CN105932111A - Method for preparing copper-indium-gallium-selenide photoelectric thin film from copper chloride and gallium chloride - Google Patents
Method for preparing copper-indium-gallium-selenide photoelectric thin film from copper chloride and gallium chloride Download PDFInfo
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- CN105932111A CN105932111A CN201610438394.8A CN201610438394A CN105932111A CN 105932111 A CN105932111 A CN 105932111A CN 201610438394 A CN201610438394 A CN 201610438394A CN 105932111 A CN105932111 A CN 105932111A
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- 239000010409 thin film Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 15
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 title claims abstract description 12
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract 6
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 17
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 14
- 230000005693 optoelectronics Effects 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- -1 gallium chlorides Chemical class 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000004528 spin coating Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
-
- 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 method for preparing a copper-indium-gallium-selenide photoelectric thin film from copper chloride and gallium chloride, and belongs to the technical field of photoelectric thin film preparation for the solar cell. The method comprises the following steps of firstly cleaning a glass substrate; then putting copper chloride, indium chloride, gallium chloride and selenium dioxide into a solvent, adjusting the pH value to be 4.0-7.0, and obtaining a precursor thin film on the glass substrate through a spin coating method; drying the precursor thin film, and putting the precursor thin film into a closed container with hydrazine hydrate to enable the precursor thin film not to be in contact with the hydrazine; putting the closed container loaded with a sample into a drying oven, carrying out heating and thermal insulating processing on the container, and finally taking out the sample and drying the sample to obtain the copper-indium-gallium-selenide photoelectric thin film. According to the method, a high-temperature high-vacuum condition is not required; meanwhile, the method is low in instrument equipment requirement, low in production cost, high in production efficiency and easy to operate; the obtained copper-indium-gallium-selenide photoelectric thin film is relatively high in continuity and uniformity; the main phase is the copper-indium-gallium-selenide phase; by adoption of the new process, the components and structure of the target product can be controlled easily; and therefore, a production method which is low in cost and can be industrialized is provided for preparing the high-performance copper-indium-gallium-selenide photoelectric thin film.
Description
Technical field
The invention belongs to solar cell optoelectronic film preparing technical field, particularly relate to a kind of method being prepared CIGS optoelectronic film by copper chloride and gallium chloride.
Background technology
Since entering 21 century, the energy and environmental problem become the focus that people focus more on, the environmental pollution brought in the face of lack of energy and traditional energy, people start progressively to find the energy revolution of the novel energy new round that can substitute for traditional fossil energy and the most slowly raise the curtain.Photovoltaic generation have safe and reliable, noiseless, pollution-free, restriction less, the advantage such as failure rate is low, easy maintenance, this cleaning of solar energy, safety and the regenerative resource of environmental protection, the research and development of solar cell the most in recent decades can be utilized to be increasingly subject to pay attention to.
CIGS thin-film solar cell may be considered one of the most promising hull cell at present, and its light absorbing zone is made up of the copper-based conductors material of low cost, and absorbing ability is much stronger than crystalline silicon, in solar spectrum district optical absorption depth in micron dimension.The absorption coefficient of light of CIGS is up to 105cm-1, hence it is evident that higher than solar cell materials such as Si and CdTe, therefore it is especially suitable for doing light absorbing material.Additionally, CIGS also have a series of a little: (1) CIGS is direct band-gap semicondictor, this can reduce to minority carrier diffusion requirement;(2) at room temperature CIGS band gap is adjustable, along with the change of gallium content, its band gap can in the range of 1.04~1.67eV consecutive variations;(3) CIGS absorptance is very big, and conversion efficiency is high, and stable performance, film thickness is little, about 2 μm, and the price of raw material is relatively low, and time prepared by large area, price is relatively low;(4) the least in wider composition range internal resistance rate;(5) capability of resistance to radiation is strong, does not has photo attenuation effect, thus service life is long;(6) lattice structure of p-type CIGS material can be mated with common N-type window material (such as CdS, ZnO) with electron affinity.
At present the preparation method of CIGS mainly have solvent-thermal method, spray pyrolysis method (Spray Prolysis), electrojet method, electro-deposition, chemical deposition, the chemical vapor transportation method of closing, chemical gaseous phase deposition, molecular beam epitaxy, reactive sputtering, vacuum vapor deposition method, Metalorganic chemical vapor deposition method, etc..Owing to CIGS cost of material is low, and its band gap can change along with gallium content, thus improve photoelectric transformation efficiency, be therefore the most rising a kind of solar cell material, but existing process route is complicated, preparation cost high, thus need also exist for exploring the preparation technology of low cost.
Method is the same as before, and other method also has different defects.Related to the present invention also has such as Publication about Document:
[1] Yusuke Oda, Masakazu Matsubayashi,
Takashi Minemoto, Hideyuki Takakura,
Fabrication of Cu(In, Ga)Se2
thin film solar cell absorbers from electrodeposited bilayers.
Current Applied Physics 10 (2010) 146-149.
Essentially describe and utilize electro-deposition bilayer to prepare method, prepare CIGS thin-film, and be tested characterizing to the CIGS thin-film electrical property of preparation.
[2] Guo
Wei, Xue Yu-ming, Zhang
Xiao-feng, Feng Shao-jun, Influence of substrate of deposited precursor layer
on structural properties of CIGS thin films. Journal of Optoelectronics·Laser 10 (2013)1936-1941.
Essentially describe and prepare the impact on CIGS thin-film architectural characteristic of the underlayer temperature of CIGS thin-film and preformed layer on a glass substrate by three stage Co-evaporation method.
[3] Li Chunei,
Zhuang Da-ming, Zhang Gong,
Luan He-xin, Liu Jiang, The influence of selenization temperature on the properties of CuInGaSe2
thin film. Chinese Journal of Materials Research.Vol.24 No.4 (2010)358-362.
Essentially describe and prepare CIGS thin-film by prefabricated selenizing method, and by the analysis of composition, pattern, structure and electric property to thin film, obtain the impact on thin film of the selenizing temperature.
[4] Pan Hui-Ping,
Bo Lian-Kun, Huang Tai-Wu, Zhang Yi, Yu Tao, Yao Shu-De, Structural analysis of Cu(In1-xGax)Se2
multi-layer thin film solar cells.Acta Phys. Sin. Vol. 61, No. 22 (2012) 228801.
The method such as sputtering and selenization technique and coevaporation that essentially describes prepares copper indium gallium selenium solar cell thin film, and analyzes the film layer structure of CIGS.
[5] F. Oliva,
C. Broussillou, M. Annibaliano,
N. Frederich, P.P. Grand, A. Roussy,
P. Collot, S. Bodnar,
Formation mechanisms of Cu(In,Ga)Se2 solar
cells prepared from electrodeposited precursors. Thin Solid Films 535 (2013)
127–132.
Essentially describing and first pass through two step electro-deposition, then the method for short annealing prepares CIGS thin-film, and affects temperature in CIGS thin-film forming process to it.
[6] Guan-Ting Pan, M.-H. Lai, Rei-Cheng Juang, T.-W. Chun, The preparation and characterization of Ga-doped
CuInS2Lms with chemical bath deposition.
Solar Energy Materials & Solar Cells 94 (2010) 1790–1796.
Essentially describe the CuInS containing Ga layer prepared with chemical bath method2The feature of thin film, and the impact that Ga is on the performance of thin film.
[7] Miaomiao
Li, Fanggao Chang, Chao Li, Cunj
un Xia, Tianxing Wang, Jihao
Wang, Mengbo Sun, CIS and CIGS thin films prepared by
magnetron sputtering. Procedia Engineering 27 (2012)
12-19.
Essentially describing employing cosputtering method and prepare CIS and CIGS thin film, be utilized respectively XRD, SEM, the EDS microcosmic crystal structure to thin film prepared by this new method, surface topography and thin film composition are analyzed.
[8] Ying Liu, Deyi
Konga, Jiawei Lia, Cong Zhao, Chilai Chen, Juergen Brugger, Preparation of
Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process. Energy
Procedia 16 (2012) 217 -222.
Essentially describe solvent thermal and spin-coating method prepares CIGS thin-film, by X-ray diffraction (XRD), the mode test analysis such as Raman spectrum (RS) and scanning electron microscope (SEM) structure of CIGS.
[9] Jiang Liu, Daming
Zhuang, Hexin Luan, Mingjie Cao, Min Xie, Xiaolong Li, Preparation of Cu(In,Ga)Se2
thin film by sputtering from Cu(In,Ga)Se2 quaternary
target. Progress in Natural Science: Materials International 2013;23(2):133–138.
Essentially describe and prepare CIGS thin-film by direct sputtering method, and by XRD, the structure of the test analysis such as AFM, SEM CIGS and component composition.
[10] Liao Rong, Zhang Haiyan, Jiang Wei, Huang Yin, Liang Zhipeng, precursor film lamination and the impact on CIGS thin-film performance of the selenizing heating mode. vacuum science and Technology 5 (2013) 496-500.
Essentially describe the method utilizing two target magnetic control sputterings, select different stacked systems to prepare copper and indium gallium precursor film.Then being put into by precursor film in special vacuum drying oven selects different heating modes to carry out selenized annealing, obtains quaternary compound copper-indium-gallium-selenium semiconductor nano thin-film, thin film is carried out every sign.
Summary of the invention
The present invention is to solve the deficiencies in the prior art, and invented a kind of diverse with the preparation method of prior art, the preparation technology of CIGS solar cell thin-film material.
The present invention uses spin coating-chemistry co-reducing process to prepare CIGS thin-film material, employing soda-lime glass is substrate, with copper chloride, indium chloride, gallium chloride, selenium dioxide is raw material, with deionized water, ethylene glycol, ethanolamine, the two or more mixture of ammonia or these four raw material is solvent, the pH value of solution is adjusted with ammonia for assist medium, amount than first prepares the certain thickness precursor thin-film containing CIGS with spin-coating method by elements, with hydrazine hydrate as reducing agent, heat at a lower temperature in hermetic container, precursor thin-film reduction concurrent GCMS computer reaction is made to obtain target product.
The concrete preparation method of the present invention includes following steps in sequence:
A. carry out the cleaning of glass substrate, be that sulphuric acid by volume put into by 20mm × 20mm sheet glass by size: in the aqueous solution of distilled water=2:1, ultrasonic waves for cleaning 30min;Sheet glass is put into volume ratio acetone again: in the solution of distilled water=5:1, ultrasonic waves for cleaning 30min;In distilled water, glass substrate is used sonic oscillation 30min again;Glass substrate obtained above is emitted in glass dish in feeding baking oven, dries for masking at 100 DEG C.
B. copper chloride, indium chloride, gallium chloride, selenium dioxide are put in solvent, make the material in solution uniformly mix, and regulate pH value.Specifically, 1.5~3.0 parts of copper chlorides, 1.0~2.0 parts of indium chloride, 1.0~2.0 parts of gallium chlorides, 2.0~4.0 parts of selenium dioxide can be put in the solvent of 110~450 parts, the material in solution is made uniformly to mix, can add 100~250 parts of ammonia to adjust the pH value of solution is 4.0~7.0, the mixed solution of at least one during wherein solvent is deionized water, ethylene glycol, ethanolamine, ammonia.
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample.Above-mentioned solution can be dripped on the glass substrate that is placed on sol evenning machine, restart sol evenning machine and rotate certain time with 300~3500 revs/min, after making the solution on dripping be coated with uniformly, after substrate being dried at 100 DEG C, dry again after again repeating to drip upper previous solu and rotary coating, so repeat 5~15 times, obtained certain thickness precursor thin-film sample the most on a glass substrate.
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, make precursor thin-film sample not contact with hydrazine.It is 35~40 parts that hydrazine hydrate is put into.The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated between 160~220 DEG C, temperature retention time 5~20 hours, is then cooled to room temperature and takes out.
E. by step d gains so that it is after room temperature natural drying, CIGS optoelectronic film is i.e. obtained.
The present invention need not high temperature high vacuum condition, requires low to instrument and equipment, and production cost is low, and production efficiency is high, it is easy to operation.Gained CIGS optoelectronic film has preferable seriality and uniformity, principal phase is CIGS phase, this new technology is easily controlled composition and the structure of target product, provides a kind of low cost for preparing high performance CIGS optoelectronic film, can realize large-scale industrial production.
Detailed description of the invention
Embodiment 1
A. the cleaning of glass substrate: be carried out glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. 1.5 parts of copper chlorides, 1.0 parts of indium chloride, 1.0 parts of gallium chlorides and 2.0 parts of selenium dioxide being put in 378.07 parts of deionized waters and uniformly mixed, adding ammonia to pH is 4.5, utilizes more than ultrasonic activation 30min, makes the material in solution uniformly mix.
C. above-mentioned solution is dripped on the glass substrate that is placed on sol evenning machine, restart sol evenning machine, sol evenning machine rotates 5 seconds with 300 revs/min, rotate 15 seconds with 3000 revs/min, after making the solution on dripping be coated with uniformly, after substrate being dried at 100 DEG C, dry again after again repeating to drip upper previous solu and rotary coating, so it is repeated 10 times, has obtained certain thickness precursor thin-film sample the most on a glass substrate.
D., the precursor thin-film sample of above-mentioned technique gained being put into sealable container, and puts into 37.807 parts of hydrazine hydrates, precursor thin film sample is placed on support and makes it not contact with hydrazine.The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated to 200 DEG C, temperature retention time 10 hours, is then cooled to room temperature and takes out.
E. by step d gains, carry out room temperature natural drying, obtain CIGS optoelectronic film.
Claims (5)
1. the method being prepared CIGS optoelectronic film by copper chloride and gallium chloride, including following steps in sequence:
A. the cleaning of glass substrate;
B. 1.5~3.0 parts of copper chlorides, 1.0~2.0 parts of indium chloride, 1.0~2.0 parts of gallium chlorides, 2.0~4.0 parts of selenium dioxide are put in the solvent of 110~450 parts, make the material in solution uniformly mix, and adjust pH value to 4.0~7.0;
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample;
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, make precursor thin-film sample not contact with hydrazine;The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated between 160~220 DEG C, temperature retention time 5~20 hours, is then cooled to room temperature and takes out;
E. by step d gains, carry out natural drying, obtain CIGS optoelectronic film.
A kind of method being prepared CIGS optoelectronic film by copper chloride and gallium chloride, it is characterized in that, clean described in step a, be to be 20mm × 20mm by glass substrate size, put into volume ratio sulphuric acid: in the solution of distilled water=2:1, ultrasonic waves for cleaning;Sheet glass is put into acetone by volume again: in the solution of distilled water=5:1, ultrasonic waves for cleaning;Again by glass substrate sonic oscillation in distilled water;Glass substrate obtained above is emitted in glass dish in feeding baking oven and dries for masking.
A kind of method being prepared CIGS optoelectronic film by copper chloride and gallium chloride, it is characterised in that the solvent described in step b is at least one in deionized water, ethanol, ethylene glycol, ethanolamine, ammonia.
A kind of method being prepared CIGS optoelectronic film by copper chloride and gallium chloride, it is characterized in that, the substrate of uniform application described in step c, it is to be smeared by sol evenning machine, sol evenning machine is with 300~3500 revs/min of rotations, then, after substrate being dried, the most so repeat 5~15 times, obtained certain thickness precursor thin-film sample.
A kind of method being prepared CIGS optoelectronic film by copper chloride and gallium chloride, it is characterised in that put into 35~40 parts of hydrazine hydrates in hermetic container described in step d.
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WO2019157562A1 (en) * | 2018-02-16 | 2019-08-22 | Newsouth Innovations Pty Limited | Adamantine semiconductor and uses thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
CN102070184A (en) * | 2010-12-01 | 2011-05-25 | 同济大学 | Preparation method of CuInS2 nanoparticles |
CN102034898B (en) * | 2010-10-20 | 2012-03-28 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
CN103334081A (en) * | 2013-06-07 | 2013-10-02 | 深圳市亚太兴实业有限公司 | Method for preparing CIGS (copper indium gallium selenide) film through selenylation at low temperature |
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2016
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CN101630701A (en) * | 2008-12-03 | 2010-01-20 | 山东建筑大学 | Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell |
CN102034898B (en) * | 2010-10-20 | 2012-03-28 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
CN102070184A (en) * | 2010-12-01 | 2011-05-25 | 同济大学 | Preparation method of CuInS2 nanoparticles |
CN103334081A (en) * | 2013-06-07 | 2013-10-02 | 深圳市亚太兴实业有限公司 | Method for preparing CIGS (copper indium gallium selenide) film through selenylation at low temperature |
Cited By (2)
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WO2019157562A1 (en) * | 2018-02-16 | 2019-08-22 | Newsouth Innovations Pty Limited | Adamantine semiconductor and uses thereof |
US11881536B2 (en) | 2018-02-16 | 2024-01-23 | Newsouth Innovations Pty Limited | Adamantine semiconductor and uses thereof |
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