CN111416007B - Copper-based light absorption layer film, preparation method thereof and copper-based film solar cell - Google Patents

Copper-based light absorption layer film, preparation method thereof and copper-based film solar cell Download PDF

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CN111416007B
CN111416007B CN202010250951.XA CN202010250951A CN111416007B CN 111416007 B CN111416007 B CN 111416007B CN 202010250951 A CN202010250951 A CN 202010250951A CN 111416007 B CN111416007 B CN 111416007B
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copper
film
light absorption
absorption layer
solar cell
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CN111416007A (en
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罗艳红
郭林宝
孟庆波
石将建
李冬梅
吴会觉
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Institute of Physics of CAS
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Abstract

The invention provides a copper-based light absorption layer film, a preparation method thereof and a copper-based film solar cell. The preparation method comprises the following steps: mixing a metal simple substance, a disulfide compound, a thiol compound, an ammonia/organic amine compound and a solvent and reacting to obtain a precursor solution of a metal-thiol salt coordination compound; forming a film on a substrate by using the precursor solution, and carrying out heating annealing treatment at a preset temperature to obtain a light absorption layer precursor film; and carrying out selenization and/or sulfurization treatment on the light absorption layer precursor film to obtain the copper-based light absorption layer film. According to the scheme of the invention, the method for preparing the copper-based light absorption layer film is simple, the anhydrous hydrazine which is high in toxicity, unstable and easy to explode is avoided being used as a solvent, and the photoelectric conversion efficiency of the copper-based film solar cell prepared based on the method is 5-16%.

Description

Copper-based light absorption layer film, preparation method thereof and copper-based film solar cell
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of a copper-based light absorption layer film, the copper-based light absorption layer film and a copper-based film solar cell.
Background
As energy and environmental problems become more severe, solar cells that convert solar energy into electrical energy have become a focus of research in various scientific communities and development in the industry. Copper-based thin-film solar cells are widely concerned by photovoltaic researchers in various countries due to high stability, interference resistance and strong radiation resistance. The performance of the solar cell is determined by the absorption layer of the copper-based thin-film solar cell, so that the research on the absorption layer is of great significance.
At present, methods for producing copper-based thin films are roughly classified into vacuum methods and non-vacuum methods. The vacuum method mainly includes an evaporation method and a sputtering method. The non-vacuum solution method, such as spin coating, spraying, slit printing, etc., has been rapidly developed due to its advantages of simple operation, low preparation cost, etc. The development of a novel copper-based light absorption layer film preparation method is very important for improving the quality of the copper-based film and the corresponding battery efficiency and even promoting the large-scale application of the copper-based film.
Disclosure of Invention
The invention aims to provide a method for preparing a copper-based light-absorbing layer film by avoiding using anhydrous hydrazine which is high in toxicity, unstable and explosive as a solvent.
Another object of the present invention is to provide a copper-based light absorbing layer thin film and a copper-based thin film solar cell obtained based on the above-mentioned preparation method.
Particularly, the invention provides a preparation method of a copper-based light absorption layer film, which comprises the following steps:
mixing a metal simple substance, a disulfide compound, a thiol compound, an ammonia/organic amine compound and a solvent and reacting to obtain a precursor solution of a metal-thiol salt coordination compound;
forming a film on a substrate by using the precursor solution, and carrying out heating annealing treatment at a preset temperature to obtain a light absorption layer precursor film;
and carrying out selenization and/or sulfurization treatment on the light absorption layer precursor film to obtain the copper-based light absorption layer film.
Optionally, the elemental metal comprises elemental copper;
the elementary metal also comprises one or more of zinc, tin, indium, gallium, germanium, iron, manganese and aluminum.
Optionally, the disulfide compound is selected from one or more of dithiodiglycolic acid, 3 '-dithiodipropionic acid, 2' -dithiodipropionic acid, 4 '-dithiodibutanoic acid, L-cystine, 2' -dithiodiethanol, cystamine dihydrochloride, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, 4 '-dithiodipyridyl, and 2,2' -dithiodipyridyl.
Optionally, the thiol compound is selected from one or more of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 4-mercaptobutyric acid, L-cysteine, mercaptoethanol, cysteamine hydrochloride, methanethiol, ethanethiol, propanethiol, butanethiol, 4-mercaptopyridine, and 2-mercaptopyridine.
Optionally, the ammonia/organic amine compound is selected from one or more of ammonia, ammonia gas, primary amines of C1-C10, ethanolamine, ethylenediamine and triethanolamine.
Optionally, the solvent is selected from one or more of water, C1-C4 alcohol compounds, tetrahydrofuran, amide compounds, dimethyl sulfoxide, acetone, diethyl ether, ethylene glycol methyl ether and ethyl acetate.
Optionally, the preset temperature for preparing the light absorption layer precursor film is 250-550 ℃;
optionally, the heating time of the heat annealing treatment for preparing the light absorbing layer precursor film is 0.5-10 min.
Optionally, in the step of selenizing or sulfurizing the light absorption layer precursor thin film, the reaction temperature of the selenization treatment is 300-650 ℃, and the reaction time of the selenization treatment is 6-120 min;
optionally, in the step of selenizing or sulfurizing the light-absorbing layer precursor thin film, the reaction temperature of the sulfurization treatment is 300-650 ℃, and the reaction time of the sulfurization treatment is 6-90 min.
Particularly, the invention provides a copper-based light absorption layer film prepared by the preparation method, and the thickness of the copper-based light absorption layer film is 800-5000 nm.
Particularly, the invention provides a copper-based thin-film solar cell, which comprises a substrate, the copper-based light absorption layer thin film, a cadmium sulfide buffer layer thin film, a zinc oxide window layer, an ITO transparent electrode layer thin film and a metal gate electrode which are sequentially arranged;
optionally, the ITO transparent electrode layer thin film is replaced with an AZO transparent electrode layer thin film.
According to the scheme of the invention, the method for preparing the copper-based light absorption layer film is simple, the anhydrous hydrazine which is high in toxicity, unstable and explosive is avoided being used as a solvent, and the used solvent is non-toxic, stable and safe.
In addition, the copper-based thin-film solar cell thus obtained was subjected to a test of photoelectric conversion under the following test conditions: simulating sunlight by using AM1.5, wherein the illumination intensity is 1000W/m2. The test result shows that: the photoelectric conversion efficiency of the copper-based thin-film solar cell is 5% -16%.
The above and other objects, advantages and features of the present invention will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 shows a schematic flow diagram of a method of making a copper-based light absorbing layer film according to one embodiment of the present invention;
fig. 2 shows a schematic structural view of a copper-based thin-film solar cell according to an embodiment of the present invention;
FIG. 3 shows an illumination I-V plot for a CZTSSe thin film solar cell of example 5 of the present invention;
FIG. 4 shows an illumination I-V curve of a CISe thin film solar cell of example 9 of the present invention;
fig. 5 shows an illumination I-V graph of a CIGSSe thin film solar cell of example 12 of the present invention;
fig. 6 shows an illumination I-V plot of a CZGTSSe thin film solar cell of example 14 of the present invention.
Detailed Description
Fig. 1 is a schematic flow chart showing a method for producing a copper-based light absorbing layer film according to a first embodiment of the present invention. As shown in fig. 1, the preparation method comprises:
step S100, mixing and reacting a metal simple substance, a disulfide compound, a thiol compound, an ammonia/organic amine compound and a solvent to obtain a precursor solution of a metal-thiol salt coordination compound;
step S200, forming a film on a substrate by using the precursor solution, and carrying out heating annealing treatment at a preset temperature to obtain a light absorption layer precursor film;
and step S300, selenizing or vulcanizing the light absorption layer precursor film to obtain the copper-based light absorption layer film.
In step S100, there is no particular limitation on the mixing order of the elemental metal, the disulfide compound, the thiol compound, the ammonia/organic amine compound, and the solvent.
The metal simple substance comprises a copper simple substance and also comprises one or more of zinc, tin, indium, gallium, germanium, iron, manganese and aluminum. In a preferred embodiment, the elemental metals include copper, zinc, and tin. In another preferred embodiment, the elemental metal comprises copper, zinc, and germanium. In another preferred embodiment, the elemental metal comprises copper and indium. In another preferred embodiment, the elemental metal comprises copper, indium, and gallium. The copper-based light absorption layer film formed by the preferred embodiments has high extinction coefficient and phase composition stability, and can obtain high photoelectric conversion efficiency of the solar cell.
The disulfide compound serves as an oxidant in the reaction, so that a metal simple substance is oxidized into metal ions, and the disulfide is reduced to generate coordination anions to be complexed with the metal ions to improve the solubility of the metal ions. The disulfide compound is selected from one or more of dithiodiglycolic acid, 3 '-dithiodipropionic acid, 2' -dithiodipropionic acid, 4 '-dithiodibutanoic acid, L-cystine, 2' -dithiodiethanol, cystamine dihydrochloride, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, 4 '-dithiodipyridyl and 2,2' -dithiodipyridyl. In a preferred embodiment, the disulfide compound is selected from one or more of thiodiglycolic acid, 3 '-dithiodipropionic acid, 2' -dithiodiethanol, and cystamine dihydrochloride.
The thiol compound is used as ligand to complex with metal ion generated by reaction, so as to increase solubility. The thiol compound is selected from one or more of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 4-mercaptobutyric acid, L-cysteine, mercaptoethanol, cysteamine hydrochloride, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, 4-mercaptopyridine and 2-mercaptopyridine. In a preferred embodiment, the thiol compound is selected from one or more of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, mercaptoethanol, cysteamine, and cysteamine hydrochloride.
The ammonia/organic amine compound provides an alkaline condition for the reaction, and regulates the deprotonation degree of SH groups and COOH groups in a solution. The ammonia/organic amine compound is selected from one or more of ammonia water, ammonia gas, C1-C10 primary amine, ethanolamine, ethylenediamine and triethanolamine. In a preferred embodiment, the ammonia/organic amine compound is selected from one or more of ammonia, methylamine, ethylamine and ethanolamine.
The solvent is one or more selected from water, C1-C4 alcohol compounds, tetrahydrofuran, amide compounds, dimethyl sulfoxide, acetone, diethyl ether, ethylene glycol methyl ether and ethyl acetate. In a preferred embodiment, the solvent is selected from one or more of water, methanol, ethanol, ethylene glycol methyl ether.
Wherein the ratio of the amount of the metal simple substance to the volume of the precursor solution is 0.1 mmol:1ml, 0.5 mmol:1ml, 1 mmol:1ml or 2 mmol:1mL, or any other ratio of (0.1-2) mmol:1 mL. If the ratio is too low, the effective concentration becomes low, the repetition times for preparing the copper light absorption layer film with the thickness of 800-; if the ratio is too high, the elemental metal cannot completely react and dissolve to form a uniform precursor solution.
Wherein the ratio of the amounts of the elemental metal and the disulfide compound is 1:0.5, 1:1. 1: 5. 1: 10. 1: 15 or 1: 20, may be 1: (0.5-20). In a preferred embodiment, the ratio of the amounts of the elemental metal and the species of the disulfide compound is 1:1, 1:2. 1: 3. 1: 4. 1: 5 or 1:6, or any other ratio of 1 (1-6). The ratio is too high, so that the metal simple substance cannot completely react and dissolve to form a uniform precursor solution; the ratio is too low, on one hand, a large amount of disulfide compounds which do not react with the metal simple substance cause waste, on the other hand, the carbon residue in the prepared precursor film is increased, and the preparation of the high-performance copper-based light absorption layer film is not facilitated.
The ratio of the amount of the metal simple substance to the amount of the thiol compound is 1:0.5, 1:1. 1: 5. 1: 10. 1: 15 or 1: 20, may be 1: (0.5-20). In a preferred embodiment, the ratio of the amount of the elemental metal to the amount of the thiol compound is 1:1, 1:2. 1: 3. 1: 4. 1: 5 or 1:6, or any other ratio of 1 (1-6). The ratio is too high, so that the metal simple substance cannot completely react and dissolve to form a uniform precursor solution; the ratio is too low, on one hand, a large amount of mercaptan compounds which are not complexed with metal ions cause waste, and on the other hand, carbon residue in the prepared precursor film is increased, which is not beneficial to the preparation of the high-performance copper-based light absorption layer film.
The ratio of the sum of the amounts of the disulfide compound and thiol compound to the amount of ammonia/amine compound may be 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, or 1:3, or may be any other ratio of 1 (0.3-3). In a preferred embodiment, the ratio of the sum of the amount of the disulfide compound and the amount of thiol compound material to the amount of ammonia/amine compound material is 1:0.5, 1:0.8, 1:1, 1:1.3, 1:1.5, 1:1.8, 1:2 or 1:2.5, and may be any other ratio of 1 (0.5-2.5).
In step S200, the precursor solution obtained in step S100 is formed into a film on a substrate, and the substrate is heated to obtain a light-absorbing layer precursor film. The substrate is not particularly limited, and those used for preparing a light absorbing layer film, which are well known to those skilled in the art, may be used. In certain embodiments of the invention, the substrate may be, for example, a molybdenum soda lime glass substrate, a molybdenum foil, and a stainless steel foil. The film-forming method is not particularly limited, and spin coating, doctor blade coating, spraying or printing is preferably used.
The preset temperature is 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or 550 ℃, and can be any other temperature value in the temperature range of 250 ℃ and 550 ℃. The heating time of the heating annealing treatment is 0.5min, 1min, 3min, 5min, 8min or 10min, or any other time value of 0.5-10 min. If the preset temperature is lower than 250 ℃, the residual impurities of the precursor film cannot be effectively removed. If the preset temperature is higher than 550 ℃, the volatile metal components in the precursor film are seriously lost, and component deviation is caused.
In step S300, in order to further grow the light absorbing layer precursor thin film, a selenization reaction and/or a sulfurization reaction is performed on the obtained light absorbing layer precursor thin film, so as to obtain a copper-based light absorbing layer thin film. The temperature of the selenization reaction is 300 ℃, 400 ℃, 500 ℃, 600 ℃ or 650 ℃, and can be any temperature value of 300 ℃ and 650 ℃. The selenization reaction time is 6min, 30min, 60min, 90min or 120min, or any time value of 6-120 min. The temperature of the vulcanization reaction is 300 ℃, 400 ℃, 500 ℃, 600 ℃ or 650 ℃, and can be any temperature value of 300 ℃ and 650 ℃. The time of the sulfuration reaction is 6min, 15min, 30min, 60min or 90min, and can be any time value of 6-90 min.
According to the scheme of the invention, the method for preparing the copper-based light absorption layer film is simple, the anhydrous hydrazine which is high in toxicity, unstable and explosive is avoided being used as a solvent, and the used solvent is non-toxic, stable and safe.
Particularly, the invention also provides a copper-based light absorption layer film, which is prepared by the preparation method, and the thickness of the prepared copper-based light absorption layer film is 800nm, 1000nm, 2000nm, 3000nm, 4000nm or 5000nm, or any other value in 800-5000 nm. Preferably, the thickness of the copper-based light absorption layer film is 1000nm, 1200nm, 1500nm, 1800nm, 2000nm, 2200nm or 2500nm, or any other value of 1000-2500 nm.
According to the scheme of the invention, the thickness of the copper-based light absorption layer film prepared by the preparation method is in the range of the thickness, so that the photoelectric conversion efficiency of the subsequently prepared copper-based film solar cell can be ensured to be as high as 5% -16%.
Particularly, the invention also provides a copper-based thin-film solar cell, and the preparation method of the copper-based thin-film solar cell comprises the following steps: preparing a cadmium sulfide (CdS) buffer layer film 3 on a copper-based light absorption layer film 2 with a substrate 1; preparing a zinc oxide (ZnO) window layer film 4 on the CdS buffer layer film 3; preparing an ITO or AZO transparent conducting layer film 5 on the ZnO window layer film 4; and depositing an Ag or Ni-Al metal gate electrode 6 by evaporation to obtain the copper-based thin-film solar cell shown in figure 2. Wherein, the ITO is indium tin oxide, and the AZO is an aluminum-doped zinc oxide transparent conductive film.
The copper-based light absorption layer film with the substrate is preferably prepared by the preparation method, and is not described herein again.
The invention has no special limitation on the sources and the preparation methods of the substrate, the CdS buffer layer, the ZnO window layer, the ITO or AZO transparent electrode layer and the metal gate electrode, and the materials and the preparation methods of the substrate, the CdS buffer layer, the ZnO window layer, the ITO or AZO transparent electrode layer and the metal gate electrode, which are well known by the technical personnel in the field, can be adopted.
The inventors carried out a test of photoelectric conversion rate on the thus obtained copper-based thin-film solar cell under the following test conditions: simulating sunlight by using AM1.5, wherein the illumination intensity is 1000W/m2. The test result shows that: the photoelectric conversion efficiency of the copper-based thin-film solar cell is 5% -16%.
In order to further illustrate the present invention, the following will describe in detail a copper-based light absorbing layer film, a method for manufacturing the same, and a copper-based thin film solar cell provided by the present invention with reference to examples, which should not be construed as limiting the scope of the present invention.
Examples 1 to 6:
adding 1.76mmol copper powder, 1.24mmol zinc powder, 1.0mmol tin powder, 588mg dithiodiglycolic acid, 1.0ml thioglycollic acid, 2ml ammonia water with the mass fraction of 25-28 wt%, 1ml water and 2ml methanol into a reaction bottle, heating, stirring and dissolving to form a copper-zinc-tin precursor solution, forming a film on a molybdenum-sodium-calcium glass substrate by a spin coating method, heating and decomposing at 400 ℃, and obtaining copper-zinc-tin-sulfur light absorption layer precursor films with different thicknesses by changing the times of spin coating and annealing. And placing the obtained light absorption layer precursor film in a selenizing furnace, adding 0.5 g of selenium powder, and carrying out selenizing reaction at 530 ℃ for 15min to obtain copper zinc tin selenium (CZTSSe) light absorption layer films with different thicknesses.
And preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained CZTSSe light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO thin film of 70nm is sputtered by radio frequency and a transparent conductive ITO thin film of 220nm is sputtered by direct current. And finally, evaporating a Ni-Al metal gate electrode to obtain the CZTSSe thin-film solar cell.
The obtained CZTSSe thin-film solar cells are tested for photoelectric conversion efficiency, examples 1-6 show solar cells assembled by CZTSSe light absorption layer thin films with different thicknesses, and the test results of the photoelectric efficiency are shown in Table 1. Fig. 3 shows an illumination I-V plot of a CZTSSe thin film solar cell of example 5 of the present invention. Calculated from FIG. 3, Voc＝505mV，Jsc＝37mA/cm2FF 70%, PCE 13.1%, and area 0.18cm2. Wherein, VocRepresents the open circuit voltage, JscThe short-circuit current density is represented, the fill factor is represented by FF, the photoelectric conversion efficiency of the solar cell is represented by PCE, and the area is the effective area of the solar cell.
The test result shows that: the CZTSSe thin-film solar cell of example 5 of the present invention has a photoelectric conversion efficiency of 13.1%.
Examples 7 to 11
Adding 0.92mmol copper powder, 1.0mmol indium powder, 588mg dithiodiglycolic acid, 1.0ml thioglycollic acid, 2.5ml 25-28% ammonia water and 2.0ml ethylene glycol monomethyl ether into a reaction bottle, placing the reaction bottle filled with the copper powder and the indium powder on a heating table at 60 ℃ to stir and react to form a copper indium precursor solution, forming a film on a molybdenum sodium calcium glass substrate by spin coating, then heating and decomposing at different preset temperatures, and controlling the thickness of the film by changing the number of coating repetition times to obtain the Copper Indium Sulfide (CIS) light absorption layer precursor film. And placing the obtained CIS light absorption layer precursor film in a selenizing furnace, adding 0.5 g of selenium powder, and carrying out selenizing reaction at 580 ℃ for 20min to further grow the light absorption layer precursor film so as to obtain a copper indium selenide (CISe) light absorption layer film.
And preparing a CdS buffer layer film with the diameter of about 60nm on the obtained CISe light absorption layer film by a chemical water bath method. Then, a 50nm high-resistance ZnO film is sputtered by magnetron radio frequency and a 230nm ITO film is sputtered by direct current. And finally, evaporating a Ni-Al metal gate electrode to obtain the CISe thin-film solar cell.
The obtained CISE thin-film solar cells are tested for photoelectric conversion efficiency, and the test results of the photoelectric conversion efficiency of the CISE thin-film solar cells prepared in examples 7-11 at different preset temperatures are shown in Table 1. Fig. 4 shows an illumination I-V plot of a CISe thin film solar cell of example 9 of the present invention. Calculated from FIG. 4, Voc＝539mV，Isc＝36.5mA/cm2FF 69.6%, PCE 13.7%, and area 0.18cm2。
The test result shows that: the photoelectric conversion efficiency of the CISe thin film solar cell is 13.7%.
Example 12
Adding 1.0mmol of copper powder, 0.2mmol of gallium powder, 0.8mmol of indium powder, 2' -dithiodipropionic acid, 1.0ml of 2-mercaptopropionic acid, 2.0ml of ethylamine and 2.0ml of ethanol into a reaction bottle, and heating and stirring the mixture on a heating table at the temperature of 40 ℃ to react to form a copper-indium-gallium precursor solution; spraying the molybdenum foil substrate with the thickness of 50 microns to form a film, controlling the thickness of the film by changing the spraying time, and heating and decomposing at the preset temperature of 340 ℃ to obtain a Copper Indium Gallium Sulfide (CIGS) light absorption layer precursor film; and (3) putting the CIGS light absorption layer precursor film into a selenizing furnace, adding 0.5 g of selenium powder and 0.1 g of sulfur powder, and carrying out selenizing reaction at 590 ℃ for 10min to further crystallize and grow the light absorption layer precursor film so as to obtain the CIGSSe light absorption layer film with the thickness of 1400 nm.
And preparing a CdS buffer layer film with the thickness of about 60nm on the obtained CIGSSe light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO film with the thickness of 70nm is subjected to radio frequency sputtering and a high-conductivity AZO film with the thickness of 200nm is subjected to direct current sputtering. And finally, evaporating a Ni-Al metal gate electrode to obtain the CIGSSe thin-film solar cell.
The obtained CIGSSe thin-film solar cell is tested for photoelectric conversion efficiency. Fig. 5 shows an illumination I-V graph of a CIGSSe thin film solar cell of example 12 of the present invention. Calculated from FIG. 5, Voc＝655mV，Isc＝33mA/cm2FF is 74%, PCE is 16.0%, and area is 0.18cm2。
The test result shows that: the photoelectric conversion efficiency of the CIGSSe thin-film solar cell obtained in example 12 of the present invention is 16.0%, which is shown in table 1.
Example 13
Adding 1.0mmol of copper powder, 0.1mmol of aluminum powder, 0.9mmol of indium powder, 1.0ml of 2,2' -dithiodiethanol, 1.0ml of mercaptoethanol, 2.0ml of ammonia water with the mass fraction of 25-28 wt% and 2.0ml of water into a reaction bottle, and placing the reaction bottle filled with the substances on a heating table at 50 ℃ for stirring and heating reaction to form a copper-aluminum-indium precursor solution. The method comprises the steps of spin-coating a molybdenum-sodium-calcium glass substrate to form a film, then preparing a light absorption layer precursor film by heating and decomposing the film at a preset temperature of 320 ℃ by adopting an ultrasonic spraying method, and controlling the thickness of the light absorption layer precursor film by changing the liquid inlet speed of spraying and the spraying time to obtain the copper-aluminum-indium-sulfur light absorption layer precursor film. Putting the copper-aluminum-indium-sulfur light absorption layer precursor film into a selenizing furnace, adding 0.4 g of selenium powder and 0.05 g of sulfur powder, and carrying out selenizing reaction at 570 ℃ for 20min to further grow the light absorption layer precursor film crystal, thereby obtaining the copper-aluminum-indium-sulfur-selenium light absorption layer film with the thickness of 1500 nm.
And preparing a CdS buffer layer film with the thickness of about 60nm on the obtained copper-aluminum-indium-sulfur-selenium light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO film with the thickness of 70nm is subjected to radio frequency sputtering and a high-conductivity AZO film with the thickness of 200nm is subjected to direct current sputtering. And finally, evaporating an Ag metal gate electrode to complete the preparation of the copper-aluminum-indium-sulfur-selenium thin-film solar cell.
The photoelectric conversion efficiency of the obtained copper-aluminum-indium-sulfur-selenium thin-film solar cell is tested. The test result shows that: the photoelectric conversion efficiency of the copper-aluminum-indium-sulfur-selenium thin-film solar cell obtained in example 13 of the present invention is 6.2%, which is shown in table 1.
Example 14
Adding 1.76mmol copper powder, 1.24mmol zinc powder, 0.2mmol germanium powder, 0.8mmol tin powder, 588mg dithiodiglycolic acid, 1.0ml thioglycolic acid, 2ml 40% methylamine water solution and 4ml methanol into a reaction bottle, heating, stirring and dissolving to form a copper-zinc-germanium-tin precursor solution, forming a film on a molybdenum-sodium-calcium glass substrate by a spin coating method, heating and decomposing at 400 ℃, and obtaining a copper-zinc-germanium-tin-sulfur CZGTS light absorption layer precursor film with a certain thickness by changing the times of spin coating and annealing; and placing the obtained light absorption layer precursor film in a selenizing furnace, adding 0.5 g of selenium powder, and carrying out selenizing reaction at 530 ℃ for 15min to obtain the copper zinc germanium tin sulfur selenium (CZGTSSe) light absorption layer film, wherein the thickness of the film is 2800 nm.
Preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained CZGTSSe light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO thin film of 70nm is sputtered by radio frequency and a transparent conductive ITO thin film of 220nm is sputtered by direct current. And finally, evaporating a Ni-Al metal gate electrode to obtain the CZGTSSe thin-film solar cell.
The obtained CZGTSSe thin-film solar cell is tested for photoelectric conversion efficiency by the present invention, and fig. 6 shows an illumination I-V curve of the CZGTSSe thin-film solar cell in embodiment 14 of the present invention. Calculated from FIG. 6, Voc＝495mV，Isc＝34.0mA/cm2FF is 66%, PCE is 11.1%, and area is 0.18cm2。
The test result shows that: the photoelectric conversion efficiency of the CISe thin film solar cell is 11.1%, see Table 1.
Example 15
Adding 1.76mmol of copper powder, 0.6mmol of iron powder, 0.6mmol of zinc powder, 1.0mmol of tin powder, 588mg of dithiodiglycolic acid, 2.0ml of thioglycollic acid, 4.0ml of ammonia water with the mass fraction of 25-28 wt% and 1ml of water into a reaction bottle, heating, stirring and dissolving to form a copper-zinc-iron-tin precursor solution, forming a film on a molybdenum-sodium-calcium glass substrate by a spin-coating method, heating and decomposing at 350 ℃, and changing the times of spin-coating and annealing to obtain the copper-zinc-iron-tin-sulfur light absorption layer precursor film. And putting the light absorption layer precursor film into a selenizing furnace, adding 0.4 g of selenium powder, and carrying out selenizing reaction at 500 ℃ for 40min to form the copper-zinc-iron-tin-sulfur-selenium light absorption layer film with the film thickness of 2000 nm.
Preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO film with the thickness of 70nm is subjected to radio frequency sputtering and a high-conductivity AZO film with the thickness of 200nm is subjected to direct current sputtering. And finally, evaporating a Ni-Al metal gate electrode to obtain the copper-zinc-iron-tin-sulfur-selenium film solar cell.
The invention tests the photoelectric conversion efficiency of the obtained copper-zinc-iron-tin-sulfur-selenium film solar cell. The test result shows that: the photoelectric conversion efficiency of the copper-zinc-iron-tin-sulfur-selenium film solar cell obtained in the embodiment of the invention is 6.1%, which is shown in table 1.
Example 16
1.0mmol of copper powder, 1.0mmol of indium, 450mg of cystamine dihydrochloride, 115mg of cysteamine hydrochloride, 2.0ml of ethylamine and 2.0ml of ethylene glycol monomethyl ether were added to a conical flask, and the conical flask containing the above substances was placed on a heating table at 60 ℃ to be stirred and heated to react to form a copper-indium precursor solution. And (3) forming a film on the molybdenum-soda-lime glass substrate by spin coating, heating and decomposing at 310 ℃, and controlling the thickness of the copper-indium-sulfur film by changing the spin coating times to obtain the precursor film of the copper-indium-sulfur light absorption layer. Then, putting the precursor film of the copper-indium-sulfur light absorption layer into a vulcanizing furnace, adding 0.4 g of sulfur powder, carrying out vulcanization reaction at 560 ℃ for 20min, and further growing the precursor film crystal of the light absorption layer to obtain CuInS2And the light absorption layer is a film with the thickness of 1500 nm.
In the obtained CuInS2And preparing a CdS buffer layer film with the thickness of about 60nm on the light absorption layer film by a chemical water bath method. Then, by radio frequency sputtering70nm high-resistance ZnO film and 200nm ITO film by direct current sputtering. Finally, evaporating a Ni-Al metal gate electrode to complete CuInS2And (4) preparing a thin film solar cell.
The invention aims at the obtained CuInS2And testing the photoelectric conversion efficiency of the thin-film solar cell. The test result shows that: CuInS obtained in the embodiment of the invention2The photoelectric conversion efficiency of the thin-film solar cell was 9.8%, as shown in table 1.
Example 17
Adding 1.76mmol of copper powder, 1.2mmol of iron powder, 1.0mmol of tin powder, 728mg of dithiodiglycolic acid, 1.5ml of thioglycollic acid and 4.0ml of ammonia water with the mass fraction of 25-28 wt% into a conical flask, heating, stirring and dissolving to form a copper-iron-tin precursor reaction solution, forming a film on a molybdenum foil substrate with the thickness of 1 mu m by an ultrasonic spraying method, and heating and decomposing at 350 ℃ to obtain the copper-iron-tin-sulfur light absorption layer precursor film. And (3) obtaining the light absorption layer precursor film with the required thickness by changing the spraying time. And then, putting the precursor film of the copper-iron-tin-sulfur light absorption layer into a selenizing furnace, adding 0.5 g of selenium powder, and carrying out selenizing reaction at 560 ℃ for 40min to obtain the copper-iron-tin-sulfur-selenium light absorption layer film with the film thickness of 3000 nm.
Preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained copper-iron-tin-sulfur-selenium light absorption layer film by a chemical water bath method. Then, a high-resistance ZnO film with the thickness of 70nm is subjected to radio frequency sputtering and a high-conductivity AZO film with the thickness of 200nm is subjected to direct current sputtering. And finally, evaporating a Ni-Al metal gate electrode to obtain the copper-iron-tin-sulfur-selenium film solar cell.
The photoelectric conversion efficiency of the obtained copper-iron-tin-sulfur-selenium film solar cell is tested. The test result shows that: the photoelectric conversion efficiency of the copper-iron-tin-sulfur-selenium film solar cell obtained in the embodiment of the invention is 5.2%, which is shown in table 1.
TABLE 1
Figure BDA0002435468930000111
Figure BDA0002435468930000121
According to the scheme of the invention, the metal simple substance, the disulfide compound, the thiol compound, the ammonia/organic amine compound and the solvent are mixed by the thiol to react, so that the precursor solution of the metal-thiol salt coordination compound can be obtained. And the precursor solution is adopted to prepare the copper-based light-absorbing layer film, and the light-absorbing layer film is used for preparing a copper-based thin-film solar cell, so that the obtained copper-based thin-film solar cell has higher photoelectric conversion efficiency. In addition, the preparation method is simple, the reaction condition is mild, and large-scale production is easy to realize.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.

Claims (11)

1. The preparation method of the copper-based light absorption layer film is characterized by comprising the following steps of:
mixing a metal simple substance, a disulfide compound, a thiol compound, an ammonia/organic amine compound and a solvent and reacting to obtain a precursor solution of a metal-thiol salt coordination compound;
forming a film on a substrate by using the precursor solution, and carrying out heating annealing treatment at a preset temperature to obtain a light absorption layer precursor film;
selenizing and/or vulcanizing the light absorption layer precursor film to obtain a copper-based light absorption layer film;
the disulfide compound is selected from one or more of dithiodiglycolic acid, 3 '-dithiodipropionic acid, 2' -dithiodipropionic acid, 4 '-dithiodibutanoic acid, L-cystine, 2' -dithiodiethanol, cystamine dihydrochloride, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, 4 '-dithiodipyridyl and 2,2' -dithiodipyridyl;
the ammonia/organic amine compound is selected from one or more of ammonia water, ammonia gas, C1-C10 primary amine, ethanolamine, ethylenediamine and triethanolamine.
2. The production method according to claim 1, wherein the elemental metal includes elemental copper;
the elementary metal also comprises one or more of zinc, tin, indium, gallium, germanium, iron, manganese and aluminum.
3. The method according to claim 1, wherein the thiol compound is one or more selected from the group consisting of thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 4-mercaptobutyric acid, L-cysteine, mercaptoethanol, cysteamine hydrochloride, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, 4-mercaptopyridine, and 2-mercaptopyridine.
4. The method according to claim 1, wherein the solvent is one or more selected from the group consisting of water, C1-C4 alcohol compounds, tetrahydrofuran, amide compounds, dimethyl sulfoxide, acetone, diethyl ether, ethylene glycol methyl ether, and ethyl acetate.
5. The method as claimed in claim 1, wherein the predetermined temperature is 250-550 ℃.
6. The production method according to claim 1, wherein the heating time of the heat annealing treatment is 0.5 to 10 min.
7. The method as claimed in claim 1, wherein in the step of selenizing or sulfurizing the light-absorbing layer precursor thin film, the reaction temperature of the selenization is 300-650 ℃, and the reaction time of the selenization is 6-120 min.
8. The method as claimed in claim 1, wherein in the step of selenizing or sulfurizing the light-absorbing layer precursor thin film, the reaction temperature of the sulfurization treatment is 300-650 ℃, and the reaction time of the sulfurization treatment is 6-90 min.
9. A copper-based light absorbing layer film prepared by the preparation method of any one of claims 1 to 8, wherein the thickness of the copper-based light absorbing layer film is 800-5000 nm.
10. A copper-based thin film solar cell comprising a substrate, the copper-based light absorbing layer thin film according to claim 9, a cadmium sulfide buffer layer thin film, a zinc oxide window layer, an ITO transparent electrode layer thin film, and a metal gate electrode, which are sequentially disposed.
11. The copper-based thin-film solar cell according to claim 10, wherein the ITO transparent electrode layer thin film is replaced with an AZO transparent electrode layer thin film.
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