CN115010166A - Preparation method of lead-free copper-based perovskite powder and scintillation film and application of film - Google Patents
Preparation method of lead-free copper-based perovskite powder and scintillation film and application of film Download PDFInfo
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- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
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Abstract
The invention belongs to the technical field of inorganic perovskite materials and medical imaging, and discloses a preparation method of lead-free copper-based perovskite powder and a scintillation film and application of the lead-free copper-based perovskite powder scintillation film, wherein a CsCu is prepared by an anti-solvent method 2 I 3 The powder has the luminescent wavelength of 575nm, good matching with the wavelength response range (300-650 nm) of a PMT detector, high PLQY (11.23%), fast fluorescence attenuation (123ns), no self-absorption and short afterglow (0.0)9 percent) and high yield (>95%). Mixing the CsCu with aging-resistant and moisture-proof RTV silica gel, PDMS, PS, PMMA and other colloids, and preparing the CsCu by using screen printing methods such as blade coating, drop coating, spin coating, infiltration and the like 2 I 3 The scintillation film is used for high-energy X-ray imaging and has application prospect in the field of nuclear medicine imaging and safety inspection.
Description
Technical Field
The invention relates to the technical field of inorganic perovskite materials and medical imaging, in particular to a preparation method of lead-free copper-based perovskite powder and a scintillation film, and also relates to an application of the lead-free copper-based perovskite powder scintillation film.
Background
The scintillation conversion screen is used as a core device for X-ray detection and imaging, and has very wide application in the fields of inertial confinement fusion, nuclear medicine imaging, nondestructive testing, security inspection and the like. With the development of X-ray imaging technology, higher requirements are put on the scintillation conversion screen. The existing scintillators (BGO, CsI, Tl and the like) grow at ultrahigh temperature, the preparation process is complex, the light yield is low, the stability is poor, the afterglow is long, and the common CsI, Tl also contains a highly toxic element Tl which can cause great harm to human bodies and the environment, so that a novel material is urgently needed in the fields of medical imaging and radiation detection to meet the use requirement.
In recent years, perovskite materials are gradually a new generation of photoelectric materials due to their strong X-ray cut-off capability and excellent photoelectric characteristics, and such materials have the advantages of large effective atomic number, high detection efficiency, good radiation stability, tunable spectrum, and the like. Therefore, in addition to being used in solar cells and light emitting diodes, they are also widely used for X-ray and gamma-ray detection. Among them, halide organic-inorganic perovskites have the characteristics of easy film formation and easy processing. However, the poor stability limits the further development of the perovskite, and the all-inorganic halide perovskite belongs to a direct band gap semiconductor material, has excellent properties such as wide light-emitting wavelength range, high fluorescence quantum efficiency and the like, is more stable than the organic-inorganic halide perovskite, and gradually becomes the research focus in the technical field.
The light yield of the scintillator is one of the important indicators that determine the X-ray detection efficiency and the imaging contrast. Studies have shown that the small Stokes shift and severe self-absorption effects of lead-perovskite halides limit the light output efficiency of thin films and crystals, requiring large thicknesses to completely cut off X-rays. For scintillators, a large stokes shift and a high photoluminescence efficiency are required to achieve high light yield. On the other hand, one serious problem limiting the application of lead halide perovskite scintillators is the toxicity of the lead element, the ionic nature and high solubility in water of the halide perovskite, which can be a serious hazard to human health and the environment.
Novel all-inorganic copper-based halide perovskite CsCu 2 I 3 The composition has the advantages of no toxicity, high radiation luminous intensity, high stability and the like, and lays a good foundation for potential application of low-dose X-ray imaging. The invention provides a CsCu-based method 2 I 3 X-ray scintillation conversion screen-CsCu of perovskite material 2 I 3 The RTV film comprises a simple, cheap and large-area production method, and a flexible scintillation conversion screen which is low in cost, applicable and high in uniformity is prepared and can be used for efficient X-ray detection and high-spatial-resolution X-ray imaging.
Disclosure of Invention
The invention aims to provide a lead-free copper-based perovskite powder, a preparation method of a scintillation film and application of the lead-free copper-based perovskite powder scintillation film, and CsCu is prepared by an anti-solvent method 2 I 3 The powder has the luminescent wavelength of 575nm, is well matched with the wavelength response range (300-650 nm) of a PMT detector, has high PLQY (11.23%), fast fluorescence attenuation (123ns), no self-absorption, short afterglow (0.09%) and high yield (>95%). Mixing the CsCu with aging-resistant and moisture-proof RTV silica gel, PDMS, PS, PMMA and other colloids, and preparing the CsCu by using screen printing methods such as blade coating, drop coating, spin coating, infiltration and the like 2 I 3 Scintillation film for high-energy X-ray imaging.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of lead-free copper-based perovskite powder comprises the following steps:
s1.1, placing cesium iodide and cuprous iodide into a glass bottle according to a certain proportion;
s1.2, adding a polar solvent to dissolve the solid in the S1.1 glass bottle to form a precursor;
s1.3, after the precursor in the S1.2 is completely dissolved to form a transparent solution, adding an anti-solvent into a glass bottle, and forming a white precipitate at the bottom of the mixed solution;
s1.4, transferring the mixed solution in the S1.3 into a centrifuge tube, centrifuging, removing supernate, and reserving white precipitate;
s1.5, cleaning the white precipitate in the S1.4 by using an organic solvent, and drying in a drying oven to obtain CsCu 2 I 3 And (3) powder.
Further, in S1.1, the ratio of the amount of cesium iodide to cuprous iodide was 1: 2.
Further, in S1.2, adding a polar solvent of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or a mixed solution of DMF and DMSO in a volume ratio of 1: 1-1: 5 to obtain a precursor with a concentration of 0.1-0.7M; in S1.3, the added anti-solvent is one or more of tert-butyl alcohol, n-butyl alcohol, isopropanol, ethanol, toluene, ethyl acetate and methyl acetate, and the volume ratio of the anti-solvent to the precursor is 1: 1-1: 6.
Further, in S1.4, the centrifugal speed of the mixed solution is 5000-10000 r/min, and the centrifugal time is 5-20 min.
Further, in S1.5, the organic solvent for cleaning the white precipitate is one or more of n-hexane and isopropanol, and the drying time is 2-10 hours.
A preparation method of a lead-free copper-based perovskite powder scintillation film comprises the following steps:
s2.1, mixing CsCu 2 I 3 Powder ofGrinding in a mortar, and filtering with a mesh screen to obtain CsCu with uniform particle size 2 I 3 Powder;
s2.2, CsCu in S2.1 2 I 3 Mixing the powder with RTV silica gel, PDMS, PS and PMMA, and uniformly stirring to form viscous slurry;
s2.3, placing the slurry in the S2.2 on one side of a substrate, and slowly coating the slurry on the substrate by using a scraper to form a layer of uniform film; or dripping the slurry on a substrate to form a film;
s2.4, placing the film in the S2.3 in a drying box for storage, and obtaining the CsCu 2 I 3 And (5) scintillation film.
Further, in S2.1, CsCu 2 I 3 Grinding the powder for 30-150 min, and filtering with a 100-600 mesh sieve to obtain CsCu 2 I 3 The particle size of the powder is 2-4 μm.
Further, in S2.2, RTV silica gel, PDMS, PS, PMMA are used as dispersing agents, CsCu 2 I 3 The mass ratio of the powder to the dispersing agent is 1: 1-1: 6; in S2.3, the substrate is one of glass plate, PET, PE, and other flexible substrates.
Further, in S2.4, the temperature for storing the film in the drying oven is 60-135 ℃, and the storage time is 5-48 h.
An application of a leadless copper-based perovskite powder scintillation film in high-energy X-ray imaging.
CsCu prepared by the invention 2 I 3 The scintillation film is used for carrying out imaging test on a Bluetooth headset in an X-ray imaging system, a TFT array plate is used for receiving images, and the prepared CsCu is used 2 I 3 After the scintillation film is arranged on the Bluetooth headset, X rays pass through the Bluetooth headset and are radiated on CsCu 2 I 3 On the scintillation screen, the scintillation screen converts high-energy X-ray photons into visible light, and the TFT panel receives the visible light to present an object image.
Compared with the prior art, the technical scheme has the beneficial effects that:
1、CsCu 2 I 3 has 1D structure, and is compared with the prior 3D lead-based perovskiteOre (CsPbBr) 3 ) The material has higher luminous quantum efficiency and better environmental stability, avoids the toxicity of lead, has larger Stokes shift (245nm), no self-absorption and excellent luminous performance, and can be used as a candidate material in the fields of future photovoltaics, photoelectric display and medical imaging;
2. CsCu in the invention 2 I 3 The powder is prepared by an anti-solvent method at room temperature, the raw materials are simple, the average yield is 95%, the afterglow is far lower than that of the existing CsI Tl scintillator, and compared with CsCu prepared by a hot injection method 2 I 3 The nanocrystalline PLQY is higher, the fluorescence attenuation is fast, and the stability is better;
3、CsCu 2 I 3 the scintillation film adopts a screen printing one-step blade coating preparation method, so that the high-quality flexible film is simply and efficiently prepared, and compared with the traditional vapor deposition preparation method, the preparation method is easy to operate and low in cost; compared with a method for preparing the film by drop coating, the thickness is easier to control;
4、CsCu 2 I 3 the film is applied to high-energy X-ray imaging, and the result shows that the film has ultrahigh imaging resolution and is combined with excellent environmental stability, so that the film has excellent comprehensive performance and lays a foundation for becoming a next-generation commercial scintillator;
5. the invention has simple principle, wide application range and easy popularization and application, and is suitable for the development requirements of the current scintillation detection field.
Drawings
FIG. 1 shows CsCu prepared by the method for preparing lead-free copper-based perovskite powder 2 I 3 Scanning electron microscopy of the powder;
FIG. 2 shows CsCu prepared by the method for preparing lead-free copper-based perovskite powder 2 I 3 Powder ultraviolet excitation spectrum, luminescence spectrum and absorption spectrum;
FIG. 3 shows CsCu prepared by the method for preparing lead-free copper-based perovskite powder 2 I 3 A powder fluorescence attenuation spectrogram;
FIG. 4 shows the lead-free copper-based perovskite powder prepared by the method of the present inventionCsCu 2 I 3 PLQY graph of powder;
FIG. 5 shows CsCu prepared by the method for preparing lead-free copper-based perovskite powder 2 I 3 Powder yield profile;
FIG. 6 is a schematic diagram illustrating the operation of a lead-free copper-based perovskite powder scintillation film according to the present invention;
FIG. 7 shows a lead-free copper-based perovskite powder scintillation film CsCu prepared by the method 2 I 3 A graph of ultraviolet excitation of the RTV flexible scintillation film under a fluorescent lamp and at 302 nm;
FIG. 8 is an afterglow diagram of the lead-free copper-based perovskite powder scintillation film prepared by the invention and the prior scintillator CsI: Tl;
FIG. 9 is a high-energy X-ray image of the lead-free copper-based perovskite powder scintillation film prepared by the method.
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
the invention adopts an anti-solvent method to synthesize the one-dimensional lead-free CsCu 2 I 3 Grinding the powder in a mortar, sieving to obtain small-size powder with uniform particle size distribution, mixing with RTV silica gel, and preparing CsCu by screen printing 2 I 3 The RTV scintillation film is used for researching the luminous performance and the imaging effect on high-energy X-rays.
Example 1:
a preparation method of lead-free copper-based perovskite powder comprises the following steps:
s1.1, adding 0.25981 g of CsI (1mmol) and 0.3809 g of CuI (2mmol) into 4ml of N, N-dimethylformamide to form a transparent precursor, and placing the transparent precursor in a glass bottle;
the concentration of the precursor obtained from S1.2 and S1.1 depends on the volume of the polar solvent such as N, N-dimethylformamide, and the concentration of the precursor also seriously affects CsCu 2 I 3 The yield of the powder is 0.25M at the optimal concentration; wherein the polar solvent can also be dimethyl sulfoxide (DMSO), a mixed solution of DMF and DMSO with the volume ratio of 1: 1-1: 5;
s1.3, adding n-butyl alcohol serving as an anti-solvent into the precursor in the step S1.1, wherein a large amount of white powder appears in a beaker; the ratio of precursor to anti-solvent strongly affects CsCu 2 I 3 The yield of the powder is 1:4 in an optimal ratio;
s1.4, transferring the substance in the beaker in the step S1.3 into a centrifugal tube, and centrifuging for 10 minutes under the condition of 10000 r/min to obtain white precipitate;
s1.5, washing the white precipitate obtained in the step S1.4 with n-hexane for 2 times, and drying in a vacuum drying oven for 5 hours to obtain CsCu 2 I 3 And (3) powder.
CsCu prepared in this example 2 I 3 The SEM image of the powder is shown in FIG. 1, and the SEM image shows that the average particle size is 2-4 microns;
CsCu prepared in this example 2 I 3 The ultraviolet excitation spectrum, emission spectrum and absorption spectrum of the powder are shown in figure 2, the excitation peak is located at 330nm, the emission peak is located at 575nm, the Stokes shift is 245nm, the absorption peak is basically overlapped with the excitation peak, and no self-absorption exists;
CsCu prepared in this example 2 I 3 The fluorescence decay pattern of the powder is shown in FIG. 3, from which CsCu can be seen 2 I 3 The fluorescence attenuation of the powder conforms to double-exponential attenuation, and the average attenuation time is 123 ns;
CsCu prepared in this example 2 I 3 The PLQY pattern of the powder is shown in FIG. 4, from which it can be seen that the PLQY is 11.36%;
CsCu prepared in this example 2 I 3 The yield distribution of the powder is shown in FIG. 5, from which it can be seen that the average yield is around 95%.
Example 2:
to study the different antisolvent pairs CsCu 2 I 3 Influence of luminescence property and yield of powder, step S1.3 in example 1 was repeated using 16 ml of n-butanol, t-butanol, isopropanol, toluene, ethyl acetate as anti-solvents, respectively, and the results are shown in table 1:
TABLE 1 different antisolvents for CsCu 2 I 3 Influence of the luminescence Properties and the yields of the powders
As can be seen from Table 1, CsCu was observed when n-butanol was used as an anti-solvent 2 I 3 The emission intensity of the powder was the highest and the yield was the greatest, so that when a thin film was prepared, CsCu prepared in example 1 was used 2 I 3 The powder was subjected to film preparation.
Example 3:
preparation of CsCu by blade coating method 2 I 3 the/RTV scintillation film comprises the following steps:
s2.1, mixing CsCu 2 I 3 The powder was ground in a mortar for 1 hour and filtered through a 200 mesh screen to form CsCu having a small particle size and a uniform distribution 2 I 3 Powder;
s2.2, CsCu obtained from S2.1 2 I 3 Mixing the powder with RTV silica gel, wherein CsCu 2 I 3 The mass ratio of the powder to the RTV silica gel is 1:3, and the powder and the RTV silica gel are uniformly stirred to obtain viscous slurry;
s2.3, dripping the slurry obtained in the S2.2 on screen printing, placing the slurry on one side of a substrate, and slowly coating the substrate by using a scraper to form a layer of uniform film; wherein, the substrate is a glass plate or a flexible substrate;
s2.4, placing the film obtained in the S2.3 in a drying oven, setting the temperature at 135 ℃, and storing for 5 hours to obtain CsCu 2 I 3 a/RTV scintillation film.
As shown in FIG. 6, CsCu 2 I 3 Placing the mixed slurry with RTV on one side of the substrate, and uniformly coating the slurry in one direction for several times by using a scraper to obtain CsCu 2 I 3 a/RTV scintillation film;
CsCu prepared in this example 2 I 3 The diagram of the/RTV flexible scintillation film is shown in FIG. 7, and it can be seen that the film can be bent and emits intense yellow light under the irradiation of a 302nm ultraviolet lamp;
this implementationExample prepared CsCu 2 I 3 The afterglow plot of the/RTV thin film and CsI/Tl scintillator is shown in FIG. 8, from which it can be seen that at 3ms CsCu 2 I 3 The afterglow of the film is one order of magnitude less than that of a commercial CsI/Tl scintillator;
CsCu prepared in this example 2 I 3 The image of the/RTV scintillation film on the Bluetooth headset under the high-energy X-ray is shown in fig. 9, and the clear internal structure of the headset can be seen from the figure, which shows that CsCu 2 I 3 the/RTV scintillation film has the potential to be applied to the fields of industrial nondestructive detection and the like as a scintillator.
Example 4:
CsCu preparation by drop coating 2 I 3 the/RTV scintillation film comprises the following steps:
S2.1、CsCu 2 I 3 the powder was ground in a mortar for 1 hour and filtered through a 200 mesh screen to form CsCu having a small particle size and a uniform distribution 2 I 3 Powder;
s2.2, CsCu obtained in S2.1 2 I 3 Mixing the powder with RTV silica gel, CsCu 2 I 3 The mass ratio of the powder to the RTV silica gel is 1:3, and the powder and the RTV silica gel are uniformly stirred to obtain viscous slurry;
s2.3, dripping the viscous slurry obtained in the S2.2 on a glass sheet with the area of 1 square centimeter, standing for 30min, then placing the glass sheet in a drying oven, setting the temperature to be 135 ℃, and preserving for 5 hours to obtain CsCu 2 I 3 a/RTV scintillation film.
The properties of the films prepared by the screen printing doctor blade method and the dispensing method are shown in table 2,
TABLE 2 Properties of films produced by Screen-printing doctor-blading and drop-coating methods
As can be seen from Table 2, CsCu prepared by the two methods of example 3 and example 4 2 I 3 The thickness of the film prepared by the knife coating method is easy to control, and the size and the shape of the film can be controlled according to the actual requirementsRegulation of CsCu 2 I 3 The RTV is prepared on a flexible substrate PET, has flexibility and can be bent, and can be used for high-energy X-ray imaging.
The above description is only an example of the present invention, and the common general knowledge of the technical solutions or characteristics known in the solutions is not described herein too much. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. The preparation method of the lead-free copper-based perovskite powder is characterized by comprising the following steps of:
s1.1, placing cesium iodide and cuprous iodide into a glass bottle according to a certain proportion;
s1.2, adding a polar solvent to dissolve the solid in the S1.1 glass bottle to form a precursor;
s1.3, after the precursor in the S1.2 is completely dissolved to form a transparent solution, adding an anti-solvent into a glass bottle, and forming a white precipitate at the bottom of the mixed solution;
s1.4, transferring the mixed solution in the S1.3 into a centrifuge tube, centrifuging, removing supernate, and reserving white precipitate;
s1.5, cleaning the white precipitate in the S1.4 by using an organic solvent, and drying in a drying oven to obtain CsCu 2 I 3 And (3) powder.
2. The method for producing a lead-free copper-based perovskite powder as claimed in claim 1, wherein: in S1.1, the mass ratio of cesium iodide to cuprous iodide was 1: 2.
3. The method for producing a lead-free copper-based perovskite powder as claimed in claim 1, wherein: in S1.2, adding a polar solvent of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or a mixed solution of DMF and DMSO in a volume ratio of 1: 1-1: 5 to obtain a precursor with a concentration of 0.1-0.7M; in S1.3, the added anti-solvent is one or more of tert-butyl alcohol, n-butyl alcohol, isopropanol, ethanol, toluene, ethyl acetate and methyl acetate, and the volume ratio of the anti-solvent to the precursor is 1: 1-1: 6.
4. The method for producing a lead-free copper-based perovskite powder according to claim 1, characterized by: in S1.4, the centrifugal speed of the mixed solution is 5000-10000 r/min, and the centrifugal time is 5-20 min.
5. The method for producing a lead-free copper-based perovskite powder according to claim 1, characterized by: in S1.5, the organic solvent for cleaning the white precipitate is one or more of n-hexane and isopropanol, and the drying time is 2-10 hours.
6. The method for preparing a scintillating thin film by using the lead-free copper-based perovskite powder as defined in any one of claims 1 to 5, which is characterized by comprising the steps of:
s2.1, mixing CsCu 2 I 3 Grinding the powder in a mortar, and filtering with a mesh screen to obtain CsCu with uniform particle size 2 I 3 Powder;
s2.2, CsCu in S2.1 2 I 3 Mixing the powder with RTV silica gel, PDMS, PS and PMMA, and uniformly stirring to form viscous slurry;
s2.3, placing the slurry in the S2.2 on one side of a substrate, and slowly coating the slurry on the substrate by using a scraper to form a layer of uniform film; or dripping the slurry on a substrate to form a film;
s2.4, placing the film in the S2.3 in a drying box for storage, and obtaining the CsCu 2 I 3 And (5) scintillation film.
7. The method for preparing a lead-free copper-based perovskite powder scintillation film as claimed in claim 1, wherein the method comprisesThe method comprises the following steps: in S2.1, CsCu 2 I 3 Grinding the powder for 30-150 min, and filtering with a 100-600 mesh sieve to obtain CsCu 2 I 3 The particle size of the powder is 2-4 μm.
8. The method for preparing a lead-free copper-based perovskite powder scintillation film as claimed in claim 1, wherein: in S2.2, RTV silica gel, PDMS, PS and PMMA are used as dispersing agents, and CsCu is used as a dispersing agent 2 I 3 The mass ratio of the powder to the dispersing agent is 1: 1-1: 6; in S2.3, the substrate is one of glass plate, PET, PE, and other flexible substrates.
9. The method for preparing a lead-free copper-based perovskite powder scintillation film as claimed in claim 1, wherein: in S2.4, the temperature for storing the film in the drying oven is 60-135 ℃, and the storage time is 5-48 h.
10. Use of a lead-free copper-based perovskite powder scintillation film as defined in any one of claims 6 to 9 in high energy X-ray imaging.
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| CN115636434A (en) * | 2022-09-28 | 2023-01-24 | 桂林电子科技大学 | Method for preparing leadless perovskite pixelized scintillation film |
| CN116478686A (en) * | 2023-04-26 | 2023-07-25 | 昆明理工大学 | Perovskite scintillator and application thereof in X-ray imaging scintillation screen |
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