PRECURSOR SOLUTION FOR COPPER-ZINC-TIN-SULFUR THIN FILM SOLAR CELL, PREPARATION METHOD THEREFOR, AND USE THEREOF

Abstract

Disclosed are a precursor solution for a copper-zinc-tin-sulfur (CZTS) thin film solar cell, a preparation method therefor, and the use thereof. The present invention discloses two types of simple metal complexes which are capable of formulating a high-quality precursor solution.

Claims

1. A precursor solution for CZTS thin film solar cell, wherein the precursor solution is prepared by using a DMSO or a DMF as a solvent, and a precursor compound as a solute; the precursor compound is composed of metal complexes, a metal salt and a thiourea, wherein the metal complexes are a copper complex formed by a copper salt, and a thiourea or thiourea derivative, and a tin complex formed by a tin salt, and a DMF or DMSO, and the metal salt is a divalent zinc salt; and the precursor compound is dissolved in the solvent of the DMSO or DMF to obtain a stable, clear and transparent precursor solution, the copper complex is a complex formed by a copper salt, and a thiourea or derivative, including a complex of Cu(Tu).sub.3X formed by a copper halide and a thiourea, wherein X is a halogen element including F, Cl, Br, and I, the formed copper complex includes Cu(Tu).sub.3Cl, [Cu.sub.2(Tu).sub.6]Cl.sub.2.2H.sub.2O, and Cu(Tu).sub.3Br, the formed copper complex further includes a complex of Cu(DMTu).sub.3Br, Cu(TMTu).sub.3Cl, and [Cu(ETu).sub.2Br].sub.2 formed by a copper halide and a thiourea derivative, wherein the DMTu is N, N-dimethylthiourea, the TMTU is tetramethylthiourea, and the Etu is ethylene thiourea; and the formed copper complex further includes a complex of Cu.sub.4(Tu).sub.10(NO.sub.3).Tu.3H.sub.2O formed by a copper nitrate salt and a thiourea; the tin complex is selected from one or more of Sn(X).sub.yCl.sub.4, Sn(X).sub.yF.sub.4, Sn(X).sub.yBr.sub.4, Sn(X).sub.yI.sub.4, and Sn(X).sub.y(CH.sub.3COO).sub.4, X is selected from one of DMSO, DMF, ethanol, and N-methylpyrrolidone, and y is a natural number greater than zero; and a specific method for preparing the precursor solution is: taking DMSO or DMF as the solvent, dissolving the copper complex and the tin complex, the zinc salt and the thiourea directly into the solvent, to obtain the clear and transparent precursor solution.

2. The precursor solution for the CZTS thin film solar cell according to claim 1, wherein the zinc salt is a divalent zinc compound, including but not limited to zinc halide, zinc acetate, zinc nitrate, and zinc sulfate.

3. The precursor solution for the CZTS thin film solar cell according to claim 1, wherein in the precursor solution, a ratio of an amount of the thiourea to an amount of a copper element is not greater than 1.

4. The precursor solution for the CZTS thin film solar cell according to claim 1, wherein in the precursor compound, a ratio of an amount of a copper element to an amount of a tin element is (1.5 to 2.5):1; a ratio of an amount of a zinc element to the amount of the tin element is (0.9 to 1.5):1; and a ratio of an amount of a sulfur element to a sum of the amounts of the copper element, the tin element and the zinc element is (1.0 to 6.0):1.

5. The precursor solution for the CZTS thin film solar cell according to claim 1, wherein in the precursor solution, a concentration of a copper element in the solution is 0.05 mol/L to 5 mol/L; a concentration of a tin element in the solution is 0.05 mol/L to 5 mol/L; a concentration of a zinc element in the solution is 0.05 mol/L to 5 mol/L; and a concentration of a sulfur element in the solution is 0.15 mol/L to 5 mol/L.

6. The precursor solution for the CZTS thin film solar cell according to claim 1, wherein methods for preparing the copper complex and the tin complex are as follows: synthesizing the copper complex: dissolving the thiourea in deionized water, adding, after the thiourea is completely dissolved, the copper salt to the solution, wherein a ratio of an amount of the added thiourea to an amount of the added copper salt is 3:1, and a temperature of the solution during the reaction is 70° C.; filtering, after dissolving the copper salt, the solution, holding the solution stand still, cooling the solution slowly, precipitating crystals of the target-product copper complex from the solution, and taking out and drying the crystal product; and synthesizing the tin complex: taking a tetravalent tin salt in a round-bottomed flask, sealing a mouth of the flask, taking the organic compound solvent DMF or DMSO and injecting the solvent into the flask, wherein a ratio of an amount of the organic compound in the solvent to an amount of the tin salt is 2 to 20; reacting the tin salt with the DMF or the DMSO solvent to generate a large amount of white precipitates, cleaning the precipitates with ethanol and drying the precipitates to obtain the corresponding target-product tin complex.

7. Use of the precursor solution for the CZTS thin film solar cell according to claim 1 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

8. Use of the precursor solution for the CZTS thin film solar cell according to claim 2 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

9. Use of the precursor solution for the CZTS thin film solar cell according to claim 3 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

10. Use of the precursor solution for the CZTS thin film solar cell according to claim 4 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

11. Use of the precursor solution for the CZTS thin film solar cell according to claim 5 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

12. Use of the precursor solution for the CZTS thin film solar cell according to claim 6 in preparing a CZTS solar cell, wherein a method for preparing the CZTS solar cell includes following steps: (1) spin-coating the prepared precursor solution on molybdenum glass, heating, and annealing to produce a CZTS precursor thin film; (2) heating the precursor thin film in an atmosphere of Se to carry out a selenization reaction, by replacing S atoms, partially or entirely, with Se atoms to produce a CZTSSe thin film material; (3) taking out the CZTSSe thin film obtained after the selenization reaction and immersing the CZTSSe thin film in ultrapure water, and then placing the CZTSSe thin film in a water-jacketed beaker containing ammonia water, cadmium sulfate and thiourea solution, carrying out the reaction under heating, and depositing a layer of CdS on a surface of the CZTSSe thin film; (4) sequentially sputtering, by a magnetron sputtering technology, ZnO and ITO on the surface of the sample in Step (3) as a window layer; and (5) evaporating, by a thermal evaporation method, metal Ni and Al on the surface of the sample obtained in Step (4) as a cathode.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG. 1 illustrates a physical picture of a copper complex Cu(Tu).sub.3Cl formed by cuprous chloride with thiourea in the embodiments.

[0045] FIG. 2 illustrates a physical picture of a tin complex Sn(DMF).sub.2Cl.sub.4 formed by tin tetrachloride and N,N-dimethylformamide in Example 3.

[0046] FIG. 3 illustrates a physical picture of a DMSO precursor solution in Example 1.

[0047] FIG. 4 illustrates a physical picture of a DMF precursor solution in Example 3.

[0048] FIG. 5 illustrates an X-ray diffraction pattern of a precursor thin film in Example 1.

[0049] FIG. 6 illustrates an X-ray diffraction pattern of the precursor thin film in Example 3.

[0050] FIG. 7 illustrates an X-ray diffraction pattern of an absorption layer thin film in Example 1.

[0051] FIG. 8 illustrates an X-ray diffraction pattern of the absorption layer thin film in Example 3.

[0052] FIG. 9 illustrates a Raman spectrum of the precursor thin film in Example 1.

[0053] FIG. 10 illustrates a Raman spectrum of the precursor thin film in Example 3.

[0054] FIG. 11 illustrates a Raman spectrum of the absorption layer thin film in Example 1.

[0055] FIG. 12 illustrates a Raman spectrum of the absorption layer thin film in Example 3.

[0056] FIG. 13 illustrates a scanning electron microscope image (a cross section of a film layer) of the absorption layer thin film in Example 1.

[0057] FIG. 14 illustrates a scanning electron microscope image (a cross section of a film layer) of the absorption layer thin film in Example 3.

[0058] FIG. 15 illustrates a scanning electron microscope image (a surface of a film layer) of the absorption layer thin film in Example 1.

[0059] FIG. 16 illustrates a scanning electron microscope image (a surface of a film layer) of the absorption layer thin film in Example 3.

[0060] FIG. 17 illustrates a voltage-current characteristic curve for a device of a CZTSSe solar cell in Example 1 under a standard sunlight intensity of AM1.5G.

[0061] FIG. 18 illustrates a voltage-current characteristic curve for the device of the CZTSSe solar cell in Example 3 under the standard sunlight intensity of AM1.5G.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0062] The present invention discloses a method for preparing a precursor solution for high-efficiency CZTS thin film solar cells, and a preparation and an application of a photovoltaic device. The present invention discloses two types of simple metal complexes which are capable of formulating a high-quality precursor solution. The precursor solution, which is formulated by using the metal complexes as precursor compounds, has a good stability and repeatability, and can be used to prepare an impurity phase-free CZTS thin film light-absorbing material having a high crystallization quality and a good thin film morphology, and the CZTS thin film solar cell prepared therefrom has a high photoelectric conversion efficiency. The use of metal complexes simplifies the formulation procedure of the precursor solution, improves the quality of the precursor solution, improves the energy conversion efficiency of a photovoltaic device, and has a great industrial potential application scope.

[0063] The embodiments of the present invention will be described in detail below. The present embodiments are implemented on the premise of the technical solutions of the present invention, and provide detailed implementations and a specific operation process, but the protection scope of the present invention is not limited to the following examples.

[0064] The present invention can be better understood from the following examples. However, those skilled in the art would easily understand that the specific material ratios, process conditions and results described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

Example 1

[0065] Step 1: The preparation of the copper complex.

[0066] 45.67 g (0.6 mol) of thiourea are weighed and dissolved in 100 mL of deionized water, heated and stirred to keep the solution temperature at 70° C., after the thiourea is completely dissolved, 19.8 g (0.2 mol) of cuprous chloride are weighed and added into the solution, after reacting for 30 minutes, most of the cuprous chloride are dissolved, the solution is filtrated when still warm, and the filtrate is held to stand still for natural cooling. After a period of time, the colorless and transparent crystals precipitated in the filtrate are the target-product copper complex Cu(TU).sub.3Cl, and then crystals are filtered and dried.

[0067] Step 2: The preparation of the tin complex.

[0068] 12.53 g of stannic chloride are weighed and taken in a round-bottomed flask, the mouth of the flask is sealed, 50 mL of DMSO are taken and injected into the flask by an injector. The two substances react violently when they come into contact and the reaction generates a large amount of white precipitates. After the reaction is complete, the reaction solution is filtered to obtain white precipitates, and the precipitates are washed with ethanol for several times, then are dried to obtain the corresponding target product Sn(DMSO).sub.4Cl.sub.4.

[0069] Step 3: The preparation of the precursor solution.

[0070] 8 mL of DMSO are weighed and put into a reagent bottle, 20 g (6.12 mmol) of the copper complex prepared in Step 1, 1.667 g (4 mmol) of the tin complex Sn(DMSO).sub.4Cl.sub.4 prepared in Step 2, 0.734 g (4 mmol) of zinc acetate and 0.2 g of thiourea are weighed and added into the reagent bottle, and stirred at the room temperature until completely dissolved.

[0071] Step 4: The preparation of the CZTS precursor thin film.

[0072] The molybdenum-coated glass is ultrasonically cleaned in acetone and isopropanol for 10 minutes respectively and then air-dried. The precursor solution prepared in Step 3 is spin-coated in a glove box, and the spin-coating parameters are a spin-coating speed of 1500 rpm and a spin-coating time of 60 s. After the spin-coating, the samples are annealed on a hot stage at 420° C. for 2 minutes. The above spin-coating-heating process is repeated 7 times to obtain the CZTS precursor thin film.

[0073] Step 5: The preparation of the CZTSSe thin film.

[0074] The two precursor thin film samples (2.45 cm×2.45 cm) prepared in Step 4 are placed in the graphite box, about 0.35 g of Se pallets are weighed and placed in the graphite box symmetrically, the valve is closed tightly, and after the vacuum is evacuated to make the degree of vacuum in the tube reach 3×10.sup.−2 Torr, argon gas is introduced into the tube, and the above operation is repeated 3 times to purge the air in the tube to ensure that the selenization reaction is carried out in an anhydrous and oxygen-free environment. The tube furnace heating program is started with a target temperature of 550° C. and a heating rate of 2° C./s, and the samples are annealed at 550° C. for 20 minutes, after annealing, the samples are naturally cooled to the room temperature.

[0075] Step 6: The preparation of the buffer layer CdS.

[0076] After the selenization reaction, the samples in the graphite box are taken out and immersed in ultrapure water for 6 minutes, and then the CdS buffer layer is deposited by a chemical bath deposition method (CBD). In Step 1, the temperature of the water bath is set to 65° C., 22 mL of thiourea solution with a concentration of 0.75 mol/L and 22 mL of cadmium sulfate solution with a concentration of 0.015 mol/L and 28 mL of ammonia water are measured with a graduated cylinder, respectively. In Step 2, the measured ammonia water and cadmium sulfate solution are poured into 150 mL of ultrapure water and mixed, the mixed solution is poured into a water-jacketed beaker, and then the sample that is immersed in ultrapure water is taken out and put into the water-jacketed beaker with mixed solution. The interlayer of the water-jacketed beaker is filled with circulating water at 65° C. for heating and start timing. In Step 3, the pre-measured thiourea solution is poured into the reaction solution after one minute, as the reaction progresses, the solution changes from clear to pale yellow, and eventually to a yellow translucent suspension. In Step 4, the sample is taken out after the solution has reacted for eight minutes, the surface of the sample is rinsed with ultrapure water to remove the CdS pallets adsorbed on the surface, and then the sample is dried with a nitrogen gun.

[0077] Step 7: The preparation of the window layer (ZnO/ITO).

[0078] Intrinsic zinc oxide (i-ZnO) and indium tin oxide (ITO) are deposited on the above samples by a magnetron sputtering method as window layer materials. The i-ZnO is sputtered by the magnetron sputtering instrument, the sputtering power is 80 W, the environment is pure argon gas, the air pressure is 0.5 Pa, and the thickness of the film layer is 50 nm. The sputtering power of sputtering the ITO is 60 W, the sputtering pressure in the pure argon environment is 0.5 Pa, and the thickness of the film layer is 200 nm.

[0079] Step 8: The preparation of the electrode (Ni/Al).

[0080] The cathode of the battery is composed of metallic Ni and Al, prepared by a thermal evaporation method. The thicknesses of Ni and Al are 50 nm and 500 nm, respectively.

[0081] The CZTS precursor film layer and the absorption film layer prepared according to the above process have no impurity phase. The absorption layer material has a high crystallinity and a good morphology, and the energy conversion efficiency of the prepared CZTS solar cell is 10.9%.

Example 2

[0082] In Step 1, the preparation of the copper complex is conducted. The operation method of this step is the same as that of Example 1.

[0083] In Step 2, 12.53 g of stannic chloride are weighed and taken in a round-bottomed flask, the mouth of the flask is sealed. 50 mL of DMF are taken and injected into the flask by an injector. The two substances react violently when they come into contact and the reaction generates a large amount of white precipitates. After the reaction is complete, the reaction solution is filtered to obtain white precipitates, and the precipitates are washed with ethanol for several times, then are dried to obtain the corresponding target product Sn(DMF).sub.2Cl.sub.4.

[0084] In Step 3, the preparation of the precursor solution is conducted. 8 mL of DMSO are weighed and put into a reagent bottle, 20 g (6.12 mmol) of the copper complex prepared in Step 1, 1.626 g (4 mmol) of the tin complex Sn(DMF).sub.2Cl.sub.4 prepared in Step 2, 0.734 g (4 mmol) of zinc acetate and 0.2 g of thiourea are weighted and added into the reagent bottle, and stirred at the room temperature until completely dissolved.

[0085] In Step 4 to Step 8, the operation methods are the same as those of Example 1.

Example 3

[0086] In Step 1, the preparation of the copper complex. The operation method of this step is the same as that of Example 1.

[0087] In Step 2, 12.53 g of stannic chloride are weighed and taken in a round-bottomed flask, the mouth of the flask is sealed, 50 mL of DMSO are taken and injected into the flask by an injector. The two substances react violently when they come into contact and the reaction generates a large amount of white precipitates. After the reaction is complete, the reaction solution is filtered to obtain white precipitates, and the precipitates are washed with ethanol for several times, then are dried to obtain the corresponding target product Sn(DMSO).sub.4Cl.sub.4.

[0088] In Step 3, the preparation of the precursor solution is conducted. 8 mL of DMF are taken and put into a reagent bottle, 20 g (6.12 mmol) of the copper complex Cu(Tu).sub.3Cl prepared in Step 1, 1.667 g (4 mmol) of the tin complex Sn(DMSO).sub.4Cl.sub.4 prepared in Step 2, 0.734 g (4 mmol) of zinc acetate and 0.2 g of thiourea are weighted and added into the reagent bottle, and stirred at the room temperature until completely dissolved.

[0089] In Step 4 to Step 8, the operation methods are the same as those of Example 1.

Example 4

[0090] In Step 1, the preparation of the copper complex is conducted. The operation method of this step is the same as that of Example 1.

[0091] In Step 2, 12.53 g of stannic chloride are weighed and taken in a round-bottomed flask, the mouth of the flask is sealed, 50 mL of DMF are taken and injected into the flask by an injector. The two substances react violently when they come into contact and the reaction generates a large amount of white precipitates. After the reaction is complete, the reaction solution is filtered to obtain white precipitates, and the precipitates are washed with ethanol for several times, then are dried to obtain the target product of the tin complex Sn(DMF).sub.2Cl.sub.4.

[0092] In Step 3, the preparation of the precursor solution is conducted. 8 mL of DMF are taken and put into a reagent bottle. 20 g (6.12 mmol) of the copper complex prepared in Step 1, 1.626 g (4 mmol) of the tin complex Sn(DMF).sub.2Cl.sub.4 prepared in Step 2, 0.734 g (4 mmol) of zinc acetate and 0.2 g of thiourea are weighted and added into the reagent bottle, and stirred at the room temperature until completely dissolved.

[0093] In Step 4 to Step 8, the operation methods are the same as those of Example 1.

[0094] The embodiments of the present invention provide four new preparation methods for preparing precursor solutions for high-efficiency CZTS solar cells, that is, by using the metal complexes as precursor compounds to prepare precursor solutions, the CZTS thin film light-absorbing material having a high crystallization quality, a good thin film morphology and no impurity phase is prepared, and then a high-efficiency CZTS solar cell is prepared.

[0095] FIG. 1 and FIG. 2 illustrate physical pictures of a copper complex and a tin complex respectively, and their chemical components as analyzed by an elemental analyzer, are Cu(Tu).sub.3Cl and Sn(DMF).sub.2Cl, respectively.

[0096] FIG. 3 and FIG. 4 illustrate physical pictures of the precursor solutions prepared in the DMSO and DMF solvents based on the above two metal complexes, respectively, which can be observed that both solutions are clear and transparent without precipitation and impurities, and the stability is good, indicating that its solution is of a high quality.

[0097] FIG. 5 and FIG. 6 illustrate X-ray diffraction patterns of the precursor thin films formed by the spin-coating and the annealing of the two precursor solutions. The two precursor thin films show weak diffraction at diffraction angles of 2-Theta=28.5, 47.3, and 56.1 degrees. These diffraction peaks correspond to the (112), (220), (312) crystal planes (PDF #26-0575) of the kesterite copper zinc tin sulfide phase (CZTS), respectively, indicating that the CZTS phase is formed in both precursor films. FIG. 9 and FIG. 10 illustrate Raman spectra of the precursor thin films, both precursor thin films have obvious Raman vibration peaks at the Raman shift of 337 cm.sup.−1, which corresponds to the CZTS phase. Both of these characterization methods show that there is only a single kesterite CZTS phase in the precursor thin film, and no other impurity phase, which is beneficial to the subsequent growth and crystallization of the thin film. FIG. 7 and FIG. 8 illustrate the X-ray diffraction patterns of the CZTSSe absorption layer thin films formed by the selenization reaction of the two precursor thin films. It can be seen from the figures that there are strong diffraction peaks at Theta=27.1, 45.0, and 53.4 on the two CZTSSe absorption layer thin films, these diffraction peaks correspond to the (112), (204), (312) crystal planes of the kesterite CZTSe phase, respectively, indicating that the absorber thin film after selenization are all CZTSe phases, and no other impurity phases can be observed.

[0098] FIG. 11 and FIG. 12 illustrate the Raman spectra of the CZTSSe absorption layer thin films. It can be seen from the figures that the two precursor thin films have obvious Raman vibration peaks at the Raman shifts of 172, 193, and 231 cm.sup.−1, which correspond to the kesterite phase CZTSe, and no Raman vibration peaks of other impurity phases can be observed, which indicates that the prepared absorption layer thin films are high-quality CZTSSe thin films. In combination with the scanning electron microscope photos of the absorption thin films with a high crystallinity, flat and dense, and no impurity phase that are observed in FIGS. 13, 14, 15 and 16, it is further shown that the absorption layer thin films prepared in the examples are of a high quality. The two groups of light-absorbing film layers are prepared into solar cell devices and their photovoltaic performance are tested. Their voltage-current characteristic curves are as illustrated in FIGS. 17 and 18. The photoelectric conversion efficiency of both devices exceed 10%, reaching an international advanced level.

[0099] In summary, a stable, clear and transparent precursor solution having a high quality is prepared by the technical solutions of the present invention, and the precursor solution is applied to the preparations of CZTSSe thin film materials and photovoltaic devices, and eventually, a CZTSSe thin film material with a high crystal quality, a good morphology and no impurity phase and a photovoltaic device with an energy conversion efficiency of more than 10% are obtained, which shows a remarkable advancement of the present invention.

[0100] The above are only the preferred implementations of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these modifications and improvements should also be regarded as the protection scope of the present invention.