CN112382725B - Method for reducing ion migration of organic-inorganic hybrid perovskite thin film - Google Patents
Method for reducing ion migration of organic-inorganic hybrid perovskite thin film Download PDFInfo
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Abstract
The invention belongs to a method for improving the stability of materials, and particularly relates to a method for reducing the ion migration of an organic-inorganic hybrid perovskite thin film. Adding an additive into a precursor in the process of preparing the organic-inorganic hybrid perovskite thin film; or, an additive thin film is formed on the surface of the formed organic-inorganic hybrid perovskite thin film. According to the invention, the small molecules or macromolecules of boric acid and boric acid derivatives are introduced into the perovskite thin film, so that the ion migration barrier of the perovskite thin film can be effectively improved, and the stability of the thin film and corresponding devices is improved; the adopted materials have low cost and are easy to realize in process.
Description
Technical Field
The invention belongs to a method for improving the stability of materials, and particularly relates to a method for reducing the ion migration of an organic-inorganic hybrid perovskite thin film.
Background
Perovskite solar cells are recently paid attention and researched by researchers in related fields as a new generation of photovoltaic devices. The organic-inorganic hybrid perovskite material is used as a light absorption layer of a perovskite solar cell, has the characteristics of long carrier diffusion length, small forbidden band width, excellent light absorption coefficient and the like, and has the photoelectric conversion efficiency of more than 25 percent at present. However, one of the current bottleneck problems is its stability. There are many factors affecting the stability of the device, one of the important reasons is the ion migration characteristic, which brings defects to the material on one hand and forms a photoelectric recombination center; on the other hand, the phase separation is accelerated, and the excellent electrical conversion characteristics of the material are lost. In addition, ion migration also has fatal influence on a carrier transmission layer of the perovskite material, for example, the migration of iodide ions can corrode a metal electrode, so that the electrode material such as aluminum, silver and the like is difficult to apply to a formal device structure. Therefore, solving the problem of ion migration in perovskite materials is crucial to improving the photoelectric conversion efficiency of devices, improving the long-term service life of devices, and reducing the preparation cost of devices.
Ion migration was discovered a few years ago, but an effective solution is still lacking. Material interfacial barriers are often employed to limit ion transport, such as the introduction of two-dimensional perovskite structures, dense oxide layers, and the like. The method can effectively limit the migration of ions and well protect the stability of the electrode, but can not limit the migration of ions in the perovskite material, and has a limited effect on improving the stability of the device. Therefore, it is very important to develop a more effective way to limit the ion migration inside the thin film material, which is one of the first problems that must be solved to realize the future industrialization.
Disclosure of Invention
The invention aims to provide a method for reducing ion migration of an organic-inorganic hybrid perovskite thin film.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for reducing ion migration of an organic-inorganic hybrid perovskite thin film comprises the steps of adding an additive into a precursor in the process of preparing the organic-inorganic hybrid perovskite thin film; or forming an additive thin film on the surface of the formed organic-inorganic hybrid perovskite thin film;
wherein the additive is one or more of boric acid, boric acid derivative small molecular substances and boric acid derivative high molecular substances.
Preferably:
adding an additive into the perovskite precursor solution, fully dissolving, and then performing film preparation and heat treatment to improve the migration barrier of iodide ions in the perovskite film;
or preparing a micromolecule or macromolecule film containing boric acid and derivatives thereof on the upper surface of the organic-inorganic hybrid perovskite film, and further diffusing the micromolecule or macromolecule containing boric acid and derivatives thereof into the perovskite film grain boundary through a subsequent heat treatment mode, so as to improve the migration barrier of iodide ions in the perovskite film.
The additive is perovskite in perovskite thin film (ABX) 3 ) Is 0.01 to 10%.
The heat treatment temperature of the film is 80-150 ℃.
Further preferably:
adding an additive into an organic-inorganic perovskite solution, spin-coating to prepare a film, heating to 80-150 ℃, and further assembling a battery device, wherein the stability of the battery device is obviously improved; the additive is perovskite in perovskite thin film (ABX) 3 ) Is 0.01 to 10%.
Further preferably:
adding an additive into an organic-inorganic perovskite solution, spin-coating to prepare a film, heating to 120-150 ℃, and further assembling a battery device, wherein the stability of the battery device is obviously improved;
the additive is perovskite in perovskite thin film (ABX) 3 ) The molar ratio of (A) is 3-6%.
The additive contains-B-OH or-B-O-R groups.
The micromolecules containing boric acid and derivatives thereof are boric acid, metaboric acid, aryl boric acid, alkyl boric acid, boric acid ester, aryl boric acid ester, alkyl boric acid ester, borate and metaborate; the polymer containing boric acid and its derivatives is a polymer having boric acid or borate group in the main chain or side chain.
Forming an additive film on the surface of the formed organic-inorganic hybrid perovskite film by preparing a film on the surface of the perovskite film by an additive through a solution method or a physical evaporation method; wherein the solvent is one or more of ethanol, isopropanol and trifluoroethanol.
The structural formula of the organic-inorganic hybrid perovskite thin film is ABX 3 A is a cation containing methylamine CH3NH3 (MA) ions and formamidine NH 2 -CH＝NH 2 One or both of (FA) ions; b is one or two of Pb metal ions and Sn metal ions; x is one or two or more of I, br and Cl ions.
The A ions are MA ions, or FA ions, or the composition of the MA ions and Cs, ru and amine ions, or the composition of the FA ions and the Cs, ru and amine ions.
The ion-containing material contains one or two of Pb metal ions and Sn metal ions, wherein the B ions are Pb metal ions, sn metal ions, or the complex formed by the Pb metal ions and Sn, bi and Eu ions, or the complex formed by the Sn metal ions and the Bi and Eu ions.
The organic-inorganic hybrid perovskite thin film prepared by the method is doped with an additive.
Use of a thin film of an additive doped organic-inorganic hybrid perovskite thin film in a solar cell, a light emitting device or a detection device to reduce ion migration of the organic-inorganic hybrid perovskite thin film.
The ion migration of the perovskite thin film obtained by the method is obviously inhibited, the stability of the thin film is obviously improved, the high efficiency of the device is ensured, and the service life of the device is greatly prolonged, which is particularly important for the commercial application of the perovskite battery device.
The invention has the advantages that:
according to the invention, the small molecules or macromolecules of boric acid and boric acid derivatives are introduced into the perovskite thin film, so that the ion migration barrier of the perovskite thin film can be effectively improved, and the stability of the thin film and corresponding devices is improved; the adopted materials have low cost and are easy to realize in process.
The small molecules or high molecules of boric acid and its derivatives introduced into the initial film of the present invention can be prepared by conventional solution methods, such as spin coating, blade coating, slit coating, printing, etc. Preparing micromolecules or macromolecules of thin boric acid and derivatives thereof on the upper surface of the perovskite film, and spin coating, blade coating, evaporation and the like can also be adopted. Boric acid or metaboric acid has a small molecular size and has a strong interaction with Pb and the like of the perovskite, so that boric acid or metaboric acid can be uniformly dispersed in the perovskite thin film.
The perovskite thin film containing the boric acid and the micromolecule or the macromolecule of the boric acid derivative prepared by the method has high compactness, good uniformity, less defects and low roughness, and reduces the exciton recombination. Under the action of an electric field, the perovskite thin film prepared based on the method shows lower ion migration behavior, shows higher voltage-resistant stability and greatly prolongs the service life of a device.
The process of the invention is easy to operate, has good repeatability and is suitable for large-scale production, and the perovskite thin film prepared by the method can be competent for various device structures, such as mesoporous and planar perovskite solar cells, diodes, lasers and the like.
Drawings
Fig. 1 is an XRD spectrum of a perovskite thin film prepared before and after introducing boric acid into the precursor solution provided in embodiment 1 of the present invention.
FIG. 2 is an SEM photograph of a perovskite thin film prepared before and after introducing boric acid into the precursor solution provided in example 1 of the present invention; wherein the left panel is before addition of boric acid and the right panel is after addition of 5mol% boric acid.
Fig. 3 is a PL spectrum of a perovskite thin film prepared before and after introducing boric acid into the precursor solution provided in embodiment 1 of the present invention.
Fig. 4 is an I-V curve of a perovskite cell prepared before and after introducing boric acid into the precursor solution provided in example 1 of the present invention.
Fig. 5 is a stability curve of a perovskite cell prepared before and after introducing boric acid into the precursor solution provided in example 1 of the present invention.
Fig. 6 is an XRD spectrum of the perovskite thin film prepared before and after the top of the perovskite thin film provided in example 2 of the present invention is spin-coated with metaboric acid.
FIG. 7 is a PL profile of a perovskite thin film prepared before and after the top of the perovskite thin film provided in example 2 of the present invention is spin coated with metaboric acid.
FIG. 8 is an I-V curve of a perovskite cell prepared before and after the top of the perovskite thin film provided in example 2 of the present invention is spin-coated with metaboric acid.
Fig. 9 is a stability curve of a perovskite cell prepared by spin-coating metaboric acid on top of a perovskite thin film provided in example 2 of the present invention and heating.
FIG. 10 shows a synthetic route of polymeric PMAPBA containing boronic acid groups provided in example 3 of the present invention.
FIG. 11 is an I-V curve of a perovskite battery manufactured before and after 0.4mol% of a polymer containing a boric acid group was introduced into a precursor solution provided in example 3 of the present invention, i.e., PMAPBA.
FIG. 12 is an I-V curve after device aging for 20 days before and after 0.4mol% of a polymer containing a boronic acid group was introduced into a precursor solution provided in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Perovskite (ABX) in perovskite thin film as referred to in the present invention 3 ) Obtainable according to the prior art.
Example 1
First, 300 cycles of TiO deposition on cleaned FTO glass using an atomic layer deposition apparatus 2 Heating the deposited FTO glass at 500 ℃ for 30min to obtain compact TiO 2 A film. Spin coating SnO on dense thin film 2 Precursor solution (SnCl) 4 Aqueous solution), spin coating at 3000rpm for 30s, and further heating at 200 deg.C for 30min to obtain compact TiO 2 /SnO 2 An electron transport layer.
Secondly, pbI was added in a molar percentage of 1 2 FAI, MAI dissolved in DMF solution, pbI in the prepared solution 2 A solution with a concentration of 50wt% of the total of FAI and MAI, the solution was divided equally into two portions, one of which was taken and added with boric acid, boric acid and perovskite material (PbI) 2 The sum of FAI and MAI) is 5%,fully dissolving, using another solution as reference, respectively spin-coating the above two solutions on TiO 2 /SnO 2 On the film, the film is prepared by an anti-solvent method, and the poor solvent is diethyl ether. And (3) annealing at 150 ℃ for 10min, and volatilizing the solvent in the film to obtain the boric acid doped perovskite film and the reference (undoped) perovskite film. The reference perovskite thin film and the boric acid doped perovskite thin film have similar surface appearance and higher compactness (see the figure 1-2). Fluorescence characterization also showed that boric acid doping showed fewer carrier recombination centers, improving the quality of the film (see fig. 3).
Finally, according to the prior art, a cavity transport layer spiro-OMeTAD and a gold-evaporated electrode are respectively coated on the surface layers of the two different perovskite thin films obtained, a solar cell device is assembled, and I-V performance measurement is carried out under the condition that scanning is carried out from 1.2V to 0V, and the initial efficiency is slightly improved (see figure 4).
The solar cell obtained in this example was placed in a humidity environment of 30%, and air stability was tested (see fig. 5), and it can be seen from fig. 5 that the stability of the doped cell is significantly improved.
As shown in the XRD patterns of undoped and boric acid doped perovskite thin films in figure 1, the orientation of the thin films is not obviously different, but the diffraction intensity is obviously improved, which shows that the introduction of boric acid improves the crystallinity of the thin films. As shown in fig. 2, SEM of undoped and boric acid doped perovskite thin films shows that after introduction of boric acid molecules, the morphology of the thin film has not changed significantly and no pore structure is found due to the low doping amount and the good compatibility between boric acid and perovskite molecules. As shown in the fluorescence spectrum of fig. 3, the fluorescence intensity of the doped material is significantly increased, which indicates that the concentration of the recombination center of the carrier is reduced, which is particularly important for the photoelectric conversion process. As shown in fig. 4, which is the device I-V curve, the initial device efficiency before and after doping was 20.2% and 21.0%, respectively, which was slightly improved. More importantly, as with the long-term stability of the device in fig. 5, the stability after doping is significantly improved, and the efficiency of the unpackaged device remains 90% of the initial efficiency after 80 days, while the undoped device has failed as early as possible.
Example 2
First, 300 cycles of TiO deposition on cleaned FTO glass using an atomic layer deposition apparatus 2 Heating the deposited FTO glass at 500 ℃ for 30min to obtain compact TiO 2 A film. Spin coating SnO on dense thin films 2 Precursor solution (SnCl) 4 Aqueous solution), spin coating at 3000rpm for 30s, and further heating at 200 deg.C for 30min to obtain compact TiO 2 /SnO 2 An electron transport layer.
Secondly, pbI was added in a molar percentage of 1 2 FAI, MAI dissolved in DMF solution, pbI in the prepared solution 2 And then preparing the perovskite thin film by an anti-solvent method under the annealing condition of 150 ℃ for 5min, then spin-coating 1mg/mL of meta-boric acid isopropanol solution on the top of the perovskite thin film, and then carrying out heating treatment under the annealing condition of 150 ℃ for 10min to obtain the boric acid doped perovskite thin film. The metaboric acid-doped perovskite thin film has uniform surface and higher compactness, and the crystallinity is similar to that of the precursor (see figures 6-7).
Finally, according to the prior art, a hole transport layer spiro-OMeTAD and an evaporated gold electrode are respectively coated on the surface layers of the obtained doped metaboric acid and undoped perovskite thin films in a spin mode, a solar cell device is assembled, and I-V performance measurement is carried out, wherein the measurement conditions are that scanning is carried out from 1.2V to 0V (see figure 8).
The solar cell obtained in this example was placed in a 30% humidity environment, and the air stability was tested, and it can be seen from fig. 9 that the initial efficiency was significantly improved after doping. The doped cell is significantly improved in terms of device stability.
Example 3
Firstly, macromolecular PMAPBA containing boric acid groups is synthesized, and a specific scheme is shown in figure 10. The specific synthesis steps are as follows:
3-Aminophenylboronic acid (3-APBA, 7.3 mmoL) was dissolved in 15mL of NaOH solution (2 moL/L) at 0 ℃; to the solution was added dropwise acrylic acid chloride (AC, 14.6 mmoL) while vigorously stirring for 15min; then, a hydrochloric acid solution (1 moL/L) was slowly added to the mixed solution until pH =1, a white precipitate was generated, filtered, and washed with cold water; extracting the filtrate with ethyl acetate for 3 times, washing the organic phase with concentrated brine, and evaporating to remove white solid; the obtained white solid was mixed with water and recrystallized to obtain (3- (acrylamido) phenyl) boronic acid (AAPBA).
Under the protection of nitrogen, adding methyl acrylate (MA, 4.2 mmoL), (3- (acrylamido) phenyl) boric acid (AAPBA, 2.1 mmoL), azobisisobutyronitrile (AIBN, 10 mg) and DMF (10 mL) into a pressure-resistant bottle; the pressure bottle was placed in a 70 ℃ oil bath and reacted for 24h. After the reaction was completed, the polymerization solution was dropped into 50mL of diethyl ether to obtain a white solid (PMAPBA) of a copolymer of acrylamide and methyl acrylate having a boronic acid side chain.
Secondly, preparing TiO on an FTO substrate 2 /SnO 2 Electron transport layer, method as above. Preparing a perovskite solution, and mixing PbI according to molar percentage of 1.5 2 FAI, MAI dissolved in DMF solution, pbI in the prepared solution 2 A solution with a concentration of 50% of the total of FAI and MAI, dividing the solution into two parts, and adding PMAPBA polymer, PMAPBA and perovskite material (PbI) into one part of the solution 2 Total of FAI and MAI) was 0.4% by mole, fully dissolved, and the other solution was used as a reference, and the two solutions were spin-coated on TiO, respectively 2 /SnO 2 On the film, the film is prepared by an anti-solvent method, and the poor solvent is diethyl ether. And (3) annealing at 150 ℃ for 10min, and volatilizing the solvent in the film to obtain the PMAPBA high-molecular doped perovskite film and a reference (undoped) perovskite film.
Finally, according to the prior art, a hole transport layer spiro and a gold-evaporated electrode are respectively coated on the surface layers of the obtained doped perovskite thin film (PMAPBA) and the reference (undoped) perovskite thin film (control) in a spin mode to assemble a solar cell device, and I-V performance measurement is carried out, wherein the measurement conditions are scanned from 1.2V to 0V (see figure 11).
As shown in fig. 11, which is an I-V curve of the device, the efficiencies before and after the initial device doping are 21.02% and 21.53%, respectively, and the device efficiency is slightly improved after the additive is introduced. After aging of the unpackaged devices for 20 days at 30% humidity in air, the performance curves are shown in FIG. 12, with the efficiency of the cell device without additives decaying to 12.4%, while the efficiency of the cell device with 0.4mol% PMAPBA was 20.3%, showing good stability.
Claims (6)
1. A method for reducing ion migration of an organic-inorganic hybrid perovskite thin film is characterized by comprising the following steps: adding an additive into a precursor in the process of preparing the organic-inorganic hybrid perovskite thin film; or forming an additive thin film on the surface of the formed organic-inorganic hybrid perovskite thin film; wherein the additive is boric acid;
adding an additive into the perovskite precursor solution, fully dissolving, and then performing film preparation and heat treatment to improve the migration barrier of iodide ions in the perovskite film;
or preparing a micromolecule or macromolecule film containing boric acid and derivatives thereof on the upper surface of the organic-inorganic hybrid perovskite film, and further diffusing the micromolecule or macromolecule containing boric acid and derivatives thereof into the crystal boundary of the perovskite film by a subsequent heat treatment mode to improve the migration barrier of iodide ions in the perovskite film;
the two heat treatment temperatures are both 80-150 deg.C o And C, obtaining the boric acid doped perovskite film after heat treatment.
2. The method for reducing ion migration of an organic-inorganic hybrid perovskite thin film as claimed in claim 1, wherein: the additive is compatible with perovskite in perovskite thin film (ABX) 3 ) Is 0.01 to 10%.
3. The method for reducing ion migration of an organic-inorganic hybrid perovskite thin film as claimed in claim 1, wherein: forming an additive film on the surface of the formed organic-inorganic hybrid perovskite film by preparing a film on the surface of the perovskite film by an additive through a solution method or a physical evaporation method; wherein the solvent is one or more of ethanol, isopropanol and trifluoroethanol.
4. According to the claimsThe method for reducing the ion migration of the organic-inorganic hybrid perovskite thin film is characterized by comprising the following steps: the structural formula of the organic-inorganic hybrid perovskite film is ABX 3 A is a cation containing methylamine CH 3 NH 3 (MA) ion and formamidine NH 2 -CH=NH 2 One or both of (FA) ions; b is one or two of metal ions containing Pb and Sn; x is I.
5. An organic-inorganic hybrid perovskite thin film prepared by the method of claim 1, wherein: an organic-inorganic hybrid perovskite thin film doped with additives is prepared according to the method of claim 1.
6. Use of a film according to claim 5, wherein: the application of the additive-doped organic-inorganic hybrid perovskite thin film in a solar cell, a luminescent device or a detection device reduces the ion migration of the organic-inorganic hybrid perovskite thin film.
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