CN103811569A - Paste and method for forming light absorbing layer of solar cell - Google Patents
Paste and method for forming light absorbing layer of solar cell Download PDFInfo
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- CN103811569A CN103811569A CN201210516825.XA CN201210516825A CN103811569A CN 103811569 A CN103811569 A CN 103811569A CN 201210516825 A CN201210516825 A CN 201210516825A CN 103811569 A CN103811569 A CN 103811569A
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- absorption layer
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 43
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 230000031700 light absorption Effects 0.000 claims description 30
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- 239000002019 doping agent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001462 antimony Chemical class 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 abstract description 23
- 239000010408 film Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 12
- 239000000956 alloy Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910001245 Sb alloy Inorganic materials 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- -1 Ether amine Chemical class 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910000928 Yellow copper Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
- H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
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- 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
- Y02E10/541—CuInSe2 material PV cells
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- 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
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Abstract
The invention relates to a slurry and a method for forming a light absorbing layer of a solar cell. The present invention provides a slurry comprising: 1 part by weight of antimony-doped CIGS nanoparticles; 0.05 to 0.15 parts by weight of a dispersant; and 4 to 7 parts by weight of an organic solvent in which the antimony-doped CIGS nanoparticles are suspended by a dispersant. The invention also provides a method for forming a light-absorbing layer of a solar cell, which comprises providing a substrate, forming a back electrode layer on the substrate; applying the paste to the back electrode layer; heating to remove the organic solvent to form a precursor layer; and thermally treating the precursor layer to form a light absorbing layer.
Description
Technical field
The present invention is about solar cell, more especially in regard to the slurry composition that forms its light-absorption layer.
Background technology
CIGS coating technique mainly can be divided into common evaporation (Co-evaporation), sputter (Sputtering) equal vacuum process technique, and is coated with the antivacuum process technique such as (Coating), chemistry sprinkling pyrolysismethod (Chemical spray pyrolysis), electro-deposition (Electrodeposition).The equipment of vacuum process and maintenance expense costliness thereof, also have an expensive problem although photoelectric conversion efficiency is high.Antivacuum process technique has advantages of low equipment cost and high materials'use rate, quite has advantage and potentiality in volume production, and therefore many companies and research institution drop into antivacuum process technique energetically.Chemistry sprays pyrolysismethod because of the shortcomings such as compactness is poor and materials'use rate is lower, less use recently in the middle of antivacuum processing procedure.Galvanoplastic often meet with the problems such as the not good and bubble of plated film uniformity, and the manufacturer therefore dropping into is less.Coating process is to be expected most, and drops into also maximum technology of manufacturer.
At present prepare with coating process the flow process that copper indium gallium selenium solar cell absorbs photosphere and roughly can be summarized as three steps: the preparation of predecessor slurry, with wet type rubbing method, slurry is plated on molybdenum base material, in high temperature selenizing mode, the element in predecessor or compound is reacted into CIGS thin-film again.The form of predecessor slurry is broadly divided into corpuscular type and solution-type, forms copper-indium-gallium-selenium compound no matter form, all needs to see through pyroreaction why, therefore in the middle of existing technology, mostly needs to prepare two above predecessors to prepare light-absorption layer.Although the CIGS thin-film efficiency of pyroreaction mode gained verifies, predecessor is prepared numerous and diverse and time-consuming, and is difficult to avoid dephasign to generate when pyroreaction and the composition that is difficult to control film.
In sum, need at present the light-absorption layer of new slurry formation solar cell badly, to overcome the problem of aforementioned multiple predecessor slurry.
Summary of the invention
One embodiment of the invention provides a kind of slurry, comprising: the copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion; The dispersant of 0.05 to 0.15 weight portion; And the organic solvent of 4 to 7 weight portions, wherein the copper-indium-gallium-selenium nanoparticles of antimony dopant is suspended in organic solvent by dispersant.
One embodiment of the invention provides a kind of formation method of light-absorption layer of solar cell, comprising: substrate is provided, forms backplate layer on substrate; Above-mentioned slurry is put on backplate layer; Heating forms precursor layer to remove organic solvent; And heat treatment precursor layer is to form light-absorption layer.
Accompanying drawing explanation
Fig. 1 is in one embodiment of the invention, Copper Indium Gallium Selenide (CIGS:Sb) alloy powder and the antimony selenide (Sb of antimony dopant
2se
3) XRD comparison diagram;
Fig. 2 is in one embodiment of the invention, Copper Indium Gallium Selenide (CIGS:Sb) alloy powder and the antimony selenide (Sb of antimony dopant
2se
3) Ramman comparison diagram; And
Fig. 3 is in one embodiment of the invention, the XRD comparison diagram of the Copper Indium Gallium Selenide (CIGS:Sb) of the antimony dopant of different I n/Ga content.
Embodiment
One embodiment of the invention provides a kind of slurry, comprising: the copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion; The dispersant of 0.05 to 0.15 weight portion; And the solvent of 4 to 7 weight portions, wherein the copper-indium-gallium-selenium nanoparticles of antimony dopant is suspended in organic solvent by dispersant.If the consumption of organic solvent is too much, the solid content of slurry is easily too low, is unfavorable for coating process.If the consumption of organic solvent is too low, slurry viscosity is easily too high, and coating is prone to be full of cracks problem.If the consumption of dispersant is too low, in slurry, the Copper Indium Gallium Selenide of antimony dopant (CIGS:Sb) nano particle is easy to assemble and cannot effectively disperses.If the consumption of dispersant is too high, slurry is too sticky causes coating to be difficult for, and in the follow-up step that adds thermosetting light-absorption layer, is difficult to remove dispersant and easily has carbon residue problem.
The composition of above-mentioned CIGS:Sb is as shown in Equation 1:
Cu
1-x(In
1-yga
y) Se
2+z: Sb
w(formula 1)
In formula 1,0≤x≤0.2,0.1≤y≤0.9,0≤z≤0.2, and 0 < w≤0.2.Weigh copper powder, indium powder, selenium powder, insert in high-pressure reactor containing gallium nitrate and the antimony selenide of the crystallization water according to stoichiometry, collocation organic solvent reacts, and gets final product to obtain the product of formula 1.Because antimony (Sb) helps the long brilliant effect of melting, the precursor layer that therefore contains CIGS:Sb can form the light-absorption layer of yellow copper structure after heat treatment.On the other hand, the CIGS:Sb slurry that first forms formula 1 can be simplified the preparation flow of multiple predecessor, and the stability of CIGS:Sb is high, is difficult for occurring the variation of element ratio in the time of heat treatment, the composition of light-absorption layer more easy to control.
In an embodiment of the present invention, organic solvent can be C
1-6monohydric alcohol (only containing a hydroxyl) methyl alcohol, normal propyl alcohol, other suitable monohydric alcohol or above-mentioned combination.In an embodiment of the present invention, dispersant can be (1) anionic: have electronegative polar group, as carboxyl.(2) cationic: to there is the polar group of positively charged, as amino.(3) electric neutrality type: as ethylene glycol.(4) nonionic: form as polyethoxylated glycol s (PEG), Alkylphenol ethoxylates (APE) etc. mainly with Oxyranyle chain.For instance, dispersant can be monoethanolamine.By CIGS:Sb powder, dispersant and organic solvent be placed in suitable dispersal device as ball mill after, get final product to obtain slurry.In an embodiment of the present invention, the average grain diameter of the CIGS:Sb particle in slurry is 10mm to 50nm.If the average grain diameter of CIGS:Sb particle is excessive, after wet type coating, easily form hole in precursor layer.Even after high-temperature heat treatment precursor layer, above-mentioned hole still can residue in the light-absorption layer of last formation, and affects the usefulness of solar cell.
One embodiment of the invention also provides the formation method of the light-absorption layer of solar cell.For instance, can first apply backplate layer on substrate.Substrate can be glass, PI film, metal forming or other suitable board-like material.Backplate layer can be any electric conducting material as metal, alloy or other suitable electric conducting material.In an embodiment of the present invention, backplate layer is molybdenum.Then above-mentioned slurry is put on backplate layer, its applying method can be wet type and is coated with as scraper for coating method, infusion method, spraying process, method of spin coating or other suitable wet type rubbing method.Then remove organic solvent to form precursor layer.The last crystal that makes again the long brilliant formation yellow copper structure of CIGS:Sb precursor layer through a heat treatment processing procedure, completes light-absorption layer.
In an embodiment of the present invention, can in the step of heating precursor layer, pass into the volatilization with selenium element in avoiding heating process of selenium steam or sulfur vapor, and the sulfur vapor of trace contributes to the regulation and control of CIGS surface level, can help the lifting of efficiency.The selenium of light-absorption layer or the content of sulphur are increased, and then adjust the band gap scope of light-absorption layer.
The temperature that removes organic solvent formation precursor layer is 90 ℃ to 150 ℃.If the temperature of heating slurry is too low, cannot remove organic solvent.Thus, in precursor layer residual organic solvent after more when the heating processing of high temperature, possible Quick-gasifying and form hole in light-absorption layer.If the excess Temperature of heating slurry, may Quick-gasifying organic solvent and form hole in light-absorption layer.
Heat treatment precursor layer is to form the temperature of light-absorption layer as 500 ℃ to 600 ℃.The main purpose of this heating steps is to make the nano particle of CIGS:Sb to grow into the crystal of chalcopyrite, and removable residual organic solvent and dispersant.If the temperature of heating precursor layer is too low, be difficult for being completed into chalcopyrite crystallization.If the excess Temperature of heating precursor layer, bottom substrate is easily because high temperature damages.
To state with other object, feature and advantage and can become apparent in order to allow on the present invention, several embodiment cited below particularly coordinate appended diagram, are described in detail below:
[embodiment]
Embodiment 1
According to the stoichiometry of table 1 weigh copper powder, indium powder, selenium powder, with gallium nitrate containing the crystallization water, put into 1L high-pressure reactor.600mL ethylenediamine solution is added in high-pressure reactor and stirred, then weigh antimony selenide (embodiment 1-8 does not need this step) and added high-pressure reactor according to the stoichiometry of table 1.After complete sealed high pressure reactor, with air in nitrogen replacement high-pressure reactor, high-pressure reactor is placed in to heater, by temperature increase to 200 ℃, react and be cooled to room temperature after 24 hours.Separate solvent and alloy powder with filter type, after oven dry, form as table 1 with ICP-MS checking alloy powder.Fig. 1 is Copper Indium Gallium Selenide (CIGS:Sb) alloy powder and the antimony selenide (Sb of the antimony dopant of embodiment 1-1
2se
3) XRD comparison diagram, and Fig. 2 implements CIGS:Sb alloy powder and the Sb of 1-1
2se
3ramman comparison diagram.From Fig. 1 and 2, the CIGS:Sb alloy powder that above-mentioned synthetic method forms does not contain the dephasign of antimony selenide.Fig. 3 is the XRD comparison diagram of the CIGS:Sb of different I n/Ga content.As shown in Figure 3, CIGS:Sb alloy powder is containing the dephasign of antimony selenide, and the composition of different I n/Ga can make characteristic absorption peak produce obvious displacement, and hence one can see that just can control light-absorption layer composition at the synthesis phase of alloy powder.
Table 1
Embodiment 2
Then disperse the alloy powder of embodiment 1 to form slurry.For making slurry and molybdenum base material have good adhesion, the surface tension coefficient of solvent need be less than 40mN/m, and dispersant to lie in 350 ℃ be heat decomposable chemicals, to avoid carbon residue to affect the photoelectric conversion efficiency of light-absorption layer.How ground rice body is placed in the solvent of 2ml to get the CIGS:Sb of 0.1g embodiment 1-3, then adds the dispersant of 0.01g, observes powder and disperse situation after 18 hours.Table 2 is the result of different solvents and dispersant dispersion powder, and solvent is better with the effect of monohydric alcohol, and dispersant is best with the effect of the dispersant that contains amido.
Table 2
? | Dispersion solvent | Dispersant | Disperse situation |
Test 1 | Ethylene glycol | Ether amine | Most precipitation |
Test 2 | Glycol dimethyl ether | Triethylamine | A little precipitation |
Test 3 | Normal propyl alcohol | Monoethanolamine | Almost without precipitation |
Test 4 | Isobutanol | PEG | Precipitation completely |
Test 5 | Methyl alcohol | Ether amine | Almost without precipitation |
Test 6 | Ethanol | PEG | Most precipitation |
Test 7 | DME | Octanol | Precipitation completely |
Test 8 | Glycol dimethyl ether | BDO | Precipitation completely |
Test 9 | Ethylenediamine | Cellulose | Precipitation completely |
Test 10 | Ethylenediamine | Octanol | Precipitation completely |
Embodiment 3
Get solvent and the dispersant of the test 3 of embodiment 2 and make slurry.The CIGS:Sb alloy powder of getting 10g embodiment 1-3 is placed in controlling wet-type finishing machine (JBM-b035), add again the normal propyl alcohol of 0.8g monoethanolamine, 70ml and yttrium zirconium pearl 480g (particle diameter be 50 μ m), under the condition of 35 ℃ and rotating speed 2000rpm, grind 3.5 hours.After grinding completes with screen cloth separating yttrium zirconium pearl ball and lapping liquid, then with the concentrated lapping liquid of decompression distillation mode to desired concn (10-15wt%).The slurry brown color being obtained.The particle size of testing CIGS:Sb particle in its slurry with dynamic light scattering (Zetasizer NanoZS), in known slurry, the average grain diameter of CIGS:Sb particle is 50nm.
Get plating molybdenum glass, above-mentioned slurry wet type is coated on the molybdenum base material of 15cm × 30cm, through being repeatedly coated with still without the phenomenon of observing disbonding.This painting is placed under atmospheric environment on the heating plate of 100-150 ℃ to remove solvent, obtains the CIGS:Sb predecessor film that thickness is greater than 2.5 μ m.Observe this predecessor film by SEM, and though be from above depending on or the SEM photo analysed and observe all to can be observed predecessor film storehouse ground very closely knit.
Get above-mentioned predecessor film and carry out high temperature selenizing processing procedure.Get 5cm
2the test piece of predecessor film be placed on quartz glass supporter, get 2g selenium powder and be positioned on quartz boat, and quartz boat and quartz glass supporter are put into the uniform temperature zone of six inches of tubular high temperature stoves.Behind closed tube high temperature furnace two ends, with vacuum pump, tubular high temperature stove is evacuated to vacuum and passes into again nitrogen to normal pressure, repeat twice ventilation action and really make no oxygen in stove.After heating tubulose high temperature furnace to 530 ℃, maintain this temperature 20 to 30 minutes, stop afterwards heating with temperature in cooling water pipe to normal temperature, test piece can be taken out.With sem analysis test piece and observe in the brilliant situation of predecessor film length at high temperature, from above depending on and the size of the known CIGS:Sb crystal of SEM photo of side-looking be increased to approximately 1 μ m by tens nanometer.Can confirm that by XRD CIGS:Sb crystal is yellow copper structure and exists without dephasign.
Comparative example 1
Similar to embodiment 3, difference is tested 5 dispersion solvent and dispersant and is ground in embodiment 2.How ground rice body is placed in controlling wet-type finishing machine (JBM-b035) to get the CIGS:Sb of 10g, add again the methyl alcohol of 0.8g ether amine, 70ml and yttrium zirconium pearl 480g (particle diameter be 50 μ m), under the condition of 35 ℃ and rotating speed 2000rpm, grind 3.5 hours.After grinding completes, with screen cloth separating yttrium zirconium pearl ball and grinding distribution liquid, then the grinding distribution liquid of obtaining is concentrated into desired concn (solid content 10-30wt%) in decompression distillation mode, before institute obtains, drives thing ink color and be dark-grey black.Test its particle size with dynamic light scattering (Zetasizer NanoZS), in known slurry, the average grain diameter of CIGS:Sb particle is 200nm.
Get plating molybdenum glass, above-mentioned slurry wet type is coated on the molybdenum base material of 15cmx30cm, through being repeatedly coated with still without the phenomenon of observing disbonding.This painting is placed under atmospheric environment on the heating plate of 100-150 ℃ to remove solvent, obtains the CIGS:Sb predecessor film that thickness is greater than 3 μ m.Observe this predecessor film by SEM, and though on being depending on or analyse and observe and all can be observed predecessor film and there are many holes, the compaction rate of its storehouse is not as the predecessor film of embodiment 3.
Get above-mentioned predecessor film and carry out high temperature selenizing processing procedure.Get 5cm
2the test piece of predecessor film be placed on quartz glass supporter, get 2g selenium powder and be positioned on quartz boat, and quartz boat and quartz glass supporter are put into the uniform temperature zone of six inches of tubular high temperature stoves.Behind closed tube high temperature furnace two ends, with vacuum pump, tubular high temperature stove is evacuated to vacuum and passes into again nitrogen to normal pressure, repeat twice ventilation action and really make no oxygen in stove.After heating tubulose high temperature furnace to 530 ℃, maintain this temperature 20 to 30 minutes, stop afterwards heating with temperature in cooling water pipe to normal temperature, test piece can be taken out.Take out test piece observe the brilliant situation of predecessor film length at high temperature with sem analysis, from above depending on the known CIGS:Sb crystal of SEM photo also have obvious long brilliantly but have obvious hole, the storehouse packing that should come from predecessor film is not good.Be confined to the surface of light-absorption layer by the brilliant situation of the known length of SEM photo of analysing and observe, under surface, only observe few part melting and obviously long crystalline substance of nothing.
From embodiment 3 and comparative example 1 relatively, in slurry, the Average Particle Diameters of CIGS:Sb particle can affect the melting degree of nano particle in the time of high temperature significantly, with the brilliant situation of length of film.
Comparative example 2
Similar to Example 3, difference is that nano particle contained in slurry is not the CIGS:Sb of embodiment 1-3 but the CIGS of embodiment 1-8.Observe the CIGS film after long crystalline substance with SEM, find the brilliant phenomenon that obviously has layering of length of film, upper half storey has obvious long brilliant, and the long brilliant situation of lower half storey is less obvious.The difference of long brilliant situation will affect the size of current producing after light-absorption layer irradiation.The film of embodiment 3 and comparative example 2 is made to assembly (be please refer to
solid-State Electronics,
vol.56, Iss.1, Feb.2011, Pages175-178) after, relatively both current values.In embodiment 3, the long crystalline substance current value that light-absorption layer (CIGS:Sb) measures is more completely about 30mA/cm
2, and the current value that in comparative example 2, long brilliant poor light-absorption layer (CIGS) measures is about 22mA/cm
2.From relatively above-mentioned, doping Sb to CIGS can promote the electric current of solar cell really.
Comparative example 3
According to the stoichiometry of table 3 weigh copper powder, indium powder, selenium powder, with gallium nitrate containing the crystallization water, put into 1L high-pressure reactor.600mL ethylenediamine solution is added in high-pressure reactor and stirred.After complete sealed high pressure reactor, with air in nitrogen replacement high-pressure reactor, high-pressure reactor is placed in to heater, by temperature increase to 200 ℃, react and be cooled to room temperature after 24 hours.Separate solvent and alloy powder with filter type, after oven dry, form as table 3 with ICP-MS checking alloy powder.
Table 3
Then get above-mentioned CIGS powder 10g and Sb
2se
3powder 0.5g carries out the ball milling processing procedure of embodiment 3, forms slurry.Except the alloy powder difference of ball milling, other ball milling parameter, wet type coat on molybdenum glass, dry and high-temperature heat treatment makes the long processing procedure such as brilliant of predecessor film identical.Observe the CIGS+Sb after long crystalline substance with SEM
2se
3film, finds that the length crystalline substance of film obviously has the phenomenon of layering, shows the melting phenomenon of its nano-powder not as expected.Above-mentioned film is made after assembly and (be please refer to
solid-State Electronics,
vol.56, Iss.1, Feb.2011, Pages 175-178), the light-absorption layer (CIGS+Sb of layering in comparative example 3
2se
3) current value that measures is about 10mA/cm
2.Can find that by electrical result the method that Sb is directly mixed with CIGS can not increase photoelectric conversion efficiency.
Although the present invention discloses as above with several preferred embodiments; so it is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the invention; when doing any change and retouching, therefore the present invention's protection range when depending on after the attached claim person of defining be as the criterion.
Claims (10)
1. a slurry, comprising:
The copper-indium-gallium-selenium nanoparticles of the antimony dopant of 1 weight portion;
The dispersant of 0.05 to 0.15 weight portion; And
The organic solvent of 4 to 7 weight portions,
Wherein the copper-indium-gallium-selenium nanoparticles of this antimony dopant is suspended in this organic solvent by this dispersant.
2. slurry as claimed in claim 1, wherein this dispersant is C
1-6monohydric alcohol.
3. slurry as claimed in claim 2, wherein this monohydric alcohol is methyl alcohol, normal propyl alcohol or above-mentioned combination.
4. as the slurry of claim 1, wherein this dispersant comprises anionic dispersing agent, cationic dispersing agent, electric neutrality type dispersant, multifunctional group dispersant or nonionic polarity dispersant.
5. slurry as claimed in claim 4, wherein this dispersant is monoethanolamine.
6. slurry as claimed in claim 1, wherein the average grain diameter of the copper-indium-gallium-selenium nanoparticles of this antimony dopant is 10 to 50nm.
7. slurry as claimed in claim 1, wherein the copper-indium-gallium-selenium nanoparticles of this antimony dopant consist of Cu
1-x(In
1-yga
y) Se
2 ± z: Sb
w, wherein 0≤x≤0.2,0.1≤y≤0.9,0≤z≤0.2, and 0<w≤0.2.
8. a formation method for the light-absorption layer of solar cell, comprising:
Substrate is provided,
Form backplate layer on this substrate;
Slurry described in claim 1 is put on this backplate layer;
Heat this slurry, to form precursor layer; And
Heat this precursor layer to form light-absorption layer.
9. the formation method of the light-absorption layer of solar cell as claimed in claim 8, wherein heats this precursor layer and is carried out under the environment of selenium steam or sulfur vapor with the step system that forms this light-absorption layer.
10. the formation method of the light-absorption layer of solar cell as claimed in claim 8, wherein heats this precursor layer take the temperature of step that forms this light-absorption layer as 500 ℃ to 600 ℃.
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CN102024858A (en) * | 2010-04-19 | 2011-04-20 | 福建欧德生光电科技有限公司 | Ink, thin film solar cell and manufacturing methods thereof |
CN102569514A (en) * | 2012-01-04 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Method for preparing copper indium gallium selenide solar cell optical absorption layer |
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CN102024858A (en) * | 2010-04-19 | 2011-04-20 | 福建欧德生光电科技有限公司 | Ink, thin film solar cell and manufacturing methods thereof |
CN102569514A (en) * | 2012-01-04 | 2012-07-11 | 中国科学院合肥物质科学研究院 | Method for preparing copper indium gallium selenide solar cell optical absorption layer |
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