CN110911566B - Perovskite single crystal particle composite film based X-ray detector and preparation method thereof - Google Patents

Perovskite single crystal particle composite film based X-ray detector and preparation method thereof Download PDF

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CN110911566B
CN110911566B CN201911244055.6A CN201911244055A CN110911566B CN 110911566 B CN110911566 B CN 110911566B CN 201911244055 A CN201911244055 A CN 201911244055A CN 110911566 B CN110911566 B CN 110911566B
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perovskite single
composite film
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CN110911566A (en
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林乾乾
彭家丽
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Wuhan University WHU
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Abstract

The invention relates to an X-ray detector based on a perovskite single crystal particle composite film and a preparation method thereof. The X-ray detector comprises a hole transport layer, a perovskite single crystal particle composite film, an electron transport layer, an interface modification layer and an electrode, wherein the perovskite single crystal particle composite film is a composite film of perovskite single crystals and polyol or polymer, the film thickness is 30-200 mu m, and the perovskite single crystals are methylamine lead bromide perovskite single crystals. The preparation method comprises the following steps: preparing methylamine lead bromide perovskite single crystals, crushing and screening the methylamine lead bromide perovskite single crystals, uniformly dispersing the methylamine lead bromide perovskite single crystals in a polyalcohol or polymer solution, then coating the methylamine lead bromide perovskite single crystals on a hole transport layer or an electron transport layer in a spinning mode, and annealing to obtain a perovskite single crystal particle composite film; and depositing an electron transport layer or a hole transport layer, an interface modification layer and an electrode on the surface of the obtained composite film to obtain the perovskite-based single crystal particle composite film X-ray detector. The preparation method is simple, can detect lower dosage rate, and has high sensitivity, quick response and excellent charge transmission performance.

Description

Perovskite single crystal particle composite film based X-ray detector and preparation method thereof
Technical Field
The invention belongs to the field of X-ray thin film devices, and particularly relates to an X-ray detector based on a perovskite single crystal particle composite film and a preparation method thereof.
Background
Organic-inorganic hybrid perovskite materials have attracted much attention in the field of optoelectronics (solar cells, light emitting diodes, photodetectors, etc.) because of their unique properties of high absorption coefficient, large hole and electron mobility, long diffusion length, adjustable band gap, convenient processing/integration, etc. In addition, the perovskite material-based X-ray detector is also a promising alternative to the current X-ray detector technology (i.e. direct conversion based on amorphous selenium or indirect conversion based on scintillation crystals), and is applied to the field of ionizing radiation detection such as high-energy X-ray or gamma ray. As with the detection of visible light photons, the detection of X-rays also includes similar steps of energy absorption, charge generation, and charge collection. It is noted that the X-ray detector must have a sufficiently thick barrier layer to absorb a sufficient amount of X-rays. In addition, to achieve good charge collection efficiency, the detector material also needs to have high charge carrier mobility and long charge carrier lifetime. X-ray detectors based on perovskite materials not only meet the above requirements, but also offer many potential advantages, such as enhanced detection sensitivity, reduced dark current, improved spatial resolution, and cost effectiveness. However, the perovskite material-based X-ray detector prepared by the prior art has large dark current and slow response, so that the lowest X-ray dose rate which can be detected by the perovskite material-based X-ray detector is limited, and the sensitivity is low.
Disclosure of Invention
The X-ray detector has a photosensitive diode type device structure, the thickness and the area of the perovskite single crystal particle composite film are adjustable, lower dose rate can be detected, the sensitivity is high, the response is fast, the charge transmission performance is excellent, and the preparation is simple and convenient.
In order to solve the technical problems, the invention provides the following technical scheme:
an X-ray detector based on a perovskite single crystal particle composite film has a photosensitive diode type device structure which is N-I-P type or P-I-N type, wherein:
the N-I-P type comprises a transparent conductive substrate, a hole transport layer, a perovskite single crystal particle composite film, an electron transport layer, an interface modification layer and an electrode, wherein all the layers are connected in sequence;
the P-I-N type comprises a transparent conductive substrate, an electron transport layer, a perovskite single crystal particle composite film, a hole transport layer, an interface modification layer and an electrode, wherein the layers are sequentially connected;
the perovskite single crystal particle composite film is a composite film of perovskite single crystal particles and polyol or polymer, the film thickness is 30-200 mu m, and the perovskite single crystal is methylamine lead bromide perovskite single crystal.
According to the scheme, the polyol is glycerol or alpha-terpineol; the polymer is polymethyl methacrylate, polyacrylonitrile, polyvinyl butyral, polyvinylidene fluoride or poly [ bis (4-phenyl) (4-butylphenyl) amine ].
According to the scheme, the particle size of the perovskite single crystal particles is 30-50 mu m.
According to the scheme, the hole transport layer is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD); the electron transport layer is zinc oxide, tin oxide, titanium dioxide or fullerene derivatives C70, C60 and PCBM; the interface modification layer is bathocuproine, molybdenum trioxide, cesium carbonate or lithium fluoride; the electrode is gold, silver, copper or aluminum;
according to the scheme, the film thickness of the hole transport layer is 20-40 nm; the thickness of the electron transport layer is 50-200 nm; the thickness of the interface modification layer is 1-8 nm; the thickness of the electrode film is 40 to 100 nm.
A preparation method of the perovskite single crystal particle composite film-based X-ray detector comprises the following specific steps:
1) preparing methylamine lead bromide perovskite single crystals;
2) drying the perovskite single crystal obtained in the step 1), and then mechanically crushing and screening to obtain perovskite single crystal particles;
3) uniformly dispersing the perovskite single crystal particles obtained in the step 2) in a polyol solution or a polymer solution to obtain a mixed suspension;
4) spin-coating the mixed suspension obtained in the step 3) on a transparent conductive substrate deposited with a hole transmission layer or an electron transmission layer, and annealing to obtain a perovskite single crystal particle composite film;
5) depositing an electron transport layer or a hole transport layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 4) to obtain the perovskite-based single crystal particle composite film X-ray detector.
According to the scheme, in the step 1), the perovskite single crystal is prepared by adopting an inverse temperature crystallization method, a cooling crystallization method, a solvent evaporation crystallization method or an anti-solvent steam auxiliary crystallization method, and the grain diameter of the single crystal is more than 2 mm.
According to the scheme, the drying in the step 2) is carried out for 12-24 hours by adopting a vacuum drying oven at the temperature of 50-80 ℃; the crushing can adopt an agate grinding bowl or a ball mill; in the step 3), magnetic stirring is adopted for uniform dispersion for not less than 12 hours or ultrasonic oscillation for not less than 1 hour.
According to the scheme, the mass-to-volume ratio of the perovskite single crystal particles to the polyol solution or the polymer solution in the step 3) is as follows: 100-5000 mg/mL, wherein the concentration of the polymer solution is 1-10 mg/mL.
According to the scheme, in the step 4), the spin coating speed is 100-1000 rpm, and the spin coating time is 80-160 s; the annealing conditions are as follows: annealing at 100-200 ℃ for 30-60 min.
The invention has the beneficial effects that:
1. the X-ray detector provided by the invention has methylamine lead bromide (CH)3NH3PbBr3) The perovskite single crystal particle composite film has high detection sensitivity, low dark current and noise, fast response (600ns), good photoelectric transmission performance and capability of detecting lower radiation dose rate (as low as 2.3 mu Gy)air/s) and has fast response and good repeatability to low dose X-rays.
2. The preparation method is simple, the cost is low, the efficiency is high, the thickness and the area of the perovskite single crystal composite film are adjustable, the limit of the effective area of the X-ray detector based on the perovskite technology in the prior art is broken through, the detector with large area can be prepared, and the preparation method has good application prospect in the aspect of X-ray detection with large area and low dosage.
Drawings
FIG. 1 is a roughness map of the surface of a perovskite single crystal particle composite film prepared in example one;
FIG. 2 is a schematic structural diagram of an X-ray detector based on a perovskite single crystal particle composite film in an embodiment of the present invention, including two photodiode device structures of an N-I-P type and a P-I-N type, where in the N-I-P type structure, a is a hole transport layer, b is a perovskite single crystal particle composite film, c is an electron transport layer, d is an interface modification layer, and e is an electrode; or in the P-I-N type structure, a is an electron transport layer, b is a perovskite single crystal particle composite film, c is a hole transport layer, d is an interface modification layer, and e is an electrode;
FIG. 3 is a scanning electron micrograph of a cross section of a perovskite single crystal particle composite film prepared in the first example;
FIG. 4 is a curve of current versus voltage curves of an X-ray detector based on a perovskite single crystal particle composite film prepared in the first example under the conditions of illumination and no illumination;
FIG. 5 is a graph showing the variation of current with the time of placing the detector in the air when the test conditions are light and the voltage is 0v after placing the perovskite single crystal particle composite film-based X-ray detector prepared in the first example in the air (the temperature is controlled at 35 ℃ and the humidity is controlled at 60% RH) for different times;
FIG. 6 is a noise curve of the perovskite single crystal particle composite film-based X-ray detector prepared in the first embodiment at different bias voltages of 0V, 0.2V, 0.5V and-1V, wherein a is a variation of noise density with frequency, and b is a magnitude of noise density at different bias voltages;
FIG. 7 is a response time curve of an X-ray detector based on a perovskite single crystal particle composite film prepared in the first embodiment;
FIG. 8 is a graph showing the variation of current with X-ray dose rate for the X-ray detector based on the perovskite single crystal particle composite film prepared in the first example.
FIG. 9 is a time response curve of an X-ray detector based on perovskite single crystal particle composite film prepared in the first example at different X-ray dose rates;
FIG. 10 shows that the perovskite-based single crystal particle composite film X-ray detector prepared in the first embodiment is 2.3-14 μ Gyair/s X-time response curve at radiation dose rate.
Detailed Description
The invention is further illustrated below with reference to the figures and examples.
FIG. 2 is a schematic structural diagram of an X-ray detector based on a perovskite single crystal particle composite film prepared according to an embodiment of the present invention, including two types of photodiode device structures, I-P type and P-I-N type, where a is a hole transport layer, b is a perovskite single crystal particle composite film, c is an electron transport layer, d is an interface modification layer, and e is an electrode; or in the P-I-N type structure, a is an electron transport layer, b is a perovskite single crystal particle composite film, c is a hole transport layer, d is an interface modification layer, and e is an electrode.
Example one
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) methylamine lead bromide (CH) is prepared by adopting an inverse temperature crystallization method3NH3PbBr3) Dissolving lead methylamine bromide solution at 40 deg.C to obtain saturated perovskite monocrystalFiltering the solution, and continuously heating at 100 ℃ for 12 hours to grow and obtain methylamine lead bromide perovskite single crystals, wherein the particle size of the large-particle perovskite single crystals is 1.5 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 24 hours at 60 ℃ by adopting a vacuum drying oven, crushing by adopting a ball mill, screening by adopting a vibrating screen, and obtaining single crystal particles with the particle size of 30-40 mu m after crushing and screening;
3) preparing a mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and polymethyl methacrylate in the step 2), wherein the mixing amount of the methylamine lead bromide perovskite single crystal particles is 2000mg/mL, and the concentration of the polymethyl methacrylate solution is 5 mg/mL;
4) uniformly dispersing the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the polymethyl methacrylate in the step 3), and carrying out ultrasonic oscillation for 1 hour;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the polymethyl methacrylate in the step 4) on a transparent conductive substrate deposited with a hole transmission layer, wherein the spin-coating rotation speed is 400rpm, the spin-coating time is 100s, and then annealing is carried out at the annealing temperature of 100 ℃ for 30min to obtain a methylamine lead bromide perovskite single crystal particle composite film;
6) evaporating an electron transmission layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to obtain the perovskite-based single crystal particle composite film X-ray detector with the N-I-P type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 40 mu m; the hole transport layer is nickel oxide, and the thickness of the film is 20 nm; the electron transport layer is fullerene derivative C70, and the film thickness is 100 nm; the interface modification material is Bathocuproine (BCP), and the film thickness is 3 nm; the electrode was gold and the film thickness was 60 nm.
FIG. 1 is a graph showing the roughness of the surface of the perovskite single crystal particle composite film prepared in the first example, and it can be seen from FIG. 1 that the surface roughness of the single crystal composite film prepared in the first example is as low as 78 nm.
FIG. 3 is a scanning electron micrograph of a cross section of the perovskite single crystal particle composite film prepared in the first example, and it can be seen from FIG. 2 that the thickness of the film of the perovskite single crystal particle composite film is 40 nm.
FIG. 4 is a curve of current versus voltage curves of an X-ray detector based on a perovskite single crystal particle composite film prepared in the first example under the conditions of illumination and no illumination; as can be seen from FIG. 4, under the condition of illumination, the photocurrent reached 1V open-circuit voltage, and under the condition of no illumination, negative bias voltage of-1V was applied to the detector, and the dark current reached 1nA/cm2The photoelectric material has extremely low dark current and excellent photoelectric performance.
FIG. 5 is a graph showing the variation of current with the time of placing the detector in the air when the test conditions are light and the voltage is 0V after placing the perovskite single crystal particle composite film-based X-ray detector prepared in the first example in the air (the temperature is controlled at 35 ℃ and the humidity is controlled at 60% RH) for different times; as can be seen from fig. 5, in the first example, after 49 days of storage in air, the photocurrent was almost unchanged, and the stability in air was good.
FIG. 6 is a noise curve of the perovskite single crystal particle composite film-based X-ray detector prepared in the first embodiment at different bias voltages of 0V, 0.2V, 0.5V and-1V, wherein a is a variation of noise density with frequency, and b is a magnitude of noise density at different bias voltages; as can be seen from FIG. 6, the noise of the X-ray detector of the complex film is low.
FIG. 7 is a response time curve of an X-ray detector based on a perovskite single crystal particle composite film prepared in the first embodiment; as can be seen from fig. 7, the detector prepared in the first embodiment has a fast response of 600ns and a very short response time.
FIG. 8 is a graph showing the variation of current with the X-ray dose rate of an X-ray detector based on a perovskite single crystal particle composite film prepared in the first example; as can be seen from FIG. 8, the lowest detectable dose rate of the perovskite single crystal particle composite film-based X-ray detector prepared in example one is 2.3 μ GyairS, lower than the detection dose rate (5.5 μ Gy) required for conventional medical applicationsairS); in addition, the sensitivity of the X-ray detector based on the perovskite single crystal particle composite film prepared in the first embodiment is as high as 70 mu C/Gyair·cm2。
FIG. 9 is a time response curve of an X-ray detector based on perovskite single crystal particle composite film prepared in the first example at different X-ray dose rates; as can be seen from FIG. 9, the perovskite single crystal particle composite film-based X-ray detector prepared in the first embodiment is sensitive to X-ray response and good in repeatability.
FIG. 10 shows that the perovskite-based single crystal particle composite film X-ray detector prepared in the first embodiment is 2.3-14 μ Gyair/s X-time response curve at radiation dose rate; as can be seen from FIG. 10, the perovskite single crystal particle composite film-based X-ray detector prepared in the first embodiment has fast response and good repeatability to low-dose X-rays.
Example two
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) methylamine lead bromide (CH) prepared by adopting solvent evaporation crystallization method3NH3PbBr3) Fully dissolving a solution of methylamine lead bromide at 40 ℃ to obtain a saturated solution, filtering, continuously heating at 70 ℃ for 12 hours to slowly evaporate the solvent to obtain a methylamine lead bromide perovskite single crystal, wherein the particle size of the large-particle perovskite single crystal is 0.5 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 24 hours at 60 ℃ by adopting a vacuum drying oven, crushing by adopting a ball mill, screening by adopting a vibrating screen, and obtaining single crystal particles with the particle size of 40-50 mu m after crushing and screening;
3) preparing a mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and poly [ bis (4-phenyl) (4-butylphenyl) amine ] in the step 2), wherein the mixing amount of the methylamine lead bromide perovskite single crystal particles is 4000mg/mL, and the concentration of the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution is 10 mg/mL;
4) uniformly dispersing the methylamine lead bromide perovskite single crystal particles in the step 3) and a mixed suspension solution of poly [ bis (4-phenyl) (4-butylphenyl) amine ], and ultrasonically oscillating for 1 hour;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and poly [ bis (4-phenyl) (4-butylphenyl) amine ] in the step 4) on a transparent conductive substrate deposited with an electron transport layer, wherein the spin-coating speed is 300rpm, the spin-coating time is 120s, and then annealing is carried out at 100 ℃ for 30min to obtain a methylamine lead bromide perovskite single crystal particle composite membrane;
6) evaporating a hole transport layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to prepare a perovskite-based single crystal particle composite film X-ray detector with a P-I-N type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 200 mu m; the electron transport layer is zinc oxide, and the thickness of the film is 50 nm; the hole transport layer is 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), and the film thickness is 30 nm; the interface modification layer is molybdenum trioxide, and the thickness of the film is 8 nm; the electrode was gold and the film thickness was 80 nm.
The perovskite single crystal particle composite film-based X-ray detector prepared in the embodiment has the following test results:
the thickness of the perovskite single crystal particle composite film is 200 nm; the roughness of the perovskite single crystal particle composite film is 95 nm; the response time is 700 ns; the minimum dose rate of X-ray detection is 3.1 mu GyairS; the sensitivity is 60 mu C/Gyair·cm2。
EXAMPLE III
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) methylamine lead bromide (CH) is prepared by adopting an inverse temperature crystallization method3NH3PbBr3) Fully dissolving a solution of methylamine lead bromide at 40 ℃ to obtain a saturated solution, filtering, and continuously heating at 120 ℃ for 14 hours to grow to obtain a methylamine lead bromide perovskite single crystal, wherein the particle size of the large-particle perovskite single crystal is 1 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 24 hours at 60 ℃ by adopting a vacuum drying oven, crushing by adopting a ball mill, screening by adopting a vibrating screen, and obtaining single crystal particles with the particle size of 40-50 mu m after crushing and screening;
3) preparing a mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and polymethyl methacrylate in the step 2), wherein the mixing amount of the methylamine lead bromide perovskite single crystal particles is 2000mg/mL, and the concentration of the polymethyl methacrylate solution is 5 mg/mL;
4) uniformly dispersing the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the polymethyl methacrylate in the step 3), and carrying out ultrasonic oscillation for 1 hour;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the polymethyl methacrylate in the step 4) on a transparent conductive substrate deposited with a hole transmission layer, wherein the spin-coating rotation speed is 200rpm, the spin-coating time is 160s, and then annealing is carried out at the annealing temperature of 100 ℃ for 30min to obtain a methylamine lead bromide perovskite single crystal particle composite film;
6) evaporating an electron transmission layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to obtain the perovskite-based single crystal particle composite film X-ray detector with the N-I-P type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 80 mu m; the hole transport layer is nickel oxide, and the thickness of the film is 20 nm; the electron transport layer is fullerene derivative C60, and the film thickness is 70 nm; the interface modification material is Bathocuproine (BCP), and the film thickness is 4 nm; the electrode was copper and the film thickness was 40 nm.
The perovskite single crystal particle composite film-based X-ray detector prepared in the embodiment has the following test results:
the thickness of the perovskite single crystal particle composite film is 80 nm; the roughness of the perovskite single crystal particle composite film is 85 nm; the response time is 650 ns; the minimum dose rate of X-ray detection is 2.5 mu GyairS; the sensitivity is 70 mu C/Gyair·cm2。
Example four
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) preparing methylamine lead by inverse temperature crystallization methodBromine salt (CH)3NH3PbBr3) Fully dissolving methylamine lead bromide at 60 ℃ to obtain a saturated solution, filtering, and continuously heating at 120 ℃ for 24 hours to grow to obtain a methylamine lead bromide perovskite single crystal, wherein the particle size of the large-particle perovskite single crystal is 1.5 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 12 hours at 80 ℃ by adopting a vacuum drying oven, grinding by using agate, screening by using a vibrating screen, and obtaining the single crystal particles with the particle size of 30-40 mu m after crushing and screening;
3) preparing a mixed suspension solution of the methylamine lead bromate perovskite single crystal particles and alpha-terpineol in the step 2), wherein the mixing amount of the methylamine lead iodate perovskite single crystal particles is 1000mg/mL, and the alpha-terpineol solution is a pure solution;
4) uniformly dispersing the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the alpha-terpineol in the step 3), and magnetically stirring for 24 hours;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and the alpha-terpineol, which is prepared in the step 4), on a transparent conductive substrate deposited with a hole transmission layer, wherein the spin-coating speed is 800rpm, the spin-coating time is 80s, and then annealing is carried out, the annealing temperature is 200 ℃, and the annealing time is 60min, so as to obtain a methylamine lead bromide perovskite single crystal particle composite film;
6) evaporating an electron transmission layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to obtain the perovskite-based single crystal particle composite film X-ray detector with the N-I-P type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 30 mu m; the hole transport layer is poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], and the film thickness is 30 nm; the electron transport layer is fullerene derivative C60, and the film thickness is 70 nm; the interface modification material is cesium carbonate, and the film thickness is 3 nm; the electrode was copper and the film thickness was 100 nm.
The perovskite single crystal particle composite film-based X-ray detector prepared in the embodiment has the following test results:
calcium titaniumThe thickness of the mineral single crystal particle composite film is 30 nm; the roughness of the perovskite single crystal particle composite film is 80 nm; response time is 750 ns; the minimum dose rate of X-ray detection is 3.5 mu GyairS; sensitivity was 58. mu.C/Gyair·cm2。
EXAMPLE five
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) methylamine lead bromide (CH) prepared by adopting anti-solvent steam assisted crystallization method3NH3PbBr3) Fully dissolving a solution of cesium-lead bromide at 50 ℃ to obtain a saturated solution, filtering, using dichloromethane as an anti-solvent, continuously diffusing dichloromethane vapor into methylamine-lead bromide solution at room temperature, and growing to obtain methylamine-lead bromide perovskite single crystals, wherein the growth time is 4-7 days, and the particle size of large-particle perovskite single crystals is 0.5 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 20 hours at 60 ℃ by adopting a vacuum drying oven, crushing by adopting a ball mill, screening by adopting a vibrating screen, and obtaining single crystal particles with the particle size of 40-50 mu m after crushing and screening;
3) preparing a mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and polyvinyl butyral in the step 2), wherein the mixing amount of the methylamine lead bromide perovskite single crystal particles is 5000mg/mL, and the concentration of the polyvinyl butyral solution is 1 mg/mL;
4) uniformly dispersing the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and polyvinyl butyral in the step 3), and ultrasonically oscillating for 1 hour;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and polyvinyl butyral, which is obtained in the step 4), on a transparent conductive substrate deposited with an electron transport layer, wherein the spin-coating rotation speed is 1000rpm, the spin-coating time is 80s, and then annealing is carried out, the annealing temperature is 120 ℃, and the annealing time is 30min, so as to obtain a methylamine lead bromide perovskite single crystal particle composite film;
6) evaporating a hole transport layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to prepare a perovskite-based single crystal particle composite film X-ray detector with a P-I-N type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 30 mu m; the electron transmission layer is tin oxide, and the thickness of the film is 80 nm; the hole transport layer is 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD), and the film thickness is 30 nm; the interface modification layer is molybdenum trioxide, and the thickness of the film is 3 nm; the electrode was gold and the film thickness was 40 nm.
The perovskite single crystal particle composite film-based X-ray detector prepared in the embodiment has the following test results:
the thickness of the perovskite single crystal particle composite film is 30 nm; the roughness of the perovskite single crystal particle composite film is 78 nm; the response time is 600 ns; the minimum dose rate of X-ray detection is 2.3 mu GyairS; the sensitivity is 68 mu C/Gyair·cm2。
EXAMPLE six
A preparation method of an X-ray detector based on a perovskite single crystal particle composite film comprises the following steps:
1) methylamine lead bromide (CH) is prepared by adopting an inverse temperature crystallization method3NH3PbBr3) Fully dissolving a solution of methylamine lead bromide at 70 ℃ to obtain a saturated solution, filtering, continuously heating at 130 ℃ for 24 hours, and growing to obtain a methylamine lead bromide perovskite single crystal, wherein the particle size of the large-particle perovskite single crystal is 0.5 cm;
2) drying the methylamine lead bromide perovskite single crystal in the step 1), then mechanically crushing and screening to obtain methylamine lead bromide perovskite single crystal particles, drying for 12 hours at 100 ℃ by adopting a vacuum drying oven, crushing by adopting a ball mill, screening by adopting a vibrating screen, and crushing and screening to obtain the single crystal particles with the particle size of 30-40 mu m;
3) preparing a mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and glycerol in the step 2), wherein the mixing amount of the methylamine lead bromide perovskite single crystal particles is 500mg/mL, and the glycerol solution is a pure solution;
4) uniformly dispersing the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles in the step 3) and glycerol, and magnetically stirring for 24 hours;
5) simply spin-coating the mixed suspension solution of the methylamine lead bromide perovskite single crystal particles and glycerol in the step 4) on a transparent conductive substrate deposited with a hole transmission layer, wherein the spin-coating rotation speed is 500rpm, the spin-coating time is 160s, and then annealing is carried out at the annealing temperature of 200 ℃ for 60min to obtain a methylamine lead bromide perovskite single crystal particle composite film;
6) evaporating an electron transmission layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 5) to obtain the perovskite-based single crystal particle composite film X-ray detector with the N-I-P type photodiode device structure; wherein: the thickness of the perovskite single crystal particle composite film is 100 mu m; the hole transport layer is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, and the film thickness is 20 nm; the electron transport layer is fullerene derivative C70, and the film thickness is 200 nm; the interface modification material is bathocuproine, and the film thickness is 3 nm; the electrode was copper and the film thickness was 60 nm.
The perovskite single crystal particle composite film-based X-ray detector prepared in the embodiment has the following test results:
the thickness of the perovskite single crystal particle composite film is 100 nm; the roughness of the perovskite single crystal particle composite film is 90 nm; the response time is 800 ns; the minimum dose rate of X-ray detection is 3.5 mu GyairS; sensitivity was 58. mu.C/Gyair·cm2。
The above embodiments are merely illustrative of the technical solutions of the present invention. The perovskite single crystal particle composite film based X-ray detector and the manufacturing method thereof are not limited to the contents described in the above embodiments, but are subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (9)

1. An X-ray detector based on a perovskite single crystal particle composite film is characterized by having a structure of a photodiode type device, which is an N-I-P type or a P-I-N type, wherein:
the N-I-P type comprises a transparent conductive substrate, a hole transport layer, a perovskite single crystal particle composite film, an electron transport layer, an interface modification layer and an electrode, wherein all the layers are connected in sequence;
the P-I-N type comprises a transparent conductive substrate, an electron transport layer, a perovskite single crystal particle composite film, a hole transport layer, an interface modification layer and an electrode, wherein the layers are sequentially connected;
the perovskite single crystal particle composite film is a composite film of perovskite single crystal particles and polyol or polymer, the film thickness is 30-200 mu m, the perovskite single crystal is methylamine lead bromide perovskite single crystal, and the particle size of the perovskite single crystal particles is 30-50 mu m.
2. The X-ray detector of claim 1, wherein the polyol is glycerol or α -terpineol; the polymer is polymethyl methacrylate, polyacrylonitrile, polyvinyl butyral, polyvinylidene fluoride or poly [ bis (4-phenyl) (4-butylphenyl) amine ].
3. An X-ray detector according to claim 1, characterized in that the hole transport layer is poly (3, 4-ethylenedioxythiophene) -polystyrenesulphonic acid, nickel oxide, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] or 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene; the electron transport layer is zinc oxide, tin oxide, titanium dioxide, C70, C60 or PCBM; the interface modification layer is bathocuproine, molybdenum trioxide, cesium carbonate or lithium fluoride; the electrode is gold, silver, copper or aluminum.
4. The X-ray detector according to claim 1, wherein the hole transport layer has a film thickness of 20 to 40 nm; the thickness of the electron transmission layer is 50-200 nm; the thickness of the interface modification layer is 1-8 nm; the thickness of the electrode film is 40-100 nm.
5. A preparation method of the perovskite single crystal particle composite film based X-ray detector as claimed in any one of claims 1 to 4, which is characterized by comprising the following specific steps:
1) preparing methylamine lead bromide perovskite single crystals;
2) drying the perovskite single crystal obtained in the step 1), and then mechanically crushing and screening to obtain perovskite single crystal particles;
3) uniformly dispersing the perovskite single crystal particles obtained in the step 2) in a polyol solution or a polymer solution to obtain a mixed suspension;
4) spin-coating the mixed suspension obtained in the step 3) on a transparent conductive substrate deposited with a hole transmission layer or an electron transmission layer, and annealing to obtain a perovskite single crystal particle composite film;
5) depositing an electron transport layer or a hole transport layer, an interface modification layer and an electrode on the surface of the composite film obtained in the step 4) to obtain the perovskite-based single crystal particle composite film X-ray detector.
6. The preparation method according to claim 5, wherein the mass-to-volume ratio of the perovskite single crystal particles to the polyol or polymer solution in the step 3) is as follows: 100-5000 mg/mL, wherein the concentration of the polymer solution is 1-10 mg/mL.
7. The preparation method according to claim 5, wherein the perovskite single crystal is prepared by an inverse temperature crystallization method, a temperature reduction crystallization method, a solvent evaporation crystallization method or an anti-solvent steam assisted crystallization method in the step 1), and the particle size of the single crystal is larger than 2 mm.
8. The preparation method according to claim 5, wherein the drying in the step 2) is performed by a vacuum drying oven at 50-80 ℃ for 12-24 hours; the crushing can adopt an agate grinding bowl or a ball mill; in the step 3), magnetic stirring is adopted for uniform dispersion for not less than 12 hours or ultrasonic oscillation for not less than 1 hour.
9. The preparation method according to claim 5, wherein the spin coating speed in the step 4) is 100-1000 rpm, and the spin coating time is 80-160 s; the annealing conditions are as follows: annealing at 100-200 ℃ for 30-60 min.
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