CN111916527A - Semiconductor material vulcanization method - Google Patents
Semiconductor material vulcanization method Download PDFInfo
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- CN111916527A CN111916527A CN201910388289.1A CN201910388289A CN111916527A CN 111916527 A CN111916527 A CN 111916527A CN 201910388289 A CN201910388289 A CN 201910388289A CN 111916527 A CN111916527 A CN 111916527A
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- 238000004073 vulcanization Methods 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 76
- 239000004065 semiconductor Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 66
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 48
- 239000011593 sulfur Substances 0.000 claims abstract description 48
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000004575 stone Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- SEAVSGQBBULBCJ-UHFFFAOYSA-N [Sn]=S.[Cu] Chemical compound [Sn]=S.[Cu] SEAVSGQBBULBCJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000005486 sulfidation Methods 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 238000005987 sulfurization reaction Methods 0.000 abstract description 8
- 239000002210 silicon-based material Substances 0.000 abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 65
- 239000010409 thin film Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000411 transmission spectrum Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- PCRGAMCZHDYVOL-UHFFFAOYSA-N copper selanylidenetin zinc Chemical compound [Cu].[Zn].[Sn]=[Se] PCRGAMCZHDYVOL-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004089 microcirculation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a semiconductor material vulcanization method. The method provided by the invention comprises the following steps: and placing the sulfur source and the semiconductor material in an incompletely sealed container, and placing the incompletely sealed container in a reactor to be heated for carrying out a vulcanization reaction to obtain the vulcanized semiconductor material. The semiconductor material sulfurization method provided by the invention can enlarge the grain size of the semiconductor, thereby better crystallizing. It is also possible to strengthen the diffraction peak of a semiconductor that is a material of an absorption layer of a solar cell and to absorb more light. The vulcanization method provided by the invention is adopted to vulcanize the amorphous silicon solar absorption layer material, so that the band gap of the amorphous silicon solar absorption layer material is closer to the band gap of the silicon material. The method provided by the invention can anneal the processed semiconductor, is particularly suitable for the sulfurization annealing of the copper-zinc-tin-sulfur film, and has the advantages of simple device and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of material processing, relates to a material vulcanization method, and particularly relates to a semiconductor material vulcanization method.
Background
In the past decades, thin film solar cells using cadmium telluride (CdTe) and Copper Indium Gallium Selenide (CIGS) as light absorbing layer materials have been rapidly developed and have been commercially produced. The highest photoelectric conversion efficiency of the cadmium telluride thin-film solar cell in a laboratory at present reaches 22.1%, and the highest photoelectric conversion efficiency of the copper indium gallium selenide cell reaches 22.6%, which both exceed the efficiency of a polycrystalline silicon cell. The continuously increasing photoelectric conversion efficiency makes the compound thin film solar cell expected to compete with the crystalline silicon solar cell. However, the extreme toxicity of Cd and the resource scarcity of In, Ga and Te elements restrict the large-scale industrialization of photovoltaic devices based on the thin-film materials. Therefore, finding a safe and environment-friendly semiconductor material with abundant raw material reserves as a light absorption layer of a solar cell becomes a research hotspot in the field.
Copper zinc tin sulfide (Cu)2ZnSnS4CZTS), copper zinc tin selenium (Cu)2ZnSnSe4CZTSe) and copper zinc tin sulfur selenium (Cu)2ZnSn(S,Se)4CZTSSe) and a Copper Indium Gallium Selenide (CIGS) material with a chalcopyrite structure, which is excellent in the field of thin-film solar cells, have a similar crystal structure and an optical band gap, and have a high theoretical conversion efficiency (32.3%), and meanwhile, raw materials of the CZTSSe and the CIGS material are extremely abundant in earth storage, low in price, safe and non-toxic, so that the CZTSSe and the CIGS material are paid attention by researchers at home and abroad in recent years.
CZTS is Cu2ZnSnS4The abbreviation of quaternary compounds, which belongs to the structure of Kesterite. CZTS is a P-type compound semiconductor, which is a direct bandgap material. Absorption coefficient of light in visible light range>104cm-1Is suitable for being used as a thin film solar cell. The four elements In the CZTS are abundant In earth reserves, so that the defect that In and Ga elements In CIGS are deficient In nature is overcome, and the method provides for realizing a cheap solar cell. And the CZTS does not contain toxic Se, so that the method is environment-friendly. The CZTS film has extremely strong photoelectric characteristics, and therefore, in the preparation of a thin film solar cell, it is considered to be a very potential absorption layer in the thin film solar cell. According to the reported literature, Cu2ZnSnS4The preparation method of the film mainly comprises a vacuum method and a non-vacuum method, and the method for preparing the CZTS film by the vacuum method mainly comprises a magnetron sputtering method, a vacuum thermal evaporation method, a vacuum evaporation method and the like. The non-vacuum method for preparing the CZTS film mainly comprises an electrochemical deposition method, a spray pyrolysis method, a sol-gel method and the like.
CN107946387A discloses a novel annealing mode of a CZTS film, which comprises the following steps: (1) placing 0.5g of powdered sulfur on the closed side of a glass tube with one closed end, placing a CZTS film in the glass tube and close to the open end of the glass tube, and connecting the open end of the glass tube to a rubber tube; the invention obtains the high-quality CZTS film by sealing the CZTS film and a certain amount of powdered sulfur in a glass tube and then carrying out heating annealing in a high-uniformity annealing furnace.
CN108550642A discloses a preparation method of a copper-zinc-tin-sulfur film, which comprises the steps of adding a copper source, a zinc source, a tin source and a sulfur source into an organic solvent according to the molar ratio of (1-2) to (4-10), stirring and carrying out ultrasonic treatment to obtain a precursor solution; ultrasonically cleaning and vacuum-drying the FTO conductive glass or silicon wafer; spin-coating a precursor solution on FTO conductive glass or a silicon wafer, vacuum-drying for 6-10 h at the temperature of 60-90 ℃, then repeatedly spin-coating the precursor solution for 3-6 times, and vacuum-drying to obtain a CZTS film precursor; annealing the CZTS film precursor; and carrying out microwave optimization treatment on the annealed CZTS film to obtain the CZTS film.
CN102593246A discloses a low-cost solution method for preparing solar cell absorption layer material Cu2ZnSnS4The preparation method of (1). The scheme is that a copper and tin containing binary or ternary sulfide mixed film is deposited on a substrate by using continuous ion layer adsorption deposition, and then a zinc sulfide film is deposited on the copper and tin containing binary or ternary sulfide mixed film by using a chemical bath to obtain a precursor film. Annealing the precursor film in a sulfur atmosphere by a certain process to obtain Cu2ZnSnS4An absorption layer.
However, in the method in the above scheme, the annealing process causes the prepared CZTS film to have more surface defects, smaller grain size, and larger difference between the optical band gap and the silicon material, which affects the use effect.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a method for vulcanizing a semiconductor material, which can perform an annealing function and is helpful for obtaining a high-quality semiconductor material, especially a solar cell absorber material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for vulcanizing a semiconductor material, which comprises the following steps:
and placing the sulfur source and the semiconductor material into an incompletely sealed container, and placing the incompletely sealed container into a reactor for heating and vulcanizing to obtain the vulcanized semiconductor material.
In the method provided by the invention, the incompletely sealed container is placed in the reactor for reaction, a relatively independent reaction space can be formed in the incompletely sealed container, and because of incomplete sealing, a plurality of channels which are communicated with the inside and the outside of the container exist on the container, and gas can circulate through the small channels, but the circulation is slow and stable, and the sulfur-containing atmosphere formed after the sulfur source is gasified can form circulation in the incompletely sealed container, so that the temperature distribution in the incompletely sealed container is relatively uniform, the vulcanization of the semiconductor material is better facilitated, the annealing effect is achieved, and more excellent semiconductor crystals are obtained.
Because the collision of gas molecules is more severe in a relatively narrow space, the incompletely sealed container can be approximately regarded as a narrow space, so that the incompletely sealed container is favorable for enabling sulfur-containing steam formed by gasifying the sulfur source to reach a steady state in the vicinity of the own vapor pressure during the vulcanization reaction, which is also extremely favorable for the vulcanization process.
The semiconductor vulcanizing method provided by the invention can enlarge the grain size of the semiconductor, thereby better crystallizing. For a semiconductor used as a material of an absorption layer of a solar cell, the vulcanization method provided by the invention can also strengthen the diffraction peak of the semiconductor and enable the semiconductor to absorb more light.
The semiconductor vulcanization method provided by the invention is adopted to vulcanize the amorphous silicon solar absorption layer material, and the band gap of the amorphous silicon solar absorption layer material can be closer to the band gap of the silicon material.
The semiconductor vulcanizing method provided by the invention can anneal the processed semiconductor, and the device used in the method is simple and is easy for large-scale production.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred technical scheme of the invention, the sulfur source comprises sulfur powder.
Although hydrogen sulfide has the advantages of higher molecular reaction activity, controllable gas concentration, easy reaction with a precursor film and the like, the prepared film has better crystallization quality, but hydrogen sulfide has high toxicity and high cost and is not beneficial to industrial production. Compared with hydrogen sulfide, the sulfur powder has the advantages of safe use and low price. But sulfur steam is difficult to control, the sulfur molecule reactivity is poor, and the prepared CZTS film has more surface defects. The method provided by the invention can well overcome the defects of sulfur powder, so that the size of the semiconductor material grain after vulcanization is larger, the crystallization is better, and the production process meets the requirements of production safety and environmental protection.
As a preferred technical solution of the present invention, the semiconductor material includes a sulfur-containing solar cell absorber layer material.
Preferably, the semiconductor material comprises copper zinc tin sulfide and/or copper tin sulfide, preferably copper zinc tin sulfide. In the invention, the copper-zinc-tin-sulfur and/or the copper-tin-sulfur can be copper-zinc-tin-sulfur or copper-tin-sulfur.
The process of the invention is particularly suitable for copper zinc tin sulfide (Cu)2ZnSnS4Namely, CZTS), since the boiling point of sulfur element in CZTS is the lowest (boiling point of sulfur is 444.6 ℃, boiling point of copper is 2562 ℃, boiling point of zinc is 906 ℃, boiling point of tin is 2260 ℃), and it is most easily lost during annealing, it is suitable for crystallization in a sulfur atmosphere during annealing, and sulfur vapor can suppress the formation of SnS impurity phase.
Preferably, the semiconductor material is in the form of a film.
Preferably, the thickness of the semiconductor material is 10nm to 2 μm, for example 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm or 2 μm, but is not limited to the recited values, and other values not recited in this numerical range are equally applicable, preferably 10nm to 1 μm. In the invention, if the thickness of the semiconductor material is too thick, the vulcanization can peel, and the crystal structure of the semiconductor material is damaged; if the thickness of the semiconductor material is too thin, holes are generated in the semiconductor material film layer, and crystals cannot grow well.
Preferably, the semiconductor material is prepared by adopting a magnetron sputtering method.
In a preferred embodiment of the invention, the incompletely sealed container comprises a slit and/or a hole, through which the container is incompletely sealed.
Preferably, when a slit is included in the incompletely sealed container, the width of the slit is 0.1cm or less, for example 0.1cm, 0.09cm, 0.08cm, 0.07cm, 0.06cm or the like.
Preferably, when the incompletely sealed container comprises a hole, the hole has a diameter of 0.1cm or less, for example 0.1cm, 0.09cm, 0.08cm, 0.07cm or 0.06 cm.
Preferably, the incompletely sealed container comprises a lidded container. The container with the cover can not be completely sealed, and can be a container with the cover without a sealing ring, the container can be incompletely sealed only through a small gap between the cover and the box body after the cover is covered, and the container can also be a container with the cover and a hole, and the container is incompletely sealed through the hole.
Preferably, the capped container comprises a capped stone ink cartridge and/or a capped polytetrafluoroethylene cartridge. The capped container has the advantages that the capped container can resist high temperature and adapt to the temperature required by vulcanization, gas can enter and exit through the gap between the cap and the box body, sulfur molecules can better perform microcirculation, collision and combination with a film are increased, a uniform heating environment is provided for a semiconductor material, and sulfur steam is helped to be maintained near the vapor pressure of the sulfur steam in the vulcanization reaction.
Preferably, the ratio of the volume of the incompletely sealed container to the mass of the sulfur source is 3.2 to 48mL/g, e.g., 3.2mL/g, 4mL/g, 5mL/g, 10mL/g, 15mL/g, 20mL/g, 25mL/g, 30mL/g, 35mL/g, 40mL/g, 45mL/g, or 48mL/g, etc., preferably 4 to 24 mL/g. Because the sulfur source is gasified during vulcanization, the steam is mainly contained in the incompletely sealed container, and the ratio of the volume of the incompletely sealed container to the quality of the sulfur source is improper, so that the concentration of the sulfur-containing steam is improper, and the vulcanization effect and the product performance are affected.
As a preferred technical scheme of the invention, the reactor comprises a vacuum tube furnace and/or a vacuum sintering furnace.
Preferably, when the reactor is a vacuum tube furnace, the incompletely sealed container is arranged in the center of the temperature zone of the reactor.
Preferably, the sulfur source and semiconductor material are separately disposed at both ends of the incompletely sealed container.
In a preferred embodiment of the present invention, the temperature of the sulfidation reaction is 520 ℃ 560 ℃, for example 520 ℃, 525 ℃, 530 ℃, 535 ℃, 540 ℃, 545 ℃, 550 ℃, 555 ℃, or 560 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable. In the present invention, if the sulfurization temperature is too high, the semiconductor material is unstable, so that the pn junction in the semiconductor material (for example, CZTS) is destroyed; if the vulcanization temperature is too low, incomplete vulcanization may result.
In a preferred embodiment of the present invention, the time for the vulcanization reaction is 10 to 20min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, or 20min, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, during the vulcanization process, the concentration of the sulfur source steam in the incompletely sealed container is 0.021-0.3125g/cm3For example 0.021g/cm3、0.03g/cm3、0.04g/cm3、0.06g/cm3、0.08g/cm3、0.1g/cm3、0.15g/cm3、0.2g/cm3、0.25g/cm3、0.3g/cm3Or 0.3125g/cm3Etc., but are not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 0.042-0.25g/cm3. In the invention, if the concentration of sulfur source steam is too high, redundant sulfur is deposited on the surface of the semiconductor material, and the component proportion is incorrect in serious cases; if the sulfur source vapor concentration is too low, it is liable to cause hemizygous crystallizationThe conductive material creates pores at the surface and causes a significant loss of sulfur in the sulfur-containing semiconductor material during annealing.
As a preferred technical scheme of the invention, before the sulfuration, protective gas is introduced into the reactor to remove air.
Preferably, the protective gas comprises any one of nitrogen, argon, helium, krypton or neon, or a combination of at least two thereof. Typical but non-limiting combinations are: a combination of nitrogen and argon, a combination of argon and helium, a combination of helium and krypton, a combination of krypton and neon, and the like.
Preferably, the method further comprises: after vulcanization, the temperature is reduced to 15-35 ℃, namely the temperature is reduced to room temperature.
Preferably, the cooling method is natural cooling.
As a further preferable embodiment of the semiconductor material vulcanization method of the present invention, the method includes the steps of:
placing sulfur powder and copper zinc tin sulfur film in an ink box with cover stone, covering the cover, placing the graphite box with cover in the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating to 520-560 ℃ for a vulcanization reaction, wherein the vulcanization time is 10-20min, and the sulfur source vapor concentration in an incompletely sealed container in the vulcanization process is 0.042-0.25g/cm3Naturally cooling to 15-35 ℃ after vulcanization to obtain a vulcanized copper-zinc-tin-sulfur film;
wherein the thickness of the copper-zinc-tin-sulfur film is 10nm-1 mu m;
the copper-zinc-tin-sulfur film is prepared by adopting a magnetron sputtering method;
the width of a gap between the cover of the ink box with the cover stone and the box body is less than 0.1 cm;
the ratio of the volume of the ink box with the cover stone to the mass of the sulfur source is 4-24 mL/g.
Compared with the prior art, the invention has the following beneficial effects:
the semiconductor material sulfurization method provided by the invention can enlarge the grain size of the semiconductor, thereby better crystallizing. For a semiconductor used as a material of an absorption layer of a solar cell, the vulcanization method provided by the invention can also strengthen the diffraction peak of the semiconductor and enable the semiconductor to absorb more light. The semiconductor vulcanization method provided by the invention is adopted to vulcanize the amorphous silicon solar absorption layer material, and the band gap of the amorphous silicon solar absorption layer material can be closer to the band gap of the silicon material. The semiconductor vulcanizing method provided by the invention can anneal the processed semiconductor, is particularly suitable for vulcanizing annealing of the copper-zinc-tin-sulfur film, and has the advantages of simple device and easy large-scale production. The semiconductor material sulfurization method provided by the invention can ensure that the average grain size of the copper-zinc-tin-sulfur semiconductor material film after sulfurization is more than 190nm, the optical band gap is less than 1.60eV, and the optical band gap is close to the optical band gap of silicon material about 1.2 eV.
Drawings
FIG. 1a is a scanning electron micrograph of a CZTS film before vulcanization in example 1 of the present invention;
FIG. 1b is a scanning electron micrograph of a cured CZTS film in example 1 of the present invention;
FIG. 2 is an XRD pattern of CZTS film before and after sulfidation in example 1 of the present invention;
FIG. 3 is a graph of the transmission spectra of CZTS film before and after vulcanization in example 1 of the present invention;
FIG. 4 is a graph of the optical band gap (Tauc) of a CZTS film before and after vulcanization in example 1 of the present invention;
FIG. 5 is a schematic view of an apparatus used for carrying out a vulcanization reaction in example 1 of the present invention, wherein 1-a vessel which is not completely sealed, 2-a reactor, 3-a sulfur source, 4-a semiconductor material, 51-an inlet valve, and 52-an outlet valve.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example carries out the vulcanization of the semiconductor material as follows:
respectively placing Copper Zinc Tin Sulfide (CZTS) film with thickness of 80nm and 1g sulfur powder at two ends of an ink box with cover stone (the ratio of the volume of the ink box with cover stone to the mass of the sulfur powder is 24mL:1g), covering with a cover, incompletely sealing the graphite box with cover through a gap between the cover and the box body, placing the graphite box with cover in the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating to 540 ℃ for vulcanization reaction, wherein the vulcanization time is 15min, and the sulfur source vapor concentration in the incompletely sealed container (the ink box with cover stone) in the vulcanization process is 0.042g/cm3And naturally cooling to 25 ℃ after vulcanization to obtain the vulcanized copper-zinc-tin-sulfur film.
In this embodiment, the copper-zinc-tin-sulfur film is prepared by a magnetron sputtering method.
In this embodiment, the width of the gap between the cover and the box body of the ink box with the cover stone is 0.08 cm.
The results of the performance tests on the sulfided copper zinc tin sulfide thin film prepared in this example are shown in Table 1.
FIG. 1a is a scanning electron micrograph of a CZTS film before vulcanization in this example, from which it can be seen that the CZTS film is dense and flat, no cracks are found, but there are still voids between grains, and the grain size is small, only a few tens of nanometers.
FIG. 1b is a scanning electron micrograph of the film of CZTS after vulcanization in this example, from which it can be seen that the grain size of CZTS after vulcanization is larger and the inter-granular voids are smaller than before vulcanization, indicating that the crystallization effect of CZTS after vulcanization is better.
FIG. 2 is an XRD pattern of the CZTS film before and after the vulcanization in this example, and it can be seen from this figure that the diffraction peak at the characteristic peak of CZTS becomes stronger after the vulcanization, which indicates that the CZTS after the vulcanization is more crystallized.
Fig. 3 is a transmission spectrum of CZTS film before and after vulcanization in this example, from which it can be seen that the transmission of the film after vulcanization annealing is significantly reduced, light is not significantly transmitted until 700nm, and the CZTS film after vulcanization can absorb more light.
Fig. 4 is a graph of the optical band gap (Tauc) of the CZTS film before and after the vulcanization in this example, and it can be seen from the graph that the band gap of the CZTS film after the vulcanization annealing is reduced from 1.72eV to 1.56eV, the conversion is very significant, and the band gap of the CZTS film after the vulcanization is closer to the band gap of the silicon material. α and hv in fig. 4 are the absorption coefficient and the photon energy, respectively, α hv being the product of the two.
Fig. 5 is a schematic diagram of the apparatus used for carrying out the sulfidation reaction in this example, in which a sulfur source 3 (sulfur powder) and a semiconductor material 4(CZTS film) are disposed at both ends of an incompletely sealed container 1 (cartridge with a cover), the cover of the incompletely sealed container 1 is already covered, the incompletely sealed container 1 is disposed in a reactor 2 (vacuum tube furnace), nitrogen gas is introduced into the reactor 2 through an inlet pipe and an outlet pipe to discharge air, and the nitrogen gas can be adjusted through an inlet pipe valve 51 and an outlet pipe valve 52.
Example 2
This example carries out the vulcanization of the semiconductor material as follows:
respectively placing a copper-zinc-tin-sulfur (CZTS) film with thickness of 120nm and 0.5g of sulfur powder at two ends of an ink box with cover stone (the volume ratio of the ink box with cover stone to the mass ratio of the sulfur powder is 48mL:1g), covering with a cover, incompletely sealing the graphite box with cover through a gap between the cover and the box body, placing the graphite box with cover in the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating to 520 ℃ for vulcanization reaction, wherein the vulcanization time is 20min, and the sulfur source vapor concentration in the incompletely sealed container (the ink box with cover stone) in the vulcanization process is 0.021g/cm3And naturally cooling to 35 ℃ after vulcanization to obtain the vulcanized copper-zinc-tin-sulfur film.
In this embodiment, the copper-zinc-tin-sulfur film is prepared by a magnetron sputtering method.
In this embodiment, the width of the gap between the cap and the case of the ink cartridge with the cap stone was 0.05 cm.
The results of the performance tests on the sulfided copper zinc tin sulfide thin film prepared in this example are shown in Table 1.
Example 3
This example carries out the vulcanization of the semiconductor material as follows:
a Copper Zinc Tin Sulfide (CZTS) film with a thickness of 1 μm was mixed with sulfurRespectively placing the powder at two ends of an ink box with cover stone (the ratio of the volume of the ink box with cover stone to the mass of the sulfur powder is 12mL:1g), covering with a cover, incompletely sealing the graphite box with cover through a gap between the cover and the box body, placing the graphite box with cover into the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating to 560 ℃ for vulcanization reaction, wherein the vulcanization time is 10min, and the sulfur source vapor concentration in the incompletely sealed container (the ink box with cover stone) in the vulcanization process is 0.083g/cm3And naturally cooling to 15 ℃ after vulcanization to obtain the vulcanized copper-zinc-tin-sulfur film.
In this embodiment, the copper-zinc-tin-sulfur film is prepared by a magnetron sputtering method.
The width of the gap between the cover and the box body of the ink box with the cover stone in the embodiment is 0.09 cm.
The results of the performance tests on the sulfided copper zinc tin sulfide thin film prepared in this example are shown in Table 1.
Example 4
The operation and the operating parameters of the sulfurization method of this embodiment were the same as those of example 1, except that the thin film of copper zinc tin sulfide was replaced with a thin film of copper tin sulfide having the same thickness.
The results of the performance tests on the sulfided copper tin sulfide thin films prepared in this example are shown in Table 1.
Example 5
The operation and operation parameters of this example were the same as those of example 1 except that 10 circular holes having a diameter of 0.05cm were uniformly distributed in the cover of the ink cartridge with covering stone, and the width of the gap between the cover and the cartridge body was the same as that of example 1.
The results of the performance tests on the sulfided copper tin sulfide thin films prepared in this example are shown in Table 1.
Example 6
Respectively placing 100nm thick Copper Zinc Tin Sulfide (CZTS) film and sulfur powder at two ends of an ink box with cover stone (the ratio of the volume of the ink box with cover stone to the mass of the sulfur powder is 3.2mL:1g), covering with a cover, sealing the graphite box with cover incompletely through the gap between the cover and the box body, placing the graphite box with cover in the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating, and coolingCarrying out vulcanization reaction at 550 deg.C for 15min, wherein the sulfur source vapor concentration in the incompletely sealed container (ink box with cover stone) is 0.3125g/cm3And naturally cooling to 25 ℃ after vulcanization to obtain the vulcanized copper-zinc-tin-sulfur film.
In this embodiment, the copper-zinc-tin-sulfur film is prepared by a magnetron sputtering method.
In this embodiment, the width of the gap between the cover and the box body of the ink box with the cover stone is 0.08 cm.
The results of the performance tests on the sulfided copper zinc tin sulfide thin film prepared in this example are shown in Table 1.
Example 7
Respectively placing Copper Zinc Tin Sulfide (CZTS) film with thickness of 2 μm and sulfur powder at two ends of an ink box with cover stone (the ratio of the volume of the ink box with cover stone to the mass of the sulfur powder is 4mL:1g), covering with a cover, incompletely sealing the graphite box with cover through the gap between the cover and the box body and the hole on the cover, placing the graphite box with cover at the center of a temperature zone of a vacuum tube furnace, introducing nitrogen to remove air, heating to 530 ℃ for vulcanization reaction, wherein the vulcanization time is 15min, and the sulfur source vapor concentration in the incompletely sealed container (the ink box with cover stone) in the vulcanization process is 0.25g/cm3And naturally cooling to 25 ℃ after vulcanization to obtain the vulcanized copper-zinc-tin-sulfur film.
In this embodiment, the copper-zinc-tin-sulfur film is prepared by a magnetron sputtering method.
In this embodiment, the width of the gap between the cover with the cover stone ink box and the box body is 0.08cm, and 10 round holes with the diameter of 0.1cm are uniformly distributed on the cover of the cover stone ink box.
The results of the performance tests on the sulfided copper zinc tin sulfide thin film prepared in this example are shown in Table 1.
Comparative example 1
The vulcanization process of this comparative example was carried out in the same manner as in example 1 except that the same Copper Zinc Tin Sulfide (CZTS) film and sulfur powder as in example 1 were directly placed in the center of the temperature zone of the vacuum tube furnace without using a mold with a cover stone, and the other operation and operation parameters were the same as in example 1.
The results of the performance tests on the sulphided copper zinc tin sulphur film prepared in the comparative example are shown in table 1.
Comparative example 2
The vulcanization process of this comparative example was carried out in the same manner as in example 1 except that the ashlar cartridge was not used, but the same Copper Zinc Tin Sulfide (CZTS) film and sulfur powder as in example 1 were placed in the ashlar cartridge, and the ashlar graphite cartridge was placed in the center of the temperature zone of the vacuum tube furnace.
Test method
The vulcanized semiconductor materials obtained in the respective examples and comparative examples were tested as follows:
the grain size of each sample was measured by scanning electron microscopy, and the grain sizes listed in table 1 are the statistical mean grain sizes.
The transmittance of each sample was tested using an ultraviolet-visible spectrometer at 200-2200nm scan range, 2nm/s scan speed, 2.0nm slit width and room temperature. Fitting the forbidden band width of the light absorption layer according to the transmittance data, and obtaining the corresponding relation (alpha hv) according to the Tauc relation2＝A(hv-Eg) And transmission spectrum (α hv)2The hv curve (i.e. the Tauc diagram) allows the optical band gap of the material to be calculated (the point of intersection of the tangent and the abscissa in the Tauc diagram, i.e. the band gap of the corresponding material).
The test results are shown in the following table:
TABLE 1
It can be seen from the above examples and comparative examples that, in the vulcanization method of examples 1 to 7 of the present invention, an independent space is formed in the incompletely sealed container (the container has a seam and/or a hole communicating with the outside), and the slit between the box cover and the box body allows the gas to enter and exit, so as to ensure a stable flow field in the box and a more stable vulcanization reaction, and thus the grain size of the semiconductor material copper zinc tin sulfide and copper tin sulfide can be increased by the vulcanization annealing, thereby achieving better crystallization, and simultaneously absorbing more light after the vulcanization annealing, and making the optical band gap thereof closer to the optical band gap (about 1.2eV) of the silicon material.
Comparative example 1 sulfur powder and semiconductor material were directly placed in a tube furnace, because the temperature difference between the various parts in the tube furnace was large, the flow field in the furnace was complex, and sulfur vapor was difficult to control, resulting in poor crystallization effect of the semiconductor material, more surface defects, and affected the performance of the product.
Comparative example 2 although the graphite case was used without directly placing the sulfur powder and the semiconductor material in the tube furnace, the graphite case of comparative example 2 has no cover and is an open space, a relatively independent stable flow field cannot be formed in the case, the temperature of the case itself is relatively uniform only by the good heat conductivity of the graphite itself, the improvement of the crystallization effect of the vulcanized product is very limited, and the product performance is inferior to that of the product of the example.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for the vulcanization of a semiconductor material, characterized in that it comprises the following steps:
and (2) placing a sulfur source and the semiconductor material into an incompletely sealed container, and placing the incompletely sealed container into a reactor to be heated for carrying out a vulcanization reaction to obtain the vulcanized semiconductor material.
2. The method of claim 1, wherein the sulfur source comprises sulfur powder.
3. The method of claim 1 or 2, wherein the semiconductor material comprises a sulfur-containing solar cell absorber layer material;
preferably, the semiconductor material comprises copper zinc tin sulfide and/or copper tin sulfide, preferably copper zinc tin sulfide;
preferably, the semiconductor material is in the form of a film;
preferably, the thickness of the semiconductor material is 10nm-2 μm, preferably 10nm-1 μm;
preferably, the semiconductor material is prepared by adopting a magnetron sputtering method.
4. A method according to any of claims 1-3, wherein the incompletely sealed container comprises apertures and/or holes through which the container is incompletely sealed;
preferably, when the incompletely sealed container comprises a gap, the width of the gap is less than 0.1 cm;
preferably, when the incompletely sealed container comprises a hole, the hole diameter is below 0.1 cm;
preferably, the incompletely sealed container comprises a lidded container;
preferably, the container with cover comprises a box of stone ink with cover and/or a box of polytetrafluoroethylene with cover;
preferably, the ratio of the volume of the incompletely sealed container to the mass of the sulfur source is from 3.2 to 48mL/g, preferably from 4 to 24 mL/g.
5. The method according to any one of claims 1 to 4, wherein the reactor comprises a vacuum tube furnace and/or a vacuum sintering furnace;
preferably, when the reactor is a vacuum tube furnace, the incompletely sealed container is arranged in the center of a temperature zone of the reactor;
preferably, the sulfur source and semiconductor material are separately disposed at both ends of the incompletely sealed container.
6. The method as claimed in any one of claims 1 to 5, wherein the temperature of the sulfidation reaction is 520 ℃ and 560 ℃.
7. The process according to any one of claims 1 to 6, characterized in that the vulcanization reaction time is 10 to 20 min.
8. The method of any one of claims 1 to 7, wherein the sulfur source vapor concentration in the incompletely sealed container during the vulcanization is from 0.021 to 0.3125g/cm3Preferably 0.042-0.25g/cm3。
9. The process according to any one of claims 1 to 8, characterized in that before said vulcanization, a protective gas is introduced into the reactor to remove air;
preferably, the protective gas comprises any one of nitrogen, argon, helium, krypton or neon, or a combination of at least two thereof;
preferably, the method further comprises: after vulcanization, cooling to 15-35 ℃;
preferably, the cooling method is natural cooling.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
placing sulfur powder and copper zinc tin sulfur film in the ink box with cover stone, covering the cover, placing the graphite box with cover in the center of the temperature region of a vacuum tube furnace, introducing nitrogen to remove air, heating to 520-560 ℃ for vulcanization reaction, wherein the vulcanization time is 10-20min, and the sulfur source vapor concentration in the ink box with cover stone in the vulcanization process is 0.042-0.25g/cm3Naturally cooling to 15-35 ℃ after vulcanization to obtain a vulcanized copper-zinc-tin-sulfur film;
wherein the thickness of the copper-zinc-tin-sulfur film is 10nm-1 mu m;
the copper-zinc-tin-sulfur film is prepared by adopting a magnetron sputtering method;
the width of a gap between the cover of the ink box with the cover stone and the box body is less than 0.1 cm;
the ratio of the volume of the ink box with the cover stone to the mass of the sulfur source is 4-24 mL/g.
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