TWI657172B - Method for synthesizing a perovskite single crystal - Google Patents

Abstract

A method for synthesizing a single crystal of perovskite, comprising: (i) preparing a precursor solution; (ii) preheating a space-constrained crystallizer to a first temperature and maintaining the first temperature; (iii) placing the precursor solution and a seed crystal Into the spatially confined crystallizer at a first temperature; (iv) heating the precursor solution in the spatially confined crystallizer to a second temperature; and (v) maintaining the second temperature to grow a perovskite single crystal.

Description

Synthetic method of perovskite single crystal

The invention relates to a method for synthesizing a single crystal of perovskite.

With the depletion of traditional fossil energy sources, solar energy as an environmentally friendly renewable energy source has become one of the most promising alternative energy sources. In recent years, the energy conversion efficiency of perovskite solar cells has exceeded 20%. At present, most of the perovskite solar cell elements are made in the form of polycrystalline thin films. Compared with polycrystalline perovskite thin films, single crystal perovskite materials have better lattice arrangement and lower defect density, so solar cells made of single crystal perovskite materials can obtain better stability and conversion. effectiveness. However, the perovskite single crystals produced in the prior art are all too thick to be applied to subsequent component processes. Therefore, how to effectively grow thin single-size perovskite crystals is very urgent and necessary.

In view of the problems faced by the prior art, the present invention provides a method for synthesizing perovskite single crystals for effectively synthesizing large-area layered perovskite single crystals with a thickness of micron order.

According to various embodiments of the present invention, a perovskite is provided. A method for synthesizing a single crystal includes: (i) preparing a precursor solution; (ii) preheating a space-constrained crystallizer to a first temperature and maintaining the first temperature; (iii) placing the precursor solution and a seed crystal in the first (Iv) heating the precursor solution in the spatially confined crystallizer to a second temperature; and (v) maintaining the second temperature to grow a perovskite single crystal.

According to some embodiments of the present invention, the seed crystal and the perovskite single crystal have a structure as shown in formula (1): ABX ₃ formula (1) where A is CH ₃ NH ₃ ⁺ , HC (NH ₂ ) ₂ ⁺ , CH ₃ (CH ₂ ) ₃ NH ₃ ⁺ or C ₆ H ₅ C ₂ H ₄ NH ₃ ⁺ , B is Pb ²⁺ , Ge ²⁺ , Sn ²⁺ , Cu ²⁺ or Ag ⁺ In ⁺ , X is Cl ^-, Br ^- or I ^-.

According to some embodiments of the present invention, configuring the precursor solution includes dissolving the halide and the metal compound in a solvent at a molar ratio of about 1: 1. The halide may be, for example, methylamine chloride (CH ₃ NH ₃ Cl), formamidine chloride (HC (NH ₂ ) ₂ Cl), butylamine chloride (CH ₃ (CH ₂ ) ₃ NH ₃ Cl), Phenethylamine chloride (C ₆ H ₅ C ₂ H ₄ NH ₃ Cl), methylamine bromide (CH ₃ NH ₃ Br), formamidine bromide (HC (NH ₂ ) ₂ Br), butyl bromide Amine (CH ₃ (CH ₂ ) ₃ NH ₃ Br), Phenethylamine Bromide (C ₆ H ₅ C ₂ H ₄ NH ₃ Br), Methyl Iodide (CH ₃ NH ₃ I), Formamidine Iodine (HC (NH ₂ ) ₂ I), butylamine iodide (CH ₃ (CH ₂ ) ₃ NH ₃ I) or phenethylamine iodide (C ₆ H ₅ C ₂ H ₄ NH ₃ I). For example, the metal compound may be lead chloride (PbCl _2), lead bromide (PbBr _2), lead iodide (Pbl _2), stannous chloride (SnCl _2), tin tetrachloride (SnCl _4), bromide Tin stannous (SnBr ₂ ), stannous iodide (SnI ₂ ), germanium chloride (GeCl ₂ ), germanium bromide (GeBr ₂ ) or germanium iodide (GeI ₂ ). The solvent includes γ-butyrolactone (GBL), dimethylformamide (DMF), dimethylsulfinium (DMSO), or N-methylpyrrolidone (NMP). After that, the solvent is heated and stirred at about 65 to 75 ° C. until the halide and the metal compound are completely dissolved.

According to some embodiments of the present invention, the concentration of the precursor solution is about 0.1-5M.

According to some embodiments of the present invention, the first temperature is about 65-80 ° C.

According to some embodiments of the invention, the second temperature is about 90-145 ° C.

According to some embodiments of the present invention, heating the spatially confined crystallizer to the second temperature includes heating the spatially confined crystallizer from the first temperature to the second temperature at a heating rate, and the heating rate is about 10 ° C / 10 minutes. .

According to some embodiments of the present invention, the space-constrained crystallizer includes a lower substrate, a thin frame located on the lower substrate, and the thin frame has an opening to expose the lower substrate; and an upper substrate, the upper substrate, and There is a gap between the substrates, and the thin frame surrounds the gap, wherein the lower substrate, the thin frame, and the upper substrate form a closed space.

According to some embodiments of the present invention, the thin frame has a thickness of about 0.1 to 100 microns.

According to some embodiments of the present invention, the spatially confined crystallizer further includes a thin film in the gap, and the thin film has a thickness of about 0.1 to 100 microns.

According to some embodiments of the present invention, the upper substrate and the lower substrate include glass, corundum, quartz, mica, single crystal silicon, polycrystalline silicon, LaAlO ₃ , titanium dioxide, gallium trioxide, GeO ₂ , zirconium dioxide, or ITO, thin frames And the film contains polytetrafluoroethylene (PTFE).

10‧‧‧Method

12, 14, 16, 18, 20‧‧‧ operation

100‧‧‧Space-Limited Crystal

102‧‧‧ lower substrate

104‧‧‧ thin frame

106‧‧‧ Upper substrate

108‧‧‧ opening

110‧‧‧ Clearance

110’‧‧‧ clearance

112‧‧‧ film

120‧‧‧ heat source

130‧‧‧Conductive metal block

140‧‧‧ metal plate

T ₁ ‧‧‧ thickness

T ₂ ‧‧‧ thickness

FIG. 1 is a flowchart of a method for synthesizing a single crystal of perovskite according to some embodiments of the present invention.

FIG. 2 is a schematic diagram of an apparatus for synthesizing a single crystal of perovskite according to some embodiments of the present invention.

3A-3B are cross-sectional views of a spatially confined crystallizer according to some embodiments of the present invention.

4 to 5 are electron micrographs of a single crystal of perovskite synthesized according to an embodiment of the present invention.

In the following, a plurality of embodiments of the present invention will be disclosed graphically. For the sake of clarity, many practical details will be described in the following description. It should be understood, however, that these practical details should not be used to limit the invention. That is, in some embodiments of the present invention, these practical details are unnecessary. In addition, in order to simplify the illustration, some conventional structures and components will be shown in a simple and schematic manner in the illustration.

In this article, spatial relative terms such as "below", "below", "above", "above", etc. are used to facilitate the description of the relative relationship between one element or feature and another element or feature, such as Shown in the figure. The true meaning of these spatial relative terms includes other directions. example For example, when the icon is flipped 180 degrees up and down, the relationship between one component and another component may change from "below" and "below" to "above" and "above". In addition, the spatially relative descriptions used in this article should be interpreted the same.

FIG. 1 is a flowchart of a method 10 for synthesizing a single crystal of perovskite according to various embodiments of the present invention. As shown in FIG. 1, the method 10 includes an operation 12, an operation 14, an operation 16, an operation 18, and an operation 20. FIG. 2 is a schematic diagram of an apparatus for synthesizing a single crystal of perovskite according to some embodiments of the present invention. 3A-3B are cross-sectional views of a spatially confined crystallizer according to some embodiments of the present invention.

Referring to FIG. 1, in operation 11 of method 10, a precursor solution is prepared. According to some embodiments of the present invention, configuring the precursor solution includes dissolving the halide and the metal compound in a solvent at a molar ratio of about 1: 1, and heating and stirring the solvent to the halide and the metal compound at a temperature of about 65 to 75 ° C. Completely dissolve, and then maintain the precursor solution at this temperature to avoid halide precipitation. In some embodiments, the concentration of the precursor solution is about 0.1-5M, such as about 0.3, 0.5, 1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 2.7, 3, 3.5, 4, 4.5M.

In some embodiments, the halide may be an organic halide or an inorganic halide. In certain embodiments, the organic halide is selected from the group consisting of methylamine chloride (CH ₃ NH ₃ Cl), formamidine chloride (HC (NH ₂ ) ₂ Cl), butylamine chloride (CH ₃ (CH ₂ ) ₃ NH ₃ Cl), phenethylamine chloride (C ₆ H ₅ C ₂ H ₄ NH ₃ Cl), methyl bromide (CH ₃ NH ₃ Br), formamidine bromide (HC (NH ₂ ) ₂ Br ), Butylamine bromide (CH ₃ (CH ₂ ) ₃ NH ₃ Br), phenethylamine bromide (C ₆ H ₅ C ₂ H ₄ NH ₃ Br), methyl iodide amine (CH ₃ NH ₃ I), formamidine iodide (HC (NH ₂ ) ₂ I), butylamine iodide (CH ₃ (CH ₂ ) ₃ NH ₃ I), and phenethylamine iodide (C ₆ H ₅ C ₂ H ₄ NH ₃ I). In certain embodiments, the inorganic halide may be, for example, cesium chloride (CsCl), cesium bromide (CsBr), cesium iodide (CsI), rubidium chloride (RbCl), rubidium bromide (RbBr), or iodide铷 (RbI).

In certain embodiments, the metal compound selected from the group consisting of lead chloride (PbCl _2), lead bromide (PbBr _2), lead iodide (Pbl _2), stannous chloride (SnCl _2), tin tetrachloride ( SnCl _4), stannous bromide (SnBr _2), stannous iodide (SnI _2), germanium chloride (GeCl _2), germanium bromide (GeBr ₂₎ germanium iodide (GeI ₂₎ the group consisting of . In some embodiments, the solvent includes γ-butyrolactone (GBL), dimethylformamide (DMF), dimethylmethylene sulfoxide (DMSO), or N-methylpyrrolidone (NMP).

Please refer to FIG. 1, FIG. 2, and FIGS. 3A to 3B. In operation 14 of method 10, the space-constrained growing crystal is preheated to the first temperature, and the space-constraining growing crystal is maintained at the first temperature. According to some embodiments of the present invention, as shown in FIG. 2, the apparatus for synthesizing a single crystal of perovskite includes a heat source 120, a thermally conductive metal block 130 disposed on the heat source 120, and a metal disposed on the thermally conductive metal block 130.板 140。 Plate 140. In some embodiments, the thermally conductive metal block 130 and the metal plate 140 may include any metal or alloy with good thermal conductivity. In some embodiments, the thermally conductive metal block 130 may be a copper block. In some embodiments, the metal plate 140 may be an iron plate. In some embodiments, preheating the spatially confined crystallizer 100 to the first temperature includes placing the spatially confined crystallizer 100 on a thermally conductive metal block 130 as shown in FIG. The crystallizer 100 is uniformly heated, and after the spatially confined crystallizer 100 reaches the first temperature, the thermally confined crystallizer 100 is maintained at the first temperature by the heat source 120. In some embodiments, the first temperature is about 65 ~ 80 ° C, for example, about 70, 75 ° C, and the first temperature is higher than or equal to the temperature of the pre-treatment solution configured above, avoiding adding the precursor solution to the space in subsequent operations. When the crystal growth device 100 is confined, the halide or the metal compound is precipitated.

According to some embodiments of the present invention, the spatially confined crystallizer 100 includes a lower substrate 102, a thin frame 104, and an upper substrate 106. As shown in FIG. 3A, the thin frame 104 is disposed on the lower substrate 102, and the thin frame 104 has a thickness T ₁ , and the thin frame 104 has an opening 108 (not shown in FIG. 3A, see FIG. 2). Lower substrate 102. The upper substrate 106 will be covered on the thin frame 104 in a subsequent process, so that the lower substrate 102, the thin frame 104 and the upper substrate 106 form a closed space. There is a gap 110 between the upper substrate 106 and the lower substrate 102. The gap 110 is surrounded by the thin frame 104, and the gap 110 is a growth space for the perovskite single crystal. More specifically, the perovskite single crystal growth will be confined in the gap 110, and thus, the thickness of the perovskite single crystal synthesized by the block 104 will not exceed a thin thickness T _1. In certain embodiments, the block 104 having a thin thickness T ₁ of from about 0.1 to about 100 microns, for example about 0.5,1,1.5,2,3.5,5,7,10,12,15,20,25,30, 40, 45, 47, 50, 55, 60, 62, 65, 70, 80, 90, 95 microns.

In other embodiments, as shown in FIG. 3B, the space-constrained crystallizer 100 further includes a thin film 112 disposed on the lower substrate 102 exposed by the opening 108 of the thin frame 104 such that the thin film 112, the thin frame 104, and the upper substrate 106 Form a closed space. In some embodiments, the thickness T _{2 of the} thin film 112 is smaller than the thickness T _{1 of the} thin frame 104, and the gap 110 ′ (FIG. 3B) is smaller than the gap 110 (FIG. 3A). Therefore, the perovskite single crystal will be further restricted to grow in the narrower gap 110 ', and the thickness of the perovskite single crystal will not exceed the thickness of the gap 110'. In some embodiments, the film 112 has a thickness T ₂ of about 0.1 to 100 microns, for example, about 0.5, 1, ₂ , 3.5, 5, 7, 10, 12, 15, 20, 25, 30, 40, 45. , 47, 50, 55, 60, 62, 65, 70, 80, 90, 95 microns. In some embodiments, the upper substrate 106 and the lower substrate 102 include glass, corundum, quartz, mica, single crystal silicon, polycrystalline silicon, LaAlO ₃ , titanium dioxide, gallium trioxide, GeO ₂ , zirconium dioxide, or ITO, but not Limited to this. In some embodiments, the thin frame 104 and the thin film 112 include polytetrafluoroethylene (PTFE). The growth space of the perovskite single crystal is limited to the closed space (i.e., the gap 110) formed by the upper substrate 106, the lower substrate 102, and the thin frame 104 or the closed space (i.e., the closed space composed of the upper substrate 106, the thin film 112, and the thin frame 104) In the gap 110 '), the thickness of the gap 110 and 110' can be controlled by using the thin frame 104 and the thin film 112 of various thicknesses, and the thickness of the perovskite single crystal will not exceed the thickness of the gap 110 or 110 '. The thicknesses T ₁ and T _{2 of the} thin frame 104 and the thin film 112 will directly affect the thickness of the subsequently synthesized perovskite single crystal, that is, the thickness of the perovskite single crystal to be synthesized can be selected. The thickness of the thin frame 104 and the thin film 112.

Please continue to refer to FIG. 1. In operation 16 of method 10, the precursor solution and the seed crystal are placed in a space-limited crystal growth device at a first temperature. In some embodiments, the seed crystal and the precursor solution are placed in the gap 110 of the space-constrained crystal growth device 100 that has been preheated to the first temperature, and the upper substrate 106 that has been heated to the first temperature covers the gap. 110, and the air remaining between the upper substrate 106 and the lower substrate 102 is extruded, so that the upper substrate 106, the lower substrate 102, and the thin frame 104 form a closed space to grow a perovskite single crystal. In some embodiments, the seed crystal may be any single perovskite crystal previously synthesized by a conventional method. The seed crystal has a structure as shown in formula (1): ABX ₃ Formula (1) According to some aspects of the present invention In an embodiment, in formula (1), A may be an organic cation, such as CH ₃ NH ₃ ⁺ , HC (NH ₂ ) ₂ ⁺ , CH ₃ (CH ₂ ) ₃ NH ₃ ⁺ , or C ₆ H ₅ C ₂ H ₄ NH ₃ ⁺ , or may be an inorganic cation, such as Cs ⁺ or Rb ⁺ , B may be a metal cation, such as Pb ²⁺ , Ge ²⁺ , Sn ²⁺ , Cu ^2+, or Ag ⁺ In ⁺ , and X may be Cl ^-, Br ^- or I ^-, and the a of any of the above can be used with any of the above B and C.

Please continue to refer to FIG. 1. In operation 18 of method 10, the precursor solution in the crystal growth chamber is heated to a second temperature in the space. According to some embodiments of the present invention, heating the precursor solution in the spatially confined crystallizer 100 to the second temperature includes heating from the first temperature to the second temperature at a heating rate of about 10 ° C / 10 minutes. In some embodiments, the second temperature is about 90-145 ° C, such as about 95, 100, 105, 110, 115, 120, 125, 130, 135, 140 ° C.

Please continue to refer to FIG. 1. In operation 20 of method 10, the second temperature is maintained to grow a single crystal of perovskite. In some embodiments, after heating the precursor solution in the spatially confined crystallizer 100 to a second temperature, maintaining the second temperature to grow the crystal and waiting for a period of time (for example, 12, 16, 18, 24, 36, 48, After 72 hours), a layered perovskite single crystal can be grown in the gap 110 of the spatially confined crystallizer 100 described above. In certain embodiments, the perovskite single crystal is a layered single crystal. In certain embodiments, perovskite single crystal The thickness is not greater than the thickness of the gap 110. In some embodiments, the shape and area of the perovskite single crystal are substantially the same as the shape and area of the opening 108 of the thin frame 104.

Figures 4 to 5 are electron micrographs of a perovskite single crystal synthesized according to an embodiment of the present invention. In this embodiment, the thickness of the perovskite single crystal is about 50 to 60 microns, and the size of the single crystal is about 50 μm. 1mmx2mm.

As described above, according to the embodiment of the present invention, a layered perovskite single crystal with a thickness of a micron order can be effectively grown using a seed crystal and a space-constrained crystal growth device. The method for synthesizing a perovskite single crystal of the present invention uses a space-limited crystal growth device to limit the growth space of the perovskite single crystal. Therefore, the thickness of the perovskite single crystal can be controlled by the thickness of the thin frame and the thin film. The area and shape of the ore single crystal can also be controlled by the area and shape of the thin frame opening. Adding seed crystals makes perovskite single crystals easier to nucleate, and can quickly grow perovskite single crystals in a short time. It is worth noting that if a thin frame with a larger area opening is used and the precursor solution is continuously replenished into the space confined crystallizer, the precursor solution in the space confined crystallizer is maintained at the second temperature for a longer time ( That is, extending the growth time), a layered perovskite single crystal with a micrometer thickness can be obtained in a large area.

The following describes the present invention in more detail with reference to various embodiments, but the present invention is not limited to the following embodiments.

Example 1: Synthesis of CH ₃ NH ₃ PbI ₃ perovskite single crystal

First configure the precursor solution, dissolve 98% of CH ₃ NH ₃ I and 99% of PbI ₂ in the gamma-butyrolactone (gamma-butyrolactone, GBL) in a glove box at a ratio of 1: 1. Continuous heating and stirring at 65 ° C. for more than 12 hours confirmed that CH ₃ NH ₃ I and PbI _{2 were} completely dissolved, and a CH ₃ NH ₃ PbI ₃ precursor solution with a concentration of about 1.3M was configured.

Wash the glass substrate in the order of detergent, acetone, and detergent, and bake to confirm that no moisture is attached. Then, the Teflon film with a thickness of about 50 microns is cut into a rectangular shape, spread on a glass substrate and placed on an iron plate, and then placed on a thermally conductive copper block, and heated at 75 ° C. to prevent the precursor solution from precipitating during the manufacturing process.

Next, the pre-synthesized CH ₃ NH ₃ PbI ₃ seed crystals were placed on a glass substrate heated to 75 ° C. in a mouth-shaped Teflon film, and an appropriate amount of CH ₃ NH ₃ PbI ₃ precursor solution was quickly extracted from the glove box and After passing through the filter core with a 0.45 micron pore size, it was dropped on the glass substrate in the T-shaped Teflon film. Then take another piece of glass substrate that has been preheated to 75 ° C and directly cover the mouth-shaped Teflon film, and squeeze out the remaining air between the two glass substrates. After that, it is heated to 120 ° C. to 140 ° C. at a rate of 10 ° C. rise every 10 minutes, and waits for more than 12 hours to slowly grow the crystal to obtain a laminar CH ₃ NH ₃ PbI ₃ perovskite single crystal.

After the area of the layered CH ₃ NH ₃ PbI ₃ perovskite single crystal has grown to the required size, the two pieces of glass are separated. First, filter paper is used to absorb the solvent on the surface of the crystal. After determining the temperature, the entire glass substrate and the crystals on it are cleaned with a polar solvent such as isopropanol (IPA). Forceps push the crystal. After confirming that the crystals are separated from the glass substrate, push the crystals onto a clean glass and store them in a glove box to complete the synthesis of all layered crystals.

Example 2: Synthesis of CH ₃ NH ₃ PbBr ₃ perovskite single crystal

CH ₃ NH ₃ PbBr synthesis of _perovskite single crystal as the above-described method for synthesizing CH ₃ NH ₃ PbI ₃ perovskite single crystal, the only difference is that in which a 1.4M solution of CH ₃ NH ₃ precursor substituted ₃ PbBr 1.3 M is CH ₃ NH ₃ PbI ₃ precursor solution to CH ₃ NH ₃ PbBr ₃ seed substituted CH ₃ NH ₃ seed crystal ₃ PbI, and the precursor solution was heated to 90 ~ 110 ℃ slowly growing crystal.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and retouches without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be determined by the scope of the attached patent application.

Claims (10)

A method for synthesizing a single crystal of perovskite, comprising: preparing a precursor solution; preheating a spatially confined crystallizer to a first temperature and maintaining the first temperature, wherein the spatially confined crystallizer includes: a lower substrate; A thin frame is located on the lower substrate and has an opening to expose the lower substrate; and an upper substrate is located on the thin frame, there is a gap between the upper substrate and the lower substrate, and the thin frame surrounds the A gap, in which the lower substrate, the thin frame, and the upper substrate constitute a closed space; the precursor solution and a seed crystal are placed in the space-limited crystal growth device at the first temperature; and the space-limited crystal growth is heated The precursor solution in the container to a second temperature; and maintaining the second temperature to grow a perovskite single crystal. The method for synthesizing a perovskite single crystal according to claim 1, wherein the seed crystal and the perovskite single crystal have a structure as shown in formula (1): ABX ₃ formula (1) where A is CH ₃ NH ₃ ⁺ , HC (NH ₂ ) ₂ ⁺ , CH ₃ (CH ₂ ) ₃ NH ₃ ⁺ or C ₆ H ₅ C ₂ H ₄ NH ₃ ⁺ , B is Pb ²⁺ , Ge ²⁺ , Sn ²⁺ , Cu ^{2 +} or Ag ⁺ In ^+, X is Cl ^-, Br ^- or I ^-. The method for synthesizing a single crystal of perovskite according to claim 1, wherein configuring the precursor solution comprises: dissolving a halide and a metal compound in a solvent at a Mohr ratio of about 1: 1; and The third temperature is about 65 ~ 75 ° C, and the solvent is heated and stirred until the halide and the metal compound are completely dissolved, wherein the halide is selected from methyl amine chloride (CH ₃ NH ₃ Cl), formamidine chloride (HC (NH ₂ ) ₂ Cl), butylamine chloride (CH ₃ (CH ₂ ) ₃ NH ₃ Cl), phenethylamine chloride (C ₆ H ₅ C ₂ H ₄ NH ₃ Cl), methyl bromide (CH ₃ NH ₃ Br), methyl bromide (HC (NH ₂ ) ₂ Br), butylamine bromide (CH ₃ (CH ₂ ) ₃ NH ₃ Br), phenethyl bromide (C ₆ H ₅ C ₂ H ₄ NH ₃ Br), methyl iodide (CH ₃ NH ₃ I), methyl iodide (HC (NH ₂ ) ₂ I), butyl iodide (CH ₃ (CH ₂ ) ₃ NH ₃ I) And phenethyl iodide amine (C ₆ H ₅ C ₂ H ₄ NH ₃ I), wherein the metal compound is selected from the group consisting of lead chloride (PbCl ₂ ), lead bromide (PbBr ₂ ), and iodination lead (Pbl _2), stannous chloride (SnCl _2), tin tetrachloride (SnCl _4), stannous bromide (SnBr _2), stannous iodide (SnI _2), germanium tetrachloride (GeCl _2), germanium bromide (GeBr ₂₎ Groups germanium iodide (GeI ₂₎ consisting of, wherein the solvent comprises γ- butyrolactone (GBL), dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or N- methylpyrrolidone (NMP). The method for synthesizing a perovskite single crystal according to claim 1, wherein the concentration of the precursor solution is about 0.1-5M. The method for synthesizing a perovskite single crystal according to claim 1, wherein the first temperature is about 65-80 ° C. The method for synthesizing a single crystal of perovskite according to claim 1, wherein the second temperature is about 90 to 145 ° C. The method for synthesizing a perovskite single crystal according to claim 1, wherein heating the space-limited condensing crystal to the second temperature includes heating the space-limited condensing crystal from the first temperature to the first temperature at a heating rate. Two temperatures, and the heating rate is about 10 ° C / 10 minutes. The method for synthesizing a single crystal of perovskite according to claim 1, wherein the thin frame has a thickness of about 0.1-100 micrometers. The method for synthesizing a perovskite single crystal according to claim 1, wherein the space-constrained crystallizer further comprises a thin film located in the gap, and the thin film has a thickness of about 0.1 to 100 microns. The synthesis method of perovskite single crystal according to claim 1, wherein the upper substrate and the lower substrate include glass, corundum, quartz, mica, single crystal silicon, polycrystalline silicon, LaAlO ₃ , titanium dioxide, gallium trioxide, GeO _2. Zirconium dioxide or ITO, the thin frame and the film comprise polytetrafluoroethylene (PTFE).