CN113754311A - Preparation method of antimony selenide sulfide thin film - Google Patents
Preparation method of antimony selenide sulfide thin film Download PDFInfo
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- CN113754311A CN113754311A CN202110926131.2A CN202110926131A CN113754311A CN 113754311 A CN113754311 A CN 113754311A CN 202110926131 A CN202110926131 A CN 202110926131A CN 113754311 A CN113754311 A CN 113754311A
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- MUYUEDVRJJRNOO-UHFFFAOYSA-N selanylidene(sulfanylidene)antimony Chemical compound S=[Sb]=[Se] MUYUEDVRJJRNOO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010409 thin film Substances 0.000 title claims description 20
- 239000011521 glass Substances 0.000 claims abstract description 74
- 238000004070 electrodeposition Methods 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 23
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 54
- 238000000151 deposition Methods 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229910052959 stibnite Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000539 dimer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- ZGZUKKMFYTUYHA-HNNXBMFYSA-N (2s)-2-amino-3-(4-phenylmethoxyphenyl)propane-1-thiol Chemical compound C1=CC(C[C@@H](CS)N)=CC=C1OCC1=CC=CC=C1 ZGZUKKMFYTUYHA-HNNXBMFYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical group S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/115—Deposition methods from solutions or suspensions electro-enhanced deposition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Abstract
The invention discloses a preparation method of an antimony selenide sulfide film, which comprises the steps of adding antimony selenide into a mixed solution of ethylenediamine and ethanedithiol to prepare an electrodeposition solution, carrying out constant potential electrodeposition in the electrodeposition solution through conductive glass to deposit a layer of prefabricated film on the surface of an electrode on the conductive glass positioned on a cathode, and carrying out heat treatment in nitrogen atmosphere through the conductive glass deposited with the prefabricated film to finally obtain the antimony selenide sulfide film; meanwhile, the invention can change Sb in the electrodeposition liquid2Se3The addition content of Sb is regulated and controlled2SexS3‑XThe forbidden bandwidth of the film further improves the device performance of the film prepared by the invention.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of an antimony selenide sulfide film.
Background
Due to Sb2S3Rich in Sb, safe and nontoxic, so that the Sb-Sb mixed material has wide application in the fields of catalysis and solar energy2S3Has a relatively large forbidden band width of about 1.7eV, so that the prepared device has a relatively high open-circuit voltage, but Sb is2S3Too large a forbidden band width will also reduce the light utilization rate of the film, narrow the light response range, and correspondingly smaller short-circuit current density, thus limiting the performance of the device to a certain extent. Although, Sb can be increased by increasing the thickness of the absorber layer and band engineering2S3The light absorption intensity of the thin film is increased, but the requirement on the material crystal structure is relatively high when the thickness of the absorption layer is increased, so that the Sb is improved by adopting a method of optimizing an energy level structure2S3The light absorption intensity of the film is more feasible.
Sb2S3And Sb2Se3Has the same stibnite structure, and can obtain Sb by the mutual exchange of S element and Se element2SexS3-X,
Sb2S3Has a forbidden band width of 1.7eV and Sb2Se3The energy gap of the light source is 1.1eV, so that the energy gap can be effectively adjusted to be too large by doping the two materials, and the light absorption intensity can be improved. In 2009 university of arizona university scholars Sb (iii) was injected into a hot paraffin fluid containing a mixture of S, Se using a colloidal synthesis process to dissolve Sb (iii) in 2-ethylhexanoic acid solution, and the temperature of the solution was maintained at 220 ℃ until the yellow liquid turned black indicating Sb2SexS3-XWith the change of the ratio of S to Se in the solution, the formation of Sb is realized2SexS3-XThe forbidden band width of the band can be controllably adjusted within the range of 1.18-1.63 eV. (Zhengtao Deng, Mass Manual, Anthony J.Muscat. simple Colloidal Synthesis ofSingle-Crystal Sb-Se-SNanotubes with Composition Dependent Band-Gap Energy in the Near-isolated. Nano Lett.,2009.9(5), 2015-2020). Carrier L of 2015
Subject group Sb with different stoichiometric ratio2O3dissolving/Se in a thiol-amine solvent, spin-coating on a glass substrate, and annealing at 350 ℃ to obtain Sb with adjustable forbidden band2SexS3-XA film. (Carrier L.McCarthy, David H.Webber, Emily C.Schueller, and Richard L.Brutchey.solution-Phase Conversion of Bulk Metal Oxides to Metal Chalcogens uses a Simple thio-Amine Solvent mixture, Angew.chem.Int.Ed.2015,54, 8378-
Hitherto, preparation of Sb has been reported2SexS3-XExamples of the film include chemical bath deposition, spray pyrolysis, vacuum evaporation, and spin coating. The film prepared by the chemical bath deposition method has poor crystallinity and a plurality of crystal defects, the spray pyrolysis method has uneven film spraying, the vacuum evaporation method needs high vacuum equipment, the film is easy to fall off, the process repeatability is poor, and the spin coating method is easy to cause particles, and is easy to crack and fall off.
Therefore, Sb is uniform in thickness, not easy to fall off and capable of being regulated2SexS3-XThe preparation method of the antimony selenide sulfide thin film with the forbidden bandwidth of the thin film needs to be researched urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of an antimony selenide sulfide thin film.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an antimony selenide sulfide thin film comprises the following steps:
(1) mixing ethylenediamine and ethanedithiol according to a volume ratio of 1:10, and adding antimony selenide into the mixed solution to prepare electrodeposition liquid;
(2) adding the electrodeposition solution prepared in the step (1) into an electrolytic bath, vertically placing two pieces of conductive glass relative to the liquid level in the electrolytic bath, and keeping the two pieces of conductive glass parallel to each other;
(3) performing constant potential electrodeposition on the two pieces of conductive glass to deposit a layer of prefabricated film on the surface of the electrode on the conductive glass positioned on the cathode;
(4) and (3) carrying out heat treatment on the conductive glass deposited with the prefabricated film in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the antimony selenide sulfide film.
Further, the adding mass of the antimony selenide in the step (1) is 0.01-0.03 g.
Further, when the two pieces of conductive glass are subjected to constant potential electrodeposition in the step (3), the deposition voltage is 2.0-8.0V.
Further, the heat treatment temperature of the conductive glass in the step (4) is 300-400 ℃ in the nitrogen atmosphere, and the heat treatment time is 30-60 min.
Further, when the conductive glass is subjected to heat treatment in the nitrogen atmosphere, the method comprises the steps of putting the conductive glass into a tubular furnace, and heating to 300-400 ℃ at a speed of 5 ℃/min in the nitrogen atmosphere.
Furthermore, before the two pieces of conductive glass are placed in the electrolytic bath, the ultrasonic cleaning of the two pieces of conductive glass by acetone, ethanol solution and deionized water is sequentially carried out.
Further, the conductive glass is ITO conductive glass or FTO conductive glass.
The invention prepares the electrodeposition liquid by adding antimony selenide into the mixed solution of ethylenediamine and ethanedithiol, and then carries out constant potential electrodeposition in the electrodeposition liquid through conductive glass to lead [ Sb ] in the dimer2SexS2-x]2+Electrodepositing on the conductive glass on the cathode to deposit a layer of prefabricated film on the surface of the electrode on the conductive glass on the cathode, and heat treating the conductive glass deposited with the prefabricated film in nitrogen atmosphere to obtain [ Sb ]2SexS2-x]2+The preparation method of the antimony selenide sulfide film can accurately control the deposition thickness and the chemical composition of substances deposited on the conductive glass, and the obtained antimony selenide sulfide filmThe antimony oxide film also has the advantages of uniform thickness, difficult shedding, simple preparation process, easy operation and the like; meanwhile, the invention can change Sb in the electrodeposition liquid2Se3The addition content of Sb is regulated and controlled2SexS3-XThe forbidden bandwidth of the film further improves the device performance of the film prepared by the invention.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 shows Sb obtained in example 1 of the present invention2SexS3-XThin film and standard Sb2S3、Sb2Se3An XRD pattern of (a);
FIG. 2 shows Sb obtained in example 2 of the present invention2SexS3-XThin film and standard Sb2S3、Sb2Se3An XRD pattern of (a);
FIG. 3 shows Sb obtained in example 1 of the present invention2SexS3-XUltraviolet absorption spectrum of the film;
FIG. 4 shows Sb obtained in example 1 of the present invention2SexS3-XFitting a forbidden band of the film;
FIG. 5 shows Sb obtained in example 2 of the present invention2SexS3-XUltraviolet absorption spectrum of the film;
FIG. 6 shows Sb obtained in example 2 of the present invention2SexS3-XFitting a forbidden band of the film;
FIG. 7 shows Sb obtained in example 1 of the present invention2SexS3-XScanning electron micrographs of the film;
FIG. 8 is a drawing showingSb obtained in EXAMPLE 2 of the present invention2SexS3-XScanning electron micrographs of the film;
FIG. 9 shows Sb obtained in example 1 of the present invention2SexS3-XEDS energy spectrum of the film;
FIG. 10 shows Sb obtained in example 2 of the present invention2SexS3-XEDS energy spectrum of the film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of an antimony selenide sulfide film, which comprises the following steps:
(1) mixing ethylenediamine and ethanedithiol according to a volume ratio of 1:10, and adding antimony selenide into the mixed solution to prepare electrodeposition liquid;
(2) adding the electrodeposition solution prepared in the step (1) into an electrolytic bath, vertically placing two pieces of conductive glass relative to the liquid level in the electrolytic bath, and keeping the two pieces of conductive glass parallel to each other;
(3) performing constant potential electrodeposition on the two pieces of conductive glass to deposit a layer of prefabricated film on the surface of the electrode on the conductive glass positioned on the cathode;
(4) and (3) carrying out heat treatment on the conductive glass deposited with the prefabricated film in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the antimony selenide sulfide film.
In the invention, Sb is added2Se3Dissolving in the mixed solution of 1, 2-ethanediamine and 1, 2-ethanedithiol to obtain the compound with the chemical formula of [ Sb][C4H8SexS4-x][C2H9N2](0. ltoreq. X. ltoreq.4) and the products obtained are in the thiol system of the inventionThe dimer of is [ Sb2SexS2-x][C4H9SexS4-x][C2H9N2]Thus, the electrodeposition bath formulated by the present invention will have [ Sb ] in the dimer during electrodeposition2SexS2-x]2+Electrodepositing on the surface of a cathode, and then decomposing an oily solvent under the condition of nitrogen heat treatment to obtain the sulfur-doped antimony selenide (Sb)2SexS3-X(X is more than or equal to 0 and less than or equal to 3)) film. The thickness of the antimony selenide sulfide film on the conductive glass can be adjusted through the adding proportion of antimony selenide in the mixed solution and the parameters of constant potential electrodeposition so as to accurately control the deposition thickness of the antimony selenide sulfide.
The invention prepares the electrodeposition liquid by adding antimony selenide into the mixed solution of ethylenediamine and ethanedithiol, and then carries out constant potential electrodeposition in the electrodeposition liquid through conductive glass to lead [ Sb ] in the dimer2SexS2-x]2+Electrodepositing on the conductive glass on the cathode to deposit a layer of prefabricated film on the surface of the electrode on the conductive glass on the cathode, and heat treating the conductive glass deposited with the prefabricated film in nitrogen atmosphere to obtain [ Sb ]2SexS2-x]2+The preparation method of the antimony selenide sulfide film can accurately control the deposition thickness and the chemical composition of substances deposited on the conductive glass, and the antimony selenide sulfide film obtained by the preparation method has the advantages of uniform thickness, difficult shedding, simple preparation process, easy operation and the like; meanwhile, the invention can change Sb in the electrodeposition liquid2Se3The addition content of Sb is regulated and controlled2SexS3-XThe forbidden bandwidth of the film further improves the device performance of the film prepared by the invention.
In some embodiments, the mass of antimony selenide added in step (1) is 0.01-0.03 g. Since the dissolution mass fraction of antimony selenide in the thiol-amine solution is about thirty percent, this embodiment is suitable for the case of antimony selenideAdding a small amount of antimony selenide to form a dilute solution system to complete the Sb2SexS3-XAnd (3) preparing a film.
In some embodiments, when the two pieces of conductive glass are subjected to potentiostatic electrodeposition in step (3), the deposition voltage is 2.0 to 8.0V, and the deposition time period is 0.5 to 15 min. The deposition rate is increased with the increase of the voltage, and the film thickness is increased with the increase of the deposition time, so that the deposition thickness can be accurately controlled by adjusting the deposition voltage and the deposition time in the embodiment.
Further, the heat treatment temperature of the conductive glass in the step (4) is 300-.
In some embodiments, the heat treatment of the conductive glass in the nitrogen atmosphere comprises placing the conductive glass in a tube furnace, and heating to 300-400 ℃ at a temperature of 5 ℃/min in the nitrogen atmosphere.
In some embodiments, before placing the two pieces of conductive glass into the electrolytic cell, the method further comprises sequentially and separately ultrasonically cleaning the two pieces of conductive glass with acetone, ethanol solution, and deionized water.
In some embodiments, the conductive glass is ITO conductive glass or FTO conductive glass.
The following provides a specific description of the preparation method of antimony selenide sulfide thin film.
Example 1
A preparation method of an antimony selenide sulfide thin film comprises the following steps:
(1) sequentially carrying out ultrasonic cleaning on the ITO conductive glass for 15min by using acetone, ethanol solution and deionized water, and drying for later use;
(2) 0.01g of Sb2Se3Dissolving in a mixed solution of 7ml of ethylenediamine and 0.7ml of ethanedithiol, and stirring at room temperature until Sb is dissolved2Se3Completely dissolving to obtain electrodeposition solution;
(3) adding electrodeposition liquid into an electrolytic bath, taking 2 pieces of ITO conductive glass with the size of 1cm multiplied by 2cm as working electrodes, vertically placing the two pieces of conductive glass relative to the liquid level in the electrolytic bath, and keeping the two pieces of conductive glass parallel to each other;
(4) performing constant potential deposition on the two pieces of ITO conductive glass by using a constant potential rectifier, wherein the deposition voltage is 4V, the deposition time is 5min, and after the deposition is finished, a layer of uniform thin film is deposited on the surface of the electrode of the ITO conductive glass positioned on the cathode;
(5) placing the working electrode with deposited film in a tube furnace, heating to 350 deg.C at 5 deg.C/min in nitrogen atmosphere, and maintaining the temperature for 30min to obtain Sb2SexS3-XA film.
Example 2
A preparation method of an antimony selenide sulfide thin film comprises the following steps:
(1) sequentially carrying out ultrasonic cleaning on the FTO conductive glass for 15min by using acetone, ethanol solution and deionized water, and drying for later use;
(2) 0.03g of Sb2Se3Dissolving in a mixed solution of 7ml of ethylenediamine and 0.7ml of ethanedithiol, and stirring at room temperature until Sb is dissolved2Se3Completely dissolving to obtain electrodeposition solution;
(3) adding electrodeposition liquid into an electrolytic bath, taking 2 pieces of ITO conductive glass with the size of 1cm multiplied by 2cm as working electrodes, vertically placing the two pieces of conductive glass relative to the liquid level in the electrolytic bath, and keeping the two pieces of conductive glass parallel to each other;
(4) performing constant potential deposition on the two pieces of ITO conductive glass by using a constant potential rectifier, wherein the deposition voltage is 2V, the deposition time is 10min, and after the deposition is finished, a layer of uniform thin film is deposited on the surface of the electrode of the ITO conductive glass positioned on the cathode;
(5) placing the working electrode with deposited film in a tube furnace, heating to 350 deg.C at 5 deg.C/min in nitrogen atmosphere, and maintaining the temperature for 30min to obtain Sb2SexS3-XA film.
FIG. 1 and FIG. 2 show Sb2SexS3-XX-ray deposition of film on ITO and FTO conductive glassLine diffraction pattern spectra. Sb can be seen from FIG. 12SexS3-XThe film contains the characteristic peaks of antimony selenide and antimony sulfide and has red shift; FIG. 2 shows Sb2SexS3-XDiffraction peaks show characteristic peaks of antimony selenide but show a red shift in position due to the increased content of antimony selenide in the solvent, also indicating effective doping of sulfur.
FIG. 3 and FIG. 5 are Sb2SexS3-XThe film is respectively deposited on the ultraviolet absorption spectra of ITO and FTO conductive glass. FIG. 4 and FIG. 6 are Sb2SexS3-XA corresponding forbidden band width fit of the film. It can be seen that when the doping amount of antimony selenide in the solvent is 0.01g, the band gap Eg is 1.54eV, and when the doping amount of antimony selenide is 0.03g, the band gap Eg is 1.32eV, so that the Sb can be realized by changing the doping amount of antimony selenide2SexS3-XAnd (4) adjusting the band gap of the thin film.
FIG. 7 and FIG. 8 show Sb2SexS3-XAnd the films are respectively deposited on the scanning electron microscope images of the ITO conductive glass and the FTO conductive glass. FIGS. 9 and 10 show Sb obtained in examples 1 and 2 of the present invention2SexS3-XEDS energy spectrum of (a). As can be seen from FIGS. 7 and 8, Sb deposited by the present invention2SexS3-XThe ITO conductive glass of the film presents the shape of a uniform and dense nanotube, and Sb is deposited2SexS3-XThe FTO conductive glass of the film is provided with uniform and dense pine needle-shaped nanorods, so that different substrates can influence the appearance of the film. Meanwhile, the EDS energy spectrograms corresponding to fig. 9 and 10 detect S, Se, and Sb elements, further illustrating effective doping of sulfur.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of an antimony selenide sulfide thin film is characterized by comprising the following steps:
(1) mixing ethylenediamine and ethanedithiol according to a volume ratio of 1:10, and adding antimony selenide into the mixed solution to prepare electrodeposition liquid;
(2) adding the electrodeposition solution prepared in the step (1) into an electrolytic bath, vertically placing two pieces of conductive glass relative to the liquid level in the electrolytic bath, and keeping the two pieces of conductive glass parallel to each other;
(3) performing constant potential electrodeposition on the two pieces of conductive glass to deposit a layer of prefabricated film on the surface of the electrode on the conductive glass positioned on the cathode;
(4) and (3) carrying out heat treatment on the conductive glass deposited with the prefabricated film in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the antimony selenide sulfide film.
2. The method of preparing an antimony selenide sulfide thin film according to claim 1, wherein the mass of antimony selenide added in the step (1) is 0.01 to 0.03 g.
3. The method for preparing an antimony selenide sulfide thin film according to claim 1, wherein, in the step (3), when constant potential electrodeposition is performed on the two pieces of conductive glass, the deposition voltage is 2.0-8.0V.
4. The method for preparing an antimony selenide sulfide thin film as claimed in claim 1, wherein the heat treatment temperature of the conductive glass in the step (4) is 300-400 ℃ in a nitrogen atmosphere, and the heat treatment time is 30-60 min.
5. The method of claim 4, wherein the heat treatment of the conductive glass in the nitrogen atmosphere comprises placing the conductive glass in a tube furnace, and heating to 300-400 ℃ at 5 ℃/min in the nitrogen atmosphere.
6. The method of claim 1, wherein the step of ultrasonically cleaning the two pieces of conductive glass with acetone, ethanol solution, and deionized water sequentially is performed before the two pieces of conductive glass are placed in the electrolytic cell.
7. The method for preparing an antimony selenide sulfide thin film according to claim 1, wherein the conductive glass is ITO conductive glass or FTO conductive glass.
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