Large-area transparent sb-based and doped perovskite scintillator materials, methods of making and applications thereof

Abstract

The application discloses a large-area transparent Sb-based and doped perovskite scintillator material and a preparation method and application thereof. The perovskite scintillator has a general formula of (R-C 18 H 15 P)2Sb y M 1‑y X5, wherein R is selected from one or more of -CH3, -CH2Cl, -CH2CH3, -CH2OCH3, -(CH2)3CH3, -CH2C6H4CH3 and -C6H5; M is a metal ion selected from B-site doping ions; X is selected from one or more of Cl ‑ , Br ‑ and I ‑ ; and y is selected from 0-1 and is not 0. The perovskite scintillator material has the advantages of high quantum yield and large X-ray absorption coefficient, and in the structure, a large-area transparent Sb-based perovskite with controllable shape is obtained for the first time, and can be applied to the field of ray detection to obtain highly clear ray imaging.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of perovskite scintillator materials. More particularly, it relates to a large-area transparent Sb-based and doped perovskite scintillator material and a preparation method and application thereof. BACKGROUND

[0002] Common rays include α, β, γ rays, x rays, and neutron rays, etc. Rays not only have application prospects in scientific research, but also have great application potential in daily fields such as security inspection, medical imaging and industrial flaw detection. The emergence of a ray detector is the premise and basic guarantee for the application of rays in the detection field. Ray detectors are generally divided into direct type detectors and indirect type detectors. Compared with direct type detectors, the advantages of indirect type detectors are low price and fast response speed, which can be used for dynamic imaging. The scintillator is a key component of the indirect type detector. Currently, the commonly used ray scintillators are mainly inorganic scintillators such as Gd2O2S:Tb, AgZnS, CsI:Tl and LYSO:Ce. However, most of the inorganic scintillators are block crystals, which have harsh preparation conditions and are expensive, and require extremely high equipment. Another disadvantage is that most of the inorganic scintillators have a fixed transition energy of the dopant, which cannot produce tunable scintillation and cannot perform color ray imaging. In addition, the crystal produced under high temperature conditions is fragile, and the preparation process of large-area thin film scintillators is complex, which seriously limits the application in large-area ray imaging and flexible ray detection.

[0003] In recent years, researchers have found that perovskite materials have advantages such as adjustable band gap and high quantum yield, and have outstanding advantages in the field of indirect detection. For example, the full inorganic perovskite nanocrystal scintillator containing Cs and Pb disclosed in the prior art realizes color light emission display of X-ray for the first time, which shows that the perovskite scintillator has the advantage of tunable emission wavelength. Existing reports also include: two-dimensional perovskite scintillators that can be used for β-ray monitoring, transparent flexible thin films that can be used for 3D imaging by combining perovskite scintillators doped with lanthanide elements with flexible substrates, breaking the traditional limitations of X-ray flat panel detectors. In addition, it is also disclosed that the radiation performance of hydrogen-rich 2D perovskite Mn-(C 18 H 37 NH3)2PbBr4 under fast neutrons has a resolution of 0.5 lp / mm. The (ETP)2MnBr4 transparent medium and (HTPP)2MnBr4 transparent medium prepared by a melting method both have high transmittance in the light emission band, and the X-ray resolution is greater than 10 lp / mm.

[0004] Sb-based perovskite has the advantages of high quantum yield and large X-ray absorption coefficient, and is considered as a potential excellent scintillator. The reported light yield of (PPN)2SbCl5 single crystal under X-ray is close to that of the commercial scintillator CsI:Tl, about 49000 ph MeV -1 The reported C 50 H 44 P2SbCl5 crystal is blended with PMMA to prepare a scintillation screen, and the spatial resolution is 8.2 lp / mm. The reported Sb-based perovskite scintillator is blended with an adhesive to form a film for X-ray imaging. The transmittance of the imaging screen is low, and there is strong light scattering, which is not conducive to clear imaging in X-ray imaging. SUMMARY

[0005] In view of the strong light scattering problem of the existing Sb-based perovskite scintillation screen, the purpose of the present application is to provide a large-area transparent Sb-based and doped perovskite scintillator material and a preparation method and application thereof. The perovskite scintillator material not only has the advantages of high quantum yield and large X-ray absorption coefficient, but also has a large space steric hindrance organic cation introduced into the Sb-based and doped perovskite structure in the structure, and a large-area transparent Sb-based perovskite with controllable shape is obtained for the first time, which can be applied in the field of radiation detection and the like, and highly clear radiation imaging is obtained, and the resolution can reach 25 lp / mm.

[0006] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] A large-area transparent Sb-based and doped perovskite scintillator material, the general formula of the perovskite scintillator can be: (R-C 18 H 15 P)2Sb y M 1-y X5;

[0008] Among them, the R is selected from one or more of -CH3, -CH2Cl, -CH2CH3, -CH2OCH3, -(CH2)3CH3, -CH2C6H4CH3 and -C6H5;

[0009] The M is a metal ion, and is selected from a B-site doping ion;

[0010] The X is selected from one or more of Cl - , Br - and I - ;

[0011] The y is selected from 0-1, and is not 0.

[0012] In the structure of the large-area transparent Sb-based and doped perovskite scintillator material, R-C 18 H15 P + Having large steric hindrance is conducive to the formation of glassy transparent perovskite, which has a transparency of up to 85% in the light-emitting band, can effectively reduce light scattering and improve spatial resolution; B-site metal ions Sb 3+ And M 3+ As the light-emitting center avoids self-absorption and improves optical performance; wherein the B-site metal ion is mainly Sb 3+ , M metal ion is a B-site doped ion, which can avoid self-absorption and improve optical performance.

[0013] The large-area transparent Sb-based and doped perovskite scintillator material can absorb the X-ray, and then convert the X-ray photons into visible light. Some neutron scintillators need to be combined with neutron absorbers (such as high molecular PS, etc.), and the neutron energy is converted and transmitted to the luminescent body to emit light through the neutron absorber, etc. There is an energy transfer process.

[0014] Further, the thickness of the perovskite scintillator material is 0.05-1.0 cm.

[0015] Further, the M is selected from one or more of Bi 3+ , In 3+ and Eu 3+ .

[0016] In another aspect, the present application provides a preparation method of the perovskite scintillator material as described above, which is prepared by a melting method.

[0017] Further, the preparation method comprises the following steps:

[0018] Mixing solid raw materials of R-C 18 H 15 PX, SbX3 and MX3 in a molar ratio of 2:y:1-y, grinding them into powder and mixing them uniformly to obtain a mixture;

[0019] Heating the mixture to a state where all the solid powders become a molten mixture;

[0020] Cooling the molten mixture in a mold to obtain the perovskite scintillator material;

[0021] Wherein, the definitions of y, R, X and M are as described above.

[0022] Further, the mixture is placed in a high-temperature resistant vessel, and then heated. The high-temperature resistant vessel includes but is not limited to one or more selected from a crucible, a glass vessel and an iron pot.

[0023] Further, the heating temperature ranges from 100-350℃.

[0024] Further, the heating time is 1-4h.

[0025] Further, the cooling mode includes but is not limited to natural cooling, air cooling or liquid cooling, and the cooling time is 5-15min.

[0026] Further, the mold is selected from one or more of graphite mold, silicone mold, silicon wafer, aluminum sheet and ceramic.

[0027] The perovskite scintillator material obtained by the above preparation method not only has good self-supporting, but also the shape and thickness of the final product can be controlled by controlling the shape of the mold and the volume of the melt poured in the method. The controllability of the shape and thickness of the product shows great potential in practical application.

[0028] In another aspect, the application provides the application of the perovskite scintillator material as described above in the field of ray detection imaging.

[0029] Further, the ray is selected from one or more of soft X-ray, hard X-ray and neutron.

[0030] Further, the application further includes the step of shielding the side of the perovskite scintillator material facing the ray source. At this time, it can prevent the occurrence of large reflected light during application.

[0031] Further, the shielding includes but is not limited to one or more of black tape shielding and aluminum plate.

[0032] In another aspect, the application provides the application of the perovskite scintillator material as described above in the field of LED, anti-counterfeiting or laser.

[0033] The beneficial effects of the application are as follows:

[0034] The perovskite scintillator material provided by the application has organic cation R-C 18 H 15 P + provides large steric hindrance, which is conducive to the formation of glassy transparent perovskite, and the transmittance is as high as 85% in the light emitting band, which can effectively reduce light scattering and improve spatial resolution, while the metal ion M 3+As a light-emitting center, self-absorption is avoided, and the optical performance is improved. The material has high transparency, low light scattering and good spatial resolution under radiation, and clear radiation imaging can be achieved. In addition, the size of the material is controllable, and can reach centimeter level (for example, a circular shape with a diameter of 6 centimeters or more). In addition, the material is a self-supporting transparent scintillator that does not need to be blended with an adhesive and has a controllable shape. In the preparation method of the perovskite scintillator material of the present application, a shape-controllable self-supporting transparent perovskite scintillator is first realized, which provides a design principle for the next generation of transparent scintillators and promotes the development of non-destructive testing with low light scattering and high spatial resolution. BRIEF DESCRIPTION OF DRAWINGS

[0035] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings.

[0036] Figure 1 The scanning electron microscope pictures and element Mapping of (C 22 H 24 P)2SbCl5 in Example 1 are shown.

[0037] Figure 2 The real photos of transparent glasses of different shapes of (C 22 H 24 P)2SbCl5 in Example 1 are shown.

[0038] Figure 3 The real photos of transparent glasses of different sizes in Example 1 are shown.

[0039] Figure 4 The X-ray absorption coefficients of (C 22 H 24 P)2SbCl5 and some commercial inorganic scintillators in Example 1 are shown.

[0040] Figure 5 The radioactive luminescence spectrum of (C 22 H 24 P)2SbCl5 in Example 1 exposed for 30s under 2.3mGy air s -1 X-ray irradiation is shown.

[0041] Figure 6 The photos of (C 19 H 18 P)2SbCl5 transparent glass under X-ray in Example 2 are shown.

[0042] Figure 7 The photos of (C 19 H 17 PCl)2SbCl5 transparent glass under X-ray in Example 3 are shown.

[0043] Figure 8 Figure 6 shows the cross-sectional scanning electron microscope image of the transparent glass of Example 6 (C 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5transparent glass. DETAILED DESCRIPTION

[0044] In order to more clearly illustrate the application, the application will be further described below with reference to the preferred embodiments and the accompanying drawings. Like components are denoted by the same reference numerals in the drawings. Those skilled in the art should understand that the specific description below is illustrative rather than limiting, and should not limit the scope of protection of the application.

[0045] Example 1

[0046] (C 22 H 24 P)2SbCl5transparent zero-dimensional perovskite scintillator material is prepared by the following method:

[0047] (C 22 H 24 P)2SbCl5synthesis: first, weigh the solid raw materials C 22 H 24 PCl7 90.7 mg and SbCl3 228.12 mg with a molar ratio of 2:1 on an analytical balance, grind them into powder and mix them uniformly in a high-temperature-resistant glass dish, then place them on a heating table for heating, heat to 200°C, then keep heating for 2 h, it can be observed that the solid powder is completely changed into a molten state, then transfer the molten melt to a graphite mold for cooling. After the melt is cooled for 15 min, transparent glassy scintillator (C 22 H 24 P)2SbCl5can be obtained. The thickness and shape of the transparent scintillator obtained can be controlled by controlling the volume of the melt poured into the mold and the shape of the mold. After demolding, a transparent glassy scintillator with bright luminescence can be obtained.

[0048] As Figure 1 shown: the synthesized (C 22 H 24 P)2SbCl5scintillator has a smooth and flat surface, and C / Sb / Cl / P elements are uniformly distributed; Figure 2 shown are (C 22 H 24 P)2SbCl5transparent glasses of different shapes, it can be seen that the glass surface is smooth and flat, and the transparency is very high. Figure 3 shown are large-area (C22 H 24 P)2SbCl5 transparent glass (it is to be noted that, Figure 3 In the above, the Chinese and English words appearing are used as background to demonstrate the transparency of the glass without any other meaning.

[0049] Performance test: under 2.3 mGy air s -1 X-ray irradiation, exposure for 30 s, 1.8 mm of (C 22 H 24 P)2SbCl5 transparent glass can reach 25 lp / mm, and its radioactive luminescence spectrum is shown in FIG. 4.

[0050] The (C 22 H 24 P)2SbCl5 scintillator prepared in this example has an X-ray absorption coefficient as shown in FIG. 6, compared with that of a commercial inorganic scintillator such as BGO, YAG:CE, Si, etc. Figure 5 As can be seen from Figure 5 , the (C 22 H 24 P)2SbCl5 transparent glass can obtain a radioactive luminescence spectrum with a peak of 635 nm under 2.3 mGy air s -1 of X-ray irradiation for 30 s, indicating that the (C 22 H 24 P)2SbCl5 transparent glass has a scintillation property.

[0051] Example 2

[0052] The preparation process is the same as that of Example 1, except that:

[0053] In the preparation of (C 19 H 18 P)2SbCl5 in Example 2, 709.07 mg of C 22 H 24 PCl in Example 1 is replaced by 625.54 mg of C 19 H 18 PCl, and then the heating temperature is changed to 190°C, and the holding time is 2.5 h, and then poured into a graphite mold. After demolding, a (C 19 H 18 P)2SbCl5 self-supporting glass product with a thickness of 2.0 mm, a smooth surface and high transparency is obtained.

[0054] Performance test: under 10.2 mGy air s -1 X-ray irradiation, exposure for 60 s, from Figure 6It can be seen that the glass product has bright luminescence under X-rays, and the resolution can reach 20 lp / mm.

[0055] Example 3

[0056] The same as the preparation process of Example 1, except that:

[0057] In the preparation of Example 3 (C 19 H 17 PCl)2SbCl5, 709.07 mg of C 22 H 24 PCl in Example 1 is replaced by 694.44 mg of C 19 H 17 PCl2, and then the heating temperature is changed to 180°C, and the holding time is 2.0 h, and then poured into a graphite mold. After demolding, a (C 19 H 17 PCl)2SbCl5self-supporting glass product with smooth surface and high transparency with a thickness of 2.2 mm is obtained.

[0058] Performance test: under 2.3 mGy air s -1 X-ray irradiation, exposure for 60 s, the glass product has bright luminescence under X-rays, and the resolution can reach 20 lp / mm. Figure 7 It can be seen that the glass product has bright luminescence under X-rays, and the resolution can reach 20 lp / mm.

[0059] Example 4

[0060] The same as the preparation process of Example 1, except that:

[0061] In the preparation of Example 4 (C 20 H 20 OP)2SbCl5, 709.07 mg of C 22 H 24 PCl in Example 1 is replaced by 685.60 mg of C 20 H 20 OPCl2, and then the heating temperature is changed to 210°C, and the holding time is 1.0 h, and then poured into a graphite mold. After demolding, a (C 20 H 20 OP)2SbCl5self-supporting glass product with smooth surface and high transparency with a thickness of 1.9 mm is obtained.

[0062] Performance test: under 2.3 mGy air s -1 X-ray irradiation, exposure for 60 s, the glass product has bright luminescence under X-rays, and the resolution can reach 20 lp / mm.

[0063] Example 5

[0064] The same as the preparation process of Example 1, except that:

[0065] In the preparation of Example 5 (C 26 H 24 P)2SbCl5, 709.07 mg of C 22 H 24 PCl in Example 1 was replaced by 805.80 mg of C 26 H 24 PCl, and then the heating temperature was changed to 190°C, and the holding time was 3.0 h. After demolding, a surface flat and highly transparent (C 26 H 24 P)2SbCl5self-supporting glass product with a thickness of 2.5 mm was obtained.

[0066] Performance test: under 2.3 mGy air s -1 X-ray irradiation, the glass product has bright luminescence under X-ray irradiation, and the resolution can reach 20 lp / mm. Under neutron ray irradiation, bright luminescence can be obtained.

[0067] Example 6

[0068] Based on (C 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5transparent perovskite scintillator material with large steric hindrance, which is prepared by the following method:

[0069] (C 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5transparent perovskite scintillator synthesis: first, weigh 709.07 mg of C 22 H 24 PCl, 114.06 mg of SbCl3 and 157.67 mg of BiCl3 on an analytical balance, respectively, with a molar ratio of 2:0.5:0.5, grind the solid raw materials into powder and mix them evenly in a high-temperature-resistant glass dish, then place it on a heating table for heating, heat to 200°C, then hold for 3.5 h, and observe that the solid powder is completely changed to a molten state, then transfer the molten melt to a graphite mold for cooling. After the melt is cooled for 30 min, a transparent glass scintillator (C 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5) can be obtained.Cl5. The thickness and shape of the final transparent scintillator can be controlled by controlling the volume of the melt poured into the mold and the shape of the mold. After demolding, a transparent vitreous scintillator with a bright luminescence with a thickness of 2.1 mm was obtained.

[0070] As shown in Figure 8 (C 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5 has a smooth and flat cross section without obvious impurities.

[0071] Performance test: under 2.3 mGy air s -1 X-ray irradiation, exposure for 60 s, bright luminescence under X-ray, and resolution can reach 20 lp / mm. 22 H 24 P)2Sb 0.5 Bi 0.5 Cl5 has a smooth and flat cross section without obvious impurities.

[0072] Example 7

[0073] The preparation process is the same as that of Example 6, except that:

[0074] In the preparation of Example 8 (C 26 H 24 P)2Sb 0.5 In 0.5 Cl5, 709.07 mg of C 22 H 24 PCl in Example 7 is changed to 805.80 mg of C 26 H 24 PCl, BiCl3 157.67 mg is changed to InCl3 110.59 mg, and then the heating temperature is changed to 190°C and the holding time is 3.0 h. After demolding, a self-supporting glass product of (C 26 H 24 P)2SbCl5 with a smooth surface and high transparency with a thickness of 2.2 mm is obtained.

[0075] Performance test: under 2.3 mGy air s -1 X-ray irradiation, exposure for 60 s, bright luminescence under X-ray, and resolution can reach 20 lp / mm.

[0076] Example 8

[0077] The preparation process is the same as that of Example 6, except that:

[0078] In the preparation of Example 8 (C 21 H 20O2P)2Sb 0.8 Bi 0.2 Cl5of Example 1, 709.07 mg of C 22 H 24 PCl was changed to 741.62 mg of C 21 H 20 O2PCl, 114.06 mg of SbCl3was changed to 182.50 mg, 157.67 mg of BiCl3was changed to 63.07 mg, and then the heating temperature was changed to 180°C and the holding time was 1.5 h, and then poured into a graphite mold. After demolding, a (C 21 H 20 O2P)2Sb 0.8 Bi 0.2 Cl5self-supporting glass product.

[0079] Performance test: under 2.3 mGy air s -1 X-ray irradiation, the exposure time was 60 s, and the glass product had bright luminescence under X-ray irradiation, and the resolution could reach 20 lp / mm.

[0080] Comparative Example 1

[0081] The same as the preparation process of Example 1, except that:

[0082] In the preparation of Comparative Example 1 (C 16 H 36 N)2SbCl5of Example 1, 709.07 mg of C 22 H 24 PCl was changed to 555.84 mg of C 21 H 20 O2PCl, the heating temperature was changed to 180°C, and the holding time was 1.5 h, and then poured into a graphite mold. After demolding, a (C 16 H 36 N)2SbCl5self-supporting white opaque product.

[0083] Performance test: under 2.3 mGy air s -1 X-ray irradiation, the exposure time was 60 s, and the white opaque product had almost no luminescence under X-ray irradiation, and the resolution could reach 2.5 lp / mm. Compared with Example 1, it shows that when R-C 18 H 15 PX is replaced by C 16 H 36 NCl, the large-area transparent glass scintillator of the application cannot be synthesized, and the resolution is reduced by nearly ten times compared with other examples.

[0084] Obviously, the above-mentioned embodiments of the present application are only examples for clearly explaining the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art, and it is impossible to enumerate all the embodiments here. Any obvious changes or variations derived from the technical solutions of the present application are still within the protection scope of the present application.

Claims

1. A large area transparent Sb-based and doped perovskite scintillator material, characterized in that, The perovskite scintillator has a general formula: (R-C 18 H 15 P)2Sb y M 1-y X5; wherein, the R is selected from one or more of -CH3, -CH2Cl, -CH2CH3, -CH2OCH3, -(CH2)3CH3, -CH2C6H4CH3, and -C6H5; said X is selected from one or several of Cl - , Br - and I - . the y is selected from 0-1, and is not 0; Said M is selected from one or several of Bi 3+ , In 3+ and Eu 3+ .

2. The method for preparing the perovskite scintillator material as described in claim 1, characterized in that, The perovskite scintillator material is prepared by a melting method.

3. The preparation method according to claim 2, characterized in that, The preparation method comprises the following steps: R-C 18 H 15 Solid feedstocks of PX, SbX3and MX3, which are ground to a powder and mixed homogeneously, to obtain a mixture; heating the mixture to a temperature range of 100-350℃ until all the solid powders become a molten mixture; cooling the molten mixture in a mold to obtain the scintillator material; wherein, the definitions of y, R, X, and M are as described in claim 1.

4. The production method according to claim 3, characterized by, The heating temperature range is 100-350℃.

5. The preparation method according to claim 3, characterized in that, The cooling method is natural cooling, air cooling, or liquid cooling, and the cooling time is 5-15 min.

6. The perovskite scintillator material of claim 1 in the field of ray detection imaging.

7. Use according to claim 6, characterized in that, The rays are selected from one or more of soft X-rays, hard X-rays, and neutrons.

8. Use according to claim 6 or claim 7, characterised in that, The application further comprises the step of shielding the side of the perovskite scintillator material that is directly opposite the ray source.

9. The perovskite scintillator material of claim 1 in the fields of LED, anti-counterfeiting, or laser.

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