CN112071992A - Phosphorus alkene/stannic oxide compound perovskite solar cell electron transport layer and preparation method thereof - Google Patents

Phosphorus alkene/stannic oxide compound perovskite solar cell electron transport layer and preparation method thereof Download PDF

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CN112071992A
CN112071992A CN202010950769.5A CN202010950769A CN112071992A CN 112071992 A CN112071992 A CN 112071992A CN 202010950769 A CN202010950769 A CN 202010950769A CN 112071992 A CN112071992 A CN 112071992A
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胡亦谦
陈达
梁俊辉
秦来顺
黄岳祥
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China Jiliang University
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Abstract

The invention belongs to the technical field of perovskite solar cells, and particularly relates to a phosphorus alkene/stannic oxide compound perovskite solar cell electronic transmission layer and a preparation method thereof. The invention provides a phosphorus alkene/SnO2The compound perovskite solar cell electron transmission layer and the preparation method thereof are characterized in that: Phosphorenes/SnO by solution spin coating2The composite dispersion liquid is coated on a conductive glass substrate in a spinning way, and the phosphorus alkene/SnO is prepared after annealing treatment2A composite electron transport layer, and then forming a layer on the obtained electron transport layerA perovskite light absorption layer, a hole transmission layer and a metal cathode layer are sequentially deposited on the surface of the composite material to construct phospholene/SnO2Perovskite solar cell. The invention introduces the phospholene two-dimensional nanosheet into SnO2The electron transmission layer is applied to the perovskite solar cell, the density, the interface contact area and the carrier mobility of the charge transmission layer can be effectively improved, and the interface energy level potential barrier is reduced, so that the cell efficiency is improved to a greater extent, and the hysteresis effect of the cell is inhibited.

Description

Phosphorus alkene/stannic oxide compound perovskite solar cell electron transport layer and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a phosphorus alkene/stannic oxide compound perovskite solar cell electronic transmission layer and a preparation method thereof.
Background
As one of the emerging photovoltaic technologies, perovskite solar cells are known as the most rapidly developing photovoltaic technology in recent years. Up to now, the conversion efficiency of perovskite solar cells has reached more than 25%. Such photovoltaic cell structures typically employ a sandwich of p-i-n or n-i-p structures, i.e., an i-type perovskite light absorbing layer sandwiched by an n-type semiconducting electron transporting layer and a p-type semiconducting hole transporting layer to achieve carrier extraction. Therefore, the energy conversion efficiency of the perovskite solar cell is not only determined by the perovskite light absorption material, but also is closely related to the quality of the carrier transport layer. It is particularly noteworthy that the "hysteresis effect" is a phenomenon common to perovskite solar cells, which is caused by charge accumulation due to imbalance in charge transport of perovskite solar cells. Therefore, designing and developing an electron transport material with strong charge transport capability to improve the electron transport efficiency of the perovskite solar cell interface is an effective means for effectively solving the hysteresis effect and improving the cell performance.
Tin dioxide (SnO 2) is an electron transport material commonly used in perovskite solar cells, and has a more compatible energy level with perovskite and high bulk phase electron mobility (249 cm)2V-1s-1) Wide band gap (-3.6 to-4.0 eV), high light transmittance, wide spectrum absorptivity, stable physicochemical properties, and the like. In addition, the tin dioxide can be prepared by a low-temperature solution method, can be compatible with flexible solar cells, photoelectric devices and the like, and has large-scale commercial application potential. However, the electron transport layer formed by tin dioxide is generally not sufficiently dense,The surface is rough, the wettability is poor, the defects seriously affect the extraction and the transmission of interface carriers, the carrier mobility is low, and the performance of the perovskite solar cell is finally reduced. In order to solve these problems, it is necessary to modify the tin dioxide electron transport layer.
In recent years, phospholene (phosphoene) has attracted attention due to its anisotropic two-dimensional layered structure, high charge carrier mobility, direct band gap tunable with thickness, and spectral absorption characteristics that are broad from ultraviolet to near-infrared light. In view of the fact that the phosphorus alkene has a unique two-dimensional structure and excellent photoelectric characteristics, the phosphorus alkene is introduced into the SnO2 electron transport layer to construct the phosphorus alkene/SnO 2 compound electron transport layer, the density, the interface contact area and the carrier migration rate of the SnO2 electron transport layer are expected to be improved, the energy level matching of the perovskite solar cell structure is improved, the effective separation of photogenerated electrons and photogenerated holes is promoted, and the electronic transport layer becomes the perovskite solar cell electron transport layer with a better application prospect.
Therefore, the invention provides a method for improving a SnO2 electron transport layer, namely, a phosphorus alkene two-dimensional nanosheet is introduced into a SnO2 electron transport layer, and the extraction and effective separation of photon-generated carriers are promoted by utilizing the unique two-dimensional nanostructure and excellent photoelectric property of phosphorus alkene, so that the aims of improving the conversion efficiency of a perovskite solar cell and relieving the hysteresis effect of the cell are fulfilled.
Disclosure of Invention
The invention aims to ultrasonically disperse a phosphorus-alkene two-dimensional nanosheet in a SnO2 nanoparticle solution through an ultrasonic dispersion process to prepare a phosphorus-alkene/SnO 2 compound, and then the phosphorus-alkene/SnO 2 compound electron transport layer film for the perovskite solar cell can be constructed and obtained through solution spin coating. According to the invention, the two-dimensional phosphorus alkene nanosheet is introduced into the SnO2 electronic transmission layer, so that the formed phosphorus alkene/SnO 2 heterojunction composite structure can improve the density, the interface contact area and the carrier migration rate of the charge transmission layer, promotes the migration and separation of photon-generated carriers, solves the problems of low density and carrier migration rate of the SnO2 electronic transmission layer, high recombination rate of the photon-generated carriers and the like to a greater extent, greatly improves the photoelectric conversion efficiency of the perovskite solar cell and slows down the 'hysteresis effect' phenomenon of the cell.
The invention provides a phosphorus alkene/SnO 2 compound perovskite solar cell electron transport layer, which is characterized in that: the perovskite solar cell electron transport layer is composed of a phosphorus alkene/SnO 2 compound, wherein SnO2 nano sol is distributed on the surface of a phosphorus alkene two-dimensional nanosheet, and the phosphorus alkene/SnO 2 heterojunction structure is formed by combining the phosphorus alkene and the SnO2 nano sol; meanwhile, the preparation method of the electron transport layer is characterized by being realized by the following technical scheme:
(1) firstly, preparing a phosphorus alkene/SnO 2 composite by a solution ultrasonic method, which comprises the following specific steps: dispersing black phosphorus powder in an N-methylpyrrolidone (NMP) solvent, stripping the black phosphorus powder in a strong ultrasonic mode under the protection of nitrogen, and obtaining a phospholene nano-sheet by means of high-speed centrifugal separation; adding the prepared phosphorus alkene nanosheet into a SnO2 sol solution according to a certain mass ratio, and ultrasonically dispersing for 30 minutes to prepare a phosphorus alkene/SnO 2 composite dispersion liquid;
(2) spin-coating the phosphorus alkene/SnO 2 compound dispersion liquid prepared in the step (1) on the pretreated ITO or FTO conductive glass substrate by adopting a solution spin-coating process;
(3) annealing the coated conductive substrate on a heating plate, and preparing a phosphorus alkene/SnO 2 composite electron transport layer on the conductive glass substrate after annealing;
(4) on the basis of preparing and obtaining a phosphorus alkene/SnO 2 compound electron transport layer, a perovskite solar cell taking a phosphorus alkene/SnO 2 compound as the electron transport layer is further constructed, and the preparation process of the solar cell comprises the following steps:
(i) preparing a phosphorus alkene/SnO 2 electronic transmission layer through the steps (1) to (3);
(ii) preparing a perovskite light absorption thin film layer on the phosphorus alkene/SnO 2 electron transport layer;
(iii) preparing a hole transport layer on the perovskite light absorption thin film layer;
(iv) and preparing a metal cathode electrode on the hole transport layer.
Further, the dispersion concentration of the black phosphorus powder in the N-methylpyrrolidone (NMP) solvent in the step (1) is 0.1-1 mg/mL, and the phosphorus alkene obtained after the strong ultrasonic stripping is a few-layer phosphorus alkene nano-sheet with the thickness of 3-6 layers; the concentration of the SnO2 sol solution is 1-10 mg/mL, and the size of the sol is 2-8 nm; the mass of the added phosphorus in the phosphorus/SnO 2 composite is 0.5-10% of that of the SnO2 sol.
Further, the conductive glass is pretreated in the step (2) of the invention, and the conductive glass is ultrasonically cleaned for 15 minutes by respectively using deionized water, acetone, isopropanol and ethanol, then dried by blowing with nitrogen gas, and then treated with ozone in an ultraviolet ozone irradiation machine for 15-30 minutes.
Furthermore, the annealing temperature of the coated conductive substrate in the step (3) is 150-200 ℃, the annealing time is 30-60 minutes, and the thickness of the electron transport layer of the phosphorus alkene/SnO 2 compound is 50-300 nm.
Further, the light absorbing material adopted by the perovskite light absorbing thin film layer in the step (4) of the invention is an ABX3 perovskite structure, wherein a is one or more of cesium ions (Cs +), methylammonium ions (MA +, CH3NH3 +) or formamidine (FA +, NH2CH = NH2 +), B is one or more of Pb2+ or Sn2+, X is one or more of Cl-, Br-or I-, and the preparation method is one or more of a spin coating method, a spray coating method or an anti-solvent method.
Further, in step (4) of the present invention, the hole transport layer is 2,2 ', 7,7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 ' -spirobifluorene (Spiro-omatad) or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), and the preparation method is spin coating or spray coating.
Further, the metal cathode electrode in the step (4) of the present invention is an Au, Ag or carbon electrode, and the preparation method is one of a vacuum thermal evaporation method, a magnetron sputtering method or a screen printing method.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the invention, two-dimensional phosphorus alkene nanosheets are introduced into the SnO2 electron transmission layer and applied to the perovskite solar cell, the density and the interface contact area of the charge transmission layer can be effectively improved by utilizing the ultrahigh specific surface area of the phosphorus alkene nanosheets, the energy level barrier of the SnO2 electron transmission layer and the perovskite light absorption layer is reduced through the energy level regulation of the phosphorus alkene nanosheets, the extraction of photon-generated carriers is promoted, meanwhile, the introduction of the phosphorus alkene nanosheets can also effectively improve the carrier mobility of the SnO2 electron transmission layer, and the electron hole recombination is reduced, so that the photoelectric conversion efficiency of the perovskite solar cell can be improved to a greater extent, and the hysteresis effect phenomenon of the cell is relieved. The preparation method of the phosphorus alkene/SnO 2 complex perovskite solar cell electronic transmission layer provided by the invention is simple and convenient in material preparation method, easy for industrial production, low in production cost and strong in practicability, and is expected to be popularized and applied in the field of perovskite solar cells.
Drawings
FIG. 1 is a schematic structural diagram of a perovskite solar cell based on a phosphorus alkene/SnO 2 composite electron transport layer provided by the invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the phospholene/SnO 2 composite prepared in example 1 (the insert in the lower left corner is a high resolution TEM image of the SnO2 sol in the composite);
fig. 3 shows the photoelectrochemical properties of the SnO2 electron transport layer thin film electrode and the phosphorus alkene/SnO 2 composite electron transport layer thin film electrode prepared in example 1 under the irradiation of a xenon lamp light source with the power of 300W: (a) a chopped photocurrent response spectrum, (b) an Electrochemical Impedance (EIS) spectrum;
fig. 4 is a graph of photocurrent density versus voltage (J-V) for forward and reverse scanning of perovskite solar cells with the electron transport layer made of SnO2 or a phosphene/SnO 2 composite prepared in example 1.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
(1) preparation of phospholene nanoplates
Placing 20 mg of black phosphorus powder into a 250 mL wide-mouth bottle in an inert atmosphere glove box, adding 100 mL of NMP solvent, stirring to form a black phosphorus/NMP dispersion liquid with the concentration of 0.2 mg/mL, sealing the wide-mouth bottle containing the black phosphorus/NMP dispersion liquid by using a rubber plug, and transferring out of the glove box; then, under the condition of nitrogen protection by blowing nitrogen into the wide-mouth bottle continuously, an ultrasonic vibrator of a powerful ultrasonic instrument is inserted into the black phosphorus/NMP dispersion liquid for carrying out intermittent powerful ultrasonic treatment for 12 hours (ultrasonic 4 seconds/stop 4 seconds), and meanwhile, in the powerful ultrasonic process, the wide-mouth bottle is placed in circulating cooling water to prevent the temperature rise phenomenon caused by the ultrasonic process; and centrifuging the suspension obtained after the ultrasonic treatment for 15 minutes at the rotating speed of 5000 r/min to remove black phosphorus precipitates which cannot be stripped, centrifuging the collected supernatant for 30 minutes at the rotating speed of 10000 r/min, collecting the centrifuged precipitates, and performing vacuum drying at room temperature to obtain the phosphoalkene nanosheet.
(2) Preparation of Phosphorenes/SnO 2 composites
Weighing a certain amount of the prepared phosphorus alkene nanosheet, adding the phosphorus alkene nanosheet into a SnO2 sol solution with the concentration of 5 mg/mL to enable the added mass of the phosphorus alkene to be 2% of the mass of the SnO2 sol, and then performing ultrasonic dispersion for 30 minutes to obtain a phosphorus alkene/SnO 2 composite dispersion liquid.
(3) Preparation of phosphorus alkene/SnO 2 composite electron transport layer
Firstly, ultrasonically cleaning ITO conductive glass for 15 minutes by using deionized water, acetone, isopropanol and ethanol, blow-drying by using nitrogen, and then carrying out ozone treatment in an ultraviolet ozone irradiation machine for 20 minutes; then, spin-coating the phosphorus alkene/SnO 2 compound dispersion liquid prepared in the step 2 on the pretreated ITO conductive glass by adopting a solution spin-coating process; and then, carrying out 150 ℃ annealing treatment on the coated ITO conductive glass on a heating plate for 30 minutes, and preparing the phosphorus alkene/SnO 2 composite electron transport layer on the conductive glass substrate after the annealing is finished. In contrast, the SnO2 electron transport layer was also prepared by a solution spin coating method under the same conditions except that the dispersion of the phospholene/SnO 2 composite was replaced with a SnO2 sol solution, and the rest was the same.
(4) Preparation of perovskite solar cell
Sequentially depositing a perovskite light absorption layer, a hole transport layer and a metal cathode layer on the prepared electron transport layer to obtain the perovskite solar cell, wherein the device structure is shown in figure 1, and the specific preparation process is as follows:
(i) preparing a perovskite light absorption layer: firstly, preparing a perovskite precursor solution in an inert atmosphere glove box, dissolving 1.55M PbI2, 1.3M FAI, 0.2M MABr, 0.3M MACl and 0.1M CsCl in a solvent with the volume ratio of 1: 9, stirring the mixture for 1 hour at 50 ℃ in a mixed solvent of Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare a perovskite precursor solution; uniformly dripping the perovskite precursor solution on the phosphorus alkene/SnO 2 compound electron transport layer or the SnO2 electron transport layer prepared in the step (3), firstly carrying out spin coating at a speed of 2000 r/min for 60 seconds, quickly dripping 200 microliters of anti-solvent chlorobenzene at the 60 th second for promoting perovskite nucleation and crystallization, and then continuing to carry out spin coating at a speed of 5000 r/min for 30 seconds; and after the spin coating is finished, taking out the sample from the glove box, annealing at 130 ℃ for 30 min in an atmospheric environment, and depositing a perovskite absorption layer on the surface of the phosphorus/SnO 2 or SnO2 electron transport layer after annealing.
(ii) Preparation of hole transport layer: Spiro-OMeTAD added with LiTFSI and 4-tertiary pyridine is adopted as a hole transport material, 80 mg of Spiro-OMeTAD powder is firstly dissolved in 1 mL of anhydrous chlorobenzene, 260 mg of Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) powder is dissolved in 1 mL of anhydrous acetonitrile, 35 mu L of Li-TFSI/acetonitrile solution is measured by a liquid transfer gun, 28.5 mu L of 4-tertiary pyridine solution is added into the Spiro-OMeTAD/chlorobenzene solution, the mixture is stirred uniformly at normal temperature, and the Spiro-OMeTAD solution is coated on the surface of a perovskite light absorption layer at the speed of 4000 r/min.
(iii) Metal cathode layer: and depositing an Au electrode on the surface of the hole transport layer by adopting a thermal evaporation mode, wherein the thickness of the Au electrode is about 80 nm. And finally, preparing the phospholene/SnO 2 perovskite solar cell, wherein the device structure is an ITO conductive glass substrate/phospholene/SnO 2 electron transport layer/perovskite light absorption layer/cyclone-OMeTAD hole transport layer/Au electrode.
FIG. 2 is a Transmission Electron Microscope (TEM) image of the phospholene/SnO 2 composite prepared in example 1 (the insert in the lower left is a high resolution TEM image of the SnO2 sol in the composite). It can be clearly observed from the figure that the SnO2 nano sol is relatively uniformly distributed on the surface of the two-dimensional phosphorus alkene nano sheet, and the two are mutually combined together, wherein the particle size of the SnO2 nano sol is about 3-8 nm, and further a high-resolution TEM image can observe clear lattice stripes of the SnO2 nano sol, the lattice spacing of the lattice stripes is 0.331 nm, and the lattice stripes correspond to a (110) crystal face of SnO2, so that the successful preparation of the phosphorus alkene/SnO 2 compound is confirmed.
Fig. 3 shows the photoelectrochemical properties of the SnO2 electron transport layer thin film electrode and the phosphorus alkene/SnO 2 composite electron transport layer thin film electrode prepared in example 1 under the irradiation of a xenon lamp light source with the power of 300W: (a) a chopped photocurrent response spectrum, (b) an Electrochemical Impedance (EIS) spectrum. Fig. 3(a) shows that both the SnO2 electron transport layer and the phosphorus alkene/SnO 2 composite electron transport layer thin film electrode have obvious photoelectric response characteristics under illumination, and the photocurrent generated by the phosphorus alkene/SnO 2 composite electron transport layer thin film is obviously greater than that generated by the SnO2 electron transport layer thin film, which indicates that the introduction of phosphorus alkene can greatly improve the photon-generated carrier migration rate of the SnO2 electron transport layer thin film, and promote the effective separation of photon-generated carriers. Fig. 3 (b) is an electrochemical impedance spectrum of a film electrode of a SnO2 electron transport layer and a phosphorus/SnO 2 composite electron transport layer under illumination, and it can be seen that a semicircular arc of a high-frequency region of the film electrode of the phosphorus/SnO 2 composite electron transport layer in the EIS spectrum is smaller than a semicircular arc of the film electrode of the SnO2 electron transport layer, and the radius of the semicircular arc reflects charge transport impedance of a photon-generated carrier, which indicates that under the same experimental conditions, the interface transport impedance value of the photon-generated carrier generated by the film electrode of the phosphorus/SnO 2 composite electron transport layer receiving illumination is obviously smaller than that of the film electrode of the SnO2 electron transport layer, and separation of the interface photon-generated carrier can be effectively promoted. From the test results of the chopped photocurrent response spectrum and the Electrochemical Impedance (EIS) spectrum, compared with the SnO2 electron transport layer film, the photogenerated carriers of the phosphorus alkene/SnO 2 compound electron transport layer film are easier to transition and can be rapidly transported under the same condition, the self-recombination of the photogenerated carriers is effectively reduced, and the photoelectric property of the perovskite solar cell is finally improved.
TABLE 1 SnO base2Or phosphenes/SnO2Battery performance test results of electron transport layer perovskite solar battery under different test modes
Figure 367779DEST_PATH_IMAGE002
As can be seen from the cell test results in table 1 and the cell J-V curve in fig. 4, the cell efficiency of the electron transport layer made of the phospholene/SnO 2 composite of the present invention is greater than 17.5% when it is applied to the perovskite solar cell, which is greatly improved compared to the perovskite solar cell efficiency (about 16%) of the SnO2 electron transport layer. The introduction of the phosphorus alkene can effectively increase the interface specific surface area and the carrier transfer efficiency of the SnO2 electron transport layer, so that the photocurrent density (Jsc) of the battery is obviously increased, and the Filling Factor (FF) is slightly increased, which means that compared with SnO2, the phosphorus alkene/SnO 2 can increase the extraction capability of the photogenerated carriers, thereby improving the efficiency of the perovskite solar battery to a greater extent. In addition, it can be seen from the comparison of the test results of the forward scanning and the reverse scanning of the cell (table 1) that the cell efficiencies of the SnO2 and the phospholene/SnO 2 perovskite solar cell in the forward scanning and the reverse scanning tests are deviated to a certain extent, which indicates that the SnO2 and the phospholene/SnO 2 perovskite solar cell show the phenomenon of 'hysteresis effect'; however, from the point of view of the deviation degree of the cell efficiency, the deviation of the efficiency between the positive scanning and the negative scanning of the phospholene/SnO 2 perovskite solar cell is smaller, which shows that the 'hysteresis effect' phenomenon of the perovskite solar cell can be inhibited to a certain extent after the phospholene is introduced into the SnO2 electron transport layer.
The test results show that the SnO2 electron transport layer is modified by introducing the phosphorus alkene two-dimensional nanosheets to prepare the phosphorus alkene/SnO 2 composite electron transport layer, so that the interface specific surface area and the carrier migration rate of the SnO2 electron transport layer can be improved to a greater extent, the extraction capacity of photo-generated carriers is increased, the photoelectric property of the perovskite solar cell is effectively improved, and the introduction of the phosphorus alkene two-dimensional nanosheets into the SnO2 electron transport layer is proved to be an effective means for improving the efficiency of the perovskite solar cell, and the application of the phosphorus alkene two-dimensional material in the field of the perovskite solar cell is expected to be promoted.

Claims (9)

1. Phosphorenes/SnO2The compound perovskite solar cell electron transport layer is characterized in that: the electronic transmission layer of the perovskite solar cell is made of phosphorus alkene/SnO2Composite of SnO2The nano sol is distributed on the surface of the phosphorus alkene two-dimensional nano sheet, and the phosphorus alkene and the SnO are combined to form phosphorus alkene/SnO2A heterojunction structure.
2. Phosphorenes/SnO2The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps:
(1) dispersing black phosphorus powder inNIn a methylpyrrolidone solvent, stripping black phosphorus powder in a strong ultrasonic mode under the protection of nitrogen and obtaining a phospholene nano sheet by means of high-speed centrifugal separation;
(2) adding the phosphorus alkene nanosheet prepared in the step (1) into SnO according to a certain mass ratio2In sol solution, and ultrasonically dispersing for 30 minutes to prepare and obtain the phosphorus alkene/SnO2A composite dispersion;
(3) adopting a solution spin coating process to carry out spin coating on the phosphorus alkene/SnO prepared in the step (2)2The compound dispersion liquid is coated on the pretreated ITO or FTO conductive glass substrate in a spinning mode, the coated conductive glass substrate is annealed on a heating plate, and the phosphorus alkene/SnO is prepared after annealing2A composite electron transport layer;
(4) further constructed as phospholene/SnO2The perovskite solar cell with the compound as the electron transport layer is firstly prepared from the phosphorus alkene/SnO obtained in the step (3)2Preparing a perovskite light-absorbing thin film layer on the electron transport layerThen preparing a hole transport layer on the perovskite light absorption film layer, and finally preparing a metal cathode electrode on the hole transport layer, thereby preparing the phosphorus alkene/SnO2An electron transport layer perovskite solar cell.
3. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: the black phosphorus powder of the step (1) isNThe dispersion concentration of the-methyl pyrrolidone in the solvent is 0.1-1 mg/mL, and the phospholene obtained after strong ultrasonic stripping is a few-layer phospholene nanosheet with the thickness of 3-6 layers.
4. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: SnO described in step (2)2The concentration of the sol solution is 1-10 mg/mL, and the size of the sol is 2-8 nm; the phospholene/SnO2The mass of the added phosphorus in the compound is SnO20.5-10% of the mass of the sol.
5. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: and (3) carrying out ultrasonic cleaning on the conductive glass for 15 minutes by respectively using deionized water, acetone, isopropanol and ethanol, blow-drying by using nitrogen, and carrying out ozone treatment in an ultraviolet ozone irradiation machine for 15-30 minutes.
6. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: the annealing treatment temperature of the coated conductive substrate in the step (3) is 150-200 DEGoC, annealing time of 30-60 minutes, and phosphorus alkene/SnO2The composite electron transport layer has a thickness of 50 to 300 nm.
7. The phosphenes/SnO of claim 22Composite perovskite solar cellThe preparation method of the energy battery electron transport layer is characterized by comprising the following steps: the perovskite light absorption film layer in the step (4) adopts ABX as light absorption material3Perovskite structure, wherein A is cesium ion (Cs)+) Methyl ammonium ion (MA)+，CH3NH3 +) Or Formamidine (FA)+，NH2CH=NH2 +) B is Pb2+Or Sn2+Wherein X is Cl-、Br-Or I-The preparation method is one or more of a spin coating method, a spray coating method or an anti-solvent method.
8. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: the hole transport layer in the step (4) is 2,2 ', 7, 7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene (Spiro-OMeTAD) or poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA) prepared by spin coating or spray coating.
9. The phosphenes/SnO of claim 22The preparation method of the electronic transmission layer of the composite perovskite solar cell is characterized by comprising the following steps: and (4) the metal cathode electrode in the step (4) is an Au, Ag or carbon electrode, and the preparation method is one of a vacuum thermal evaporation method, a magnetron sputtering method or a screen printing method.
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