CN114447128A - Method for preparing zinc-yellow-tin-ore-structure thin-film solar cell absorption layer based on sulfur-source-free precursor - Google Patents

Method for preparing zinc-yellow-tin-ore-structure thin-film solar cell absorption layer based on sulfur-source-free precursor Download PDF

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CN114447128A
CN114447128A CN202210112259.XA CN202210112259A CN114447128A CN 114447128 A CN114447128 A CN 114447128A CN 202210112259 A CN202210112259 A CN 202210112259A CN 114447128 A CN114447128 A CN 114447128A
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CN114447128B (en
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韩修训
方奕锟
刘为振
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Ganzhou Rare Gold New Material Research Institute Co ltd
Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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Abstract

The invention provides a method for preparing a kesterite-structure thin-film solar cell absorption layer based on a sulfur-source-free precursor, which comprises the following steps: ethanolamine and DMF are mixed according to a volume ratio of 6: 4-10: and (3) taking the mixed solution of 0 as a solvent, preparing a sulfur-source-free CZT precursor solution containing Cu, Zn and Sn elements, preparing a sulfur-source-free CZT precursor film by a solution spin coating method, and selenizing and/or vulcanizing the sulfur-source-free CZT precursor film. The invention adopts a new solution method to synthesize the CZT precursor film without the sulfur source, and then selenizing or vulcanizing or selenizing and vulcanizing simultaneously to prepare the kesterite structure absorption layer film which can be used for preparing the thin film solar cell. The method does not contain a sulfur source in the process of preparing the precursor, does not release sulfur-containing gas, reduces the emission of toxic gas, is simple and convenient to operate, and has a good application value in the field of solar cells.

Description

Method for preparing casserole structure thin-film solar cell absorption layer based on sulfur-source-free precursor
Technical Field
The invention relates to the field of solar cells, in particular to a method for preparing a kesterite-structure thin-film solar cell absorption layer based on a sulfur-source-free precursor.
Background
With the continuous development of human society, the demand of human beings on energy is more and more, but the quantity of non-renewable energy sources is limited, and waste water, waste gas and solid waste discharged in the using process have great pollution to the environment. Solar energy is a current research hotspot because of its advantages of greenness, no pollution, no region limitation and the like, and has a broad prospect.
The CZTSSe semiconductor material with the kesterite structure has rich earth content and large absorption coefficient to visible light (due to the composition elements of the CZTSSe semiconductor material)>104cm-1) The forbidden band width can be adjusted (1.0-1.5 eV) and the theoretical conversion efficiency (>30%) of the film, and can be used as an absorption layer of a thin film solar cell.
Among the various preparation methods of the CZTSSe thin-film solar cell absorption layer, a vacuum method (evaporation method, sputtering method and the like) and a non-vacuum method (spraying method, spin coating method, blade coating method and the like) are commonly used, the vacuum method has high requirements on equipment, the preparation cost is generally higher than that of the non-vacuum method, and the operation is complex; the non-vacuum method is simple and convenient to operate and low in cost, and the prepared absorption layer is more uniform, so that the high-quality CZTSSe absorption layer is formed. In the early preparation, most vacuum methods were adopted, and most of the methods used at present are non-vacuum methods, among which the solution spin coating method is widely used. However, sulfur element is often introduced when the precursor thin film of the CZTSSe absorption layer is prepared by the solution method, sulfur-containing gas is generated in the annealing process, and the damage to the environment is large.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a kesterite-structure thin-film solar cell absorption layer based on a sulfur-source-free precursor.
The invention provides a method for preparing a kesterite-structure thin-film solar cell absorption layer based on a sulfur-source-free precursor, which comprises the following steps of: ethanolamine and DMF are mixed according to a volume ratio of 6: 4-10: and (3) taking the mixed solution of 0 as a solvent, preparing a sulfur-source-free CZT precursor solution containing Cu, Zn and Sn elements, preparing a sulfur-source-free CZT precursor film by a solution spin coating method, and selenizing and/or vulcanizing the sulfur-source-free CZT precursor film.
The method successfully uses a solution spin coating method to prepare the CZT precursor film without the sulfur source, and then selenizes the precursor film to obtain the CZTSe absorption layer film, or sulfurizes the CZTS absorption layer film, or selenizes and sulfurizes the CZTSSe absorption layer film at the same time. The synthesis method of the sulfur source-free precursor is simple and convenient to operate, high in efficiency, environment-friendly and wide in development prospect, and can reduce the emission of toxic gases. The invention discloses a method for preparing a composite material, which is characterized in that a solvent is selected more critically, and the invention discovers that ethanolamine or ethanolamine-DMF mixed solution is required to be selected as the solvent through research.
Further, the volume ratio of the ethanolamine to the DMF in the mixed solution is 6: 4-7: 3. DMF refers to N, N-dimethylformamide.
When the volume ratio of the ethanolamine is increased, the viscosity of the precursor solution is increased, the wettability between the solution and the Mo substrate is reduced, and the film-forming quality of the precursor film is reduced during spin coating; since the film after selenization is exfoliated when the volume ratio of DMF is increased, the volume ratio of ethanolamine to DMF is preferably controlled within the above range.
Furthermore, Zn/Sn in the sulfur-source-free CZT precursor solution is 1.0-1.5, and Cu/(Zn + Sn) is 0.6-0.7.
Further preferably, in the sulfur-source-free CZT precursor solution, Zn/Sn is 1.4, and Cu/(Zn + Sn) is 0.65.
More preferably, the concentration of the Cu element in the sulfur-source-free CZT precursor solution is 0.20-0.50 mol/L, the concentration of the Zn element is 0.20-0.50 mol/L, and the concentration of the Sn element is 0.15-0.30 mol/L. When the concentrations of the metal sources in the precursor solution are different, the number of spin-coating layers is different.
Furthermore, the sulfur-source-free CZT precursor solution can be used for doping alkali metal ions such as Li ions, Na ions and K ions, and can also be used for doping cations such as Ag ions, Ge ions and Cd ions. After doping, the performance of the absorption layer can be further improved.
Further, the preparation process of the solution spin coating method comprises the following steps: and spin-coating the sulfur-source-free CZT precursor solution on a molybdenum-plated soda-lime glass substrate, annealing for 2-10 min at 300-500 ℃, and repeatedly spin-coating for 5-7 times to obtain the sulfur-source-free CZT precursor film.
Further preferably, the annealing treatment temperature is 400 +/-20 ℃, and the time is 4-6 min. The longer the annealing/drying time of the precursor solution is, the more obvious the alloy phase elements of the precursor film gather to the surface layer, so that the elements in the film are not uniformly distributed, and the partial component difference of the CZTSe absorption layer can be caused after selenization, thereby influencing the conversion efficiency.
Wherein the thickness of the molybdenum plating on the soda-lime glass substrate is preferably 800-1000 nm.
The molybdenum-plated soda-lime glass substrate needs to be cleaned and dried before use, and the method specifically comprises the following steps: firstly, ultrasonically cleaning a molybdenum-plated soda-lime glass substrate for 15min by using a detergent aqueous solution, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate for 15min in deionized water, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate for 15min in acetone, then ultrasonically cleaning the molybdenum-plated soda-lime glass substrate for 15min in ethanol, and finally drying the molybdenum-plated soda-lime glass substrate in a drying box.
In the specific implementation mode of the invention, a spin coater can be adopted to spin-coat the CZT precursor solution on a cleaned molybdenum-sodium-calcium-coated glass substrate, and then the substrate spin-coated with the sulfur-source-free CZT precursor solution is placed on a heating table for annealing.
Further, the temperature rise rate of the selenization and/or the vulcanization is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃. The selenization and/or the sulfurization can be carried out in a rapid heating annealing furnace, and protective gas is continuously introduced in the process of the selenization and/or the sulfurization.
In a preferred embodiment of the present invention, the method for preparing an absorber layer of a kesterite-structure thin-film solar cell based on a sulfur-source-free precursor comprises the following steps:
(1) mixing Cu (CH)3COO)2·H2O、Zn(CH3COO)2·2H2O and SnCl2·2H2Mixing O with the solvent, and stirring until the O is completely dissolved to form a sulfur source-free CZT precursor solution;
(2) spin-coating the sulfur-source-free CZT precursor solution on a soda-lime glass substrate plated with molybdenum with the thickness of 800-1000nm, annealing for 2-10 min at 300-500 ℃, and repeatedly spin-coating for 5-7 times to obtain the sulfur-source-free CZT precursor film;
(3) and under the condition of continuously introducing protective gas, selenizing and/or vulcanizing the sulfur-source-free CZT precursor film, wherein the temperature rise rate of the selenizing and/or vulcanizing is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃.
Wherein, in the step (1), the Sn source can also use anhydrous stannous chloride, and the result is almost the same as that of using stannous chloride hydrate.
Further, the thickness of the absorption layer is 1-3 μm.
The invention also provides a preparation method of the thin film solar cell, which comprises the step of preparing the absorption layer used by the thin film solar cell by the method. Namely, after the absorption layer is prepared according to the method, the thin film solar cell is obtained through subsequent preparation/assembly.
In a specific embodiment of the present invention, the thin film solar cell has a SLG/Mo/czt(s) Se/CdS/ZnO/ITO/Al structure, and the preparation method thereof includes the steps of:
(1) adding ammonia water into the cadmium salt aqueous solution, uniformly stirring, putting the prepared absorption layer, adding thiourea aqueous solution, performing water bath deposition, and depositing a CdS buffer layer on the absorption layer;
(2) depositing a layer of intrinsic zinc oxide i-ZnO on the CdS buffer layer by adopting a radio frequency magnetron sputtering method;
(3) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method;
(4) and preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method.
Preferably, the more detailed condition control is as follows:
(1) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared absorption layer, adding a thiourea aqueous solution, performing water bath deposition at 70 ℃ for 7-10 min, depositing a CdS buffer layer on the absorption layer, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(2) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background vacuum is less than 5x10-4 Pa, the sputtering power is 130W, the working pressure is 0.2Pa, and the sputtering time is 15 min;
(3) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(4) preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
The invention provides a method for preparing a kesterite-structure thin-film solar cell absorption layer based on a sulfur-source-free precursor. The method does not contain a sulfur source in the process of preparing the precursor, does not release sulfur-containing gas, reduces the emission of toxic gas, is simple and convenient to operate, and has a good application value in the field of solar cells.
Drawings
FIG. 1 is an XRD pattern of the CZTSe absorbing layer prepared in example 2;
FIG. 2 is a surface and cross-sectional topography of a CZT precursor film prepared in example 2 and an SEM surface and cross-sectional topography of a selenized CZTSe film;
FIG. 3 is a pictorial representation of a CZTSe thin film solar cell prepared in example 2;
FIG. 4 is a J-V plot of a CZTSe thin film solar cell prepared in example 2;
FIG. 5 is a graph of the efficiency statistics for CZTSe thin film solar cells prepared in examples 1-5;
FIG. 6 is a graph showing the efficiency statistics of CZTSe thin film solar cell devices prepared in example 6 using ethanolamine alone as a solvent;
fig. 7 is a graph showing the efficiency statistics of CZTSe thin-film solar cell devices prepared in example 7 using a mixed solvent of ethanolamine and ethanol (ethanolamine: ethanol: 7: 3) as a solvent;
FIG. 8 is a graph showing the efficiency statistics of CZTSe thin film solar cell devices prepared in example 8 by using DMF alone as a solvent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanolamine: DMF: 7:3 by volume), and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum (800nm) sodium calcium plated glass substrate by using a spin coater, then placing the substrate on a heating table (400 ℃) for annealing for 2min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Example 2
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanolamine: DMF: 7:3 by volume), and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-coated glass substrate by using a spin coater, then placing the substrate on a heating table (400 ℃) for annealing for 4min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, evaporation time 10 min.
FIG. 1 is an XRD pattern of the absorption layer of CZTSe prepared in this example; FIG. 2 is a surface and cross-sectional profile of a CZT precursor film and an SEM surface and cross-sectional profile of a selenized CZTSe film prepared in this example; FIG. 3 is a schematic diagram of a CZTSe thin-film solar cell prepared by the present example; fig. 4 is a J-V plot of a CZTSe thin film solar cell prepared in this example.
From the results, the prepared CZTSe absorption layer only contains CZTSe, molybdenum selenide and Mo characteristic peaks, and does not contain other secondary phases; the CZTSe absorption layer film is large in grain size and compact, and the absorption layer is composed of a large grain layer, a small grain layer and a carbon-rich layer from top to bottom. Due to the existence of the carbon-rich layer, the series resistance of the device is large, and the performance of the device is affected.
Example 3
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanolamine: DMF: 7:3 by volume), and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table (400 ℃) for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argonGas, background vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Example 4
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanolamine: DMF: 7:3 by volume), and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table (400 ℃) for annealing for 8min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) by usingSputtering an ITO transparent conducting layer on the i-ZnO by a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Example 5
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanolamine: DMF: 7:3 by volume), and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table (400 ℃) for annealing for 10min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, sputteringThe power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Example 6
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of ethanolamine solvent, and completely dissolving to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, and preparing a process parameterThe number is as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, evaporation time 10 min.
Example 7
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of solvent (ethanol amine: ethanol in a volume ratio of 7: 3) to completely dissolve to form a CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Example 8
The embodiment provides a method for preparing a CZTSe thin-film solar cell absorption layer based on a sulfur-source-free precursor, which specifically comprises the following steps:
(1) 0.93436g of Cu (CH) were weighed out3COO)2·H2O、0.92194g Zn(CH3COO)2·2H2O and 0.67695g SnCl2·2H2Dissolving O in 10mL of DMF solvent to form CZT precursor solution;
(2) spin-coating the CZT precursor solution on a cleaned molybdenum-sodium-calcium-plated glass substrate by using a spin coater, then placing the substrate on a heating table for annealing for 6min, and repeatedly spin-coating for 7 times to obtain a CZT precursor film;
(3) and under the condition of continuously introducing protective gas, putting the obtained CZT precursor film into a rapid heating annealing furnace for selenizing treatment, heating to 530 ℃ within 500s, preserving heat for 600s, and then naturally cooling to obtain the CZTSe absorption layer film.
In this embodiment, a thin film solar cell is further prepared from the CZTSe absorption layer thin film obtained as above, and the steps are as follows:
(4) adding ammonia water into a cadmium salt aqueous solution, uniformly stirring, placing the prepared CZTSe film, adding a thiourea aqueous solution, depositing in a 70 ℃ water bath for 7-10 min, depositing a CdS buffer layer on the CZTSe film, washing the deposited film with a large amount of deionized water, drying by blowing, and finally drying in a drying oven;
(5) depositing a layer of intrinsic zinc oxide (i-ZnO) on the CdS buffer layer by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.2Pa, and the sputtering time is 15 min;
(6) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method, wherein the process parameters are as follows: the sputtering gas is argon, the background is vacuum<5x10-4Pa, the sputtering power is 130W, the working air pressure is 0.12Pa, and the sputtering time is 30 min;
(7) preparing a grid Al electrode on the ITO conductive layer by adopting a thermal evaporation method, wherein the process parameters are as follows: background vacuum<5x10-4Pa, evaporation power supply current 120A, and evaporation time 10 min.
Fig. 5 is a statistical graph of the efficiencies of CZTSe thin-film solar cells prepared in examples 1 to 5, and fig. 6, 7 and 8 are statistical graphs of the efficiencies of CZTSe thin-film solar cells prepared in examples 6, 7 and 8, respectively.
It can be seen that the CZTSe thin-film solar cell prepared by using the ethanolamine-DMF mixed solution as the solvent has high efficiency, wherein the highest efficiency can reach 6.8% after annealing the precursor for 4min in the embodiment 2, but the efficiency of the device is not uniform and the efficiency distribution interval is large; when annealing is performed for 6min in example 3, the average efficiency of the device is the highest, and the efficiency distribution is also the most uniform.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A method for preparing an absorption layer of a kesterite-structure thin-film solar cell based on a sulfur-source-free precursor is characterized by comprising the following steps of: ethanolamine and DMF are mixed according to a volume ratio of 6: 4-10: and (3) taking the mixed solution of 0 as a solvent, preparing a sulfur-source-free CZT precursor solution containing Cu, Zn and Sn elements, preparing a sulfur-source-free CZT precursor film by a solution spin coating method, and selenizing and/or vulcanizing the sulfur-source-free CZT precursor film.
2. The method for preparing the zinc kesterite structure thin-film solar cell absorption layer based on the sulfur-source-free precursor as claimed in claim 1, wherein the volume ratio of ethanolamine to DMF in the mixed solution is 6: 4-7: 3.
3. The method for preparing the zincite structure thin-film solar cell absorber layer based on the sulfur-source-free precursor as claimed in claim 1 or 2, wherein the sulfur-source-free CZT precursor solution has Zn/Sn of 1.0-1.5 and Cu/(Zn + Sn) of 0.6-0.7.
4. The method of claim 3, wherein the sulfur-source-free CZT precursor solution is subjected to Li+、Na+、K+、Ag+Ge ion and Cd ion doping.
5. The method for preparing an absorber layer of a kesterite-structure thin-film solar cell based on a sulfur-source-free precursor according to claim 1 or 2, wherein the solution spin-coating preparation process comprises: and spin-coating the sulfur-source-free CZT precursor solution on a molybdenum-plated soda-lime glass substrate, annealing for 2-10 min at 300-500 ℃, and repeatedly spin-coating for 5-7 times to obtain the sulfur-source-free CZT precursor film.
6. The method for preparing the zinc yellow tin ore structure thin-film solar cell absorption layer based on the sulfur-source-free precursor as claimed in claim 1 or 2, wherein the temperature rise rate of the selenization and/or the sulfurization is 0.5-5 ℃/s, the time is 10-30 min, and the temperature is 530-570 ℃.
7. The method for preparing an absorber layer of a kesterite-structured thin-film solar cell based on a sulfur-free precursor according to claim 1, comprising the following steps:
(1) mixing Cu (CH)3COO)2·H2O、Zn(CH3COO)2·2H2O and SnCl2·2H2Mixing O with the solvent, and stirring until the O is completely dissolved to form a sulfur source-free CZT precursor solution;
(2) spin-coating the sulfur-source-free CZT precursor solution on a soda-lime glass substrate plated with molybdenum with the thickness of 800-1000nm, annealing for 2-10 min at 300-500 ℃, and repeatedly spin-coating for 5-7 times to obtain the sulfur-source-free CZT precursor film;
(3) and under the condition of continuously introducing protective gas, selenizing and/or vulcanizing the CZT precursor film without the sulfur source.
8. The method for preparing the kesterite-structure thin-film solar cell absorber layer based on the sulfur-source-free precursor as claimed in claim 7, wherein the thickness of the absorber layer is 1-3 μm.
9. A method for manufacturing a thin film solar cell, comprising the step of manufacturing an absorption layer for a thin film solar cell by the method according to any one of claims 1 to 8.
10. The method of claim 9, wherein the thin film solar cell has an SLG/Mo/kesterite/CdS/ZnO/ITO/Al structure, and the method comprises the steps of:
(1) adding ammonia water into the cadmium salt aqueous solution, uniformly stirring, putting the prepared absorption layer, adding thiourea aqueous solution, performing water bath deposition, and depositing a CdS buffer layer on the absorption layer;
(2) depositing a layer of intrinsic zinc oxide i-ZnO on the CdS buffer layer by adopting a radio frequency magnetron sputtering method;
(3) sputtering an ITO transparent conducting layer on the i-ZnO by adopting a radio frequency magnetron sputtering method;
(4) and preparing a grid Al electrode on the ITO transparent conductive layer by adopting a thermal evaporation method.
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