CN113130759B - Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell - Google Patents
Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell Download PDFInfo
- Publication number
- CN113130759B CN113130759B CN202110245927.1A CN202110245927A CN113130759B CN 113130759 B CN113130759 B CN 113130759B CN 202110245927 A CN202110245927 A CN 202110245927A CN 113130759 B CN113130759 B CN 113130759B
- Authority
- CN
- China
- Prior art keywords
- perovskite
- thin film
- film
- transport layer
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a method for quickly removing surface defects of a halide perovskite thin film and application of the method in a perovskite solar cell. The method comprises the following steps: depositing a halide perovskite precursor on a substrate, annealing and crystallizing to obtain a perovskite film, soaking the perovskite film in a washing solvent for ultrasonic cleaning, washing, volatilizing the solvent on the surface of the perovskite film, and obtaining the perovskite film with the surface rich defect layer removed. The method can be rapidly completed at room temperature, and has the advantages of simple process flow and low cost. The invention can greatly reduce the surface defect density of the perovskite film and reduce the non-radiative recombination loss of charges. When the prepared perovskite light absorption layer with low defect density is applied to a perovskite solar cell, the photoelectric conversion efficiency of the rigid planar structure cell can be over 20 percent. The invention lays a solid foundation for large-area and rapid preparation of the high-performance perovskite solar cell, and has application prospects in the fields of photoelectronic devices, LEDs and the like.
Description
Technical Field
The invention belongs to the field of photoelectron materials and devices, and particularly relates to a method for quickly removing surface defects of a halide perovskite thin film and application of the method in a perovskite solar cell.
Background
Due to the problems of increasing exhaustion and environmental pollution caused by the use of fossil fuels such as coal and petroleum, the development of clean energy is a focus of great attention. Halide perovskites have the characteristics of high absorption coefficient, long carrier diffusion length, excellent carrier mobility and the like, and perovskite solar cells prepared by using the halide perovskites as photoactive layers have shown wide development prospects in the photovoltaic field. The photoelectric conversion efficiency of the perovskite solar cell first reported in 2009 is 3.8%, and has been improved to 25.2% by 2019, and the improvement speed is very rapid. In addition, the halide perovskite thin film has wide application prospect in the fields of LEDs, photoelectric detectors, lasers and the like.
At present, the perovskite thin film is prepared by spin coating, chemical vapor deposition, evaporation and the like. Formation of defects, such as impurities, component defects such as incompletely reacted raw materials, or crystal defects such as vacancies or lattice distortion, is often accompanied in the production of halide perovskite thin films. These defects can trap carriers, which in turn cause non-radiative recombination losses of charge, affecting the optoelectronic performance of the device. Research shows that the defect density of the surface of the halide perovskite thin film is 2-3 orders of magnitude higher than that of the interior of the thin film, and interface recombination is one of the main factors influencing the performance of the device.
Organic salt, organic molecules and other materials are adopted to passivate the surface defects of the perovskite, and then non-radiative recombination of charges is the most common means for improving the photoelectric conversion efficiency of the perovskite solar cell. Although surface defect passivation is an effective method for improving the efficiency of perovskite solar cells, the introduction of a passivation layer not only increases the manufacturing cost of the solar cell from the material and process aspects. At the same time, the use of organic passivation materials will also introduce chemical instability. Furthermore, the choice of passivation material tends to vary from perovskite composition to perovskite composition. In 2020, Chen's research found that the defect-rich layer on the surface of the polycrystalline perovskite thin film was relatively loose, and the loose defect was removed by tape bonding (Chen et al Joule,2020,4, 1-14). However, the surface of the polycrystalline perovskite thin film is a rough surface in a nanometer level, and a defect layer cannot be completely removed by mechanical tape adhesion. In addition, the adhesive tape may leave adhesive on the surface of the perovskite thin film, which affects the performance of the perovskite electrode. Therefore, the invention provides a novel method with simple process flow, low cost, high repeatability and wide applicability, which is necessary for reducing the surface defect density of the perovskite to the maximum extent and reducing the non-radiative recombination of charges, thereby preparing the perovskite solar cell or other perovskite optoelectronic devices with excellent performance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for quickly removing surface defects of a halide perovskite thin film and application of the method in a perovskite solar cell.
The invention aims to provide a method for simply and efficiently removing a defect-rich layer on the surface of a halide perovskite thin film and application of the method in a perovskite solar cell.
The invention carries out ultrasonic cleaning treatment on the perovskite film in a solvent which does not dissolve or decompose halide perovskite to remove a relatively loose defect-rich layer on the surface of the perovskite film, and the method can be rapidly finished at room temperature. The defect-rich layer on the surface of the perovskite film can be effectively removed by adjusting the polarity, the viscosity and other parameters of the solvent, the defect density on the surface of the film is greatly reduced, the non-radiative recombination loss of charges is reduced, the open-circuit voltage of the perovskite solar cell is obviously improved, the perovskite solar cell with high photoelectric conversion efficiency is realized, and the repeatability is good.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a method for quickly removing a surface defect layer of a halide perovskite thin film and application of the method in a perovskite solar cell. The removal of the surface defects of the perovskite thin film comprises two main steps of preparation of the perovskite thin film and ultrasonic post-treatment of the perovskite thin film in a solvent; the perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode. The transparent conductive substrate is FTO conductive glass, ITO conductive glass and an ITO/PET flexible substrate; or is TiO 2 、SnO 2 The transparent conductive substrate is modified by n-type semiconductor thin films and p-type semiconductors such as PTAA and NiO.
The method for rapidly removing the surface defects of the halide perovskite thin film provided by the invention is to perform ultrasonic cleaning treatment on the perovskite thin film in a solvent which does not dissolve or decompose the halide perovskite, and remove a relatively loose defect-rich layer on the surface of the perovskite thin film through ultrasonic impact.
The method for rapidly removing the surface defects of the halide perovskite thin film, provided by the invention, specifically comprises the following steps:
(1) depositing a halide perovskite precursor on a substrate surface (a clean transparent conductive substrate surface);
(2) transferring the substrate deposited with the perovskite precursor film to a heating platform, heating up and carrying out annealing crystallization treatment to obtain the perovskite film;
(3) soaking the perovskite thin film obtained in the step (2) in a washing solvent in a container, placing the container in an ultrasonic washing tank for ultrasonic washing treatment (ultrasonic impact is utilized to enable a relatively loose defect-rich layer to fall off from the surface of the perovskite thin film), taking out the perovskite thin film to obtain the perovskite thin film after ultrasonic treatment, washing (washing by using the washing solvent), volatilizing the solvent on the surface of the perovskite thin film, and obtaining the perovskite thin film with the defect-rich layer removed on the surface.
Further, the halide perovskite precursor in the step (1) is FA 1-x MA x PbI 3 、Cs 1-x FA x PbI 3 Organic-inorganic perovskite and CsPbI 2 One of Br all-inorganic perovskites; the substrate is one of blank glass, FTO conductive glass, ITO conductive glass, an ITO/PET flexible substrate, a substrate modified by an n-type semiconductor film and a substrate modified by a p-type semiconductor. The film forming method of the perovskite precursor film is one of a spin coating method, a vapor deposition method, a thermal evaporation method, spraying and blade coating.
Preferably, the FA 1-x MA x PbI 3 FA in the organic-inorganic perovskite is formamidino NH 2 CH＝NH + MA is methylamino CH 3 NH + (ii) a The substrate modified by the n-type semiconductor film is TiO 2 Semiconductor thin film-modified substrate, SnO 2 A substrate modified with a semiconductor thin film, a substrate modified with a ZnO semiconductor thin film, or the like; the p-type semiconductor modified substrate is one of a PTAA semiconductor modified substrate, a NiO semiconductor modified substrate and the like.
Further, the temperature of the annealing and crystallization treatment in the step (2) is 90-380 ℃, and the time of the annealing and crystallization treatment is 15-60 minutes.
Preferably, when the halide perovskite precursor in the step (1) is selected from FA 1-x MA x PbI 3 When the organic-inorganic perovskite is adopted, the temperature of the annealing crystallization treatment in the step (2) is 90-180 ℃; when the halide perovskite precursor in the step (1) is CsPbI2Br all-inorganic perovskite, the annealing crystallization treatment temperature in the step (2) is 200-380 ℃.
Further, the washing solvent of step (3) is a solvent that does not dissolve and does not decompose the perovskite; the washing solvent is one or more of isopropanol, chlorobenzene, toluene, ethyl acetate, diethyl ether, alkane, and fluoroalkane (such as fluorohexane).
Further, the power of the ultrasonic cleaning treatment is 50-1000W, and the time of the ultrasonic cleaning treatment is 1-60 minutes.
Further, the temperature of volatilizing the solvent on the surface of the perovskite thin film is 70-150 ℃, and the time of volatilizing the solvent on the surface of the perovskite thin film is 1-10 minutes.
The washing solvent is common organic solvent or ionic liquid solvent such as alcohols (such as isopropanol, cyclohexanol, ethylene glycol, 1-chloro-2-propanol, etc.), benzenes (such as chlorobenzene, toluene, xylene, etc.), esters (such as ethyl acetate, propyl benzoate, etc.), ethers (such as diethyl ether, butyl ether, etc.), alkanes (such as hexane, cyclohexane, etc.), fluoroalkanes (such as fluorohexane, etc.), etc.
The invention provides a perovskite thin film with a surface defect-rich layer removed, which is prepared by the method.
The invention provides a perovskite solar cell, which comprises: the electronic device comprises a conductive substrate, an electron transport layer, the perovskite thin film with the surface defect-rich layer removed, a hole transport layer and a metal electrode; the perovskite thin film with the surface defect-rich layer removed is a light absorption layer.
When the perovskite solar cell provided by the invention adopts a positive structure, the preparation method comprises the following steps:
(1) firstly, a conductive substrate (transparent conductive substrate) is adoptedCleaning by a semiconductor process, and drying by nitrogen; depositing an electron transport layer on a conductive substrate; the electron transport layer is SnO 2 、TiO 2 Or a ZnO thin film;
(2) preparing the perovskite thin film with the surface defect-rich layer removed on the electron transport layer (firstly preparing the perovskite light absorption layer, and then removing the surface defect-rich layer of the perovskite light absorption layer according to the method to obtain the perovskite thin film with the surface defect-rich layer removed);
(3) spin-coating a hole transport layer on the perovskite thin film with the surface defect-rich layer removed; the hole transport layer is obtained by spin coating a mixed solution of 2, 2 ', 7, 7 ' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene, lithium bistrifluoromethylsulfonic acid imide and 4-tert-butylpyridine; in the mixed solution, the concentration of 2, 2 ', 7, 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene was 68mM, the concentration of lithium bistrifluoromethylsulfonimide was 26mM, the concentration of 4-tert-butylpyridine was 55mM, and the solvent of the mixed solution was a solvent in a volume ratio of 10: 1, a mixture of chlorobenzene and acetonitrile;
(4) and (3) evaporating a metal electrode (Au or Ag electrode) on the hole transport layer to obtain the perovskite solar cell.
When the perovskite solar cell provided by the invention adopts an inverted structure, the preparation method comprises the following steps:
(1) cleaning a conductive substrate (a transparent conductive substrate) by adopting a semiconductor process, and drying by using nitrogen; depositing a hole transport layer on a conductive substrate; the hole transport layer is a NiO film or a PTAA film;
(2) preparing the perovskite thin film with the surface defect-rich layer removed on the hole transport layer (firstly preparing the perovskite light absorption layer, and then removing the surface defect-rich layer of the perovskite light absorption layer according to the method to obtain the perovskite thin film with the surface defect-rich layer removed);
(3) spin-coating an electron transport layer on the perovskite thin film with the surface defect-rich layer removed; the electron transport layer is a PCBM electron transport layer;
(4) and evaporating a metal electrode on the electron transport layer to obtain the perovskite solar cell.
The method has the advantages of simple process, room temperature, low cost, easy repetition and the like. The defect-rich layer on the surface of the halide perovskite can be removed through simple ultrasonic vibration treatment, the interface defect density is greatly reduced, and the non-radiative recombination of charges can be obviously reduced when the halide perovskite is used as a photovoltaic device and a photoelectronic device. When the perovskite light absorption layer is used as a light absorption layer of a perovskite solar cell, the photoelectric conversion efficiency and the repeatability of the solar cell can be obviously improved, and the perovskite light absorption layer is beneficial to the application and popularization of the technology.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method for quickly removing the surface defects of the halide perovskite thin film has stronger universality, and different solvents can be selected to quickly and effectively remove defect-rich layers on the surfaces of different types of halide perovskite thin films so as to reduce the surface defect density of the thin film;
(2) the method for rapidly removing the surface defects of the halide perovskite thin film can remove a defect-rich layer, effectively eliminate perovskite instability caused by the defects and simultaneously avoid device instability caused by the use of an organic passivation material;
(3) the method for rapidly removing the surface defects of the halide perovskite thin film, provided by the invention, has a simple ultrasonic treatment process, simplifies the preparation process of the high-performance perovskite solar cell, greatly reduces the cost of the solar cell, and is suitable for preparing the flexible and large-area perovskite solar cell;
(4) the perovskite thin film with low surface defect density prepared by the method for quickly removing the surface defects of the halide perovskite thin film has wide application prospect in the fields of perovskite photovoltaics, photoelectric detection, LEDs and the like.
Drawings
FIG. 1 is a scanning electron microscope picture of the surface of the perovskite prepared in example 1 without ultrasonic post-treatment.
FIG. 2 is a scanning electron microscope picture of the surface of the post-sonicated perovskite prepared in example 1.
Fig. 3 is a device configuration diagram of a perovskite solar cell.
FIG. 4 is an I-V curve of the perovskite solar cell prepared in example 1.
FIG. 5 is an I-V curve of the perovskite solar cell prepared in example 2.
FIG. 6 is an I-V curve for the perovskite solar cell prepared in example 3.
FIG. 7 is the I-V curve of the perovskite solar cell prepared in example 4.
FIG. 8 is the I-V curve of the perovskite solar cell prepared in example 5.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
1) And (5) cleaning the ITO conductive glass.
Firstly, carrying out ultrasonic treatment on ITO conductive glass for 30 minutes by using isopropanol, then carrying out ultrasonic treatment on deionized water and detergent for 30 minutes to remove surface oil stains, then carrying out ultrasonic treatment on the ITO conductive glass for 30 minutes by using the deionized water and the isopropanol in sequence, cleaning the ITO conductive glass for 30 minutes, and then carrying out blow-drying by using nitrogen to obtain a clean ITO glass substrate for later use.
2)SnO 2 And preparing an electron transport layer.
SnO with the volume of 50 mu L is treated by adopting a glue homogenizing machine 2 The slurry (1.5 wt.%, purchased from Alfa, diluted with deionized water) was spin-coated onto a clean ITO glass substrate exposed to ultraviolet light for 15 minutes, followed by annealing at 150 ℃ for 30 minutes to obtain SnO 2 An electron transport layer.
3) And (3) preparing a perovskite active layer (perovskite light absorption layer).
(1) Preparing a perovskite precursor solution: 0.3260g of lead iodide (PbI) 2 ) 0.1089g formamidine iodide (FAI), 0.0087g cesium iodide (CsI) in 05ml of DMF and DMSO mixed solvent (volume ratio of DMF to DMSO is 1:4), magnetically stirring for 12 hours, and filtering for later use;
(2) preparing a perovskite thin film: spin-coating the perovskite precursor solution on the electron transport layer by using a glue homogenizing machine, and finally dripping 70 mu l of chlorobenzene for 8 seconds.
(3) After the spin coating is finished, the substrate is placed on a hot plate at 100 ℃ for heating and annealing for 30 minutes to prepare the Cs x FA 1- x PbI 3 Perovskite polycrystalline thin film (perovskite polycrystalline thin film without ultrasonic post-treatment).
FIG. 1 is a scanning electron microscope picture of the surface of the perovskite prepared in example 1 without ultrasonic post-treatment. Referring to FIG. 1, scanning electron microscope observation shows that, besides perovskite crystal grains with the size of 300-500 nm, other small-particle-size impurity phases exist at grain boundaries, the grain boundaries are not clear enough, and the prepared Cs is shown x FA 1-x PbI 3 The perovskite surface is covered by other substances. The test of space charge limited current method shows that the surface defect state density of the perovskite film is as high as 3.07 x 10 16 cm -3 。
4) And removing the defect-rich layer on the surface of the perovskite film by ultrasonic waves.
(1) Perovskite thin film (Cs) to be annealed x FA 1-x PbI 3 Perovskite polycrystalline film) is cooled to room temperature, and then the perovskite polycrystalline film is soaked in a container filled with 100ml of chlorobenzene (chlorobenzene is a solvent which does not dissolve or decompose perovskite), and then the container is placed in an ultrasonic cleaning machine with the power of 100W for ultrasonic vibration treatment for 10 minutes;
(2) then taking out the perovskite thin film electrode, and flushing the surface of the perovskite thin film for 3 times by chlorobenzene;
(3) and finally, placing the perovskite film electrode on a heating table at 100 ℃ for 5 minutes to volatilize the residual solvent, thereby obtaining the perovskite polycrystalline film subjected to ultrasonic post-treatment.
FIG. 2 is a scanning electron microscope picture of the surface of the post-sonicated perovskite prepared in example 1. As shown in FIG. 2, the observation of the scanning electron microscope shows that the surface of the perovskite thin film treated by ultrasonic vibration has small particle sizeThe phase is reduced and the perovskite grain boundary profile becomes clearer. The test of space charge limited current method shows that the surface defect density of the perovskite film is reduced to 2.12 multiplied by 10 15 cm -3 。
5) And preparing a hole transport layer.
68mM of 2, 2 ', 7, 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene, 26mM of lithium bistrifluoromethylsulfonimide and 55mM of 4-tert-butylpyridine were mixed with a solvent in a volume ratio of 10: 1, the volume of the solvent is 1 mL; spin coating the hole transport layer solution on the perovskite light absorption layer by a spin coater, and then placing in dry air for oxidation for 12 hours.
6) And (4) preparing a metal electrode.
The sample with the hole transport layer coated by the spin coating is placed in a vacuum thermal evaporation device, and a layer of gold electrode with the thickness of 80nm is evaporated to obtain the perovskite solar cell (the solar cell prepared by removing the perovskite thin film with the defect-rich layer can be seen in the structure shown in figure 3).
7) And (6) testing. At AM1.5 standard, 100mW cm -2 Under light intensity to the effective active layer area of 0.09cm 2 The perovskite solar cell is used for carrying out photoelectric performance test.
The photoelectric performance parameters of the cell are as follows: open circuit voltage 1.15V and short circuit current density 24.55mA cm -2 The fill factor was 0.74, and the photoelectric conversion efficiency was 20.89%, as shown in fig. 4. The only difference between the preparation method of the solar cell prepared by removing the perovskite thin film rich in defects and the preparation method of the solar cell prepared by removing the perovskite thin film rich in defects is that the Cs of the cell which is not subjected to the step 4) is different from the solar cell prepared by not removing the perovskite thin film rich in defects (the preparation method can refer to the step 6) x FA 1-x PbI 3 Perovskite polycrystalline film ultrasonic treatment, the same below), the open circuit voltage of the cell is improved from 1.08V to 1.15V, and the photoelectric conversion efficiency is improved from 19.2% to 20.89%.
Example 2
1) And (5) cleaning the ITO conductive glass. The same as in example 1.
2)SnO 2 And preparing an electron transport layer. Same as example 1。
3) And preparing the perovskite active layer.
In the embodiment, the organic-inorganic halide perovskite thin film is prepared by a two-step method, which comprises the following specific steps:
(1) will PbI 2 Dissolving in mixed solvent of Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (volume ratio of DMF to DMSO is 9:1) to obtain 1.5M PbI 2 Stirring the solution at room temperature for 3 hours, filtering with a micro-filter (0.22 μm organic system), and collecting the filtrate to obtain PbI 2 A solution;
(2) dissolving 90mg of iodoformamidine (FAI), 6.4mg of iodomethylamine (MAI) and 9mg of chloromethylamine (MACl) in isopropanol (volume is 1mL), stirring at room temperature for 3 hours, filtering with a micro-filter (0.22 μm organic system), and collecting the filtrate to obtain FAI/MAI/MACl solution;
(3) mixing PbI with spin coater 2 Solution spin coating annealed SnO uniformly 2 On the electrode of the electron transport layer, annealing was carried out at 70 ℃ for 30 seconds to obtain PbI 2 A layer;
(4)PbI 2 after the film was cooled to room temperature, the FAI/MAI/MACl solution was spin-coated onto PbI 2 On the layer, annealing at 150 deg.C for 20 min in air with humidity of 30% -40% to obtain FA x MA 1-x PbI 3 A perovskite light absorbing layer.
The observation of a scanning electron microscope (as shown in figure 1) shows that except the perovskite crystal grains with the size of 250-400nm, other impurity phases with small grain diameters exist at the grain boundaries, the grain boundaries are not clear enough, and the FA prepared by the perovskite is shown x MA 1-x PbI 3 The perovskite surface is covered by other substances. The test of space charge limited current method shows that the surface defect state density of the perovskite film is as high as 5.56 multiplied by 10 16 cm -3 。
4) And removing the defect-rich layer on the surface of the perovskite film by ultrasonic waves.
(1) Perovskite film to be annealed (the FA) x MA 1-x PbI 3 Perovskite light-absorbing layer) to room temperature, soaking in a container containing 50ml of fluorohexane, and subjecting the container to ultrasonic vibration treatment in an ultrasonic cleaning machine with power of 150W for 8 minA clock;
(2) then taking out the perovskite film electrode, and washing the surface of the perovskite film for 3 times by using isopropanol;
(3) finally, the perovskite thin film electrode is placed on a hot bench at 70 ℃ for 5 minutes to volatilize the residual solvent.
The test of space charge limited current method shows that the surface defect state density of the perovskite thin film is reduced to 3.21 multiplied by 10 15 cm -3 。
5) And preparing a hole transport layer. The same as in example 1.
6) And (4) preparing a metal electrode. The same as in example 1.
7) And (6) testing. The test conditions were the same as in example 1. The photoelectric performance parameters of the cell are as follows: open circuit voltage 1.13V, short circuit current density 23.75mA cm -2 The fill factor was 0.75, and the photoelectric conversion efficiency was 20.13%, as shown in fig. 5. Compared with a solar cell prepared by adopting the perovskite thin film which is not subjected to ultrasonic treatment, the open-circuit voltage is improved from 1.09V to 1.13V.
Example 3
1) And cleaning the FTO conductive glass. The same as in example 1.
2)TiO 2 And preparing an electron transport layer. Dissolving isopropyl titanate (0.5mL) in isopropanol/n-butanol mixed solvent (4mL), wherein the volume ratio of isopropanol/n-butanol is 1:3, shaking up, and aging for 24 hours to obtain TiO 2 Sol; adopting a glue homogenizing machine to filter the TiO 2 Spin coating the sol on a clean FTO glass substrate which is irradiated by ultraviolet for 15 minutes; then annealing at 450 ℃ for 30min to obtain uniform TiO 2 An electron transport layer film.
3) And preparing the perovskite active layer. The same as in example 1. The test of space charge limited current method shows that the surface defect state density of the perovskite film is as high as 1.28 multiplied by 10 16 cm -3 。
4) And removing the defect-rich layer on the surface of the perovskite film by ultrasonic waves.
(1) Perovskite thin film (Cs) to be annealed x FA 1-x PbI 3 Perovskite polycrystalline film) was cooled to room temperature, and then immersed in a container containing 100ml of ethyl acetate, and the container was filled with ethyl acetateThe device is placed in an ultrasonic cleaning machine with the power of 50W for ultrasonic vibration treatment for 60 minutes;
(2) then taking out the perovskite thin film electrode, and washing the surface of the perovskite thin film for 3 times by using ethyl acetate;
(3) finally, the perovskite thin film electrode is placed on a hot bench at 100 ℃ for 3 minutes to volatilize the residual solvent. The test of space charge limited current method shows that the surface defect state density of the perovskite film is reduced to 2.02 multiplied by 10 15 cm -3 。
5) And preparing a hole transport layer. The same as in example 1.
6) And (4) preparing a metal electrode. The same as in example 1.
7) And (6) testing. The test conditions were the same as in example 1. The photoelectric performance parameters of the cell are as follows: open circuit voltage 1.11V, short circuit current density 24.85mA cm -2 The fill factor was 0.72, and the photoelectric conversion efficiency was 19.86%. Compared with a solar cell prepared by using the perovskite thin film without removing the defect-rich layer, the open-circuit voltage of the cell is improved from 1.04V to 1.11V, which can be seen in figure 6.
Example 4
1) And (5) cleaning the ITO conductive glass. The same as in example 1.
2)SnO 2 And preparing an electron transport layer. The same as in example 1.
3) And preparing the perovskite active layer. The same as in example 1.
4) And removing the defect-rich layer on the surface of the perovskite film by ultrasonic waves. The difference from example 1 is that the solvent used for the perovskite dissolution and non-decomposition is a mixed solution of chlorobenzene and toluene (volume ratio of chlorobenzene to toluene is 8: 2).
5) And preparing a hole transport layer. The same as in example 1.
6) And (4) preparing a metal electrode. The same as in example 1.
7) And (6) testing. The test conditions were the same as in example 1. The photoelectric performance parameters of the cell are as follows: open circuit voltage 1.14V, short circuit current density 24.25mA cm -2 The fill factor was 0.73, and the photoelectric conversion efficiency was 20.18%, as shown in fig. 7.
Example 5
1) And (5) cleaning the ITO conductive glass. The same as in example 1.
2) And preparing a NiO hole transport layer. The method comprises the following steps:
(1) adding 248mg of nickel acetate and 100 mu M of ethylamine into 10mL of absolute ethyl alcohol, stirring at 65 ℃ for 2 hours, cooling to room temperature, and filtering to obtain a filtrate, thereby obtaining a NiO precursor;
(2) spin coating the NiO precursor on the clean ITO surface by a spin coater to obtain a uniform film;
(3) annealing the NiO precursor film for 1 hour at 300 ℃ in an air atmosphere to obtain a NiO hole transport layer;
3) and preparing the perovskite active layer. The difference from example 1 is that the perovskite layer is deposited on the NiO hole transport layer;
4) and removing the defect-rich layer on the surface of the perovskite film by ultrasonic waves. The difference from example 1 is that the ultrasonic power used is 1000W and the treatment time is 1 minute.
5) And preparing an electron transport layer. 20mg mL of 40. mu.L in volume was mixed by a homogenizer -1 PCBM ([6,6 ]]phenyl-C61-butyl acid methyl ester) on the perovskite layer to obtain a uniform PCBM layer; then 2mg mL in a volume of 40. mu.L -1 The Bathocuproine (BCP) is coated on the PCBM layer in a spin mode;
6) and (3) preparing a metal electrode. And putting the sample on which the electron transport layer is coated in a vacuum thermal evaporation device, and evaporating a silver electrode with the thickness of 80 nm.
7) And (6) testing. The test conditions were the same as in example 1. The photoelectric performance parameters of the cell are as follows: open circuit voltage 1.08V and short circuit current density 21.05mA cm -2 The fill factor was 0.76, and the photoelectric conversion efficiency was 17.28%, as shown in fig. 8. Compared with a solar cell prepared by using the perovskite thin film without the defect-rich layer, the open-circuit voltage of the cell is improved from 1.01V to 1.08V, and the photoelectric conversion efficiency is improved from 15.46% to 17.28%. The perovskite thin film with the defect-rich layer removed by ultrasonic aftertreatment not only has excellent performance in the solar cell with the positive structure, but also can greatly improve the photoelectric conversion efficiency of the perovskite solar cell with the inverted structure.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (9)
1. A method for rapidly removing surface defects of a halide perovskite thin film is characterized by comprising the following steps:
(1) depositing a halide perovskite precursor on the substrate surface;
(2) heating the substrate deposited with the perovskite precursor film to perform annealing crystallization treatment, and cooling to room temperature to obtain the perovskite film;
(3) soaking the perovskite film obtained in the step (2) in a washing solvent for ultrasonic cleaning treatment to obtain the perovskite film subjected to ultrasonic treatment, washing, volatilizing the solvent on the surface of the perovskite film to obtain the perovskite film with the surface rich defect layer removed; the washing solvent is a solvent which does not dissolve and does not decompose the perovskite; the washing solvent is more than one of chlorobenzene, toluene, ethyl acetate, diethyl ether, alkane and fluorinated alkane.
2. The method for rapidly removing surface defects of halide perovskite thin film according to claim 1, wherein the halide perovskite precursor in step (1) is FA 1-x MA x PbI 3 、Cs 1-x FA x PbI 3 Organic-inorganic perovskite and CsPbI 2 One of Br all-inorganic perovskites; the substrate is one of blank glass, FTO conductive glass, ITO conductive glass, an ITO/PET flexible substrate, a substrate modified by an n-type semiconductor film and a substrate modified by a p-type semiconductor.
3. The method for rapidly removing surface defects of halide perovskite thin film according to claim 2, wherein the FA is selected from the group consisting of 1-x MA x PbI 3 FA in the organic-inorganic perovskite is formamidine group, and MA is methylamino; the substrate modified by the n-type semiconductor film is TiO 2 Conductive substrate modified by semiconductor thin film, SnO 2 One of a conductive substrate modified by a semiconductor film and a conductive substrate modified by a ZnO semiconductor film; the p-type semiconductor modified substrate is one of a PTAA semiconductor modified conductive substrate and a NiO semiconductor modified conductive substrate.
4. The method for rapidly removing the surface defects of the halide perovskite thin film according to claim 1, wherein the power of the ultrasonic cleaning treatment is 30-1000W, and the time of the ultrasonic cleaning treatment is 1-60 minutes.
5. The method for rapidly removing surface defects of halide perovskite thin film according to claim 1, wherein the temperature of the solvent on the surface of the perovskite thin film is volatilized to be 70-150 ℃, and the time for volatilizing the solvent on the surface of the perovskite thin film is 1-10 minutes.
6. A surface defect-rich layer-removed perovskite thin film produced by the method as claimed in any one of claims 1 to 5.
7. A perovskite solar cell, comprising: a conductive substrate, an electron transport layer, the surface defect-rich layer-removed perovskite thin film as defined in claim 6, a hole transport layer and a metal electrode; the perovskite thin film with the surface defect-rich layer removed is a light absorption layer.
8. The perovskite solar cell according to claim 7, wherein when the cell adopts a face-up structure, the preparation method comprises:
(1) depositing an electron transport layer on a conductive substrate; the electron transport layer is SnO 2 、TiO 2 Or a ZnO film;
(2) preparing the perovskite thin film with the surface defect-rich layer removed on the electron transport layer;
(3) spin-coating a hole transport layer on the perovskite thin film with the surface defect-rich layer removed;
(4) and evaporating a metal electrode on the hole transport layer to obtain the perovskite solar cell.
9. The perovskite solar cell according to claim 7, wherein when the cell adopts an inverted structure, the preparation method comprises:
(1) depositing a hole transport layer on a conductive substrate; the hole transport layer is a NiO film or a PTAA film;
(2) preparing the perovskite thin film with the surface defect-rich layer removed on the hole transport layer;
(3) spin-coating an electron transport layer on the perovskite thin film with the surface defect-rich layer removed; the electron transport layer is a PCBM electron transport layer;
(4) and evaporating a metal electrode on the electron transport layer to obtain the perovskite solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110245927.1A CN113130759B (en) | 2021-03-05 | 2021-03-05 | Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110245927.1A CN113130759B (en) | 2021-03-05 | 2021-03-05 | Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113130759A CN113130759A (en) | 2021-07-16 |
| CN113130759B true CN113130759B (en) | 2022-08-16 |
Family
ID=76772630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110245927.1A Active CN113130759B (en) | 2021-03-05 | 2021-03-05 | Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113130759B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115843189B (en) * | 2022-12-22 | 2023-07-25 | 浙江科鼐尔机电制造有限公司 | Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10971690B2 (en) * | 2015-08-24 | 2021-04-06 | King Abdullah University Of Science And Technology | Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof |
| CN107293644A (en) * | 2016-04-01 | 2017-10-24 | 中央大学 | Large area perovskite film and perovskite solar module and preparation method thereof |
| JP6600670B2 (en) * | 2017-09-15 | 2019-10-30 | 株式会社東芝 | Photoelectric conversion element, manufacturing method thereof, and manufacturing apparatus thereof |
| CN110047774B (en) * | 2018-01-17 | 2021-08-27 | 杭州纤纳光电科技有限公司 | Equipment for preparing perovskite thin film in immersion mode, use method and application |
| US11177439B2 (en) * | 2019-03-06 | 2021-11-16 | Tandem PV, Inc. | Processing of perovskite films using inks with complexing agents |
| CN111435708B (en) * | 2019-06-25 | 2022-09-13 | 杭州纤纳光电科技有限公司 | Method for repairing defect of perovskite thin film |
| CN111180589B (en) * | 2019-12-30 | 2022-04-19 | 电子科技大学 | High-stability perovskite solar cell prepared based on ultrasonic oscillation annealing process |
-
2021
- 2021-03-05 CN CN202110245927.1A patent/CN113130759B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113130759A (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109545970B (en) | Method for improving efficiency and stability of perovskite solar cell and perovskite solar cell | |
| CN109980092B (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| CN112635675B (en) | Perovskite solar cell based on 3-thiophene acetic acid interface modification layer and preparation method thereof | |
| CN108807694B (en) | Flat perovskite solar cell with ultralow temperature stability and preparation method thereof | |
| CN107919403B (en) | Efficient selenium cadmium telluride alloy nanocrystalline solar cell and preparation method thereof | |
| CN110311038B (en) | Method for increasing crystal grain size of perovskite film layer of perovskite solar cell | |
| CN113130759B (en) | Method for quickly removing surface defects of halide perovskite thin film and application of method in perovskite solar cell | |
| CN113363387B (en) | Perovskite solar cell electron transport layer and preparation method thereof | |
| CN111192964B (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| CN111063805A (en) | Organic-inorganic perovskite solar cell and preparation and recovery method | |
| CN115347120A (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| CN113707816B (en) | Preparation method of perovskite solar cell | |
| CN116234331A (en) | Perovskite solar cell based on benzamide bromine modification and preparation method thereof | |
| CN113054114B (en) | Solar cell based on D-A type organic micromolecule doped ZnO electron transport layer and preparation method thereof | |
| CN113054045B (en) | Bi (Fe, Zn) O for high-speed photoelectric detection3NiO full oxide film heterojunction | |
| CN114784191A (en) | Perovskite thin film with interface modified by organic small molecular compound, preparation method of perovskite thin film and solar cell | |
| CN113903862A (en) | SnO modified based on phenylboronic acid derivatives2Preparation method of perovskite solar cell | |
| CN116507139B (en) | Long-branched chain alkyl ammonium modified formamidine perovskite solar cell and preparation method thereof | |
| CN116507185B (en) | Formamidine perovskite solar cell and preparation method thereof | |
| CN116234330B (en) | Perovskite solar cell and preparation method thereof | |
| CN114574193B (en) | Method for extracting residual lead iodide from lead halogen perovskite material | |
| CN113437225B (en) | Perovskite solar cell modified by photonic crystal and preparation method thereof | |
| CN115843205B (en) | Perovskite film layer preparation method and perovskite solar cell | |
| CN114944457B (en) | Perovskite solar cell and preparation method thereof | |
| CN109216553B (en) | CsSnI3Doped organic solar cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |