solution is the mixed solution of one or more in ammonia, isopropanol or ammonium acetate.
As the scheme of a kind of optimization of thin-film solar cells cushion aftertreatment technology of the present invention, the concentration of described aqueous solution is
5～15mol/L, soak time is 5～20min.
As it has been described above, the thin-film solar cells cushion aftertreatment technology of the present invention, including: provide surface to be formed with absorbed layer
Thin-film solar cells, configure reaction solution, use chemical bath method described reaction solution is deposited on described absorbed layer surface
Form cushion, described cushion is placed in aqueous solution carries out immersion treatment afterwards, finally take out, dry up with nitrogen.This
Bright cushion aftertreatment technology can improve buffer-layer surface flatness, reduces buffer-layer surface floccule, increases and parent window
The contact area of layer and Lattice Matching, reduce carrier being combined at cushion/Window layer interface, can improve thin-film solar cells
Short-circuit current density 1.0-2.0mA/cm2, improve battery conversion efficiency absolute value 1-3%.The ammonia used due to immersion treatment
Water, isopropanol, ammonium acetate etc. are conventional reagent, repeatable utilization, process costs is low, equipment is simple and reliable, operation is safe,
It is applicable to industrialized production.
Accompanying drawing explanation
The schematic flow sheet of the thin-film solar cells cushion aftertreatment technology that Fig. 1 provides for the present invention.
The absorbing layer of thin film solar cell structural representation that Fig. 2 provides for the present invention.
The thin-film solar cells buffer layer structure schematic diagram that Fig. 3 provides for the present invention.
The thin-film solar cells overall structure schematic diagram that Fig. 4 provides for the present invention.
Fig. 5 is the buffer-layer surface SEM photograph not carrying out aftertreatment technology.
Fig. 6 is the buffer-layer surface SEM photograph after the present invention carries out aftertreatment technology.
Fig. 7 is that the CIGS thin film solaode using technique of the present invention to prepare is prepared without aftertreatment technology with cushion
CIGS thin film solar cell I-V curve and battery output parameter comparison diagram.
Element numbers explanation
S1～S5 step
1 substrate
2 dorsum electrode layers
3 absorbed layers
4 cushions
5 Window layer
51 intrinsic transparent oxide layer
52 including transparent conducting oxide layers
6 electrode layers
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by disclosed by this specification
Content understand other advantages and effect of the present invention easily.The present invention can also be added by the most different detailed description of the invention
To implement or application, the every details in this specification can also be based on different viewpoints and application, in the essence without departing from the present invention
Various modification or change is carried out under god.
Refer to accompanying drawing.It should be noted that the diagram provided in the present embodiment illustrates that the present invention's is basic the most in a schematic way
Conception, the most graphic in component count, shape and size time only display with relevant assembly in the present invention rather than is implemented according to reality
Drawing, during its actual enforcement, the kenel of each assembly, quantity and ratio can be a kind of random change, and its assembly layout kenel is also
It is likely more complexity.
As it is shown in figure 1, the present invention provides a kind of thin-film solar cells cushion aftertreatment technology, described aftertreatment technology is at least
Comprise the following steps:
S1, it is provided that surface is formed with the thin-film solar cells of absorbed layer；
S2, the reaction solution of configuration buffer layer；
S3, uses chemical bath method that described reaction solution is deposited on described absorbed layer surface and forms cushion；
S4, is placed in the cushion deposited in aqueous solution and carries out immersion treatment；
S5, takes out, dries up with nitrogen.
The thin-film solar cells cushion aftertreatment technology of the present invention is discussed in detail below according to accompanying drawing.
Step S1 is first carried out, it is provided that surface is formed with the thin-film solar cells of absorbed layer.
In the present invention, the structure of the absorbing layer of thin film solar cell provided as in figure 2 it is shown, include substrate 1, dorsum electrode layer 2,
Absorbed layer 3.Substrate 1 therein can be soda-lime glass, low Fe glass, solar energy float glass, stainless steel foil, Ti paper tinsel,
Al paper tinsel, Mo paper tinsel, Cu paper tinsel, polyimides (PI), pet resin (PET) or the substrate that he is suitable for.
Described dorsum electrode layer 2 is Mo layer, can use magnetically controlled DC sputtering vacuum moulding machine, and thickness is 0.1-2 μm.Described absorbed layer 3
The modes such as evaporation, sputtering and selenization technique or nanometer coating can be used to prepare, and described absorber thickness is 0.5-3 μm.Described absorbed layer
Material can be CuInGaSe absorbed layer or the CIS similar with CuInGaSe absorbed layer, Cu-In-Ga-Se-S, copper-zinc-tin-sulfur,
Copper-zinc-tin-selenium, copper zinc tin sulfur selenium etc..
Then step S2, the reaction solution of configuration buffer layer are performed.
If cushion is cadmium sulfide, configure cadmium source, sulfur source, the aqueous solution of chelating agent；If cushion is zinc sulfide, configuration zinc source,
Sulfur source, the aqueous solution of chelating agent.Described cadmium source is to select at least one in cadmium iodide, Caddy (Cleary) and cadmium sulfate, preferably iodine
Cadmium, configures cadmium iodide solution concentration 1.0umol/L-5.0umol/L；Described zinc source is zinc chloride, zinc hydroxide and zinc sulfate
In select at least one, preferably sulfuric acid zinc, configure solution of zinc sulfate concentration 1.0umol/L-5.0umol/L；Described sulfur source is
At least one is selected by thiourea, sodium sulfide and thioacetamide, preferably thiourea, configure thiourea solution concentration
20.0umol/L-0.1mol/L；Described chelating agent be ammonia, ammonium acetate, ammonium chloride, ammonium nitrate and ammonium sulfate are selected to
Few one, preferably ammonia, configure ammonia spirit concentration 0.1mol/L-3.0mol/L.Certainly, described cushion can also be other
Suitably material.
Then perform step S3, use chemical bath method that described reaction solution is deposited on described absorbed layer surface and form cushion.
Reaction solution mixing step S2 configured, uses chemical bath method by buffer layer deposition in absorbed layer surface.Mixed
Reacting solution pH value is 9.5-12.0, and reaction temperature is 25-80 DEG C, and the response time is 5-40min, stirring employing electric stirring,
Magnetic agitation or sonic oscillation, preferably electric stirring, rotating speed is 200-2000r/min.It is deposited on the buffering thickness on absorbed layer surface
Degree is 20-200nm.Described thin-film solar cells buffer layer structure is as shown in Figure 3.
Then perform step S4, the cushion deposited is placed in aqueous solution and carries out immersion treatment.
The mixed solution of one or more in configuration ammonia, isopropanol or ammonium acetate.As the aqueous solution of immersion treatment, join
The concentration putting aqueous solution is 5mol/L-15mol/L, and the cushion prepared by S3 is placed in aqueous solution immersion 5-20min.
Finally perform step S5 again, take out, dry up with nitrogen.
So far, thin-film solar cells cushion aftertreatment technology completes.If Fig. 5 is the cushion table not carrying out aftertreatment technology
Face SEM photograph；Fig. 6 is the buffer-layer surface SEM photograph after the present invention carries out aftertreatment technology.Find through contrast, enter
Padded surface floccule after row aftertreatment technology greatly reduces, and buffer-layer surface flatness is improved, and is conducive to improving thin film
The short circuit current of solaode and conversion efficiency.
After described thin-film solar cells cushion processes, then carry out subsequent technique and complete the making of thin-film solar cells.Electricity
The structure in pond as shown in Figure 4, including substrate 1, dorsum electrode layer 2, absorbed layer 3, cushion 4, Window layer 5 and electrode layer 6.
Cell manufacturing process is: buffer-layer surface deposition Window layer 5 the most after treatment (includes deposition intrinsic transparent oxide successively
Layer 51 and transparent conductive oxide Window layer 52) and the film layer such as electrode layer 6, complete the preparation of thin-film solar cells.
The present invention provides a kind of thin-film solar cells cushion aftertreatment technology, can improve buffer-layer surface flatness, reduces
Buffer-layer surface floccule, increases the contact area with parent window layer and Lattice Matching, reduces carrier in cushion/Window layer
Being combined of interface, improves short circuit current and the conversion efficiency of thin-film solar cells.This process method equipment is simple and reliable, operation
Safety, the repeatable utilization of soaking solution, process costs is low, be applicable to industrialized production.
Thin-film solar cells cushion aftertreatment technology of the present invention, following example are explained below by specific embodiment
All illustrate as a example by CIGS (CIGS) absorbed layer.
Embodiment 1
Step one, using soda-lime glass as substrate, carry out ultrasonic cleaning, then dry up loading magnetron sputtered vacuum chamber with pure nitrogen gas
Room, is dehydrated degassing, uses Deposited By Dc Magnetron Sputtering bilayer Mo dorsum electrode layer, and thickness is 0.6um；
Step 2, preparation is had Mo dorsum electrode layer substrate load vacuum chamber, treat that vacuum is better than 1 × 10-3After Pa, use
CuGa alloys target (Ga content at.25%) and In target cosputtering deposition CuInGa (CIG) metal preformed layer, thickness is
0.6um；
Step 3, preparation has the substrate of metal preformed layer load in selenizing stove, use H2Se as selenium source, 400 DEG C of selenizings
30min, anneal in 580 DEG C of nitrogen atmospheres 30min, then natural cooling, prepare CIGS absorbed layer, thickness is 1.2um；
Step 4, the cadmium iodide solution of configuration 1.5umol/L, the thiourea solution of 75umol/L, the ammonia spirit of 0.5mol/L,
Chemical bath method is used to prepare cushion cadmium sulfide.The pH value of reaction solution is 10.5, and reaction temperature is 25-50.5 DEG C, reaction
Time is 10min, and stirring uses electric stirring, and rotating speed is 1000r/min, and the thickness preparing cadmium sulfide cushion is 50nm；
Step 5, the ammonia spirit of configuration 10mol/L, put into the ammonia spirit of configuration by the cadmium sulfide cushion that step 4 prepares
Middle immersion 5min, takes out, dries up with nitrogen；
Step 6, ZnO:Al Window layer thick for i-ZnO and 500nm thick for employing magnetron sputtering deposition 80nm；
Step 7, Ni/Ag two-layer electrode layer thick for employing evaporation deposition 3um.
The CIGS thin film solaode phase that the CIGS thin film solaode using said method to prepare is prepared with prior art
Ratio, short-circuit current density promotes 1.62mA/cm2, the conversion efficiency absolute value of battery improves 1.97%, as it is shown in fig. 7, solid line
Represent CIGS thin film solaode prepared by the present embodiment；Dotted line represents the CIGS thin film that cushion is prepared without aftertreatment technology
The IV curve of solaode.
Embodiment 2
Step one, soda-lime glass carrying out ultrasonic cleaning, then dry up loading magnetron sputtered vacuum chamber with pure nitrogen gas, dehydration is gone
Gas, uses Deposited By Dc Magnetron Sputtering bilayer Mo dorsum electrode layer, and thickness is 0.6um；
Step 2, preparation is had Mo dorsum electrode layer substrate load vacuum chamber, treat that vacuum is better than 1 × 10-3After Pa, use
CuGa alloys target (Ga content at.25%) and In target cosputtering deposition CuInGa (CIG) metal preformed layer, thickness is
0.6um；
Step 3, preparation has the substrate of metal preformed layer load in selenizing stove, use H2Se as selenium source, 400 DEG C of selenizings
30min, anneal in 580 DEG C of nitrogen atmospheres 30min, then natural cooling, prepare CIGS absorbed layer, thickness is 1.2um；
Step 4, the solution of zinc sulfate of configuration 1.5umol/L, the thiourea solution of 75umol/L, the ammonia spirit of 0.5mol/L,
Chemical bath method is used to prepare cushion zinc sulfide.The pH value of reaction solution is 10.5, and reaction temperature is 25-50.5 DEG C, reaction
Time is 10min, and stirring uses electric stirring, and rotating speed is 1000r/min, and the thickness preparing zinc sulfide cushion is 50nm；
Step 5, the ammonia spirit of configuration 10mol/L, put into the ammonia spirit of configuration by the zinc sulfide cushion that step 4 prepares
Middle immersion 5min, takes out, dries up with nitrogen；
Step 6, ZnO:Al Window layer thick for i-ZnO and 500nm thick for employing magnetron sputtering deposition 80nm；
Step 7, Ni/Ag two-layer electrode layer thick for employing evaporation deposition 3um.
The CIGS thin film solaode phase that the CIGS thin film solaode using said method to prepare is prepared with prior art
Ratio, short-circuit current density promotes 1.0-2.0mA/cm2, the conversion efficiency absolute value of battery can improve 1-3%.
Embodiment 3
Step one, soda-lime glass carrying out ultrasonic cleaning, then dry up loading magnetron sputtered vacuum chamber with pure nitrogen gas, dehydration is gone
Gas, uses Deposited By Dc Magnetron Sputtering bilayer Mo dorsum electrode layer, and thickness is 0.6um；
Step 2, preparation is had Mo dorsum electrode layer substrate load vacuum chamber, treat that vacuum is better than 1 × 10-3After Pa, use
CuGa alloys target (Ga content at.25%) and In target cosputtering deposition CuInGa (CIG) metal preformed layer, thickness is
0.6um；
Step 3, preparation has the substrate of metal preformed layer load in selenizing stove, use H2Se as selenium source, 400 DEG C of selenizings
30min, anneal in 580 DEG C of nitrogen atmospheres 30min, then natural cooling, prepare CIGS absorbed layer, thickness is 1.2um；
Step 4, the cadmium iodide solution of configuration 1.5umol/L, the thiourea solution of 75umol/L, the ammonia spirit of 0.5mol/L,
Chemical bath method is used to prepare cushion cadmium sulfide.The pH value of reaction solution is 10.5, and reaction temperature is 25-50.5 DEG C, reaction
Time is 10min, and stirring uses electric stirring, and rotating speed is 1000r/min, and the thickness preparing cadmium sulfide cushion is 50nm；
Step 5, the aqueous isopropanol of configuration 10mol/L, put into the isopropanol of configuration by the cadmium sulfide cushion that step 4 prepares
Solution soaks 5min, takes out, dry up with nitrogen；
Step 6, ZnO:Al Window layer thick for i-ZnO and 500nm thick for employing magnetron sputtering deposition 80nm；
Step 7, Ni/Ag two-layer electrode layer thick for employing evaporation deposition 3um.
The CIGS thin film solaode phase that the CIGS thin film solaode using said method to prepare is prepared with prior art
Ratio, short-circuit current density promotes 1.0-2.0mA/cm2, the conversion efficiency absolute value of battery can improve 1-3%.
Embodiment 4
Step one, soda-lime glass carrying out ultrasonic cleaning, then dry up loading magnetron sputtered vacuum chamber with pure nitrogen gas, dehydration is gone
Gas, uses Deposited By Dc Magnetron Sputtering bilayer Mo dorsum electrode layer, and thickness is 0.6um；
Step 2, preparation is had Mo dorsum electrode layer substrate load vacuum chamber, treat that vacuum is better than 1 × 10-3After Pa, use
CuGa alloys target (Ga content at.25%) and In target cosputtering deposition CuInGa (CIG) metal preformed layer, thickness is
0.6um；
Step 3, preparation has the substrate of metal preformed layer load in selenizing stove, use H2Se as selenium source, 400 DEG C of selenizings
30min, anneal in 580 DEG C of nitrogen atmospheres 30min, then natural cooling, prepare CIGS absorbed layer, thickness is 1.2um；
Step 4, the cadmium iodide solution of configuration 1.5umol/L, the thiourea solution of 75umol/L, the ammonia spirit of 0.5mol/L,
Chemical bath method is used to prepare cushion cadmium sulfide.The pH value of reaction solution is 10.5, and reaction temperature is 25-50.5 DEG C, reaction
Time is 10min, and stirring uses electric stirring, and rotating speed is 1000r/min, and the thickness preparing cadmium sulfide cushion is 50nm；
Step 5, the Spirit of Mindererus. of configuration 10mol/L, put into the cadmium sulfide cushion that step 4 prepares in Spirit of Mindererus.
Soak 5min, take out, use N2Dry up；
Step 6, ZnO:Al Window layer thick for i-ZnO and 500nm thick for employing magnetron sputtering deposition 80nm；
Step 7, Ni/Ag two-layer electrode layer thick for employing evaporation deposition 3um.
The CIGS thin film solaode phase that the CIGS thin film solaode using said method to prepare is prepared with prior art
Ratio, short-circuit current density promotes 1.0-2.0mA/cm2, the conversion efficiency absolute value of battery can improve 1-3%.
In sum, the present invention provides a kind of thin-film solar cells cushion aftertreatment technology, including: provide surface to be formed
The thin-film solar cells of absorbed layer, configures reaction solution, uses chemical bath method that described reaction solution is deposited on described absorption
Layer surface forms cushion, is placed in aqueous solution by described cushion afterwards and carries out immersion treatment, finally takes out, dry up with nitrogen.
Cushion aftertreatment technology of the present invention can improve buffer-layer surface flatness, reduces buffer-layer surface floccule, increases and upper strata
The contact area of Window layer and Lattice Matching, reduce carrier being combined at cushion/Window layer interface, can improve thin film solar
The short-circuit current density 1.0-2.0mA/cm of battery2, improve battery conversion efficiency absolute value 1-3%.Owing to immersion treatment is used
Ammonia, isopropanol, ammonium acetate etc. be conventional reagent, repeatable utilization, process costs is low, equipment is simple and reliable, operation peace
Entirely, it is applicable to industrialized production.
So, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any it is familiar with this skill
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage of art.Therefore, such as
All that in art, tool usually intellectual is completed under without departing from disclosed spirit and technological thought etc.
Effect is modified or changes, and must be contained by the claim of the present invention.
Claims (13)
1. a thin-film solar cells cushion aftertreatment technology, it is characterised in that described aftertreatment technology at least includes:
There is provided surface to be formed with the thin-film solar cells of absorbed layer, configure reaction solution, use chemical bath method by described
Reaction solution is deposited on described absorbed layer surface and forms cushion, is placed in aqueous solution by described cushion afterwards and carries out at immersion
Reason, finally takes out, dries up with nitrogen.
Thin-film solar cells cushion aftertreatment technology the most according to claim 1, it is characterised in that: described absorbed layer is copper
Indium gallium selenium, CIS, Cu-In-Ga-Se-S, copper-zinc-tin-sulfur, copper-zinc-tin-selenium or copper zinc tin sulfur selenium.
Thin-film solar cells cushion aftertreatment technology the most according to claim 1, it is characterised in that: the described buffering of formation
Layer is cadmium sulfide or zinc sulfide.
Thin-film solar cells cushion aftertreatment technology the most according to claim 1, it is characterised in that: the reaction of described configuration
Solution is cadmium source, sulfur source, the aqueous solution of chelating agent or zinc source, sulfur source, the aqueous solution of chelating agent, by described reaction solution
Mixing, uses cushion described in chemical bath method formation of deposits.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: described cadmium source is iodate
One or more in cadmium, Caddy (Cleary) or cadmium sulfate, the concentration of cadmium source solution is 1.0～5.0umol/L.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: described zinc source is chlorination
One or more in zinc, zinc hydroxide or zinc sulfate, the concentration of zinc source solution is 1.0～5.0umol/L.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: described sulfur source be thiourea,
One or more in sodium sulfide or thioacetamide, the concentration of sulfur source solution is 20.0umol/L-0.1mol/L.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: described chelating agent is ammonia
One or more in water, ammonium acetate, ammonium chloride, ammonium nitrate or ammonium sulfate, the concentration of enveloping agent solution is 0.1～3.0mol/L.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: the described reaction of configuration
The mixed pH value of solution is 9.5～12.0.
Thin-film solar cells cushion aftertreatment technology the most according to claim 4, it is characterised in that: reaction temperature is
25～80 DEG C, the response time is 5～40min, uses in electric stirring, magnetic agitation and sonic oscillation in deposition process
Plant or the alr mode of multiple combination is stirred.
11. according to the thin-film solar cells cushion aftertreatment technology described in claim 1 or 4, it is characterised in that: the institute of formation
The thickness stating cushion is 20～200nm.
12. thin-film solar cells cushion aftertreatment technologys according to claim 1, it is characterised in that: carry out described immersion
The aqueous solution processed is the mixed solution of one or more in ammonia, isopropanol or ammonium acetate.
13. thin-film solar cells cushion aftertreatment technologys according to claim 12, it is characterised in that: described aqueous solution
Concentration is 5～15mol/L, and soak time is 5～20min.
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| CN110896109A (en) * | 2018-09-13 | 2020-03-20 | 香港中文大学 | Method for post-treatment and buffer layer deposition of light absorption layer of Cu-based thin film solar cell |
| CN113745362A (en) * | 2020-05-28 | 2021-12-03 | 神华（北京）光伏科技研发有限公司 | Solar cell buffer layer and preparation method thereof |
| CN114171636A (en) * | 2021-11-24 | 2022-03-11 | 湖北工业大学 | Preparation method of Cd-free tunneling buffer layer for CZTS thin-film solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110400753A (en) * | 2018-04-24 | 2019-11-01 | 北京铂阳顶荣光伏科技有限公司 | The treatment process and preparation method of solar film battery buffer layer |
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| CN113745362A (en) * | 2020-05-28 | 2021-12-03 | 神华（北京）光伏科技研发有限公司 | Solar cell buffer layer and preparation method thereof |
| CN114171636A (en) * | 2021-11-24 | 2022-03-11 | 湖北工业大学 | Preparation method of Cd-free tunneling buffer layer for CZTS thin-film solar cell |
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