CN107681009A - A kind of preparation method and applications of copper zinc tin sulfur selenium semiconductive thin film - Google Patents
A kind of preparation method and applications of copper zinc tin sulfur selenium semiconductive thin film Download PDFInfo
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- CN107681009A CN107681009A CN201710742083.5A CN201710742083A CN107681009A CN 107681009 A CN107681009 A CN 107681009A CN 201710742083 A CN201710742083 A CN 201710742083A CN 107681009 A CN107681009 A CN 107681009A
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- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000010408 film Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 33
- 239000011669 selenium Substances 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 238000013019 agitation Methods 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 12
- 235000005074 zinc chloride Nutrition 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 4
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000012327 Ruthenium complex Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 3
- 235000011150 stannous chloride Nutrition 0.000 description 7
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000011649 selenium Nutrition 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWBFNUKTNRHYKJ-UHFFFAOYSA-N Br.CCCCCCCCCCCCCCCC Chemical compound Br.CCCCCCCCCCCCCCCC LWBFNUKTNRHYKJ-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- -1 energy gap 1.54eV Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- ZAPAMMDQEWCVAM-UHFFFAOYSA-N tin;hydrate Chemical compound O.[Sn] ZAPAMMDQEWCVAM-UHFFFAOYSA-N 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—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
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a kind of preparation method and applications of copper zinc tin sulfur selenium semiconductive thin film, are directly to prepare Cu in FTO glass substrates using solvent-thermal process technology2ZnSn(Sx,Se1‑x)4Semiconductive thin film, can be applied to thin-film solar cells absorbed layer and dye-sensitized cell to electrode.The thiocarbamide and the ratio of selenourea that the present invention is added by driving before the reaction in solution are different, realize the regulation and control to two kinds of element ratios of sulphur in CZTSSe films and selenium, so as to realize the regulation to the optical band gap of film, it is closer to the optimal band gap needed for solar cell, required equipment and preparation technology are simple, cost is cheap, can directly obtain thing mutually uniformly, the higher product of well-crystallized, purity.
Description
Technical field
The present invention relates to the preparation field of semiconductive thin film, more particularly to a kind of preparation of copper zinc tin sulfur selenium semiconductive thin film
Method and its application.
Background technology
The research of solar cell is significant to alleviating energy crisis and improving the ecological environment.In the past few decades
In, the thin-film solar cells based on cadmium antimonide and CIGS is developed rapidly, and has been achieved with being commercialized, but due to
Cd is poisonous, and In, Ga, Te are rare metal, causes the industrialization of its photovoltaic device to receive restriction.In the last few years, I-II-IV-
VI compound semiconductor copper zinc tin sulfur seleniums (Cu2ZnSn(Sx,Se1-x)4, abbreviation CZTSSe) film be considered as be expected to substitute copper
Indium gallium selenium (CuInxGa1-xSe2, abbreviation CIGS) and film, received much concern in new energy research field.CZTSSe has advantages below：
(1) have up to 10 in ultraviolet-visible optical band4cm-1Absorption coefficient, only need several microns of thick films i.e. absorbable most of
Sunshine；(2) direct band-gap semicondictor, can be by controlling S and Se ratio to realize that band gap is entered between 1.0eV-1.5eV
Row regulation and control, with solar cell needed for optimal energy gap approach；(3) it is environmentally friendly without toxic elements such as Cd；(4) institute
There are abundant reserves in the earth's crust containing element, cost is cheap.Based on above advantage, it is most potential that CZTSSe will turn into a new generation
Novel solar battery material, be adapted to efficient, green, the cheap solar cell of development.
The preparation method of CZTSSe films is divided into vacuum method and the major class of antivacuum method two.Vacuum method has thermal evaporation, magnetic control
Sputtering method etc., antivacuum method have electrochemical deposition method, chemical baths, solvent-thermal method, slurry method, sol-gel process, You Jirong
Liquid method and hydrazine solution method etc..Evaporation and sputtering require to carry out in high vacuum system, and cost is high and power consumption is big.With other sides
Method compares, and solvent-thermal process technology possesses the plurality of advantages that other methods can not possibly be provided simultaneously with, it not only technique it is simple, into
This is low, power consumption is small, and can realize the controllable growth of the film of nanostructured, can directly obtain thing mutually uniformly, crystallization it is good
Product good, purity is higher.The film of nanostructured advantageously reduces the reflection of light, strengthens the scattering of light so as to improve the suction of light
Receive, be advantageous to improve the efficiency of solar cell.Solvent-thermal process technology is commonly used for preparing nano-powder, then again powder
Material is prepared into slurry, and prepare film on substrate using the methods of spin coating, silk-screen printing is sintered again, and not only process is answered
It is miscellaneous, and directly limit the popularization and application of the technology.
The content of the invention
It is an object of the invention to overcome shortcoming present in prior art, there is provided a kind of preparation technology is simple, environment is friendly
Well, the preparation method for the copper zinc tin sulfur selenium semiconductive thin film that cost is low, band gap is controllable and is directly grown in FTO glass substrates.
The purpose of the present invention is achieved through the following technical solutions：
A kind of copper zinc tin sulfur selenium (chemical formula Cu2ZnSn(Sx,Se1-x)4) semiconductive thin film preparation method, be using molten
Agent thermal synthesis technology directly prepares Cu in FTO glass substrates2ZnSn(Sx,Se1-x)4Semiconductive thin film, comprise the steps：
(1) reaction precursor liquid is configured：With absolute ethyl alcohol (C2H5OH it is) solvent, cetyl ammonium bromide (C19H42BrN, letter
CTAB) it is referred to as surfactant, chlorination copper hydrate (CuCl2·2H2O it is) copper source, zinc chloride (ZnCl2) it is zinc source, protochloride
Tin hydrate (SnCl2·2H2O it is) tin source, thiocarbamide (CS (NH2)2) it is sulphur source, selenourea (CSe (NH2)2) it is selenium source, configuration reaction
Precursor liquid；
(2) after FTO glass cleanings, the conduction of FTO glass is put into the liner of autoclave down, then will be matched somebody with somebody
The reaction precursor liquid put is poured into autoclave liner, sealing autoclave, 200~220 DEG C of 20~24h of isothermal reaction,
Obtain the Cu being grown in FTO glass substrates2ZnSn(Sx,Se1-x)4Film.
In step (1), the dosage of chlorination copper hydrate is 1.5 molar parts, zinc chloride is 3 molar parts, stannous chloride hydration
Thing is 0.75 molar part, cetyl ammonium bromide is 0.375 molar part, thiocarbamide is 0~15 molar part, selenourea is 0~15 mole
Part, and total dosage of thiocarbamide and selenourea is 15 molar parts.
In step (1), copper chloride, zinc chloride, stannous chloride and hexadecane bromide are sequentially added in anhydrous ethanol solvent
Change ammonium, magnetic agitation is to being completely dissolved；Then thiocarbamide is added, continues stirring to being completely dissolved；It is eventually adding selenourea, magnetic agitation
To being completely dissolved, reaction precursor liquid is obtained.
In step (2), the FTO glass is the SnO for mixing F2Transparent conducting glass, its square resistance are 14 Ω/cm2, transmission
Rate is more than 90%.
In step (2), the cleaning is that FTO glass is sequentially placed into each ultrasound in acetone, absolute ethyl alcohol and deionized water
Clean 10~15min, drying.
In step (2), the conduction of FTO glass is put into the polytetrafluoroethyllining lining of autoclave down, and with gathering
The inwall of tetrafluoroethene liner forms 30~45° angle degree.
In step (2), after isothermal reaction terminates, FTO glass is taken out, cleans three with absolute ethyl alcohol and deionized water respectively
Time, then its 60 DEG C are dried in vacuo 4 hours, obtain the Cu being grown on FTO glass2ZnSn(Sx,Se1-x)4Film.
The Cu2ZnSn(Sx,Se1-x)4Semiconductive thin film, absorbed layer and dye sensitization applied to thin-film solar cells
Battery to electrode.
The Cu2ZnSn(Sx,Se1-x)4Semiconductor film applications are to use FTO when the absorbed layer of thin-film solar cells
Directly as the light anode of battery, Cu2ZnSn(Sx,Se1-x)4As the absorbed layer of hull cell, made immediately above in absorbed layer
Standby cushion, Window layer and back electrode, are prepared into Cu2ZnSn(Sx,Se1-x)4Thin-film solar cells.Cu2ZnSn(Sx,Se1-x)4
The characteristics of absorbed layer as hull cell is that the sunshine of incidence can be allowed to carry out multiple reflections, strengthens the utilization rate to light.
The Cu2ZnSn(Sx,Se1-x)4Semiconductor film applications are to be adsorbed with ruthenium when DSSC
(structural formula of N719 dyestuffs is (n-2Bu to complex N719 dyestuffs4N)2-cis-Ru(L1)2(NCS)2) TiO2Nanoporous is thin
Film is light anode, with the Cu being grown directly upon on FTO substrates2ZnSn(Sx,Se1-x)4Semiconductive thin film is to electrode, with KI/I2
Solution is electrolyte (KI/I2The solute of solution is 0.5mol/L KI+0.05mol/L I2, solvent is that percent by volume is 20%
Isopropanol and percent by volume are 80% acetonitrile), it is assembled into DSSC.With the CZTSSe films being prepared
Pt electrodes can be substituted, as in DSSC, effective reduction of cost of implementation, being advantageous to application of electrode
The development of industrialization.
The present invention has the following advantages that compared with prior art and effect：
(1) thiocarbamide and the ratio of selenourea that the present invention is added by driving before the reaction in solution are different, realize to CZTSSe
The regulation and control of two kinds of element ratios of sulphur and selenium, so as to realize the regulation to the optical band gap of film, are allowed to more connect in film
Optimal band gap needed for nearly solar cell.
(2) the CZTSSe films that are prepared of the present invention can substitute Pt electrodes, as to application of electrode in dye sensitization
In solar cell, effective reduction of cost of implementation, be advantageous to the development of industrialization.
(3) the CZTSSe films that the present invention grows on FTO glass can be directly used for preparing CZTSSe thin film solars electricity
Pond, i.e. FTO layers are as light anode, absorbed layers of the CZTSSe as hull cell, prepared on absorbed layer cushion, Window layer and
Back electrode, you can thin-film solar cells is prepared.
(4) equipment needed for and preparation technology is simple, cost is cheap, can directly obtain thing mutually uniformly, well-crystallized, purity compared with
High product.
Brief description of the drawings
Fig. 1 is the SEM pictures of CZTSSe films prepared by embodiment 1.
Fig. 2 is the SEM pictures of CZTSSe films prepared by embodiment 3.
Fig. 3 is the SEM pictures of CZTSe films prepared by embodiment 4.
Fig. 4 is the Raman spectrum of CZTSSe films prepared by embodiment 2.
Fig. 5 is the EDS figures of CZTSSe films prepared by embodiment 2.
Fig. 6 is the absorption spectrum of CZTSSe films prepared by embodiment 1.
Embodiment
Further detailed description is done to the present invention with reference to embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
Sequentially added in 60ml ethanol solutions 1.5mmol copper chlorides, 3mmol zinc chloride, 0.75mmol stannous chlorides and
0.375mmol CTAB, magnetic agitation is to being completely dissolved；Then 7.5mmol thiocarbamides are added, magnetic agitation is to being completely dissolved；Finally
7.5mmol selenoureas are added, magnetic agitation obtains reaction precursor liquid to being completely dissolved.The FTO glass cleaned up is put into high pressure
In the polytetrafluoroethyllining lining of reactor, with wall into 30 ° of angles and conductive placed face down.By the above-mentioned reaction precursor liquid prepared
It is transferred in liner, seals kettle.Autoclave is put into high-temperature blast drying oven, 200 DEG C of reaction 24h.After reaction terminates, from
So cooling.Taking out deposition has the FTO glass of CZTSSe films, is cleaned three times with absolute ethyl alcohol and deionized water respectively, then by its
60 DEG C of vacuum drying obtain CZTSSe semiconductive thin films in 4 hours.
CZTSSe films are made up of spheric granules of uniform size, and spheric granules surface is very uniform and smooth, and its SEM picture is such as
Shown in Fig. 1, Fig. 6 is the absorption spectrum of CZTSSe films.Film energy gap 1.47eV, film mainly have custerite structure
CZTSSe is formed, but contains a small amount of impurities phase.
Embodiment 2
Sequentially added in 60ml ethanol solutions 1.5mmol copper chlorides, 3mmol zinc chloride, 0.75mmol stannous chlorides and
0.375mmolCTAB, magnetic agitation is to being completely dissolved；Then 12mmol thiocarbamides are added, magnetic agitation is to being completely dissolved；Finally plus
Enter 3mmol selenoureas, magnetic agitation obtains reaction precursor liquid to being completely dissolved.The FTO glass cleaned up is put into reaction under high pressure
In the polytetrafluoroethyllining lining of kettle, with wall into 35 ° of angles and conductive placed face down.The above-mentioned reaction precursor liquid prepared is shifted
Into liner, kettle is sealed.Autoclave is put into high-temperature blast drying oven, 210 DEG C of reaction 22h.It is naturally cold after reaction terminates
But.Taking out deposition has the FTO glass of CZTSSe films, is cleaned three times with absolute ethyl alcohol and deionized water respectively, then by its 60 DEG C
Vacuum drying obtains CZTSSe semiconductive thin films in 4 hours.The pattern of CZTSSe films is similar to the film shape that embodiment 1 grows
Looks.Fig. 4 is the Raman spectrum of CZTSSe films, and Fig. 5 is that the EDS of CZTSSe films schemes.Film is mainly by average diameter 250nm's
Spherical particle forms, and be evenly distributed densification, energy gap 1.51eV, the atomic ratio S/ (S+Se)=0.69 in film.
Embodiment 3
Sequentially added in 60ml ethanol solutions 1.5mmol copper chlorides, 3mmol zinc chloride, 0.75mmol stannous chlorides and
0.375mmol CTAB, magnetic agitation is to being completely dissolved；Then 3mmol thiocarbamides are added, magnetic agitation is to being completely dissolved；Finally plus
Enter 12mmol selenoureas, magnetic agitation obtains reaction precursor liquid to being completely dissolved.It is anti-that the FTO glass cleaned up is put into high pressure
In the polytetrafluoroethyllining lining for answering kettle, with wall into about 40 ° of angles and conductive placed face down.By the above-mentioned reaction precursor prepared
Liquid is transferred in liner, seals kettle.Autoclave is put into high-temperature blast drying oven, 200 DEG C of reaction 24h.After reaction terminates,
Natural cooling.Taking out deposition has the FTO glass of CZTSSe films, is cleaned three times with absolute ethyl alcohol and deionized water respectively, then will
Its 60 DEG C vacuum drying obtain CZTSSe semiconductive thin films in 4 hours.
CZTSSe films are made up of spheric granules of uniform size, but spheric granules surface is to be by many thickness
10-20nm nanometer scraps of paper composition, its SEM picture are as shown in Figure 2.Energy gap 1.43eV, the atomic ratio S/ (S+Se) in film
=0.18.
Embodiment 4
Sequentially added in 60ml ethanol solutions 1.5mmol copper chlorides, 3mmol zinc chloride, 0.75mmol stannous chlorides and
0.375mmolCTAB, magnetic agitation is to being completely dissolved；Then 15mmol selenoureas are added, magnetic agitation obtains anti-to being completely dissolved
Answer precursor liquid.The FTO glass cleaned up is put into the polytetrafluoroethyllining lining of autoclave, with wall into 30 ° of angles and
Conductive placed face down.The above-mentioned reaction precursor liquid prepared is transferred in liner, seals kettle.Put autoclave into high temperature drum
In wind drying box, 210 DEG C of reaction 20h.After reaction terminates, natural cooling.Taking out deposition has the FTO glass of CZTSe films, respectively
Cleaned three times with absolute ethyl alcohol and deionized water, then its 60 DEG C vacuum drying are obtained into CZTSe semiconductive thin films in 4 hours.
CZTSe films are directly laid on FTO substrates by the substantial amounts of nanometer scraps of paper and formed, and these nanometer sheets are mutually connected
Connect to form network structure, its SEM picture is as shown in Figure 3.Energy gap 1.38eV, in precursor liquid without plus thiocarbamide, so film is
CZTSe films, there is custerite structure, be practically free of impurities phase.
Embodiment 5
Sequentially added in 60ml ethanol solutions 1.5mmol copper chlorides, 3mmol zinc chloride, 0.75mmol stannous chlorides and
0.375mmolCTAB, magnetic agitation is to being completely dissolved；Then 15mmol thiocarbamides are added, magnetic agitation obtains anti-to being completely dissolved
Answer precursor liquid.The FTO glass cleaned up is put into the polytetrafluoroethyllining lining of autoclave, with wall into 35 ° of angles and
Conductive placed face down.The above-mentioned reaction precursor liquid prepared is transferred in liner, seals kettle.Put autoclave into high temperature drum
In wind drying box, 220 DEG C of reaction 22h.After reaction terminates, natural cooling.Taking out deposition has the FTO glass of CZTS films, respectively
Cleaned three times with absolute ethyl alcohol and deionized water, then its 60 DEG C vacuum drying are obtained into CZTS semiconductive thin films in 4 hours.
CZTS films are made up of substantial amounts of average diameter 300nm spheric granules, energy gap 1.54eV, precursor liquid
In without plus selenourea, so film be CZTS films, there is custerite structure, be practically free of impurities phase.
Claims (10)
- A kind of 1. preparation method of copper zinc tin sulfur selenium semiconductive thin film, it is characterised in that：It is direct using solvent-thermal process technology Cu is prepared in FTO glass substrates2ZnSn(Sx,Se1-x)4Semiconductive thin film, comprise the steps：(1) reaction precursor liquid is configured：Using absolute ethyl alcohol as solvent, cetyl ammonium bromide is surfactant, and copper chloride is hydrated Thing is copper source, and zinc chloride is zinc source, and stannous chloride hydrate is tin source, and thiocarbamide is sulphur source, and selenourea is selenium source, configures reaction precursor Liquid；(2) after FTO glass cleanings, the conduction of FTO glass is put into the polytetrafluoroethyllining lining of autoclave down, so The reaction precursor liquid of configuration is poured into autoclave liner afterwards, seals autoclave, 200~220 DEG C of isothermal reactions 20 ~24h, obtain the Cu being grown in FTO glass substrates2ZnSn(Sx,Se1-x)4Film.
- 2. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (1), The dosage of chlorination copper hydrate is 1.5 molar parts, zinc chloride is 3 molar parts, stannous chloride hydrate is 0.75 molar part, 16 Alkyl bromination ammonium is 0.375 molar part, thiocarbamide is 0~15 molar part, selenourea is 0~15 molar part, and thiocarbamide and selenourea is total Dosage is 15 molar parts.
- 3. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (1), Chlorination copper hydrate, zinc chloride, stannous chloride hydrate and cetyl ammonium bromide, magnetic are sequentially added in anhydrous ethanol solvent Power is stirred to being completely dissolved；Then thiocarbamide is added, continues stirring to being completely dissolved；It is eventually adding selenourea, magnetic agitation is to complete Dissolving, obtains reaction precursor liquid.
- 4. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (2), The FTO glass is the SnO for mixing F2Transparent conducting glass, its square resistance are 14 Ω/cm2, transmissivity is more than 90%.
- 5. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (2), The cleaning is that FTO glass is sequentially placed into acetone, absolute ethyl alcohol and deionized water into 10~15min of each ultrasonic cleaning, drying.
- 6. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (2), FTO glass conduction be put into down in the polytetrafluoroethyllining lining of autoclave, and with the inwall of polytetrafluoroethyllining lining Form 30~45° angle degree.
- 7. the preparation method of copper zinc tin sulfur selenium semiconductive thin film according to claim 1, it is characterised in that：In step (2), After isothermal reaction terminates, FTO glass is taken out, cleaned respectively with absolute ethyl alcohol and deionized water, then be dried in vacuo, grown Cu on FTO glass2ZnSn(Sx,Se1-x)4Film.
- 8. the purposes for the copper zinc tin sulfur selenium semiconductive thin film that a kind of any one of claim 1~7 is prepared, its feature exist In：Cu2ZnSn(Sx,Se1-x)4Semiconductive thin film can be applied to the absorbed layer and dye-sensitized cell of thin-film solar cells To electrode.
- 9. the purposes of copper zinc tin sulfur selenium semiconductive thin film according to claim 8, it is characterised in that：The Cu2ZnSn(Sx, Se1-x)4Semiconductor film applications are the light anodes with FTO directly as battery when the absorbed layer of thin-film solar cells, Cu2ZnSn(Sx,Se1-x)4As the absorbed layer of hull cell, cushion, Window layer and back of the body electricity are prepared immediately above in absorbed layer Pole, it is prepared into Cu2ZnSn(Sx,Se1-x)4Thin-film solar cells.
- 10. the purposes of copper zinc tin sulfur selenium semiconductive thin film according to claim 8, it is characterised in that：The Cu2ZnSn (Sx,Se1-x)4Semiconductor film applications are that will be adsorbed with ruthenium complex N719 dyestuffs when DSSC TiO2Nano-porous film is light anode, with the Cu being grown directly upon on FTO substrates2ZnSn(Sx,Se1-x)4Semiconductive thin film is To electrode, with KI/I2Solution is electrolyte, is assembled into DSSC.
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