CN113845896B - Curved organic ammonium metal halide film, preparation method, solar cell and application - Google Patents

Curved organic ammonium metal halide film, preparation method, solar cell and application Download PDF

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CN113845896B
CN113845896B CN202111059145.5A CN202111059145A CN113845896B CN 113845896 B CN113845896 B CN 113845896B CN 202111059145 A CN202111059145 A CN 202111059145A CN 113845896 B CN113845896 B CN 113845896B
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film
curved
metal halide
organic ammonium
halide
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CN113845896A (en
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曹焕奇
印寿根
钱奕成
李孜怡
杨利营
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Tianjin University of Technology
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Abstract

The invention provides a curved organic ammonium metal halide film, a preparation method, a solar cell and an application thereof, which belong to the field of photoelectric materials, wherein a physical vapor deposition method is used for preparing a metal halide curved substrate, a polar aprotic solvent fumigation treatment is used for preparing the metal halide curved substrate by the physical vapor deposition method, and finally a close-range sublimation method is used for combining solid-solid reaction diffusion kinetics control, so that a two-step vapor phase method is successfully used for preparing high-quality and high-uniformity ABX on a curved substrate 3 The perovskite thin film is further subjected to characterization analysis by means of X-ray diffraction spectrogram analysis, a scanning electron microscope, a current density-voltage (J-V) curve under simulated sunlight and the like.

Description

Curved organic ammonium metal halide film, preparation method, solar cell and application
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to a curved organic ammonium metal halide film, a preparation method, a solar cell and application. In particular to a preparation method of a curved surface organic ammonium metal halide perovskite film.
Background
Solar energy is widely popularized and applied as clean energy in all parts of the world, such as photovoltaic power stations, photovoltaic Building Integrated (BIPV), vehicles, wearable equipment and the like. Perovskite thin film solar cells have been rapidly developed in recent years, and the highest photoelectric conversion efficiency of single junction perovskite solar cells has been over 25% at present.
The preparation method of the perovskite film comprises two main types of solution method and gas phase method. The solution method refers to preparing the precursor solution containing perovskite materials into the nano film by spin coating, knife coating and other technologies, and has the characteristic of rapid process. However, the solution method is limited to preparing perovskite thin films on planar substrates, is not applicable to curved substrate solution rules any more, and is harmful to the environment because volatile organic solvents are used in the solution method process.
The double/multisource co-evaporation Physical Vapor Deposition (PVD) method is a one-step vapor phase method, and is a method for preparing uniform and compact perovskite thin films by adopting a mode of evaporating organic matters and inorganic matters simultaneously in the same cavity. Preparation of MAPbI by double-source co-steaming method 3 Perovskite, an efficiency of 15.4% was achieved. However, the organic ammonium halide is difficult to calibrate the evaporation rate in high vacuum degree and severely pollutes the coating cavity, so that the method is not suitable for large-scale application. The one-step CVD method is to transport inorganic matters and organic matters onto a substrate through inert gases in a tube furnace, and finally heating to obtain the perovskite film. The preparation of the metal halide film followed by reaction with an organoammonium halide to give a perovskite film is a two-step gas phase process. Yang Yang team first prepared MAPbI using a vapor assisted solution process (VASP, which generally includes two steps of spin-on-CVD) 3 Perovskite. They used spin coating to prepare lead iodide precursor film, after which lead iodide was reacted with MAI vapor in a petri dish to produce MAPbI 3 The trans device achieves an efficiency of 12.1%. The Dai Song team annealed the spin-coated lead iodide film and then treated its surface with DMSO to promote MAI diffusion. The spin-coating-CVD method uses a spin-coating method to prepare a lead iodide film, and the surface of the spin-coated lead iodide consists of disordered nano particles, which is quite different from vapor-deposited lead iodide. The surface of the evaporated lead iodide is formed by oriented inclined flaky nano particles, so that the compactness is high, and the diffusion of organic salt is not facilitated. Among the two-step gas phase methods reported, the PVD-CVD method or the PVD-soak method is widely used, which means that a lead halide precursor film is prepared by PVD and then converted into perovskite by CVD or the soak method. Team Li Meicheng to soak sputtered PbO toIn isopropanol-dissolved MAI, this method can produce perovskite thin films on curved substrates, but sputtering requires precise Ar/O control 2 The surface of the prepared perovskite film is very rough, which is unfavorable for preparing a thin film perovskite photoelectric device. Bolink promotes the diffusion of organoammonium halides in vapor deposited lead iodide films by spin coating MACl, MABr, and mixtures of the two, effectively converting them to perovskite layers. However, the method also uses a spin coating process, which is disadvantageous for large-area preparation. Qi Yabing group first prepares PbCl by thermal evaporation method 2 PbCl is then added 2 Placing into a tube furnace, placing MAI solid powder on the other side, and heating to make MAI become gas, passing through N 2 Carrying MAI gas to PbCl 2 The reaction produced perovskite, eventually achieving an efficiency of 11.8%. However, this gas-carried method may cause the metal halide closer to the evaporation source to deposit excessive MAI, undergo side reactions with the perovskite that has been generated, destroy perovskite crystals, and the metal halide further from the evaporation source may be insufficiently reacted. The foregoing methods all have difficulty in preparing uniform high quality perovskite thin films on large area curved substrates.
In summary, the following drawbacks mainly exist in the prior art: 1. the solution method is not suitable for preparing a metal halide perovskite thin film on a curved substrate, and a large amount of volatile harmful organic solvents are used; 2. the one-step gas phase process requires high vacuum and severely contaminates the cavity; 3. the surface of the evaporated lead halide film is formed by stacking nano sheets, if PVD-CVD reaction directly occurs, the surface density is too high, so that the conversion rate of the evaporated lead halide to a perovskite phase is low, and a perovskite film with the thickness exceeding 500nm can not be obtained; 4. the organic halide single-source evaporation source in the two-step gas phase method is not suitable for preparing the perovskite with the large-area curved surface substrate.
Disclosure of Invention
In order to overcome the defects, the invention provides a curved organic ammonium metal halide film, a preparation method, a solar cell and application, which are realized by the following technical scheme:
a method for preparing a curved organic ammonium metal halide perovskite film with high conversion rate and low defect density uses a two-step gas phase method. The preparation method comprises the following steps:
evaporating a metal halide film conformal with a curved surface on a pre-cleaned curved surface substrate with different curvatures by adopting a multi-source evaporation method;
step two, fumigating a metal halide film sample by using a polar aprotic solvent to obtain a metal halide complex film fumigated on the surface;
and thirdly, placing the surface fumigated metal halide film sample and the organic ammonium halide powder in a two-step device together for reaction. The organic ammonium halide is coated on the transparent curved surface heating upper substrate with the same curvature as the film by adopting a thermal spraying method, and faces the lower substrate. The surface fumigated metal halide is placed on the lower substrate with the same curvature as the film, facing the upper substrate. And (3) firstly, in the sublimation stage, heating the upper substrate to 110-130 ℃ by a step heating method under the condition that the lower substrate is not heated, and uniformly depositing the organic ammonium halide on the curved film until the surface of the film is colored due to the refraction of the deposited organic ammonium halide on visible light. Then heating the upper and lower substrates simultaneously, heating the curved film and the organic ammonium halide powder to 110-130 ℃ together for reaction for 30-50 minutes, and carrying out a crystal grain nucleation growth stage;
alternatively, the following method may be used in the step (iii):
placing a curved substrate of a metal halide film sample fumigated on the surface and organic ammonium halide powder together in a two-step device for reaction, firstly performing a sublimation stage, heating the organic ammonium halide powder by a transparent curved organic ammonium halide evaporation source with the same curvature under the condition that a compact metal halide film curved substrate is not heated, depositing the organic ammonium halide powder on the curved substrate with the compact metal halide film sample, then performing a crystal grain nucleation growth stage, and heating the compact metal halide curved film and the organic ammonium halide powder together to 110-130 ℃ for reaction;
and fourthly, stopping heating after the reaction is finished, and taking out the successfully prepared curved surface organic ammonium metal halide film.
Preferably, in the first step, the metal halide is one or more of lead chloride, lead bromide, lead iodide, tin chloride, tin bromide, tin iodide, and the like. The vapor deposited metal halide in the first step has high compactness, and complete conversion to the organic ammonium metal halide cannot be realized by using the existing two-step method.
Further, in the second step, the nonpolar protic solvent is most preferably a 1, 3-dimethyl-2-imidazolidinone (DMI) solvent.
Further, in the second step, the thickness of the curved metal halide is different, and the steaming time of the nonpolar proton solvent is 2-3 min.
Further, in the second step, the thickness of the curved metal halide is different, and the steam fumigation temperature of the nonpolar proton solvent is 35-40 ℃ or 35-38 ℃. The DMI solvent fumigated curved surface metal halide film has high thermal stability, high air stability and moderate complexing reaction degree.
Further, in the second step, the surface nanostructure anisotropy of the metal halide is eliminated and the diffusion of the organoammonium halide into the bottom metal halide is successfully promoted.
Preferably, the organic ammonium halide in the third step is one or more of ammonium chloride, ammonium chloride formamidine salt, ammonium bromide formamidine salt, ammonium iodide formamidine salt, ammonium iodide and the like.
Further, the curved organic ammonium metal halide film prepared in the fourth step comprises CH with high conversion rate and low defect density 3 NH 3 PbI 3 And/or NH 2 CHNH 2 PbI 3 . The product prepared by the two-step gas phase method comprises an organic ammonium metal halide film with high conversion rate and low defect density.
It is another object of the present invention to provide a curved organoammonium metal halide film prepared according to the preparation method.
Another object of the present invention is to provide a solar cell textured on the surface, wherein the solar cell textured on the surface is conformally prepared on the surface by using the curved organic ammonium metal halide film, so as to obtain a laminated cell;
the bendable carbon cloth of the solar cell with the textured surface is of a porous sandwich structure and is used for adsorbing polar aprotic solvent vapor; sandwiching a hydrophilic carbon cloth wetted by a polar aprotic solvent between two pieces of hydrophobic carbon cloth, and uniformly fumigating the surface of the curved halide film; the hydrophilic carbon cloth is loose carbon cloth, and the hydrophobic carbon cloth is compact carbon cloth.
It is another object of the present invention to provide a method of characterizing a curved organoammonium metal halide film, the method of characterizing a curved organoammonium metal halide film comprising: the particles of the curved organic ammonium metal halide film are analyzed and characterized by utilizing an X-ray diffraction analysis or a scanning electron microscope, and in addition, the photoelectric conversion efficiency of the organic ammonium metal halide film can be characterized and analyzed according to the current density-voltage (J-V) curve characteristic of the curved organic ammonium metal halide film under simulated sunlight.
The invention further aims to provide application of the curved organic ammonium metal halide film to perovskite thin film solar cells in photovoltaic power stations, photovoltaic building integration, vehicles and wearable equipment.
Compared with the prior art, the invention has the remarkable technical effects that:
1. the invention provides a gas phase method for preparing a curved surface organic ammonium metal halide perovskite film without relying on gravity; the conversion rate of the metal halide film to the organic ammonium metal halide is high and the defect density is reduced by a fumigation-assisted two-step gas phase method.
2. The invention reduces the anisotropy of the nano structure on the surface of the metal halide and successfully promotes the diffusion of the organic halide to the bottom compact metal halide. And the stability of the perovskite film is improved.
3. The method can be applied to the preparation of the curved organic ammonium metal halide solar cell, and the curved organic ammonium metal halide solar cell is prepared for the first time, and the photoelectric conversion efficiency reaches 9%.
4. The perovskite thin film can be conformally prepared on the surface of the battery with the textured surface, and a simple, convenient and efficient preparation method is provided for preparing the high-performance laminated battery.
5. The method can be applied to uniform preparation of the organic ammonium metal halide film on different curved surfaces, and paves the way for realizing photovoltaic automobiles, photovoltaic building integration, wearable photovoltaic and the like in the future.
Through the technical scheme, chemical balance exists when the curved organic ammonium metal halide film is generated, the curved organic ammonium metal halide film is not easy to decompose in air, and the stability of the curved organic ammonium metal halide film is improved.
6. Through the technical scheme, when the curved organic ammonium metal halide film is prepared, the redundant organic ammonium halide can be effectively prevented from being decomposed in the synthesis process.
7. By the technical scheme, the prepared curved organic ammonium metal halide film is not easy to decompose under the action of light and heat, and the stability of the curved organic ammonium metal halide film is improved.
8. By the technical proposal, the film can generate surface texture, thus being applicable to the preparation of laminated batteries, such as surface textured Si, cuInGaSe 2 The preparation of perovskite stacked cells is performed on the surface of (CIGS) or CdTe.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a diagram of a process for preparing a curved organometallic ammonium halide film according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) characterization of the curved metal halide film prepared in step one of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) characterization chart of the surface fumigated curved metal halide film prepared in step two of the present invention;
FIG. 4 is a comparison of the stability of lead iodide complexes prepared in accordance with the present invention;
FIG. 5 is a view showing a Scanning Electron Microscope (SEM) characterization of the surface of a curved organometallic ammonium halide film prepared according to the present invention and a cross section of a photovoltaic device for analytical characterization;
FIG. 6 is an X-ray diffraction pattern of an instrument for analytical characterization of curved organometallic ammonium halide films prepared according to the present invention;
FIG. 7 is a graph of current density versus voltage (J-V) under simulated sunlight for a device used in a solar cell that analytically characterizes the fabricated product provided by an embodiment of the present invention;
fig. 8 is a graph of the effect of a curved solar cell in a solar cell, which is provided in the embodiment of the invention and is used for analyzing and characterizing a prepared product;
FIG. 9 is a pictorial representation of a curved substrate organoammonium metal halide perovskite thin film prepared in accordance with the present invention;
FIG. 10 is an X-ray diffraction pattern of a curved substrate organoammonium metal halide film prepared in accordance with the present invention, as characterized by analysis at different locations in FIG. 8;
fig. 11 is a schematic illustration of conformal CH prepared on CIGS cell surface in accordance with the present invention 3 NH 3 PbI 3 A cross-sectional SEM image of the film;
FIG. 12 is a grazing incidence wide-angle X-ray scattering spectrum of an analytical characterization of the surface of unfused vapor deposited lead iodide (comparative example 1) in accordance with the present invention;
FIG. 13 is a grazing incidence wide-angle X-ray scattering spectrum comparison of analytical characterization instruments for films of organic ammonium metal halides converted from unfused lead iodide (comparative example 1) and fumigated lead iodide (example 1) in accordance with the present invention;
fig. 14 is a graph comparing the current density versus voltage (J-V) front-back scan of a solar cell prepared by the preparation method provided in comparative example 1 in the present invention and a perovskite solar cell prepared by the preparation method provided in example 1 under simulated sunlight.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the following detailed description will be presented with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a curved organic ammonium metal halide film, which uses a two-step gas phase method to prepare the curved organic ammonium metal halide perovskite film with high conversion rate and low defect density. The preparation method comprises the following steps:
evaporating a metal halide film conformal with a curved surface on a pre-cleaned curved surface substrate with different curvatures by adopting a multi-source evaporation method;
step two, fumigating a metal halide film sample by using a polar aprotic solvent to obtain a metal halide complex film fumigated on the surface;
and thirdly, placing the surface fumigated metal halide film sample and the organic ammonium halide powder in a two-step device together for reaction. The organic ammonium halide is coated on the transparent curved surface heating upper substrate with the same curvature as the film by adopting a thermal spraying method, and faces the lower substrate. The surface fumigated metal halide is placed on the lower substrate with the same curvature as the film, facing the upper substrate. And (3) firstly, in the sublimation stage, heating the upper substrate to 110-130 ℃ by a step heating method under the condition that the lower substrate is not heated, and uniformly depositing the organic ammonium halide on the curved film until the surface of the film is colored due to the refraction of the deposited organic ammonium halide on visible light. Then heating the upper and lower substrates simultaneously, heating the curved film and the organic ammonium halide powder to 110-130 ℃ together for reaction for 30-50 minutes, and carrying out a crystal grain nucleation growth stage;
alternatively, the following method may be used in the step (iii):
placing a curved substrate of a metal halide film sample fumigated on the surface and organic ammonium halide powder together in a two-step device for reaction, firstly performing a sublimation stage, heating the organic ammonium halide powder by a transparent curved organic ammonium halide evaporation source with the same curvature under the condition that a compact metal halide film curved substrate is not heated, depositing the organic ammonium halide powder on the curved substrate with the compact metal halide film sample, then performing a crystal grain nucleation growth stage, and heating the compact metal halide curved film and the organic ammonium halide powder together to 110-130 ℃ for reaction;
and fourthly, stopping heating after the reaction is finished, and taking out the successfully prepared curved surface organic ammonium metal halide film.
Specifically, as shown in fig. 1, the invention provides a method for preparing a curved surface organic ammonium halide perovskite film with high conversion rate and low defect density by using a two-step gas phase method according to the action of gravity, which comprises the following steps of:
firstly, preparing a curved rotatable heating plate 1, wherein the curved rotatable heating plate is used for fixing a curved substrate and controlling the temperature of the curved substrate;
secondly, preparing a curved substrate 2;
thirdly, rotating the curved substrate 3;
fourth, metal halide evaporation process 4;
fifth, preparing a multi-source metal halide evaporation source 5;
sixthly, preparing porous carbon cloth 6, wherein the porous carbon cloth is used for covering a curved substrate, so that fumigation uniformity is improved;
seventh, fumigating the polar aprotic solvent 7;
eighth step, preparing a transparent curved surface organic ammonium halide evaporation source 8;
ninth, organic halide diffusion process 9;
tenth, the high-quality curved surface perovskite thin film 10 is obtained.
Just as the prior art has the following main disadvantages: the vapor-deposited metal halide film has high compactness and low conversion rate of metal halide to perovskite. The reason is that the nano structure on the surface of the metal halide has anisotropy (shown in figure 2) to prevent the organic ammonium halide from diffusing to the bottom metal halide, and meanwhile, the organic ammonium halide single-source evaporation source in the two-step gas phase method is not suitable for preparing the organic ammonium metal halide on the curved substrate.
Fig. 2 is an SEM image of the surface and cross-sectional morphology of a vacuum evaporated lead iodide film. SEM left panels show: the prepared lead iodide surface is formed by stacking nano sheets with high orientation degree, and the nano sheets are subjected to volume expansion in the perovskite generating process to prevent subsequent MAI from diffusing into the lead iodide. The right hand graph shows: the surface of the prepared lead iodide consists of inclined nano-sheets.
Fig. 3 is an SEM image of the surface and cross-sectional morphology of the fumigated lead iodide film. SEM left panels show: the stacked nano-sheet structure on the surface of the film disappears after fumigation, and an irregular loose porous structure is replaced. The right hand graph shows: the inclined nano-sheet structure on the surface of the film disappears, which is beneficial to the subsequent MAI diffusion to the inside of the film.
FIG. 4 shows the thermal stability analysis of different lead iodide complexes prepared by the preparation method provided by the invention, and shows that the metal halide complex formed by DMI used in the invention is more stable when the temperature is slightly raised (60 ℃), while the complex formed by dimethyl sulfoxide (DMSO) is more unstable, and decomposition occurs easily at the early stage of CVD reaction, which is unfavorable for the diffusion of MAI into the film.
FIG. 5 shows CH prepared by fumigation-assisted two-step vapor deposition 3 NH 3 PbI 3 SEM images of the cross-sectional morphology of the film surface and of the photovoltaic device produced, the left-hand SEM image below shows: generated CH 3 NH 3 PbI 3 The film is mainly composed of large particles, and has large and uniform particle size. The right hand graph shows: generated CH 3 NH 3 PbI 3 The crystal grains of the film longitudinally penetrate and have uniform size.
FIG. 6 shows CH prepared by fumigation-assisted two-step vapor deposition 3 NH 3 PbI 3 X-ray diffraction pattern of the film, shown in the figure: pbI 2 The peaks are not substantially present and are all converted to CH 3 NH 3 PbI 3 . Description of the invention the vapor deposition of metal halide films to organoammonium metal halides is achievedComplete conversion of the film.
Fig. 7 is a graph of current density-voltage (J-V) curve of a curved perovskite solar cell prepared by the preparation method provided by the invention under simulated sunlight, the efficiency of the curved cell is 8.9%, and the efficiency of the curved cell has not been reported in the past. The method is very beneficial to improving the performance of the curved surface photoelectric device with perovskite as the semiconductor material.
Fig. 8 is a physical diagram of a curved perovskite solar cell, and it can be seen that the curved photovoltaic device is very tightly attached to the back of the hand even without any external pressure applied, which improves the feasibility of future wearable curved device fabrication.
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
1) The curved glass sputtered with ITO is washed by washing agent and deionized water for 20 minutes. Drying with infrared light for 15 minutes.
2) The curved ITO surface was treated with uv/ozone for 15 minutes. Then soaking in absolute ethanol to dissolve MeO-2PACZ (SAM) 2 ) In solution, the solution was then rinsed with absolute ethanol and annealed at 100℃for 15 minutes.
3) A lead iodide thin film was deposited by resistance heating PVD using a multi-source metal halide evaporation source in a vacuum chamber while rotating the substrate.
4) The hydrophilic carbon cloth (loose carbon cloth) is wetted by using a DMI solvent, the wetted hydrophilic carbon cloth is clamped between two pieces of clean hydrophobic carbon cloth (compact carbon cloth), the carbon cloth with the sandwich structure is clung to the surface of curved lead iodide, and the surface of the curved lead iodide is subjected to heat treatment for 2 minutes at 35 ℃ to obtain the lead iodide film with the surface being complexed.
5) MAI is sprayed on a transparent upper substrate with the same radian as the curved substrate to serve as an MAI evaporation source. The lead iodide film with the surface being complexed is upwards arranged on a lower base plate with the radian the same as that of the curved surface substrate. The upper substrate is placed downwards above the lead iodide film with the surface being complexed, and perovskite is prepared by adopting a close range CVD method. The distance between the MAI evaporation source and the surface-complexed lead iodide film was 0.8cm, the vacuum degree was 600Pa, and the curved heating plate and the MAI evaporation source were heated to 110℃for 80 minutes.
6) Stopping heating after the reaction is finished, and inflating the device to take out the prepared CH 3 NH 3 PbI 3 The film adopts a vacuum evaporation method to deposit on CH 3 NH 3 PbI 3 Preparation of C on film in sequence 60 The vapor deposition rates of BCP and Ag are respectively 2nm/s, 0.1nm/s and 10nm/s, and the thicknesses of the BCP and Ag are respectively 22nm,8nm and 100nm.
Example 2
1) The non-planar substrate was ultrasonically cleaned with detergent and deionized water sequentially for 20 minutes. Drying with infrared light for 15 minutes.
2) The non-planar substrate surface was treated with uv/ozone for 15 minutes. Next, a lead iodide thin film is deposited by resistance heating PVD using a multi-source metal halide evaporation source in a vacuum chamber while rotating the substrate.
3) The hydrophilic carbon cloth (loose carbon cloth) is wetted by using a DMI solvent, the wetted hydrophilic carbon cloth is clamped between two pieces of clean hydrophobic carbon cloth (compact carbon cloth), the carbon cloth with the sandwich structure is clung to the surface of non-planar lead iodide, and the surface of the carbon cloth is subjected to heat treatment at 35 ℃ for 2 minutes and 30 seconds, so that the lead iodide film with the complex surface is obtained.
4) MAI is sprayed on a transparent upper substrate with the same radian as the curved substrate to serve as an MAI evaporation source. The lead iodide film with the surface being complexed is upwards arranged on a lower base plate with the radian the same as that of the curved surface substrate. The upper substrate is placed downwards above the lead iodide film with the surface being complexed, and perovskite is prepared by adopting a close range CVD method. The distance between the MAI evaporation source and the surface-complexed lead iodide film was 0.8cm, the vacuum degree was 600Pa, and the non-planar heating plate and the MAI evaporation source were heated to 115℃for 90 minutes.
5) Stopping heating after the reaction is finished, and inflating the device to take out the prepared non-planar CH 3 NH 3 PbI 3 A film.
Fig. 9 shows a curved surface CH prepared at the bottom of the can according to the present invention 3 NH 3 PbI 3 The film physical image shows that the color reaction of the film surface is uniform, and CH is obtained by the reaction 3 NH 3 PbI 3 High conversion rate, and different parts are bright and blackColor. To further confirm the curved surface CH 3 NH 3 PbI 3 Uniformity problem of film for curved surface CH prepared according to the present invention 3 NH 3 PbI 3 The films were tested for X-ray diffraction patterns. From fig. 10 we can find that: lead iodide films at different positions realize the direction of CH 3 NH 3 PbI 3 The film was completely transformed and crystallized to substantially the same degree. From this we can get the curved surface CH prepared by this invention 3 NH 3 PbI 3 The film is very uniform, and the preparation is fully carried out for preparing a large-area non-planar photoelectric device in the future.
Example 3:
1) CIGS cells with submicron scale relief on the surface were sequentially subjected to ultrasonic cleaning with detergent and deionized water for 20 minutes as a substrate. Drying with infrared light for 15 minutes.
2) The non-planar substrate surface was treated with uv/ozone for 15 minutes. Next, a lead iodide thin film is deposited by resistance heating PVD using a multi-source metal halide evaporation source in a vacuum chamber while rotating the substrate.
3) The hydrophilic carbon cloth (loose carbon cloth) is wetted by using a DMI solvent, the wetted hydrophilic carbon cloth is clamped between two pieces of clean hydrophobic carbon cloth (compact carbon cloth), the carbon cloth with the sandwich structure is clung to the surface of lead iodide, and the lead iodide film with the surface being complexed is obtained by heating at 35 ℃ for 2 minutes and 30 seconds.
4) MAI is sprayed on a transparent upper substrate with the same radian as the substrate to serve as an MAI evaporation source. The lead iodide film with the surface being complexed is upwards arranged on a lower base plate with the radian the same as that of the curved surface substrate. The upper substrate is placed downwards above the lead iodide film with the surface being complexed, and perovskite is prepared by adopting a close range CVD method. The distance between the MAI evaporation source and the surface-complexed lead iodide film was 0.8cm, the vacuum degree was 600Pa, and the non-planar heating plate and the MAI evaporation source were heated to 115℃for 90 minutes.
5) Stopping heating after the reaction is finished, and inflating the device to take out the prepared CH 3 NH 3 PbI 3 A film. Fig. 11 shows a curved surface CH prepared on the surface of a CIGS cell according to the present invention 3 NH 3 PbI 3 Cross section of filmSEM images, from which it can be seen that the film is highly crystalline and surface conformal to the original textured surface is achieved. When the laminated battery is subsequently prepared, perovskite is used as a top battery, the perovskite can be tightly combined with a bottom battery with a textured surface, carrier transportation efficiency is improved, and the textured surface is beneficial to enhancing the absorption of incident light.
Comparative example 1:
1) The curved glass sputtered with ITO is washed by washing agent and deionized water for 20 minutes. Drying with infrared light for 15 minutes.
2) The curved ITO surface was treated with uv/ozone for 15 minutes. Then soaking in absolute ethanol to dissolve MeO-2PACZ (SAM) 2 ) In solution, the solution was then rinsed with absolute ethanol and annealed at 100℃for 15 minutes.
3) A lead iodide thin film was deposited by resistance heating PVD using a multi-source metal halide evaporation source in a vacuum chamber while rotating the substrate.
4) MAI is sprayed on a transparent upper substrate with the same radian as the curved substrate to serve as an MAI evaporation source. The lead iodide film with the surface being complexed is upwards arranged on a lower base plate with the radian the same as that of the curved surface substrate. The upper substrate is placed downwards above the lead iodide film with the surface being complexed, and perovskite is prepared by adopting a close range CVD method. The distance between the MAI evaporation source and the surface-complexed lead iodide film was 0.8cm, the vacuum degree was 600Pa, and the curved heating plate and the MAI evaporation source were heated to 110℃for 80 minutes.
5) Stopping heating after the reaction is finished, and inflating the device to take out the prepared CH 3 NH 3 PbI 3 The film adopts a vacuum evaporation method to deposit on CH 3 NH 3 PbI 3 Preparation of C on film in sequence 60 The vapor deposition rates of BCP and Ag are respectively 2nm/s, 0.1nm/s and 10nm/s, and the thicknesses of the BCP and Ag are respectively 22nm,8nm and 100nm.
FIG. 12 is a graph of a grazing incidence wide-angle X-ray scattering spectrum of an unflavored lead iodide film, from which it can be seen that a vapor-deposited lead iodide film without a DMI fumigation treatment has a high degree of anisotropy (left-right asymmetry) relative to that obtained by the two-step process of the present invention, consistent with that obtained by SEM characterization, and disadvantageousDiffusion of MAI into the bottom dense lead iodide results in CH prepared 3 NH 3 PbI 3 The film has low conversion rate, large defect density and low photoelectric efficiency of the device.
To further compare curved surfaces CH with or without DMI fumigation 3 NH 3 PbI 3 Conversion problem of film for curved surface CH prepared according to the present invention 3 NH 3 PbI 3 Film and curved surface CH without DMI fumigation treatment 3 NH 3 PbI 3 The film tested the grazing incidence wide angle X-ray scatter spectrum, as we can see from fig. 13: curved surface CH without DMI fumigation treatment 3 NH 3 PbI 3 The film being provided with lead iodide (q z About 9.1nm -1 ) Is not completely converted into CH 3 NH 3 PbI 3 . Indicating that the conversion rate of the evaporated metal halide film to the organic ammonium metal halide film is low; and the curved surface CH is fumigated by DMI 3 NH 3 PbI 3 The film had almost no lead iodide peaks. The complete conversion of the evaporated metal halide film to an organoammonium metal halide film is illustrated. Fig. 14 is a graph of current density versus voltage (J-V) for a planar perovskite solar cell prepared without DMI fumigation two-step process (comparative example 1) and a planar perovskite solar cell prepared according to a preparation method provided by the invention (example 1). The former is less efficient than the latter, indicating that since vapor deposited lead iodide has anisotropy, MAI does not diffuse completely to the bottom of lead iodide, resulting in CH 3 NH 3 PbI 3 The conversion rate is low, a large number of defects are present, and the photoelectric conversion efficiency of the battery is low.
Comparative example 2:
1) The glass sputtered with ITO is washed by washing agent and deionized water for 20 minutes. And drying by infrared light for 15 minutes.
2) The ITO surface was treated with uv/ozone for 15 minutes. 0.3g PbI 2 Dissolve in 0.5mL anhydrous DMF and add 80. Mu.l anhydrous DMI, heat to 70 ℃, magnetically stir for 120 min, mix well, spin-coat PbI at 4000rpm 2 Precursor solution 30s to form spin-coating PbI 2 A film.
3) MAI is sprayed on the transparent upper substrate to serve as an MAI evaporation source. The spin-coated lead iodide film is upwards arranged on a lower substrate with the same radian as the curved substrate. The upper substrate is placed downwards above the spin-coated lead iodide film, and the perovskite is prepared by adopting a close range CVD method reaction. The distance between the MAI evaporation source and the spin-coated lead iodide film was 0.8cm, the vacuum degree was 600Pa, and the curved heating plate and the MAI evaporation source were heated to 110℃for 80 minutes.
4) Stopping heating after the reaction is finished, and inflating the device to take out the prepared CH 3 NH 3 PbI 3 A film.
Comparative example 2 in comparison with the two-step method used in the present invention, the lead iodide precursor film in comparative example 2 was spin-coated using a solution, and the nano-structure of the spin-coated lead iodide thin film had no anisotropy because the solution had fluidity and undergone a high-speed spin process. The preparation of porous structured lead iodide surfaces has been widely reported in the literature, all in favor of complete transformation to the perovskite phase. In summary, the problem of the difficulty in spreading MAI to the bottom of spin-coated lead iodide can be easily overcome. The vapor-deposited lead iodide has strong anisotropy of the nano structure, is unfavorable for the diffusion of MAI to the bottom of the lead iodide film, but after the DMI fumigation treatment, the anisotropy of the lead iodide film is weakened, and the diffusion of MAI to the bottom of the lead iodide film is favorable, so that the final complete conversion to perovskite is realized.
By combining the application examples and the comparison examples, we can know that the method adopted by the invention greatly reduces the anisotropy of the nano structure on the surface of the metal halide and successfully promotes the diffusion of the organic halide to the bottom of the dense metal halide film. And the stability of the perovskite film is improved, and the curved surface perovskite type ABX with high conversion rate, high crystallinity and less defect density can be prepared by evaporating the lead iodide film 3 The method solves the problem that the solution method can not prepare the curved battery and the two-step gas phase method can prepare the film ABX 3 The conversion is not high and the dense metal halide surface diffusion has a problem of self-limiting.
By X-ray diffraction (XRD), grazing incidence wide angle X-ray scattering, scanning electron microscopyThe analysis of the conversion rate, the uniformity of the conversion rate, the crystal structure and the surface morphology of the thin film by a mirror (SEM) and a current density-voltage (J-V) test means under simulated sunlight can prove that the method adopted by the invention can prepare the curved perovskite type ABX with high conversion rate, high crystallinity and less defect density 3 A film. The method solves the problems that the solution method can not prepare the curved battery and the two-step gas phase method can prepare the film ABX 3 The conversion is not high and the dense metal halide surface diffusion has a problem of self-limiting. The first curved surface organic ammonium metal halide solar cell is successfully prepared by a two-step gas phase method under the condition of not depending on gravity, the efficiency reaches 8.9%, and the method lays a road for realizing photovoltaic automobiles, photovoltaic building integration, wearable photovoltaics and the like.
While the invention has been described with respect to the preferred embodiments, the scope of the invention is not limited thereto, and modifications, equivalents, improvements and the like which will occur to those skilled in the art are intended to be included within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A preparation method of a curved organic ammonium metal halide film is characterized in that: the preparation method of the curved organic ammonium metal halide film adopts a fumigation-assisted two-step vapor deposition method to prepare the organic ammonium metal halide film, and specifically comprises the following steps:
evaporating a metal halide film conformal with a curved surface on a pre-cleaned curved surface substrate with different curvatures by adopting a multi-source evaporation method;
step two, fumigating a metal halide film sample by using a polar aprotic solvent to obtain a metal halide complex film fumigated on the surface; the nonpolar aprotic solvent is a 1, 3-dimethyl-2-imidazolidinone solvent; the steam fumigation time is 2-3 min;
the steam fumigation temperature of the nonpolar proton solvent is 35-40 ℃;
step three, placing the surface fumigated metal halide film sample and organic ammonium halide powder together in a two-step device for reaction; spraying organic ammonium halide on the transparent curved surface upper substrate with the same curvature as the film, and placing the surface fumigated metal halide on the lower substrate with the same curvature as the film; heating the upper substrate under the condition that the lower substrate is not heated, and depositing organic ammonium halide on the curved film; then heating the curved film and the organic ammonium halide powder to 110-130 ℃ together for reaction, and carrying out a crystal grain nucleation growth stage;
and fourthly, stopping heating after the reaction is finished, and taking out the successfully prepared curved surface organic ammonium metal halide film.
2. The method for preparing a curved organoammonium metal halide film as recited in claim 1, wherein: the step one metal halide is one or more of lead halide and selenium halide.
3. The method for preparing a curved organoammonium metal halide film as recited in claim 1, wherein: the metal halide complex film obtained by fumigation in the second step comprises compact PbI 2 Is a complex of (a) and (b).
4. The method for preparing a curved organoammonium metal halide film as recited in claim 1, wherein: the step three organic ammonium halide is one or more of methyl ammonium halide and formamidine halide formed by reacting methylamine with halogen acid.
5. The method for preparing a curved organoammonium metal halide film as recited in claim 1, wherein: the third step adopts the following method:
the method comprises the steps of (1) placing a curved substrate of a metal halide film sample subjected to surface fumigation and organic ammonium halide powder together in a two-step device for reaction, then performing a sublimation stage, heating the organic ammonium halide powder by a transparent curved organic ammonium halide evaporation source with the same curvature under the condition that a compact metal halide film curved substrate is not heated, depositing the organic ammonium halide powder on the curved substrate with the compact metal halide film sample, then performing a crystal grain nucleation growth stage, and heating the compact metal halide curved film and the organic ammonium halide powder together to 110-130 ℃ for reaction;
the transparent curved organic ammonium halide evaporation source is a transparent curved heating substrate.
6. A curved organoammonium metal halide film prepared according to the method of any one of claims 1 to 5.
7. A solar cell textured on a surface, characterized by: the solar cell with the textured surface is prepared conformally by texturing the surface of the curved organic ammonium metal halide film according to the claim 6, so as to obtain a laminated cell;
the bendable carbon cloth of the solar cell with the textured surface is of a porous sandwich structure and is used for adsorbing polar aprotic solvent vapor; sandwiching a hydrophilic carbon cloth wetted by a polar aprotic solvent between two pieces of hydrophobic carbon cloth, and uniformly fumigating the surface of the curved halide film; the hydrophilic carbon cloth is loose carbon cloth, and the hydrophobic carbon cloth is compact carbon cloth.
8. Use of the curved organoammonium metal halide film of claim 6 in perovskite thin film solar cells in photovoltaic power stations, photovoltaic building integration, vehicles, wearable devices.
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