CN104393096A - Preparation method of copper zinc tin sulfur selenium (CZTSSe) thin film material with controllable band gap - Google Patents
Preparation method of copper zinc tin sulfur selenium (CZTSSe) thin film material with controllable band gap Download PDFInfo
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- CN104393096A CN104393096A CN201410514152.3A CN201410514152A CN104393096A CN 104393096 A CN104393096 A CN 104393096A CN 201410514152 A CN201410514152 A CN 201410514152A CN 104393096 A CN104393096 A CN 104393096A
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- 239000000463 material Substances 0.000 title claims abstract description 97
- 239000010409 thin film Substances 0.000 title claims abstract description 71
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 75
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011669 selenium Substances 0.000 claims abstract description 50
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910001370 Se alloy Inorganic materials 0.000 claims abstract description 19
- VSKWIQRKBCVBAG-UHFFFAOYSA-N [Cu].[Zn].[Se] Chemical compound [Cu].[Zn].[Se] VSKWIQRKBCVBAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims description 77
- 238000000137 annealing Methods 0.000 claims description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 210000001142 back Anatomy 0.000 claims description 35
- 239000005864 Sulphur Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 32
- 238000000151 deposition Methods 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 238000004544 sputter deposition Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- 239000010408 film Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 229910052743 krypton Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000005987 sulfurization reaction Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 229910000058 selane Inorganic materials 0.000 description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 19
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 9
- 239000011135 tin Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000846 In alloy Inorganic materials 0.000 description 4
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 sulfo- Chemical class 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of a copper zinc tin sulfur selenium (CZTSSe) thin film material with a controllable band gap. The method comprises the following steps: preparing a copper zinc selenium alloy prefabricated layer on a substrate with a back electrode deposited thereon; and performing thermal processing on the copper zinc selenium alloy prefabricated layer in an inert atmosphere environment with a sulfur source and a selenium source to obtain the CZTSSe thin film material. By employing the scheme provided by the invention, a method of synchronizing sulfuration and selenium is adopted, the material uniformity is good, the element ingredients of the CZTSSe thin film material can be accurately controlled, and the band gap is adjustable. Therefore, the preparation method provided by the invention has a quite high market application value.
Description
Technical field
The present invention relates to copper-zinc-tin-sulfur selenium photovoltaic material, in particular, the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap (BandGap) is controlled.
Background technology
Along with the development of economic society, the mankind are more and more many to the demand of the energy, and traditional energy in the foreseeable time by approach exhaustion, this impels people to find regenerative resource.Solar energy is a kind of clean, free of contamination regenerative resource, nexhaustible.Solar energy is converted into electric energy by solar cell, has advantages such as utilizing convenience, clean and effective.Therefore, how to utilize solar energy preferably, be subject to the attention of countries in the world.
In recent years, the advantage that Copper Indium Gallium Selenide (CIGS) thin-film solar cells has due to it is studied widely.But In and Ga element is all rare element, and on the earth, reserves are limited, be unfavorable for its extensive use.Copper-zinc-tin-sulfur (CZTS) material is a kind of emerging thin-film solar cells material, has custerite structure.CZTS is I
2-II-IV-VI
4race's p-type semiconductor material, it, with the gallium in tin and zinc replacement Copper Indium Gallium Selenide and indium, is formed for selenium with sulfo-, and CIGS structural similarity.Cu, Zn, Sn and S element in CZTS is nontoxic at occurring in nature rich content, wherein: Cu is 50 × 10
-6, Zn is 75 × 10
-6, Sn is 2.2 × 10
-6, S is 260 × 10
-6, and the content of indium and selenium is only 0.05 × 10
-6or it is less.Its energy gap is 1.4-1.6eV, and the best energy gap 1.5eV expected with solar cell ten points is close, and CZTS is direct gap semiconductor material, high to the absorption coefficient of sunlight, absorption coefficient >10
4cm
-1, theoretical conversion efficiencies reaches 32.2%, and this makes it become potential novel thin film solar cell material.
Copper-zinc-tin-selenium (CZTSe) material is the photoelectric material that the S element in selenium element substitution CZTS is prepared, and energy gap is at about 1eV.The preparation method of CZTS and CZTSe thin-film material is mainly divided into vacuum technology and adopting non-vacuum process two class.Vacuum technology has evaporation, sputtering method and pulsed laser deposition etc., and adopting non-vacuum process comprises the method such as electrochemical deposition and Hydrothermal Synthesis.If replace S element with part selenium element, copper zinc tin sulfur selenium Cu can be obtained
2znSn (S, Se)
4photoelectric material, i.e. CZTSSe material.Contrast CZTS, CZTSe and CZTSSe tri-kinds of materials are known, and the crystallite dimension of CZTS is minimum, and condition prepared by material is the harshest.And the crystallite dimension of CZTSe is maximum, preparation condition is comparatively easy.Along with the change of Se content in material, the energy gap of CZTSSe material is adjustable within the scope of 1-1.5eV, is conducive to preparing the photoelectric absorption layer material be applicable under varying environment condition.The simultaneously increase of Se content in system, is conducive to the raising of material photoelectric conversion efficiency, has great importance to the photo absorption performance of photovoltaic cell.
But how improving the preparation method of CZTSSe material, is the technical issues that need to address.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the controlled copper zinc tin sulfur selenium thin-film material of a kind of new energy gap.
Technical scheme of the present invention is as follows: the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap is controlled, and it comprises the following steps: clean substrate, deposits dorsum electrode layer from the teeth outwards; The substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Described Jackson's alloy preformed layer is put in annealing furnace, heat-treats, obtain copper zinc tin sulfur selenium thin-film material under the inert ambient environment with sulphur source and selenium source.
In order to solve the technical problem how obtaining better deposition effect, preferably, described substrate comprises glass substrate.
In order to solve the technical problem how obtaining better deposition effect, preferably, describedly cleaning is carried out to substrate comprise the following steps: in running water, acetone, isopropyl alcohol, use absolute ethyl alcohol to rinse after ultrasonic process successively substrate.Like this, more preferably deposition effect can be reached.
In order to solve the technical problem how obtaining better deposition effect, preferably, the dorsum electrode layer on described substrate comprises metal molybdenum layer.
In order to solve the technical problem how to deposit, preferably, described in deposit the substrate of dorsum electrode layer, realized by following steps: adopt the mode of magnetron sputtering to deposit at least layer of metal molybdenum film over the substrate.Like this, more preferably deposition effect can be reached.
In order to solve the technical problem how to deposit, preferably, in described magnetron sputtering, in alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10-4Pa, and sputter gas is high-purity argon gas, air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.2A.Like this, more preferably deposition effect can be reached.
In order to solve the technical problem how preparing copper zinc selenium alloy preformed layer, preferably, adopt evaporation, sputtering method, pulsed deposition method, electrodeposition process or hydrothermal synthesis method, the substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer.Like this, copper zinc selenium alloy preformed layer can be prepared on the substrate depositing dorsum electrode layer.
In order to solve how heat treated technical problem, preferably, described inert atmosphere comprises neon, argon, nitrogen and/or krypton.Like this, be conducive to forming copper zinc tin sulfur selenium thin-film material.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, the pressure of the inert ambient environment in annealing furnace is 0.1 to 10 atmospheric pressure, and the reaction time is 0.1 to 4 hour, and annealing temperature is 300 to 700 DEG C.Like this, be conducive to forming copper zinc tin sulfur selenium thin-film material.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, described preparation method comprises the following steps: clean substrate, deposits dorsum electrode layer from the teeth outwards; The substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Described Jackson's alloy preformed layer is put in annealing furnace, passes into inert gas, element sulphur gaseous compound and selenium element gaseous compound and form inert ambient environment after vacuumizing; Wherein, the pressure of the inert ambient environment in annealing furnace is 0.1 to 10 atmospheric pressure, and the reaction time is 0.1 to 4 hour, and annealing temperature is 300 to 700 DEG C; The volume fraction of element sulphur gaseous compound is 0.01% to 80%, and the volume fraction of selenium element gaseous compound is 0.01% to 80%.Like this, be conducive to preparing copper zinc tin sulfur selenium thin-film material better.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, the volume fraction of element sulphur gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; The volume fraction of selenium element gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; Pressure is 0.01 to 1 atmospheric pressure, and annealing temperature is 400 to 600 DEG C.Like this, be conducive to preparing copper zinc tin sulfur selenium thin-film material better.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, the volume fraction of element sulphur gaseous compound is 0.01% to 30%; The volume fraction of selenium element gaseous compound is 0.01% to 30%, and pressure is 0.5 to 1 atmospheric pressure, and the reaction time is 0.1 to 2 hour, and annealing temperature is 400 to 600 DEG C.Like this, be conducive to preparing copper zinc tin sulfur selenium thin-film material better.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, annealing pan vulcanization and selenizing time are 0.1 to 4 hour, are preferably 0.01 to 2 hour.Like this, be conducive to preparing copper zinc tin sulfur selenium thin-film material better.
In order to solve the technical problem preparing copper zinc tin sulfur selenium thin-film material how better, preferably, described preparation method is further comprising the steps of: the volume ratio being regulated inert gas, element sulphur gaseous compound and selenium element gaseous compound by gas flowmeter.Like this, be conducive to preparing copper zinc tin sulfur selenium thin-film material better.
Adopt such scheme, the present invention adopts synchronic curing, selenizing method, technological process is simple, material homogeneity is good, the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls, prepare the copper zinc tin sulfur selenium thin-film material that energy gap is adjustable, thus effectively control the energy gap of copper zinc tin sulfur selenium thin-film material, there is very high market using value.
Each scheme of the present invention, also achieve and prepare copper zinc selenium alloy preformed layer on the substrate depositing dorsum electrode layer, and, heat-treat in an inert atmosphere and be conducive to forming copper zinc tin sulfur selenium thin-film material, also optimize the preparation method of copper zinc tin sulfur selenium thin-film material, prepare the copper zinc tin sulfur selenium thin-film material that energy gap is controlled better.
Accompanying drawing explanation
Fig. 1 is the annealing furnace structure schematic diagram of one embodiment of the present of invention;
Fig. 2 is the schematic flow sheet of one embodiment of the present of invention.
Embodiment
For the ease of understanding the present invention, below in conjunction with the drawings and specific embodiments, the present invention will be described in more detail.It should be noted that, when element is stated " being fixed on " another element, it can directly on another element or can there is one or more element placed in the middle therebetween.When an element is stated " connection " another element, it can be directly connected to another element or can there is one or more element placed in the middle therebetween.The term " vertical " that this specification uses, " level ", "left", "right" and similar statement are just for illustrative purposes.
Unless otherwise defined, all technology of using of this specification and scientific terminology are identical with belonging to the implication that those skilled in the art of the present invention understand usually.The object of term used in the description of the invention in this specification just in order to describe specific embodiment is not for limiting the present invention.The term "and/or" that this specification uses comprises arbitrary and all combinations of one or more relevant Listed Items.
Embodiment 1
One embodiment of the present of invention are, the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap is controlled, and it comprises the following steps: clean substrate, deposits dorsum electrode layer from the teeth outwards; The substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Jackson's alloy preformed layer is heat-treated under the inert ambient environment with sulphur source and selenium source, obtains copper zinc tin sulfur selenium thin-film material; Such as, described Jackson's alloy preformed layer is put in annealing furnace, heat-treats under the inert ambient environment with sulphur source and selenium source.Like this, by the element sulphur in adjustment inert ambient environment and/or the content of selenium element, the copper zinc tin sulfur selenium thin-film material that the content that can obtain element sulphur and/or selenium element there are differences, thus the energy gap adjusting CZTSSe thin film photovoltaic material to a certain extent; Further, adopt hydrogen sulfide and hydrogen selenide to carry out synchronic curing and selenizing to Jackson's alloy preformed layer, material homogeneity is good.Preferably, described substrate comprises glass substrate.Preferably, the dorsum electrode layer on described substrate comprises metal molybdenum layer.Preferably, the pressure of the inert ambient environment in annealing furnace is 0.1 to 10 atmospheric pressure, and the reaction time is 0.1 to 4 hour, and annealing temperature is 300 to 700 DEG C.Preferably, the volume fraction of element sulphur gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; The volume fraction of selenium element gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; Pressure is 0.01 to 1 atmospheric pressure, and annealing temperature is 400 to 600 DEG C.Preferably, annealing pan vulcanization and selenizing time are 0.1 to 4 hour, are preferably 0.01 to 2 hour.Like this, adopt synchronic curing, selenizing method, can prepare the copper zinc tin sulfur selenium thin-film material that energy gap is controlled, technological process is simple, and material homogeneity is good.
Embodiment 2
Such as, first prepare Cu-Zn-Sn (CZT) alloy preformed layer in different ways, then CZT alloy preformed layer is carried out synchronic curing, selenizing obtains CZTSSe thin film photovoltaic material.Such as, described preparation method comprises the following steps: on the substrate depositing dorsum electrode layer, prepare copper zinc selenium alloy preformed layer; Jackson's alloy preformed layer is heat-treated under the inert ambient environment with hydrogen sulfide and hydrogen selenide, obtain copper zinc tin sulfur selenium thin-film material, adopt the inert ambient environment of hydrogen sulfide and hydrogen selenide, synchronic curing, selenizing, technological process is simple, material homogeneity is good, and the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls.
Embodiment 3
And for example, as shown in Figure 2, one embodiment of the present of invention are, the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap is controlled, and it comprises the following steps: clean substrate, deposits dorsum electrode layer from the teeth outwards; The substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Described Jackson's alloy preformed layer is put in annealing furnace, heat-treats under the inert ambient environment with sulphur source and selenium source; Such as, Jackson's alloy preformed layer is heat-treated under the inert ambient environment passing into inert gas, hydrogen sulfide gas and hydrogen selenide gas; And for example, heat-treat after carry out nature cooling.And for example, under inert ambient environment, carry out bring down a fever cooling or cooling naturally after heat-treating, then obtain copper zinc tin sulfur selenium thin-film material; Like this, optimize the preparation method of copper zinc tin sulfur selenium thin-film material, be conducive to preparing the controlled copper zinc tin sulfur selenium thin-film material of energy gap better.
Embodiment 4
Such as, described preparation method comprises the following steps: on the substrate depositing dorsum electrode layer, prepare copper zinc selenium alloy preformed layer; Jackson's alloy preformed layer is heat-treated under the inert ambient environment passing into inert gas, hydrogen sulfide gas and hydrogen selenide gas, obtains copper zinc tin sulfur selenium thin-film material under inert ambient environment after carrying out nature cooling.Like this, the content of hydrogen sulfide gas and hydrogen selenide gas can be adjusted flexibly, to adjust the sulphur Se content in copper zinc tin sulfur selenium thin-film material, thus effectively control the energy gap of last obtained copper zinc tin sulfur selenium thin-film material, further, the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls.
Embodiment 5
Preferably, before deposition dorsum electrode layer, also following steps are performed: substrate is cleaned.Such as, described preparation method comprises the following steps: clean substrate, then at deposited on substrates dorsum electrode layer, prepares copper zinc selenium alloy preformed layer afterwards on the substrate depositing dorsum electrode layer; Jackson's alloy preformed layer is heat-treated under the inert ambient environment with sulphur source and selenium source, obtains copper zinc tin sulfur selenium thin-film material.Preferably, described inert atmosphere comprises neon, argon and/or krypton, and such as, described inert atmosphere comprises neon, argon or krypton; And for example, described inert atmosphere comprises neon and argon; And for example, described inert atmosphere comprises argon and krypton etc., like this, heat-treats under inert ambient environment, effectively can control the energy gap of copper zinc tin sulfur selenium thin-film material.
Embodiment 6
Preferably, describedly cleaning is carried out to substrate comprise the following steps: in running water, acetone, isopropyl alcohol, use absolute ethyl alcohol to rinse after ultrasonic process successively substrate, like this, good cleaning performance can be obtained, be conducive to the deposition of dorsum electrode layer.
Embodiment 7
And for example, the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap is controlled, it comprises the following steps: on the substrate depositing dorsum electrode layer, prepare copper zinc selenium alloy preformed layer; Preferably, adopt evaporation, sputtering method, pulsed deposition method, electrodeposition process or hydrothermal synthesis method, the substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Jackson's alloy preformed layer is heat-treated under the inert ambient environment passing into inert gas, hydrogen sulfide gas and hydrogen selenide gas; Copper zinc tin sulfur selenium thin-film material is obtained after cooling; Like this, the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls, and prepares the copper zinc tin sulfur selenium thin-film material that energy gap is adjustable.
Embodiment 8
Preferably, described in deposit the substrate of dorsum electrode layer, realized by following steps: adopt the mode of magnetron sputtering to deposit at least layer of metal molybdenum film over the substrate.Preferably, in described magnetron sputtering, in alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10-4Pa, and sputter gas is high-purity argon gas, and air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.2A.Such as, in described high-purity argon gas, purity of argon >99.999%, nitrogen content <5ppm, oxygen content <2ppm, hydrogen content <1ppm, total carbon content (with methanometer) <2ppm, moisture <4ppm; Like this, the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls, and prepares the copper zinc tin sulfur selenium thin-film material that energy gap is adjustable.
Embodiment 9
Preferably, described preparation method comprises the following steps: clean substrate, deposits dorsum electrode layer from the teeth outwards; The substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer; Described Jackson's alloy preformed layer is put in annealing furnace, passes into inert gas, element sulphur gaseous compound and selenium element gaseous compound and form inert ambient environment after vacuumizing; Wherein, the pressure of the inert ambient environment in annealing furnace is 0.1 to 10 atmospheric pressure, and the reaction time is 0.1 to 4 hour, and annealing temperature is 300 to 700 DEG C; The volume fraction of element sulphur gaseous compound is 0.01% to 80%, and the volume fraction of selenium element gaseous compound is 0.01% to 80%.Preferably, the volume fraction of element sulphur gaseous compound is 0.01% to 30%; The volume fraction of selenium element gaseous compound is 0.01% to 30%, and pressure is 0.01 to 1 atmospheric pressure, and annealing temperature is 400 to 600 DEG C.Preferably, pressure is 0.5 to 1 atmospheric pressure, and the reaction time is 0.1 to 2 hour, and annealing temperature is 400 to 600 DEG C.Like this, by controlling the volume fraction of the gas of element sulphur gaseous compound and selenium element gaseous compound in inert atmosphere, both volume ratio i.e., the mixed ratio of element sulphur and selenium element in copper zinc tin sulfur selenium material can be controlled preferably, prepare the copper-zinc-tin-sulfur selenium photovoltaic material of different energy gap, easy and simple to handle, technique is simple.
Embodiment 10
Preferably, described preparation method is further comprising the steps of: the volume ratio being regulated inert gas, element sulphur gaseous compound and selenium element gaseous compound by gas flowmeter.Preferably, first pass into inert gas, after pressure reaches 0.5 atmospheric pressure, then pass into element sulphur and selenium element from below, preferably, more slowly pass into element sulphur and selenium element from below; Such as pass into hydrogen sulfide gas and hydrogen selenide gas from below.Preferably, element sulphur gaseous compound is hydrogen sulfide gas, selenium element gaseous compound is hydrogen selenide gas, like this, by controlling the volume fraction of the gas of hydrogen sulfide and hydrogen selenide in inert atmosphere, both volume ratio i.e., can control the mixed ratio of element sulphur and selenium element in copper zinc tin sulfur selenium material preferably, prepare the copper-zinc-tin-sulfur selenium photovoltaic material of different energy gap.
Embodiment 11
Preferably, input hydrogen sulfide gas and hydrogen selenide gas simultaneously, enter in described annealing furnace after mixed.Preferably, input hydrogen sulfide gas and hydrogen selenide gas from two inputs respectively, that is, an input input hydrogen sulfide gas, another input input hydrogen selenide gas simultaneously; Preferably, the hydrogen sulfide gas simultaneously inputted from two inputs respectively and hydrogen selenide gas through a mixed district, and then enter and pass in the annealing furnace of inert gas; Like this, be easy to the consumption controlling sulphur and selenium, thus the elemental constituent realizing copper zinc tin sulfur selenium thin-film material accurately controls.
Embodiment 12
As shown in Figure 1, hydrogen sulfide gas, hydrogen selenide gas and argon gas enter in the annealing furnace being placed with copper zinc selenium alloy preformed layer behind a mixed district, annealing furnace outer setting heater strip, for regulating and controlling the temperature of annealing furnace, mixed gas by sodium hydroxide solution, disengage after charcoal absorption or reclaim.Such as, the flow-rate ratio of element sulphur gaseous compound, selenium element gaseous compound and inert gas is (0.01 to 2): (0.01 to 2): (3 to 8), and namely in inert ambient environment, the volume ratio of element sulphur gaseous compound, selenium element gaseous compound and inert gas is (0.01 to 2): (0.01 to 2): (3 to 8); Such as, H
2s:H
2the flow-rate ratio of Se:Ar gas is (0.01 to 2): (0.01 to 2): (3 to 8), and for example, and H
2s:H
2the volume ratio of Se:Ar gas is 1:1.1:3.5; Like this, be easy to the consumption controlling sulphur and selenium, thus the elemental constituent realizing copper zinc tin sulfur selenium thin-film material accurately controls.
Embodiment 13
And for example, the preparation method of the copper zinc tin sulfur selenium thin-film material that a kind of energy gap is controlled, it comprises the following steps.
(1) substrate depositing metallic back electrode layer is prepared; Substrate is cleaned, plates one deck dorsum electrode layer from the teeth outwards or at least one deck dorsum electrode layer is set.Wherein, described substrate including, but not limited to glass substrate, such as, at the bottom of plastic, stainless steel lining or PET substrate etc.Dorsum electrode layer on substrate including, but not limited to metal molybdenum (Mo) layer, such as nickel or gold etc.
(2) on the substrate depositing dorsum electrode layer, Jackson's alloy preformed layer is prepared in different ways; Such as, the substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer, the method selected is the one in evaporation, sputtering method, pulsed deposition method, electrodeposition process, hydrothermal synthesis method.
(3) carry out sulfuration and selenization under Jackson's alloy preformed layer being placed in inert atmosphere, hydrogen sulfide and hydrogen selenide environment, after cooling, obtain copper zinc tin sulfur selenium thin-film material.Annealing furnace is heat-treated under inert ambient environment, preferred Ar or Kr atmosphere, and the inert atmosphere pressure in stove is 0-10 atmospheric pressure; Such as, the inert atmosphere pressure in stove is 0.1 to 10 atmospheric pressure, is preferably 0.5 to 1 atmospheric pressure.
(4) after Jackson's alloy preformed layer is put in annealing furnace, vacuumize, pass into inert gas and hydrogen sulfide and hydrogen selenide gas subsequently.The volume ratio of three is regulated by gas flowmeter.Annealing furnace adopts certain lifting/lowering temperature system to run.Such as, annealing furnace adopts each degree Celsius to carry out the operation of lifting/lowering temperature system; And for example, annealing furnace adopts every five degrees Celsius to carry out the operation of lifting/lowering temperature system.Such as, sulphur source used is hydrogen sulfide gas, and in annealing furnace, under inert ambient environment, the volume fraction of hydrogen sulfide is 0-80%, preferably, 0.01% to 80%, be preferably 0.01-30%; The present invention's selenium source used is hydrogen selenide gas, and in annealing furnace, under inert ambient environment, the volume fraction of hydrogen selenide is 0-80%, preferably, 0.01% to 80%, be preferably 0.01-30%; Preferably, the gas volume fractions of pan vulcanization hydrogen, hydrogen selenide and argon gas is controlled by adjusting gas flow meter; Like this, can the energy gap of control and regulation end product easily.
Embodiment 14
And for example, in above-described embodiment, the annealing range that annealing furnace is selected is 300-700 DEG C, and such as, 300 DEG C, 320 DEG C, 370 DEG C, 410 DEG C, 502 DEG C, 547 DEG C, 586 DEG C, 600 DEG C, 670 DEG C or 700 DEG C etc., be preferably 400-600 DEG C; Annealing pan vulcanization and selenizing time are 0.1-4h, such as, and 0.1 hour, 0.3 hour, 0.5 hour, 0.8 hour, 1.1 hours, 1.8 hours, 2.7 hours, 3.6 hours or 4 hours etc.; Be preferably 0.5-2h; Like this, the energy gap scope of prepared copper zinc tin sulfur selenium thin-film material is 0.9-1.6eV, and can adjust flexibly along with the relative usage of sulphur and selenium.
Various embodiments of the present invention provide a kind of preparation method of different energy gap CZTSSe photoelectric material respectively.The method technique is simple, and element chemistry metering is more convenient than controlling, and with low cost, the material homogeneity of preparation is good.Continue to provide concrete example below to be again described.
Embodiment 15
Select soda-lime glass as glass substrate, substrate is ultrasonic in running water, acetone, isopropyl alcohol successively, use absolute ethyl alcohol to rinse.
Adopt the mode of magnetron sputtering on substrate, plate the thick metal M o film of one deck 600nm, sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and sputtering voltage is 320V, and electric current is 0.5A.
On plating molybdenum substrate, magnetron sputtering is adopted to prepare CZT alloy preformed layer.In alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.2A.
Alloy-layer previous step prepared is put in annealing furnace, vacuumizes, and then passing into gas to stove internal gas pressure is 1 atmospheric pressure.H
2s:H
2the flow-rate ratio of Se:Ar gas is 1:1:3.Be warmed up to 550 DEG C of insulation 30min with the heating rate of 20 DEG C/min, be then cooled to normal temperature with the rate of temperature fall of 20 DEG C/min.The energy gap of the copper zinc tin sulfur selenium thin-film material prepared by this embodiment is 1.1-1.4eV.
Embodiment 16
Select soda-lime glass as glass substrate, substrate is ultrasonic in running water, acetone, isopropyl alcohol successively, use absolute ethyl alcohol to rinse.
Adopt the mode of magnetron sputtering on substrate, plate the thick metal M o film of one deck 800nm, sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and sputtering voltage is 320V, and electric current is 0.5A.
On plating molybdenum substrate, magnetron sputtering is adopted to prepare CZT alloy preformed layer.In alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10
-4pa, sputter gas is high-purity argon gas, and air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.2A.
Alloy-layer previous step prepared is put in annealing furnace, vacuumizes, and then passing into gas to stove internal gas pressure is 0.8 atmospheric pressure.H
2s:H
2the flow-rate ratio of Se:Ar gas is 1:0.01:4.Be warmed up to 500 DEG C of insulation 30min with the heating rate of 40 DEG C/min, be then cooled to normal temperature with the rate of temperature fall of 10 DEG C/min.The energy gap of copper zinc tin sulfur selenium thin-film material prepared by this embodiment is 1.4-1.6eV.
Embodiment 17
Select soda-lime glass as glass substrate, substrate is ultrasonic in running water, acetone, isopropyl alcohol successively, use absolute ethyl alcohol to rinse.
Adopt the mode of magnetron sputtering on substrate, plate the thick metal M o film of one deck 600nm, sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and sputtering voltage is 320V, and electric current is 0.5A.
On plating molybdenum substrate, magnetron sputtering is adopted to prepare CZT alloy preformed layer.In alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.2A.
Alloy-layer previous step prepared is put in annealing furnace, vacuumizes, and then passing into gas to stove internal gas pressure is 1 atmospheric pressure.H
2s:H
2the flow-rate ratio of Se:Ar gas is 0.01:1:4.Be warmed up to 550 DEG C of insulation 30min with the heating rate of 20 DEG C/min, be then cooled to normal temperature with the rate of temperature fall of 10 DEG C/min.The energy gap of copper zinc tin sulfur selenium thin-film material prepared by this embodiment is 0.9-1.1eV.
Embodiment 18
Select soda-lime glass as glass substrate, substrate is ultrasonic in running water, acetone, isopropyl alcohol successively, use absolute ethyl alcohol to rinse.
Adopt the mode of magnetron sputtering on substrate, plate the thick metal M o film of one deck 600nm, sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and sputtering voltage is 320V, and electric current is 0.5A.
On plating molybdenum substrate, magnetron sputtering is adopted to prepare CZT alloy preformed layer.In alloys target, the ratio of Cu, Zn, Sn element is 2:1:1, and sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and air pressure is 0.5Pa, and voltage is 150V, and electric current is 0.5A.
Alloy-layer previous step prepared is put in annealing furnace, vacuumizes, and then passing into gas to stove internal gas pressure is 0.8 atmospheric pressure.H
2s:H
2the flow-rate ratio of Se:Ar gas is 1:2:7.Be warmed up to 500 DEG C of insulation 1h with the heating rate of 40 DEG C/min, be then cooled to normal temperature with the rate of temperature fall of 40 DEG C/min.The energy gap of copper zinc tin sulfur selenium thin-film material prepared by this embodiment is 1.1-1.3eV.
Embodiment 19
Select soda-lime glass as glass substrate, substrate is strictly cleaned.Adopt the mode of magnetron sputtering on substrate, plate the thick metal M o film of one deck 600nm, sputtering vacuum degree is 1 × 10
-3pa, sputter gas is high-purity argon gas, and sputtering voltage is 320V, and electric current is 0.5A.
Electro-deposition CZT alloy preformed layer, electrolyte is chosen for the mixed liquor of copper sulphate, zinc sulfate, stannous sulfate and natrium citricum, goes out alloy-layer when magnetic agitation at Mo substrate substrates.Anneal alloy-layer under 300 DEG C of vacuum 30min.
Alloy-layer previous step prepared is put in annealing furnace, vacuumizes, and then passing into gas to stove internal gas pressure is 1 atmospheric pressure.H
2s:H
2the flow-rate ratio of Se:Ar gas is 1:1:3.Be warmed up to 550 DEG C of insulation 30min with the heating rate of 20 DEG C/min, be then cooled to normal temperature with the rate of temperature fall of 10 DEG C/min.The energy gap of copper zinc tin sulfur selenium thin-film material prepared by this embodiment is 1.1-1.4eV.
And for example, after tested, above-mentioned preparation method is adopted, adjustment H
2s:H
2the flow-rate ratio of Se:Ar gas, such as, flow-rate ratio is respectively 1:0.5:4,0.5:0.9:2,0.1:1:5,1:0.6:5,2:1.2:5,0.2:1.5:3,1.1:0.2:4,1:1:4,1:1.5:4 or 0.8:1.1:3 etc., the energy gap of prepared copper zinc tin sulfur selenium thin-film material is 0.9 to 1.6eV, and, adopt preparation method described in the various embodiments described above, corresponding energy gap can be determined in reasoning from logic or limited test, not repeat them here.
Further, embodiments of the invention also comprise, each technical characteristic of the various embodiments described above, and/or the various embodiments described above, the preparation method of the copper zinc tin sulfur selenium thin-film material that the energy gap be mutually combined to form is controlled, the method adopts synchronic curing, selenizing method, technological process is simple, material homogeneity is good, and the elemental constituent that can realize copper zinc tin sulfur selenium thin-film material accurately controls, and energy gap is adjustable.
It should be noted that, preferred embodiment of the present invention is given in specification of the present invention and accompanying drawing thereof, but, the present invention can be realized by many different forms, be not limited to the embodiment described by this specification, these embodiments not as the extra restriction to content of the present invention, provide the object of these embodiments be make the understanding of disclosure of the present invention more comprehensively thorough.Further, above-mentioned each technical characteristic continues combination mutually, is formed not in above-named various embodiment, is all considered as the scope that specification of the present invention is recorded; Further, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection range that all should belong to claims of the present invention.
Claims (10)
1. a preparation method for the copper zinc tin sulfur selenium thin-film material that energy gap is controlled, is characterized in that, comprising:
Substrate is cleaned, deposits dorsum electrode layer from the teeth outwards;
The substrate depositing dorsum electrode layer is prepared Jackson's alloy preformed layer;
Described Jackson's alloy preformed layer is put in annealing furnace, heat-treats, obtain copper zinc tin sulfur selenium thin-film material under the inert ambient environment with sulphur source and selenium source.
2. preparation method according to claim 1, it is characterized in that, described substrate comprises glass substrate.
3. preparation method according to claim 1, is characterized in that, describedly carries out cleaning to substrate and comprises the following steps: in running water, acetone, isopropyl alcohol, use absolute ethyl alcohol to rinse after ultrasonic process successively substrate.
4. preparation method according to claim 1, it is characterized in that, the dorsum electrode layer on described substrate comprises metal molybdenum layer.
5. preparation method according to claim 1, is characterized in that, described in deposit the substrate of dorsum electrode layer, realized by following steps: adopt the mode of magnetron sputtering to deposit at least layer of metal molybdenum film over the substrate.
6. preparation method according to claim 1, is characterized in that, adopts evaporation, sputtering method, pulsed deposition method, electrodeposition process or hydrothermal synthesis method, the substrate depositing dorsum electrode layer is prepared copper zinc selenium alloy preformed layer.
7. preparation method according to claim 1, it is characterized in that, described inert atmosphere comprises neon, argon and/or krypton.
8. preparation method according to claim 1, it is characterized in that, the pressure of the inert ambient environment in annealing furnace is 0.1 to 10 atmospheric pressure, and the reaction time is 0.1 to 4 hour, and annealing temperature is 300 to 700 DEG C.
9. preparation method according to claim 1, it is characterized in that, the volume fraction of element sulphur gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; The volume fraction of selenium element gaseous compound is 0.01% to 80%, is preferably 0.01% to 30%; Pressure is 0.01 to 1 atmospheric pressure, and annealing temperature is 400 to 600 DEG C; And/or annealing pan vulcanization and selenizing time are 0.1 to 4 hour, be preferably 0.01 to 2 hour.
10. preparation method according to claim 1, is characterized in that, further comprising the steps of: the volume ratio being regulated inert gas, element sulphur gaseous compound and selenium element gaseous compound by gas flowmeter.
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