CN114864752A - Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application - Google Patents

Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application Download PDF

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CN114864752A
CN114864752A CN202210678780.XA CN202210678780A CN114864752A CN 114864752 A CN114864752 A CN 114864752A CN 202210678780 A CN202210678780 A CN 202210678780A CN 114864752 A CN114864752 A CN 114864752A
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layer
cztsse
flexible
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孙孪鸿
陈春阳
郝凌云
王威
赵毅杰
叶原丰
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Jinling Institute of Technology
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Abstract

The invention discloses a method for improving the residual stress of an absorption layer of a flexible CZTSSe thin film solar cell, which is characterized in that when a precursor thin film of the flexible CZTSSe thin film solar cell is prepared, the CZTS precursor thin film is heated during sputtering. The invention further provides a method for preparing the flexible CZTSSe thin film solar cell by using the method. According to the invention, by heating the CZTS precursor during sputtering of the precursor, the internal stress in the film is effectively reduced, the crystallization quality of the film is improved, the porosity of the film is reduced, and the recombination of carriers is reduced. Meanwhile, the invention improves the mechanical strength and the conversion efficiency of the flexible device, and the PCE also shows weak attenuation even under various severe bending environments.

Description

Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application
Technical Field
The invention relates to the field of solar cells, in particular to a method for improving residual stress of an absorption layer of a flexible CZTSSe thin-film solar cell and application thereof.
Background
With the consumption of non-renewable energy resources such as petroleum and coal and the aggravation of environmental pollution such as air pollution and water pollution, people gradually turn attention to the non-renewable energy resources, and governments of various countries also regard the non-renewable energy resources as the key points of future development. The solar energy is inexhaustible clean energy, and the development of the solar energy can reduce primary energy consumption, protect the environment and realize energy conservation and emission reduction to the maximum extent.
The utilization of solar energy is mainly achieved by solar cells, the solar cells are mainly achieved by monocrystalline silicon and polycrystalline silicon cells at first, and through decades of development, the monocrystalline silicon solar cells have the highest conversion efficiency and the most mature technology. However, the crystalline silicon solar cell has high manufacturing cost and a complicated process, and compared with a flexible thin film cell, the crystalline silicon solar cell cannot be applied to a flexible curved surface, so people gradually shift the research center to the flexible thin film solar cell. The novel thin-film solar cell is based on CdTe and Cu (In, Ga) Se In the past decades due to the advantages of low cost, relatively simple raw material purification process, simple manufacturing process, high absorption coefficient and the like 2 Thin film solar Cells of (CIGS) absorber layer materials have been developed very rapidly. However, In and Cd In CIGS and CdTe are toxic and scarce In elemental reserves, limiting the development of CIGS and CdTe. And copper zinc tin sulfur selenium (Cu) 2 ZnSn(S，Se) 4 CZTSSe) thin film solar cell has the advantages of rich composition elements, no toxicity, high light absorption coefficient, proper optical band gap, high theoretical photoelectric conversion efficiency, good stability and the like, and becomes a novel thin film solar cell which can replace CIGS and has large-scale application potential.
However, the residual stress inevitable in flexible solar cells remains a troublesome problem to be solved, mainly originating from thermal and internal stresses. By adding a material havingThe thermal stress can be effectively controlled by materials with proper thermal expansion coefficients, such as CZTSSe and CuInSe 2 Has been implemented in solar cells. However, there is little research on internal stress caused by structural defects (e.g., impurities, vacancies, defects, grain boundaries, etc.) during growth of CZTSSe thin films.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art, and provides a method for improving the internal stress of an absorption layer of a flexible CZTSSe thin film solar cell, so that the residual stress of the CZTSSe thin film is effectively reduced.
According to the surface tension and grain boundary relaxation models proposed by j.d. finegan and r.w. hoffman, the internal stress will rise at the early stage of island merger in the Volmer-Weber mechanism. Corresponding to the sputtering process of the CZTS precursor, atomic and molecular groups within the CZTS target encounter the same island coalescence, resulting in increased stress during the CZTSSe precursor and subsequent alloying. Accordingly, the present invention proposes a method of heating the substrate to relieve island boundary stress during sputtering of CZTS precursors, i.e. heating the CZTS precursor film during sputtering when preparing flexible CZTSSe thin film solar cell precursor films.
Preferably, heating of the CZTS precursor thin film is achieved by heating the substrate, such as with a resistive wire, at a temperature in the range of 50 ℃ to 200 ℃.
Based on the method, the invention further provides a preparation method of the absorption layer of the flexible CZTSSe thin-film solar cell, which comprises the following steps:
(1) preparing a CZTS precursor film: co-sputtering by adopting a magnetron sputtering method to prepare an upper layer and a lower layer of an interlayer precursor, then preparing a middle layer of the precursor, and heating a CZTS precursor film during sputtering;
(2) preparation of CZTSSe absorbing layer: placing the CZTS precursor film obtained in the step (1) and selenium particles into a small quartz tube with an opening end sealed by a quartz plug with a small hole in the center, placing the small quartz tube into a single-temperature-zone tube annealing furnace for annealing, and introducing N in the selenizing annealing process 2 Preventing the precursor from being thinThe film undergoes oxidation reaction to obtain a CZTSSe absorbing layer.
Wherein, in the step (1), the sputtering power when preparing the upper layer and the lower layer of the interlayer precursor is as follows: zn 13-15W, CZTS 40-60W, and the sputtering time is 600-800 s; the sputtering power when preparing the middle layer of the precursor is as follows: cu 6-8W, CZTS 40-60W, and the sputtering time is 4700 and 4900 s.
Preferably, in step (1), the heating temperature is from room temperature to 200 ℃.
The annealing temperature in the step (2) is 560- 2 The flux is 50-70sccm, and the Se/(S + Se) atomic ratio in the finally prepared CZTSSe is 0.7-0.9.
Furthermore, the invention provides a flexible CZTSSe thin film solar cell comprising the flexible CZTSSe thin film solar cell absorption layer prepared by the method.
Specifically, the flexible CZTSSe thin-film solar cell comprises a flexible substrate Ti, a Mo back electrode, a flexible CZTSSe thin-film solar cell absorption layer, a CdS buffer layer, an i-ZnO window layer, an ITO transparent conducting layer and an Ag electrode.
Preferably, the flexible substrate Ti has dimensions of 2 x 2cm 2 The thickness is 40-60 μm; the thickness of the Mo back electrode layer is 800-1100 nm; the thickness of the CZTSSe absorption layer is 1-1.5 μm; the CdS buffer layer is 55-65nm thick; the thicknesses of the i-ZnO and the ITO are respectively 40-60nm and 150-250 nm.
Specifically, titanium foil is used as a Ti substrate, a Mo layer is prepared by a direct current sputtering method, a CdS buffer layer is deposited by a chemical water bath deposition method, an i-ZnO window layer and an ITO transparent conducting layer are generated by a magnetron sputtering method, and an Ag layer is prepared by an evaporation method.
In a preferred embodiment, a flexible CZTSSe thin film solar cell is prepared by:
(1) preparing a Ti substrate: firstly, respectively placing the cleaning powder and the cleaning liquid into a beaker provided with a titanium foil substrate, washing by using deionized water, then sequentially placing the cleaning powder and the cleaning liquid into the beaker provided with alcohol, acetone and ultrapure water, carrying out ultrasonic cleaning on the cleaning liquid, finally blowing the cleaning liquid by using nitrogen for standby, preferably,the ultrasonic cleaning time is 15min, and the size of the prepared titanium foil is 2 x 2cm 2 The thickness is 50 mu m;
(2) preparing a Mo layer: the Mo layer is prepared by a direct-current sputtering method, the sputtering pressure during deposition is firstly high and then low, firstly, the Mo layer is deposited for 5min in a chamber with the argon flow of 80sccm, then the argon flow is reduced by 10sccm at intervals of 1min, and finally, the Mo layer is sputtered for 10min at intervals of 20sccm to obtain a Mo back electrode layer; wherein the purity of the Mo target material is 99.99%, and the diameter is 60 mm; background vacuum of 6 x 10 in magnetron sputtering chamber -4 Pa, the working air pressure is 0.1-0.2Pa, and the power of the radio frequency power supply is 240-260W. The thickness of the obtained Mo back electrode layer is 800-1100 nm;
(3) preparing a CZTS precursor film: co-sputtering by adopting a magnetron sputtering method to prepare an upper layer and a lower layer of an interlayer precursor, then preparing a middle layer of the precursor, and heating a CZTS precursor film during sputtering; wherein the sputtering power is Zn (13-15W) and CZTS (40-60W) when the upper layer and the lower layer of the interlayer precursor are prepared, and the sputtering time is 600-800 s; the sputtering power is Cu (6-8W) and CZTS (40-60W) when the middle layer of the precursor is prepared, and the sputtering time is 4700-4900 s; the temperature for heating the CZTS precursor film is between Room Temperature (RT) and 200 ℃;
(4) preparation of CZTSSe absorbing layer: placing the CZTS precursor film obtained in the step (3) and selenium particles into a small quartz tube with an opening end sealed by a quartz plug with a small hole in the center, placing the small quartz tube into a single-temperature-zone tube annealing furnace for annealing, and introducing N in the selenizing annealing process 2 Preventing the precursor film from generating oxidation reaction; wherein the annealing temperature is 580 ℃, the heat preservation time is 10min, the selenium particle amount is 20mg, the heating rate is 50 ℃/min, N 2 The flow rate was 60 sccm.
(5) Depositing a CdS buffer layer by adopting a chemical water bath deposition method, generating an i-ZnO window layer and an ITO transparent conducting layer by adopting a magnetron sputtering method, and preparing an Ag layer by adopting an evaporation method, wherein the thickness of the prepared CdS buffer layer is 60nm, and the thicknesses of the prepared i-ZnO and the prepared ITO are respectively 50nm and 200 nm.
The invention principle is as follows:
according to the invention, by heating the CZTS precursor, sputtered atoms or molecular groups are distributed on the substrate more uniformly and densely in the sputtering process of the precursor, and a dynamic distribution equilibrium state is achieved, so that collision between islands and generated tensile stress are reduced, and the problem of residual stress in the CZTSSe thin-film solar cell is effectively relieved.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) according to the invention, by heating the CZTS precursor during sputtering of the precursor, the internal stress in the film is effectively reduced, the crystallization quality of the film is improved, the porosity of the film is reduced, and the recombination of carriers is reduced.
(2) The invention improves the mechanical strength and the conversion efficiency of the flexible device, and the PCE also shows weak attenuation even under various severe bending environments.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a graph of a linear fit of 2 θ to sin2 ψ for CZTSSe films at different precursor heating temperatures
FIG. 2 is an SEM topography of CZTSSe at different precursor heating temperatures: (a, e) RT, (b, f)50 ℃, (c, g)100 ℃, (d, h)200 ℃.
FIG. 3 is (a) a J-V curve of a flexible device; and (b) the PCE of the flexible device heated by the precursor at 100 ℃ under different bending conditions is attenuated, wherein (b) the bending time, (C) the bending degree and (d) the bending duration are controlled.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of examples of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
Comparative example 1
The structure of the CZTSSe cell prepared in this comparative example was: ti substrate/Mo back electrode/CZTSSe absorption layer/CdS buffer layer/i-ZnO window layer/ITO transparent conductive layer/Ag electrode.
The method comprises the following specific steps:
step one, preparing a Ti substrate. Firstly, respectively placing the cleaning powder and the detergent into a beaker provided with a substrate, washing by using deionized water, then sequentially placing the cleaning powder and the detergent into the beaker provided with alcohol, acetone and ultrapure water, carrying out ultrasonic cleaning for 15min, and finally blowing the cleaning powder and the detergent by using nitrogen for standby.
And step two, preparing the Mo layer. At a size of 2X 2cm 2 The Mo layer is sputtered on the titanium foil with the thickness of 50 mu m by a direct current sputtering method, and the sputtering air pressure is firstly high and then low during sputtering. Firstly, a Mo target with the target purity of 99.99 percent is selected, and the diameter is 60 mm. Vacuum pumping the background of the sputtering chamber to 6X 10 -4 Pa, opening an argon bottle valve, and introducing Ar gas with the flow rate of 80 sccm. Setting the direct current sputtering power to be 250W, and depositing for 5min under the vacuum of a chamber with 0.1 Pa. Then the flow of Ar gas is reduced by 10sccm at intervals of 1min, and finally the Mo back electrode layer with the thickness of about 900nm is obtained by sputtering for 10min at the time of 20 sccm.
And step three, preparing a CZTS precursor. Firstly, Zn (14W) and CZTS (50W) are adopted for co-sputtering for 700s to prepare upper and lower layers of a sandwich precursor, and then Cu (7W) and CZTS (50W) are respectively adopted for co-sputtering for 4800s to prepare a middle layer of the precursor. During sputtering, the substrate is not heated to Room Temperature (RT).
And step four, preparing a CZTSSe absorption layer. Placing the CZTS precursor film obtained in the third step and two 10mg selenium particles in a small quartz tube with an opening at one end, sealing the opening end with a quartz plug with a small hole at the center, placing the small quartz tube in a tube annealing furnace, pumping air out of the large quartz tube before the initiation of selenizing annealing, and introducing N 2 Cleaning, completely removing air in the quartz tube by pumping the air in the quartz tube to prevent the oxygen in the air from oxidizing the prefabricated layer, and finally introducing 60sccm nitrogen to start selenizing, wherein the selenizing temperature is 580 ℃, the heat preservation time is 10min, and the temperature rise rate is 50 ℃/min.
Step five, preparing a 60nm CdS buffer layer by a chemical water bath deposition method, and mixing 140mL of ultrapure water and 20mL of CdSO 4 Solutions of(0.014-0.016mol/L), 20mL of thiourea solution (0.7-0.8mol/L) and 20mL of ammonia water were poured into a glass container in this order. The reaction time is 8 minutes in total, and the stirring speed of the stirrer in the container in the first 4min is 12-16 r/min. The stirring speed of the stirrer in the container is 8-12r/min after 4 min. After 8min, the sample was taken out of the reaction solution and washed clean with ultrapure water repeatedly. Then placing the mixture on a hot bench with the temperature of 50-70 ℃ for drying.
And sixthly, depositing a 50nm i-ZnO window layer and a 200nm ITO transparent conducting layer by using a magnetron sputtering method. The i-ZnO film with the thickness of 40-60nm is prepared by adopting the technological parameters of sputtering power of 140-160W, sputtering pressure of 0.05-0.15Pa, sputtering time of 6-8min and Ar flow of 40-50 sccm. Then preparing the 150-250nm ITO film by using the process parameters of 25-35W of sputtering power, 0.05-0.15Pa of sputtering pressure, 3500-4500s of sputtering time and 25-35sccm of Ar flow. The sheet resistance of the obtained ITO film is about 18-22 omega/□, and the transmittance in a visible light range exceeds 85%.
And step seven, preparing the silver electrode by an evaporation method.
The resulting product was analyzed and fig. 1 is a straight line fit of 2 θ to sin2 ψ for CZTSSe films at different precursor heating temperatures. The detection method and the calculation formula of the residual stress are as follows: the residual stress of the film is calculated by adopting an Omega stress XRD method, and the basic principle is that when the stress exists in a sample, the interplanar spacing changes, when Bragg diffraction occurs, the generated diffraction peak moves along with the interplanar spacing, and the size of the moving distance is related to the size of the stress. The experiment selects psi incidence angle range of 5-50 deg. to obtain XRD diffraction data, and the residual stress is calculated according to the diffraction peak of CZTSSe film (112). FIG. 1 shows 2 θ and sin 2 Ψ the relationship fits a straight line graph. The residual stress σ can be calculated by the following equation:
Figure BDA0003695658550000061
Figure BDA0003695658550000062
σ＝K·M(4.4)
where E is the Young's modulus of the film, μ is the Poisson's ratio, θ 0 For the diffraction angle of the film without stress, M is the slope of the fitted line in FIG. 1. Therefore, according to the above formula, the residual stress of the CZTSSe film can be calculated. As can be seen from the figure, the residual stress of CZTSSe is-3.39 GPa when the substrate is not heated. FIG. 2 is an SEM topography of CZTSSe at different precursor heating temperatures, and it can be seen from the SEM topography that when the substrate is not heated, the CZTSSe thin film is composed of irregular grains and dispersed fine grains, and a more porous structure can be observed obviously, and the porosity is 7.57%. FIG. 3 is (a) a J-V curve of a flexible device; the table in fig. 3(a) is the battery parameters calculated from the J-V curve. Voc is open-circuit voltage, Jsc is short-circuit current, FF is filling factor, and PCE is conversion efficiency. The bending test of the flexible battery is completed by adjusting the length of the movable end on a clamp with one end movable and the other end fixed. The PCE of the flexible device heated by the precursor at 100 ℃ under different bending conditions decayed (b) the bending time, (c) the bending degree, and (d) the bending duration, and it can be seen from the figure that the PCE of the sample obtained in comparative example 1 is 3.07%, the open-circuit voltage (Voc) is 317.82mV, and the current density (Jsc) is 23.82mA/cm 2 The Fill Factor (FF) was 40.58%, the PCE of comparative example 1 decayed from 3.07% to 2.24% during bending times from 0 to 100, from 3.07% to 2.02% during bending times from 0 to 100, and from 3.07% to 1.44% during bending times from 0 to 10s, and it can be seen that the mechanical stability of the flexible CZTSSe thin film solar cell without precursor heat treatment was poor.
Example 1
The structure of the CZTSSe cell prepared in this example was: ti substrate/Mo back electrode/CZTSSe absorption layer/CdS buffer layer/i-ZnO window layer/ITO transparent conductive layer/Ag electrode.
The method of preparation of each layer in the cell was identical to that of comparative example 1, with the only difference that: during sputtering, the substrate was heated with a resistance wire at a temperature of 50 ℃.
The resulting product was analyzed and FIG. 1 is a straight line fit of 2 θ to sin2 ψ for CZTSSe thin films at different precursor heating temperatures, from which it can be seen that when the substrate was heated at 50 ℃ the residual stress of CZTSSe was-2.02 GPa, and the residual stress of CZTSSe thin films was somewhat reduced compared to comparative example 1. FIG. 2 is an SEM topography of CZTSSe at different precursor heating temperatures, and it can be seen that when the substrate is heated at 50 ℃, the CZTSSe film tends to be flat and dense, and the grain size slightly increases. The porosity at this time was 7.23%, and the porosity was reduced compared to comparative example 1. FIG. 3 is (a) a J-V curve of a flexible device; the PCE of the flexible device heated by the precursor at 100 ℃ under different bending conditions decayed (b) the bending time, (C) the bending degree, and (d) the bending duration, and it can be seen from the figure that the PCE of the sample obtained in example 1 is 3.35%, the open-circuit voltage (Voc) is 320.41mV, and the current density (Jsc) is 23.86mA/cm 2 The Fill Factor (FF) was 43.79% and the electrical properties of the device were improved compared to comparative example 1.
Example 2
The structure of the CZTSSe cell prepared in this example was: ti substrate/Mo back electrode/CZTSSe absorption layer/CdS buffer layer/i-ZnO window layer/ITO transparent conductive layer/Ag electrode.
The method of preparation of each layer in the cell was identical to that of comparative example 1, with the only difference that: during sputtering, the substrate was heated to a temperature of 100 ℃.
The resulting product was analyzed and FIG. 1 is a straight line fit of 2 θ to sin2 ψ for CZTSSe thin films at different precursor heating temperatures, from which it can be seen that the residual stress of CZTSSe was-0.71 GPa when the substrate was heated at 100 ℃, and the residual stress was significantly reduced compared to comparative example 1 and example 1. FIG. 2 is a SEM topography of CZTSSe at different precursor heating temperatures, and it can be seen from the figure that when the substrate is heated at 100 ℃, the morphology of the CZTSSe thin film tends to be more flat and compact, the porosity at this time is 5.30%, the porosity is greatly reduced, the compactness and mechanical strength of CZTSSe are further improved, and the recombination degree of carriers is further reduced. FIG. 3 shows (a) flexibilityJ-V curve of the device; the PCE of the flexible device heated by the precursor at 100 ℃ under different bending conditions decayed (b) the bending time, (C) the bending degree, and (d) the bending duration, and it can be seen from the figure that the PCE of the sample obtained in example 2 is 4.40%, the open-circuit voltage (Voc) is 351.24mV, and the current density (Jsc) is 25.68mA/cm 2 The Fill Factor (FF) was 48.83%, and the electrical performance of the solar cell was further improved compared to comparative example 1 and example 1. Secondly, compared with comparative example 1, the PCE of the sample of example 2 decays from 4.40% to 3.87% in the process of 0 to 100 bending times, 4.40% to 3.74% in the process of 0 to 100 bending angles, and 4.40% to 3.21% in the process of 0 to 10s bending time, and the flexible CZTSSe thin-film solar cell subjected to precursor heat treatment has good mechanical stability and high mechanical strength.
Example 3
The structure of the CZTSSe cell prepared in this example was: ti substrate/Mo back electrode/CZTSSe absorption layer/CdS buffer layer/i-ZnO window layer/ITO transparent conductive layer/Ag electrode.
The method of preparation of each layer in the cell was identical to that of comparative example 1, with the only difference that: during sputtering, the substrate was heated to a temperature of 200 ℃.
The resulting product was analyzed and FIG. 1 is a straight line fit of 2 θ to sin2 ψ for CZTSSe thin films at different precursor heating temperatures, from which it can be seen that the residual stress of CZTSSe was-1.31 GPa when the substrate was heated at 200 ℃, which is reflected compared to comparative example 1, example 1 and example 2. FIG. 2 is a SEM image of CZTSSe at different precursor heating temperatures, and it can be seen that when the substrate is heated at 200 ℃, the flatness and the compactness of the CZTSSe film are reduced, and the porosity is 6.39% and is increased to some extent. FIG. 3 is (a) a J-V curve of a flexible device; the PCE of the flexible device heated by the precursor at 100 ℃ under different bending conditions decays (b) the bending time, (C) the bending degree, and (d) the bending duration, and it can be seen from the figure that the PCE of the sample obtained in example 3 is 4.09%, the open-circuit voltage (Voc) is 334.52mV, and the current density (Jsc) is25.17mA/cm 2 The Fill Factor (FF) was 48.65%. From the above results, it can be seen that excessive temperature increases the residual stress of the CZTSSe thin film solar cell and degrades the electrical performance.
The present invention provides a method and a concept for improving the residual stress of the absorber layer of the flexible CZTSSe thin film solar cell, and a method and a way for implementing the method are many, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and embellishments can be made without departing from the principle of the present invention, and these improvements and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in this embodiment can be implemented by the prior art.

Claims (10)

1. A method for improving the residual stress of an absorption layer of a flexible CZTSSe thin film solar cell is characterized in that when a precursor thin film of the flexible CZTSSe thin film solar cell is prepared, the precursor thin film of the CZTS is heated during sputtering.
2. The method of claim 1, wherein the heating of the CZTS precursor film is achieved by heating the substrate during sputtering, the heating temperature being in a range of 50 ℃ to 200 ℃.
3. A preparation method of an absorption layer of a flexible CZTSSe thin film solar cell is characterized by comprising the following steps:
(1) preparing a CZTS precursor film: co-sputtering by adopting a magnetron sputtering method to prepare an upper layer and a lower layer of an interlayer precursor, then preparing a middle layer of the precursor, and heating a CZTS precursor film during sputtering;
(2) preparation of CZTSSe absorbing layer: placing the CZTS precursor film obtained in the step (1) and selenium particles into a small quartz tube with an opening end sealed by a quartz plug with a small hole in the center, placing the small quartz tube into a single-temperature-zone tube annealing furnace for annealing, and introducing N in the selenizing annealing process 2 Preventing the precursor film from generating oxygenAnd carrying out chemical reaction to obtain the CZTSSe absorption layer.
4. The method according to claim 3, wherein in the step (1), the sputtering power for preparing the upper and lower layers of the interlayer precursor is: zn 13-15W, CZTS 40-60W, and the sputtering time is 600-800 s; the sputtering power when preparing the middle layer of the precursor is as follows: cu 6-8W, CZTS 40-60W, and the sputtering time is 4700 and 4900 s.
5. The method according to claim 3, wherein the heating temperature in step (1) is 50 to 200 ℃.
6. The method as claimed in claim 3, wherein the annealing temperature in step (2) is 560- 2 The flow rate is 50-70 sccm; the atomic ratio of Se/(S + Se) in the finally prepared CZTSSe is 0.7-0.9.
7. A flexible CZTSSe thin film solar cell, which is characterized by comprising the absorption layer of the flexible CZTSSe thin film solar cell prepared by the preparation method of any one of claims 3 to 6.
8. The flexible CZTSSe thin film solar cell of claim 7, further comprising a flexible substrate Ti, a Mo back electrode, a CdS buffer layer, an i-ZnO window layer, an ITO transparent conductive layer, and an Ag electrode.
9. The flexible CZTSSe thin film solar cell of claim 7, wherein the flexible substrate Ti has dimensions of 2 x 2cm 2 The thickness is 40-60 μm; the thickness of the Mo back electrode layer is 800-1100 nm; the thickness of the CZTSSe absorption layer is 1-1.5 μm; the CdS buffer layer is 55-65nm thick; the thicknesses of the i-ZnO and the ITO are respectively 40-60nm and 150-250 nm.
10. The flexible CZTSSe thin film solar cell of claim 7, wherein a Ti substrate is a titanium foil, a Mo layer is formed by a dc sputtering method, a CdS buffer layer is deposited by a chemical water bath deposition method, an i-ZnO window layer and an ITO transparent conductive layer are formed by a magnetron sputtering method, and an Ag layer is formed by an evaporation method.
CN202210678780.XA 2022-06-15 2022-06-15 Method for improving residual stress of absorption layer of flexible CZTSSe thin-film solar cell and application Pending CN114864752A (en)

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