CN104795456B - Electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials - Google Patents
Electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 46
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005864 Sulphur Substances 0.000 title claims abstract description 38
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 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
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 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
- 239000011521 glass Substances 0.000 claims description 22
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 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
- 230000005611 electricity Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 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
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 27
- 238000000137 annealing Methods 0.000 abstract description 26
- 239000010408 film Substances 0.000 abstract description 21
- 239000010409 thin film Substances 0.000 abstract description 17
- 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 5
- 238000000280 densification Methods 0.000 abstract description 4
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- 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
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000005987 sulfurization reaction Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000003708 ampul Substances 0.000 description 15
- 239000010453 quartz Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 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
- 238000003756 stirring Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000036755 cellular response Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000928 Yellow copper Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000002149 energy-dispersive X-ray emission spectroscopy 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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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
-
- 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
-
- 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 discloses a kind of method that electrodeposition process prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials.Comprising the steps: first to be dissolved in copper chloride, gallium chloride, iron chloride in ionic liquid, in substrate, permanent electromotive force deposition Cu, Ga, Fe preformed layer, then carries out sulfuration annealing again, finally prepares Fe2O3 doping copper gallium sulphur thin-film material to preformed layer.It is solvent that the present invention selects ionic liquid, can effectively prevent the adverse effect to film quality for the evolving hydrogen reaction, and preparation technology is simple, utilization rate of raw materials is high, low cost product, and controllability is strong, favorable repeatability, it is easy to accomplish large area, the preparation of high-quality thin film and large-scale production；Resulting materials of the present invention, good crystallinity, surface topography densification is smooth, the introducing of ferro element, and the subband gap of formation has widened the absorption to solar spectral for the material, hence it is evident that add the photogenerated current of material.
Description
Technical field
The invention belongs to photoelectric material technical field of new energies, relate to belonging in third generation solar cell material
The preparation method of a kind of multi-band-gap solar battery obsorbing layer material, relates to a kind of electro-deposition three band gap
The preparation method of Fe2O3 doping copper gallium sulphur solar cell material.
Background technology
With social development, energy crisis and environmental pollution are increasingly severe.Develop the new of cleanliness without any pollution
The traditional fossil energy of energy substitution solves the two to concern the maximally effective of human survival and development problem by being
Method.Solar energy with its cleaning, pollution-free and reserves are huge becomes the emphasis that people develop at new energy field.
The exploitation of solar energy be unable to do without the application of solar cell, and solar cell is to utilize photovoltaic effect, will
Luminous energy is converted to a kind of device of electric energy.Since French scientist Becquerel finds photoproduction volt in 1839 first
Since special efficacy is answered, solar cell experienced by very long evolution.Up to now, solar cell is substantially
Experienced by the development of three generations, the first generation is crystalline silicon solar cell, and its electricity conversion alreadys more than
25%, technology of preparing also comparative maturity, commercially produced product has captured the 90% of whole solar cell market
Above, but its higher preparation cost and (crystalline silicon is too already close to the conversion efficiency of the theoretical efficiency limit
Sun can the battery theoretical efficiency limit about 29%) constrain its further development.Second on behalf of silica-based thin
Film, the compound film such as CIGS, CdTe, GaAs,The thin-film solar cells such as organic film,
This generation solar cell, although preparation cost is less than first generation solar cell, it is easy to accomplish large area electricity
The production in pond, but the development of its conversion efficiency is faced with bottleneck, and can not be beyond single-unit solar cell
Limiting efficiency 33.5%, and the Kano upper limit of solar energy photoelectric conversion is 95%, this just illustrates solar cell
Can also have very big development space.Third generation solar cell is efficient novel solar battery, mesh
Before be also in concept and simple experimental study stage, it has been suggested that mainly have lamination solar cell, carry more
Gap solar cell and hot carrier solar cell etc..As the one of third generation solar cell, carry more
Gap solar cell is up to the theoretical conversion efficiencies of 86.8%, great tempting research and development prospect with it.
CuGaS2It is the straight gap semiconductor material of a kind of yellow copper structure, have absorption coefficient high, anti-interference and radiation
A series of advantages as solar cell material such as ability is strong.The energy gap of its about 2.43eV, close
Optimal value 2.41eV of the mid-gap host material of three band gap solar cells, can be as preferable centre
The host material of band gap solar cell.Related calculating shows, VIII race (Co, Fe, Ir, Ni, Pd, Rh, Sn) and IV
Race (Ge, Si) element doping is to CuGaS2Stable compound structure can be formed after in lattice, also can draw simultaneously
Enter intermediate level, and with the CuGaS of Fe doping2Theoretical efficiency for three band gap solar cells of absorbed layer
47% can be reached.
CuGaS2The preparation method of material mainly has metal-organic chemical vapour deposition technique, vacuum evaporation deposition
Method, molecular beam epitaxy, method of electrostatic spinning, solvent-thermal method and electrochemical deposition method etc..At present, success
For preparing the CuGaS of Fe doping2The method of material have vacuum vapor deposition, chemical vapor transport method and
Solvent-thermal method etc..Comparing other methods, electrodeposition process has low temperature, antivacuum, low cost, high efficiency etc.
Feature is more suitable for preparing the CuGaS of large-area Fe doping2Thin-film solar cells material.In addition,
Use electrodeposition process, can also be by control deposition voltage and electric current, solution component, pH value, temperature and dense
The technological parameters such as degree are accurately controlled the thickness of film, chemical composition and surface topography.
Content of the invention
It is an object of the invention to provide a kind of high efficiency, low cost, utilization rate of raw materials is high and is easy to big
The method that the electrodeposition process of area deposition prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials.
The present invention realizes that the technical scheme of above-mentioned purpose is:
A kind of electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials, and its feature exists
In comprising the following steps:
(1) Choline Chloride and urea mixing final vacuum are dried, are configured to ionic liquid；
(2) copper chloride, gallium chloride i.e. gallium trichloride and iron chloride are dissolved into step (1) gained ionic liquid
In, obtain electric depositing solution, with Mo electro-conductive glass as working electrode, saturated calomel electrode is reference electrode,
Platinum filament is for electrode, using the preformed layer i.e. copper gallium presoma of three electrode potentiostatic method deposition Cu, Ga and Fe
Film；
(3) it is placed in step (2) gained preformed layer in the vacuum containing sulphur powder, nitrogen or argon gas and carries out at heat
Reason, finally obtains three band gap Fe2O3 doping copper gallium sulphur solar cell materials, also can be expressed as three band gap Fe2O3 doping
Copper gallium sulphur thin-film material, sketch as Fe2O3 doping copper gallium sulphur film.
Further, the mol ratio of described Choline Chloride and urea is 1:2, and vacuum drying temperature is 80 DEG C,
Time is 8～14 hours.
Further, the temperature of described heat treatment is 400～500 DEG C, and the time is 30～90 minutes.
Further, described Mo electro-conductive glass is first surpassed by any two kinds in acetone, ethanol, ammoniacal liquor before using
Sound cleans 10～30 minutes, then with deionized water Ultrasonic Cleaning 10～30 minutes.
Further, the molar concentration rate of described copper chloride, gallium chloride and iron chloride be 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～-1.3V
Vs.SCE, sedimentation time is 20～40min, and in deposition process, the mixing speed of solution is 250～350rpm.
The copper gallium precursor thin-film thickness obtaining in said process is 0.5～2um, copper, gallium, ferro element former
Sub-percentage is close or equal to 1:1:0.05～0.1.
Above-mentioned steps (3) i.e. annealing process, need in annealing process first by preparation copper gallium precursor thin-film and
A certain amount of sulphur powder is put in the quartz ampoule that one end is closed, and seals after being passed through inert gas or vacuumizing
Pipe process, then annealing furnace is warming up to 400～500 DEG C of simultaneously constant temperature 1～4 hours, then quick have sample by envelope
Quartz ampoule push annealing furnace vulcanize annealing 30～90 minutes, quartz ampoule is taken out rapidly after completing by annealing
Air is cooled to room temperature.
The structure of the material prepared for research institute, pattern, composition and optical property, to prepared sample
Carried out X-ray diffraction analysis (XRD), scanning electron microscope analysis (SEM), energy dispersion X penetrate
Line spectrum analyzes (EDS), ultraviolet-visible light-near infrared spectrum (UV-Vis-NIR) is analyzed and photochemistry electricity
Pond response test.
According to the material of the Fe2O3 doping copper gallium sulphur solar cell that the method disclosed in the present is prepared from, right
Its XRD spectrum, SEM, EDS analysis understand the copper gallium sulphur of the Fe2O3 doping of the yellow copper structure that product is pure phase,
The good crystallinity of material and pattern are respectively uniformly.By UV-Vis-NIR analysis is carried out to the sample of preparation, can
To find the incorporation of Fe element, really in copper gallium sulfur materials, introduce intermediate level, make material create two
Individual sub-band gap.By carrying out photochemical cell response test to Fe2O3 doping copper gallium sulphur sample, display Fe adulterates it
After the photogenerated current of sample be substantially greater than unadulterated sample.
The beneficial effects of the present invention is:
(1) present invention is successfully realized three band gap Fe2O3 doping copper gallium sulphur solar cell materials by electrodeposition process
Preparation, prepared thin-film material good crystallinity, surface topography densification is smooth, the introducing of ferro element, shape
The subband gap becoming has widened the absorption to solar spectral for the material, hence it is evident that add the photogenerated current of material, tool
For the potential quality producing three band gap solar cell devices.
(2) present invention first electro-deposition presoma after cure annealing, has technique and equipment is simple, raw material are sharp
By a series of advantages such as rate is high, thin film composition is controlled, the solion system being used, can effectively keep away
Exempt from the adverse effect to film quality for the evolving hydrogen reaction present in water solution system, it is easier to realize extensive raw
Produce.
Brief description
The XRD of the copper gallium sulphur of the Fe2O3 doping that Fig. 1 embodiment 1 prepares, abscissa represents the incidence of x-ray
The twice of angle, unit degree of being, ordinate represent diffraction after intensity, unit is any amount.
The SEM figure of the copper gallium sulphur of the Fe2O3 doping that Fig. 2 embodiment 1 prepares.
The EDS figure of the copper gallium sulphur of the Fe2O3 doping that Fig. 3 embodiment 1 prepares, abscissa represents X-ray energy,
Unit is kilo electron volt, and ordinate represents intensity, and unit is any amount.
The UV-Vis NIR collection of illustrative plates of the copper gallium sulphur of the Fe2O3 doping that Fig. 4 embodiment 1 prepares, abscissa represents ripple
Long, unit is nanometer, and ordinate represents absorbance, and unit is any amount.
The photochemical cell response diagram of the copper gallium sulphur of the Fe2O3 doping that Fig. 5 embodiment 1 prepares, when abscissa represents
Between, unit is the second, and ordinate represents current density, and unit is milliampere every square centimeter, and light on represents and meets
The light time, light off represents the shading time.
Detailed description of the invention
It in order to be better understood from the present invention, is further elucidated with present disclosure below in conjunction with embodiment, but this
The content of invention is not limited solely to the following examples.
Embodiment 1
The preparation method of the copper gallium sulphur thin-film material of a kind of three band gap Fe2O3 doping, comprises the following steps:
(1) successively using acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 15 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 12 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.03mol/L, 0.1mol/L, 0.0005
The copper chloride of mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with cleaned in step (1)
Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with the permanent electricity of-1.2V
Gesture deposits 30 minutes, and the temperature of electric depositing solution is 60 DEG C, and in deposition process, the mixing speed of solution is
300rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 60 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
In the present embodiment, characterization result and the photochemical cell response test result of sample are as follows:
Fig. 1 is the XRD characterization result of the sample of embodiment 1 preparation, and the position of each characteristic peak of sample is corresponding
CuGaS2(112), (220/204) and (312) crystal plane direction, built-in partial enlarged drawing shows (112)
The characteristic peak of crystal plane direction is compared with CuGaS2Standard card collection of illustrative plates (JCPDS#25-0279) offsets to the right, and this is
Because Fe3+Ionic radius be less than Ga3+The ionic radius of ion, when the iron atom displacement gallium atomic time, can lead
Cause CuGaS2The lattice paprmeter of crystal diminishes, and diminishing of lattice paprmeter is reflected in X-ray characteristic peak diffraction maximum
Change to be peak offset to wide-angle direction, this shows the CuGaS of the Fe doping that product is yellow copper structure2
Material, in addition to the diffraction maximum of substrate Mo, does not has other the miscellaneous peak of diffraction in XRD spectrum, illustrates made
Standby sample is the copper gallium sulfur materials of the Fe2O3 doping of pure phase.
Fig. 2 is the SEM collection of illustrative plates of the sample of embodiment 1 preparation, it can be seen that prepared thin-film material surface
The more smooth densification of pattern, granular size also ratio is more uniform, and film is also preferable with the tack of substrate.
Fig. 3 is the EDS collection of illustrative plates of the sample of embodiment 1 preparation, it can be seen that be implicitly present in prepared sample
Having ferro element, this is doped to CuGaS with the Fe that XRD draws2Crystal structure in cause CuGaS2Lattice
The result diminishing of constant is consistent.
Fig. 4 is the UV-Vis NIR collection of illustrative plates of sample of embodiment 1 preparation, by with unadulterated CuGaS2
Contrast, it appeared that: the CuGaS of Fe doping2Crystal is brilliant except there are matrix at about 500nm
Outside the absorption band edge of body, define two new very strong wide suctions at about 650nm and about 1000nm
Take-up, the incorporation of this explanation Fe element, successfully at CuGaS2Straight gap semiconductor material introduces centre
Energy level, defines two sub-band gap that size is about 1.2eV and 1.9eV.
Fig. 5 is the photochemical cell response diagram of sample of embodiment 1 preparation, by with unadulterated CuGaS2
Contrast, it appeared that: under conditions of having illumination, the CuGaS of Fe doping2The photogenerated current of sample
Intensity is substantially better than unadulterated CuGaS2Sample, semiconductor material has been widened in the existence of this explanation intermediate level
The absorption to solar spectral for the material, the CuGaS of prepared Fe doping2Thin-film material has preparation three band gap too
The potential quality of sun energy battery.
In sum, the present invention is capable of 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, can absorb in solar spectrum
The photon of different-waveband, it is achieved the increase of photogenerated current, the CuGaS of prepared Fe doping2Thin-film material
There is the potential quality of preparation three band gap solar cells.
Embodiment 2
The preparation method of the copper gallium sulphur thin-film material of a kind of three band gap Fe2O3 doping, comprises the following steps:
(1) successively using acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 10 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 8 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.035mol/L, 0.1mol/L, 0.01
The copper chloride of mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with cleaned in step (1)
Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with the permanent electricity of-1.15V
Gesture deposits 20 minutes, and the temperature of electric depositing solution is 45 DEG C, and in deposition process, the mixing speed of solution is
350rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 30 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
Embodiment 3
The preparation method of the copper gallium sulphur thin-film material of a kind of three band gap Fe2O3 doping, comprises the following steps:
(1) successively using acetone, ethanol and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 14 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.035mol/L, 0.1mol/L, 0.01
The copper chloride of mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with cleaned in step (1)
Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with the permanent electricity of-1.15V
Gesture deposits 20 minutes, and the temperature of electric depositing solution is 45 DEG C, and in deposition process, the mixing speed of solution is
350rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 90 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
Embodiment 4
(1) successively using acetone, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 10 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 14 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.025mol/L, 0.075mol/L,
The copper chloride of 0.0003mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with clear in step (1)
Washed Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with-1.3V
Permanent electromotive force deposits 40 minutes, and the temperature of electric depositing solution is 65 DEG C, and in deposition process, the mixing speed of solution is
250rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 30 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
Embodiment 5
(1) successively using acetone, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 8 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.025mol/L, 0.075mol/L,
The copper chloride of 0.0003mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with clear in step (1)
Washed Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with-1.3V
Permanent electromotive force deposits 40 minutes, and the temperature of electric depositing solution is 65 DEG C, and in deposition process, the mixing speed of solution is
250rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 90 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
Embodiment 6
(1) successively using ethanol, ammoniacal liquor and deionized water, ultrasonic cleaning Mo electro-conductive glass is after 30 minutes respectively,
Again Mo electro-conductive glass is placed in drying box 80 DEG C to be vacuum dried 30 minutes.
(2) by 1:2 mole measure Choline Chloride and urea stir after 80 DEG C of dryings 8 in vacuum drying chamber
Hour is configured to the ionic liquid of 40ml, and add in the solution successively 0.025mol/L, 0.075mol/L,
The copper chloride of 0.0003mol/L, gallium chloride and iron chloride, use single groove electrolytic cell, with clear in step (1)
Washed Mo substrate of glass is working electrode, and platinum filament is for electrode, and saturated calomel is reference electrode, with-1.3V
Permanent electromotive force deposits 40 minutes, and the temperature of electric depositing solution is 65 DEG C, and in deposition process, the mixing speed of solution is
250rpm。
(3) preformed layer film and a certain amount of sublimed sulfur powder of preparation in step (2) are put into the stone that one end is closed
Ying Guanzhong, carries out being evacuated and hermetically sealed quartz ampoule process under the protection of argon gas.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 to anneal 30 minutes by envelope, annealing
After completing, sample is taken out rapidly and be cooled to room temperature in atmosphere, finally prepare the Fe2O3 doping copper gallium of the present invention
Sulphur film.
Claims (5)
1. the method that electrodeposition process prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials, its feature
It is to comprise the following steps:
(1) Choline Chloride and urea mixing final vacuum are dried, are configured to ionic liquid；
(2) it is dissolved into copper chloride, gallium chloride and iron chloride in step (1) gained ionic liquid, obtain electricity
Deposition solution, with Mo electro-conductive glass as working electrode, saturated calomel electrode is reference electrode, and platinum filament is for electricity
Pole, uses the preformed layer of three electrode potentiostatic method deposition Cu, Ga and Fe；
(3) it is placed in step (2) gained preformed layer in the vacuum containing sulphur powder, nitrogen or argon gas and carries out at heat
Reason, finally obtains three band gap Fe2O3 doping copper gallium sulphur solar cell materials；
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.
2. electrodeposition process according to claim 1 prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials
The method of material, it is characterised in that: the mol ratio of described Choline Chloride and urea is 1:2, vacuum drying temperature
Degree is 80 DEG C, and the time is 8～14 hours.
3. electrodeposition process according to claim 1 prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials
The method of material, it is characterised in that: the temperature of described heat treatment is 400～500 DEG C, and the time is 30～90 points
Clock.
4. electrodeposition process according to claim 1 prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials
The method of material, it is characterised in that: described Mo electro-conductive glass is first used in acetone, ethanol, ammoniacal liquor before using
Any two kinds of ultrasonic cleaning 10～30 minutes, then with deionized water Ultrasonic Cleaning 10～30 minutes.
5. electrodeposition process according to claim 1 prepares three band gap Fe2O3 doping copper gallium sulphur solar cell materials
The method of material, it is characterised in that: the depositing temperature of described step (2) is 45～65 DEG C, sedimentation potential for-1.15～
-1.3V vs.SCE, sedimentation time is 20～40min, in deposition process the mixing speed of solution be 250～
350rpm。
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