CN113540288A - Room-temperature vulcanized copper-based absorption layer thin film, solar cell and preparation method of solar cell - Google Patents

Room-temperature vulcanized copper-based absorption layer thin film, solar cell and preparation method of solar cell Download PDF

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CN113540288A
CN113540288A CN202110767251.2A CN202110767251A CN113540288A CN 113540288 A CN113540288 A CN 113540288A CN 202110767251 A CN202110767251 A CN 202110767251A CN 113540288 A CN113540288 A CN 113540288A
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copper
layer
absorption layer
solar cell
thin film
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CN113540288B (en
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张毅
王思宇
申展
刘越
王作允
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Nankai University
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Abstract

The invention provides a room temperature vulcanized copper-based absorption layer film, a solar cell and a preparation method thereof, wherein the room temperature vulcanized copper-based absorption layer film, the solar cell and the preparation method thereof comprise the following steps: depositing a copper-based absorption layer film on the Mo electrode; and treating the surface of the copper-based absorption layer film by using ammonia water and ammonia sulfide vapor to obtain the copper-based film solar cell with a surface gradient band gap. According to the invention, ammonia water is used for etching the surface of the copper-based film to leave dangling bonds and selenium vacancies on the surface. Then ammonia sulfide vapor is used for vulcanizing the surface of the copper-based film, so that the surface band gap is increased, and the surface gradient band gap is formed. After room temperature vulcanization, the open-circuit voltage of the battery is greatly improved, so that the efficiency is improved. The surface process of the copper sulfide base film by the ammonia sulfide vapor is simple, and the manufacturing cost of the solar cell is reduced.

Description

Room-temperature vulcanized copper-based absorption layer thin film, solar cell and preparation method of solar cell
Technical Field
The invention belongs to the field of solar cells, and relates to a room-temperature copper sulfide-based absorption layer film and a preparation method thereof, and a copper-based film solar cell and a preparation method thereof.
Background
The energy crisis and environmental pollution become more serious, and the development of clean green energy is now a major issue facing human beings. Solar power generation is an internationally recognized new energy industry with development potential, and all countries develop solar photovoltaic technology completely, and solar photovoltaic development and utilization are taken as an important strategy for sustainable energy development. The copper-based thin film solar cell is a thin film cell with a copper-based compound as an absorption layer, and has stable performance, strong radiation resistance and high photoelectric conversion efficiency.
At present, the efficiency of the copper-based thin film solar cell is still lower than the theoretical efficiency, and one of the key limiting factors is the open circuit voltage. In order to increase the open circuit voltage, one of effective methods is a copper sulfide-based thin film. However, the conventional vulcanization method has the following problems: (1) the traditional vulcanization method is carried out at high temperature, which is easy to cause the decomposition of a copper-based film and the loss of certain elements, thereby deteriorating the performance of a device; (2) the traditional high-temperature vulcanization method ensures that the doping depth of sulfur is difficult to control and is not beneficial to the formation of the front gradient band gap; (3) the traditional high-temperature vulcanization method can cause deep energy level defects to be introduced into the copper-based film, so that the performance of a device is reduced.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a room-temperature vulcanized copper-based absorption layer film and a preparation method thereof, and a copper-based film solar cell and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions.
The invention provides a preparation method of a room-temperature vulcanized copper-based absorption layer film, which comprises the following steps:
1) sequentially sputtering Mo/M2/M1/M3/M1 metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of M1 metal is sputtered at constant power of a direct-current power supply, the power is 85W, the sputtering time is 4min, the second layer of M1 metal is sputtered at constant power of the direct-current power supply, the power is 80W, and the sputtering time is 5 min; the metal M3 is also sputtered with a direct-current power supply at constant power, the power is 26W, and the sputtering time is 25.5 min; the metal M2 is sputtered by a direct-current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under the X atmosphere to obtain a copper-based absorption layer film; the copper-based absorption layer thin film includes a compound having M1, M2, M3, X, and a combination thereof, wherein M1 is copper (Cu), silver (Ag), or a combination thereof, M2 is indium (In), aluminum (Al), zinc (Zn), or a combination thereof, M3 is gallium (Ga), germanium (Ge), tin (Sn), or a combination thereof, and X is selenium (Se), sulfur (S), or a combination thereof;
2) and treating the surface of the copper-based absorption layer film by using ammonia sulfide vapor to obtain the copper-based absorption layer film with the front surface gradient band gap.
The concentration of the ammonia sulfide solution for volatilizing to generate the ammonia sulfide vapor is 20 wt%, and the treatment time of the ammonia sulfide vapor is 5-60 min.
As a further improvement of the technical scheme, ammonia water etching is needed before the copper-based absorption layer film is treated by ammonia sulfide vapor, and the concentration of the ammonia water solution is 25 wt%.
The thickness of the copper-based absorption layer film is 0.4-3 mu m.
The invention provides a room temperature vulcanized copper-based absorption layer film prepared by the method.
The invention provides a room temperature vulcanized copper-based thin film solar cell, wherein an absorption layer of the copper-based thin film solar cell is the copper-based absorption layer thin film of the second aspect.
The copper-based thin film solar cell comprises a substrate, a positive electrode, an absorption layer, a buffer layer, a window layer and a top electrode which are sequentially stacked.
As a further improvement of the technical scheme, the substrate is made of soda-lime glass, sodium-free glass or quartz glass, the positive electrode is a Mo metal electrode prepared on the substrate, and the thickness of the positive electrode is 1-2 μm.
The thickness of the absorption layer is 0.4-3 mu m;
the buffer layer is made of CdS, ZnS, (Cd, Zn) S, Zn (O, S) or In2S3(ii) a The thickness of the buffer layer is 30-100 nm.
The window layer comprises an intrinsic zinc oxide layer and a doped zinc oxide layer which are sequentially stacked; the thickness of the intrinsic zinc oxide layer is 30-150 nm; the thickness of the doped zinc oxide layer is 300-1500 nm.
The top electrode is made of aluminum or nickel-aluminum alloy; the top electrode has a thickness of 0.5 to 4 μm.
The fourth aspect of the invention provides a method for preparing a room-temperature vulcanized copper-based thin film solar cell, which comprises the following steps:
forming a positive electrode on a substrate;
depositing and preparing an absorption layer of the copper-based thin film solar cell according to the preparation method of the first aspect;
forming a buffer layer on the absorption layer;
forming a window layer on the buffer layer;
a top electrode is formed on the window layer.
The invention has the advantages and beneficial effects that:
according to the invention, ammonia water and ammonia sulfide vapor are used for treating the copper-based absorption layer film, and the ammonia water etches the surface of the copper-based absorption layer film to leave dangling bonds and selenium vacancies. Subsequent ammonia sulfide vapor passivates dangling bonds and selenium vacancies on the surface, so that the surface band gap of the copper-based absorption layer film is increased, and the interface energy band alignment between the absorption layer and the buffer layer is improved. After the treatment, the open-circuit voltage of the battery is greatly improved, so that the efficiency is improved. The process for treating the absorption layer film of the copper-based cell at room temperature by using the ammonia sulfide vapor is simple, and the manufacturing cost of the solar cell is reduced.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
Fig. 1 is a schematic structural view of a room-temperature-vulcanized copper-based thin-film solar cell in example 4.
Fig. 2 is a graph of the efficiency of a room temperature vulcanized copper-based thin film solar cell.
Detailed Description
The terminology as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "including," "has," "having," "contains," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A preparation method of a room-temperature vulcanized copper-based absorption layer film comprises the following steps:
sequentially sputtering Mo/Zn/Cu/Sn/Cu metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 85W, the sputtering time is 4min, the second layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 80W, and the sputtering time is 5 min; the metal Sn is also sputtered at constant power of a direct-current power supply, the power is 26W, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain a copper-based absorption layer film CZTSe; the copper-based absorption layer film is etched for 5min by 25 wt% of ammonia water, and then treated for 5min by vapor volatilized by 20 wt% of ammonia sulfide solution, so that the absorption layer CZTSSe of the room-temperature vulcanized copper-based film solar cell with the thickness of 1.5 mu m is obtained.
Example 2
The difference from example 1 was that the time for the vapor treatment for volatilizing the ammonia sulfide solution was changed to 40 min.
Example 3
The difference from example 1 is that the time for the vapor treatment in which the ammonia sulfide solution was volatilized was changed to 60 min.
Example 4
A preparation method of a room-temperature vulcanized copper-based absorption layer film comprises the following steps:
the Mo positive electrode is sputtered in sequence by adopting a magnetron sputtering methodEjecting a Mo/Zn/Ag/Ge/Ag metal preset layer, sputtering a first layer of Ag at a constant power of 85W for 4min by using a direct-current power supply, and sputtering a second layer of Ag at a constant power of 80W for 5min by using a direct-current power supply; the Ge metal is sputtered at constant power of 26W by adopting a direct-current power supply, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain the copper-based absorption layer film Ag2ZnGeSe4(ii) a Etching the copper-based absorption layer film for 5min by using 25 wt% of ammonia water, and then treating for 5min by using vapor volatilized by using 20 wt% of ammonia sulfide solution to obtain the absorption layer Ag of the room-temperature-vulcanized copper-based film solar cell with the thickness of 1.5 mu m2ZnGe(S,Se)4。
Example 5
The difference from example 4 was that the time for the vapor treatment for volatilizing the ammonia sulfide solution was changed to 40 min.
Example 6
The difference from example 4 is that the time for the vapor treatment in which the ammonia sulfide solution was volatilized was changed to 60 min.
Example 7
A preparation method of a room-temperature vulcanized copper-based thin film solar cell comprises the following steps:
1. a Mo metal positive electrode with the thickness of 1 mu m is prepared on soda-lime glass by a magnetron sputtering method.
2. Sequentially sputtering Mo/Zn/Cu/Sn/Cu metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 85W, the sputtering time is 4min, the second layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 80W, and the sputtering time is 5 min; the metal Sn is also sputtered at constant power of a direct-current power supply, the power is 26W, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain a copper-based absorption layer film CZTSe; the copper-based absorption layer film is etched for 5min by 25 wt% of ammonia water, and then treated for 5min by vapor volatilized by 20 wt% of ammonia sulfide solution, so that the absorption layer CZTSSe of the room-temperature vulcanized copper-based film solar cell with the thickness of 1.5 mu m is obtained.
3. And preparing a 50 nm-thick CdS buffer layer on the absorption layer by adopting a chemical water bath method.
4. And preparing an intrinsic zinc oxide (i-ZnO) layer on the CdS buffer layer by adopting a magnetron sputtering method, wherein the thickness of the film is 50 nm. Similarly, a 500nm thick aluminum-doped zinc oxide (AZO) layer was prepared by magnetron sputtering.
5. An aluminum layer with the thickness of 1 mu m is prepared on the aluminum-doped zinc oxide layer by adopting an evaporation method to be used as a top electrode.
The structure of the prepared copper-based thin film solar cell is shown in figure 1.
Example 8
The difference from example 7 was that the time for the vapor treatment for volatilizing the ammonia sulfide solution was changed to 40 min.
Example 9
The difference from example 7 is that the time for the vapor treatment in which the ammonia sulfide solution was volatilized was changed to 60 min.
Example 10
A preparation method of a room-temperature vulcanized copper-based thin film solar cell comprises the following steps:
1. a Mo metal positive electrode with the thickness of 1 mu m is prepared on soda-lime glass by a magnetron sputtering method.
2. Sequentially sputtering Mo/Zn/Ag/Ge/Ag metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of Ag is sputtered at constant power of a direct-current power supply, the power is 85W, the sputtering time is 4min, the second layer of Ag is sputtered at constant power of the direct-current power supply, the power is 80W, and the sputtering time is 5 min; the Ge metal is sputtered at constant power of 26W by adopting a direct-current power supply, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain the copper-based absorption layer film Ag2ZnGeSe4(ii) a Etching the copper-based absorption layer film for 5min by using 25 wt% of ammonia water, and then treating for 5min by using vapor volatilized by using 20 wt% of ammonia sulfide solution to obtain the absorption layer Ag of the room-temperature-vulcanized copper-based film solar cell with the thickness of 1.5 mu m2ZnGe(S,Se)4。
3. And preparing a 50 nm-thick CdS buffer layer on the absorption layer by adopting a chemical water bath method.
4. And preparing an intrinsic zinc oxide (i-ZnO) layer on the CdS buffer layer by adopting a magnetron sputtering method, wherein the thickness of the film is 50 nm. Similarly, a 500nm thick aluminum-doped zinc oxide (AZO) layer was prepared by magnetron sputtering.
5. An aluminum layer with the thickness of 1 mu m is prepared on the aluminum-doped zinc oxide layer by adopting an evaporation method to be used as a top electrode.
Example 11
The difference from example 10 was that the time for vapor treatment for volatilization of the ammonia sulfide solution was changed to 40 min.
Example 12
The difference from example 10 is that the time for the vapor treatment in which the ammonia sulfide solution was volatilized was changed to 60 min.
Comparative example 1
A preparation method of a copper-based thin film solar cell comprises the following steps:
1. a Mo metal positive electrode with the thickness of 1 mu m is prepared on soda-lime glass by a magnetron sputtering method.
2. Sequentially sputtering Mo/Zn/Cu/Sn/Cu metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 85W, the sputtering time is 4min, the second layer of Cu is sputtered by adopting a direct-current power supply with constant power, the power is 80W, and the sputtering time is 5 min; the metal Sn is also sputtered at constant power of a direct-current power supply, the power is 26W, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain the copper-based absorption layer film CZTSe with the thickness of 1.5 mu m.
3. And preparing a 50 nm-thick CdS buffer layer on the absorption layer by adopting a chemical water bath method.
4. And preparing an intrinsic zinc oxide (i-ZnO) layer on the CdS buffer layer by adopting a magnetron sputtering method, wherein the thickness of the film is 50 nm. Similarly, a 500nm thick aluminum-doped zinc oxide (AZO) layer was prepared by magnetron sputtering.
5. An aluminum layer with the thickness of 1 mu m is prepared on the aluminum-doped zinc oxide layer by adopting an evaporation method to be used as a top electrode.
Comparative example 2
1. A Mo metal positive electrode with the thickness of 1 mu m is prepared on soda-lime glass by a magnetron sputtering method.
2. Sequentially sputtering Mo/Zn/Ag/Ge/Ag metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of Ag is sputtered at constant power of a direct-current power supply, the power is 85W, the sputtering time is 4min, the second layer of Ag is sputtered at constant power of the direct-current power supply, the power is 80W, and the sputtering time is 5 min; the Ge metal is sputtered at constant power of 26W by adopting a direct-current power supply, and the sputtering time is 25.5 min; the metal Zn is sputtered by adopting a direct current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under Se atmosphere to obtain a copper-based absorption layer film Ag with the thickness of 1.5 mu m2ZnGeSe4。
3. And preparing a 50 nm-thick CdS buffer layer on the absorption layer by adopting a chemical water bath method.
4. And preparing an intrinsic zinc oxide (i-ZnO) layer on the CdS buffer layer by adopting a magnetron sputtering method, wherein the thickness of the film is 50 nm. Similarly, a 500nm thick aluminum-doped zinc oxide (AZO) layer was prepared by magnetron sputtering.
5. An aluminum layer with the thickness of 1 mu m is prepared on the aluminum-doped zinc oxide layer by adopting an evaporation method to be used as a top electrode.
Effect verification
The efficiencies of the copper-based thin film solar cells prepared in examples 7, 8 and 9 and comparative example 1 were measured by the following methods:
and connecting the anode and the cathode of the manufactured solar cell into a solar cell IV performance tester, and obtaining a cell voltage-current curve under the irradiation of standard sunlight intensity.
As shown in fig. 2, it can be seen from fig. 2 that the open circuit voltage of the solar cell treated with the ammonia sulfide vapor is increased compared to the solar cell not treated with the ammonia sulfide vapor, and the short circuit current of the solar cell treated with the ammonia sulfide vapor for 40min is 430mV, which is increased by about 66mV compared to the untreated solar cell.

Claims (9)

1. A method for preparing a room-temperature vulcanized copper-based absorption layer film is characterized by comprising the following steps:
1) sequentially sputtering Mo/M2/M1/M3/M1 metal preset layers on a Mo positive electrode by adopting a magnetron sputtering method, wherein the first layer of M1 metal is sputtered at constant power of a direct-current power supply, the power is 85W, the sputtering time is 4min, the second layer of M1 metal is sputtered at constant power of the direct-current power supply, the power is 80W, and the sputtering time is 5 min; the metal M3 is also sputtered with a direct-current power supply at constant power, the power is 26W, and the sputtering time is 25.5 min; the metal M2 is sputtered by a direct-current power supply with constant current, the current is 110mA, and the sputtering time is 10.5 min; then annealing the metal preset layer at 550 ℃ for 10min under the X atmosphere to obtain a copper-based absorption layer film; the copper-based absorption layer thin film includes a compound having M1, M2, M3, X, and a combination thereof, wherein M1 is copper (Cu), silver (Ag), or a combination thereof, M2 is indium (In), aluminum (Al), zinc (Zn), or a combination thereof, M3 is gallium (Ga), germanium (Ge), tin (Sn), or a combination thereof, and X is selenium (Se), sulfur (S), or a combination thereof;
2) treating the surface of the copper-based absorption layer film obtained in the step 1) by using ammonia water and ammonia sulfide vapor to obtain the copper-based absorption layer film with a front surface gradient band gap.
2. The production method according to claim 1, wherein the concentration of the aqueous ammonia solution is 25 wt%, the concentration of the ammonia sulfide solution for volatilizing to generate the ammonia sulfide vapor is 20 wt%, and the treatment time of the ammonia sulfide vapor is 5 to 60 min.
3. The method according to claim 1, wherein the thickness of the copper-based absorption layer film is 0.4 to 3 μm.
4. A room-temperature vulcanized copper-based absorption layer film, which is characterized by being prepared by the preparation method of any one of claims 1 to 3.
5. A room temperature vulcanized copper-based thin film solar cell, characterized in that the absorption layer of the copper-based thin film solar cell is the copper-based absorption layer thin film of claim 4.
6. The copper-based thin film solar cell according to claim 5, comprising a substrate, a positive electrode, an absorber layer, a buffer layer, a window layer and a top electrode, which are sequentially stacked.
7. The copper-based thin film solar cell according to claim 6, wherein the substrate is made of soda-lime glass, sodium-free glass or quartz glass, and the positive electrode is made of metal Mo;
preferably, the material of the buffer layer is CdS, ZnS, (Cd, Zn) S, Zn (O, S) or In2S3；
Preferably, the window layer comprises an intrinsic zinc oxide layer and a doped zinc oxide layer which are sequentially stacked;
preferably, the material of the top electrode is aluminum or nickel-aluminum alloy.
8. The copper-based thin film solar cell according to claim 7, wherein the positive electrode is a Mo metal electrode fabricated on a substrate; the thickness of the positive electrode is 1-2 μm;
preferably, the thickness of the absorption layer is 0.4-3 μm;
preferably, the thickness of the buffer layer is 30-100 nm;
preferably, the thickness of the intrinsic zinc oxide layer in the window layer is 30-150 nm;
preferably, the thickness of the doped zinc oxide layer in the window layer is 300-1500 nm;
preferably, the thickness of the top electrode is 0.5-4 μm.
9. A method for preparing a room-temperature vulcanized copper-based thin film solar cell is characterized by comprising the following steps:
a substrate;
forming a positive electrode on the substrate;
preparing a copper-based absorption layer film according to the preparation method of any one of claims 1 to 3;
forming a buffer layer on the absorption layer;
forming a window layer on the buffer layer;
a top electrode is formed on the window layer.
CN202110767251.2A 2021-07-07 2021-07-07 Room-temperature vulcanized copper-based absorption layer thin film, solar cell and preparation method of solar cell Active CN113540288B (en)

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CN107623046A (en) * 2017-08-25 2018-01-23 中国科学院上海微系统与信息技术研究所 CuInGaSe absorbed layer post-processing approach and the solar cell preparation method based on it
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