阅读说明：本技术 一种硫硒化锑薄膜的制备方法 (Preparation method of antimony selenide sulfide thin film ) 是由 侯文龙 陆蕾 张文婧 张建平 尹庚文 杨越冬 张海全 于 2021-08-12 设计创作，主要内容包括：本发明公开了一种硫硒化锑薄膜的制备方法,通过将硒化锑加入到乙二胺和乙二硫醇的混合溶液中配制电沉积液,再通过导电玻璃在电沉积液中进行恒电位电沉积,使位于阴极上的导电玻璃上的电极表面沉积出一层预制膜,再通过沉积有预制膜的导电玻璃在氮气气氛下进行热处理,最终获得硫硒化锑薄膜,本发明提供的硫硒化锑薄膜的制备方法,可精准控制沉积厚度、以及沉积在导电玻璃上的物质的化学组成,并且通过本发明获得的硫硒化锑薄膜还具有厚度均匀、不易脱落、制备工艺简单、以及操作容易等优点；同时,本发明还能够通过改变电沉积液中Sb-(2)Se-(3)的添加含量,实现调控Sb-(2)Se-(x)S-(3-X)薄膜的禁带宽度,进而提高应用本发明制得的薄膜的器件性能。(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 liquid 2 Se 3 The addition content of Sb is regulated and controlled 2 Se x S 3‑X The forbidden bandwidth of the film further improves the device performance of the film prepared by the invention.)

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.

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 element₂Se_xS_3-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 Sb₂Se_xS_3-XWith the change of the ratio of S to Se in the solution, the formation of Sb is realized₂Se_xS_3-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 band₂Se_xS_3-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 reported₂Se_xS_3-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 regulated₂Se_xS_3-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 dimer₂Se_xS_2-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 ]₂Se_xS_2-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 controlled₂Se_xS_3-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 invention₂Se_xS_3-XThin film and standard Sb₂S₃、Sb₂Se₃An XRD pattern of (a);

FIG. 2 shows Sb obtained in example 2 of the present invention₂Se_xS_3-XThin film and standard Sb₂S₃、Sb₂Se₃An XRD pattern of (a);

FIG. 3 shows Sb obtained in example 1 of the present invention₂Se_xS_3-XUltraviolet absorption spectrum of the film;

FIG. 4 shows Sb obtained in example 1 of the present invention₂Se_xS_3-XFitting a forbidden band of the film;

FIG. 5 shows Sb obtained in example 2 of the present invention₂Se_xS_3-XUltraviolet absorption spectrum of the film;

FIG. 6 shows Sb obtained in example 2 of the present invention₂Se_xS_3-XFitting a forbidden band of the film;

FIG. 7 shows Sb obtained in example 1 of the present invention₂Se_xS_3-XScanning electron micrographs of the film;

FIG. 8 is a drawing showingSb obtained in EXAMPLE 2 of the present invention₂Se_xS_3-XScanning electron micrographs of the film;

FIG. 9 shows Sb obtained in example 1 of the present invention₂Se_xS_3-XEDS energy spectrum of the film;

FIG. 10 shows Sb obtained in example 2 of the present invention₂Se_xS_3-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][C₄H₈Se_xS_4-x][C₂H₉N₂](0. ltoreq. X. ltoreq.4) and the products obtained are in the thiol system of the inventionThe dimer of is [ Sb₂Se_xS_2-x][C₄H₉Se_xS_4-x][C₂H₉N₂]Thus, the electrodeposition bath formulated by the present invention will have [ Sb ] in the dimer during electrodeposition₂Se_xS_2-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)₂Se_xS_3-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 dimer₂Se_xS_2-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 ]₂Se_xS_2-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 controlled₂Se_xS_3-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 Sb₂Se_xS_3-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 Sb₂Se_xS_3-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 Sb₂Se_xS_3-XA film.

FIG. 1 and FIG. 2 show Sb₂Se_xS_3-XX-ray deposition of film on ITO and FTO conductive glassLine diffraction pattern spectra. Sb can be seen from FIG. 1₂Se_xS_3-XThe film contains the characteristic peaks of antimony selenide and antimony sulfide and has red shift; FIG. 2 shows Sb₂Se_xS_3-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 Sb₂Se_xS_3-XThe film is respectively deposited on the ultraviolet absorption spectra of ITO and FTO conductive glass. FIG. 4 and FIG. 6 are Sb₂Se_xS_3-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 selenide₂Se_xS_3-XAnd (4) adjusting the band gap of the thin film.

FIG. 7 and FIG. 8 show Sb₂Se_xS_3-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 invention₂Se_xS_3-XEDS energy spectrum of (a). As can be seen from FIGS. 7 and 8, Sb deposited by the present invention₂Se_xS_3-XThe ITO conductive glass of the film presents the shape of a uniform and dense nanotube, and Sb is deposited₂Se_xS_3-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.