Trace neodymium-doped phenylethylamine lead-bromine single crystal capable of simultaneously enhancing light yield and shortening decay time and application of trace neodymium-doped phenylethylamine lead-bromine single crystal

Abstract

The invention particularly relates to a trace neodymium-doped phenylethylamine lead-bromine single crystal capable of simultaneously enhancing the light yield and shortening the decay time and application thereof, and solves the technical problem that in the prior art, the light yield is difficult to increase and the luminescence decay time is difficult to shorten at the same time. The trace neodymium-doped phenylethylamine lead-bromine single crystal capable of simultaneously enhancing the light yield and shortening the decay time is prepared by the following steps: 1) weighing; the preparation method comprises the following steps: weighing phenylethylamine hydrobromide, lead bromide and neodymium bromide, and putting into a glass bottle; the molar ratio of the phenylethylamine hydrobromide to the lead bromide to the neodymium bromide is 2: 1: (0.02-0.05); 2) obtaining a precursor solution; adding N, N-dimethylformamide into the glass bottle, heating and stirring until the N, N-dimethylformamide is completely dissolved to obtain a precursor solution; 3) obtaining a crystal; the precursor solution is filtered and then put into a glass beaker to be crystallized, and the neodymium-doped phenylethylamine lead-bromine single crystal is obtained; the radiation recombination rate is improved by adjusting the crystal energy band structure through neodymium.

Description

Technical Field

[0001] The invention specifically relates to a trace amount of neodymium doped phenylethylamine lead bromine single crystal capable of simultaneously enhancing light yield and shortening decay time and application thereof. Background Art

[0002] As a key component of the indirect radiation detection system, the light yield and decay time of the scintillator directly affect the detection sensitivity, signal-to-noise ratio, and time resolution of the system. Improving the light yield of the scintillator and shortening its luminescence decay time have always been the requirements of ultrafast radiation detection, but it is difficult to achieve both at the same time. Among the existing commercial scintillators, LYSO has a higher light yield and its decay time is faster than NaI, but it is still about 46ns long. The response times of BaF2, CsCl, and ZnO:Ga can reach 0.8ns, 0.9ns, and 0.7ns, respectively, but the light yields of the three are all lower than 1500 / MeV and the cost is relatively high.

[0003] As a typical representative of two-dimensional perovskite materials, phenylethylamine lead bromide (PEA2PbBr4) has a high light yield (>11000 / MeV), fast luminescence decay, simple preparation process, and strong performance designability. Further improving its light yield and shortening the luminescence decay time are important means to improve its performance as a scintillator. However, it is difficult to simultaneously improve the light yield and shorten the luminescence decay time. Summary of the invention

[0004] The purpose of the present invention is to solve the technical problem that it is difficult to simultaneously increase the light yield and shorten the luminescence decay time in the prior art, and to provide a trace neodymium-doped phenylethylamine lead bromine single crystal that can simultaneously enhance the light yield and shorten the decay time.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] A trace amount of neodymium doped phenylethylamine lead bromide single crystal which can simultaneously enhance light yield and shorten decay time is special in that it is prepared by the following steps:

[0007] 1) Weighing;

[0008] Weigh phenethylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the molar ratio of phenethylamine hydrobromide, lead bromide, and neodymium bromide is 2:1:(0.02-0.05);

[0009] 2) obtaining a precursor solution;

[0010] Add N,N-dimethylformamide to a glass bottle, heat and stir until completely dissolved to obtain a precursor solution;

[0011] 3) obtaining crystals;

[0012] The precursor solution is filtered and placed in a glass beaker for crystallization to obtain a neodymium-doped phenylethylamine lead bromide single crystal;

[0013] The amount of neodymium in the neodymium-doped phenylethylamine lead bromine single crystal is 0.02%-0.04% of lead.

[0014] Furthermore, in step 1), the concentration ratio of phenylethylamine hydrobromide, lead bromide and neodymium bromide in the precursor solution is 2:1:0.05.

[0015] Further, step 3) is specifically as follows:

[0016] The precursor solution is filtered and placed in a glass beaker, and a neodymium-doped phenylethylamine lead bromide single crystal is obtained by a solvent evaporation method, a cooling crystallization method, or an anti-solvent crystallization method.

[0017] Furthermore, the method further comprises step 4):

[0018] The neodymium-doped phenylethylamine lead bromide single crystal is taken out, the surface solution is dried, and the crystal is cleaned with an anti-solvent and then vacuum-dried at room temperature to obtain a neodymium-doped phenylethylamine lead bromide scintillator.

[0019] Furthermore, in step 4), the anti-solvent is cyclohexane or chlorobenzene.

[0020] At the same time, the present invention also proposes the application of the single crystal in ionizing radiation detection.

[0021] The application of the above single crystal in γ / α ray detection.

[0022] Beneficial effects of the present invention:

[0023] (1) The present invention can simultaneously enhance the light yield and shorten the decay time of trace neodymium-doped phenylethylamine lead bromide single crystals. A trace amount of neodymium is doped into the crystal to obtain a neodymium-doped phenylethylamine lead bromide single crystal. The radiation recombination rate is improved by adjusting the crystal band structure by neodymium.

[0024] (2) The present invention can simultaneously enhance the light yield and shorten the decay time of the trace neodymium-doped phenylethylamine lead bromide single crystal, and at the same time achieve the goal of increasing its light yield for α-rays and γ-rays and shortening the decay time.

[0025] (3) The present invention can simultaneously enhance the light yield and shorten the decay time of trace neodymium-doped phenylethylamine lead bromide single crystals, providing a new idea for adjusting the luminescence properties of two-dimensional perovskites. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 To use 137 The gamma rays generated by Cs excite the pulse height spectra of the commercial scintillator BGO, the undoped neodymium crystal prepared in the comparative example, and the trace neodymium-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention;

[0027] Figure 2 To use 241 The α rays generated by Am respectively excite the pulse height spectra of the commercial scintillator LYSO, the undoped neodymium crystal prepared in the comparative example, and the trace neodymium-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention;

[0028] Figure 3 To use 137 The luminescence decay curves of the gamma rays generated by Cs respectively exciting the undoped Nd crystal prepared in the comparative example and the Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention;

[0029] Figure 4 To use 241 The luminescence attenuation curves of the α-rays generated by Am respectively exciting the undoped Nd crystal prepared in the comparative example and the Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] The present invention discloses a trace amount of neodymium doped phenylethylamine lead bromine single crystal which can simultaneously enhance light yield and shorten decay time, and is prepared by the following method:

[0033] Weigh 20mmol (4.0500g) of phenylethylamine hydrobromide (PEABr), 10mmol (3.6700g) of lead bromide (PbBr2), and 0.5mmol (0.1921g) of neodymium bromide (NdBr3) in a glass reagent bottle, add 7.695mL of N,N-dimethylformamide (DMF), heat and stir to completely dissolve, filter the solution with a nylon filter head with a pore size of 0.45μm, and transfer it to a 100mL glass beaker. Seal the beaker with tin foil and transfer it to a constant temperature and low humidity environment at 25℃. Punch two holes of about 1mm in size on the tin foil to control the solvent evaporation rate; prepare neodymium-doped phenylethylamine lead bromide single crystals by solvent evaporation method. Take out the neodymium-doped phenylethylamine lead bromide single crystals with tweezers and dry the surface solution with filter paper, then wash with cyclohexane and vacuum dry for 24h before storage. After testing, the amount of neodymium in the neodymium-doped single crystal is 0.04% of lead.

[0034] The neodymium-doped phenylethylamine lead bromide single crystal prepared in this embodiment 1 can be used in ionizing radiation detection and gamma / alpha ray detection.

[0035] Comparative Example

[0036] Weigh 20mmol PEABr (4.0500g) and 10mmol PbBr2 (3.6700g) in a glass reagent bottle, add 7.695mL DMF, heat and stir to completely dissolve, make a 1.3mol / L solution, filter the solution and transfer it to a 100mL glass beaker, and prepare phenylethylamine lead bromide single crystal by solvent evaporation method. Take out the crystal with tweezers, absorb the surface solution with filter paper, wash it with cyclohexane, vacuum dry it for 24h, and then store it.

[0037] like Figure 1 As shown, using 137 The pulse height spectra of the gamma rays generated by Cs exciting the commercial scintillator BGO, the undoped Nd crystal prepared in the comparative example, and the trace Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention are shown in FIG. Figure 1 It can be seen that all three crystals have measured 137 The full energy peak of the gamma rays generated by Cs has a full energy peak address of 480 for undoped Nd phenylethylamine lead bromide single crystal, a full energy peak address of 507 for trace Nd doped Nd phenylethylamine lead bromide single crystal, and a full energy peak address of 184 for the commercial scintillator BGO; among them, the peak addresses of undoped Nd phenylethylamine lead bromide single crystal and trace Nd doped Nd phenylethylamine lead bromide single crystal are both higher than the commercial scintillator BGO, indicating that the crystal has a higher light yield under gamma ray excitation; in addition, the peak address of trace Nd doped Nd phenylethylamine lead bromide single crystal is 5.6% higher than that of the undoped crystal, indicating that trace Nd doping increases the light yield of the phenylethylamine lead bromide single crystal under gamma ray excitation.

[0038] like Figure 2 As shown, using 241 The α rays generated by Am excite the pulse height spectra of the commercial scintillator LYSO, the undoped Nd crystal prepared in the comparative example, and the trace Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention, respectively. Figure 2 It can be seen that the full energy peak of α rays was measured for all three crystals, the full energy peak address of the undoped Nd phenylethylamine lead bromide single crystal was 1226, the full energy peak address of the trace Nd doped Nd phenylethylamine lead bromide single crystal was 1567, and the full energy peak address of the commercial scintillator LYSO was 746; among them, the peak position addresses of the undoped Nd phenylethylamine lead bromide single crystal and the trace Nd doped Nd phenylethylamine lead bromide single crystal were higher than those of the commercial scintillator LYSO, indicating that the crystal had a higher light yield under α ray excitation; in addition, the peak position address of the trace Nd doped Nd phenylethylamine lead bromide single crystal was 27.8% higher than that of the undoped crystal, indicating that trace Nd doping increased the light yield of the phenylethylamine lead bromide single crystal under α ray excitation.

[0039] like Figure 3 As shown, using 137 The γ-rays generated by Cs excite the luminescence decay curves of the undoped Nd crystal prepared in the comparative example and the Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention, respectively. Figure 3 It can be seen that after doping with trace amounts of neodymium, the luminescence decay of the phenylethylamine lead bromide single crystal under gamma-ray excitation becomes faster.

[0040] like Figure 4 As shown, using 241 The α-rays generated by Am respectively excite the luminescence attenuation curves of the undoped Nd crystal prepared in the comparative example and the Nd-doped phenylethylamine lead bromide single crystal prepared in Example 1 of the present invention. Figure 4 It can be seen that after doping with trace amounts of neodymium, the luminescence decay of the phenylethylamine lead bromide single crystal under α-ray excitation becomes significantly faster.

[0041] Example 2

[0042] Weigh 20mmol (4.0500g) of phenylethylamine hydrobromide (PEABr), 10mmol (3.6700g) of lead bromide (PbBr2), and 0.3mmol (0.1153g) of neodymium bromide (NdBr3) in a glass reagent bottle, add 6.665mL of N,N-dimethylformamide (DMF), heat to 60°C, stir until completely dissolved, filter the solution while hot using a nylon filter with a pore size of 0.45μm, and transfer it to a 100mL glass beaker. Seal the beaker with tin foil and transfer it to a forced air drying oven, keep it at 50°C for 0.5 hours, and cool it to room temperature at a rate of 2°C / day to obtain a neodymium-doped phenylethylamine lead bromide single crystal. Take out the neodymium-doped phenylethylamine lead bromide single crystal with tweezers, dry the surface solution with filter paper, wash it with cyclohexane, and vacuum dry it for 24 hours before storage. After testing, the amount of neodymium in the neodymium-doped single crystal is 0.03% of lead.

[0043] Example 3

[0044] Weigh 20mmol (4.0500g) of phenylethylamine hydrobromide (PEABr), 10mmol (3.6700g) of lead bromide (PbBr2), and 0.2mmol (0.0768g) of neodymium bromide (NdBr3) in a glass reagent bottle, add 7.695mL of N,N-dimethylformamide (DMF), heat and stir to completely dissolve, filter the solution with a nylon filter head with a pore size of 0.45μm, and transfer it to a 100mL glass beaker, seal the beaker with tin foil, poke two holes of about 1mm in size on the tin foil, and transfer it to a large beaker containing chlorobenzene, seal the large beaker, and prepare neodymium-doped phenylethylamine lead bromide single crystals by anti-solvent evaporation method. Take out the neodymium-doped phenylethylamine lead bromide single crystal with tweezers and dry the surface solution with filter paper, then wash it with chlorobenzene and vacuum dry it for 24h before storage. After testing, the amount of neodymium in the neodymium-doped single crystal is 0.02% of lead.

[0045] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A trace amount of neodymium doped phenylethylamine lead bromide single crystal that can simultaneously enhance light yield and shorten decay time, characterized in that: Prepared using the following steps: 1) Weighing; Weigh phenethylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the molar ratio of phenethylamine hydrobromide, lead bromide, and neodymium bromide is 2:1:(0.02-0.05); 2) obtaining a precursor solution; Add N,N-dimethylformamide to a glass bottle, heat and stir until completely dissolved to obtain a precursor solution; 3) obtaining crystals; The precursor solution is filtered and placed in a glass beaker for crystallization to obtain a neodymium-doped phenylethylamine lead bromide single crystal; The amount of neodymium in the neodymium-doped phenylethylamine lead bromine single crystal is 0.02%-0.04% of lead.

2. The trace neodymium-doped phenylethylamine lead bromide single crystal capable of simultaneously enhancing light yield and shortening decay time according to claim 1, characterized in that: In step 1), the concentration ratio of phenylethylamine hydrobromide, lead bromide and neodymium bromide in the precursor solution is 2:1:0.

05.

3. The trace neodymium-doped phenylethylamine lead bromide single crystal capable of simultaneously enhancing light yield and shortening decay time according to claim 2, characterized in that: Step 3) is specifically: The precursor solution is filtered and placed in a glass beaker, and a neodymium-doped phenylethylamine lead bromide single crystal is obtained by a solvent evaporation method, a cooling crystallization method, or an anti-solvent crystallization method.

4. The trace neodymium-doped phenylethylamine lead bromide single crystal capable of simultaneously enhancing light yield and shortening decay time according to claim 3, characterized in that: Also includes step 4): The neodymium-doped phenylethylamine lead bromide single crystal is taken out, the surface solution is dried, and the crystal is cleaned with an anti-solvent and then vacuum-dried at room temperature to obtain a neodymium-doped phenylethylamine lead bromide scintillator.

5. The trace neodymium-doped phenylethylamine lead bromide single crystal capable of simultaneously enhancing light yield and shortening decay time according to claim 4, characterized in that: In step 4), the anti-solvent is cyclohexane or chlorobenzene.

6. Use of the trace neodymium-doped phenylethylamine lead bromide single crystal as claimed in any one of claims 1 to 5, which can simultaneously enhance light yield and shorten decay time, in ionizing radiation detection.

7. Use of the trace neodymium-doped phenylethylamine lead bromide single crystal as claimed in any one of claims 1 to 5, which can simultaneously enhance light yield and shorten decay time, in γ / α ray detection.

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