CN102887539B - Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film - Google Patents
Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film Download PDFInfo
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Abstract
The invention discloses a chemical method for performing in-situ preparation of a nano sulfur-tin-zinc-copper quaternary compound photovoltaic film. The method comprises the following steps of: putting a substrate material with a nano copper-tin-zinc surface, elementary substance sulfur powder and an absolute ethanol solvent in a polyphenyl (PPL) liner of a reaction kettle, wherein the content of the elementary substance sulfur powder is 0.001g/ml; reacting at the temperature of between 240 and 270 DEG C for 8 to 24 hours; after reaction, naturally cooling to room temperature; sequentially washing a product by using deionized water and absolute ethanol; and naturally airing at room temperature to obtain a meshy Cu2ZnSnS4 quaternary compound photovoltaic film consisting nano sheets. The method belongs to a mild wet chemical synthesis method, the reaction temperature is reduced obviously, and the method is environment-friendly; a vacuum device or atmosphere protection are not required in the reaction process, and the product is high in purity; and the feature of the product is controlled by controlling the sputtering sequence and thickness of metal, reaction temperature and reaction time, so that controllable synthesis is realized. The film is formed at one step by an in-situ growth method, and a solar cell device is convenient to assemble.
Description
Technical field
The invention belongs to material chemistry technical field, relate in particular to a kind of netted sulphur tin zinc-copper (Cu that original position preparation is comprised of nano flake in different base
2znSnS
4) chemical process of quaternary compound optoelectronic thin film material.
Background technology
Since nearly half a century, CuIn
1-xga
xse
2(CIGS) thin-film solar cells has been subject to broad research and has obtained developing rapidly.Repins in 2008 etc. have made first optoelectronic transformation efficiency and have reached 19.9% CIGS thin-film solar cells, it is the CIGS battery that current transformation efficiency is the highest, but due to In, Ga scarcity of resources, (indium is mainly present in cassiterite and zink sulphide, and its content in the earth's crust is only 0.049ppm.Gallium is mainly present in aluminium and zink sulphide, and the content in the earth's crust is about 18ppm) cost is higher, thus limited the large-scale application of CIGS thin-film solar cells, only in the laboratory study stage, do not carry out suitability for industrialized production at present.Therefore find the research emphasis that the novel thin-film solar cells material that is suitable for scale operation has just become investigator.In recent years, Cu
2znSnS
4crystal parent similar to CIGS crystal structure properties and that be subject to investigators look at.Cu
2znSnS
4(hereinafter to be referred as CZTS) thin-film solar cells belongs to I-II-IV-VI family quaternary compound hull cell, has custerite structure.Semi-conductor is as CuInSe
2, CuFeS
2the structure Deng compound with chalcopyrite is very similar with zincblende lattce structure.In yellow copper structure, with the Fe atom that Sn atom substitutes wherein half, obtain the compound of stannite structure, i.e. Cu
2feSnS
4, with Cu, Zn, partly replace the Cu that Fe atom wherein can obtain having custerite structure
2znSnS
4.CZTS and CIGS are similar, have higher photoabsorption coefficient (>10
4cm
-1), energy gap approximately 1.50 eV, match with the needed best energy gap of solar cell, and zinc and tin rich content in the earth's crust, thereby can greatly reduce production costs, and wherein not containing toxic ingredient, be the thin-film solar cells material of a kind of green, cheapness, safety, applicable scale operation.Katagiri in 1996 etc. on PVSEC-9 reported first use vacuum vapor deposition method to make the CZTS thin-film solar cells of ZnO:Al/CdS/CZTS/Mo/SLG structure; its transformation efficiency only has 0.66%, and progressively improvement project makes transformation efficiency reach 5.45% again subsequently; The first passage radio-frequency magnetron sputter methods such as Katagiri in 2008 have made transformation efficiency higher than 6.7% CZTS thin-film solar cells.2009, the scientist of Purdue Univ-West Lafayette USA utilize a kind of take solution as basis antivacuum Film forming method prepared CZTS solar cell, this battery is easy to scale operation and performance is highly stable, its universe transformation efficiency is up to 7.2%.The thin-film solar cells effciency of energy transfer of CZTS has reached 9.6% at present.But the volt-ampere characteristic based on photon balance (being similar to Shockley and Queisser method) is derived shows, theoretical limit efficiency of conversion can reach 32.2%.The efficiency of conversion of CZTS thin film solar cell still has very large room for promotion.Can improve transformation efficiency by improvement technology.The method of preparing at present CZTS film has a lot, as electrodip process, spray pyrolysis method, sputter postcure method, sol-gel method, chemical deposition, pulsed laser deposition etc.Although these methods make some progress, for these methods of volume production of CZTS, still there are a lot of drawbacks.As spray pyrolysis method, sputter postcure method, these technology all need the environment of high vacuum, the turnout that this technology is low, and low material use efficiency, harsh implementation condition, expensive cost has limited its large-scale production.
P.A.Fernandes is at its article Growth and Raman scattering characterization of Cu
2znSnS
4in thin film, adopt two-step approach to obtain CZTS film.First use mixture ultrasonic cleaning soda-lime glass (SLG) substrate of acetone alcohol deionized water, then under the atmosphere of argon gas, adopt magnetically controlled DC sputtering instrument in substrate, to deposit successively Cu/Zn/Sn film (target purity is 99.99%), finally film is heated to 525 ℃ of sulfurations with the heat-up rate of 10k/min under the atmosphere of nitrogen and obtains product.
Applicant has used a kind of gentleness, simple, green wet chemical synthesis in the present invention; without any need for atmosphere protection; the needed temperature of sulfuration is reduced to 250 ℃ by 525 ℃, and has obtained the higher product of purity, the suitability for industrialized production of CZTS is from now on had a very big significance.
The experimental technique that the present invention adopts is to have tin copper zinc alloy or the three-layer metal base material of sputtering for Sn, Cu, Zn respectively according to the order of sequence, elemental sulfur powder (S), and anhydrous ethanol solvent is placed in the reactor of contraposition polyphenyl (PPL) inner bag altogether, at 240 ~ 270 ℃ of temperature, direct reaction is 8 ~ 24 hours, and in substrate, successfully growth in situ has gone out the netted Cu being comprised of nano flake
2znSnS
4quaternary compound optoelectronic thin film material.
Summary of the invention
The present invention is directed to the Cu preparing at present
2znSnS
4in the method for nanocrystalline material, have that base reservoir temperature is higher, complex process, severe reaction conditions and the shortcoming such as pattern is undesirable.Provide a kind of without any need for template, do not need to add any tensio-active agent, needn't, through loaded down with trivial details post-processing operation such as removal of impurities, at lower temperature, can make the Cu of highly purified Nanostructure Network
2znSnS
4the method of quaternary compound optoelectronic thin film material.The method is passed through directly growth in situ Cu in substrate of a step chemical reaction
2znSnS
4quaternary compound optoelectronic thin film material, has industrial application value widely,
The technical solution used in the present invention is:
A kind of nano-sulfur tin zinc-copper (Cu
2znSnS
4) quaternary compound optoelectronic thin film material, it is characterized in that: this material is to have on the base material of nanometer Cu-Sn-Zn metallic surface, the netted Cu being comprised of nano flake prepared by original position
2znSnS
4quaternary compound optoelectronic thin film material.
The preparation method of nano-sulfur tin zinc-copper quaternary compound optoelectronic thin film material of the present invention, be base material, elemental sulfur powder and the anhydrous ethanol solvent with nanometer Cu-Sn-Zn metallic surface to be placed in altogether to the contraposition polyphenyl inner bag of reactor, the content of elemental sulfur powder is
0.001gram sulphur/milliliter anhydrous ethanol solvent reacts 8 ~ 24 hours at 240 ~ 270 ℃ of temperature, after reaction finishes, naturally cool to room temperature, final product cleans more than 2 times with deionized water and dehydrated alcohol successively, under room temperature, naturally dries, and original position makes the netted Cu that nano flake forms
2znSnS
4quaternary compound optoelectronic thin film material.
In preparation method of the present invention, preferable reaction temperature is 250 ℃, and the reaction times is 18 hours.
In preparation method of the present invention, the described base material with nanometer Cu-Sn-Zn metallic surface, refer to by ion sputtering, at sheet glass or stainless steel substrates substrate material surface, plated one deck nanometer tin platina or plated respectively according to the order of sequence the material of tin, copper, zinc, three-layer metal.
In preparation method of the present invention, described plating one deck nanometer tin platina, be the tin copper zinc alloy film that adopts alloy sputter plating on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1; Sputter tin, copper, zinc three-layer metal are sequentially Sn, Cu, Zn respectively, and the mol ratio of this three-layer metal changes between Cu:Zn:Sn=1.5:1:1 and Cu:Zn:Sn=1:1:1.
The mol ratio of three-layer metal changes between Cu:Zn:Sn=2:1:1 and Cu:Zn:Sn=1:1:1, all can obtain pure netted Cu
2znSnS
4quaternary compound optoelectronic thin film material (PDF card number: 26-575).
Advantage of the present invention:
1, the method for preparing CZTS with other is compared, and temperature of reaction significantly reduces, and belongs to gentle wet chemical synthesis, is convenient to scale operation.
2, reaction process is without any need for vacuum unit or atmosphere protection, and product purity is high.
3, adopt in situ synthesis one one-step film forming, do not need further spin-coating film process, be convenient to assembling solar battery device.
4, pass through the control in metal sputtering order and thickness, temperature of reaction, reaction times etc. and then the pattern of control CZTS product, realized controlledly synthesis.
5, whole experimentation is only used ethanol to make solvent, environmentally friendly.
accompanying drawing explanation
Fig. 1,
embodiment 1the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 2,
embodiment 2the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 3,
embodiment 3the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 4,
embodiment 3the XRD figure of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 5,
embodiment 3the laser raman figure of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 6,
embodiment 4the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 7,
embodiment 4the XRD figure of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 8,
embodiment 5the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Fig. 9,
embodiment 5the XRD figure of the sulphur tin zinc-copper nano crystal thin film material of preparation
Figure 10,
embodiment 6the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Figure 11,
embodiment 6the XRD figure of the sulphur tin zinc-copper nano crystal thin film material of preparation
Figure 12,
embodiment 7the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Figure 13,
embodiment 8the electron photomicrograph of the sulphur tin zinc-copper nano crystal thin film material of preparation
Embodiment
The present invention prepares the implementation method of sulphur tin zinc-copper quaternary compound optoelectronic thin film material, first the base material on Nanometer Copper Zinc-tin alloy surface will be there is, elemental sulfur powder, and anhydrous ethanol solvent blend in the PPL of reactor inner bag, sealing is placed in the constant temperature blast drying oven of temperature programming function, and at 240 ~ 270 ℃ of temperature, direct reaction is 8 ~ 24 hours; After reaction finishes, question response still is cooled to after room temperature in constant temperature blast drying oven, and reactor is taken out; Finally product is taken out successively and cleaned more than 2 times with deionized water and dehydrated alcohol, under room temperature, naturally dry.
embodiment 1
(1) preparation work: adopt alloy sputter plating a layer thickness on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1 to be about
400nmtin copper zinc alloy film cleans the common glass sheet that is coated with tin copper zinc alloy film 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then takes out to be placed on filter paper and naturally dries; The PPL inner bag of reactor is used to tap water, distilled water wash 2 times successively, dry rear stand-by; The mol ratio of three-layer metal is at Cu:Zn:Sn=2:1:1
(2) reactions steps: the PPL inner bag of the substrate of glass with nanometer tin copper zinc alloy surface of processing being put into reactor, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder content is 0.001 grams per milliliter, the PPL inner bag of reactor is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to 250 ℃ of reactions 8 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products 2 times, sample is placed under room temperature and is naturally dried.The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is black.Electron photomicrograph is shown in Fig. 1, and XRD figure, with embodiment 3, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 2
(1) preparation work: adopt alloy sputter plating a layer thickness on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1 to be about
400nmtin copper zinc alloy film cleans the common glass sheet that is coated with tin copper zinc alloy film 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then takes out to be placed on filter paper and naturally dries; The PPL inner bag of reactor is used to tap water, distilled water wash 2 times successively, dry rear stand-by;
(2) reactions steps: the PPL inner bag of the substrate of glass with nanometer tin copper zinc alloy surface of processing being put into reactor, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder content is 0.001 grams per milliliter, the PPL inner bag of reactor is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to 250 ℃ of reactions 12 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products 2 times, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is black.Electron photomicrograph is shown in Fig. 2, and XRD figure, with embodiment 3, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 3
(1) preparation work: adopt alloy sputter plating a layer thickness on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1 to be about
400nmtin copper zinc alloy film cleans the common glass sheet that is coated with tin copper zinc alloy film 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then takes out to be placed on filter paper and naturally dries; The PPL inner bag of reactor is used to tap water, distilled water wash 2 times successively, dry rear stand-by;
(2) reactions steps: the PPL inner bag of the substrate of glass with nanometer tin copper zinc alloy surface of processing being put into reactor, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder content is 0.001 grams per milliliter, the PPL inner bag of reactor is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to
250 ℃ are reacted 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products 2 times, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is that black shows slightly metalluster, and the microtexture under electron microscope is latticed nanocrystalline.Electron photomicrograph is shown in Fig. 3, and XRD figure spectrum is shown in Fig. 4, and Fig. 5 is shown in by Raman collection of illustrative plates, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 4
(1) preparation work: adopt alloy sputter plating a layer thickness on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1 to be about
400nmtin copper zinc alloy film cleans the common glass sheet that is coated with tin copper zinc alloy film 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then takes out to be placed on filter paper and naturally dries; The PPL inner bag of reactor is used to tap water, distilled water wash 2 times successively, dry rear stand-by;
(2) reactions steps: the PPL inner bag of being put into reactor the stainless steel-based end with nanometer tin copper zinc alloy surface of processing, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder content is 0.001 grams per milliliter, the PPL inner bag of reactor is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to
250 ℃ are reacted 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products 2 times, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is bright black, and the microtexture under electron microscope is latticed nanocrystalline.Electron photomicrograph is shown in Fig. 6, and XRD figure spectrum is shown in Fig. 7, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 5
(1) preparation work: the stainless steel substrates that is coated with successively Sn, Cu, Zn three-layer metal film (mol ratio of three-layer metal is Cu:Zn:Sn=1.5:1:1) is cleaned 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then take out to be placed on filter paper and naturally dry; The PPL inner bag of reactor is used to tap water, distilled water wash successively, dry rear stand-by;
(2) reactions steps: PPL inner bag is put into in the stainless steel-based end with nanometer tin, copper, zinc three-layer metal surface of processing, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder concentration is 0.001 grams per milliliter, PPL inner bag is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to
250 ℃ are reacted 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products 2 times, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is bright black, and the microtexture under electron microscope is latticed nanocrystalline.Electron photomicrograph is shown in Fig. 8, and XRD figure spectrum is shown in Fig. 9, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 6
(1) preparation work: the stainless steel substrates that is coated with successively three-layer metal Sn, Cu, Zn film (mol ratio of three-layer metal is Cu:Zn:Sn=1:1:1) is cleaned 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then take out to be placed on filter paper and naturally dry; The PPL inner bag of reactor is used to tap water, distilled water wash successively, dry rear stand-by;
(2) reactions steps: PPL inner bag is put into in the stainless steel-based end with nanometer tin, copper, zinc three-layer metal surface of processing, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder concentration is 0.001 grams per milliliter, PPL inner bag is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to 250 ℃ of reactions 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is bright black.Electron photomicrograph is shown in Figure 10, and XRD figure spectrum is shown in Figure 11, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 7
(1) preparation work: adopt alloy sputter plating a layer thickness on common glass sheet that mol ratio is Cu:Zn:Sn=2:1:1 to be about
400nmtin copper zinc alloy film cleans the common glass sheet that is coated with tin copper zinc alloy film 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then takes out to be placed on filter paper and naturally dries; The PPL inner bag of reactor is used to tap water, distilled water wash successively, dry rear stand-by;
(2) reactions steps: PPL inner bag is put into in the stainless steel-based end with nanometer tin copper zinc alloy surface of processing, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder concentration is 0.001 grams per milliliter, PPL inner bag is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to 240 ℃ of reactions 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is bright black.Electron photomicrograph is shown in Figure 12, and XRD figure is composed with embodiment 4, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
embodiment 8
(1) preparation work: the stainless steel substrates that is coated with successively three-layer metal Sn, Cu, Zn film (mol ratio of three-layer metal is Cu:Zn:Sn=1.5:1:1) is cleaned 5 minutes with deionized water and dehydrated alcohol successively in ultrasonic cleaner, then take out to be placed on filter paper and naturally dry; The PPL inner bag of reactor is used to tap water, distilled water wash successively, dry rear stand-by;
(2) reactions steps: PPL inner bag is put into in the stainless steel-based end with three-layer metal Sn, Cu, Zn film of processing, add sulphur powder, then add anhydrous ethanol solvent to the height of container 75%, sulphur powder concentration is 0.001 grams per milliliter, PPL inner bag is put into stainless steel outer sleeve and is placed in the constant temperature blast drying oven with temperature programming function, be warmed up to 270 ℃ of reactions 18 hours;
(3) aftertreatment: after reaction finishes, close constant temperature blast drying oven and naturally cool to room temperature, use successively after deionized water and dehydrated alcohol wash products, sample is placed under room temperature and is naturally dried; The sulphur tin zinc-copper film sample obtaining is carefully proceeded in sample bottle, in lucifuge, dry environment, preserve.Product colour is black.Electron photomicrograph is shown in Figure 13, and XRD figure is composed with embodiment 5, proves that product is pure Cu
2znSnS
4(PDF card number: 26-575) quaternary compound.
The present invention directly adopts elemental sulfur and the glass or the stainless steel-based end that are coated with tin copper zinc alloy to prepare nano mesh-like sulfur tin zinc-copper quaternary compound optoelectronic thin film material through single step reaction; and use the simplest; to the very friendly anhydrous ethanol solvent of environment as reaction medium; the method of preparing CZTS with other is compared; temperature of reaction significantly reduces; reaction process is without any need for vacuum unit or atmosphere protection, and product purity is high.Belong to gentle wet chemical synthesis, be convenient to scale operation.Low-temperature original position growth is reproducible, Nanostructure Network pattern homogeneous, perfection, and an one-step film forming, does not need further spin coating process, is convenient to assembling solar battery device.Reaction is quick, easy to operate, is convenient to suitability for industrialized production and technology popularization.Because its preparation facilities is simple, without advantages such as carrying out aftertreatment, greatly reduce cost, be suitable for applying widely in area of solar cell.
Claims (3)
1. a nano-sulfur tin zinc-copper quaternary compound optoelectronic thin film material, is characterized in that: this material is to have on the base material of nanometer Cu-Sn-Zn metallic surface, the netted Cu being comprised of nano flake prepared by original position
2znSnS
4quaternary compound optoelectronic thin film material.
2. the preparation method of nano-sulfur tin zinc-copper quaternary compound optoelectronic thin film material as claimed in claim 1, it is characterized in that: the method is the base material with nanometer Cu-Sn-Zn metallic surface, elemental sulfur powder and anhydrous ethanol solvent are placed in the contraposition polyphenyl inner bag of reactor altogether, the content of elemental sulfur powder is 0.001 gram of sulphur/milliliter anhydrous ethanol solvent, at 240 ~ 270 ℃ of temperature, react 8 ~ 24 hours, after reaction finishes, naturally cool to room temperature, final product cleans more than 2 times with deionized water and dehydrated alcohol successively, under room temperature, naturally dry, be that original position makes the netted Cu that nano flake forms
2znSnS
4quaternary compound optoelectronic thin film material,
The described base material with nanometer Cu-Sn-Zn metallic surface refers to by ion sputtering, at sheet glass or stainless steel substrates substrate material surface, plated one deck nanometer tin platina or plated respectively the material of tin, zinc, copper three-layer metal, wherein: described nanometer tin platina is to adopt the alloy sputter that mol ratio is Cu:Zn:Sn=2:1:1; Described sputter tin, copper, zinc three-layer metal are sequentially Sn, Cu, Zn, and the mol ratio of this three-layer metal changes between Cu:Zn:Sn=1.5:1:1 and Cu:Zn:Sn=1:1:1.
3. the preparation method of nano-sulfur tin zinc-copper quaternary compound optoelectronic thin film material as claimed in claim 2, is characterized in that: temperature of reaction is 250 ℃, and the reaction times is 18 hours.
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