CN107359251B - Organic-inorganic hybrid perovskite photoelectric detector and preparation method thereof - Google Patents

Organic-inorganic hybrid perovskite photoelectric detector and preparation method thereof Download PDF

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CN107359251B
CN107359251B CN201710615010.XA CN201710615010A CN107359251B CN 107359251 B CN107359251 B CN 107359251B CN 201710615010 A CN201710615010 A CN 201710615010A CN 107359251 B CN107359251 B CN 107359251B
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inorganic hybrid
hybrid perovskite
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CN107359251A (en
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李金华
王强
王贤保
梅涛
王建颖
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Wuhan Shunyuansheng Biomedical Technology Co ltd
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Hubei University
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Abstract

The invention provides an organic-inorganic hybrid perovskite photoelectric detector and a preparation method thereof. The invention provides an organic-inorganic hybrid perovskite photoelectric detector which comprises an organic-inorganic hybrid perovskite single crystal with a planar structure and a metal electrode pair which is in contact with and arranged on the same plane of the organic-inorganic hybrid perovskite single crystal. The invention takes the organic-inorganic hybrid perovskite single crystal as the photosensitive material, the perovskite with the single crystal structure has less internal defects and has the gain effect on photocurrent, and the obtained light has sensitive response to light with different wavelengths and simultaneously has high response rate and fast response speed. Experimental results show that the detection wavelength of the organic-inorganic hybrid perovskite photoelectric detector provided by the invention is 440-895 nm, and the response sensitivity can reach 811A/W.

Description

Organic-inorganic hybrid perovskite photoelectric detector and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric elements, in particular to an organic-inorganic hybrid perovskite photoelectric detector and a preparation method thereof.
Background
The photoelectric detector has the function of converting optical signals into electric signals, is a basic device for supporting the technical field of optical information, and has wide application in the fields of optical communication, sensing, safety, biological sensing and the like. The current commercial photodetectors are mainly based on inorganic semiconductor materials such as Si, GaN, InGaAs, etc. The detector has good performance in response speed, sensitivity and stability. However, the preparation process of the photodetector based on Si, GaN and InGaAs is complex and high in cost. Therefore, the development of a photodetector with good performance and low cost has great significance for the development of the field of optical information.
Along with rapid improvement of photoelectric conversion efficiency of organic-inorganic hybrid perovskite (perovskite for short) solar cell, perovskite material has good light absorption systemThe characteristics of the number epsilon, high carrier mobility, low-cost solution method preparation process and the like are widely concerned. These characteristics indicate that perovskite materials can be used to fabricate photodetectors with both low cost and good performance. The first report on the PCBM/CH-based Yangyang project group in the university of California of the United states of 2014 in los Angeles3NH3PbI3-xClxand/PEDOT is a perovskite photoelectric detector with a PSS structure. The detector is obviously superior to the organic photoelectric detector and the quantum dot photoelectric detector reported at present in the aspects of sensitivity, dynamic range and response speed. Huxin of China science and technology university and the like adopt ITO/CH3NH3PbI3The flexible perovskite photoelectric detector is prepared on the PET substrate, and bending tests show that the photoelectric conversion performance of the flexible perovskite photoelectric detector is not obviously degraded after 120 bending cycles. In order to improve the stability of the perovskite photoelectric detector in the air, the protective layer of the perovskite photoelectric detector is prepared by spin coating a hydrophobic polymer material, such as Guo Yunlong, and the like, so that the service life of the perovskite photoelectric detector in the air reaches 100 days.
However, in the existing literature reports, researchers mainly study the photoelectric detector based on the perovskite thin film structure, and the internal defects of the perovskite of the thin film structure are more, and the surface multi-island structure of the perovskite thin film can be observed under SEM, and the defects influence the further improvement of the response rate and the response speed of the photoelectric detector.
Disclosure of Invention
The invention aims to provide an organic-inorganic hybrid perovskite photoelectric detector and a preparation method thereof. The organic-inorganic hybrid perovskite photoelectric detector provided by the invention has high response rate and high response speed.
The invention provides an organic-inorganic hybrid perovskite photoelectric detector which comprises an organic-inorganic hybrid perovskite single crystal with a planar structure and a metal electrode pair which is in contact with and arranged on the same plane of the organic-inorganic hybrid perovskite single crystal.
Preferably, the organic-inorganic hybrid perovskite single crystal comprises methylamine lead bromide single crystal or methylamine lead iodide single crystal.
Preferably, the organic-inorganic hybrid perovskite single crystal is a cuboid, the length and the width of the cuboid are independently 3-6 mm, and the thickness of the cuboid is 2-3 mm.
Preferably, the metal electrode pair is arranged on the largest plane of the organic-inorganic hybrid perovskite single crystal in a contact mode.
Preferably, the thickness of the metal electrode pair is independently 60 to 80 nm.
Preferably, the distance between the metal electrode pairs is 10-200 μm.
Preferably, the metal electrode pair is made of gold, silver or aluminum independently.
The invention provides a preparation method of the organic-inorganic hybrid perovskite photoelectric detector, which comprises the following steps:
(1) providing an organic-inorganic hybrid perovskite precursor liquid;
(2) performing induced crystallization on the organic-inorganic hybrid perovskite precursor liquid in the step (1) to obtain an organic-inorganic hybrid perovskite single crystal;
(3) covering electrodes on the surface of the organic-inorganic hybrid perovskite single crystal obtained in the step (2) to obtain the organic-inorganic hybrid perovskite photoelectric detector.
Preferably, the induced crystallization in the step (2) is performed under a gradient temperature rise condition, wherein the initial temperature of the gradient temperature rise is 45-85 ℃, and the final temperature of the gradient temperature rise is 75-115 ℃.
Preferably, the gradient of the gradient temperature rise is increased by 4-6 ℃ every 30-60 min.
The invention provides an organic-inorganic hybrid perovskite photoelectric detector which comprises an organic-inorganic hybrid perovskite single crystal with a planar structure and a metal electrode pair which is in contact with and arranged on the same plane of the organic-inorganic hybrid perovskite single crystal. The organic-inorganic hybrid perovskite single crystal is used as a photosensitive material, the perovskite with a single crystal structure has fewer internal defects and has a gain effect on photocurrent, and the obtained organic-inorganic hybrid perovskite photoelectric detector has sensitive response to light with different wavelengths and simultaneously has high response rate and high response speed. Experimental results show that the detection wavelength of the organic-inorganic hybrid perovskite photoelectric detector provided by the invention is 440-895 nm, and the response sensitivity can reach 811A/W.
Drawings
FIG. 1 is an X-ray diffraction pattern of methylamine lead bromide in example 1 of this invention;
FIG. 2 is an X-ray diffraction pattern of methylamine lead iodide in example 2 of this invention;
FIG. 3 is an absorption spectrum of methylamine lead bromide in example 1 of the present invention;
FIG. 4 is an absorption spectrum of methylamine lead iodide in example 2 of the present invention;
FIG. 5 is a schematic structural diagram of an organic-inorganic hybrid perovskite photodetector prepared in examples 1 and 2 of the present invention;
FIG. 6 is a graph showing the transmission curve of the methylamine lead bromide photodetector prepared in example 1 of the present invention under illumination of 440nm wavelength;
FIG. 7 is a graph showing the relationship between drain and source voltages and responsivity of the methylamine lead bromide photodetector prepared in example 1 of the present invention under different illumination intensities at a wavelength of 440 nm;
FIG. 8 is a graph of a transient photoresponse test of the methylamine lead bromide photodetector prepared in example 1 of the present invention under illumination of a wavelength of 440 nm;
FIG. 9 is a graph showing the transmission curve of the methylamine lead bromide photodetector prepared in example 1 of the present invention under illumination at 520 nm;
FIG. 10 is a graph showing the relationship between drain and source voltages and responsivity of the methylamine lead bromide photodetector prepared in example 1 of the present invention under different illumination intensities at a wavelength of 520 nm;
FIG. 11 is a graph of a transient photoresponse test of the methylamine lead bromide photodetector prepared in example 1 of the present invention under illumination of 520nm wavelength;
FIG. 12 is a graph showing the transmission curve of the methylamine lead iodine photodetector prepared in example 2 of the present invention under illumination with a wavelength of 660 nm;
fig. 13 is a graph showing the relationship between drain and source voltages and responsivity of the methylamine lead iodine photodetector prepared in example 2 of the present invention under different illumination intensities with 660nm wavelength;
FIG. 14 is a graph of transient photoresponse test of the methylamine lead iodine photodetector prepared in example 2 of the present invention under 660nm wavelength illumination;
FIG. 15 is a graph showing the transmission curve of the methylamine lead iodine photodetector prepared in example 2 of the present invention under illumination at a wavelength of 895 nm;
FIG. 16 is a graph showing the relationship between drain and source voltages and responsivity of the methylamine lead iodine photodetector prepared in example 2 of the present invention under different illumination intensities at 895nm wavelength;
fig. 17 is a graph of a transient photoresponse test of the methylamine lead iodine photodetector prepared in example 2 of the present invention under the illumination of 895nm wavelength.
Detailed Description
The invention provides an organic-inorganic hybrid perovskite photoelectric detector which comprises an organic-inorganic hybrid perovskite single crystal with a planar structure and a metal electrode pair which is in contact with and arranged on the same plane of the organic-inorganic hybrid perovskite single crystal.
The organic-inorganic hybrid perovskite photoelectric detector provided by the invention comprises an organic-inorganic hybrid perovskite single crystal with a planar structure. In the present invention, the organic-inorganic hybrid perovskite single crystal preferably comprises methylamine lead bromide single crystal or methylamine lead iodide single crystal. In the present invention, the organic-inorganic hybrid perovskite single crystal is preferably a rectangular parallelepiped; the length and the width of the cuboid are independently preferably 3-6 mm, and more preferably 4-5 mm; the thickness of cuboid is preferably 2 ~ 3 mm.
The organic-inorganic hybrid perovskite photoelectric detector provided by the invention comprises a metal electrode pair which is arranged on the same plane of the organic-inorganic hybrid perovskite single crystal in a contact manner. In the present invention, the pair of metal electrodes is preferably disposed in contact with the largest plane of the organic-inorganic hybrid perovskite single crystal. In the present invention, the thickness of the metal electrode pair is preferably 60 to 80nm, and more preferably 65 to 75nm, independently. In the present invention, the distance between the metal electrode pairs is preferably 10 to 200 μm, more preferably 50 to 150 μm, and most preferably 80 to 120 μm. In the present invention, the material of the metal electrode pair is preferably gold, silver, or aluminum, and more preferably the same material.
The organic-inorganic hybrid perovskite single crystal is used as a photosensitive material, the perovskite with a single crystal structure has fewer internal defects and has a gain effect on photocurrent, and the obtained organic-inorganic hybrid perovskite photoelectric detector has sensitive response to light with different wavelengths and simultaneously has high response rate and high response speed. In the invention, the detection wavelength of the organic-inorganic hybrid perovskite photoelectric detector is preferably 440-895 nm, and more preferably 500-800 nm. In the invention, the response sensitivity of the organic-inorganic hybrid perovskite photoelectric detector is preferably 22-811A/W. In the invention, the response time of the organic-inorganic hybrid perovskite photoelectric detector is preferably 0.1-0.2 s; the recovery time of the organic-inorganic hybrid perovskite photoelectric detector is preferably 0.1-0.2 s.
The invention also provides a preparation method of the organic-inorganic hybrid perovskite photoelectric detector, which comprises the following steps:
(1) providing an organic-inorganic hybrid perovskite precursor liquid;
(2) performing induced crystallization on the organic-inorganic hybrid perovskite precursor liquid in the step (1) to obtain an organic-inorganic hybrid perovskite single crystal;
(3) covering electrodes on the surface of the organic-inorganic hybrid perovskite single crystal obtained in the step (2) to obtain the organic-inorganic hybrid perovskite photoelectric detector.
The invention provides an organic-inorganic hybrid perovskite precursor liquid. In the invention, the organic-inorganic hybrid perovskite precursor liquid is preferably methylamine lead bromide precursor liquid or methylamine lead iodide precursor liquid. In the present invention, when the organic-inorganic hybrid perovskite precursor liquid is a methylamine lead bromide precursor liquid, the organic-inorganic hybrid perovskite precursor liquid preferably includes lead bromide, methyl ammonium bromide and N, N-dimethylformamide. In the present invention, the volume ratio of the amount of the lead bromide substance, the amount of the methylammonium bromide substance, and the N, N-dimethylformamide is preferably (0.001 to 0.003mol):2mL, and more preferably 0.002mol:0.002mol:2 mL.
The sources of the lead bromide, the methyl ammonium bromide and the N, N-dimethylformamide are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the present invention, the purity of the lead bromide is preferably 99.9%; the purity of the methyl ammonium bromide is preferably 99%; the purity of the N, N-dimethylformamide is preferably 99.9%.
In the present invention, when the organic-inorganic hybrid perovskite precursor liquid is a methylamine lead iodide precursor liquid, the organic-inorganic hybrid perovskite precursor liquid preferably includes lead iodide, methyl ammonium iodide and γ -butyrolactone. In the present invention, the volume ratio of the amount of the lead iodide substance, the amount of the methylammonium iodide substance, and the γ -butyrolactone is preferably (0.001 to 0.003mol):2mL, and more preferably 0.002mol:0.002mol:2 mL.
The sources of the lead iodide, methylammonium iodide and γ -butyrolactone in the present invention are not particularly limited, and commercially available products well known to those skilled in the art may be used. In the present invention, the purity of the lead iodide is preferably 99.9%; the purity of the methyl ammonium bromide is preferably 99%; the purity of gamma-butyrolactone is preferably 99%.
The preparation method of the organic-inorganic hybrid perovskite precursor is not particularly limited, and the organic-inorganic hybrid perovskite precursor can be prepared by a preparation method of a mixed solution well known to those skilled in the art.
The present invention preferably performs filtration to filter out undissolved particles before using the organic-inorganic hybrid perovskite precursor liquid. In the present invention, the filtration is preferably performed using a PVDF filter head. The source of the PVDF filter head is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the pore diameter of the PVDF filter head is preferably 0.4-0.5 μm, and more preferably 0.45 μm.
After obtaining the organic-inorganic hybrid perovskite precursor liquid, the invention carries out induced crystallization on the organic-inorganic hybrid perovskite precursor liquid to obtain the organic-inorganic hybrid perovskite single crystal. The invention preferably places single crystal seeds in the organic-inorganic hybrid perovskite precursor liquid for induced crystallization. The seed crystal for inducing crystallization is not specially limited, and the small crystal of the same material as the single crystal to be prepared is adopted. In the present invention, the particle size of the crystallization-inducing seed crystal is preferably 0.5mm or less, and more preferably 0.1 to 0.3 mm. In the invention, the seed crystal provides a nucleation core for induced crystallization, and in the gradient temperature rise process, the organic-inorganic hybrid perovskite nucleates on the surface of the seed crystal and then grows into a single crystal.
In the present invention, the induced crystallization is preferably performed under a gradient temperature rise condition; the initial temperature of the gradient temperature rise is preferably 45-85 ℃, and more preferably 48-82 ℃; the final temperature of the gradient temperature rise is preferably 75-115 ℃, and more preferably 78-112 ℃. In the invention, the gradient of the gradient temperature rise is preferably increased by 4-6 ℃ every 30-60 min, and more preferably increased by 5 ℃ every 30-60 min; the time from the initial temperature of the gradient temperature rise to the final temperature is preferably 3-8 h. The temperature rise rate during gradient temperature rise is not particularly limited, and the temperature rise rate can be adjusted according to the time from the initial temperature to the end temperature.
In the invention, when the organic-inorganic hybrid perovskite precursor liquid is methylamine lead bromide precursor liquid, the initial temperature of gradient temperature rise is preferably 45-55 ℃, and more preferably 48-52 ℃; the final temperature of the gradient temperature rise is preferably 75-85 ℃, and more preferably 78-82 ℃. In the invention, the gradient of the gradient temperature rise is preferably increased by 4-6 ℃ every 30min, and more preferably increased by 5 ℃ every 30 min; the time from the initial temperature of the gradient temperature rise to the final temperature is preferably 3-4 h.
In the invention, when the organic-inorganic hybrid perovskite precursor liquid is methylamine lead iodide precursor liquid, the initial temperature of gradient temperature rise is preferably 75-85 ℃, and more preferably 78-82 ℃; the final temperature of the gradient temperature rise is preferably 105-115 ℃, and more preferably 108-112 ℃. In the invention, the gradient of the gradient temperature rise is preferably increased by 4-6 ℃ every 60min, and more preferably increased by 5 ℃ every 60 min; the time from the initial temperature of the gradient temperature rise to the final temperature is preferably 7-8 h.
In the invention, the solubility of the organic-inorganic hybrid perovskite in the solution is inversely proportional to the temperature, the higher the temperature is, the lower the solubility is, the precipitation and crystallization speeds can be adjusted in real time through gradient temperature rise, the two speeds are kept consistent as much as possible, the crystallization speed is ensured to be the same as the precipitation speed, and finally a larger single crystal is formed in the solution.
The heating method of the gradient temperature rise is not particularly limited, and the gradient temperature rise can be performed by a heating device well known to those skilled in the art. In the invention, the heating of gradient temperature rise is preferably water bath heating; in the embodiment of the present invention, it is preferable to use a heat collecting water bath for heating.
The container for inducing crystallization in the present invention is not particularly limited, and a container for growing a single crystal known to those skilled in the art may be used. In the present invention, the container for inducing crystallization is preferably a flat-bottom container, more preferably a flat-bottom test tube. In the invention, the diameter of the flat-bottom test tube is preferably 12-18 mm, and more preferably 15 mm; the length of the flat-bottom test tube is preferably 140-160 mm, and more preferably 150 mm.
After the induced crystallization is finished, the product of the induced crystallization is preferably washed and dried in sequence to obtain the organic-inorganic hybrid perovskite single crystal. The washing and drying operations are not particularly limited in the present invention, and washing and drying techniques known to those skilled in the art may be used. In the present invention, the detergent for washing the methylamine lead bromide single crystal is preferably N, N-dimethylformamide; the detergent for washing the methylamine lead iodine single crystal is preferably gamma-butyrolactone; the washing times of the methylamine lead bromide single crystal and methylamine lead iodide single crystal are preferably 2-3 times independently. In the present invention, the drying is preferably normal temperature drying; the drying is preferably carried out under the protection of inert gas; the drying time is preferably 8-16 h, and more preferably 10-12 h.
In the present invention, the organic-inorganic hybrid perovskite single crystal is preferably stored without air. In the invention, the air-isolated preservation can avoid the decomposition of the organic-inorganic hybrid perovskite single crystal in air.
After the organic-inorganic hybrid perovskite single crystal is obtained, the surface of the organic-inorganic hybrid perovskite single crystal is covered with an electrode to obtain the organic-inorganic hybrid perovskite photoelectric detector. The operation of the covered electrode is not particularly limited in the present invention, and the technical scheme for preparing the electrode, which is well known to those skilled in the art, can be adopted. In the present invention, the method of covering the electrode is preferably vapor deposition, more preferably vacuum vapor deposition; the temperature of the vacuum evaporation is preferably 1000-1200 ℃, and more preferably 1050-1150 ℃; the time of the vacuum evaporation is preferably 250-350 s, and more preferably 280-320 s; the vacuum degree of the vacuum evaporation is preferably 3-4 x 10-4Pa。
In order to form the electrode layer as a metal electrode pair disposed opposite to each other, it is preferable in the present invention that a mask plate is attached to the surface of the organic-inorganic hybrid perovskite single crystal before the vapor deposition, and then removed after the vapor deposition is completed. The invention has no special requirements on the shape and the size of the mask plate, and can adjust the shape and the size of the mask plate according to the single crystal and the size of the needed metal electrode pair.
The invention preferably polishes the surface to be covered of the organic-inorganic hybrid perovskite single crystal before covering the electrode. The operation of the polishing is not particularly limited in the present invention, and the technical scheme of polishing the crystal, which is well known to those skilled in the art, can be adopted. The invention preferably polishes the surface of the organic-inorganic hybrid perovskite single crystal until the surface has metallic luster. The emery paper for polishing in the present invention is not particularly limited, and emery paper known to those skilled in the art may be used. In the present invention, the roughness of the surface of the emery paper is preferably in the order of micrometers.
In the present invention, the organic-inorganic hybrid perovskite photodetector is preferably used under inert conditions of no water and no oxygen. The connection mode of the organic-inorganic hybrid perovskite photoelectric detector is not particularly limited, and the organic-inorganic hybrid perovskite photoelectric detector can be connected with a power supply in a manner well known to those skilled in the art.
For further illustration of the present invention, the following examples are provided to describe the organic-inorganic hybrid perovskite photodetectors and the methods for making the same in detail, but they should not be construed as limiting the scope of the present invention.
Example 1:
dissolving 0.002mol (0.223g) of methyl ammonium bromide and 0.002mol (0.734g) of lead bromide in a flat-bottom test tube filled with 2mLN, N-dimethylformamide, and stirring to obtain a clear and transparent methylamine lead bromine precursor solution with the concentration of 1 mol/L; in the present invention, the flat-bottomed test tube needs to be cleaned with acetone, isopropanol and deionized water; the invention preferably adopts acetone and isopropanol to wash for 2 times respectively in sequence, and then uses deionized water to wash for 3 times; absorbing the methylamine lead bromine precursor solution by using an injector with the capacity of 5mL, and then filtering by using a PVDF filter head with the aperture of 0.45 mu m to obtain colorless and clear methylamine lead bromine precursor solution; placing a small methylamine lead bromide single crystal with a particle size of 0.1mm and good appearance in the middle of the bottom of a flat-bottom test tube filled with methylamine lead bromide precursor solution; placing the flat-bottom test tube into a heat collection water bath kettle, setting the initial temperature to be 50 ℃, then increasing the temperature by 5 ℃ every half hour until the temperature is increased to 80 ℃, and continuing the crystallization process for 3-4 hours; after crystallization is finished, the methylamine lead bromide is washed for many times by N-N, dimethyl formamide, the methyl ammonium bromide and the lead bromide on the surface of the crystal are removed, and then the crystal is put into a glove box filled with argon gas for drying treatment, so that methylamine lead bromide single crystal is obtained.
Fixing the single crystals on the back of the supporting plate by using a double-sided adhesive tape, and then polishing the surfaces of carborundum paper until the surfaces of the two single crystals have metallic luster;
and (3) sticking the polished surface of the monocrystal on a mask plate with a specific shape, evaporating a 60nm thick gold electrode layer in vacuum, and removing the mask plate to obtain the organic-inorganic hybrid perovskite photoelectric detector.
The X-ray diffraction pattern of methylamine lead bromide single crystal in this example is shown in fig. 1, and it can be seen from fig. 1 that the crystallinity of single crystal is good, and methylamine lead bromide is oriented in (100) plane.
The absorption spectrum and photoluminescence spectrum of the methylamine lead bromide single crystal in the embodiment are shown in fig. 3, and as can be seen from fig. 3, the absorption peak range of methylamine lead bromide is 400-570 nm.
The structure of the photodetector prepared in this example is shown in fig. 5, and it can be seen from the figure that the photodetector prepared in this example includes a methylamine lead bromide single crystal and a gold electrode pair which are sequentially disposed.
In the photodetector prepared in this example, the length of the methylamine lead bromide single crystal is 5mm, the thickness of the electrode layer is 60nm, and the electrode pair distance is 140 μm.
Graphs of the relationship between voltage and current of the methylamine lead bromide photoelectric detector prepared in this example under different light intensities of illumination with wavelengths of 440nm and 520nm are respectively shown in fig. 6 and fig. 9. As can be seen from fig. 6 and 9, as the voltage and light intensity increase, the photocurrent increases, because the larger the voltage and light intensity, the higher the carrier concentration, and the larger the photocurrent;
the graphs of the test curves of the cyclic light response of the methylamine lead bromide photoelectric detector prepared in the embodiment of the invention under different light intensities of illumination with the wavelengths of 440nm and 520nm and the relationship between the voltage and the current are respectively shown in fig. 8 and fig. 11, and it can be seen from the graphs that both the response time and the recovery time are less than 0.300 s;
the graph of the relationship between the drain and source voltages and the responsivity of the methylamine lead bromide photodetector prepared in this example under different illumination intensities at the wavelengths of 440nm and 520nm is shown in fig. 7 and 10, and it can be seen from the graph that the highest response reaches 35AW-1。
Example 2:
the invention dissolves 0.002mol (0.317g) of methyl ammonium iodide and 0.002mol (0.992g) of lead iodide into a flat-bottomed test tube filled with 2mL of gamma-butyrolactone; stirring to obtain a clear and transparent methylamine lead iodine precursor solution with the concentration of 1 mol/L; in the present invention, the flat-bottomed test tube needs to be cleaned with acetone, isopropanol and deionized water; the invention preferably adopts acetone and isopropanol to wash for 2 times respectively in sequence, and then uses deionized water to wash for 3 times; absorbing the methylamine lead iodine precursor solution by using an injector with the capacity of 5mL, and then filtering by using a PVDF filter head with the aperture of 0.45 mu m to obtain colorless and clear methylamine lead iodine precursor solution; placing a small methylamine lead iodine monocrystal with a particle size of 0.2mm and good appearance in the middle of the bottom of a flat-bottom test tube filled with methylamine lead iodine precursor solution; placing the flat-bottom test tube into a heat collection oil bath kettle, setting the initial temperature to be 80 ℃, then increasing the temperature by 5 ℃ every hour until the temperature is increased to 110 ℃, and continuing the crystallization process for 7-8 hours; after crystallization is finished, the methylamine lead iodine is washed for a plurality of times by gamma-butyrolactone to remove methyl ammonium iodide and lead iodide on the surface of the crystal, and then the crystal is put into a glove box filled with argon gas for drying treatment to obtain methylamine lead iodine single crystal.
Fixing the single crystals on the back of the supporting plate by using a double-sided adhesive tape, and then polishing the surfaces of carborundum paper until the surfaces of the two single crystals have metallic luster;
and (3) sticking the polished surface of the monocrystal on a mask plate with a specific shape, evaporating a 60nm thick gold electrode layer in vacuum, and removing the mask plate to obtain the organic-inorganic hybrid perovskite photoelectric detector.
The structure of the photodetector prepared in this example is shown in fig. 5, and it can be seen from the figure that the photodetector prepared in this example includes a methylamine lead bromide single crystal and a gold electrode pair which are sequentially disposed.
The X-ray diffraction pattern of the methylamine lead iodide single crystal in this example is shown in fig. 2, and it can be seen from fig. 2 that the crystallinity of the single crystal is good, and methylamine lead iodide is oriented in the (112) plane.
In the embodiment, the absorption spectrum and photoluminescence spectrum of the methylamine lead iodine monocrystal are shown in fig. 4, and as can be seen from fig. 4, the absorption peak range of methylamine lead iodine is 400-850 nm, which shows that the photoelectric detector has strong absorption to light with the wavelength less than or equal to 850 nm;
the length of the methylamine lead iodine single crystal in the photoelectric detector prepared by the embodiment is 4mm, the thickness of the electrode layer is 60nm, and the distance between the electrode pairs is 140 μm.
The graph of the relationship between voltage and current of the methylamine lead iodine photoelectric detector prepared in this embodiment under different light intensities of 660nm and 895nm light is shown in fig. 12 and 15, and it can be seen from fig. 12 and 15 that the photocurrent increases with the increase of voltage and light intensity, because the larger the voltage and light intensity is, the higher the carrier concentration is, the larger the photocurrent is;
the graph of the test of the cyclic light response of the methylamine lead iodine photodetector prepared in this embodiment on the relationship between voltage and current under different light intensities of 660nm and 895nm illumination is shown in fig. 14 and 17, and it can be seen from the graph that both the response and the recovery time of the transistor are less than 0.300 s;
the graph of the relationship between drain and source voltages and responsivity of the methylamine lead iodine photoelectric detector prepared in the embodiment under different light intensities of 660nm and 895nm illumination is shown in fig. 13 and 16, and it can be seen from the graph that the highest response reaches 811AW-1。
Example 3:
0.002mol (0.223g) of methyl ammonium bromide and 0.002mol (0.734g) of lead bromide were dissolved in a flat-bottomed test tube containing 2mLN-N, dimethylformamide; stirring to obtain a clear and transparent methylamine lead bromide precursor solution with the concentration of 1 mol/L; in the present invention, the flat-bottomed test tube needs to be cleaned with acetone, isopropanol and deionized water; the invention preferably adopts acetone and isopropanol to wash for 1 time respectively in sequence, and then uses deionized water to wash for 2 times; absorbing the methylamine lead bromine precursor solution by using an injector with the capacity of 5mL, and then filtering by using a PVDF filter head with the aperture of 0.45 mu m to obtain colorless and clear methylamine lead bromine precursor solution; placing a small methylamine lead bromide single crystal with a particle size of 0.1mm and good appearance in the middle of the bottom of a flat-bottom test tube filled with methylamine lead bromide precursor solution; placing the flat-bottom test tube into a heat collection water bath kettle, setting the initial temperature to be 50 ℃, then increasing the temperature by 5 ℃ every half hour until the temperature is increased to 80 ℃, and continuing the crystallization process for 3-4 hours; after crystallization is finished, the methylamine lead bromide is washed for many times by N-N, dimethyl formamide, the methyl ammonium bromide and the lead bromide on the surface of the crystal are removed, and then the crystal is put into a glove box filled with argon gas for drying treatment, so that methylamine lead bromide single crystal is obtained.
Fixing the single crystal on the back of the supporting plate by using a double-sided adhesive tape, and then polishing the surface of carborundum paper until the surface of the single crystal has metallic luster;
and (3) sticking the polished surface of the single crystal on a mask plate with a specific shape, evaporating a layer of gold electrode with the thickness of 80nm in vacuum, and removing the mask plate to obtain the photoelectric detector.
The length of the methylamine lead bromide single crystal in the photoelectric detector prepared by the embodiment is 4mm, the thickness of the electrode layer is 80nm, and the electrode pair distance is 140 μm. The response and the recovery time of the photoelectric detector prepared by the embodiment are both less than 0.300s, and the highest response reaches 811AW under different light intensities of illumination with the wavelengths of 440nm and 520nm-1。
Example 4:
the present invention dissolves 0.002mol (0.317g) of methyl ammonium iodide and 0.002mol (0.992g) of lead iodide in a flat-bottomed test tube containing 2mL of gamma-butyrolactone. Stirring to obtain a clear and transparent methylamine lead iodine precursor solution with the concentration of 1 mol/L; in the present invention, the flat-bottomed test tube needs to be cleaned with acetone, isopropanol and deionized water; the invention preferably adopts acetone and isopropanol to wash for 1 time respectively in sequence, and then uses deionized water to wash for 2 times; absorbing the methylamine lead iodine precursor solution by using an injector with the capacity of 5mL, and then filtering by using a PVDF filter head with the aperture of 0.45 mu m to obtain colorless and clear methylamine lead iodine precursor solution; placing a small methylamine lead iodine monocrystal with a particle size of 0.1mm and good appearance in the middle of the bottom of a flat-bottom test tube filled with methylamine lead iodine precursor solution; placing the flat-bottom test tube into a heat collection oil bath kettle, setting the initial temperature to be 80 ℃, then increasing the temperature by 5 ℃ every hour until the temperature is increased to 110 ℃, and continuing the crystallization process for 7-8 hours; after crystallization is finished, the methylamine lead iodine is washed for a plurality of times by gamma-butyrolactone to remove methyl ammonium iodide and lead iodide on the surface of the crystal, and then the crystal is put into a glove box filled with argon gas for drying treatment to obtain methylamine lead iodine single crystal.
Fixing the single crystal on the back of the supporting plate by using a double-sided adhesive tape, and then polishing the surface of carborundum paper until the surface of the single crystal has metallic luster;
and (3) sticking the polished surface of the single crystal on a mask plate with a specific shape, evaporating a layer of gold electrode with the thickness of 80nm in vacuum, and removing the mask plate to obtain the photoelectric detector.
The length of the methylamine lead iodine single crystal in the photoelectric detector prepared by the embodiment is 5mm, the thickness of the electrode layer is 80nm, and the distance between the electrode pairs is 140 μm. The response and the recovery time of the photoelectric detector prepared by the embodiment are both less than 0.300s, and the highest response reaches 811AW under different light intensities of illumination with the wavelengths of 660nm and 895nm-1。
The embodiments show that the organic-inorganic hybrid perovskite photoelectric detector provided by the invention has high response rate and fast response speed, the detection wavelength is 440-895 nm, and the response sensitivity can reach 811A/W.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (6)

1. A preparation method of an organic-inorganic hybrid perovskite photoelectric detector is characterized by comprising the following steps:
(1) providing an organic-inorganic hybrid perovskite precursor liquid;
(2) performing induced crystallization on the organic-inorganic hybrid perovskite precursor liquid in the step (1) to obtain an organic-inorganic hybrid perovskite single crystal;
(3) covering electrodes on the surface of the organic-inorganic hybrid perovskite single crystal obtained in the step (2) to obtain an organic-inorganic hybrid perovskite photoelectric detector;
the induced crystallization in the step (2) is carried out under the condition of gradient temperature rise, wherein the initial temperature of the gradient temperature rise is 80 ℃, and the final temperature of the gradient temperature rise is 110 ℃;
the gradient of the gradient temperature rise is increased by 4-6 ℃ every 30-60 min;
the time from the initial temperature of the gradient temperature rise to the final temperature is 7-8 h;
the organic-inorganic hybrid perovskite precursor liquid is methylamine lead iodide precursor liquid;
the organic-inorganic hybrid perovskite photoelectric detector obtained by the preparation method of the organic-inorganic hybrid perovskite photoelectric detector comprises an organic-inorganic hybrid perovskite single crystal with a planar structure and a metal electrode pair which is in contact with and arranged on the same plane of the organic-inorganic hybrid perovskite single crystal.
2. The method for preparing an organic-inorganic hybrid perovskite photodetector as claimed in claim 1, wherein the organic-inorganic hybrid perovskite single crystal is methylamine lead iodine single crystal.
3. The method for preparing an organic-inorganic hybrid perovskite photodetector as claimed in claim 1, wherein the metal electrode pair is disposed in contact with the largest plane of the organic-inorganic hybrid perovskite single crystal.
4. The method for preparing an organic-inorganic hybrid perovskite photodetector as claimed in claim 1, wherein the thickness of the metal electrode pair is 60-80 nm independently.
5. The method for preparing the organic-inorganic hybrid perovskite photodetector as claimed in claim 1 or 4, wherein the distance between the metal electrode pairs is 10-200 μm.
6. The method for preparing an organic-inorganic hybrid perovskite photodetector as claimed in claim 4, wherein the material of the metal electrode pair is gold, silver or aluminum independently.
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