Method for preparing antimony-based hybrid scintillating single crystals assisted by divalent manganese ion doping

Abstract

The present invention relates to a method for preparing an antimony-based hybrid scintillating single crystal by doping with divalent manganese ions, and provides an antimony-based hybrid scintillating single crystal doped with divalent manganese ions, the general composition formula of which is DPA 3 SbCl 6 :Mn, wherein DPA is dipropylamine. The method of the present application introduces a small amount of divalent manganese ions (Mn 2+ ), and seed crystal induction was used to evaporate the solvent at a constant temperature, thereby obtaining large-sized, high-quality zero-dimensional hybrid antimony-based scintillating single crystals, which can be directly used for X-ray imaging.

Description

Technical Field

[0001] The present application belongs to the technical field of luminescence and radiation detection, and relates to a novel type of antimony-based hybrid scintillating single crystal doped with divalent manganese ions, and specifically to a method for preparing antimony-based hybrid scintillating single crystals with the assistance of divalent manganese ion doping. Background Art

[0002] The detection of high-energy photons and ionizing particles is crucial to a wide range of scientific and technological fields, including high-energy physics, homeland security, oil extraction, medical diagnosis, and space exploration. Radiation detection mainly uses scintillating materials to convert ionizing radiation into ultraviolet or visible light, which is then collected and converted into electrical signals by efficient photodetectors coupled to the scintillators. At present, traditional inorganic scintillators such as NaI:Tl, CsI:Tl, LYSO, etc. have received widespread attention and are well applied to commercial X-ray detection and imaging. However, these materials still have problems such as complex manufacturing process, high cost, and high toxicity. In addition, organic scintillators have been gradually explored, but their scintillation performance is not ideal due to low exciton utilization and weak X-ray absorption ability.

[0003] Metal-based organic-inorganic hybrid halides are usually prepared by low-cost solution methods. They also have the advantages of simple production process, strong adjustability, and excellent scintillation performance, which make them show great application potential in the field of luminescence and radiation detection. 2 Lead-based organic-inorganic hybrid halide scintillators with highly stereoactive lone pairs of electrons usually exhibit efficient broadband emission and large Stokes shift. However, their toxicity and instability violate the strategy of sustainable development. Therefore, other ns 2 Electronic configuration of metal-based organic-inorganic hybrid halide scintillators (Sb 3+ Sn 2+ ,Ge 2+ ) are attracting more and more attention as substitutes. In particular, antimony-based organic-inorganic hybrid halides are not only non-toxic but also have a higher affinity with Ge. 2+ and Sn 2+ Larger atomic number and good stability.

[0004] However, the research on the preparation of single crystals by solution method is focused on lead-based materials, and there is less research on other metal-based organic-inorganic hybrid perovskite materials. Currently reported organic-inorganic hybrid antimony halide scintillators are mostly polycrystalline powders or small-sized single crystals, and single crystals usually show better physical properties than polycrystalline materials, which greatly limits its application. Therefore, providing a method for preparing large-sized, high-quality antimony-based organic-inorganic hybrid halide perovskite single crystals is of great significance to promote their practical application.

[0005] Therefore, the field urgently needs to develop novel methods for preparing large-sized, high-quality organic-inorganic zero-dimensional hybrid antimony-based halide perovskite scintillating single crystals to obtain new divalent manganese ions (Mn 2+ ) doped antimony-based hybrid scintillating single crystals. Summary of the invention

[0006] The present application provides a method for preparing antimony-based hybrid scintillating single crystals assisted by divalent manganese ion doping, and a novel divalent manganese ion-doped antimony-based hybrid scintillating single crystal prepared by the method and directly used for X-ray imaging, thereby solving the problems existing in the prior art.

[0007] According to the first aspect of the present application, there is provided a divalent manganese ion-doped antimony-based hybrid scintillating single crystal having the following general composition formula:

[0008] DPA3SbCl6:Mn, where:

[0009] DPA is dipropylamine.

[0010] According to a second aspect of the present application, a method for preparing an antimony-based hybrid scintillating single crystal by doping with divalent manganese ions is provided, the method comprising the following steps:

[0011] (1) In a first glass bottle, weigh an organic salt DPACl and an inorganic salt SbCl3 in a molar ratio of 2:1 to 3:1, and MnCl2 in an amount not higher than 1 / 3 of the molar amount of SbCl3, add ethanol to the bottle, heat and stir to completely dissolve, and obtain a clear precursor solution;

[0012] (2) Filter the precursor solution obtained in step (1) into a second glass bottle, seal it with tin foil or dust-free paper with small holes, and place it at a constant temperature for evaporation;

[0013] (3) After the precursor solution in step (2) evaporates and crystals are precipitated, single crystals with regular shapes are selected as seed crystals and taken out from the second glass bottle; ethanol is added to the second glass bottle and heated and stirred to completely dissolve the remaining precipitated crystals, and the solution is filtered into a third glass bottle;

[0014] (4) adding the seed crystals selected in step (3) to the filtrate in the third glass bottle and sealing the third glass bottle containing the filtrate and the seed crystals and placing it on a heating platform to dissolve the edges of the seed crystals, then sealing it with tin foil or dust-free paper with small holes, and placing it at a constant temperature for evaporation to allow the seed crystals to continue to grow into large-sized single crystals;

[0015] (5) The large-sized single crystal obtained in step (4) is taken out and cleaned with a poor solvent, and then naturally air-dried and stored in a dry and light-proof environment.

[0016] In a preferred embodiment, in step (1), the molar ratio of the organic salt DPACl to the inorganic salt SbCl3 is 3:1, and the mixture is heated to 30-40°C and stirred for 10-15 hours.

[0017] In another preferred embodiment, in step (1), the mixture is heated to 30° C. in a glove box under N 2 atmosphere and stirred for 12 hours.

[0018] In another preferred embodiment, in step (1), MnCl2 is added in an amount not higher than 1 / 5 of the molar amount of SbCl3.

[0019] In another preferred embodiment, in step (2), evaporation is performed at 30-35°C.

[0020] In another preferred embodiment, in step (3), the temperature is heated to 35-45°C.

[0021] In another preferred embodiment, in step (3), heating is performed to 40°C.

[0022] In another preferred embodiment, in step (4), the mixture is heated to 30-40°C and then evaporated at 30-35°C.

[0023] In another preferred embodiment, in step (5), the poor solvent includes anhydrous ether.

[0024] Beneficial effect: By introducing Mn 2+ The nucleation barrier of DPA3SbCl6 is improved, the number of nuclei in the early stage of single crystal growth is controlled and stabilized in the crystal growth zone to obtain single crystals with better quality. At the same time, the solvent volatilization method induced by the seed crystal is used to further grow the crystal to obtain large-size, high-quality single crystals. In addition, the DPA3SbCl6:Mn prepared in this application has the advantages of low raw material cost, easy preparation and environmental friendliness.

[0025] These and other features and advantages will become apparent by reading the following detailed description and by reference to the associated drawings.It is to be understood that the foregoing general description and the following detailed description are illustrative only and are not restrictive of the aspects of what is claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A physical picture of the DPA3SbCl6 single crystal prepared in Comparative Example 1 of the present application is shown.

[0027] Figure 2 A physical picture of the DPA3SbCl6 single crystal prepared in Comparative Example 2 of the present application is shown.

[0028] Figure 3A physical picture of the DPA3SbCl6:Mn single crystal prepared in Example 1 of the present application is shown.

[0029] Figure 4 The transmittance spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown.

[0030] Figure 5 The rocking curves of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown.

[0031] Figure 6 The fluorescence luminescence spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown.

[0032] Figure 7 The irradiated luminescence spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown.

[0033] Figure 8 An X-ray imaging photograph of the DPA3SbCl6:Mn single crystal prepared in Example 1 of the present application is shown.

[0034] Fig. 9 A physical picture of the DPA3SbCl6:Mn single crystal prepared in Example 2 of the present application is shown. DETAILED DESCRIPTION

[0035] The present application is described in detail below in conjunction with the accompanying drawings, and the features of the present application will be further revealed in the following specific description.

[0036] "Scope" disclosed herein is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0037] In this application, if there is no special description, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution. In this application, if there is no special description, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0038] In this application, unless otherwise specified, the terms "include" and "comprising" mentioned herein may be open-ended or closed-ended. For example, the terms "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0039] In the description herein, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0040] In view of the problems that the research on the preparation of single crystals by solution method in the prior art focuses on lead-based materials, and there is little research on other metal-based organic-inorganic hybrid perovskite materials, and most of the organic-inorganic hybrid antimony halide scintillators are polycrystalline powders or small-sized single crystals, this application introduces a small amount of Mn 2+At the same time, seed crystal induction was used to evaporate the solvent at a constant temperature, thereby obtaining large-size, high-quality organic-inorganic hybrid antimony-based zero-dimensional perovskite scintillating single crystals that can be directly used for X-ray imaging.

[0041] Antimony-based hybrid scintillating single crystals doped with divalent manganese ions

[0042] In a first aspect of the present application, a divalent manganese ion-doped antimony-based hybrid scintillating single crystal is provided, which has the following general composition formula:

[0043] DPA3SbCl6:Mn, where:

[0044] DPA is dipropylamine.

[0045] Method for preparing antimony-based hybrid scintillating single crystals assisted by divalent manganese ion doping

[0046] In a second aspect of the present application, a method for preparing an antimony-based hybrid scintillating single crystal by doping with divalent manganese ions is provided, the method comprising the following steps:

[0047] (1) In a first glass bottle, weigh an organic salt DPACl (dipropylamine hydrochloride) and an inorganic salt SbCl3 (antimony trichloride), as well as a small amount of MnCl2 in a certain proportion, add ethanol to the bottle, heat and stir to completely dissolve, and obtain a clear precursor solution;

[0048] (2) Filter the precursor solution obtained in step (1) into a second glass bottle, seal it with tin foil or dust-free paper with small holes, and place it at a constant temperature for evaporation;

[0049] (3) After the precursor solution in step (2) evaporates and crystals are precipitated, single crystals with regular shapes are selected as seed crystals and taken out from the second glass bottle; a small amount of ethanol is added to the second glass bottle, heated and stirred to completely dissolve the remaining precipitated crystals, and the solution is filtered into a third glass bottle;

[0050] (4) adding the seed crystals selected in step (3) to the filtrate in the third glass bottle and sealing the third glass bottle containing the filtrate and the seed crystals and placing it on a heating platform to dissolve the edges of the seed crystals, then sealing it with tin foil or dust-free paper with small holes, and placing it at a constant temperature for evaporation to allow the seed crystals to continue to grow into large-sized single crystals;

[0051] (5) The large-sized single crystal obtained in step (4) is taken out and cleaned with a poor solvent, and then naturally air-dried and stored in a dry and light-proof environment.

[0052] In the present application, in step (1), DPACl and SbCl3 are weighed in a molar ratio of 2:1 to 3:1, preferably 3:1.

[0053] In the present application, in step (1), MnCl2 is added in an amount not higher than 1 / 3 of the molar amount of SbCl3, preferably not higher than 1 / 5 of the molar amount of SbCl3.

[0054] In the present application, in step (1), the temperature is heated to 30-40°C, preferably to 30°C in a glove box with N2 atmosphere.

[0055] In the present application, in step (1), stirring is performed for 10-15 hours, preferably 12 hours.

[0056] In the present application, in step (2), the evaporation is carried out at 30-35°C, preferably 30°C.

[0057] In the present application, in step (3), heating is performed to 35-45°C, preferably 40°C.

[0058] In the present application, in step (4), heating is performed to 30-40°C.

[0059] In the present application, in step (4), evaporation is carried out at 30-35°C, preferably 30°C.

[0060] In the present application, in step (5), the poor solvent includes anhydrous ether.

[0061] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0062] Comparative Example 1: 3 mmol DPACl and 1 mmol SbCl3 were weighed and mixed in 6 mL ethanol according to the stoichiometric ratio of DPA3SbCl6 in the first glass bottle, and then heated to 30 °C in a glove box with N2 atmosphere and stirred for 12 hours to form a transparent precursor solution; then the transparent precursor solution was filtered into the second glass bottle with a 0.22 μm filter head to prevent the impurities therein from affecting the formation of crystal nuclei; the second glass bottle containing the filtrate was sealed with tin foil and the tin foil was pierced with a needle, and then the second glass bottle was placed in a 30 °C oil bath for evaporation; two days later, colorless crystals precipitated at the bottom of the bottle. After taking out the crystals, they were quickly washed twice with anhydrous ether, then dried at room temperature and stored in a dark environment.

[0063] Figure 1 The actual picture of DPA3SbCl6 single crystal prepared in Comparative Example 1 of the present application is shown. Figure 1 As shown, the obtained crystals are of poor quality, almost opaque and are all polycrystalline stacks with irregular shapes.

[0064] Comparative Example 2: In a first glass bottle, 3 mmol DPACl and 1 mmol SbCl3 were weighed according to the stoichiometric ratio of DPA3SbCl6, mixed and dissolved in 6 mL ethanol, heated to 30°C in a glove box with N2 atmosphere, and stirred for 12 hours to form a transparent precursor solution; the transparent precursor solution was then filtered into a second glass bottle with a 0.22 μm filter head to prevent the impurities therein from affecting the formation of crystal nuclei; the second glass bottle containing the filtrate was sealed with tin foil and the tin foil was pierced with a needle, and then the second glass bottle was placed in a 30°C oil bath for evaporation; after one day, it was observed that smaller crystals were precipitated at the bottom of the bottle; single crystals with regular shapes were picked out from the bottle and taken out, the second glass bottle was placed on a 40°C heating platform and ethanol was added and stirred to completely dissolve the remaining precipitated crystals, and the solution was filtered again into a third glass bottle, and the small crystals selected in the previous step were added to the filtrate as seed crystals; the third glass bottle containing the filtrate and seed crystals was sealed with tin foil and placed at 40 ℃ heating platform to dissolve the edge of the seed crystal, then pierce holes in the tin foil and transfer the third glass bottle to a 30 ℃ oil bath for evaporation. After 4-5 days, large crystals are generated. Take out the crystals and quickly wash them twice with anhydrous ether, then dry them at room temperature and store them in a dark environment.

[0065] Figure 2 The actual picture of DPA3SbCl6 single crystal prepared in Comparative Example 2 of the present application is shown. Figure 2 As shown, after seed induction, the crystals are still opaque, but have a regular cubic shape.

[0066] Example 1: 3 mmol DPACl and 1 mmol SbCl3 and 0.2 mmol MnCl2 were weighed and mixed and dissolved in 6 mL ethanol in a first glass bottle according to the stoichiometric ratio of DPA3SbCl6, and the mixture was heated to 30°C in a glove box under N2 atmosphere, and stirred for 12 hours to form a clear precursor solution; the clear precursor solution was filtered into a second glass bottle with a 0.22 μm filter head to prevent the impurities therein from affecting the formation of crystal nuclei; the second glass bottle containing the filtrate was sealed with tin foil and the tin foil was pierced with a needle, and then the second glass bottle was placed in a 30°C oil bath for evaporation. After one day, it was observed that small crystals were precipitated at the bottom of the bottle, and single crystals with regular shapes were picked out from the bottle and taken out, and the second glass bottle was placed at 40 ℃ heating platform and add ethanol to stir to completely dissolve the remaining precipitated crystals, and filter the solution again into the third glass bottle, add the small crystals selected in the previous step as seed crystals to the filtrate; seal the third glass bottle containing the filtrate and seed crystals with tin foil and place it on a 40 ℃ heating platform to dissolve the edges of the seed crystals, then pierce holes in the tin foil and transfer the glass bottle to a 30 ℃ oil bath for evaporation. After 4-5 days, large crystals are generated. Take out the crystals and quickly wash them twice with anhydrous ether, then air-dry them naturally, and store them in a dry and dark environment.

[0067] Figure 3 The actual picture of DPA3SbCl6:Mn single crystal prepared in Example 1 of the present application is shown. Figure 3 As shown, after the introduction of MnCl2 and the use of seed crystals to induce growth, the crystal shape is a regular cube with high light transmittance.

[0068] Figure 4 The transmittance spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown. Figure 4 As shown in the figure, the light transmittance of the crystal is significantly improved after the introduction of MnCl2, approaching 90%.

[0069] Figure 5 The rocking curves of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown. Figure 5 As shown in the figure, after the introduction of MnCl2, the half-peak width of the plane rocking curve of the single crystal (1, 0, -2) changed from 0.038° to 0.0099°, indicating that the crystallinity was significantly improved.

[0070] Figure 6 The fluorescence spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown. Figure 6 As shown, the introduction of MnCl2 did not change the luminescence peak position of the single crystal.

[0071] Figure 7 The irradiated luminescence spectra of DPA3SbCl6 and DPA3SbCl6:Mn single crystals prepared in Comparative Example 2 and Example 1 of the present application are shown. Figure 7 As shown, the peak position of the irradiated luminescence spectrum of the crystal did not change before and after the introduction of MnCl2, and its luminescence intensity was significantly improved.

[0072] Figure 8 The X-ray imaging photograph of the DPA3SbCl6:Mn single crystal prepared in Example 1 of the present application is shown. Figure 8 As shown, single crystals optimized by the introduction of MnCl2 can be directly used for X-ray imaging.

[0073] Example 2: 3 mmol DPACl and 1 mmol SbCl3 and 0.33 mmol MnCl2 were weighed and mixed and dissolved in 6 mL ethanol in a first glass bottle according to the stoichiometric ratio of DPA3SbCl6, and the mixture was heated to 30°C in a glove box under N2 atmosphere, and stirred for 12 hours to form a clear precursor solution; the clear precursor solution was filtered into a second glass bottle with a 0.22 μm filter head to prevent the impurities therein from affecting the formation of crystal nuclei; the second glass bottle containing the filtrate was sealed with tin foil and the tin foil was pierced with a needle, and then the second glass bottle was placed in a 30°C oil bath for evaporation. After one day, it was observed that small crystals were precipitated at the bottom of the bottle, and single crystals with regular shapes were picked out from the bottle and taken out, and the second glass bottle was placed at 40 ℃ heating platform and add ethanol to stir to completely dissolve the remaining precipitated crystals, and filter the solution again into the third glass bottle, add the small crystals selected in the previous step as seed crystals to the filtrate; seal the third glass bottle containing the filtrate and seed crystals with tin foil and place it on a 40 ℃ heating platform to dissolve the edges of the seed crystals, then pierce holes in the tin foil and transfer the glass bottle to a 30 ℃ oil bath for evaporation. After 4-5 days, large crystals are generated. Take out the crystals and quickly wash them twice with anhydrous ether, then air-dry them naturally, and store them in a dry and dark environment.

[0074] Fig. 9 The actual picture of DPA3SbCl6:Mn single crystal prepared in Example 2 of the present application is shown. Fig. 9 As shown, when MnCl2 and SbCl3 are added in a molar ratio of 1:3, the obtained single crystal is compared with the single crystal prepared in Example 1 (MnCl2 and SbCl3 are added in a molar ratio of 1:5), and the crystal shape is also a regular cube, but the light transmittance is slightly worse.

[0075] Finally, it is necessary to explain here that the above embodiments are only used to further illustrate the technical solution of the present application in detail and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by technicians in this field based on the above content of the present application are all within the scope of protection of the present application.

Claims

1. A divalent manganese ion doped antimony-based hybrid scintillating single crystal, characterized in that: It has the following general formula: DPA3SbCl6:Mn, where: DPA is dipropylamine, Among them, Mn 2+ The molar amount is not higher than Sb 3+ 1 / 3 of the molar amount.

2. A method for preparing antimony-based hybrid scintillating single crystals assisted by divalent manganese ion doping, wherein the scintillating single crystal has the following general composition formula: DPA3SbCl6:Mn, wherein DPA is dipropylamine, characterized in that: The method comprises the following steps: (1) In a first glass bottle, weigh an organic salt DPACl and an inorganic salt SbCl3 in a molar ratio of 2:1 to 3:1, and MnCl2 in an amount not higher than 1 / 3 of the molar amount of SbCl3, add ethanol to the bottle, heat and stir to completely dissolve, and obtain a clear precursor solution; (2) Filter the precursor solution obtained in step (1) into a second glass bottle, seal it with perforated tin foil or dust-free paper, and place it at a constant temperature for evaporation; (3) After the precursor solution in step (2) evaporates and crystals are precipitated, single crystals with regular shapes are selected as seed crystals and taken out from the second glass bottle; ethanol is added to the second glass bottle and heated and stirred to completely dissolve the remaining precipitated crystals, and the solution is filtered into a third glass bottle; (4) adding the seed crystals selected in step (3) to the filtrate in the third glass bottle and sealing the third glass bottle containing the filtrate and the seed crystals and placing it on a heating platform to dissolve the edges of the seed crystals, then sealing it with pierced tin foil or dust-free paper, and placing it at a constant temperature for evaporation to allow the seed crystals to continue to grow into single crystals; (5) The single crystal obtained in step (4) is taken out and cleaned with a poor solvent, and then naturally air-dried and stored in a dry and light-proof environment.

3. The method according to claim 2, characterized in that In step (1), the molar ratio of the organic salt DPACl to the inorganic salt SbCl3 is 3:1, heated to 30-40°C, and stirred for 10-15 hours.

4. The method according to claim 2, characterized in that In step (1), the mixture was heated to 30° C. in a glove box under a N 2 atmosphere and stirred for 12 hours.

5. The method according to claim 2, characterized in that In step (1), MnCl2 is added in an amount not higher than 1 / 5 of the molar amount of SbCl3.

6. The method according to claim 2, characterized in that In step (2), place at 30-35°C for evaporation.

7. The method according to claim 2, characterized in that In step (3), heating is performed to 35-45°C.

8. The method according to claim 2, characterized in that In step (3), heating is performed to 40°C.

9. The method according to claim 2, characterized in that In step (4), the mixture is heated to 30-40°C and placed at 30-35°C for evaporation.

10. The method according to claim 2, characterized in that In step (5), the poor solvent includes anhydrous ether.

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