CN110911509B - Copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and preparation method thereof - Google Patents
Copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and preparation method thereof Download PDFInfo
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 154
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 title claims abstract description 135
- 239000002096 quantum dot Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010408 film Substances 0.000 claims abstract description 90
- 238000004070 electrodeposition Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 22
- 239000002073 nanorod Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 20
- 229960001484 edetic acid Drugs 0.000 claims description 20
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 19
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 229940075397 calomel Drugs 0.000 claims description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 10
- 238000003487 electrochemical reaction Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract description 10
- 238000005215 recombination Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- 239000010949 copper Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 13
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 9
- 229940116357 potassium thiocyanate Drugs 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 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
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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Abstract
The invention belongs to the technical field of semiconductor photoelectricity, and particularly relates to a copper sulfide quantum dot/cuprous thiocyanate (CuS QDs/CuSCN) heterojunction photoelectric film and a preparation method thereof. The invention provides a CuS QDs/CuSCN heterojunction photoelectric film and a preparation method thereof, and is characterized in that: loading the CuS quantum dots on the surface of the CuSCN nanorod film through an electrochemical deposition process, and constructing and preparing the CuS quantum dots/CuSCN heterojunction photoelectric film; the heterojunction formed by the CuS quantum dot and the CuSCN effectively promotes the separation of photo-generated charges and reduces the recombination of photo-generated carriers, thereby greatly improving the photoelectrochemical property of the CuSCN photoelectric film. The CuS QDs/CuSCN heterojunction photoelectric thin film and the preparation method thereof have the advantages of simple modification means, easy regulation and control of a heterojunction structure, obvious modification effect, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of semiconductor photoelectricity, and particularly relates to a copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and a preparation method thereof.
Background
The cuprous thiocyanate (CuSCN) is a wide-bandgap (3.6 eV) p-type semiconductor, and has stable chemical properties, high film light transmittance and hole carrier mobility (0.01-0.1 cm)2V-1s-1) High and the like, and recently, the organic hole transporting layer or the photocathode material is used in the photoelectrochemical field (such as: photoelectrocatalytic decomposition of water, photocatalysis, solar cells, photovoltaic devices, sensors, etc.) are receiving great attention and are widely used. Has been proved to be useful as a hole transport material for dye-sensitized solar cells, perovskite solar cells and quantum dot-sensitized solar cells. However, CuSCN photovoltaic films have a high carrier recombination rate, which results in low photoelectric conversion efficiency. Therefore, it is critical to improve the properties of the CuSCN thin film as a hole transport layer, to increase the hole mobility at the CuSCN interface and to reduce the electron-hole recombination at the interface.
Obviously, constructing a heterojunction is an important means for effectively separating carriers, thereby inhibiting the recombination of electrons and holes and reducing dark current. In recent years, CuS has been found to absorb light well as a kind of lightA semiconductor material having good conductivity, capable of reacting with TiO2、ZnS、BiVO4And the like to form a heterojunction, and show good photoelectrochemical properties. In view of the fact that quantum dots have unique size effect and quantum effect, the CuS Quantum Dots (QDs) are loaded on the surface of the CuSCN film to construct the CuS QDs/CuSCN heterojunction film, so that the migration rate of photogenerated carriers can be improved, the photodegradation and the photo-corrosion of the CuSCN film are reduced, the photoelectrochemical property of the material is greatly improved, and the CuS/CuSCN heterojunction film becomes a hole transport material or a photocathode material with better application prospect.
Therefore, the invention provides a method for improving a CuSCN photoelectric film, which is to load CuS quantum dots on the surface of the CuSCN photoelectric film to construct and obtain a CuS QDs/CuSCN heterojunction photoelectric film so as to achieve the purpose of improving the photoelectrochemical property of the CuSCN photoelectric film.
Disclosure of Invention
The invention aims to load CuS quantum dots on the surface of a CuSCN nanorod film through an electrochemical deposition process, and construct and prepare the CuS quantum dot/CuSCN nanorod heterojunction photoelectric film. According to the invention, CuS quantum dots are loaded on the surface of the CuSCN photoelectric film, so that the formed CuS/CuSCN heterojunction structure promotes the migration and separation of photon-generated carriers, the problem of high recombination rate of the photon-generated carriers of the CuSCN photoelectric film is solved to a greater extent, and the photoelectrochemical property of the cuprous thiocyanate photoelectric film is greatly improved.
The invention provides a copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and a preparation method thereof, which are characterized by being realized by the following technical scheme:
(1) firstly, preparing and obtaining CuS quantum dots by a soft chemistry method, wherein the specific process comprises the following steps: firstly, sequentially dissolving surfactant polyvinylpyrrolidone and anhydrous copper acetate into deionized water according to a certain molar ratio (1-3: 1000), and dissolving the mixture in 70 partsoStirring for 30 minutes under the condition of C to form a copper acetate solution with the molar concentration of 0.1M; then at constant temperature 70oC, dropwise adding 0.1M thiourea solution into the copper acetate solution under the stirring condition, and continuously keeping the constant temperature of 70 ℃ after the dropwise addingoC stirring for 60 minutes and stoppingStopping heating; after the solution is naturally cooled to room temperature, the precipitate is collected by high-speed centrifugation, the precipitate is alternately cleaned for a plurality of times by deionized water and absolute ethyl alcohol, and finally the precipitate is put in a vacuum oven 50oDrying the mixture overnight under the condition of C to obtain the CuS quantum dots;
(2) on the basis of the obtained CuS quantum dot, a CdS quantum dot/CuSCN heterojunction photoelectric film is further prepared by an electrochemical deposition method, and the specific process is as follows: dispersing the obtained CuS quantum dots into deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 10-50 mg/L; then adding copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), Ethylene Diamine Tetraacetic Acid (EDTA) and potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence according to a certain molar ratio (1: 1: 0.25), and stirring uniformly to obtain CuSO4The precursor solution is 12mM in concentration and contains CuS quantum dots with different concentrations; transferring the prepared precursor solution into an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO conductive glass, performing electrochemical deposition on the surface of the conductive glass by using an electrochemical workstation, controlling the deposition potential to be-0.1-0.4V, and controlling the deposition electric quantity to be 20-80 mC/cm2After the electrochemical deposition is finished, the conductive glass is taken out and washed by deionized water for 3 times at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
The invention has the advantages and positive effects that:
the CuS quantum dot/CuSCN heterojunction photoelectric film is prepared by modifying the CuSCN photoelectric film in a CuS quantum dot introduction mode, and has the advantages of simple modification means, easy regulation and control of a heterojunction structure, obvious modification effect, low cost and the like. Compared with other modification means for constructing the heterojunction, the method has the advantages that CuS quantum dots are added into the precursor solution and then subjected to the electrochemical deposition process, so that the CuS quantum dots can be introduced into the surface of the CuSCN film, the CuS quantum dot/CuSCN heterojunction photoelectric film is constructed and obtained, and the loading concentration of the CuS quantum dots on the surface of the CuSCN photoelectric film can be regulated and controlled by changing the concentration of the added CuS quantum dots; compared with an unmodified CuSCN photoelectric film, the prepared CuS quantum dot/CuSCN heterojunction photoelectric film can improve the spectrum absorption performance, effectively promote the separation of photo-generated charges and reduce the recombination of photo-generated carriers due to the heterojunction structure formed on the interface of the CuS quantum dot and the CuSCN, and therefore the photoelectrochemical performance of the CuSCN film can be greatly improved.
Drawings
FIG. 1 is an XRD spectrum of CuSCN and CuS QDs/CuSCN films prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of (a) CuSCN and (b) CuS QDs/CuSCN thin films prepared in example 1, and (c) and (d) are a Transmission Electron Microscope (TEM) image and a high resolution TEM image of the CuS QDs/CuSCN thin films;
FIG. 3 is a (a) Cu 2p and (b) S2 p X ray photoelectron spectroscopy (XPS) spectra of the CuSCN film prepared in example 1, and (c) Cu 2p and (d) S2 p XPS spectra of the CuS QDs/CuSCN film;
FIG. 4 is a graph of CuSCN and CuS QDs/CuSCN films prepared in example 1 in an ultraviolet LED lamp (λ = 365 nm, light intensity 300W/m2) A chopped wave photocurrent response spectrogram under an illumination condition;
FIG. 5 shows the UV LED lamp intensity of CuSCN and CuS QDs/CuSCN films prepared in example 1 (λ = 365 nm, light intensity 300W/m)2) Photoelectrochemical properties under light conditions: (a) chopped linear cyclic voltammetry (CLV) spectra, (b) Mott-Schottky (Mott-Schottky) spectra, (c) Electrochemical Impedance (EIS) spectra.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
(1) 4 mmol of anhydrous copper acetate were dissolved in 40 mL of an aqueous solution containing 0.01 mmol of polyvinylpyrrolidone (PVP, molecular weight 58000 g/mol) as a surfactant at 70oC, stirring for 30 minutes to form a 0.1M copper acetate solution; then at constant temperature 70oC stirring copper acetate40 mL of 0.1M thiourea solution is added into the solution dropwise, and the constant temperature is kept at 70 ℃ after the additionoC, stirring for 60 minutes, and then stopping heating; after the solution is naturally cooled to room temperature, the precipitate is collected by high-speed centrifugation, finally the precipitate is alternately cleaned for 3 times by deionized water and absolute ethyl alcohol, and then the precipitate is put in a vacuum oven 50oAnd drying the mixture overnight under the condition of C to obtain the CuS quantum dots.
(2) Dispersing the obtained 3.2 mg CuS quantum dots into 200 mL of deionized water to prepare CuS quantum dot dispersion liquid with the concentration of 16 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.4V and 80mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 2:
(1) the procedure for preparing CuS quantum dots is the same as in example 1.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 2 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 10 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.4V of deposition potential and deposited electric quantityIs 80mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 3:
(1) the procedure for preparing CuS quantum dots is the same as in example 1.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 6 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 30 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.3V and 60 mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 4:
(1) the procedure for preparing CuS quantum dots is the same as in example 1.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 10 mg of CuS quantum dots into 200 mL of deionized water to prepare CuS quantum dot dispersion liquid with the concentration of 50 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to a three-electrode body provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glassIn the electrochemical reaction tank, the deposition potential is-0.2V, and the deposition electric quantity is 80mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 5:
(1) 4 mmol of anhydrous copper acetate were dissolved in 40 mL of an aqueous solution containing 0.008 mmol of polyvinylpyrrolidone (PVP, molecular weight 58000 g/mol) as a surfactant at 70%oC, stirring for 30 minutes to form a 0.1M copper acetate solution; then at constant temperature 70oC, dripping 40 mL of 0.1M thiourea solution into the copper acetate solution under the stirring condition, and continuing to keep the constant temperature at 70 ℃ after the dripping is finishedoC, stirring for 60 minutes, and then stopping heating; after the solution is naturally cooled to room temperature, the precipitate is collected by high-speed centrifugation, finally the precipitate is alternately cleaned for 3 times by deionized water and absolute ethyl alcohol, and then the precipitate is put in a vacuum oven 50oAnd drying the mixture overnight under the condition of C to obtain the CuS quantum dots.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 4 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 20 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.4V and 80mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 6:
(1) 4 mmol of anhydrous copper acetate was dissolved in 40 mL0.012 mmol of surfactant polyvinylpyrrolidone (PVP, molecular weight 58000 g/mol) in 70% aqueous solutionoC, stirring for 30 minutes to form a 0.1M copper acetate solution; then at constant temperature 70oC, dripping 40 mL of 0.1M thiourea solution into the copper acetate solution under the stirring condition, and continuing to keep the constant temperature at 70 ℃ after the dripping is finishedoC, stirring for 60 minutes, and then stopping heating; after the solution is naturally cooled to room temperature, the precipitate is collected by high-speed centrifugation, finally the precipitate is alternately cleaned for 3 times by deionized water and absolute ethyl alcohol, and then the precipitate is put in a vacuum oven 50oAnd drying the mixture overnight under the condition of C to obtain the CuS quantum dots.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 8 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 40 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.4V and 80mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 7:
(1) the procedure for preparing CuS quantum dots is the same as in example 5.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 6 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 30 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain the CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.4V and 60 mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
Example 8:
(1) the procedure for preparing CuS quantum dots is the same as in example 6.
(2) Under the premise of obtaining the CuS quantum dots, dispersing the obtained 4 mg of CuS quantum dots into 200 mL of deionized water to prepare a CuS quantum dot dispersion liquid with the concentration of 20 mg/L; then 2.4 mmol of copper sulfate pentahydrate (CuSO)4∙5H2Dissolving O), 2.4 mmol of Ethylene Diamine Tetraacetic Acid (EDTA) and 0.6 mmol of potassium thiocyanate (KSCN) into the CuS quantum dot dispersion liquid in sequence, and stirring uniformly to obtain CuSO4A precursor solution with the concentration of 12mM and containing CuS quantum dots; transferring the prepared precursor solution to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO or ITO conductive glass, and depositing at-0.3V and 40 mC/cm2Performing electrochemical deposition under the condition; after the electrochemical deposition is finished, the conductive glass is taken out and washed for 3 times by deionized water at 60oAnd drying the film in a vacuum oven to obtain the CuS quantum dot/CuSCN heterojunction photoelectric film.
FIG. 1 is an XRD spectrum of CuSCN and CuS QDs/CuSCN films prepared in example 1. As can be seen from the figure, the characteristic diffraction peak of the CuSCN photoelectric thin film prepared by the electrochemical deposition method at 2 θ = 16.16 ° corresponds to the (003) crystal plane of the β -CuSCN crystal phase structure (JCPDS card No.29-0581), and the rest diffraction peaks are the diffraction peaks of the FTO conductive glass substrate, which proves that the CuSCN photoelectric thin film is successfully prepared; the XRD pattern of the CuS QDs/CuSCN heterojunction photoelectric film is basically consistent with that of a pure CuSCN photoelectric film, only the intensity of a diffraction peak is slightly reduced, and a characteristic diffraction peak of CuS is not observed, which is probably because the loading amount of CuS quantum dots on the surface of CuSCN is too small.
FIG. 2 is a Scanning Electron Microscope (SEM) image of (a) CuSCN and (b) CuS QDs/CuSCN thin films prepared in example 1, and (c) and (d) are a Transmission Electron Microscope (TEM) image and a high resolution TEM image of the CuS QDs/CuSCN thin films. In FIG. 2 (a), it can be seen that the pure CuSCN film is a uniform and closely-arranged nanorod array (with a diameter of about 90 nm), and in FIG. 2 (b), it can be seen that the CuS QDs/CuSCN surface is still a closely-arranged nanorod array, which proves that the loading of the CuS QDs does not change the morphology of the CuSCN nanorods. In order to further explore the existence mode of CuS QDs and CuSCN, a transmission electron microscope test is carried out on the sample. In a transmission electron microscope picture (fig. 2 c), it can be seen that CuS quantum dot particles with the particle size of 2-4 nm are relatively uniformly distributed on the surface of the prepared CuSCN nanorod, and CuS QDs are tightly bonded on the surface of the CuSCN nanorod to form a heterojunction structure; the high-power TEM image (FIG. 2 d) can clearly observe two different lattice fringes of CuS and CuSCN, and further confirms that the tightly combined CuS QDs/CuSCN heterojunction photoelectric thin film is successfully prepared.
FIG. 3 is a ray photoelectron spectroscopy (XPS) spectra of (a) Cu 2p and (b) S2 p X of the CuSCN film prepared in example 1, and (c) Cu 2p and (d) S2 p XPS spectra of the CuS QDs/CuSCN film. The Cu 2p XPS spectrum of the CuSCN film (FIG. 3 (a)) appeared at 952.4 eV (Cu 2 p)3/2) And 932.5 eV (Cu 2 p)1/2) Two characteristic peaks of (2), respectively belonging to the cuprous ion (Cu) of CuSCN film+) (ii) a The Cu 2p XPS spectrum of the CuS QDs/CuSCN film (FIG. 3 (c)) is shown to exclude cuprous ions (Cu) corresponding to the CuSCN film+) At 952.4 eV (Cu 2 p)3/2) And 932.5 eV (Cu 2 p)1/2) In addition to the two characteristic peaks, a new characteristic peak at 933.1 eV appears, which is located in association with the divalent copper ion (Cu)2+) Cu 2p of3/2Consistent peak positions are expected, attributed to divalent copper ions (Cu) of CuS quantum dots2+). Meanwhile, S2 p XPS spectrum (FIG. 3 (b)) of CuSCN film appeared at 164.4 eV and 163.2 eTwo characteristic peaks of V, separated by about 1.2 eV, are considered to be the presence of sulfur atoms in the CuSCN film in the S-C form; the S2 p XPS spectrum of the CuS QDs/CuSCN film (FIG. 3 (d)) shows a new characteristic peak at 161.5 eV, which is attributed to the Cu-S characteristic peak of the CuS quantum dot. XPS test results further demonstrate that CuS QDs/CuSCN films are synthesized.
FIG. 4 shows the UV LED lamp (λ = 365 nm, 300W/m intensity) of CuSCN and CuS QDs/CuSCN films prepared in example 12) And (3) chopping photocurrent response spectrogram under illumination condition. According to the graph, the CuSCN and the CuS QDs/CuSCN thin films have obvious photoelectric response characteristics under illumination, the photocurrent generated by the CuS QDs/CuSCN thin films is obviously greater than that of the CuSCN thin films, and the average photocurrent is about 2 times of that of the CuSCN thin films, so that the CuS QDs/CuSCN heterojunction can greatly improve the photon-generated carrier migration rate and the photoelectrochemical property of the CuSCN thin films.
FIG. 5 shows the UV LED lamp (λ = 365 nm, 300W/m intensity) prepared in example 1 with CuSCN and CuS QDs/CuSCN films2) Photoelectrochemical properties under light conditions: (a) chopped linear cyclic voltammetry (CLV) spectra, (b) Mott-Schottky (Mott-Schottky) spectra, (c) Electrochemical Impedance (EIS) spectra. From the CLV test result of FIG. 5 (a), in the region from-0.3V to-0.05V, under the condition of almost constant dark current, the photocurrent of the CuS QDs/CuSCN thin film is obviously increased during illumination, which shows that the introduction of the CuS QDs greatly reduces the self-recombination process of CuSCN photo-generated carriers, and effectively promotes the migration of the photo-generated carriers and the interface photoelectrochemical reaction. From the Mott-Schottky (Mott-Schottky) spectrum (fig. 5 (b)), it can be seen that the slopes of the Mott-Schottky curves of the CuSCN photovoltaic thin film and the CuS QDs/CuSCN heterojunction photovoltaic thin film are negative values, which proves that the synthesized CuSCN photovoltaic thin film and the CuS QDs/CuSCN heterojunction photovoltaic thin film are both p-type semiconductor characteristics, and also shows that the p-type semiconductor characteristics of the CuSCN photovoltaic thin film are not changed by the CuS QDs/CuSCN heterojunction structure formed by introducing the CuS QDs; furthermore, the flat band potential of CuS QDs/CuSCN is negatively shifted with respect to CuSCN, which means that the Fermi level is reduced for p-type semiconductor, which is advantageousThe electron transition is beneficial to separating the photo-generated electrons from the holes. FIG. 5 (c) is an impedance spectrum of the CuSCN film and the CuS QDs/CuSCN film under illumination, and it can be seen that a semi-circular arc of a high-frequency region of the CuS QDs/CuSCN film in the EIS spectrum is smaller than a semi-circular arc of the CuSCN film, and a radius of the semi-circular arc reflects a charge transfer impedance of a photo-generated carrier, indicating that under the same experimental conditions, an interface transfer impedance value of the photo-generated carrier generated by the CuS QDs/CuSCN film receiving illumination is obviously smaller than that of the CuSCN film. From the CLV, Mott-schottky and EIS results, compared with the CuSCN film, the photogenerated carriers of the CuS QDs/CuSCN heterojunction film are easier to jump and can be rapidly transmitted under the same condition, and the self-recombination of the photogenerated carriers is effectively reduced, so that the photoelectrochemical property is finally improved.
The test result shows that the CuSCN photoelectric film is modified by introducing the CuS quantum dot mode to prepare the CuS quantum dot/CuSCN heterojunction photoelectric film; and the formed CuS quantum dot/CuSCN heterojunction structure does not change the p-type semiconductor characteristic of CuSCN, can improve the photoelectrochemical property of the CuSCN photoelectric film to a great extent, proves that the loaded CuS quantum dot is an effective means for improving the photoelectrochemical property of the p-type CuSCN, and promotes the photoelectrochemical application thereof.
Claims (5)
1. A preparation method of a copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film is characterized by comprising the following steps: loading the CuS quantum dots on the surface of the CuSCN nanorod film through an electrochemical deposition process to construct and prepare the CuS quantum dot/CuSCN heterojunction photoelectric film, wherein the specific technical scheme is as follows:
(1) sequentially dissolving surfactant polyvinylpyrrolidone and anhydrous copper acetate into deionized water according to a molar ratio of 1-3: 1000, and stirring for 30 minutes at 70 ℃ to form a copper acetate solution with a molar concentration of 0.1M;
(2) dropwise adding 0.1M thiourea solution into the copper acetate solution formed in the step (1) until thiourea and copper acetate in the solution have the same molar weight, continuously stirring at a constant temperature of 70 ℃ for 60 minutes after the dropwise adding is finished, stopping heating, naturally cooling the solution to room temperature, then centrifuging at a high speed to collect precipitates, alternately cleaning the precipitates for multiple times by using deionized water and absolute ethyl alcohol, and finally drying in a vacuum oven at 50 ℃ for overnight to obtain the CuS quantum dots;
(3) dispersing the CuS quantum dots obtained in the step (2) into deionized water to prepare a CuS quantum dot dispersion liquid with a certain concentration;
(4) mixing CuSO4·5H2Dissolving O, ethylene diamine tetraacetic acid and KSCN into the CuS quantum dot dispersion liquid prepared in the step (3) in sequence according to the molar ratio of 1:1:0.25, and stirring and dissolving to prepare a precursor solution;
(5) transferring the precursor solution prepared in the step (4) to an electrochemical reaction tank of a three-electrode system provided with a platinum wire counter electrode, a calomel reference electrode and cleaned FTO conductive glass, performing electrochemical deposition on the surface of the conductive glass by using an electrochemical workstation, and controlling the deposition potential and the deposition electric quantity in the electrochemical deposition process;
(6) and (4) taking out the conductive glass after the electrochemical deposition in the step (5), washing the conductive glass for 3 times by using deionized water, and drying the conductive glass in a vacuum oven at the temperature of 60 ℃ to obtain the copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film.
2. The method for preparing the copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film as claimed in claim 1, wherein the method comprises the following steps: the concentration of the CuS quantum dot dispersion liquid prepared in the step (3) is 10-50 mg/L.
3. The method for preparing the copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film as claimed in claim 1, wherein the method comprises the following steps: CuSO in the precursor solution prepared in the step (4)4And the molarity of the ethylenediaminetetraacetic acid was 12 mM.
4. The method for preparing the copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the electrochemical deposition potential is-0.1 to-0.4V, and the deposition electric quantity is 20 to 80mC/cm2。
5. A copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric thin film prepared by the method for preparing the copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric thin film according to claim 1, wherein the method comprises the following steps: the film has a nanorod array structure, CuS quantum dot particles with the particle size of 2-4 nanometers are distributed on the surface of a CuSCN nanorod, and the CuS quantum dot and the CuSCN nanorod are tightly combined to form a heterojunction structure.
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