CN111540831A - Titanium ore solar cell and preparation method thereof - Google Patents

Titanium ore solar cell and preparation method thereof Download PDF

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CN111540831A
CN111540831A CN202010388820.8A CN202010388820A CN111540831A CN 111540831 A CN111540831 A CN 111540831A CN 202010388820 A CN202010388820 A CN 202010388820A CN 111540831 A CN111540831 A CN 111540831A
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back electrode
boron
precursor solution
solar cell
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CN111540831B (en
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罗伟
李雁鸿
任辉彩
庞茂印
曹原
胡臻玉
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Valiant Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a titanium ore solar cell and a preparation method thereof, and belongs to the field of new photovoltaic energy. The titanium ore solar cell comprises a glass substrate, a front electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protection layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film. The back electrode protective layer is a boron-doped zinc oxide or indium oxide conductive film with high environmental stability, and a boron-doped zinc oxide or indium oxide protective layer is added on the surface of the metal back electrode, so that the metal electrode can be protected from oxidation and sulfidation corrosion, and meanwhile, the perovskite layer can be further isolated from contacting water, oxygen and corrosive substances, so that the environmental stability of the perovskite solar cell is improved. And the back electrode protective layer is in a transparent state, so that the light transmittance of the cell can be improved, and the cell is more suitable for being applied to buildings such as glass curtain walls.

Description

Titanium ore solar cell and preparation method thereof
Technical Field
The invention relates to the field of new photovoltaic energy, in particular to a titanium ore solar cell and a preparation method thereof.
Background
The solar cell has the advantages of environmental protection, abundant energy storage and the like, and is known as the most promising green energy. In recent years, organic-inorganic hybrid perovskite solar cells are developed rapidly, the photoelectric conversion efficiency of the organic-inorganic hybrid perovskite solar cells reaches about 25%, the perovskite solar cells are rich in raw material sources, simple in process and low in cost, and the organic-inorganic hybrid perovskite solar cells can be prepared into flexible cells and are widely regarded by academia and industry.
The main reason for limiting the commercialization of perovskite solar cells is that they are poor in environmental stability and are easily damaged by water, oxygen and corrosive substances in the environment, so that it is a key problem to be solved at present to improve the environmental stability.
In addition, the back electrode of the perovskite battery is a metal layer and is easily oxidized and corroded by oxygen, sulfur and the like. The traditional thin-film battery back electrode protective layer is titanium, which is easily corroded by acidic substances in the air, and the titanium is opaque, so that the application of the battery on buildings is limited.
Therefore, it is important to develop a novel back electrode protection layer capable of improving light transmittance and preventing the back electrode from being oxidized and corroded.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a titanium ore solar cell and a preparation method thereof. The preparation method of the titanium ore solar cell is simple, the back electrode protective layer of the titanium ore solar cell can protect the metal back electrode from being oxidized or vulcanized, and can further isolate the perovskite layer from contacting water, oxygen and corrosive substances; and the back electrode protective layer is transparent, so that the light transmittance of the cell can be improved, and the cell is more suitable for application on a glass curtain wall.
The technical scheme of the invention is as follows:
a titanium ore solar cell comprises a glass substrate, a front electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protection layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film.
Preferably, the thickness of the back electrode protection layer is 10-100 nm.
Preferably, the thickness of the hole transport layer is 5-30 nm, the thickness of the perovskite absorption layer is 400-500 nm, the thickness of the electron transport layer is 50-80 nm, the thickness of the buffer layer is 10-15 nm, and the thickness of the metal back electrode layer is 70-200 nm.
The preparation method of the titanium ore solar cell comprises the following steps:
1) and processing the glass conductive substrate: carrying out ultraviolet ozone treatment on the glass conductive substrate for later use;
2) and preparing a hole transport layer: adding the NiOx nano particles into a solvent for ultrasonic dispersion to prepare NiOx suspension as a first precursor solution; coating the first precursor solution on the conductive surface of the conductive glass, carrying out heating annealing treatment after the coating is finished, and naturally cooling to room temperature to form a hole transport layer;
3) and preparing a perovskite absorption layer: dissolving lead halide and methyl halide methylamine in an organic solvent according to a certain proportion to prepare a second precursor solution, stirring and dissolving to obtain a perovskite precursor solution, coating the perovskite precursor solution on a hole transport layer, and annealing on a heating plate to obtain a perovskite absorption layer;
4) and preparing an electron transport layer: dissolving a fullerene derivative in chlorobenzene, heating, stirring and dissolving to obtain a third precursor solution, coating the third precursor solution on the perovskite absorption layer, and annealing on a heating plate to obtain an electron transmission layer;
5) and preparing a buffer layer: adding BCP into methanol to obtain a supersaturated solution, coating the supersaturated solution on an electron transport layer, and then annealing on a heating plate;
6) preparing a metal back electrode layer, namely placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 × 10-4When the pressure is higher than Pa, Au, Ag or Al is evaporated on the surface of the buffer layer to form a metal back electrode layer;
7) preparing a back electrode protective layer, namely placing the semi-finished product of the battery obtained in the step 6) in a magnetron sputtering coating chamber, wherein the vacuum degree reaches 5 × 10-4And Pa or above, and sputtering a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film on the metal back electrode layer.
Preferably, in the step 7), a sputtering source of magnetron sputtering is argon, and the oxygen flow is 10-20 cm3The temperature of the substrate is 80-120 ℃, and the background vacuum degree is 10-4Pa, the target base distance is 6cm, the sputtering time is 1-10 min, the working pressure is 1-2 Pa, and the sputtering power is 100-200W. Under the technological parameters, the back electrode protective layer sputtered on the surface of the metal back electrode is compact and uniform.
Preferably, in the step 7), the target material for sputtering the boron-doped zinc oxide transparent conductive film back electrode protection layer is ZnO to B in mass ratio2O3A ceramic target of 98-99: 1-2; the target material for sputtering the protective layer of the back electrode of the indium oxide transparent conductive film doped with boron is In by mass ratio2O3:B2O3The ceramic target is 97-99: 1-3.
As a preferable scheme:
in the step 1), the time of ultraviolet ozone treatment is 5-30 min;
in the step 2), the solvent is deionized water, ethanol or n-butanol; the heating and annealing temperature is 100-200 ℃, and the time is 10-30 min
In the step 3), the organic solvent is DMF and/or DMSO; the temperature of the heating plate is controlled to be 100-120 ℃, and the annealing time is controlled to be 10-30 min;
in the step 4), the dissolving temperature is controlled to be 40-50 ℃, the temperature of a heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min;
in the step 5), the temperature of the heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min.
Preferably, in step 3), the lead halide is PbCl2、PbBr2Or PbI2One or two of them; the halogenated methylamine being CH3NH3Cl、CH3NH3Br or CH3NH3One of I; the molar ratio of the lead halide to the methyl halide amine is 1: 1-3: 1.
Preferably, in the step 3), the molar concentration of lead ions in the second precursor solution is 0.5-2 mol/L; in the step 4), the mass-volume concentration of the fullerene derivative in the third precursor solution is 10-20 mg/mL.
Preferably, in step 4), the fullerene derivative is PC61BM、PC71BM, ICBA or bis-PC61BM。
The invention has the beneficial effects that:
1. the back electrode protective layer is creatively arranged to be a boron-doped zinc oxide or indium oxide conductive film with high environmental stability, and the compact and uniform back electrode protective layer is obtained through proper technological parameters.
2. The surface of the metal back electrode is additionally provided with a boron-doped zinc oxide and indium oxide protective layer, so that the metal electrode can be protected from oxidation and sulfidation corrosion, and meanwhile, the perovskite layer can be further isolated from contacting water, oxygen and corrosive substances, so that the environmental stability of the perovskite solar cell is improved, and the attenuation of the photoelectric efficiency of the perovskite solar cell is remarkably reduced.
3. The back electrode protective layer is in a transparent state, so that the light transmittance of the cell can be improved, and the cell is more suitable for being applied to buildings such as glass curtain walls.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a titanium ore solar cell according to the present invention;
in the drawings, the components represented by the respective reference numerals are listed below:
1. the solar cell comprises a glass substrate, 2, a front electrode, 3, a hole transport layer, 4, a perovskite absorption layer, 5, an electron transport layer, 6, a buffer layer, 7, a metal back electrode layer, 8 and a back electrode protection layer.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Example 1
As shown in fig. 1, a titanium ore solar cell comprises a glass substrate 1, a front electrode 2, a hole transport layer 3, a perovskite absorption layer 4, an electron transport layer 5, a buffer layer 6, a metal back electrode layer 7 and a back electrode protection layer 8 which are sequentially laminated from bottom to top; the back electrode protection layer 8 is a boron-doped zinc oxide transparent conductive film.
The preparation method of the titanium ore solar cell comprises the following steps:
1) and processing the glass conductive substrate: selecting a common glass substrate as the substrate, wherein the sheet resistance of the front electrode layer is 5-40 omega, the transmittance is 75-90%, and after the conductive substrate is cleaned, carrying out ultraviolet ozone treatment on the glass conductive substrate for 25min for later use;
2) and preparing a hole transport layer: adding 3mg of nickel oxide nano particles into 1mL of deionized water, and ultrasonically dispersing for 24h to prepare uniform suspension serving as a first precursor solution;
placing the conductive surface of the conductive glass on the table top of a spin coater at the speed of 2000rpm in an upward mode, dropwise adding a first precursor solution, performing spin coating for 30s, heating and annealing at 100-200 ℃ for 10-20 min after the coating is finished, and naturally cooling to room temperature to obtain a compact nickel oxide hole transport layer;
3) perovskite absorption layer (CH)3NH3Preparation of PbX, X ═ Cl, Br, I): mixing CH with the molar ratio of 1: 1-3: 13NH3X and PbX2Dissolving the precursor solution in DMF or DMSO or a mixed solution of the DMF and the DMSO to prepare a second precursor solution with the molar concentration of 0.5-2 mol/L, and stirring and dissolving for 4 hours to form the perovskite precursor solution. Spin coating the perovskite precursor solution on NiOxSpin-coating on the hole transport layer at 6000rpm for 30s, and then annealing at 80-100 ℃ for 10-30 min to form a 400-500 nm perovskite absorption layer;
4) and preparing an electron transport layer: will PC61BM is dissolved in anhydrous chlorobenzene to prepare a third precursor solution of 10-20 mg/mL, and the third precursor solution is stirred and dissolved for 3-4 hours at the temperature of 40-50 ℃. The above PC61Spin-coating BM chlorobenzene solution on the perovskite absorption layer at 1500rpm for 30s at 70 deg.C for 10min to form 50-80 nm thick PC61BM electron transport layer;
5) and preparing a buffer layer: spin-coating a methanol saturated solution of BCP on the electron transport layer, and annealing at 70 ℃ for 10min to form a BCP buffer layer with the thickness of 10-15 nm;
6) preparing a metal electrode layer, namely placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 × 10-4Depositing 100nm Ag by vapor deposition with more than Pa to form an Ag electrode;
7) and preparing a back electrode protective layer: placing the semi-finished product of the battery obtained in the step 6) in a magnetron sputtering coating chamber, wherein the oxygen flow is 15cm3Min, vacuum degree up to 10-4And Pa or above, sputtering a BZO protective layer on the metal back electrode layer. The target material is ZnO to B in mass ratio2O3The sputtering source of magnetron sputtering is argon, the substrate temperature is 100 ℃, the target base distance is 6cm, the sputtering time is 2min, the working pressure is 1Pa, the sputtering power is 180W, and a BZO protective layer with the film thickness of 15nm is formed.
Example 2
As shown in fig. 1, a titanium ore solar cell comprises a glass substrate 1, a front electrode 2, a hole transport layer 3, a perovskite absorption layer 4, an electron transport layer 5, a buffer layer 6, a metal back electrode layer 7 and a back electrode protection layer 8 which are sequentially laminated from bottom to top; the back electrode protection layer 8 is a boron-doped zinc oxide transparent conductive film.
The preparation method of the titanium ore solar cell comprises the following steps:
1) and processing the glass conductive substrate: selecting a common glass substrate as the substrate, wherein the sheet resistance of the front electrode layer is 5-40 omega, the transmittance is 75-90%, and after the conductive substrate is cleaned, carrying out ultraviolet ozone treatment on the glass conductive substrate for 25min for later use;
2) and preparing a hole transport layer: adding 3mg of nickel oxide nano particles into 1mL of deionized water, and ultrasonically dispersing for 24h to prepare uniform suspension serving as a first precursor solution;
placing the conductive surface of the conductive glass on the table top of a spin coater at the speed of 2000rpm in an upward mode, dropwise adding a first precursor solution, performing spin coating for 30s, heating and annealing at 100-200 ℃ for 10-20 min after the coating is finished, and naturally cooling to room temperature to obtain a compact nickel oxide hole transport layer;
3) perovskite absorption layer (CH)3NH3Preparation of PbX, X ═ Cl, Br, I): mixing CH with the molar ratio of 1: 1-3: 13NH3X and PbX2Dissolving the precursor solution in DMF or DMSO or a mixed solution of the DMF and the DMSO to prepare a second precursor solution with the molar concentration of 0.5-2 mol/L, and stirring and dissolving for 4 hours to form the perovskite precursor solution. Spin coating the perovskite precursor solution on NiOxSpin-coating on the hole transport layer at 6000rpm for 30s, and then annealing at 80-100 ℃ for 10-30 min to form a 400-500 nm perovskite absorption layer;
4) and preparing an electron transport layer: will PC61BM is dissolved in anhydrous chlorobenzene to prepare a third precursor solution of 10-20 mg/mL, and the third precursor solution is stirred and dissolved for 3-4 hours at the temperature of 40-50 ℃. The above PC61Spin-coating BM chlorobenzene solution on the perovskite absorption layer at 1500rpm for 30s at 70 deg.C for 10min to form 50-80 nm thick PC61BM electron transport layer;
5) and preparing a buffer layer: spin-coating a methanol saturated solution of BCP on the electron transport layer, and annealing at 70 ℃ for 10min to form a BCP buffer layer with the thickness of 10-15 nm;
6) preparing a metal electrode layer, namely placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 × 10-4Depositing 100nm Ag by vapor deposition with more than Pa to form an Ag electrode;
7) and preparing a back electrode protective layer: placing the semi-finished product of the battery obtained in the step 6) in a magnetron sputtering coating chamber, wherein the oxygen flow is 15cm3Min, vacuum degree up to 10-4And Pa, sputtering a BIO protective layer on the metal back electrode layer. The target material is InO to B in mass ratio2O3The ceramic target is 98:2, a sputtering source of magnetron sputtering is argon, the substrate temperature is 135 ℃, the target base distance is 6cm, the sputtering time is 2min, the working pressure is 1Pa, the sputtering power is 120W, and a BIO protective layer with the film thickness of 18nm is formed.
In other embodiments, the thickness of the back electrode protection layer may also be greater.
Comparative example 1
Compared to example 1, step 7) is omitted, i.e., the titanium ore solar cell of comparative example 1 does not include a back electrode protection layer.
Comparative example 2
In contrast to example 1, the back electrode protection layer was Ti in the prior art.
According to the embodiment 1, the embodiment 2, the comparative example 1 and the comparative example 2, 20 titanium ore solar cells are respectively manufactured; four groups of titanium ore solar cells are provided, and each group comprises 20 titanium ore solar cells; in the preparation process of 20 batteries in each group, the process parameters are adjusted within the ranges described in the examples, and the specific process parameters corresponding to each group are not described in detail. After all the perovskite solar test data prepared in example 1, example 2, comparative example 1 and comparative example 2 were subjected to an outdoor exposure test at the same time, the exposure time was 1000 hours, the electrical data after exposure was measured, and then the average value was calculated, and the results are shown in table 1.
Table 1 electrical data before and after exposure of perovskite solar cells of each example and comparative example
Figure BDA0002484937680000071
As can be seen from table 1, the electrical properties of the batteries with the back electrode protection layers respectively of titanium (Ti), BZO and BIO before exposure are basically the same, and are slightly higher than the power generation Efficiency (EFF) of the battery without the back electrode protection layer, after 1000 hours of outdoor exposure, the battery attenuation rate of the back electrode protection layer is obviously reduced, and the battery attenuation rate of the back electrode protection layer of BZO or BIO is also obviously reduced than that of the battery with the back electrode protection layer of Ti.

Claims (10)

1. A titanium ore solar cell, characterized by: the device comprises a glass substrate, a front electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, a buffer layer, a metal back electrode layer and a back electrode protection layer which are sequentially laminated from bottom to top; the back electrode protection layer is a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film.
2. The titanium ore solar cell of claim 1, wherein: the thickness of the back electrode protection layer is 10-100 nm.
3. The titanium ore solar cell of claim 1 or 2, wherein: the thickness of the hole transmission layer is 5-30 nm, the thickness of the perovskite absorption layer is 400-500 nm, the thickness of the electron transmission layer is 50-80 nm, the thickness of the buffer layer is 10-15 nm, and the thickness of the metal back electrode layer is 70-200 nm.
4. The method of claim 1, comprising the steps of:
1) and processing the glass conductive substrate: carrying out ultraviolet ozone treatment on the glass conductive substrate for later use;
2) and preparing a hole transport layer: adding the NiOx nano particles into a solvent for ultrasonic dispersion to prepare NiOx suspension as a first precursor solution; coating the first precursor solution on the conductive surface of the conductive glass, carrying out heating annealing treatment after the coating is finished, and naturally cooling to room temperature to form a hole transport layer;
3) and preparing a perovskite absorption layer: dissolving lead halide and methyl halide methylamine in an organic solvent according to a certain proportion to prepare a second precursor solution, stirring and dissolving to obtain a perovskite precursor solution, coating the perovskite precursor solution on a hole transport layer, and annealing on a heating plate to obtain a perovskite absorption layer;
4) and preparing an electron transport layer: dissolving a fullerene derivative in chlorobenzene, heating, stirring and dissolving to obtain a third precursor solution, coating the third precursor solution on the perovskite absorption layer, and annealing on a heating plate to obtain an electron transmission layer;
5) and preparing a buffer layer: adding BCP into methanol to obtain a supersaturated solution, coating the supersaturated solution on an electron transport layer, and then annealing on a heating plate;
6) preparing a metal back electrode layer, namely placing the semi-finished product of the battery obtained in the step 5) in a vacuum evaporation chamber, wherein the vacuum degree reaches 1 × 10-4When the pressure is higher than Pa, Au, Ag or Al is evaporated on the surface of the buffer layer to form a metal back electrode layer;
7) preparing a back electrode protective layer, namely placing the semi-finished product of the battery obtained in the step 6) in a magnetron sputtering coating chamber, wherein the vacuum degree reaches 5 × 10-4And Pa or above, and sputtering a boron-doped zinc oxide transparent conductive film or a boron-doped indium oxide transparent conductive film on the metal back electrode layer.
5. The method of claim 4, wherein: in the step 7), a sputtering source of magnetron sputtering is argon, and the oxygen flow is 10-20 cm3The temperature of the substrate is 80-120 ℃, and the background vacuum degree is 10-4Pa, the target base distance is 6cm, the sputtering time is 1-10 min, the working pressure is 1-2 Pa, and the sputtering power is 100-200W.
6. The method for manufacturing a titanium ore solar cell according to claim 4 or 5, wherein: in the step 7), the target material for sputtering the boron-doped zinc oxide transparent conductive film back electrode protection layer is ZnO to B in mass ratio2O3A ceramic target of 98-99: 1-2; the target material for sputtering the protective layer of the back electrode of the indium oxide transparent conductive film doped with boron is In by mass ratio2O3:B2O3The ceramic target is 97-99: 1-3.
7. The method of claim 4, wherein:
in the step 1), the time of ultraviolet ozone treatment is 5-30 min;
in the step 2), the solvent is deionized water, ethanol or n-butanol; the heating and annealing temperature is 100-200 ℃, and the time is 10-30 min
In the step 3), the organic solvent is DMF and/or DMSO; the temperature of the heating plate is controlled to be 100-120 ℃, and the annealing time is controlled to be 10-30 min;
in the step 4), the dissolving temperature is controlled to be 40-50 ℃, the temperature of a heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min;
in the step 5), the temperature of the heating plate is controlled to be 60-80 ℃, and the annealing time is controlled to be 10-30 min.
8. The method of claim 4, wherein: in step 3), the lead halide is PbCl2、PbBr2Or PbI2One or two of them; the halogenated methylamine being CH3NH3Cl、CH3NH3Br or CH3NH3One of I; the molar ratio of the lead halide to the methyl halide amine is 1: 1-3: 1.
9. The method of claim 4, wherein: in the step 3), the molar concentration of lead ions in the second precursor solution is 0.5-2 mol/L; in the step 4), the mass-volume concentration of the fullerene derivative in the third precursor solution is 10-20 mg/mL.
10. The method of claim 4, wherein: in step 4), the fullereneThe alkene derivative is PC61BM、PC71BM, ICBA or bis-PC61BM。
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