CN112410884A - Rare earth doped single crystal perovskite and preparation method thereof and photoelectric detector - Google Patents

Rare earth doped single crystal perovskite and preparation method thereof and photoelectric detector Download PDF

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CN112410884A
CN112410884A CN202011302620.2A CN202011302620A CN112410884A CN 112410884 A CN112410884 A CN 112410884A CN 202011302620 A CN202011302620 A CN 202011302620A CN 112410884 A CN112410884 A CN 112410884A
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rare earth
single crystal
crystal perovskite
doped single
perovskite
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徐文
訾陆
宋宏伟
丁楠
周东磊
白雪
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Jilin University
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Jilin University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention is applicable to the field of photoelectric technology, and provides a rare earth doped single crystal perovskite, a preparation method thereof and a photoelectric detector3NH3PbX3A single crystal perovskite; wherein X is halogen. The photoelectric detector comprises the rare earth doped single crystal perovskite and a silver electrode deposited on the rare earth doped single crystal perovskite. According to the invention, rare earth ions are doped into the single crystal perovskite material, so that the single crystal perovskite not only shows good stability, long carrier diffusion length and high carrier mobility, but also shows infrared luminescence of the rare earth ions in an infrared bandThe prepared photoelectric detection device can accurately detect infrared light such as 980nm and 1540nm, has good responsivity and sensitivity, has a simple structure, has high environmental stability and has a great market application prospect.

Description

Rare earth doped single crystal perovskite and preparation method thereof and photoelectric detector
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to rare earth doped single crystal perovskite, a preparation method thereof and a photoelectric detector.
Background
With the continuous development of the optoelectronic technology, the photodetector, which is the core of the optoelectronic system, is widely used in various fields of military and national economy because of its ability to convert an optical signal into a storable electrical signal. Photodetectors are classified into wide-band photodetectors and narrow-band photodetectors according to their spectral response ranges. Currently, most photodetectors are broadband photodetectors and are mainly used for multi-color detection in low-light conditions because of their need to broaden the spectral response range as much as possible. However, detection for the fields of biosensing, image sensing arrays, environmental monitoring, military and aviation is achieved by wavelength-selective narrow-band photodetectors. Although wavelength-selective narrow-band photoelectric detection can be achieved by adjusting and controlling the photoelectric field direction of the device, configuring a corresponding band-pass filter for a wide-band photoelectric detector, enhancing the absorption of specific wavelengths by using a plasma-assisted technology, and the like, these methods increase the complexity of design, limit the quality of color discrimination, and cause the reduction of photoelectric conversion efficiency. Therefore, a narrow-band photodetector with high sensitivity, fast response speed and good stability, especially a narrow-band near-infrared photodetector, is urgently needed.
In recent years, a semiconductor material such as perovskite has been widely used in the fields of photodetection, photovoltaics, and the like due to its characteristics such as high absorption coefficient, high carrier mobility, long carrier diffusion length, large extinction coefficient, and the like. At present, researchers have made a lot of researches on organic-inorganic hybrid perovskite polycrystalline thin films or nanowires and achieved excellent performance, but grain boundary and surface defects in the system cause the reduction of ion migration energy barrier and the reduction of carrier mobility. And the single crystal perovskite has no crystal boundary inside, few surface defects and higher environmental stability, so that the photoelectric detector based on the single crystal perovskite is certainly superior to the photoelectric detector of a polycrystalline perovskite thin film in performance. Although single crystal perovskite-based photodetectors have high stability, fast response speed, and tunable broadband response window, it is still difficult to achieve detection of spectra with wavelengths greater than 1000 nm, which severely limits their spectral response in the near infrared region. Therefore, in order to solve these problems, development of a novel perovskite material having high sensitivity, high selectivity and low cost for wavelength-selective narrow-band photodetection is urgently required.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a rare earth-doped single crystal perovskite, which aims to solve the problems proposed in the background art.
The embodiment of the invention is realized by the fact that the rare earth doped single crystal perovskite is CH doped with rare earth ions3NH3PbX3A single crystal perovskite; wherein X is halogen and the rare earth ion is Yb3+、Ce3+、Tb3+、Eu3+、Nd3+、Er3+、Dy3+At least two of them.
As a preferable scheme of the embodiment of the invention, X is Br or I.
Another object of an embodiment of the present invention is to provide a method for preparing the above rare earth-doped single crystal perovskite, which includes the following steps:
mixing aqueous solutions of lead acetate and hydrogen halide, and then mixing the aqueous solutions with chlorides of rare earth ions to obtain a mixed solution;
and adding a methylamine aqueous solution and a hydrogen halide aqueous solution into the mixed solution, carrying out heat preservation reaction, and then carrying out cooling treatment to obtain the rare earth doped single crystal perovskite.
As another preferable mode of the embodiment of the present invention, the aqueous solution of hydrogen halide is hydroiodic acid or hydrobromic acid.
As another preferable scheme of the embodiment of the invention, the molar mass of the chloride of the rare earth ions is 20-30% of that of the lead acetate.
As another preferable scheme of the embodiment of the invention, the chloride of the rare earth ions is YbCl3·6H2O、CeCl3·6H2O、TbCl3·6H2O、EuCl3·6H2O、NdCl3·6H2O、ErCl3·6H2O、DyCl3·6H2At least two of O.
As another preferable scheme of the embodiment of the invention, the chloride of the rare earth ions is YbCl3·6H2O and ErCl3·6H2O。
As another preferable scheme of the embodiment of the invention, the YbCl3·6H2O and ErCl3·6H2The molar ratio of O is (15-25): 5.
As another preferable scheme of the embodiment of the invention, in the step, the temperature of the heat preservation reaction is 170-200 ℃.
Another object of the embodiments of the present invention is to provide a rare earth doped single crystal perovskite prepared by the above preparation method.
It is a further object of embodiments of the present invention to provide a photodetector comprising the above rare earth doped single crystal perovskite and a silver electrode layer deposited on the rare earth doped single crystal perovskite.
According to the rare earth doped single crystal perovskite provided by the embodiment of the invention, some rare earth ions which emit light in an infrared region are doped into a single crystal perovskite material, so that the single crystal perovskite not only shows good stability, long carrier diffusion length and high carrier mobility, but also shows infrared light emission of the rare earth ions in an infrared band, and the prepared photoelectric detection device can accurately detect infrared light of 980nm, 1540nm and the like, has good responsivity and sensitivity, is simple in structure, has high environmental stability and has a great market application prospect.
The embodiment of the invention provides a narrow-band photoelectric detector, which adopts rare earth doped monocrystalline perovskite as a light conversion layer material, has good environmental stability and low cost, and overcomes the defect of poor environmental stability of the existing semiconductor material for the narrow-band photoelectric detector. And the photoelectric detector based on the rare earth doped single crystal perovskite can accurately detect 980nm and 1540nm infrared light, and has higher responsivity and detection sensitivity, so that the bottleneck problem of low sensitivity of the integrated narrow-band infrared photoelectric detector is well solved.
In addition, the preparation method of the photoelectric detector provided by the embodiment of the invention is simple and easy to operate, so that the cost can be greatly saved.
Drawings
FIG. 1 is a graph of the morphology and size of rare earth doped single crystal perovskites made in example 1.
FIG. 2 is an X-ray diffraction pattern of the rare earth-doped single crystal perovskite produced in example 1.
FIG. 3 is an absorption spectrum of a rare earth-doped single crystal perovskite or an undoped single crystal perovskite produced in example 1 and comparative examples 1 to 3.
FIG. 4 is a fluorescence spectrum of a rare earth-doped single crystal perovskite or an undoped single crystal perovskite obtained in example 1 and comparative examples 1 to 3.
FIG. 5 is a scanning electron micrograph of the rare earth doped single crystal perovskite prepared in example 1.
FIG. 6 is an XPS spectrum of a rare earth doped single crystal perovskite produced in example 1 and an undoped single crystal perovskite produced in comparative example 1.
FIG. 7 is an I-T characteristic curve of the photodetectors obtained in example 1 and comparative examples 1 to 3.
FIG. 8 is a photostability map of the photodetector made in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 2.93g of lead acetate trihydrate and 10mL of saturated hydroiodic acid are placed in a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.55mmol of YbCl is added3·6H2O, 0.38mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite marked as MAPbI3:Yb,Er。
In addition, this embodiment also provides a photodetector comprising the above rare earth-doped single crystal perovskite and a silver electrode layer deposited on the rare earth-doped single crystal perovskite. Specifically, a silver metal layer with the thickness of 200nm can be deposited on the polished surface of the rare earth doped single crystal perovskite by an evaporation method to form a silver electrode layer.
Example 2
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 7.7mmol of lead acetate trihydrate and 10mL of saturated hydrobromic acid are put into a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.155mmol of YbCl is added3·6H2O, 0.385mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydrobromic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle into an oven for reaction at 170 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 3
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, placing 7.7mmol of lead acetate trihydrate and 10mL of saturated hydrobromic acid in a glass bottle, stirring and mixing the mixture by a magnetic heating stirrer until the lead acetate is completely dissolved, and then adding 1.925mmol of YbCl3·6H2O, 0.385mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydrobromic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle into an oven for reaction at 200 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 4
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, placing 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid in a glass bottle, stirring and mixing the mixture by using a magnetic heating stirrer until the lead acetate is completely dissolved, and then adding 1.55mmol of CeCl3·6H2O, 0.38mmol of DyCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling rate of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 5
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, placing 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid in a glass bottle, stirring and mixing the mixture by using a magnetic heating stirrer until the lead acetate is completely dissolved, and then adding 1.55mmol of TbCl3·6H2O, 0.2mmol of EuCl3·6H2O, 0.2mmol of NdCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle in an oven for heat preservation reaction at 170 ℃ and 200 ℃ for 24 hours, and then cooling at the cooling rate of 2 ℃/h to cool to room temperature to obtain the rare earth doped single crystal perovskite.
Example 6
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, placing 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid in a glass bottle, stirring and mixing the mixture by using a magnetic heating stirrer until the lead acetate is completely dissolved, and then adding 1mmol of YbCl3·6H2O, 0.925mmol of DyCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven, keeping the temperature of 190 ℃ for reaction for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 7
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, placing 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid in a glass bottle, stirring and mixing the mixture by using a magnetic heating stirrer until the lead acetate is completely dissolved, and then adding 1.386mmol of YbCl3·6H2O, 0.385mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling rate of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 8
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid are placed in a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.694mmol of YbCl is added3·6H2O, 0.385mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydrobromic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling rate of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 9
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 7.7mmol of lead acetate trihydrate and 10mL of saturated hydroiodic acid are placed in a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.54mmol of YbCl is added3·6H2O, 0.385mmol of ErCl3·6H2O, andstirring at 80 deg.C to obtain clear mixture.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydrobromic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling rate of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Example 10
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 7.7mmol of lead acetate trihydrate and 10mL of saturated hydrobromic acid are put into a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.232mmol of YbCl is added3·6H2O, 0.308mmol of ErCl3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydrobromic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene inner container, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling rate of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite.
Comparative example 1
This comparative example provides a single crystal perovskite, the preparation method of which comprises the steps of:
s1, placing 2.93g of lead acetate trihydrate and 10mL of saturated hydroiodic acid in a glass bottle, and stirring and mixing the mixture by using a magnetic heating stirrer until the lead acetate is completely dissolved to obtain a mixed solution.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, cooling to room temperature to obtain single crystal perovskite, and adding a sodium hydroxide solution into the mixed solutionIs MAPbI3。
In addition, the comparative example also provides a photodetector comprising the single crystal perovskite described above and a silver electrode layer deposited on the single crystal perovskite. Specifically, a silver metal layer with a thickness of 200nm can be deposited on the polished surface of the single crystal perovskite by evaporation to form a silver electrode layer.
Comparative example 2
The comparative example provides a rare earth doped single crystal perovskite, the preparation method of which comprises the following steps:
s1, 2.93g of lead acetate trihydrate and 10mL of saturated hydroiodic acid are placed in a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 1.55mmol of YbCl is added3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite marked as MAPbI3:Yb。
In addition, the comparative example also provides a photodetector comprising the above rare earth-doped single crystal perovskite and a silver electrode layer deposited on the rare earth-doped single crystal perovskite. Specifically, a silver metal layer with the thickness of 200nm can be deposited on the polished surface of the rare earth doped single crystal perovskite by an evaporation method to form a silver electrode layer.
Comparative example 3
The embodiment provides a rare earth doped single crystal perovskite, and the preparation method comprises the following steps:
s1, 2.93g of lead acetate trihydrate and 10mL of saturated hydroiodic acid are placed in a glass bottle and stirred and mixed by a magnetic heating stirrer until the lead acetate is completely dissolved, and then 0.38mmol of ErCl is added3·6H2O, and stirring at the temperature of 80 ℃ until a clear mixed solution is obtained.
S2, adding a methylamine water solution containing 0.5979g of methylamine and 2mL of saturated hydroiodic acid into the mixed solution, stirring overnight at 100 ℃, transferring the mixture into a reaction kettle with a polytetrafluoroethylene liner, placing the reaction kettle into an oven for reaction at 180 ℃ for 24 hours, cooling at the cooling speed of 2 ℃/h, and cooling to room temperature to obtain the rare earth doped single crystal perovskite marked as MAPbI3:Er。
In addition, the comparative example also provides a photodetector comprising the above rare earth-doped single crystal perovskite and a silver electrode layer deposited on the rare earth-doped single crystal perovskite. Specifically, a silver metal layer with the thickness of 200nm can be deposited on the polished surface of the rare earth doped single crystal perovskite by an evaporation method to form a silver electrode layer.
Experimental example:
firstly, the morphology and the size of the rare earth doped single crystal perovskite prepared in the embodiment 1 are shown in the attached figure 1.
Second, the X-ray diffraction pattern of the rare earth-doped single crystal perovskite obtained in example 1 is shown in fig. 2. In FIG. 2, "Sample just modulated" refers to the X-ray diffraction pattern of the rare earth-doped single crystal perovskite as just produced in example 1, and "Sample after 300days in air" refers to the X-ray diffraction pattern of the rare earth-doped single crystal perovskite produced in example 1 after exposure to air for 300 days. In addition, X-ray diffraction patterns were recorded on samples of rare earth-doped single-crystal perovskite powders by using a Rigaku TTR III type X-ray diffractometer. Specifically, a copper target Kalpha ray (lambda =0.15406 nm) is used as a radiation source, the scanning range is 5-65 degrees, the scanning speed is 10 degrees/min, the tube current is 200mA, and the tube voltage is 40 kV. As can be seen from fig. 2, the X-ray diffraction pattern shows that the rare earth doped single crystalline perovskite is a typical tetragonal phase perovskite crystal structure. Moreover, after the rare earth doped single crystal perovskite is exposed in the air for 300days, the XRD pattern is not changed, and no obvious new diffraction peak appears, which indicates that the perovskite is stable for a long time.
Thirdly, the rare earth doped single crystal perovskite or undoped single crystal perovskite prepared in the embodiment 1 and the comparative examples 1 to 3 are respectively absorbed and fluorescedTesting of the spectrum: in a room temperature environment, a UV/vis-NIR absorption spectrum of a sample is measured by using a Shimadzu UV-1800 spectrometer, and the information of the fluorescence spectrum of the exciton of the single crystal perovskite is collected by using a Hitachi F-4500 (the slit width is 5.0nm, the voltage of a photomultiplier is 700V, and the lambda = 700-900 nm) fluorescence spectrophotometer. The emission spectrum of the rare earth ion in the infrared region of the sample is collected by using an infrared photomultiplier of a double grating monochromator under the excitation of a semiconductor Laser Diode (LD) with a wavelength of 808 nm. As shown in fig. 3, after introduction of rare earth ions in the single crystal MAPbI3 matrix, the absorption peak appeared slightly blue-shifted and the sample showed a clear band-edge absorption cutoff, indicating a minimal number of trap states in the sample bandgap. As shown in FIG. 4, which is a fluorescence spectrum of a sample, it is demonstrated that the introduction of rare earth ions indeed improved single crystal MAPbI3The optical properties of (1).
Fourthly, the rare earth doped single crystal perovskite prepared in the above example 1 is measured by a scanning electron microscope: scanning electron microscopy was tested using a JEOL JSM-7500F scanning electron microscope equipped with X-ray energy dispersive spectroscopy. As shown in fig. 5, the rare earth-doped single crystal perovskite prepared in example 1 has a smooth surface.
Fifthly, the rare earth doped single crystal perovskite prepared in the example 1 and the undoped single crystal perovskite prepared in the comparative example 1 are respectively subjected to X-ray photoelectron spectrum tests: x-ray photoelectron spectroscopy (XPS) testing of samples was performed on a Kratos Axis Ultra DLD spectrometer equipped with a monochromatic Al K α X-ray source (hv = 1486.6 eV) with a drive power of 150W. As shown in FIG. 4, the example of the present invention successfully prepared MAPbI3Yb, Er single crystal perovskites.
Sixthly, I-V tests are respectively carried out on the photoelectric detectors prepared in the embodiment 1 and the comparative examples 1 to 3: the I-V curves were recorded using a Keithly 2400 system at different optical power densities and applied bias voltages. As shown in fig. 7, the device shows a broadband response from ultraviolet to infrared. Notably, the incorporation of rare earth ions also makes semiconductor based MAPbI3The intrinsic spectral response of the photodetector of (1) is broadened. Of detectors under 3v biasDark current (Idark) as low as only about 10-9A, the photosensitivity of the photodetector is very good.
Seventhly, the photo-stability of the photodetector obtained in example 1 was measured under continuous illumination for 2000s, and as a result, as shown in fig. 8, the photo-stability of the photodetector was relatively good under continuous irradiation with 650nm, 980nm, and 1540nm excitation lights.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The rare earth doped single crystal perovskite is characterized in that the rare earth doped single crystal perovskite is rare earth ion doped CH3NH3PbX3A single crystal perovskite; wherein X is halogen and the rare earth ion is Yb3+、Ce3+、Tb3+、Eu3+、Nd3+、Er3+、Dy3+At least two of them.
2. A rare earth doped monocrystalline perovskite according to claim 1, characterized in that X is Br or I.
3. A method for preparing a rare earth doped single crystal perovskite according to any one of claims 1 to 2, comprising the steps of:
mixing aqueous solutions of lead acetate and hydrogen halide, and then mixing the aqueous solutions with chlorides of rare earth ions to obtain a mixed solution;
and adding a methylamine aqueous solution and a hydrogen halide aqueous solution into the mixed solution, carrying out heat preservation reaction, and then carrying out cooling treatment to obtain the rare earth doped single crystal perovskite.
4. The method according to claim 3, wherein the aqueous solution of hydrogen halide is hydroiodic acid or hydrobromic acid.
5. The method for preparing a rare earth-doped single crystal perovskite according to claim 3, wherein the molar mass of the chloride of the rare earth ions is 20-30% of the molar mass of lead acetate.
6. The method according to claim 3, wherein the chloride of the rare earth ions is YbCl3·6H2O、CeCl3·6H2O、TbCl3·6H2O、EuCl3·6H2O、NdCl3·6H2O、ErCl3·6H2O、DyCl3·6H2At least two of O.
7. The method according to claim 6, wherein the chloride of the rare earth ions is YbCl3·6H2O and ErCl3·6H2O; wherein, the YbCl3·6H2O and ErCl3·6H2The molar ratio of O is (15-25): 5.
8. The method for preparing a rare earth-doped single crystal perovskite according to claim 3, wherein the temperature of the heat preservation reaction in the step is 170-200 ℃.
9. A rare earth-doped single crystal perovskite produced by the production method according to any one of claims 3 to 8.
10. A photodetector comprising a rare earth doped single crystal perovskite according to any one of claims 1 to 2 or 9 and a silver electrode layer deposited on the rare earth doped single crystal perovskite.
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