CN114016133A - Method for directly integrating single crystal perovskite on substrate and application thereof - Google Patents
Method for directly integrating single crystal perovskite on substrate and application thereof Download PDFInfo
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Abstract
The invention discloses a method for directly integrating single crystal perovskite on a substrate and application thereof, wherein the method comprises the following steps: (1) will CH3NH3X、PbX2Mixing with organic solvent to obtain CH3NH3PbX3A perovskite precursor solution; (2) placing a substrate on the CH3NH3PbX3In a perovskite precursor solution and reacting said CH with an anti-solvent in a closed system3NH3PbX3Subjecting the perovskite precursor solution to vapor phase diffusion to cause said CH3NH3PbX3Direct integration of single crystal CH by perovskite on said substrate3NH3PbX3Perovskite, wherein, in step (1), the CH3NH3X comprises CH3NH3Cl、CH3NH3Br and CH3NH3At least one of the components in the group I,the PbX is2Comprising PbCl2、PbBr2And PbI2At least one of (a). Thus, by adopting the method, the single crystal perovskite with large size and high crystallization quality can be directly grown on a given substrate.
Description
Technical Field
The invention belongs to the technical field of perovskite single crystal preparation, and particularly relates to a method for directly integrating single crystal perovskite on a substrate and application thereof.
Background
Organic-inorganic hybrid perovskites have long electron-hole diffusion lengths, high mobility and excellent photoelectric conversion capability, and are receiving attention in the field of optoelectronic devices. In recent years, optoelectronic devices based on pure perovskites have been greatly developed, and better photoelectric properties are obtained. However, the intrinsic optical band gap (<800nm) of perovskites limits their development in the broad spectrum area, and the response time constraints of pure perovskite photoconductive devices further hinder the application of perovskite devices.
In order to solve the problems faced by pure perovskite devices, many researches integrate a polycrystalline perovskite thin film with a substrate, however, the inherent grain boundary and defect of the polycrystalline thin film have extremely adverse effects on the transmission of current carriers, and the performance of the perovskite optoelectronic device is greatly reduced. Therefore, the direct integration of the single crystal perovskite on the substrate is of great significance to further improvement of device performance and solving of the process problem of the single crystal perovskite.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to propose a method for the direct integration of single crystalline perovskites on a substrate and the use thereof, with which large-size, high-crystalline-quality single crystalline perovskites can be grown directly on a given substrate.
In one aspect of the invention, the invention provides a method of directly integrating a single crystal perovskite on a substrate. According to an embodiment of the invention, the method comprises:
(1) will CH3NH3X、PbX2Mixing with organic solvent to obtain CH3NH3PbX3A perovskite precursor solution;
(2) placing a substrate on the CH3NH3PbX3In a perovskite precursor solution and reacting said CH with an anti-solvent in a closed system3NH3PbX3Subjecting the perovskite precursor solution to vapor phase diffusion to cause said CH3NH3PbX3Direct integration of single crystal CH by perovskite on said substrate3NH3PbX3A perovskite of the type having a high degree of thermal expansion,
wherein, in the step (1), the CH3NH3X comprises CH3NH3Cl、CH3NH3Br and CH3NH3At least one of I, the PbX2Comprising PbCl2、PbBr2And PbI2At least one of (a).
According to the method for directly integrating the single crystal perovskite on the substrate, the substrate comprises CH3NH3Cl、CH3NH3Br and CH3NH3CH of at least one of I3NH3X, comprising PbCl2、PbBr2And PbI2PbX of at least one of2Mixing with organic solvents, CH3NH3X and PbX2Reaction to form CH3NH3PbX3Perovskite, i.e. to obtain CH3NH3PbX3A perovskite precursor solution; the substrate is then placed in CH3NH3PbX3In a perovskite precursor solution and using an anti-solvent for CH in a closed system3NH3PbX3And carrying out gas phase diffusion on the perovskite precursor solution. Since the anti-solvent will diffuse first to the surface of the precursor solution causing the solubility of the perovskite to decrease, the crystals will be first in CH3NH3PbX3Crystal seeds are precipitated from the surface of the perovskite precursor solution and fall to the surface of the substrate under the action of self gravity. As the anti-solvent diffusion continues, the solubility of the perovskite continues to decrease providing sufficient kinetics for seed growth. The single crystal perovskite grown by the optimized anti-solvent methodThe atomic-level flat surface is arranged, the distance between the atomic-level flat surface and the substrate reaches the Van der Waals distance, the Van der Waals interaction is fully activated, and finally, the single crystal CH with large size and high crystallization quality is directly grown on the substrate3NH3PbX3Perovskite. Single crystal CH3NH3PbX3The direct integration of perovskite on the substrate not only can realize the advantage complementation between different materials, but also can optimize the interface characteristics of perovskite so as to construct a wide-spectrum and high-speed photoelectric device.
In addition, the method of directly integrating single crystal perovskites on a substrate according to the above embodiments of the present invention may also have the following additional technical features:
in some embodiments of the invention, in step (1), the CH3NH3PbX3CH in perovskite precursor solution3NH3PbX3The concentration of the perovskite is 0.5-2 mol/L. Thus, large-size, high-crystalline-quality single-crystal perovskites can be grown directly on a given substrate.
In some embodiments of the invention, in step (1), the CH3NH3X and the PbX2The molar ratio of (0.8-1.2): 1. this can improve the raw material utilization rate.
In some embodiments of the invention, in step (1), the organic solvent comprises at least one of γ -GBA, DMF and DMSO. Thus, large-size, high-crystalline-quality single-crystal perovskites can be grown directly on a given substrate.
In some embodiments of the invention, in step (2), the gas phase diffusion is achieved by: the CH soaked with the substrate3NH3PbX3The perovskite precursor solution is placed in a first container, the anti-solvent is placed in a second container, the first container is communicated with the second container through a pipeline, and the anti-solvent is used for treating the CH3NH3PbX3The perovskite precursor solution is subjected to gas phase diffusion through the pipeline, and the pipeline is provided with a valve through which the gas phase diffusion rate is controlled. Thereby, can be atThe single crystal perovskite with large size and high crystallization quality is directly grown on a given substrate.
In some embodiments of the invention, the CH is pretreated with a filter having a pore size of not more than 1 μm before step (2)3NH3PbX3And filtering the perovskite precursor solution.
In some embodiments of the present invention, the substrate is previously patterned by using a photolithography technique before performing the step (2). Therefore, patterning of the perovskite can be effectively avoided, and the device preparation process is simplified.
In some embodiments of the invention, in step (2), the anti-solvent comprises at least one of dichloromethane, chlorobenzene, anhydrous acetonitrile and diethyl ether. Thus, large-size, high-crystalline-quality single-crystal perovskites can be grown directly on a given substrate.
In some embodiments of the invention, in step (2), the substrate comprises at least one of a germanium sheet, a silicon sheet, a quartz sheet, a chip of a pre-fabricated circuit, a TFT backplane, and an FTO.
In some embodiments of the invention, in step (2), the CH3NH3PbX3The volume ratio of the perovskite precursor solution to the anti-solvent is (0.5-2): 1. thus, large-size, high-crystalline-quality single-crystal perovskites can be grown directly on a given substrate.
In some embodiments of the present invention, in the step (2), the temperature of the gas phase diffusion is 5 to 35 ℃. Thus, large-size, high-crystalline-quality single-crystal perovskites can be grown directly on a given substrate.
In some embodiments of the invention, in step (2), the substrate is fully immersed in or partially immersed in the CH3NH3PbX3Perovskite precursor solution.
In a second aspect of the invention, a single crystal perovskite component is presented. According to an embodiment of the invention, the single crystal perovskite component comprises a substrate and a single crystal CH3NH3PbX3Perovskite, and single crystal of CH3NH3PbX3The perovskite is directly integrated on the substrate using the method described above. Thereby, the substrate is contacted with the large-sized, high-crystalline-quality single crystal CH3NH3PbX3The perovskite is combined, so that the complementary advantages of different materials can be realized, and the interface characteristics of the perovskite can be optimized, so that a wide-spectrum and high-speed photoelectric device can be constructed.
In a third aspect of the invention, an optoelectronic device is presented. According to an embodiment of the invention, the optoelectronic device has a single crystal perovskite component as described above. Thus, the optoelectronic device has the advantages of a broad spectrum and high speed.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of integrating a single crystal perovskite directly on a substrate according to one embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a device for direct integration of single crystal perovskites on a substrate according to one embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a device for directly integrating single crystal perovskites on a substrate according to yet another embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a single crystal perovskite component according to one embodiment of the invention;
FIG. 5 is an electron micrograph of a single crystal perovskite component produced in example 1;
FIG. 6 is a TEM image of a single crystal perovskite component produced in example 1 after thinning of the silicon and perovskite heterojunction interface by means of a focused ion beam;
FIG. 7 is an XRD pattern of a single crystal perovskite in a single crystal perovskite assembly produced in example 1;
FIG. 8 is a sheet of example 2 integrated directly on quartzCrystal CH3NH3Pb(ClxI1-x)3(X ≈ 0.7) optical photographs of perovskite;
FIG. 9 shows a single crystal CH in the assembly of example 23NH3Pb(ClxI1-x)3(X ≈ 0.7) EDS spectra of perovskite;
FIG. 10 is perovskite CH in comparative example3NH3PbBr3Micrographs of the films.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In a first aspect of the invention, the invention proposes a method of integrating a single crystal perovskite directly on a substrate. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: will CH3NH3X、PbX2Mixing with organic solvent
In this step, CH is added with stirring (e.g., magnetic stirring)3NH3X、PbX2Mixed with an organic solvent, CH3NH3X and PbX2Reaction to form CH3NH3PbX3Perovskite, i.e. to obtain CH3NH3PbX3A perovskite precursor solution. It should be noted that those skilled in the art can apply the CH to the channel according to actual needs3NH3X and PbX2Is selected, e.g. CH3NH3X comprises CH3NH3Cl、CH3NH3Br and CH3NH3At least one of I; PbX2Comprising PbCl2、PbBr2And PbI2At least one of (a).
Further, the above CH3NH3PbX3CH in perovskite precursor solution3NH3PbX3The concentration of the perovskite is 0.5-2 mol/L. The inventors found that if CH3NH3PbX3The concentration of the perovskite is too high, and the precipitation rate of crystals is too high to cause precipitation of a large number of seed crystals, so that the growth size of the perovskite is reduced, and the crystal quality is influenced; and if CH3NH3PbX3The concentration of perovskite is too low, the crystal lacks sufficient growth power, and precipitation of crystal or growth of large-size crystal is difficult to achieve even if the anti-solvent is fully diffused into the precursor solution. Thus, the CH of the present application is adopted3NH3PbX3The concentration of perovskite is favorable for directly growing large-size and high-crystallization-quality single crystal CH on the substrate3NH3PbX3Perovskite.
Further, the above CH3NH3X and PbX2The molar ratio of (0.8-1.2): 1. the inventors found that if CH3NH3X and PbX2Is too small, the growing single crystal perovskite will have rich PbX2The miscellaneous phase of (a); and if CH3NH3X and PbX2Too large a molar ratio of (A) and the grown single crystal perovskite may have a CH-rich content3NH3A hetero phase of X. Thus, the molar ratio of the present application can be used to avoid the presence of PbX-rich single crystal perovskites grown2Hetero-phase or rich in CH of3NH3A hetero phase of X.
It should be noted that the specific type of the organic solvent is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the organic solvent includes at least one of γ -GBA, DMF and DMSO. The inventors found that CH3NH3PbCl3，CH3NH3PbBr3，CH3NH3PbI3The maximum synthetic yield can be obtained by using DMSO, DMF and gamma-GBA as organic solvents respectively.
S200: placing the substrate in CH3NH3PbX3In a perovskite precursor solution and using an anti-solvent for CH in a closed system3NH3PbX3Vapor phase expansion of perovskite precursor solutionAnd (6) dispersing.
In this step, by placing the substrate on CH3NH3PbX3In a perovskite precursor solution and using an anti-solvent for CH in a closed system3NH3PbX3The perovskite precursor solution is subjected to gas phase diffusion, the anti-solvent can firstly diffuse to the surface of the precursor solution to cause the reduction of the solubility of the perovskite, and the crystal is firstly in advance of CH3NH3PbX3Crystal seeds are precipitated from the surface of the perovskite precursor solution and fall to the surface of the substrate under the action of self gravity. As the anti-solvent diffusion continues, the solubility of the perovskite continues to decrease providing sufficient kinetics for seed growth. The single crystal perovskite grown by the optimized anti-solvent method has an atomically flat surface, the distance between the single crystal perovskite and the substrate reaches the Van der Waals distance, Van der Waals interaction is fully activated, and finally, the single crystal CH with large size and high crystallization quality is directly grown on the substrate3NH3PbX3Perovskite.
It should be noted that, in this step, a person skilled in the art may also place a seed crystal directly on the substrate for growth. In addition, the specific manner of the above-mentioned gas phase diffusion is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, referring to fig. 2, and can be implemented in the following manner: the substrate 11 cleaned in advance is dried and then placed in a container containing the above CH3NH3PbX3An open container 12 for the perovskite precursor solution, and placing the open container 12 in a closed container 13 containing an anti-solvent, the level of the anti-solvent in the closed container 13 being below the opening of the open container 12, such that the anti-solvent can be applied to the CH in the open container 123NH3PbX3The perovskite precursor solution is subjected to gas phase diffusion, the gas phase diffusion rate can be controlled by controlling the opening size of the opening container 12, and finally the single crystal CH is directly integrated on the substrate 113NH3PbX3A perovskite 14. Preferably, with reference to fig. 3, the gas phase diffusion process described above is achieved in the following manner: the substrate 11 is washed in advance and dried, and then CH impregnated with the substrate 113NH3PbX3The perovskite precursor solution is placed in a first container 21, the anti-solvent is placed in a second container 22, the first container 21 is communicated with the second container 22 through a pipeline 23, the pipeline 23 is provided with a valve 24, and after the valve 24 is opened, the anti-solvent in the second container 22 is opposite to CH in the first container 213NH3PbX3The perovskite precursor solution is subjected to gas phase diffusion through a pipeline 23, the gas phase diffusion rate can be controlled through a valve 24, and finally the single crystal CH is directly integrated on the substrate 113NH3PbX3A perovskite 14. The inventor finds that the mode of pipeline communication is more beneficial to large-scale production of enterprises. Specifically, in the above vapor diffusion process, the substrate may be completely immersed in or partially immersed in CH3NH3PbX3Soaking single crystal perovskite in CH in perovskite precursor solution3NH3PbX3And growing the substrate surface in the perovskite precursor solution.
Further, before performing step S200, the CH is preliminarily treated with a filter having a pore size of not more than 1 μm3NH3PbX3And filtering the perovskite precursor solution. The inventors have found that unfiltered precursor solutions contain large-sized seed crystals, which makes it easy to form competitive growth during crystal growth, and makes it difficult to synthesize large-sized single crystals.
Further, before performing step S200, the substrate is subjected to patterning processing using a photolithography technique in advance. The inventor finds that the single crystal organic-inorganic hybrid perovskite has great difficulty in patterning, for example, the structure of the single crystal perovskite is easy to damage in the patterning process, and the like, and the patterning of the perovskite can be effectively avoided and the device manufacturing process can be simplified by patterning the substrate by using the photolithography technology before the single crystal perovskite is directly integrated on the substrate. Specifically, the patterning process is implemented as follows: coating a layer of photoresist outside the part to be patterned on the substrate, patterning the substrate by utilizing a photoetching technology, etching holes in the area which is not covered by the photoresist by using a dry method, and removing the photoresist by using acetone to finish patterning treatment. It should be noted that the above-mentioned photolithography technique is a conventional technique in the art, and is not described herein again, and meanwhile, a person skilled in the art can select a specific shape and depth of the etched hole according to actual needs.
It should be noted that the specific types of the above-mentioned antisolvent and substrate are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the antisolvent includes at least one of dichloromethane, chlorobenzene, anhydrous acetonitrile, and diethyl ether; the substrate comprises at least one of a germanium sheet, a silicon wafer, a quartz sheet, a chip of a prefabricated circuit and an FTO (fiber to the optical fiber), and specifically, the chip of the prefabricated circuit can be a TFT (thin film transistor) backboard.
Further, the above CH3NH3PbX3The volume ratio of the perovskite precursor solution to the anti-solvent is (0.5-2): 1. the inventors have found that if the volume ratio is too small, rapid supersaturation of the perovskite solution may result, not only in wastage of anti-solvent, but also in less susceptibility to nucleation on the substrate. If the volume ratio of the two is too large, the antisolvent diffusion is difficult to continue, and the large-size growth of the crystal is limited. Therefore, the volume ratio of the method is favorable for directly growing large-size and high-crystallization-quality single crystal CH on the substrate3NH3PbX3Perovskite, while avoiding the waste of anti-solvent.
Further, the temperature of the gas phase diffusion is 5 to 35 ℃. The inventors found that if the temperature of vapor phase diffusion is too low, the anti-solvent is difficult to diffuse into the perovskite solution, and crystal growth is difficult to occur. If the temperature of the gas phase diffusion is too high, the anti-solvent is diffused too fast, so that the crystal growth is irregular and difficult to integrate directly on the substrate. Therefore, the adoption of the gas phase diffusion temperature of the method is beneficial to directly growing the single crystal CH with large size and high crystallization quality on the substrate3NH3PbX3Perovskite.
The inventors have found that by including CH3NH3Cl、CH3NH3Br and CH3NH3CH of at least one of I3NH3X, comprising PbCl2、PbBr2And PbI2PbX of at least one of2Mixing with organic solvents, CH3NH3X and PbX2Reaction to form CH3NH3PbX3Perovskite, i.e. to obtain CH3NH3PbX3A perovskite precursor solution; the substrate is then placed in CH3NH3PbX3In a perovskite precursor solution and using an anti-solvent for CH in a closed system3NH3PbX3And carrying out gas phase diffusion on the perovskite precursor solution. Since the anti-solvent will diffuse first to the surface of the precursor solution causing the solubility of the perovskite to decrease, the crystals will be first in CH3NH3PbX3Crystal seeds are precipitated from the surface of the perovskite precursor solution and fall to the surface of the substrate under the action of self gravity. As the anti-solvent diffusion continues, the solubility of the perovskite continues to decrease providing sufficient kinetics for seed growth. The single crystal perovskite grown by the optimized anti-solvent method has an atomically flat surface, the distance between the single crystal perovskite and the substrate reaches the Van der Waals distance, Van der Waals interaction is fully activated, and finally, the single crystal CH with large size and high crystallization quality is directly grown on the substrate3NH3PbX3Perovskite. Single crystal CH3NH3PbX3The direct integration of perovskite on the substrate not only can realize the advantage complementation between different materials, but also can optimize the interface characteristics of perovskite so as to construct a wide-spectrum and high-speed photoelectric device.
In a second aspect of the invention, a single crystal perovskite component is presented. According to an embodiment of the invention, referring to fig. 4, the single crystal perovskite component comprises a substrate 101 and a single crystal CH3NH3PbX3Perovskite 102, and single crystal CH3NH3PbX3The perovskite 102 is integrated directly on the substrate 101 using the methods described above. Thereby, the substrate is contacted with the large-sized, high-crystalline-quality single crystal CH3NH3PbX3The perovskite is combined, so that the complementary advantages of different materials can be realized, and the interface characteristics of the perovskite can be optimized, so that a wide-spectrum and high-speed photoelectric device can be constructed. Need to make sure thatIt is noted that the features and advantages described above for the method of integrating a single crystal perovskite directly on a substrate and the use thereof apply equally to the single crystal perovskite component and will not be described in further detail herein.
In a third aspect of the invention, an optoelectronic device is presented. According to an embodiment of the invention, the optoelectronic device has a single crystal perovskite component as described above. Thus, the optoelectronic device has the advantages of a broad spectrum and high speed. It should be noted that the features and advantages described above for the single crystal perovskite component apply equally to the optoelectronic device and are not described in further detail here.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Step 1: the same molar amount of CH3NH3Br and PbBr2Dissolving in DMF organic solvent, magnetically stirring at room temperature for 24 hr to ensure CH3NH3Br and PbBr2Fully dissolve, react to obtain 2.2mL CH3NH3PbBr3Perovskite precursor solution, CH in solution3NH3PbBr3The concentration of perovskite was controlled at 1.2mol/L and the resulting clear transparent solution was filtered using a 0.45 μm pore size syringe filter and transferred to the first vessel (glass vial).
Step 2: patterning on the planar silicon by utilizing a photoetching technology, etching a square hole with the depth of 40 mu m in a region which is not covered by the photoresist by using a dry method, and then removing the photoresist by using acetone.
And step 3: obliquely placing a silicon wafer with holes on the substrate containing the CH3NH3PbBr3In a first container of perovskite solution, in a second container (glass bottle)2mL of dichloromethane is dripped into the perovskite solution as an anti-solvent, the first container and the second container are communicated only through a pipeline, a valve is arranged on the pipeline, then the whole device is placed in a room temperature environment, and the valve is opened until the dichloromethane is completely diffused into the perovskite solution through the pipeline.
The single crystal perovskite directly grown in the silicon pores is shown in fig. 5, the perovskite completely grows over the entire pores, has a lateral dimension of about 160 μm, and is tightly bonded to the silicon substrate. The interface of the silicon and perovskite heterojunction is thinned by using focused ion beams, and then TEM characterization is carried out, and the test result is shown in FIG. 6. As can be seen from the figure, the lattice fringes of silicon and perovskite single crystals have good periodicity, and the amorphous layer of the heterojunction interface is thin. The XRD test results of the single crystal perovskite are shown in fig. 7, and the upper surface of the crystal is a (00l) crystal plane, confirming that the crystal prepared by the method has good orientation growth and excellent single crystal characteristics.
Example 2
Step 1: the same molar amount of CH3NH3I and PbCl2Dissolving in organic solvent of gamma-GBA and DMSO (volume ratio of 1:1), and magnetically stirring at room temperature for 24 hr to ensure CH3NH3I and PbCl2Fully dissolved and reacted to obtain 2mL CH3NH3PbICl2The concentration of perovskite in the perovskite precursor solution is controlled to be 1mol/L, and the obtained transparent clear solution is filtered by using a 0.45 mu m pore size syringe filter and transferred into a first container (glass bottle).
Step 2: and cleaning the quartz plate by using acetone, alcohol and deionized water in sequence, blow-drying surface moisture by using a nitrogen gun, and drying the quartz plate in a blast drying oven.
And step 3: placing the cleaned and dried quartz piece into a first container filled with the perovskite solution in an inclined mode, dripping 3mL of dichloromethane serving as an anti-solvent of the perovskite into a second container (a glass bottle), communicating the first container and the second container only through a pipeline, arranging a valve on the pipeline, placing the whole device into a room-temperature environment, and opening the valve until the dichloromethane is completely diffused into the perovskite solution through the pipeline.
Single crystal perovskite CH directly grown on quartz plate3NH3Pb(ClxI1-x)3(X0.7) As shown in FIG. 8, the perovskite is more regular and transparent, has a lateral dimension of about 2.2mm, and is tightly bonded to the quartz substrate. EDS (electron-dispersive spectroscopy) testing of FIG. 9 shows that the crystal contains I element and Cl element, and the I element and the Cl element are matched with elements in the precursor.
Comparative example
Step 1: the same molar amount of CH3NH3Br and PbBr2Dissolving in DMF organic solvent, magnetically stirring at room temperature for 24 hr to ensure CH3NH3Br and PbBr2Fully dissolved and reacted to obtain 2mL CH3NH3PbBr3Perovskite precursor solution, CH in solution3NH3PbBr3Controlling the concentration of the perovskite at 1.8mol/L, and filtering the obtained transparent clear solution by using a needle filter with the pore size of 0.45 mu m;
step 2: the solution obtained by filtration was spin-coated on a silicon wafer, and after drying, the substrate-bonded polycrystalline perovskite was obtained as shown in fig. 10. The inventors found that single crystal perovskite has fewer grain boundaries and defect states than polycrystalline perovskite, and the carrier transport characteristics are more excellent.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of directly integrating a single crystal perovskite on a substrate, comprising:
(1) will CH3NH3X、PbX2Mixing with organic solvent to obtain CH3NH3PbX3A perovskite precursor solution;
(2) placing a substrate on the CH3NH3PbX3In a perovskite precursor solution and reacting said CH with an anti-solvent in a closed system3NH3PbX3Subjecting the perovskite precursor solution to vapor phase diffusion to cause said CH3NH3PbX3Direct integration of single crystal CH by perovskite on said substrate3NH3PbX3A perovskite of the type having a high degree of thermal expansion,
wherein, in the step (1), the CH3NH3X comprises CH3NH3Cl、CH3NH3Br and CH3NH3At least one of I, the PbX2Comprising PbCl2、PbBr2And PbI2At least one of (a).
2. The method of claim 1, wherein in step (1), the CH3NH3PbX3CH in perovskite precursor solution3NH3PbX3The concentration of the perovskite is 0.5-2 mol/L.
3. The method of claim 1, wherein in step (1), the CH3NH3X and the PbX2The molar ratio of (0.8-1.2): 1;
optionally, in step (1), the organic solvent comprises at least one of γ -GBA, DMF and DMSO.
4. The method according to claim 1, wherein in step (2), the gas phase diffusion is achieved by: the CH soaked with the substrate3NH3PbX3The perovskite precursor solution is placed in a first container, the anti-solvent is placed in a second container, the first container is communicated with the second container through a pipeline, and the anti-solvent is used for treating the CH3NH3PbX3The perovskite precursor solution is subjected to gas phase diffusion through the pipeline, and the pipeline is provided with a valve through which the gas phase diffusion rate is controlled.
5. The method according to claim 1 or 4, wherein the CH is preliminarily treated with a filter having a pore size of not more than 1 μm before the step (2)3NH3PbX3Filtering the perovskite precursor solution;
optionally, before performing step (2), patterning the substrate by using a photolithography technique in advance;
optionally, in step (2), the anti-solvent comprises at least one of dichloromethane, chlorobenzene, anhydrous acetonitrile and diethyl ether;
optionally, in the step (2), the substrate includes at least one of a germanium sheet, a silicon sheet, a quartz sheet, a chip of a prefabricated circuit, and an FTO.
6. The method of claim 1 or 4, wherein in step (2), the CH3NH3PbX3The volume ratio of the perovskite precursor solution to the anti-solvent is (0.5-2): 1.
7. the method according to claim 1 or 4, wherein in the step (2), the temperature of the gas phase diffusion is 5 to 35 ℃.
8. According to claim 1The method of claim 4, wherein in step (2), the substrate is completely or partially immersed in the CH3NH3PbX3Perovskite precursor solution.
9. A single crystal perovskite component comprising a substrate and a single crystal CH3NH3PbX3Perovskite, and said single crystal CH3NH3PbX3The perovskite being directly integrated on the substrate using the method of any one of claims 1 to 8.
10. An optoelectronic device comprising the single crystal perovskite component of claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034989A (en) * | 2017-12-04 | 2018-05-15 | 山东大学 | The method and device of controllable anti-solvent diffusion method for growing large scale methylamine bromine leading crystal |
| US20180248142A1 (en) * | 2015-08-24 | 2018-08-30 | King Abdullah University Of Science And Technology | Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof |
| CN108624953A (en) * | 2018-06-12 | 2018-10-09 | 苏州大学 | A kind of preparation method of ultra-thin perovskite monocrystal material |
| CN109087849A (en) * | 2018-08-06 | 2018-12-25 | 合肥工业大学 | A kind of method of the located growth perovskite thin film of graphene auxiliary |
-
2021
- 2021-10-29 CN CN202111268564.XA patent/CN114016133A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180248142A1 (en) * | 2015-08-24 | 2018-08-30 | King Abdullah University Of Science And Technology | Solar cells, structures including organometallic halide perovskite monocrystalline films, and methods of preparation thereof |
| CN108034989A (en) * | 2017-12-04 | 2018-05-15 | 山东大学 | The method and device of controllable anti-solvent diffusion method for growing large scale methylamine bromine leading crystal |
| CN108624953A (en) * | 2018-06-12 | 2018-10-09 | 苏州大学 | A kind of preparation method of ultra-thin perovskite monocrystal material |
| CN109087849A (en) * | 2018-08-06 | 2018-12-25 | 合肥工业大学 | A kind of method of the located growth perovskite thin film of graphene auxiliary |
Non-Patent Citations (2)
| Title |
|---|
| MURGULOV,V等: "Growth and Characterization of Radiation Sensors Based on Single Crystals of Hybrid Metal-Organic Methylammonium Lead Bromide and Iodide Perovskite", 《《CRYSTAL RESEARCH AND TECHNOLOGY》 * |
| ZHANG,LL等: "Exploring Anisotropy on Oriented Wafers of MAPbBr(3) Crystals Grown by Controlled Antisolvent Diffusion", 《CRYSTAL GROWTH & DESIGN》 * |
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