CN104795456A - Electro-deposition method for preparing three band gap Fe-doped with copper gallium sulfur solar cell materials - Google Patents
Electro-deposition method for preparing three band gap Fe-doped with copper gallium sulfur solar cell materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 47
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 6
- 239000011593 sulfur Substances 0.000 title abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 15
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 36
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 33
- 239000011521 glass Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 10
- 235000019743 Choline chloride Nutrition 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 10
- 229960003178 choline chloride Drugs 0.000 claims description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005137 deposition process Methods 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 23
- 238000000137 annealing Methods 0.000 abstract description 19
- 239000010409 thin film Substances 0.000 abstract description 18
- 239000000758 substrate Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000012876 topography Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000010408 film Substances 0.000 description 20
- 239000003708 ampul Substances 0.000 description 15
- 239000010453 quartz Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000036755 cellular response Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910000928 Yellow copper Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 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
- H01L31/0248—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- 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
-
- 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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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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 discloses an electro-deposition method for preparing the three band gap Fe-doped with copper gallium sulfur solar cell materials. The method includes the following steps: dissolving the copper chloride, the gallium chloride and the ferric chloride in the ionic liquid, depositing the Cu, Ga and Fe prefabricated layers on the constant potential of the substrate, conducting the vulcanization annealing treatment on the prefabricated layers, and finally preparing the Fe-doped with copper gallium sulfur thin film materials. The electro-deposition method for preparing the three band gap Fe-doped with copper gallium sulfur solar cell materials can effectively reduce the adverse effect of the hydrogen evolution reaction on the quality of the thin film due to the fact that the ionic liquid is used as the solvent, simple in preparation technology, high in utilization rate of raw materials, low in production cost, strong in controllability, good in repeatability, capable of realizing the preparation of the large-area high-quality thin film and large-scale production, good in crystallinity, compact and flat in surface topography, and capable of broadening the absorption of the solar energy spectral by the materials through the generated sub-band gap and obviously increasing the photo-generated current of materials.
Description
Technical field
The invention belongs to photoelectric material technical field of new energies, relate to the preparation method belonging to a kind of multi-band-gap solar battery obsorbing layer material in third generation solar cell material, be specifically related to a kind of preparation method of electro-deposition three band gap Fe2O3 doping copper gallium sulphur solar cell material.
Background technology
Along with the development of society, energy crisis and environmental pollution more and more serious.The new forms of energy of development cleanliness without any pollution substitute traditional fossil energy and solve being the most effective method that these two are concerned human survival and development problem.Clean with it, the pollution-free and huge emphasis becoming people and develop at new energy field of reserves of solar energy.The exploitation of solar energy be unable to do without the application of solar cell, and solar cell utilizes photovoltaic effect, is a kind of device of electric energy by transform light energy.Since French scientist Becquerel Late Cambrian photovoltaic effect in 1839, solar cell experienced by very long evolution.Up to now, solar cell roughly experienced by the development of three generations, the first generation is crystalline silicon solar cell, its electricity conversion has exceeded 25%, technology of preparing is comparative maturity also, commercially produced product has captured more than 90% of whole solar cell market, but its higher preparation cost and constrain it close to the conversion efficiency (the crystal silicon solar energy battery theoretical efficiency limit is about 29%) of the theoretical efficiency limit and further develop.Second on behalf of silica-base film, the compound films such as CIGS, CdTe, GaAs,
the thin-film solar cells such as organic film, this generation solar cell, although preparation cost is lower than first generation solar cell, be easy to the production realizing area battery, but the development of its conversion efficiency is faced with bottleneck, and the limiting efficiency 33.5% of single-unit solar cell can not be exceeded, and the Kano upper limit of solar photovoltaic conversion is 95%, this just illustrates that solar cell properties also has very large development space.Third generation solar cell is efficient novel solar battery, is also in concept and simple experimental study stage at present, and what proposed mainly contains lamination solar cell, multi-band-gap solar cell and hot carrier solar cell etc.As the one of third generation solar cell, multi-band-gap solar cell up to the theoretical conversion efficiencies of 86.8%, has tempting research and development prospect with it.CuGaS
2be a kind of straight gap semiconductor material of yellow copper structure, have absorption coefficient high, a series of advantages as solar cell material such as anti-interference and radianting capacity is strong.The energy gap of its about 2.43eV, close to the optimal value 2.41eV of the mid-gap host material of three band gap solar cells, can as the host material of desirable mid-gap solar cell.Relevant calculating shows, VIII race (Co, Fe, Ir, Ni, Pd, Rh, Sn) and IV race (Ge, Si) element doping are to CuGaS
2stable compound structure can be formed after in lattice, also can introduce intermediate level simultaneously, and with the CuGaS of Fe doping
2for the theoretical efficiency of three band gap solar cells of absorbed layer can reach 47%.
CuGaS
2the preparation method of material mainly contains metal-organic chemical vapour deposition technique, vacuum vapor deposition, molecular beam epitaxy, method of electrostatic spinning, solvent-thermal method and electrochemical deposition method etc.At present, the CuGaS of preparation Fe doping has been used successfully to
2the method of material has vacuum vapor deposition, chemical vapor transport method and solvent-thermal method etc.Compare other method, the CuGaS that electrodeposition process has the feature such as low temperature, antivacuum, low cost, high efficiency to be more suitable for preparing large-area Fe to adulterate
2thin-film solar cells material.In addition, adopting electrodeposition process, the thickness of film, chemical composition and surface topography can also be controlled by controlling the technological parameter such as deposition voltage and electric current, solution component, pH value, temperature and concentration accurately.
Summary of the invention
The object of the present invention is to provide a kind of high efficiency, low cost, utilization rate of raw materials high and the electrodeposition process being easy to extensive deposition prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials.
The technical scheme that the present invention realizes above-mentioned purpose is:
Electrodeposition process prepares a method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, it is characterized in that comprising the following steps:
(1) by Choline Chloride and the drying of urea mixing final vacuum, ionic liquid is mixed with;
(2) copper chloride, gallium chloride and gallium trichloride and iron chloride are dissolved in step (1) gained ionic liquid, obtain electric depositing solution, with Mo electro-conductive glass for work electrode, saturated calomel electrode is reference electrode, platinum filament is to electrode, adopts preformed layer and the copper gallium precursor thin-film of three electrode potentiostatic method deposition Cu, Ga and Fe;
(3) vacuum, nitrogen or argon gas that step (2) gained preformed layer is placed in containing sulphur powder are heat-treated, finally obtain three band gap Fe2O3 doping copper gallium sulphur solar cell materials, also can be expressed as the copper gallium sulphur thin-film material of three band gap Fe2O3 doping, sketch as Fe2O3 doping copper gallium sulphur film.
Further, described Choline Chloride and the mol ratio of urea are 1:2, and vacuumize temperature is 80 DEG C, and the time is 8 ~ 14 hours.
Further, described heat treated temperature is 400 ~ 500 DEG C, and the time is 30 ~ 90 minutes.
Further, described Mo electro-conductive glass first uses any two kinds of ultrasonic cleaning in acetone, ethanol, ammoniacal liquor 10 ~ 30 minutes before using, then uses deionized water Ultrasonic Cleaning 10 ~ 30 minutes.
Further, the molar concentration rate of described copper chloride, gallium chloride and iron chloride is 0.025 ~ 0.035:0.075 ~ 0.1:0.0003 ~ 0.01.
Further, the depositing temperature of described step (2) is 45 ~ 65 DEG C, and sedimentation potential is-1.15 ~-1.3Vvs.SCE, and sedimentation time is 20 ~ 40min, and in deposition process, the mixing speed of solution is 250 ~ 350rpm.
The copper gallium precursor thin-film thickness obtained in said process is 0.5 ~ 2um, and the atomic percent of copper, gallium, ferro element is close or equal 1:1:0.05 ~ 0.1.
Above-mentioned steps (3) i.e. annealing process, need first the copper gallium precursor thin-film of preparation and a certain amount of sulphur powder to be put into the quartz ampoule closed one end in annealing process, pass into inert gas or carry out tube sealing process after vacuumizing, again annealing furnace is warming up to 400 ~ 500 DEG C and constant temperature 1 ~ 4 hour, then quick have the quartz ampoule of sample to push in annealing furnace sulfuration annealing 30 ~ 90 minutes by envelope, taken out rapidly by quartz ampoule and be cooled to room temperature in atmosphere after having annealed.
The structure of the material prepared for research institute, pattern, composition and optical property, carried out X-ray diffraction analysis (XRD) to prepared sample, scanning electron microscope analysis (SEM), energy dispersion X-ray spectrum analysis (EDS), ultraviolet-visible light-near infrared spectrum (UV-Vis-NIR) analyzed and photochemical cell response test.
The material of the Fe2O3 doping copper gallium sulphur solar cell be prepared from according to the method disclosed in the present, analyzes to its XRD collection of illustrative plates, SEM, EDS the copper gallium sulphur that known product is the Fe2O3 doping of the yellow copper structure of pure phase, and the good crystallinity of material and pattern are respectively evenly.By carrying out UV-Vis-NIR analysis to the sample of preparation, mixing of Fe element can be found, really in copper gallium sulfur materials, introduce intermediate level, making material create two sub-band gap.By carrying out photochemical cell response test to Fe2O3 doping copper gallium sulphur sample, the photogenerated current of the sample after display Fe doping is obviously greater than unadulterated sample.
Beneficial effect of the present invention is:
(1) the present invention successfully achieves the preparation of three band gap Fe2O3 doping copper gallium sulphur solar cell materials by electrodeposition process, prepared thin-film material good crystallinity, surface topography densification is smooth, the introducing of ferro element, the subband gap formed has widened the absorption of material to solar spectral, significantly increase the photogenerated current of material, possess the potential quality of producing three band gap solar cell devices.
(2) the present invention's first electro-deposition presoma after cure annealing, there is a series of advantages such as technology and equipment is simple, utilization rate of raw materials is high, thin film composition is controlled, the solion system adopted, the evolving hydrogen reaction existed in water solution system effectively can be avoided the adverse effect of film quality, be easier to realize large-scale production.
Accompanying drawing explanation
The XRD figure of the copper gallium sulphur of the Fe2O3 doping that Fig. 1 embodiment 1 is obtained.
The SEM figure of the copper gallium sulphur of the Fe2O3 doping that Fig. 2 embodiment 1 is obtained.
The EDS figure of the copper gallium sulphur of the Fe2O3 doping that Fig. 3 embodiment 1 is obtained.
UV-Vis-NIR collection of illustrative plates of the copper gallium sulphur of the Fe2O3 doping that Fig. 4 embodiment 1 is obtained.
The photochemical cell response diagram of the copper gallium sulphur of the Fe2O3 doping that Fig. 5 embodiment 1 is obtained.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
A preparation method for the copper gallium sulphur thin-film material of three band gap Fe2O3 doping, comprises the following steps:
(1) successively adopt acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 15 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 12 hours, be mixed with the ionic liquid of 40ml, and add the copper chloride of 0.03mol/L, 0.1mol/L, 0.0005mol/L, gallium chloride and iron chloride successively in the solution, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 30 minutes are deposited with the permanent electromotive force of-1.2V, the temperature of electric depositing solution is 60 DEG C, and in deposition process, the mixing speed of solution is 300rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 1 hour, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 60 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
In the present embodiment the characterization result of sample and photochemical cell response test result as follows:
Fig. 1 is the XRD characterization result of sample prepared by embodiment 1, the corresponding CuGaS in position of each characteristic peak of sample
2(112), (220/204) and (312) crystal plane direction, the characteristic peak comparatively CuGaS of built-in partial enlarged drawing display (112) crystal plane direction
2standard card collection of illustrative plates (JCPDS#25-0279) offsets to the right, this is because Fe
3+ionic radius be less than Ga
3+the ionic radius of ion, when the iron atom displacement gallium atomic time, can cause CuGaS
2the lattice constant of crystal diminishes, and the change be reflected in X ray characteristic peak diffraction maximum that diminishes of lattice constant is that peak offsets to wide-angle direction, and this shows that product is the CuGaS of the Fe doping of yellow copper structure
2material, except the diffraction maximum of substrate Mo, do not have other diffraction to mix peak in XRD collection of illustrative plates, the sample prepared by explanation is the copper gallium sulfur materials of the Fe2O3 doping of pure phase.
Fig. 2 is the SEM collection of illustrative plates of sample prepared by embodiment 1, can find out the prepared more smooth densification of thin-film material surface pattern, and granular size is also relatively more even, and the tack of film and substrate is also better.
Fig. 3 is the EDS collection of illustrative plates of sample prepared by embodiment 1, and can find out in prepared sample and really have ferro element, the Fe that this and XRD draw is doped to CuGaS
2crystal structure in cause CuGaS
2the result diminished of lattice constant is consistent.
Fig. 4 is UV-Vis-NIR collection of illustrative plates of sample prepared by embodiment 1, by with unadulterated CuGaS
2contrast, can find: the CuGaS of Fe doping
2crystal is except having except the absorption band edge of host crystal at about 500nm, define two new very strong wide absorption bands at about 650nm and about 1000nm, this illustrates mixing, successfully at CuGaS of Fe element
2introduce intermediate level in straight gap semiconductor material, define two sub-band gap that size is about 1.2eV and 1.9eV.
Fig. 5 is the photochemical cell response diagram of sample prepared by embodiment 1, by with unadulterated CuGaS
2contrast, can find: under the condition having illumination, the CuGaS of Fe doping
2the photogenerated current intensity of sample is obviously better than unadulterated CuGaS
2sample, this illustrates that the absorption of semi-conducting material to solar spectral has been widened in the existence of intermediate level, the CuGaS of prepared Fe doping
2thin-film material has the potential quality of preparation three band gap solar cell.
In sum, the present invention can realize the preparation of the copper gallium sulphur solar cell material of three band gap Fe doping, and the thin-film material crystalline phase prepared is purer, film surface appearance densification is smooth, the photon of different-waveband in solar spectrum can be absorbed, realize the increase of photogenerated current, the CuGaS of prepared Fe doping
2thin-film material has the potential quality of preparation three band gap solar cell.
Embodiment 2
A preparation method for the copper gallium sulphur thin-film material of three band gap Fe2O3 doping, comprises the following steps:
(1) successively adopt acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 10 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 8 hours, be mixed with the ionic liquid of 40ml, and add the copper chloride of 0.035mol/L, 0.1mol/L, 0.01mol/L, gallium chloride and iron chloride successively in the solution, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 20 minutes are deposited with the permanent electromotive force of-1.15V, the temperature of electric depositing solution is 45 DEG C, and in deposition process, the mixing speed of solution is 350rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 1 hour, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 30 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
Embodiment 3
A preparation method for the copper gallium sulphur thin-film material of three band gap Fe2O3 doping, comprises the following steps:
(1) successively adopt acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 14 hours, be mixed with the ionic liquid of 40ml, and add the copper chloride of 0.035mol/L, 0.1mol/L, 0.01mol/L, gallium chloride and iron chloride successively in the solution, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 20 minutes are deposited with the permanent electromotive force of-1.15V, the temperature of electric depositing solution is 45 DEG C, and in deposition process, the mixing speed of solution is 350rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 1 hour, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 90 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
Embodiment 4
(1) successively adopt acetone, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 10 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 14 hours, be mixed with the ionic liquid of 40ml, and add 0.025mol/L in the solution successively, 0.075mol/L, the copper chloride of 0.0003mol/L, gallium chloride and iron chloride, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 40 minutes are deposited with the permanent electromotive force of-1.3V, the temperature of electric depositing solution is 65 DEG C, in deposition process, the mixing speed of solution is 250rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 1 hour, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 30 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
Embodiment 5
(1) successively adopt acetone, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 8 hours, be mixed with the ionic liquid of 40ml, and add 0.025mol/L in the solution successively, 0.075mol/L, the copper chloride of 0.0003mol/L, gallium chloride and iron chloride, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 40 minutes are deposited with the permanent electromotive force of-1.3V, the temperature of electric depositing solution is 65 DEG C, in deposition process, the mixing speed of solution is 250rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 1 hour, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 90 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
Embodiment 6
(1) successively adopt ethanol, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively, then Mo electro-conductive glass to be placed in drying box 80 DEG C of vacuumizes 30 minutes.
(2) by 1:2 mole to measure Choline Chloride and urea stir after in vacuum drying chamber 80 DEG C of dryings within 8 hours, be mixed with the ionic liquid of 40ml, and add 0.025mol/L in the solution successively, 0.075mol/L, the copper chloride of 0.0003mol/L, gallium chloride and iron chloride, adopt single groove electrolysis tank, with Mo substrate of glass cleaned in step (1) for work electrode, platinum filament is to electrode, saturated calomel is reference electrode, 40 minutes are deposited with the permanent electromotive force of-1.3V, the temperature of electric depositing solution is 65 DEG C, in deposition process, the mixing speed of solution is 250rpm.
(3) the preformed layer film of preparation in step (2) and a certain amount of sublimed sulfur powder are put into the quartz ampoule closed one end, carry out vacuumizing under the protection of argon gas and sealed silica envelope process.Annealing furnace is warming up to 450 DEG C and constant temperature 4 hours, then quick have the quartz ampoule of sample to push in annealing furnace envelope to anneal 30 minutes, taken out rapidly by sample and be cooled to room temperature in atmosphere, finally prepare Fe2O3 doping copper gallium sulphur film of the present invention after having annealed.
Claims (6)
1. electrodeposition process prepares a method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, it is characterized in that comprising the following steps:
(1) by Choline Chloride and the drying of urea mixing final vacuum, ionic liquid is mixed with;
(2) copper chloride, gallium chloride and iron chloride are dissolved in step (1) gained ionic liquid, obtain electric depositing solution, with Mo electro-conductive glass for work electrode, saturated calomel electrode is reference electrode, platinum filament is to electrode, adopts the preformed layer of three electrode potentiostatic method deposition Cu, Ga and Fe;
(3) vacuum, nitrogen or argon gas that step (2) gained preformed layer is placed in containing sulphur powder are heat-treated, finally obtain three band gap Fe2O3 doping copper gallium sulphur solar cell materials.
2. electrodeposition process according to claim 1 prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, and it is characterized in that: described Choline Chloride and the mol ratio of urea are 1:2, vacuumize temperature is 80 DEG C, and the time is 8 ~ 14 hours.
3. electrodeposition process according to claim 1 prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, and it is characterized in that: described heat treated temperature is 400 ~ 500 DEG C, the time is 30 ~ 90 minutes.
4. electrodeposition process according to claim 1 prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, it is characterized in that: described Mo electro-conductive glass first uses any two kinds of ultrasonic cleaning in acetone, ethanol, ammoniacal liquor 10 ~ 30 minutes before using, then uses deionized water Ultrasonic Cleaning 10 ~ 30 minutes.
5. electrodeposition process according to claim 1 prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, it is characterized in that: the molar concentration rate of described copper chloride, gallium chloride and iron chloride is 0.025 ~ 0.035:0.075 ~ 0.1:0.0003 ~ 0.01.
6. electrodeposition process according to claim 1 prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, it is characterized in that: the depositing temperature of described step (2) is 45 ~ 65 DEG C, sedimentation potential is-1.15 ~-1.3V vs.SCE, sedimentation time is 20 ~ 40min, and in deposition process, the mixing speed of solution is 250 ~ 350rpm.
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| CN105970253A (en) * | 2016-05-24 | 2016-09-28 | 湘潭大学 | Method for preparing three-band-gap tin-doped copper-gallium-sulfur solar cell thin film material through sulfuration annealing after double-potential deposition |
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| CN109904255A (en) * | 2019-03-19 | 2019-06-18 | 湘潭大学 | A kind of preparation method of Cr-Se codope zinc sulphide solar battery buffer layer thin film material |
| CN111244197A (en) * | 2020-01-20 | 2020-06-05 | 南开大学 | Copper-based thin film solar cell positive electrode and preparation method thereof |
| CN115612863A (en) * | 2022-08-30 | 2023-01-17 | 中南大学 | Method for separating gallium from alkaline solution |
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| CN105970253A (en) * | 2016-05-24 | 2016-09-28 | 湘潭大学 | Method for preparing three-band-gap tin-doped copper-gallium-sulfur solar cell thin film material through sulfuration annealing after double-potential deposition |
| CN108039382A (en) * | 2017-12-21 | 2018-05-15 | 叶芳 | A kind of new type solar energy material and preparation method thereof |
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| CN115612863A (en) * | 2022-08-30 | 2023-01-17 | 中南大学 | Method for separating gallium from alkaline solution |
| CN115612863B (en) * | 2022-08-30 | 2024-01-16 | 中南大学 | Method for separating gallium from alkaline solution |
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