CN111926387B - Preparation method of ultrathin strip-shaped perovskite single crystal - Google Patents

Preparation method of ultrathin strip-shaped perovskite single crystal Download PDF

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CN111926387B
CN111926387B CN202010578301.8A CN202010578301A CN111926387B CN 111926387 B CN111926387 B CN 111926387B CN 202010578301 A CN202010578301 A CN 202010578301A CN 111926387 B CN111926387 B CN 111926387B
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CN111926387A (en
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张青
李美丽
尚秋宇
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Peking University
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Abstract

The invention discloses a preparation method of an ultrathin perovskite single crystal with a nano-belt structure, which comprises the following steps: 1) mixing AX and PbX2Dissolving the raw materials in a precursor solvent according to the molar ratio of n to 1, heating and stirring to obtain the three-dimensional perovskite APbX3The precursor solution of (1); 2) three-dimensional perovskite APbX3Dripping a proper amount of the precursor solution on a substrate, placing the substrate in a vessel containing an anti-solvent, and sealing the opening of the vessel; placing the perovskite single crystal in a drying oven, standing the perovskite single crystal for crystal growth to obtain the ultrathin strip-shaped perovskite single crystal; wherein: AX is selected from one or more of methylamine bromide, formamidine bromide and cesium bromide; x is a halogen anion and n is 1-2.2. The optimal luminescence wavelength of the ultrathin perovskite single crystal obtained by the invention is 508-512nm, and low-threshold laser lasing at room temperature and continuous optical pumping laser lasing at liquid nitrogen temperature are realized.

Description

Preparation method of ultrathin strip-shaped perovskite single crystal
Technical Field
The invention belongs to the technical field of semiconductor photoelectric material preparation, relates to a preparation method of a high-quality low-laser-threshold one-dimensional nano single crystal, and particularly relates to a liquid-phase growth method of a perovskite single crystal with an ultrathin structure.
Background
In recent years, metal halide perovskite materials have attracted great attention from researchers in the fields of solar cells, light emitting diodes, photodetectors, lasers and the like due to their characteristics of high crystal quality, high fluorescence quantum yield, high absorption coefficient, bipolar carrier transport, long carrier diffusion length, solution processibility and the like. Since the quality of the material often determines the performance of the device, much research is currently devoted to the synthesis of high quality perovskite materials, such as perovskite single crystals or single crystal thin films. Compared with a perovskite polycrystalline film, the perovskite polycrystalline film has the advantages of less single crystal defects with high crystallinity, strong light emission and fast carrier migration, and is more suitable for the research of photoelectric devices. In addition, single crystals exhibit different optoelectronic properties of anisotropy of crystal planes and are more stable in external environments such as temperature, humidity and light irradiation.
At present, the perovskite single crystal growth method mainly comprises a chemical vapor deposition method, an anti-solvent steam induced crystallization method, a slow evaporation method, a cooling crystallization method and the like. However, the synthesized single crystal morphology is generally a nano-sheet, a nano-wire, a nano-cone, etc., and often has a certain thickness, which is mainly caused by different growth conditions of the crystal. It is to be noted that, in the past, studies on single crystals have mainly focused on how to grow single crystals having higher crystallinity, with emphasis on the crystal quality of the crystals, and studies on ultra-thin perovskite single crystals have been rare. Therefore, the growth method of the single crystal is improved, and the supersaturation degree in the perovskite precursor solution is controlled, so that the growth speed of the single crystal is reduced, the dominant growth surface of the single crystal is rapidly grown, and the ultrathin perovskite single crystal with high crystallization quality is obtained. Because the ultrathin single crystal structure is more beneficial to heat dissipation after being contacted with the heat conducting substrate, the ultrathin single crystal structure is designed into an optoelectronic device and has important significance in reducing power consumption.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrathin strip-shaped perovskite single crystal, which can be used for preparing a high-quality low-laser-threshold one-dimensional nano single crystal, utilizes an anti-solvent to assist in growing the ultrathin strip-shaped perovskite single crystal with the ultrathin thickness at a low temperature, and can overcome the influences of the over-high evaporation rate and the supersaturation degree of a solution to form the ultrathin strip-shaped crystal. The ultra-thin single crystal exhibits excellent optical properties, extremely narrow full width at half maximum, and strong fluorescence emission. In addition, the heat dissipation rate between the single crystal and the substrate is increased due to the ultrathin thickness, so that continuous optical pumping laser can be realized under continuous optical pumping irradiation.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an ultrathin strip-shaped perovskite single crystal comprises the following steps:
1) mixing AX and PbX2Dissolving the mixture in a precursor solvent according to the molar ratio of n to 1Heating and stirring to obtain three-dimensional (3D) perovskite APbX3The precursor solution of (1);
2) the above APbX is mixed3Dripping a proper amount of the precursor solution on a substrate, placing the substrate in a glass vessel containing an anti-solvent, and sealing the opening of the glass vessel by using a sealing film;
3) statically placing the glass device in a heated oven, and standing to grow crystals to obtain ultrathin strip-shaped perovskite single crystals;
wherein: a is a short-chain organic or inorganic cation and X is a halogen anion.
The AX comprises one or more of methylamine bromide, formamidine bromide and cesium bromide.
The thickness of the ultrathin strip-shaped perovskite single crystal is less than 100 nm.
Preferably, PbX2Is PbBr2。
Preferably, the 3D perovskite APbX3The concentration of the solution is in the range of 0.001-0.02 mol.L-1。
In step 1), AX is PbX2In a molar ratio of n to 1, wherein "n" is in the range of 1 to 2.2.
Preferably, in step 1), the precursor solvent may be any one of N-N Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylethanolamine and γ -butyrolactone.
Preferably, a proper amount of precursor solution APbX is taken in the step 2)3Dropping on the substrate, wherein the proper amount is in the range of 20-50 μ L.
Preferably, the substrate used in step 2) may be one of glass, silica, mica, sapphire, and the like.
The anti-solvent in the step 2) can adopt the same solvent or a mixed solvent; preferably, the anti-solvent is one or two of toluene, chlorobenzene, acetonitrile and dichloromethane.
In the step 2), the sealing glass ware can adopt a sealing film, and a certain number of pinholes can be punctured on the sealing film, wherein the range of the pinholes is 20-60, and the pinholes are used for controlling the volatilization speed of the solvent.
The temperature range of the oven in the step 3) is 30-60 ℃, and the time range of crystal growth is 12-24 h.
The light-emitting wavelength range of the ultrathin perovskite single crystal grown by the method is 505-522 nm. The optimal light-emitting wavelength range for achieving continuous optical pumping lasing is 520-522 nm.
The present invention considers not only the crystallization quality of the crystal, but also the spatial thickness of the crystal, which is lacking in the single crystal research field. The invention provides a perovskite single crystal with ultrathin thickness and a growth method thereof, namely a liquid phase method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the ultrathin strip-shaped perovskite single crystal is prepared by controlling the growth temperature of the crystal, the supersaturation degree of a precursor solution, the volatilization speed of an anti-solvent and other conditions, the single crystal is regular in shape, the length-width ratio range is 2-2.5, the thickness is 20-100nm, and the ultrathin strip-shaped perovskite single crystal has good fluorescence emission properties (as shown in figure 1).
(2) The prepared ultrathin perovskite single crystal is characterized by atomic force microscope spectrum, and the surface of the ultrathin perovskite single crystal is smooth and flat, and the roughness of the ultrathin perovskite single crystal is less than 1 nm.
(3) The prepared ultrathin perovskite single crystal is characterized by atomic force microscope spectroscopy (AFM), and the thickness of the perovskite single crystal is less than 100nm (shown in figure 2).
(4) The prepared ultrathin perovskite single crystal is found to have a crystal structure belonging to an orthorhombic system (ICSD 97851) stable at room temperature through X-ray diffraction spectroscopy (XRD) and Transmission Electron Microscopy (TEM) (as shown in figure 3).
(5) The prepared ultrathin perovskite single crystal is characterized by a steady-state fluorescence spectrum (PL), and is found to have strong fluorescence emission property, and the half-peak width of a PL peak is less than 14nm (as shown in figure 4).
(6) The PL lifetime of the prepared ultrathin perovskite single crystal is more than 5ns (shown in figure 5) through the characterization of time-resolved fluorescence spectroscopy (TRPL).
The ultrathin perovskite single crystal prepared by the invention realizes low threshold (less than 5 mu J cm) at room temperature-2) The laser lasing realizes the continuous optical pumping laser lasing (as shown in figure 6) at the temperature of liquid nitrogen, and further promotesPractical application of the laser.
Drawings
FIG. 1 is a fluorescent microscope photograph of bright field and dark field of an ultra-thin perovskite single crystal prepared according to example two of the present invention.
FIG. 2 is an AFM spectrum of an ultra-thin perovskite single crystal prepared according to example four of the present invention.
FIG. 3 is an XRD spectrum and a TEM spectrum of an ultrathin perovskite single crystal prepared in example nine of the present invention.
FIG. 4 is a steady state PL profile of an ultra-thin perovskite single crystal prepared according to example eleven of the present invention.
FIG. 5 is a TRPL profile of an ultra-thin perovskite single crystal prepared in example twelve of the present invention.
Fig. 6 is a laser spectrum of an ultra-thin perovskite single crystal prepared according to example twenty of the present invention.
Detailed Description
The method for preparing a high-quality low-laser-threshold one-dimensional nano single crystal provided by the invention will be further described in detail with reference to the accompanying drawings and specific examples.
A preparation method of ultrathin strip-shaped perovskite single crystal comprises the following steps:
1) mixing AX and PbX2Dissolving the raw materials in a precursor solvent according to the molar ratio of n to 1, heating and stirring to obtain the three-dimensional (3D) perovskite APbX3The concentration of the precursor solution is in the range of 0.001-0.02mol L-1；
2) The above APbX is mixed3Dripping a proper amount of the precursor solution on a substrate, placing the substrate in a glass vessel containing an anti-solvent, sealing the opening of the glass vessel by using a sealing film, and pricking a certain number of pinholes on the sealing film, wherein the pinholes range is 20-60 and are used for controlling the volatilization speed of the solvent;
3) statically placing the glass device in a heated oven, and standing for growth;
wherein the structure of the ultrathin perovskite single crystal is APbX3Wherein A is a short-chain organic or inorganic cation, and X is a halogen anion.
The AX comprises one of methylamine bromide (MABr), formamidine bromide (FABr) and cesium bromide (CsBr).
The PbX2Is PbBr2。
In the present invention, 3D perovskite APbX3Including CH3NH3PbBr3(MAPbBr3)、HC(NH2)2PbBr3(FAPbBr3)、CsPbBr3One of (1); the 3D perovskite APbX3The concentration range of the solution is 0.001-0.02mol L-1The optimum concentration range is 0.005-0.01mol L-1。
The AX is PbX2Wherein "n" is in the range of 1 to 2.2, and most preferably n is in the range of 1 to 1.6.
The precursor solvent can be any one of N-N Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylethanolamine and gamma-butyrolactone.
The precursor solution APbX3The amount dropped on the substrate was 20-50. mu.L.
The substrate may be glass, silica, mica, sapphire, etc.
The anti-solvents may be the same or different; the anti-solvent is one or two of toluene, chlorobenzene, acetonitrile and dichloromethane.
The number of pinholes on the sealing film of the sealed glass ware is 20-60 holes, the number of the pinholes is used for controlling the volatilization speed of the solvent, and the optimal number of the pinholes is 40-50 holes.
The temperature range of the oven is 30-60 ℃.
The time range of the crystal growth is 12-24 h.
The thickness of the ultrathin perovskite single crystal is less than 100nm, and the optimal thickness range of the single crystal is 60-80 nm.
The light-emitting wavelength range of the ultrathin perovskite single crystal is 505-515 nm.
The structure of the ultrathin perovskite single crystal comprises: MAPbBr3、FAPbBr3、CsPbBr3。
Example one
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (1) is 0.005mol L-1；
2) The above MAPbBr was added3 Dripping 30 mu L of the precursor solution on a silicon dioxide substrate, placing the silicon dioxide substrate in a glass vessel filled with toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for growth for 20 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 100nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example two
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMF according to the molar ratio of 1.2:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.008mol L-1；
2) Mixing the above CsPbBr3Dripping 20 mu L of the precursor solution on a silicon dioxide substrate, placing the silicon dioxide substrate in a glass vessel filled with toluene and dichloromethane, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 24 hours;
wherein, as shown in FIG. 1, CsPbBr3Bright field (left image) and dark field (right image) microscope pictures of the perovskite single crystal. The single crystal is in an ultrathin strip shape, the thickness of the single crystal is 70nm, the length-width ratio is 2.3, the size is uniform, strong fluorescence emission is realized, the light emitting wavelength is 522nm, and the phenomena of laser lasing of pulsed light pumping and continuous light pumping lasing at the temperature of liquid nitrogen can be realized at room temperature.
EXAMPLE III
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMF according to the molar ratio of 1.3:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.01mol L-1；
2) Mixing the above CsPbBr3Dripping 50 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel filled with toluene and acetonitrile, sealing the opening of the glass vessel by using a sealing film, and pricking 20 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 18 h;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal is 75nm, the light-emitting wavelength is 510nm, and the laser lasing of pulsed light pumping and the continuous light pumping lasing phenomenon at the liquid nitrogen temperature can be realized at room temperature.
Example four
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMF according to the molar ratio of 1.5:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.004mol L-1；
2) Mixing the above CsPbBr3Dripping 30 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel filled with toluene and dichloromethane, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 24 hours;
wherein, FIG. 2 is the ultra-thin perovskite CsPbBr3The thickness of the single crystal AFM picture is 85nm, the light-emitting wavelength is 506nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
EXAMPLE five
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMF according to the molar ratio of 1.8:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.01mol L-1；
2) Mixing the above CsPbBr3Dripping 30 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel filled with toluene and dichloromethane, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for growth for 20 hours;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal is 20nm, the light-emitting wavelength is 507.6nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
EXAMPLE six
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMF according to the molar ratio of 2.2:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.008mol L-1；
2) Mixing the above CsPbBr3Dripping 35 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel filled with toluene and dichloromethane, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for growth for 20 hours;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal is 80nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
EXAMPLE seven
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding FABr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1:1, heating and stirring to obtain 3D perovskite FAPBBr3The concentration of the precursor solution of (2) is 0.007mol L-1；
2) The FAPBBr is added3Dripping 50 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in a baking oven at 35 ℃, and standing for growth for 20 hours;
wherein, the ultrathin perovskite FAPBBr3The thickness of the single crystal is 95nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example eight
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional nano single crystal includes the following steps:
1) adding FABr and PbBr2Dissolving the raw materials in DMF according to the molar ratio of 1.3:1, heating and stirring to obtain 3D perovskite FAPBBr3The concentration of the precursor solution of (1) is 0.015mol L-1；
2) The FAPBBr is added3Dripping 30 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for growth for 20 hours;
wherein, the ultrathin perovskite FAPBBr3The thickness of the single crystal is 65nm, the light-emitting wavelength is 505nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example nine
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1.5:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.018mol L-1；
2) Mixing the above CsPbBr3Dripping 30 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 24 hours;
wherein, the ultrathin perovskite CsPbBr3The crystal form of the single crystal belongs to an orthorhombic system and is characterized in that splitting double peaks appear at 15 degrees, as shown in figure 3, the left side image is an XRD (X-ray diffraction) image, and the right side image is a TEM (transverse electric and magnetic field) image. The thickness of the single crystal is 75nm, the light-emitting wavelength is 509nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the lasing phenomenon of the continuous optical pumping is avoided.
Example ten
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding FABr and PbBr2Dissolving the raw materials in DMF according to the molar ratio of 1.7:1, heating and stirring to obtain 3D perovskite FAPBBr3The concentration of the precursor solution of (2) is 0.02mol L-1；
2) The FAPBBr is added3Dripping 30 mu L of the precursor solution on a sapphire substrate, placing the sapphire substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for 12 h;
wherein, the ultrathin perovskite FAPBBr3The thickness of the single crystal is 65nm, the light-emitting wavelength is 513nm, laser lasing of pulse optical pumping can be realized at room temperature, and the phenomenon of lasing of continuous optical pumping is avoided.
EXAMPLE eleven
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1.7:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.01mol L-1；
2) Mixing the above CsPbBr3Dripping 40 mu L of the precursor solution on a sapphire substrate, placing the sapphire substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for growth for 20 hours;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal was 75nm, and the emission wavelength of the steady-state fluorescence PL spectrum was 521nm, and the half-peak width was 13.7nm, as shown in FIG. 4. The laser pumping phenomenon of pulse light pumping and the continuous light pumping phenomenon at liquid nitrogen temperature can be realized at room temperature without the laser pumping of the pulse light pumping.
Example twelve
In this embodiment, the preparation method of the high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in gamma-butyrolactone according to the molar ratio of 1.6:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution is 0.011mol L-1；
2) Mixing the above CsPbBr3Dripping 20 mu L of the precursor solution on a sapphire substrate, placing the sapphire substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in an oven at 50 ℃, and standing for 24 hours;
wherein, the ultrathin perovskite CsPbBr3Time resolved TRPL of single crystals showed a lifetime of 5.3ns as shown in fig. 5. The thickness of the single crystal is 65nm, the light-emitting wavelength is 508nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
EXAMPLE thirteen
In this embodiment, a high quality low laser threshold one-dimensional APbX3The preparation method of the nano single crystal comprises the following steps:
1) adding MABr and PbBr2Dissolving the mixture in gamma-butyrolactone according to the molar ratio of 1.3:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (2) is 0.006mol L-1；
2) The above MAPbBr was added3Dripping 40 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 50 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for 24 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 70nm, the light-emitting wavelength is 512nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example fourteen
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in gamma-butyrolactone according to the molar ratio of 1.5:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (1) is 0.015mol L-1；
2) The above MAPbBr was added3Dripping 40 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 50 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for 24 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 70nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example fifteen
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in gamma-butyrolactone according to the molar ratio of 1.5:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (2) is 0.004mol L-1；
2) The above MAPbBr was added3Dripping 40 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing toluene, sealing the opening of the glass vessel by using a sealing film, and pricking 50 small holes;
3) slowly placing the glass device in an oven at 60 ℃, and standing for 12 h;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 70nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example sixteen
In this embodiment, the preparation method of the high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1.7:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (2) is 0.009mol L-1；
2) The above MAPbBr was added3 Dripping 20 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for 24 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 65nm, the light-emitting wavelength is 513nm, laser lasing of pulse optical pumping can be realized at room temperature, and the phenomenon of lasing of continuous optical pumping is avoided.
Example seventeen
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 2:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (2) is 0.003mol L-1；
2) The above MAPbBr was added3 Dripping 30 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 24 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 85nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
EXAMPLE eighteen
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) adding MABr and PbBr2Dissolving the mixture in DMSO according to the molar ratio of 2.2:1, heating and stirring to obtain 3D perovskite MAPbBr3The concentration of the precursor solution of (2) is 0.013mol L-1；
2) The above MAPbBr was added3 Dripping 50 mu L of the precursor solution on a glass substrate, placing the glass substrate in a glass vessel containing chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 60 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for growth for 20 hours;
wherein, the ultra-thin perovskite MAPbBr3The thickness of the single crystal is 75nm, the light-emitting wavelength is 508nm, laser lasing of pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example nineteen
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 2.2:1, and heating and stirring to obtain 3D calcium titaniumMine CsPbBr3The concentration of the precursor solution of (2) is 0.017mol L-1；
2) Mixing the above CsPbBr3Dripping 20 mu L of the precursor solution on a sapphire substrate, placing the sapphire substrate in a glass vessel containing chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 40 small holes;
3) slowly placing the glass device in an oven at 40 ℃, and standing for 18 h;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal is 100nm, the light-emitting wavelength is 515nm, the laser lasing of the pulse optical pumping can be realized at room temperature, and the phenomenon of continuous optical pumping lasing is avoided.
Example twenty
In this embodiment, a method for preparing a high-quality low-laser-threshold one-dimensional ultrathin strip-shaped perovskite single crystal includes the following steps:
1) reacting CsBr and PbBr2Dissolving the mixture in DMSO according to a molar ratio of 1.3:1, heating and stirring to obtain 3D perovskite CsPbBr3The concentration of the precursor solution of (2) is 0.01mol L-1；
2) Mixing the above CsPbBr3Dripping 20 mu L of the precursor solution on a sapphire substrate, placing the sapphire substrate in a glass vessel containing toluene and chlorobenzene, sealing the opening of the glass vessel by using a sealing film, and pricking 30 small holes;
3) slowly placing the glass device in an oven at 30 ℃, and standing for 22 h;
wherein, the ultrathin perovskite CsPbBr3The thickness of the single crystal is 80nm, the light-emitting wavelength is 520nm, and the phenomena of laser lasing of pulsed light pumping and continuous light pumping lasing at liquid nitrogen temperature can be realized at room temperature, as shown in fig. 6. The left graph shows the change of laser emission of the nanobelts with temperature, and as the temperature rises, the mode of the laser peak becomes less and the half-peak width becomes wider. The upper right panel shows the half-peak width of the laser peak at 80K of the nanobelt, which is 0.1 nm. The lower right graph shows that the threshold of the laser of the nanoribbon changes with temperature, and becomes larger with increasing temperature.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A preparation method of an ultrathin perovskite single crystal with a nano-belt structure comprises the following steps:
1) mixing AX and PbX2Dissolving the raw materials in a precursor solvent according to the molar ratio of n to 1, heating and stirring to obtain the three-dimensional perovskite APbX3The precursor solution of (1);
2) three-dimensional perovskite APbX3Dripping 20-50 mu L of the precursor solution on a substrate, placing the substrate in a vessel containing an anti-solvent, sealing the opening of the vessel, and arranging pinholes with the number of 20-60 holes on the sealing; placing the perovskite single crystal in a drying oven, standing the perovskite single crystal for crystal growth to obtain the ultrathin strip-shaped perovskite single crystal;
wherein: AX is selected from one or more of methylamine bromide, formamidine bromide and cesium bromide; x is a halogen anion, n is 1-2.2;
in step 1), three-dimensional perovskite APbX3The concentration of the precursor solution is 0.005-0.01mol L-1；
In the step 2), the temperature of the oven is 30-60 ℃, and the time of crystal growth is 12-24 h;
the ultra-thin strip-shaped perovskite single crystal has regular morphology, the length-width ratio range of 2-2.5, the thickness of 20-100nm, smooth and flat surface and the roughness of less than 1 nm.
2. The method according to claim 1, wherein in step 1), the precursor solvent is any one of N-N dimethylformamide, dimethyl sulfoxide, dimethylethanolamine and γ -butyrolactone.
3. The method of claim 1, wherein in step 2), the substrate is one of glass, silica, mica, and sapphire.
4. The method of claim 1, wherein the anti-solvent is one or two of toluene, chlorobenzene, acetonitrile and dichloromethane.
5. The method according to claim 1, wherein the luminescent wavelength of the ultrathin ribbon-like perovskite single crystal is 505-515 nm.
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