CN115637430A - High-performance chalcogenide compound-based photocathode and preparation method thereof - Google Patents
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
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Abstract
The invention disclosesA high-performance chalcogenide-based photocathode and a preparation method thereof are disclosed, the method comprises the steps of preparing a CZTSSe absorption layer thin film with high compactness by adopting a solution method of an ethylene glycol monomethyl ether system, and then annealing the CZTS precursor film in a selenium atmosphere to obtain the CZTSSe thin film; depositing a CdS buffer layer film by combining a simple chemical water bath process, and constructing a CZTSSe/CdS heterojunction type high-performance chalcogenide compound-based photoelectric cathode according to the CdS buffer layer film; with ALD deposition System, with TiCl 4 And H 2 Deposition of TiO with O as Ti and O sources 2 As a protective layer; finally, pt as catalyst was sputtered in an automatic sputter on TiO 2 Sputtering Pt on the protective layer to obtain Glass/Mo/CZTSSe/CdS/TiO 2 Pt heterojunction semiconductor high-performance chalcogenide-based photocathode. The high-performance chalcogenide compound-based photocathode prepared by the preparation method provided by the invention is Cu of a CZTSSe film Zn The inversion defect is obviously reduced, and the reduction of the density of the bulk defect is beneficial to reducing the recombination of photon-generated carriers and prolonging the service life of the carriers.
Description
Technical Field
The invention relates to the technical field of preparation of photoelectric catalytic materials, in particular to a high-performance chalcogenide compound-based photocathode and a preparation method thereof.
Background
Photoelectrocatalysis is an electrochemical reaction under illumination, and a photocathode is a light energy-chemical energy conversion device which is prepared by utilizing the absorption of a semiconductor to light to enable electrons to be in an excited state, generating a charge transfer process and combining thermodynamics and kinetics.
The collection of sunlight to produce clean hydrogen fuel remains one of the major challenges to address the energy crisis and to overcome global warming. Compared with photocatalysis, in the photoelectrocatalysis reaction, photoelectrode can generate photoproduction electron by utilizing sunlight irradiation, and the reaction activity and the catalysis efficiency are improved. Compared with electrocatalysis, the photoelectrocatalysis reaction greatly reduces the injection of external energy, and can effectively reduce energy consumption and environmental pollution. The quick separation of photon-generated carriers is realized based on the photovoltaic effect of the semiconductor p-n junction, and the photoelectric catalytic photo-voltaic device has great application potential. The application requirements of environmental friendliness, high efficiency and stability are met, and the semiconductor photocatalysis with the film characteristics becomes a research hotspot. Wherein, the p-type semiconductor copper zinc tin sulfur selenium (CuZnSn (S, se) 4 ) By virtue of the advantages of abundant raw material reserves, greenness, low toxicity, high light absorption coefficient, excellent photoelectric property and the like, the method attracts attention in the research field of novel high-performance thin-film photocathodes.
Currently, CZTS/HfO 2 /CdS/HfO 2 Pt and CZTSe/CdS/TCO/TiO 2 The research and report of the photoelectric cathode of/Pt and the like are obtained. The conversion efficiency of the half cell is improved from 1 percent to 7.27 percent. However, the n-type material CdS is easily subjected to photo-corrosion, so that the stability is poor; and the catalyst using noble metal such as Pt has high cost, so that the development of a catalyst with low price and equivalent catalytic effect to noble metal is urgently needed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a high-performance chalcogenide-based photocathode and a method for preparing the same, and aims to solve the problem of high cost of the conventional photocathode.
A preparation method of a high-performance chalcogenide compound-based photocathode comprises the following steps:
preparing a CZTS precursor film on a substrate coated with metal molybdenum on the surface;
annealing the CZTS precursor film in a selenium atmosphere to obtain a CZTSSe film;
depositing a layer of cadmium sulfide on the surface of the CZTSSe thin film, and depositing a layer of titanium dioxide on the surface of the cadmium sulfide by adopting an atomic layer deposition technology;
and sputtering platinum on the surface of the titanium dioxide layer to obtain the high-performance chalcogenide compound-based photocathode.
Optionally, the method for preparing a high-performance chalcogenide compound-based photocathode includes the step of preparing a CZTS precursor film on a substrate coated with molybdenum metal on a surface, and specifically includes:
by SnCl 4 ·5H 2 O、CuCl、Zn(CH 3 COO) 2 ·2H 2 O、SC(NH 2 ) 2 Preparation of Sn 4+ A raw solution; snCl 2 ·2H 2 O、Cu(CH 3 COO) 2 ·H 2 O、ZnCl 2 、SC(NH 2 ) 2 Preparation of Sn 2+ A raw solution; wherein, snCl 4 ·5H 2 The addition amount of O can be (about 0.83M), cuCl (about 1.42M), zn (CH) 3 COO) 2 ·2H 2 O(～1.0M)、SC(NH 2 ) 2 (～6.4M)；SnCl 2 ·2H 2 O(～0.83M)、Cu(CH 3 COO) 2 ·H 2 O(～1.42M)、ZnCl 2 (～1.0M)、SC(NH 2 ) 2 (～6.4M)。
The Sn is prepared by adopting glycol methyl ether solvent 4+ Raw solution and Sn 2+ Respectively diluting and mixing the original solutions 1:1, and stirring for 2-3 hours at 50-70 ℃ to obtain a transparent yellow solution; preferably, stirring is carried out at 70 ℃ for 2-3 hours;
the CZTSSe absorption layer film with high compactness is prepared by a solution method of ethylene glycol monomethyl ether system, and ethylene glycol monomethyl ether is used as a solvent, so that the formation of broken crystals can be effectively reduced, the quality of the CZTSSe absorption layer is improved, and the thickness is easy to control.
And coating the transparent yellow solution on a substrate coated with molybdenum to obtain the CZTS precursor film. The coating can be carried out by spin coating, such as 30s at 3000 rpm.
Optionally, the method for preparing a high-performance chalcogenide-based photocathode includes the step of annealing the CZTS precursor film in a selenium atmosphere to obtain a CZTSSe thin film, and specifically includes:
filling the CZTS precursor film, the selenium particles and the tin sulfide powder into a graphite sealing box;
and (3) placing the graphite sealed box in a heat treatment device, and annealing in argon flow at a preset temperature to obtain the CZTSSe film. The excess elements can be removed through annealing treatment, so that the obtained CZTSSe thin film has higher purity and is more compact.
Optionally, the method for preparing a high-performance chalcogenide-based photocathode, wherein depositing a layer of cadmium sulfide on the surface of the CZTSSe thin film, includes the following steps:
and (3) placing the CZTSSe film in an ammonia water solution containing cadmium sulfate and thiourea, depositing cadmium sulfide in a chemical water bath at 78-82 ℃, and forming a cadmium sulfide layer on the CZTSSe film. Wherein the concentration of the cadmium sulfate is 0.014-0.016 mol/L, and the concentration of the thiourea is 0.74-0.76 mol/L. The CdS buffer layer film is deposited by adopting a chemical water bath with a simple process to form a CZTSSe/CdS heterojunction, so that the separation of current carriers can be effectively promoted.
Optionally, the method for preparing the high-performance chalcogenide compound-based photocathode, wherein depositing a layer of titanium dioxide on the surface of the cadmium sulfide by using an atomic layer deposition technique specifically includes:
and depositing a layer of titanium dioxide on the surface of the cadmium sulfide by adopting an atomic layer deposition system and respectively using titanium tetrachloride and water as a titanium source and an oxygen source.
Optionally, the method for preparing a high-performance chalcogenide-based photocathode, wherein after the step of coating the transparent yellow solution on the substrate coated with molybdenum to obtain the CZTS precursor film, the method further comprises:
coating the transparent yellow solution on a substrate coated with molybdenum, and placing the substrate on a heating table for heating; the heating time is 1-2 minutes, and the heating temperature is 250-300 ℃; preferably, the heating temperature is 280 ℃.
Optionally, the method for preparing a high-performance chalcogenide-based photocathode, wherein the thickness of the CZTS precursor film is 1.0-2.0 μm; preferably, the thickness is about 1.6 μm.
Optionally, the preparation method of the high-performance chalcogenide compound-based photocathode, wherein the predetermined temperature is 500-600 ℃; preferably, the predetermined temperature is 555 ℃. When the thickness of the precursor film is about 1.6 μm, the growth of the film can be effectively promoted at the temperature of 555 ℃, and the CZTSSe film with micron-sized grains tightly packed can be obtained after about 15 min.
Optionally, the method for preparing a high-performance chalcogenide-based photocathode includes forming a titanium dioxide layer having a thickness of 10-15nm; the thickness of the cadmium sulfide layer is 80-100nm. The stability can be improved by controlling the thickness of the titanium dioxide layer, and the photoproduction electrons are promoted to be transferred to the electrode/electrolyte interface to reduce hydrogen ions in the solution so as to generate hydrogen.
Based on the same inventive concept, the invention provides a high-performance chalcogenide compound-based photocathode, wherein the high-performance chalcogenide compound-based photocathode is prepared by the preparation method.
Has the beneficial effects that: compared with the prior art, the preparation method of the high-performance chalcogenide compound-based photocathode provided by the invention is simple in process and easy to operate. The film thickness of the CZTSSe film with the absorption function can be controllably prepared, and the quality of the photocathode is improved. The usage amount of the noble metal adopted in the preparation process is less, so that the obtained photocathode has low price.
Drawings
FIG. 1 is a schematic structural diagram of a high-performance chalcogenide-based photocathode according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of the preparation of CZTSSe thin films;
FIG. 3 is a J-V curve of a high performance chalcogenide based photocathode in the dark state under illumination with light;
FIG. 4 is a theoretical photocurrent density curve of a high performance chalcogenide-based photocathode;
figure 5 is a graph of half-cell efficiency for a high performance chalcogenide-based photocathode.
Detailed Description
The invention provides a high-performance chalcogenide compound-based photocathode and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Noun interpretation
Copper zinc tin sulfide (Cu) 2 ZnSnS 4 CZTS), copper zinc tin selenium (Cu) 2 ZnSnSe 4 CZTSe) and copper zinc tin sulfur selenium (Cu) 2 ZnSn(S,Se) 4 CZTSSe), atomic Layer Deposition (ALD)
Example 1
Using raw material SnCl 4 ·5H 2 O(～0.80M)、CuCl(～1.35M)、Zn(CH 3 COO) 2 ·2H 2 O(～1.0M)、SC(NH 2 ) 2 (-6.1M) preparation of Sn 4+ Raw solution of SnCl 2 ·2H 2 O(～0.80M)、Cu(CH 3 COO) 2 ·H 2 O(～1.42M)、ZnCl 2 (～1.0M)、SC(NH 2 ) 2 (-6.1M) preparation of Sn 2+ Diluting the two original solutions 1:1 respectively by using an ethylene glycol methyl ether solvent, mixing, and stirring at 60 ℃ for 2 hours to obtain a transparent yellow solution; subsequently, referring to fig. 2, a CZTS precursor film was prepared on a soda-lime-silica glass (Mo-SLG) substrate coated with molybdenum by spin coating at 3000rpm for 30s, and transferred to a heating stage preheated to 280 ℃ after spin coating for heat treatment for 2min, and the thickness of the resulting CZTS precursor film was about 1.3 μm.
And putting the CZTS precursor film, the selenium particles and SnS powder into a graphite sealing box, annealing in a rapid thermal treatment furnace for 20min in pure argon gas flow at 500 ℃ by different heating processes, and naturally cooling along with the furnace.
And depositing a 80nm CdS buffer layer based on 0.014mol/L cadmium sulfate, 0.74mol/L thiourea and an aqueous ammonia solution in a chemical water bath at 78 ℃ to form a CZTSSe/CdS heterojunction.
Using an ALD deposition system with TiCl at a substrate temperature of 180 DEG C 4 And H 2 Deposition of 10nm TiO with O as Ti and O sources 2 As a protective layer.
Finally, pt is used as a catalyst, and an automatic sputtering machine is adopted to sputter for 50s under the current of 20 mA; thus, glass/Mo/CZTSSe/CdS/TiO is constructed 2 The structure of the Pt heterojunction semiconductor high-performance chalcogenide compound-based photocathode is shown in figure 1.
Example 2
Using raw material SnCl 4 ·5H 2 O(～0.81M)、CuCl(～1.40M)、Zn(CH 3 COO) 2 ·2H 2 O(～1.0M)、SC(NH 2 ) 2 (-6.2M) preparation of Sn 4+ Starting solution of SnCl 2 ·2H 2 O(～0.81M)、Cu(CH 3 COO) 2 ·H 2 O(～1.41M)、ZnCl 2 (～0.95M)、SC(NH 2 ) 2 (-6.2M) preparation of Sn 2+ Diluting the two original solutions 1:1 respectively by using an ethylene glycol methyl ether solvent, mixing, and stirring at 60 ℃ for 2.5 hours to obtain a transparent yellow solution; subsequently, referring to FIG. 2, a CZTS precursor film was prepared on a molybdenum-coated soda-lime glass (Mo-SLG) substrate by spin coating at 3500rpm for 30s, followed by spin coatingThe film was transferred to a heating stage preheated to 280 ℃ for heat treatment for 1min, and then spin-coated again to give a CZTS precursor film having a thickness of about 1.6. Mu.m.
And putting the CZTS precursor film, the selenium particles and SnS powder into a graphite sealing box, annealing in a rapid thermal treatment furnace for 20min in pure argon gas flow at 555 ℃ by different heating processes, and naturally cooling along with the furnace.
And depositing a 90nm CdS buffer layer based on 0.015mol/L cadmium sulfate, 0.75mol/L thiourea and an aqueous ammonia solution in a chemical water bath at 80 ℃ to form a CZTSSe/CdS heterojunction.
Using an ALD deposition system with TiCl at a substrate temperature of 185 deg.C 4 And H 2 Deposition of 13nm TiO with O as Ti and O sources 2 As a protective layer.
Finally, pt is used as a catalyst, and an automatic sputtering machine is adopted to sputter for 55s under the current of 20 mA; thus, glass/Mo/CZTSSe/CdS/TiO is constructed 2 Pt heterojunction semiconductor high-performance chalcogenide-based photocathode.
Example 3
Using raw material SnCl 4 ·5H 2 O(～0.83M)、CuCl(～1.42M)、Zn(CH 3 COO) 2 ·2H 2 O(～1.0M)、SC(NH 2 ) 2 (-6.4M) preparation of Sn 4+ Starting solution of SnCl 2 ·2H 2 O(～0.83M)、Cu(CH 3 COO) 2 ·H 2 O(～1.42M)、ZnCl 2 (～1.0M)、SC(NH 2 ) 2 (-6.4M) preparation of Sn 2+ Diluting the two original solutions 1:1 respectively by using an ethylene glycol methyl ether solvent, mixing, and stirring at 65 ℃ for 3 hours to obtain a transparent yellow solution; subsequently, referring to fig. 2, a CZTS precursor film was prepared on a soda-lime-silica glass (Mo-SLG) substrate coated with molybdenum by spin coating at 3000rpm for 30s, and after the spin coating, the substrate was moved to a heating stage preheated to 280 ℃ for heat treatment for 2min, and the spin coating step was repeated so that the thickness of the resulting CZTS precursor film was about 1.9 μm.
And putting the CZTS precursor film, the selenium particles and SnS powder into a graphite sealing box, annealing in a rapid thermal treatment furnace for 25min in pure argon gas flow at 600 ℃ by different heating processes, and naturally cooling along with the furnace.
And depositing a 100nm CdS buffer layer at 82 ℃ in a chemical water bath based on 0.016mol/L cadmium sulfate, 0.76mol/L thiourea and an aqueous ammonia solution to form the CZTSSe/CdS heterojunction.
Using an ALD deposition system with TiCl at a substrate temperature of 190 deg.C 4 And H 2 Deposition of 15nm TiO with O as Ti and O sources 2 As a protective layer.
Finally, sputtering Pt as a catalyst for 50s by adopting an automatic sputtering machine under the condition that the current is 20 mA; thus, glass/Mo/CZTSSe/CdS/TiO is constructed 2 Pt heterojunction semiconductor high-performance chalcogenide-based photocathode.
The system represents the microstructure and key performance of the device, conducts admittance test on the device, finds Cu of the CZTSSe film for optimizing the growth process through defect energy level distribution Zn Flip defects are significantly reduced, and Cu Zn Flip defects are one of the major factors limiting device performance; bulk defects of photocathodes with different absorption layer thicknesses obtained according to different times of spin coating are obviously reduced, such as bulk defect densities of CZTSSe-L (-1.3 μm) in example 1 and CZTSSe-H (-1.9 μm) absorption layer devices in example 3 of 4.34 x 10 16 cm -3 And 9.16X 10 14 cm -3 In contrast, in example 2, the bulk defect density of CZTSSe-M (. About.1.6 μ M) was 6.51X 10 14 cm -3 The reduction of the density of the bulk defects is beneficial to reducing the recombination of photon-generated carriers and prolonging the service life of the carriers. At the same time, optimization of the thickness of the absorber layer also reduces the defect density of the heterojunction interface (from 2.44 × 10) 15 cm -3 Reduced to 1.30 × 10 15 cm -3 ) The carrier transport is enhanced, and the carrier recombination loss is reduced, so that the photocurrent density and the half-cell efficiency of the photocathode device are improved. Based on this, the semiconductor photocathode achieved values close to the theoretical photocurrent density (shown in fig. 3 to 4), with half-cell efficiency increased to 6.14% (shown in fig. 5). The photocurrent density described above represents the highest value of current CZTSSe-based semiconductor photocathodes.
In summary, the invention provides a high-performance chalcogenide-based photocathode and a preparation method thereof, wherein the method comprises the step of adopting ethylene glycol monomethyl etherPreparing a CZTSSe absorption layer thin film with high compactness by a solution method, and annealing a CZTS precursor film in a selenium atmosphere to obtain a CZTSSe thin film; depositing a CdS buffer layer film by combining a simple chemical water bath process, and constructing a CZTSSe/CdS heterojunction type high-performance chalcogenide compound-based photoelectric cathode according to the CdS buffer layer film; with ALD deposition System, with TiCl 4 And H 2 Deposition of TiO with O as Ti and O sources 2 As a protective layer; finally, pt as catalyst was sputtered in an automatic sputter on TiO 2 Sputtering Pt on the protective layer to obtain Glass/Mo/CZTSSe/CdS/TiO 2 A Pt heterojunction type semiconductor high-performance chalcogenide-based photocathode.
The high-performance chalcogenide compound-based photocathode prepared by the preparation method provided by the invention is Cu of a CZTSSe film Zn The inversion defect is obviously reduced, and the reduction of the density of the bulk defect is beneficial to reducing the recombination of photon-generated carriers and prolonging the service life of the carriers. At the same time, optimization of the thickness of the absorber layer also reduces the defect density of the heterojunction interface (from 2.44 × 10) 15 cm -3 Reduced to 1.30 × 10 15 cm -3 ) The carrier transport is enhanced, and the carrier recombination loss is reduced, so that the photocurrent density and the half-cell efficiency of the photocathode device are improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a high-performance chalcogenide compound-based photocathode is characterized by comprising the following steps:
preparing a CZTS precursor film on a substrate coated with metal molybdenum on the surface;
annealing the CZTS precursor film in a selenium atmosphere to obtain a CZTSSe film;
depositing a layer of cadmium sulfide on the surface of the CZTSSe thin film, and depositing a layer of titanium dioxide on the surface of the cadmium sulfide by adopting an atomic layer deposition technology;
and sputtering platinum on the surface of the titanium dioxide layer to obtain the high-performance chalcogenide compound-based photocathode.
2. The method for preparing a high-performance chalcogenide compound-based photocathode according to claim 1, wherein the step of preparing the CZTS precursor film on the substrate coated with the metallic molybdenum comprises:
by SnCl 4 ·5H 2 O、CuCl、Zn(CH 3 COO) 2 ·2H 2 O、SC(NH 2 ) 2 Preparation of Sn 4+ A raw solution; snCl 2 ·2H 2 O、Cu(CH 3 COO) 2 ·H 2 O、ZnCl 2 、SC(NH 2 ) 2 Preparation of Sn 2+ A raw solution;
the Sn is dissolved by ethylene glycol monomethyl ether solvent 4+ Raw solution and Sn 2+ Respectively diluting and mixing the original solutions 1:1, and stirring for 2-3 hours at 50-70 ℃ to obtain a transparent yellow solution;
and coating the transparent yellow solution on a substrate coated with molybdenum to obtain the CZTS precursor film.
3. The method of claim 1, wherein the step of annealing the CZTS precursor film in a selenium atmosphere to obtain a CZTSSe thin film comprises:
filling the CZTS precursor film, the selenium particles and the tin sulfide powder into a graphite sealing box;
and (3) placing the graphite sealed box in a heat treatment device, and annealing in argon flow at a preset temperature to obtain the CZTSSe film.
4. The method for preparing a high-performance chalcogenide-based photocathode according to claim 1, wherein the step of depositing a layer of cadmium sulfide on the surface of the CZTSSe thin film comprises the following steps:
and (3) placing the CZTSSe film in an ammonia water solution containing cadmium sulfate and thiourea, depositing cadmium sulfide in a chemical water bath at 78-82 ℃, and forming a cadmium sulfide layer on the CZTSSe film.
5. The method for preparing a high-performance chalcogenide compound-based photocathode according to claim 4, wherein the depositing a layer of titanium dioxide on the surface of the cadmium sulfide by using an atomic layer deposition technique specifically comprises:
and depositing a layer of titanium dioxide on the surface of the cadmium sulfide by adopting an atomic layer deposition system and respectively using titanium tetrachloride and water as a titanium source and an oxygen source.
6. The method of claim 2, wherein the step of applying the transparent yellow solution to a substrate coated with molybdenum to obtain a CZTS precursor film further comprises:
coating the transparent yellow solution on a substrate coated with molybdenum, and placing the substrate on a heating table for heating; the heating time is 1-2 minutes, and the heating temperature is 250-300 ℃.
7. The method of claim 1, wherein the thickness of the CZTS precursor film is 1.0-2.0 μm.
8. The method of claim 3, wherein the predetermined temperature is 500-600 ℃.
9. The method of claim 5, wherein the titanium dioxide layer has a thickness of 10-15nm; the thickness of the cadmium sulfide layer is 80-100nm.
10. A high-performance chalcogenide-based photocathode characterized by being prepared by the preparation method of any one of claims 1 to 9.
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