CN114843354A - Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof - Google Patents

Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof Download PDF

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Publication number
CN114843354A
CN114843354A CN202210422925.XA CN202210422925A CN114843354A CN 114843354 A CN114843354 A CN 114843354A CN 202210422925 A CN202210422925 A CN 202210422925A CN 114843354 A CN114843354 A CN 114843354A
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zto
cds
buffer layer
flexible
cztsse
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程树英
林蓓蓓
邓辉
孙全震
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Fuzhou University
Mindu Innovation Laboratory
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Fuzhou University
Mindu Innovation Laboratory
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a flexible CZTSSe solar cell based on an ultrathin CdS/ZTO double buffer layer and a preparation method thereof. The flexible CZTSSe solar cell adopts the ultrathin CdS/ZTO double buffer layers, reduces the content of Cd in a device, and is efficient and environment-friendly.

Description

Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof
Technical Field
The invention belongs to the field of thin film solar cells, and particularly relates to a flexible CZTSSe solar cell based on an ultrathin CdS/ZTO double buffer layer and a preparation method thereof.
Background
The flexible CZTSSe solar cell has wide application prospect in the application fields of portable equipment, photovoltaic buildings, non-planar occasions and the like due to the advantages of soft, portable, bendable and the like of materials, and meanwhile, the flexible CZTSSe solar cell has rich and easily obtained raw material sources and low production cost and has huge commercial application value. At present, a 50-70 nm CdS thin film is generally used as a buffer layer of a high-efficiency flexible CZTSSe solar cell. The CdS layer prepared by adopting a chemical water bath method can prevent the damage of the subsequent sputtering to the absorption layer; meanwhile, the chemical action in the water bath deposition process can dissolve the natural oxide on the surface of the absorbing layer so as to clean the surface of the absorbing layer; in addition, Cd 2+ And the PN junction is diffused to the absorption layer, and a shallow and uniform PN junction is formed on the surface layer of the absorption layer, so that the surface defects are greatly reduced, and the quality of the PN junction is improved. However, the application of the CdS material to the flexible CZTSSe solar cell has some problems: (1) the band gap (2.4-2.5 eV) of the CdS material is narrow, so that light in a short-wavelength region cannot be utilized; (2) heavy metal Cd is extremely harmful to the environment, and hazardous waste liquid generated in the deposition process needs special waste treatment, so that the production cost is increased. Therefore, the thinning of the CdS layer is an effective solution for improving the light utilization rate of the device and reducing the cadmium content in the device, and has important significance for developing a high-efficiency and environment-friendly flexible CZTSSe solar cell. However, the thin CdS buffer layer can cause holes to appear on the CZTSSe/CdS interface, thereby increasing the leakage current and causing the performance of the solar cell to be reduced.
Disclosure of Invention
The invention aims to provide a flexible CZTSSe solar cell based on an ultrathin CdS/ZTO double buffer layer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a flexible CZTSSe solar cell based on an ultrathin CdS/ZTO double buffer layer is characterized in that a flexible Mo foil substrate, a CZTSSe absorption layer, a CdS/ZTO double buffer layer, an ITO window layer and an Ag electrode are sequentially arranged from bottom to top from a substrate, and the CdS/ZTO double buffer layer is composed of a CdS buffer layer and a ZTO buffer layer.
Furthermore, the thickness of the flexible Mo foil substrate is less than 0.1 mm, the purity is more than 99.99%, and the flexible Mo foil substrate has bendability.
Further, the CdS buffer layer is 10 nm thick.
Further, the ZTO buffer layer is Zn x Sn 1-x O film, 0<x<1, having an adjustable bandgap.
The invention also provides a preparation method of the flexible CZTSSe solar cell based on the ultrathin CdS/ZTO double buffer layers, which comprises the following steps:
(1) cleaning the flexible Mo foil substrate;
(2) preparing a CZTSSe thin film with good crystallinity on a clean flexible Mo foil by using a precursor solution spin-coating method and a high-temperature selenization technology to form a CZTSSe absorption layer;
(3) depositing an ultrathin CdS buffer layer on the CZTSSe film by using a chemical water bath deposition method;
(4) preparing a ZTO film on the ultrathin CdS buffer layer to form a ZTO buffer layer;
(5) depositing an ITO window layer on the ZTO buffer layer by a magnetron sputtering method;
(6) and evaporating an Ag electrode on the ITO window layer.
Further, in the step (4), the preparation method of the ZTO film comprises a sol-gel method, a magnetron sputtering method and an atomic layer deposition method.
Compared with the prior art, the invention has the following beneficial effects: according to the flexible CZTSSe solar cell based on the ultrathin CdS/ZTO double buffer layers, the CdS buffer layer is ultrathin and 10 nm, the adverse effect of Cd on the environment is effectively reduced, and a new thought is provided for the research of environment-friendly solar cells. In addition, the wide-bandgap ZTO buffer layer is used for replacing part of the narrow-bandgap CdS buffer layer, so that the utilization of the solar cell to sunlight is obviously improved, and the performance of the device is effectively improved. Meanwhile, the ZTO buffer layer has rich material source, low cost and environmental protection, and can be used for large-scale industrial production. The invention has low manufacturing cost, low technical requirement, strong practicability and wide application prospect.
Drawings
Fig. 1 is a schematic diagram of a flexible CZTSSe solar cell according to an embodiment of the invention.
FIG. 2 is an SEM topography of a ZTO buffer layer in an embodiment of the invention.
Fig. 3 is a SEM cross-sectional view of a flexible CZTSSe solar cell in an embodiment of the invention.
FIG. 4 is a schematic representation of a flexible CZTSSe solar cell in an embodiment of the present inventionJ—VCurve line.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As shown in fig. 1, the present embodiment provides a flexible CZTSSe solar cell based on an ultrathin CdS/ZTO double buffer layer, which includes a flexible Mo foil substrate 1, a CZTSSe absorption layer 2, a CdS/ZTO double buffer layer, an ITO window layer 5, and an Ag electrode 6, sequentially arranged from bottom to top, where the CdS/ZTO double buffer layer is composed of a CdS buffer layer 3 and a ZTO buffer layer 4.
In the embodiment, the thickness of the flexible Mo foil substrate is less than 0.1 mm, the purity is more than 99.99%, and the flexible Mo foil substrate has bendability. The CdS buffer layer has a thickness of 10 nm. The ZTO buffer layer is Zn x Sn 1-x O film, 0<x<1, having an adjustable bandgap.
The ZTO film can be prepared by a sol-gel method, a magnetron sputtering method, an atomic layer deposition method and the like, and in the embodiment, the ZTO film is prepared by the magnetron sputtering method which has the advantages of high deposition rate, low cost, no waste liquid and the like.
In this example, a ZTO film was prepared as follows:
s1, preparing a substrate: the cleaned sample was mounted on a sample holder and placed on the sputter sample substrate.
S2, mounting the target: high-purity tin (Sn, 99.99%) target material is arranged at a direct current source target position, and zinc oxide (ZnO, 99.99%) target material is arranged at a radio frequency source target position.
S3, pre-sputtering: closing the chamber door, opening the vacuum pump, and vacuumizing the chamber to 7 × 10 -4 And Pa, filling argon to 3 Pa, setting the output power of the direct current source to be 3-6W and the output power of the radio frequency source to be 50W, opening the direct current source and the radio frequency source, starting, adjusting the air pressure to 2 Pa, and keeping for 3-7 min to stabilize the sputtering rate.
S4, sputtering ZTO film: after the pre-sputtering is finished, the substrate rotation and the substrate baffle are opened, then the deposition of the ZTO film is started on the surface of the sample, and the thickness of the ZTO film is controlled according to the sputtering time.
S5, annealing the ZTO film: and after the sputtering is finished, closing the substrate rotation and the substrate baffle, filling argon into the chamber to an atmospheric state, opening the chamber door, taking out the sample, and annealing the sample on a hot table at 200 ℃ for 30 min to obtain the ZTO film with good crystallinity.
FIG. 2 is an SEM image of the ZTO film of this example, which has a uniform and flat surface topography and a high degree of densification.
In this embodiment, the preparation method of the ultrathin CdS/ZTO double-buffer-layer-based flexible CZTSSe solar cell is as follows:
(1) treatment of Mo foil: impurities and oxides on the surface of the Mo foil were treated electrochemically in a mixed solution of sulfuric acid and methanol.
(2) Preparation of CZTSSe absorbing layer: preparing a CZTSSe precursor solution, then preparing a CZTSSe prefabricated layer by a spin coating method in a glove box filled with Ar, transferring the CZTSSe prefabricated layer into a rapid thermal annealing furnace filled with nitrogen, and keeping the CZTSSe prefabricated layer at 550 ℃ for 15-20 min to obtain a CZTSSe absorption layer with good crystallization.
(3) Preparing an ultrathin CdS buffer layer: and depositing a CdS layer on the surface of the CZTSSe absorption layer by adopting a chemical water bath method, and depositing for 4 min under the constant temperature condition that the water temperature is 75 ℃ to obtain a CdS film with the thickness of 10 nm.
(4) Preparation of ZTO buffer layer: in the same step S1-S5, the thickness of the ZTO film is controlled by controlling the sputtering time, wherein the thickness of the ZTO film corresponding to the sputtering time of 24 min, 36min, 48 min and 60min is respectively 50 nm, 75 nm, 100 nm and 125 nm.
(5) Preparing an ITO window layer: depositing an ITO layer on the ultrathin CdS/ZTO double buffer layer by a sputtering method, wherein the process parameters are as follows: background vacuum degree<1.0×10 -3 Pa, Ar as sputtering gas, 0.5 Pa as working vacuum degree, 35W as radio-frequency sputtering power, 32 min as sputtering time and 200-240 nm as thickness.
(4) Preparing an Ag electrode: preparing an Ag electrode on the window layer by using a vacuum evaporation technology, wherein the process parameters are as follows: vacuum degree less than 8 x 10 -5 Pa, the evaporation rate of 1A/s, and the deposition thickness of 450-650 nm.
Fig. 3 is a SEM cross-sectional view of the flexible CZTSSe solar cell of the present embodiment, which can be seen from the substrate, in the order: the flexible Mo foil, the CZTSSe absorption layer, the CdS buffer layer, the ZTO buffer layer, the ITO window layer and the Ag electrode correspond to the flexible CZTSSe solar cell structure one to one.
FIG. 4 shows the flexible CZTSSe solar cell of the present embodiment under the condition of different thickness ZTO buffer layersJ—VAs can be seen from the curves, the performance is optimal with a ZTO film thickness of 100 nm, and the highest efficiency reaches 9.3%.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (6)

1. The flexible CZTSSe solar cell based on the ultrathin CdS/ZTO double buffer layer is characterized in that a flexible Mo foil substrate, a CZTSSe absorption layer, a CdS/ZTO double buffer layer, an ITO window layer and an Ag electrode are sequentially arranged from bottom to top from a substrate, wherein the CdS/ZTO double buffer layer is composed of a CdS buffer layer and a ZTO buffer layer.
2. The ultra-thin CdS/ZTO double buffer layer based flexible CZTSSe solar cell according to claim 1, wherein the flexible Mo foil substrate has a thickness less than 0.1 mm, a purity greater than 99.99%, and is flexible.
3. The ultra thin CdS/ZTO double buffer layer based flexible CZTSSe solar cell according to claim 1, wherein the CdS buffer layer has a thickness of 10 nm.
4. The ultra-thin CdS/ZTTO double buffer layer-based flexible CZTSSe solar cell as claimed in claim 1, wherein the ZTO buffer layer is Zn x Sn 1-x O film, 0<x<1, having an adjustable bandgap.
5. A method of preparing an ultra thin CdS/ZTO double buffer layer based flexible CZTSSe solar cell as claimed in any one of claims 1 to 4, comprising the steps of:
(1) cleaning the flexible Mo foil substrate;
(2) preparing a CZTSSe thin film with good crystallinity on a clean flexible Mo foil by using a precursor solution spin-coating method and a high-temperature selenization technology to form a CZTSSe absorption layer;
(3) depositing an ultrathin CdS buffer layer on the CZTSSe film by using a chemical water bath deposition method;
(4) preparing a ZTO film on the ultrathin CdS buffer layer to form a ZTO buffer layer;
(5) depositing an ITO window layer on the ZTO buffer layer by a magnetron sputtering method;
(6) and evaporating an Ag electrode on the ITO window layer.
6. The method for preparing the flexible CZTSSe solar cell based on the ultrathin CdS/ZTO double buffer layers as claimed in claim 5, wherein in the step (4), the method for preparing the ZTO thin film comprises a sol-gel method, a magnetron sputtering method and an atomic layer deposition method.
CN202210422925.XA 2022-04-21 2022-04-21 Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof Pending CN114843354A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120060900A1 (en) * 2010-09-08 2012-03-15 Ascent Solar Technologies, Inc. Cd-Free, Oxide Buffer Layers For Thin Film CIGS Solar Cells By Chemical Solution Deposition Methods
CN105590973A (en) * 2014-11-17 2016-05-18 中国电子科技集团公司第十八研究所 Flexible thin film solar cell having high-adhesion absorbing layer
JP2017017129A (en) * 2015-06-30 2017-01-19 株式会社豊田中央研究所 Photoelectric conversion element
CN109166972A (en) * 2018-09-21 2019-01-08 北京恒信卓元科技有限公司 A kind of double-buffering layer perovskite method for manufacturing solar battery
CN109326718A (en) * 2018-09-21 2019-02-12 北京恒信卓元科技有限公司 A kind of double-buffering layer perovskite method for manufacturing solar battery
CN112038439A (en) * 2020-09-11 2020-12-04 福州大学 CZTSSe flexible double-sided solar cell and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120060900A1 (en) * 2010-09-08 2012-03-15 Ascent Solar Technologies, Inc. Cd-Free, Oxide Buffer Layers For Thin Film CIGS Solar Cells By Chemical Solution Deposition Methods
CN105590973A (en) * 2014-11-17 2016-05-18 中国电子科技集团公司第十八研究所 Flexible thin film solar cell having high-adhesion absorbing layer
JP2017017129A (en) * 2015-06-30 2017-01-19 株式会社豊田中央研究所 Photoelectric conversion element
CN109166972A (en) * 2018-09-21 2019-01-08 北京恒信卓元科技有限公司 A kind of double-buffering layer perovskite method for manufacturing solar battery
CN109326718A (en) * 2018-09-21 2019-02-12 北京恒信卓元科技有限公司 A kind of double-buffering layer perovskite method for manufacturing solar battery
CN112038439A (en) * 2020-09-11 2020-12-04 福州大学 CZTSSe flexible double-sided solar cell and preparation method thereof

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