CN118338749B - Semitransparent perovskite solar cell and preparation method thereof - Google Patents
Semitransparent perovskite solar cell and preparation method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. 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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- 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
- H10K30/50—Photovoltaic [PV] devices
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- 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
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- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
A semitransparent perovskite solar cell and a preparation method thereof belong to the field of perovskite solar cells and overcome the defect that the perovskite light absorption layer material is easy to damage and the performance of the semitransparent perovskite solar cell is reduced when a hole transport layer is prepared by nickel oxide in the prior art. The preparation method of the semitransparent perovskite solar cell comprises the following steps: sequentially preparing a first transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second transparent electrode on a substrate; preparing the hole transport layer by adopting a reaction plasma deposition process: the target material comprises nickel oxide ceramic, sputtering gas is Ar, reaction gas is O 2, ar flow is 80-150 sccm, O 2 flow is 3-30 sccm, deposition air pressure is 0.3-0.4 Pa, and deposition temperature is 25-120 ℃. The deposition process of the nickel oxide film does not damage the perovskite light absorption layer.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a semitransparent perovskite solar cell and a preparation method thereof.
Background
Crystalline silicon solar cells and corresponding photovoltaic modules dominate the photovoltaic market for a long time, but crystalline silicon solar cells have limited application scenes, which greatly limits the continued growth of the photovoltaic market. In recent years, the rapid development of perovskite solar cells has provided a new idea to solve this problem. By regulating and controlling the components of the constituent elements of the perovskite light absorption layer, the optical band gap of the perovskite light absorption layer material can be regulated and controlled within 1.2-2.3 eV, and the semitransparent perovskite solar cell prepared based on the optical band gap can greatly widen the application scene of the photovoltaic power generation technology, such as building photovoltaic integration, agricultural photovoltaic integration and the like.
The hole transport layer is used as an important component in the semitransparent perovskite solar cell and plays a key role in the aspects of carrier extraction, carrier transmission, carrier recombination inhibition and the like. Typical hole transport layer materials are organic or inorganic materials such as nickel oxide, poly (3, 4-ethylenedioxythiophene) (PEDOT: PSS), cuprous thiocyanate (CuSCN), poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), and poly (3, 4-ethylenedioxythiophene) (Spiro-OMeTAD). Among them, PEDOT: PSS, cuSCN, PTAA and spira-ome tad are commonly used hole transport layer materials, but in order to improve the photoelectric conversion efficiency of the semitransparent perovskite solar cell, li-TFSI (lithium bis (trifluoromethylsulfonyl) imide) needs to be added to these hole transport layer materials to improve the efficiency of extracting photogenerated carriers from the hole transport layer. The Li-TFSI introduced lithium ions easily adsorb water molecules in the air, so that positive-charged free radicals are formed at the interface of the perovskite light absorption layer/the hole transmission layer to promote migration of halogen ions in the perovskite light absorption layer and accelerate degradation of the perovskite light absorption layer material. Meanwhile, the PTAA, PEDOT, PSS, spiro-OMeTAD and other organic hole transport layer materials have the disadvantages of longer synthesis steps and high price.
Nickel oxide is used as a semitransparent perovskite solar cell hole transport layer material, and although the semitransparent perovskite solar cell hole transport layer material does not have the defects, the preparation method is mainly magnetron sputtering deposition or spin coating of a nickel oxide nanoparticle aqueous solution, and the two preparation methods can lead to damage of a perovskite light absorption layer material and deterioration of the semitransparent perovskite solar cell performance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the perovskite light absorption layer material is easy to damage and the performance of the perovskite solar cell is reduced when the nickel oxide is adopted to prepare the hole transport layer in the prior art, so that the semitransparent perovskite solar cell and the preparation method thereof are provided.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the present invention provides a method for preparing a translucent perovskite solar cell, comprising the steps of:
sequentially preparing a first transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second transparent electrode on a substrate;
Preparing the hole transport layer by adopting a reaction plasma deposition process: the target material comprises nickel oxide ceramic (NOx), wherein the sputtering gas is Ar, the reaction gas is O 2, the Ar flow is 80-150 sccm, the O 2 flow is 3-30 sccm, the deposition air pressure is 0.3-0.4 Pa, and the deposition temperature is 25-120 ℃.
In one possible embodiment, the target is a lithium/magnesium/lead co-doped nickel oxide ceramic, wherein the MgO content is 0.5-4.0wt%, the Li 2 O content is 0.1-2.0wt%, the PbO content is 0.1-1.5 wt%, and the balance is nickel oxide. The lithium/magnesium/lead co-doped nickel oxide ceramic refers to a nickel oxide ceramic that includes three doping elements of lithium, magnesium and lead simultaneously.
In one possible embodiment, the thickness of the first transparent electrode is 80-600 nm.
In one possible embodiment, the first transparent electrode is prepared using chemical vapor deposition, sol gel, physical vapor deposition, or reactive plasma deposition processes. By way of example, physical vapor deposition may be magnetron sputtering.
In one possible embodiment, the material of the first transparent electrode includes a first metal oxide, which is indium oxide, zinc oxide, or tin oxide.
Further, the material of the first transparent electrode comprises doping elements, wherein the doping elements are one or more of Al, ga, in, sn, zn, F, and the doping elements are different from the metal elements in the first metal oxide; the total doping amount of the doping elements in the first transparent electrode material is 0.1-10wt%. In the present invention, the doping amount of the doping element refers to only the mass percentage of the doping element, not the mass percentage of the compound containing the doping element.
The electron transport layer material is an N-type semiconductor material. In one possible embodiment, the electron transport layer material comprises tin oxide (SnO 2), indium oxide (In 2O3), titanium oxide (TiO 2) or zinc oxide (ZnO 2).
In one possible embodiment, the perovskite light absorbing layer is prepared using spin coating, knife coating, or vacuum evaporation.
In one possible embodiment, the perovskite light absorbing layer is an ABX 3 type perovskite film, where a + is CH3NH3 +、CH3CH2NH3 +、HN=(NH2)+ or Cs +;B2+ is Pb 2+ or Sn 2+;X- is Cl -、Br- or I -.
In one possible embodiment, the second transparent electrode is prepared using a physical vapor deposition or reactive plasma deposition process. By way of example, physical vapor deposition may be magnetron sputtering.
In one possible embodiment, the material of the second transparent electrode includes a second metal oxide, which is indium oxide, zinc oxide, or tin oxide. Further, the material of the second transparent electrode comprises doping elements, wherein the doping elements are one or more of Ga, in, sn, W, the doping elements are different from the metal elements in the second metal oxide, and the total doping amount of the doping elements in the material of the second transparent electrode is 0.1-10wt%.
The second transparent electrode work function change of the translucent perovskite solar cell affects cell performance, and doping of high work function metal oxide materials (e.g., WO 3) helps to raise the second transparent electrode work function. When the work function of the second transparent electrode is larger than that of the hole transport layer, electrons flow from the hole transport layer to the second transparent electrode to realize thermionic emission, which is equivalent to that of holes flowing from the second transparent electrode to the hole transport layer. Excessive holes are accumulated in the hole transmission layer, so that a positive space charge region is formed at the interface, the electric field direction points to the second transparent electrode from the hole transmission layer, the energy band is bent upwards, the top of the valence band of the hole transmission layer is closer to the fermi level of the second transparent electrode, the photo-generated holes in the hole transmission layer are more easily migrated into the second transparent electrode, and the performance of the semitransparent perovskite solar cell is improved.
In one possible embodiment, the thickness of the second transparent electrode is 80-200 nm.
Further, the preparation method of the semitransparent perovskite solar cell further comprises the steps of preparing a first grid line on the first transparent electrode and preparing a second grid line on the second transparent electrode;
the preparation methods of the first grid line and the second grid line are respectively and independently selected from any one of thermal evaporation, electron beam evaporation, magnetron sputtering deposition and screen printing.
Optionally, the first gate line or the second gate line is prepared by depositing metal materials such as Au, al, ag or Cu by thermal evaporation, electron beam evaporation or magnetron sputtering.
Optionally, the first grid line or the second grid line is prepared by adopting conductive paste such as copper paste, silver paste, carbon paste, aluminum paste and the like through screen printing.
In one possible embodiment, the method for preparing a semitransparent perovskite solar cell adopts magnetron sputtering, chemical vapor deposition or reactive plasma deposition process to prepare a first transparent electrode; the thickness of the first transparent electrode is 80-600 nm; the first transparent electrode material comprises a first metal oxide, wherein the first metal oxide is indium oxide, zinc oxide or tin oxide; the material of the first transparent electrode comprises doping elements, wherein the doping elements are one or more of Al, ga, in, sn, zn, F, and the doping elements are different from the metal elements in the first metal oxide; the total doping amount of the doping elements in the first transparent electrode material is 0.1-10wt%;
The electron transport layer material comprises tin oxide, indium oxide, titanium oxide or zinc oxide;
Preparing a perovskite light absorption layer by spin coating, knife coating or vacuum evaporation; the perovskite light absorption layer is an ABX 3 perovskite film, wherein A + is CH3NH3 +、CH3CH2NH3 +、HN=(NH2)+ or Cs +;B2+ is Pb 2+ or Sn 2+;X- is Cl -、Br- or I -;
Preparing a second transparent electrode by adopting a magnetron sputtering or reactive plasma deposition process; the material of the second transparent electrode comprises a second metal oxide, wherein the second metal oxide is indium oxide, zinc oxide or tin oxide; the thickness of the second transparent electrode is 80-200 nm;
Preparing a first grid line on the first transparent electrode, and preparing a second grid line on the second transparent electrode; the preparation methods of the first grid line and the second grid line are respectively and independently selected from any one of thermal evaporation, electron beam evaporation, magnetron sputtering deposition and screen printing. The first grid line is used as a negative electrode of the semitransparent perovskite solar cell, and the second grid line is used as a positive electrode of the semitransparent perovskite solar cell.
Further, the substrate is a transparent substrate, and exemplary transparent substrates are materials with good optical transmittance such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or glass.
Further, before preparing the first transparent electrode on the bottom, the substrate needs to be cleaned by oxygen plasma or ultraviolet-ozone; the time for oxygen plasma cleaning or ultraviolet-ozone cleaning is 5-20 min. Aiming at the n-i-p type semitransparent perovskite solar cell hole transport layer, nickel oxide is introduced to replace organic hole transport layer materials such as Spiro-OMeTAD and the like. Meanwhile, by applying the reaction plasma deposition process, the nickel oxide film with high optical transmittance is prepared, and the perovskite light absorption layer damage caused by high-energy plasma bombardment is avoided. The nickel oxide film prepared by adopting the reaction plasma deposition process can effectively protect the perovskite light absorption layer from the influence of subsequent process steps, and the process tolerance range of the second transparent electrode is widened. The photoelectric conversion performance of the semitransparent perovskite solar cell is improved, and meanwhile, the flexibility of the semitransparent perovskite solar cell production process is improved.
In a second aspect, the present invention provides a translucent perovskite solar cell, made according to a method of making the translucent perovskite solar cell.
The technical scheme of the invention has the following advantages:
1. The preparation method of the semitransparent perovskite solar cell comprises the following steps: sequentially preparing a first transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second transparent electrode on a substrate; preparing the hole transport layer by adopting a reaction plasma deposition process: the target material comprises nickel oxide ceramic, sputtering gas is Ar, reaction gas is O 2, ar flow is 80-150 sccm, O 2 flow is 3-30 sccm, deposition pressure is 0.3-0.4 Pa, and deposition temperature is 25-120 ℃.
The hole transport layer is prepared by adopting a reactive plasma deposition process and limiting the condition range of the invention, the energy of effective plasmas is distributed in the range of 20-30 eV in the nickel oxide film deposition process, high-energy plasmas with energy higher than 40 eV are hardly generated, and the perovskite light absorption layer is not damaged in the nickel oxide film deposition process.
The nickel oxide film prepared by the method has good optical transmittance and density, can realize high photoelectric conversion efficiency of the semitransparent perovskite solar cell without other additional treatment processes, and greatly reduces the production cost of the semitransparent perovskite solar cell.
The nickel oxide film is deposited by adopting a reaction plasma deposition process, so that the nickel oxide film can replace the traditional nickel oxide preparation process and organic hole transport layer materials such as Spiro-OMeTAD and the like to be a semitransparent perovskite solar cell hole transport layer, the nickel oxide film effectively protects a perovskite light absorption layer from being damaged by a subsequent process, the tolerance range of a second transparent electrode preparation process is greatly increased, no buffer layer is needed between the hole transport layer and the second transparent electrode, the complexity and the production cost of the semitransparent perovskite solar cell production process are reduced, the flexibility of the semitransparent perovskite solar cell production process can be greatly improved, and the performances of the semitransparent perovskite solar cell are improved.
The nickel oxide has the characteristics of low toxicity, low price and the like, and enhances the environmental friendliness of the semitransparent perovskite solar cell while reducing the production cost of the semitransparent perovskite solar cell.
2. The target material for preparing the hole transport layer is lithium/magnesium/lead co-doped nickel oxide ceramic, wherein the content of MgO is 0.5-4.0 wt%, the content of Li 2 O is 0.1-2.0 wt%, the content of PbO is 0.1-1.5 wt% and the balance is nickel oxide.
Compared with an undoped nickel oxide film, the lithium/magnesium/lead co-doped nickel oxide film has higher conductivity. Meanwhile, the lithium/magnesium/lead co-doped nickel oxide film also has higher hole mobility, so that the energy band bending degree of the interface between the perovskite light absorption layer and the hole transport layer is greatly improved, the built-in electric field is increased, the energy level mismatch of the perovskite light absorption layer and the hole transport layer is reduced, the hole extraction capability from the perovskite light absorption layer to the hole transport layer is enhanced, and the collection efficiency of photo-generated electrons/holes is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a semitransparent perovskite solar cell of the present invention;
FIG. 2 is a J-V curve of the semitransparent perovskite solar cell produced in example 1;
FIG. 3 is an optical transmittance of the nickel oxide thin film prepared in example 1;
FIG. 4 is an SEM image of a nickel oxide film prepared according to example 1;
FIG. 5 is an X-ray diffraction pattern of the nickel oxide thin film prepared in example 1;
FIG. 6 is a J-V curve of the semitransparent perovskite solar cell produced according to example 2;
FIG. 7 is a J-V curve of the semitransparent perovskite solar cell produced according to example 3;
FIG. 8 is an X-ray diffraction pattern of the lithium/magnesium/lead co-doped nickel oxide thin film prepared in example 3;
FIG. 9 is a J-V curve of the semitransparent perovskite solar cell produced according to example 4;
FIG. 10 is a J-V curve of the semitransparent perovskite solar cell of comparative example 1;
FIG. 11 is a J-V curve of the semitransparent perovskite solar cell produced according to comparative example 2.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a semitransparent perovskite solar cell, the structure of the semitransparent perovskite solar cell is shown in fig. 1, and the preparation method of the semitransparent perovskite solar cell comprises the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): adopting a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer treated in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a nickel oxide hole transport layer on the CH 3NH3PbI3 perovskite light absorption layer prepared in the step (7): using a reaction plasma deposition process, and taking a nickel oxide ceramic target with the purity of 99.99% as a target material; the sputtering gas is Ar, the flow rate of Ar is regulated to be 100sccm, the reaction gas is O 2, the flow rate of oxygen is regulated to be 15sccm, the deposition air pressure is 0.35Pa, the deposition temperature is room temperature, and the thickness of the hole transport layer is 25nm.
(9) Preparing a second transparent electrode-tin doped indium oxide film on the nickel oxide hole transport layer prepared in the step (8): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the tin-doped indium oxide ceramic target comprises 10 percent wt percent of SnO 2 by weight, the balance of indium oxide, wherein the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, the deposition temperature is room temperature, and the thickness of the second transparent electrode is 100 nm.
(10) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (9), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curve measured under the AM 1.5 illumination condition of the semitransparent perovskite solar cell obtained in the embodiment is shown in figure 2. Wherein the open circuit voltage is 1.05V, the short circuit current density is 20.70 mA/cm 2, the filling factor is 74.3%, and the photoelectric conversion efficiency is 16.2%.
The nickel oxide film was prepared on the glass substrate using the conditions of the reactive plasma deposition process of step (8) of this example, and then the optical transmittance was tested and XRD test was performed thereon, and the test results are shown in fig. 3 and 5. As shown in fig. 3, the nickel oxide film prepared by the reactive plasma deposition process has good optical transmittance in the wavelength range of 300-1200 nm, and meets the optical transmittance requirement of the semitransparent perovskite solar cell on the hole transport layer. As can be seen from fig. 5, the nickel oxide thin film prepared by the reactive plasma deposition process is an amorphous thin film.
The scanning electron microscope image of the surface of the translucent perovskite battery in which step (8) was completed in this example is shown in fig. 4. The perovskite light absorption layer is completely covered by the nickel oxide film prepared by the reaction plasma deposition process, and the nickel oxide film has good integrity and compactness.
Example 2
The embodiment provides a preparation method of a semitransparent perovskite solar cell, which comprises the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): adopting a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer treated in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a nickel oxide hole transport layer on the CH 3NH3PbI3 perovskite light absorption layer prepared in the step (7): using a reaction plasma deposition process, and taking a nickel oxide ceramic target with the purity of 99.99% as a target material; the sputtering gas is Ar, the flow rate of Ar is regulated to be 100sccm, the reaction gas is O 2, the flow rate of oxygen is regulated to be 15sccm, the deposition air pressure is 0.35Pa, the deposition temperature is room temperature, and the thickness of the hole transport layer is 25nm.
(9) Preparing a second transparent electrode-tin doped indium oxide film on the nickel oxide hole transport layer prepared in the step (8): the direct-current magnetron sputtering technology is utilized, a tin-doped indium oxide ceramic target is used as a target material, the doped weight percentage of SnO 2 in the tin-doped indium oxide ceramic target is 10 wt percent, the rest is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; the sputtering gas is Ar, the reaction gas is O 2, the flow rate of argon is regulated to be 40 sccm, and the flow rate of oxygen is 8 sccm; the DC magnetron sputtering power is 120W; the background vacuum is: 8.5X10 -4 Pa; the deposition air pressure was 0.40 Pa, the sample tray rotation speed was 2000 rpm, the substrate temperature was room temperature, and the film thickness was 120 nm.
(10) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (9), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curve measured under AM 1.5 illumination for the translucent perovskite solar cell obtained in this example is shown in FIG. 6. Wherein the open circuit voltage is 1.05V, the short circuit current density is 20.8 mA/cm 2, the filling factor is 73.1%, and the photoelectric conversion efficiency is 16.0%.
Example 3
The embodiment provides a preparation method of a semitransparent perovskite solar cell, which comprises the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer treated in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a lithium/magnesium/lead co-doped nickel oxide hole transport layer on the CH 3NH3PbI3 perovskite light absorption layer prepared in the step (7): the method comprises the steps of utilizing a reactive plasma deposition process, taking a lithium/magnesium/lead co-doped nickel oxide ceramic target as a target material, wherein in the lithium/magnesium/lead co-doped nickel oxide ceramic target, the content of MgO is 4.0wt%, the content of Li 2 O is 0.5 wt%, the content of PbO is 1.0 wt%, and the balance is nickel oxide; the sputtering gas was Ar, the Ar flow was 100 sccm, the reaction gas was O 2,O2 flow was 15 sccm, the deposition gas pressure was 0.35 Pa, the deposition temperature was room temperature, and the hole transport layer thickness was 25 nm.
(9) Preparing a second transparent electrode-tin doped indium oxide film on the hole transport layer prepared in the step (8): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the tin-doped indium oxide ceramic target comprises 10 percent wt percent of SnO 2 by weight, the balance of indium oxide, wherein the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, the deposition temperature is room temperature, and the thickness of the second transparent electrode is 100 nm.
(10) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (9), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curve measured under the AM 1.5 illumination condition of the semitransparent perovskite solar cell obtained in the embodiment is shown in FIG. 7. Wherein the open circuit voltage is 1.06V, the short circuit current density is 21.8 mA/cm 2, the filling factor is 74.4%, and the photoelectric conversion efficiency is 16.9%.
The lithium/magnesium/lead co-doped nickel oxide thin film was prepared on the glass substrate using the conditions of the reactive plasma deposition process of step (8) of this example, and XRD test was performed thereon, and the test results are shown in fig. 8. As can be seen from fig. 8, the lithium/magnesium/lead co-doped nickel oxide thin film prepared by the reactive plasma deposition process is an amorphous thin film.
Example 4
The embodiment provides a preparation method of a semitransparent perovskite solar cell, which comprises the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer treated in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a nickel oxide hole transport layer on the CH 3NH3PbI3 perovskite light absorption layer prepared in the step (7): using a reaction plasma deposition process, and taking a nickel oxide ceramic target with the purity of 99.99% as a target material; the sputtering gas was Ar, the Ar flow was adjusted to 100sccm, the reaction gas was O 2, the oxygen flow was adjusted to 25sccm, the deposition pressure was 0.37Pa, the deposition temperature was room temperature, and the hole transport layer thickness was 25nm.
(9) Preparing a second transparent electrode-tin doped indium oxide film on the nickel oxide hole transport layer prepared in the step (8): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the tin-doped indium oxide ceramic target comprises 10 percent wt percent of SnO 2 by weight, the balance of indium oxide, wherein the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, the deposition temperature is room temperature, and the thickness of the second transparent electrode is 100 nm.
(10) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (9), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curve of translucency obtained in this example under AM 1.5 illumination is shown in FIG. 9. Wherein the open circuit voltage is 1.03V, the short circuit current density is 20.90 mA/cm 2, the filling factor is 72.7%, and the photoelectric conversion efficiency is 15.7%.
Comparative example 1
The comparative example provides a method for preparing a semitransparent perovskite solar cell, comprising the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer prepared in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a Spiro-ome tad hole transport layer on the CH 3NH3PbI3 perovskite light absorption layer prepared in step (7): before spin coating of the Spiro-OMeTAD film was started, 4.5 h was weighed 72.3 mg of Spiro-OMeTAD powder in a clean reagent bottle, 1mL chlorobenzene was added, and stirred at room temperature for 30 min at a rotational speed of 700 rpm. Subsequently, 30 μl of 4-tert-butylpyridine (4-tert-butylpyridine, 26 mg. ML -1), 35 μl of Li-TFSI solution, and 15 μl of cobalt salt solution were sequentially added at intervals of 30 min. The solution was kept under agitation until use. The spin solution was obtained by once filtration through a PTFE filter having a pore size of 0.22 μm in 15 min of the spiral-OMeTAD film before the spin coating was started. The spin coating machine is set to have acceleration of 1000 rpm/s, rotation speed of 5000 rpm and spin coating duration of 40 s. In the fifth second after the start of rotation, 70. Mu.L of spin solution was taken and rapidly dropped.
The comparative cobalt salt solution was: tris [ 4-tert-butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt (III) tris (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methanesulfonamide salt )（（tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III)Tris(bis-(trifluoromethylsulfonyl)imide)） was dissolved in acetonitrile, and stirred at room temperature for 2 to H or more to prepare a solution having a concentration of 300 mg.mL -1.
(9) And (3) placing the sample prepared in the step (8) in an electronic drying cabinet with humidity lower than 15%, and standing for 8 h.
(10) Preparing a second transparent electrode-tin doped indium oxide film on the Spiro-OMeTAD hole transport layer prepared in the step (9): the direct-current magnetron sputtering technology is utilized, a tin-doped indium oxide ceramic target is used as a target material, the doped weight percentage of SnO 2 in the tin-doped indium oxide ceramic target is 10 wt percent, the rest is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; the sputtering gas is Ar, the reaction gas is O 2, the flow rate of argon is regulated to be 40 sccm, and the flow rate of oxygen is 8 sccm; the DC magnetron sputtering power is 120W; the background vacuum is: 8.5X10 -4 Pa; the deposition air pressure was 0.40 Pa, the sample tray rotation speed was 2000 rpm, the substrate temperature was room temperature, and the film thickness was 120 nm.
(11) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (10), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curve measured under the AM 1.5 illumination condition of the semitransparent perovskite solar cell obtained in the comparative example is shown in FIG. 10. Wherein the open circuit voltage is 0.98V, the short circuit current density is 18.0 mA/cm 2, the filling factor is 52.1%, and the photoelectric conversion efficiency is 9.22%.
Comparative example 2
The comparative example provides a method for preparing a semitransparent perovskite solar cell, comprising the following steps:
(1) Glass is sequentially ultrasonically treated with glass cleaning agent, isopropanol, acetone, alcohol and deionized water for 15 min, and then dried by a nitrogen gun.
(2) And (3) treating the glass treated in the step (1) by using an ultraviolet-ozone cleaning machine for 10 min.
(3) Preparing a first transparent electrode-tin doped indium oxide film on the glass treated in the step (2): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the doping amount of SnO 2 in the tin-doped indium oxide ceramic target is 10: 10 wt percent, the balance is indium oxide, the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is 200 ℃, and a thickness of the first transparent electrode is 200 nm.
(4) The first transparent electrode prepared in step (3) was treated with an ultraviolet-ozone cleaning machine 15 min.
(5) Preparing an electron transport layer on the first transparent electrode processed in the step (4): the aqueous solution of SnO 2 nanoparticles purchased (SnO 2 weight percent 15 wt%) was prepared according to a 1:6.5 volume ratio with deionized water. 3 h was stirred at 800 rpm f at room temperature and then filtered once using a PTFE filter with a pore size of 0.22 μm to give a spin-on solution. 70. Mu.L of spin solution was pipetted down onto the substrate so that the spin solution covered the surface completely. The spin coater is set to have acceleration of 1000 rpm/s, rotating speed of 3000 rpm and spin coating time of 30 s. After spin coating was completed, the sample was placed on a heating plate at 155℃and heat-treated for a period of 15 min hours.
(6) And (3) treating the electron transport layer prepared in the step (5) by using an ultraviolet-ozone cleaning machine 15 min.
(7) Preparing a CH 3NH3PbI3 perovskite light absorption layer on the electron transport layer prepared in the step (6): 0.142 mL dimethyl sulfoxide and 1.266 mLN, N-dimethylformamide were placed in a reagent bottle and stirred at 1000rpm for 10min to allow the two solvents to mix thoroughly. Subsequently, 0.922gPbI 2 and 0.318gCH 3NH3 I were added to the flask, and after stirring was continued for 3.5 hours at 60℃the solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.22. Mu.m. Setting two parameters of a spin coater: setting the acceleration at 200rpm/s, the rotating speed at 1000rpm and the spin-coating time period at 5s; the second step sets the acceleration at 1000rpm/s, the rotation speed at 4000rpm and the spin-coating time period at 30s. 80. Mu.L of the filtered solution was dropped onto the electron transport layer, followed by starting the spin coater. At 13s after the start of spin coating, 200 μl of chlorobenzene was rapidly dropped onto the electron transport layer using a pipette. After spin coating, the sample was rapidly transferred to a heating plate for heat treatment, and 100. Mu.L of gamma-butyrolactone was dropped around the sample, the temperature of the heating plate was 105℃and the heat treatment time was 10min.
(8) Preparing a hole transport layer-nickel oxide film on the CH 3NH3PbI3 perovskite light absorption layer prepared in the step (7): and (3) using a nickel oxide ceramic target with the purity of 99.99% as a target raw material by using radio frequency magnetron sputtering equipment. Sputtering gas is Ar, and the flow rate of the argon is regulated to be 120 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 5 sccm; the deposition air pressure is as follows: 0.40 Pa, a deposition temperature is room temperature, and a thickness of the hole transport layer is 25 nm.
(9) Preparing a second transparent electrode-tin doped indium oxide film on the hole transport layer prepared in the step (8): utilizing a reactive plasma deposition process, taking a tin-doped indium oxide ceramic target as a target material, wherein the tin-doped indium oxide ceramic target comprises 10 percent wt percent of SnO 2 by weight, the balance of indium oxide, wherein the purity of SnO 2 is 99.99 percent, and the purity of indium oxide is 99.99 percent; sputtering gas is Ar, and the flow rate of the argon is regulated to be 100 sccm; the reaction gas is O 2, and the oxygen flow is regulated to be 35 sccm; the deposition air pressure is as follows: 0.40 Pa, the deposition temperature is room temperature, and the thickness of the second transparent electrode is 100 nm.
(10) Preparing a first grid line and a second grid line on the first transparent electrode and the second transparent electrode prepared in the steps (3) and (9), respectively: silver particles with the purity of 99.999% are used as raw materials for thermal evaporation deposition by utilizing a resistance type thermal evaporation coating technology; the vacuum degree of the chamber before deposition is 1 multiplied by 10 -4 Pa, the deposition temperature is room temperature, and the thicknesses of the first grid line and the second grid line are 250 nm.
The J-V curves measured under AM 1.5 illumination for the translucent perovskite solar cell obtained in this comparative example are shown in FIG. 11. Wherein the open circuit voltage is 0.52V, the short circuit current density is 17.80 mA/cm 2, the filling factor is 41.5%, and the photoelectric conversion efficiency is 3.8%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (14)
1. A method for preparing a semitransparent perovskite solar cell, comprising the steps of:
sequentially preparing a first transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a second transparent electrode on a substrate;
preparing the hole transport layer by adopting a reaction plasma deposition process: the target material comprises nickel oxide ceramic, wherein the sputtering gas is Ar, the reaction gas is O 2, the Ar flow is 80-150 sccm, the O 2 flow is 3-30 sccm, the deposition air pressure is 0.3-0.4 Pa, and the deposition temperature is 25-120 ℃;
The target is lithium/magnesium/lead co-doped nickel oxide ceramic, the content of MgO in the target is 0.5-4.0wt%, the content of Li 2 O is 0.1-2.0wt%, the content of PbO is 0.1-1.5 wt%, and the balance is nickel oxide;
The substrate is a transparent substrate, and the transparent substrate is polyethylene terephthalate, polyethylene naphthalate or glass.
2. The method for manufacturing a semitransparent perovskite solar cell according to claim 1, wherein the thickness of the first transparent electrode is 80-600 nm.
3. The method of claim 1, wherein the first transparent electrode is prepared by chemical vapor deposition, sol-gel method, physical vapor deposition, or reactive plasma deposition.
4. The method of manufacturing a translucent perovskite solar cell according to claim 1, wherein the material of the first transparent electrode comprises a first metal oxide, the first metal oxide being indium oxide, zinc oxide or tin oxide.
5. The method of manufacturing a translucent perovskite solar cell according to claim 4, wherein the material of the first transparent electrode comprises a doping element, the doping element being one or more of Al, ga, in, sn, zn, F;
the doping element is different from the metal element in the first metal oxide;
the total doping amount of the doping elements in the first transparent electrode material is 0.1-10wt%.
6. The method of manufacturing a semitransparent perovskite solar cell according to any one of claims 1 to 5, wherein the material of the electron transport layer comprises tin oxide, indium oxide, titanium oxide or zinc oxide.
7. The method of manufacturing a semitransparent perovskite solar cell according to any one of claims 1 to 5, wherein the perovskite light absorbing layer is manufactured by spin coating, knife coating or vacuum evaporation.
8. The method of any one of claims 1 to 5, wherein the perovskite light absorbing layer is an ABX 3 type perovskite thin film, a + in the ABX 3 type perovskite thin film is CH3NH3 +、CH3CH2NH3 +、HN=(NH2)+ or Cs +;B2+ is Pb 2+ or Sn 2+;X- is Cl -、Br - or I -.
9. The method of any one of claims 1 to 5, wherein the second transparent electrode is prepared by physical vapor deposition or reactive plasma deposition.
10. The method of manufacturing a translucent perovskite solar cell according to any one of claims 1 to 5, wherein the material of the second transparent electrode comprises a second metal oxide, the second metal oxide being indium oxide, zinc oxide or tin oxide.
11. The method of manufacturing a translucent perovskite solar cell according to any one of claims 1 to 5, wherein the thickness of the second transparent electrode is 80 to 200 nm.
12. The method of fabricating a translucent perovskite solar cell according to any one of claims 1 to 5, further comprising fabricating a first grid line on a first transparent electrode and a second grid line on a second transparent electrode;
the preparation methods of the first grid line and the second grid line are respectively and independently selected from any one of thermal evaporation, electron beam evaporation, magnetron sputtering deposition and screen printing.
13. The method for producing a translucent perovskite solar cell according to claim 1, wherein,
Preparing a first transparent electrode by adopting a magnetron sputtering, chemical vapor deposition or reactive plasma deposition process; the thickness of the first transparent electrode is 80-600 nm; the first transparent electrode material comprises a first metal oxide, wherein the first metal oxide is indium oxide, zinc oxide or tin oxide; the material of the first transparent electrode comprises doping elements, wherein the doping elements are one or more of Al, ga, in, sn, zn, F, and the doping elements are different from the metal elements in the first metal oxide; the total doping amount of the doping elements in the first transparent electrode material is 0.1-10wt%;
The material of the electron transport layer comprises tin oxide, indium oxide, titanium oxide or zinc oxide;
Preparing a perovskite light absorption layer by spin coating, knife coating or vacuum evaporation; the perovskite light absorption layer is an ABX 3 type perovskite film, A + in the ABX 3 type perovskite film is CH3NH3 +、CH3CH2NH3 +、HN=(NH2)+ or Cs +;B2+ is Pb 2+ or Sn 2+;X- is Cl -、Br- or I -;
Preparing a second transparent electrode by adopting a magnetron sputtering or reactive plasma deposition process; the material of the second transparent electrode comprises a second metal oxide, wherein the second metal oxide is indium oxide, zinc oxide or tin oxide; the thickness of the second transparent electrode is 80-200 nm;
Preparing a first grid line on the first transparent electrode, and preparing a second grid line on the second transparent electrode; the preparation methods of the first grid line and the second grid line are respectively and independently selected from any one of thermal evaporation, electron beam evaporation, magnetron sputtering deposition and screen printing.
14. A translucent perovskite solar cell, characterized in that it is produced according to the method of producing a translucent perovskite solar cell according to any one of claims 1-13.
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