CN112746309A - Preparation method and application of large-size perovskite single crystal with continuously adjustable cesium content - Google Patents
Preparation method and application of large-size perovskite single crystal with continuously adjustable cesium content Download PDFInfo
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Abstract
The invention relates to the field of preparation and crystal growth of organic-inorganic hybrid mixed halogen perovskite materials, in particular to a preparation method and application of a perovskite single crystal with large size and continuously adjustable cesium content. The method comprises the following steps: separating out single crystals in a solvent by utilizing the inverse temperature solubility characteristic of the ternary cation and binary anion perovskite single crystals; the perovskite single crystal of the ternary cation and the binary anion is (FA)1‑x‑yMAxCsy)Pb(I1‑zBrz)3. The perovskite single crystal obtained by the method can effectively regulate and control the content of Cs in the single crystal; and the stability of the crystal is improved based on different Cs doping contents, and the finally obtained single crystal is a 4mm large-size single crystal. The grown large-size perovskite single crystal has excellent stability and excellent performanceThe photoelectric properties of (1).
Description
Technical Field
The invention relates to the field of preparation and crystal growth of organic-inorganic hybrid halogen perovskite materials, in particular to a preparation method and application of a perovskite single crystal with large size and continuously adjustable cesium content, and more particularly relates to a ternary mixed cation and mixed anion (FA) with continuously adjustable cesium content and ultrahigh moisture-proof stability1-x-yMAxCsy)Pb(I1-zBrz)3A preparation method and application of perovskite single crystal.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The organic-inorganic hybrid perovskite has the advantages of direct band gap, good carrier migration performance, high light absorption coefficient, high photoelectric conversion efficiency, adjustable photoelectric property and the like, and gradually shows great significance in the fields of solar cells, photoelectric detection and the like. However, the poor stability of organic-inorganic hybrid perovskites under heat, humidity, light, etc. conditions has severely hindered their commercial application. In recent years, based on the research of perovskite thin films, ternary mixed cations and mixed anions have high stability, and simultaneously can inhibit the migration of ions and the recombination of carriers, and maintain the photoelectric properties of perovskite materials, so (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Perovskites are widely studied. However, studies on the stability and photoelectric properties of multi-component perovskite materials are still being conducted on polycrystalline thin films, which have inherent causes such as grain boundaries, composition segregation, and grain size, and extrinsic causes such as film formation temperature, spin coating process, and atmosphere. Based on the research of perovskite single crystal, the interference of grain boundary and component segregation in the preparation process of the film can be better avoided.
At present, for growth (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Of a single crystal of (4), a suitable crystalIn particular, methods and techniques for bulk growth are important. The temperature rising method is growth (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal is the most suitable method, however, the inventors have found that the Cs content is grown by the temperature raising method>7%, i.e. y>Mixed cation crystals of 0.07 are very difficult. Especially when the cesium content exceeds 7%, δ -CsPbI grows more easily from the solution3Hindrance (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Obtaining the perovskite single crystal.
Disclosure of Invention
In order to solve the problem that the high Cs content exists in the prior art>7%) of (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The invention provides a preparation method and application of a perovskite single crystal with large size and continuously adjustable cesium content, and solves the problems that the perovskite single crystal is high in difficulty and the Cs content is difficult to continuously change. Obtained Using the method of the invention (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal can effectively regulate and control the content of Cs in the single crystal; and the stability of the crystal is improved based on different Cs doping contents, and the finally obtained single crystal is a 4mm large-size single crystal. In addition, large size of growth (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal has excellent high moisture-proof stability and excellent photoelectric property, can be further used as a light absorption material of a perovskite solar cell to improve photoelectric conversion efficiency, and has extremely important significance for the development of organic-inorganic hybrid perovskite materials and the application of the organic-inorganic hybrid perovskite materials in photovoltaic devices.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a preparation method of a perovskite single crystal with large size and continuously adjustable cesium content is provided, which comprises the following steps: separating out single crystals in a solvent by utilizing the inverse temperature solubility characteristic of the ternary cation and binary anion perovskite single crystals; the perovskite single crystal of the ternary cation and the binary anion is (FA)1-x-yMAxCsy)Pb(I1-zBrz)3(ii) a x is the doping amount of MA and is any value from 0 to 1, y is the doping content of Cs and is any value from 0 to 1, and z is the doping content of Br and is any value from 0 to 1.
In a second aspect of the invention, the perovskite single crystal with the continuously adjustable large size and cesium content is prepared by the preparation method of the perovskite single crystal with the continuously adjustable large size and cesium content.
In a third aspect of the invention, the application of a large-size perovskite single crystal with continuously adjustable cesium content as a photoelectric material is provided, and the photoelectric material is further a solar cell material.
One or more embodiments of the present invention have the following advantageous effects:
(1) different from the prior art (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The invention provides perovskite powder or film, and provides a method for growing large-size ternary cation and binary anion (FA) with continuously adjustable cesium content1-x-yMAxCsy)Pb(I1- zBrz)3Compared with powder, thin film and quantum dot, the perovskite single crystal material is purer and less influenced by environment, and has the advantages of lower defect state density, higher carrier mobility, longer carrier recombination life and the like which are proved by common single crystal materials. In addition, the single crystal can ensure that doping elements MA, Cs and Br enter perovskite single crystal lattices, and the problems that the grain boundary of quantum dots, powder or films is uncontrollable, the grain boundary of MA, Cs and Br exists and the like are solved.
(2) The single crystal growth method adopts a unique growth system taking crystals as raw materials, and can be (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal growth provides a higher-concentration and purer solution system, and can effectively prevent other substances in the solution system from being separated out; and in the growth system, spontaneous crystallization can be realized without the environment higher than 120 ℃.
(3) The raw materials required by the single crystal growth method are more environment-friendly, the growth temperature is lower, an oil bath condition higher than 120 ℃ is not needed, a strong acid environment is not needed, the solution is easy to prepare, and the growth condition is easy to realize.
(4) Large size of growth (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal has excellent high moisture-proof stability and excellent photoelectric property, can be used as a light absorption material of a perovskite solar cell to improve the photoelectric conversion efficiency,
(5) the single crystal growth method is simple and easy to control, has low requirements on equipment and reaction conditions, has a short period, and is favorable for reducing cost and realizing large-scale industrialization. Compared with the method, the method of the invention is environment-friendly, avoids the corrosion of strong acid to equipment and realizes the growth of large-size single crystals.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows (FA) of example 1 of the present invention0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3A single crystal photo;
FIG. 2 shows (FA) of example 2 of the present invention0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A single crystal photo;
FIG. 3 shows (FA) of example 3 of the present invention0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A single crystal photo;
FIG. 4 shows examples 1 to 3 (FA) of the present invention1-x-yMAxCsy)Pb(I1-zBrz)3XRD pattern of single crystal; wherein, XRD adopts D/Max2500PC X-ray diffractometer to analyze the phase of the sample, Cu Ka radiation (lambda is 0.154056nm), and the measuring range is 10-6%0°。
Wherein curve A is (FA) of example 10.9MA0.05Cs0.05)Pb(I0.9Br0.1)3A single crystal XRD pattern; curve B is (FA) of example 20.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A single crystal XRD pattern; curve C is (FA) of example 30.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A single crystal XRD pattern;
FIG. 5 shows (FA) obtained in example 1 of the present invention0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3Performing nuclear magnetic resonance hydrogen spectrum analysis on the single crystal;
FIG. 6 shows (FA) in examples 1 to 3 of the present invention1-x-yMAxCsy)Pb(I1-zBrz)3A UV-visible absorption profile of the single crystal; the ultraviolet-visible absorption spectrum adopts an Shimadzu UV-2550 ultraviolet-visible spectrophotometer, a small integrating sphere accessory is adopted, barium sulfate powder is used as a reference, a test sample is powder particles, and the scanning wavelength range is 600-900 nm.
Wherein curve A is (FA) of example 10.9MA0.05Cs0.05)Pb(I0.9Br0.1)3A UV-visible absorption profile of the single crystal; curve B is (FA) of example 20.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A UV-visible absorption profile of the single crystal; curve C is (FA) of example 30.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A UV-visible absorption profile of the single crystal;
FIG. 7 shows (FA) in examples 1 to 3 of the present invention1-x-yMAxCsy)Pb(I1-zBrz)3Photoluminescence spectra of single crystals; wherein, a HORIBA Fluorolog-3 fluorescence spectrometer with 495nm as an excitation light source tests the emission spectrum of the sample;
wherein curve A is (FA) of example 10.9MA0.05Cs0.05)Pb(I0.9Br0.1)3(Single Crystal)A photoluminescence spectrum of (a); curve B is (FA) of example 20.85MA0.05Cs0.1)Pb(I0.85Br0.15)3Photoluminescence spectra of single crystals; curve C is (FA) of example 30.85MA0.05Cs0.1)Pb(I0.85Br0.15)3Photoluminescence spectra of single crystals;
FIG. 8 shows (FA) in example 1 of the present invention0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3A crystal color change diagram of the single crystal at 75% humidity;
wherein, FAPBI3The initial color of the single crystal is black, and the color changes into yellow after 2 days, so that phase change occurs; the MAPbI3 crystal is black in initial color, and is changed into yellow after 2 days, so that decomposition occurs; (FA0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3The initial color of the single crystal is black, the single crystal still keeps black after 20 days, and decomposition and phase transition do not occur.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
To grow (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Particularly, suitable crystal growth methods and techniques are important. The temperature rising method is growth (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal is the most suitable method, however, the inventors have found that the Cs content is grown by the temperature raising method>7%, i.e. y>Mixed cation crystals of 0.07 are very difficult. Especially when the cesium content exceeds 7%, δ -CsPbI grows more easily from the solution3Hindrance (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Obtaining the perovskite single crystal. In order to solve the problem in the future, the invention provides a preparation method and application of a perovskite single crystal with large size and continuously adjustable cesium content. The single crystal grown by the method can be successfully doped with elements Cs, MA and Br to enter FAPBI3Can effectively regulate and control the Cs doping amount, realizes the regulation and control of the Cs doping concentration in the single crystal, and can improve (FA) by using the method of the invention1-x- yMAxCsy)Pb(I1-zBrz)3The doping amount of Cs in the crystal successfully grows to 10 percent of Cs (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The single crystal of (2) has better stability.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a preparation method of a large-size perovskite single crystal with continuously adjustable cesium content is provided, and comprises the following steps: separating out single crystals in a solvent by utilizing the inverse temperature solubility characteristic of the ternary cation and binary anion perovskite single crystals; the perovskite single crystal of the ternary cation and the binary anion is (FA)1-x-yMAxCsy)Pb(I1-zBrz)3(ii) a x is the doping amount of MA and is any value from 0 to 1, y is the doping content of Cs and is any value from 0 to 1, and z is the doping content of Br and is any value from 0 to 1.
In one or more embodiments of the present invention, the inverse temperature solubility refers to a growth mode in which a multi-component raw material is dissolved at a low temperature and then slowly increased to a high temperature to obtain a crystal;
the low temperature is 40-60 ℃, and is further 60 ℃;
the high temperature is 80 to 120 ℃, further 90 to 120 ℃, and further preferably 90 ℃.
In one or more embodiments of the present invention, the solvent is selected from one or more of gamma-butyrolactone (GBL), Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO).
In one or more embodiments of the invention, x is selected from any number from 0 to 0.15;
further, y is any value of 0-0.1;
further, z is any value selected from 0 to 0.2.
The FA is formamidine and MA is methylamine.
Further, by controlling the incorporation amount of Cs, large size (FA) with specific x, y and z values can be grown1-x-yMAxCsy)Pb(I1-zBrz)3A perovskite single crystal. Such as: (FA0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3、(FA0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3、(FA0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3And the like.
In one or more embodiments of the invention, the (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The size of the perovskite single crystal is millimeter grade, further is 1-10 mm, and further is 5 mm;
further, said (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The absorption spectrum range of the perovskite single crystal is 810-840 nm.
In one or more embodiments of the invention, the cesium source is selected from CsPbBr3；
Further, the raw material is selected from FAI, MABr, CsBr, PbI2、PbBr2(ii) a Further, FAI: MABr: CsBr: PbI2:PbBr2The molar ratio is 17-20:0.5-1.5:0.5-1.5:17-20:1-3, preferably 18:1:1:18: 2;
further, the raw material is selected from FAI, MABr and PbI2、PbBr2、CsPbBr3；
Further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3In a growth system, FAPBI is selected as raw material3、CsPbBr3、MABr、PbBr2(ii) a Further, FAPBI3：CsPbBr3：MABr：PbBr2The molar ratio is 15-19:1.5-2.5:0.5-1.5:0.5-1.5, preferably 17:2:1: 1;
further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3In a growth system, FAPBI is selected as raw material3、CsPbBr3、MAPbBr3(ii) a Further, FAPBI3：CsPbBr3：MAPbBr3The molar ratio is 15-19:1.5-2.5:1.5-2.5, preferably 17:2: 2;
further, growth of high cesium content (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Perovskite single crystal, raw material is selected From (FA)1-x-yMAxCsy)Pb(I1-zBrz)3、CsPbBr3(ii) a Further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3：CsPbBr3The molar ratio is 15-20:0.5-1.5, preferably 18: 1.
The high cesium content means cesium mass fraction > 7%.
In one or more embodiments of the invention, the (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The sum of the raw material concentrations of the growth system is not more than 1.5mol/L, and preferably 1.0 mol/L.
In one or more embodiments of the invention, the method comprises: proportionally mixing and dissolving the raw materials in a solvent, stirring and dissolving at low temperature to obtain a precursor solution required by the growth of the single crystal, and heating to reach a saturated concentration to grow the ternary cations and the binary anions (FA) of the perovskite single crystal with large size and continuously adjustable cesium content1-x-yMAxCsy)Pb(I1-zBrz)3A perovskite single crystal;
further, after stirring and dissolving, dropwise adding hydriodic acid or hypophosphorous acid; still further, the hydriodic acid or hypophosphorous acid concentration is AAA;
further, the crystallization finishing temperature is 80-120 ℃, and further 90 ℃.
In a second aspect of the invention, the perovskite single crystal with the continuously adjustable large size and cesium content is prepared by the preparation method of the perovskite single crystal with the continuously adjustable large size and cesium content.
The invention provides large-size ternary cations and binary anions (FA) with continuously adjustable cesium content, which are grown by the method1-x-yMAxCsy)Pb(I1-zBrz)3A perovskite single crystal; the method uses low-cost FAI, MABr, CsBr and PbI2、PbBr2The material is solute raw material, common nontoxic GBL is used as solvent, and the growth is carried out in low temperature and strong acid-free environment through simpler and environment-friendly equipment and process. Perovskite (FA) grown by the method provided by the invention1-x-yMAxCsy)Pb(I1-zBrz)3The doping amount of Cs in the ternary cation and binary anion perovskite single crystal can be greatly improved, and the single crystal has a large size of about 5mm and is in a millimeter level.
In a third aspect of the invention, there is provided the use of a large-size, continuously tunable cesium content perovskite single crystal as a photovoltaic material, which is further a solar cell material.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
The invention provides a method for growing large-size ternary cations and binary anions (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The perovskite single crystal method, the single crystal grown by the method can be successfully doped with elements Cs, MA and Br to enter FAPbI3Can effectively regulate and control the Cs doping amount, realizes the regulation and control of the Cs doping concentration in the single crystal, and can improve (FA) by using the method of the invention1-x-yMAxCsy)Pb(I1-zBrz)3The doping amount of Cs in the crystal successfully grows to 10 percent of Cs (FA)1-x-yMAxCsy)Pb(I1- zBrz)3The single crystal of (2) has better stability.
The invention is not intended to be exhaustive of all single crystals, and in order to demonstrate the effectiveness of the invention, only four examples of proportional single crystal growth are shown in the following examples, all of which have FAPBI with cubic phase3And (5) structure.
The reagents used in example 1 below are all commercially available; lead formamidine iodide and lead cesium bromide used in example 2 were used as raw materials with the grown single crystal and the remaining reagents were commercially available; however, the growth of crystals with high cesium content (> 7%) using the method of example 3 must utilize the crystal grown in example 1 to grow efficiently.
Example 1
Formamidine iodide, methylamine bromide, cesium bromide, lead iodide and lead bromide are mixed and dissolved in GBL according to the molar ratio of 18:1:1:18:2 to obtain a mixed solution with the concentration of 1 mol/L. Stirring the solution at 60 deg.C, adding hypophosphorous acid or hydriodic acid to obtain mixed precursor solution, sealing, transferring into growth tank, heating to 90 deg.C to start crystal growth, and spontaneous crystallization to obtain large size (FA)0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3The perovskite single crystal has the size of about 5mm, the ultraviolet absorption edge is 842nm, and the optical band gap is 1.51 eV. The actual ratio of FA to MA was about 1:0.5 as measured by NMR, the Cs content was about 1.33747% according to ICP test, the Pb content was about 36.2142%, and the converted ratio of FA to MA to Cs was about 0.89:0.045: 0.058.
Example 2
Mixing and dissolving lead iodide formamidine, lead cesium bromide, methylamine bromide and lead bromide in a molar ratio of 17:2:1:1 in GBL to obtain a mixed solution with the concentration of 1 mol/L. The single crystal was grown according to the method of example 1 to finally obtain a large size (FA) having a cesium content of 10%0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A perovskite single crystal.
Example 3
The compound of example 1 (FA)0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3Single crystal with CsPbBr3The mixture was dissolved in GBL in a molar ratio of 18:1 to obtain a 1mol/L mixed solution. The single crystal was grown according to the method of example 1 to finally obtain a large size (FA) having a cesium content of 10%0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A perovskite single crystal.
Performance characterization
FIGS. 1 to 3 are pictorial views showing real photographs of perovskite single crystals prepared in examples 1 to 3, and FIG. 1 is (FA) of example 10.9MA0.05Cs0.05)Pb(I0.9Br0.1)3Single crystal, the color of the crystal is black; FIG. 2 is (FA) of example 20.85MA0.05Cs0.1)Pb(I0.85Br0.15)3Single crystal, the color of the crystal is black; FIG. 3 is (FA) of example 30.85MA0.05Cs0.1)Pb(I0.85Br0.15)3The crystal is black in color.
FIGS. 1 to 3 show that the perovskite single crystal prepared in examples 1 to 3 has a size of 2.5 to 4mm, and is a large-sized single crystal.
In order to observe the crystal form of the single crystal, XRD characterization was also performed on the perovskite single crystals prepared in examples 1-3, as shown in fig. 4. Example 1 (curve A) is standard (FA) compared to standard PDF card0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3A single crystal XRD pattern; example 2 (curve B) is standard (FA)0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3A single crystal XRD pattern; example 3 (curve C) is standard (FA)0.85MA0.05Cs0.1)Pb(I0.85Br0.15)3Single crystal XRD patterns, which illustrate the successful preparation of perovskite single crystals in examples 1-3.
To further determine the perovskite single crystal structure prepared in example 1, the product of example 1 was subjected to hydrogen nuclear magnetic resonance spectroscopy, as shown in fig. 5. The UV-Vis absorption profiles of the products of examples 1-3 were also examined, as shown in FIG. 6. The absorption spectrum range of the perovskite single crystal of the embodiment 1-3 is 810-840 nm.
Photoluminescence Spectroscopy (PL spectrum for short) refers to a process in which an electron transits from a valence band to a conduction band and leaves a hole in the valence band when a substance is excited by light; the electrons and holes reach the respective unoccupied lowest excited states (in the intrinsic semiconductor, i.e., the conduction band bottom and the valence band top) in the respective conduction band and valence band by relaxation, becoming quasi-equilibrium states; the electrons and holes in quasi-equilibrium state emit light through recombination to form a spectrogram of the intensity or energy distribution of light with different wavelengths. Photoluminescence spectroscopy represents a potential for the application of a material in the field of luminescence. FIG. 7 shows photoluminescence spectra of perovskite single crystals of examples 1 to 3. As can be seen from the graphs, the photoluminescence spectrum range of the perovskite single crystal of example 1-3 is 750 to 800nm, which shows that the perovskite single crystal prepared in example 1-3 has photoluminescence effect.
In addition, in order to further observe the stability of the perovskite single crystal prepared according to the present invention, (FA) of example 1 was tested0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3The crystal color of the single crystal at 75% humidity changes as shown in fig. 8. FAPBI3The initial color of the single crystal is black, and the color changes into yellow after 2 days, so that phase change occurs; the MAPbI3 crystal is black in initial color, and is changed into yellow after 2 days, so that decomposition occurs; (FA0.9MA0.05Cs0.05)Pb(I0.9Br0.1)3The initial color of the single crystal is black, the single crystal still keeps black after 20 days, and decomposition and phase transition do not occur. It is demonstrated that the perovskite single crystal prepared in this example has excellent high moisture resistance stability.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the perovskite single crystal with large size and continuously adjustable cesium content is characterized by comprising the following steps: separating out single crystals in a solvent by utilizing the inverse temperature solubility characteristic of the ternary cation and binary anion perovskite single crystals;
the perovskite single crystal of the ternary cation and the binary anion is (FA)1-x-yMAxCsy)Pb(I1-zBrz)3，
x is the doping amount of MA and is any value from 0 to 1, y is the doping content of Cs and is any value from 0 to 1, and z is the doping content of Br and is any value from 0 to 1.
2. The method for preparing a large-size, cesium-content continuously adjustable perovskite single crystal according to claim 1, wherein said inverse temperature solubility is a growth mode of obtaining a crystal by dissolving a multi-component raw material at a low temperature and slowly raising the temperature to a high temperature;
the low temperature is 40-60 ℃, and is further 60 ℃;
the high temperature is 80 to 120 ℃, further 90 to 120 ℃, and further preferably 90 ℃.
3. The method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 1, wherein said solvent is selected from one or more of γ -butyrolactone, dimethylformamide and dimethylsulfoxide.
4. The method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 1, wherein x is selected from any value of 0 to 0.15;
further, y is any value of 0-0.1;
further, z is any value of 0-0.2;
further, by controlling the incorporation amount of Cs, large size (FA) with specific x, y and z values can be grown1-x-yMAxCsy)Pb(I1- zBrz)3A perovskite single crystal.
5. Method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 1, characterized in that said (FA) is1-x-yMAxCsy)Pb(I1-zBrz)3The size of the perovskite single crystal is millimeter grade, further is 1-10 mm, and further is 5 mm;
further, said (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The absorption spectrum range of the perovskite single crystal is 810-840 nm.
6. The method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 1, wherein cesium source is selected from the group consisting of CsPbBr3；
Further, the raw material is selected from FAI, MABr, CsBr, PbI2、PbBr2(ii) a Further, FAI: MABr: CsBr: PbI2:PbBr2The molar ratio is 17-20:0.5-1.5:0.5-1.5:17-20:1-3, preferably 18:1:1:18: 2;
further, the raw material is selected from FAI, MABr and PbI2、PbBr2、CsPbBr3；
Further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3In a growth system, FAPBI is selected as raw material3、CsPbBr3、MABr、PbBr2(ii) a Further, FAPBI3：CsPbBr3：MABr：PbBr2The molar ratio is 15-19:1.5-2.5:0.5-1.5:0.5-1.5, preferably 17:2:1: 1;
further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3In the growth system, raw materials are selectedIs FAPBI3、CsPbBr3、MAPbBr3(ii) a Further, FAPBI3：CsPbBr3：MAPbBr3The molar ratio is 15-19:1.5-2.5:1.5-2.5, preferably 17:2: 2;
further, growth of high cesium content (FA)1-x-yMAxCsy)Pb(I1-zBrz)3Perovskite single crystal, raw material is selected From (FA)1-x- yMAxCsy)Pb(I1-zBrz)3、CsPbBr3(ii) a Further, (FA)1-x-yMAxCsy)Pb(I1-zBrz)3：CsPbBr3The molar ratio is 15-20:0.5-1.5, preferably 18: 1;
high cesium content means cesium content > 7%.
7. Method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 6, characterized in that said (FA)1-x-yMAxCsy)Pb(I1-zBrz)3The sum of the raw material concentrations of the growth system is not more than 1.5mol/L, and preferably 1.0 mol/L.
8. The method for preparing a large-size, cesium-content continuously tunable perovskite single crystal according to claim 1, characterized in that said method comprises: proportionally mixing and dissolving the raw materials in a solvent, stirring and dissolving at low temperature to obtain a precursor solution required by the growth of the single crystal, and heating to reach a saturated concentration to grow the ternary cations and the binary anions (FA) of the perovskite single crystal with large size and continuously adjustable cesium content1-x-yMAxCsy)Pb(I1-zBrz)3A perovskite single crystal;
further, after stirring and dissolving, dropwise adding hydriodic acid or hypophosphorous acid; still further, the hydriodic acid or hypophosphorous acid concentration is AAA;
further, the crystallization finishing temperature is 60-100 ℃, and further 90 ℃.
9. The large-size, cesium-content continuously tunable perovskite single crystal produced by the method for producing a large-size, cesium-content continuously tunable perovskite single crystal according to any one of claims 1 to 8.
10. Use of the large-size, cesium-content continuously tunable perovskite single crystal as claimed in claim 9 as a photovoltaic material, further a solar cell material.
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