Micro-doped neodymium phenethylamine lead bromide monocrystal with enhanced light yield and shortened decay time and application thereof

Abstract

The present application relates to a trace neodymium doped phenethylamine lead bromide monocrystal capable of simultaneously enhancing light yield and shortening decay time and application thereof, which solves the technical problem that the prior art is difficult to simultaneously improve light yield and shorten luminescence decay time. The trace neodymium doped phenethylamine lead bromide monocrystal capable of simultaneously enhancing light yield and shortening decay time is prepared by the following steps: 1) weighing; phenethylamine hydrobromide, lead bromide and neodymium bromide are weighed and placed in a glass bottle; the molar ratio of the phenethylamine hydrobromide, lead bromide and neodymium bromide is 2:1:(0.02-0.05); 2) obtaining a precursor solution; N,N-dimethylformamide is added to the glass bottle, heated and stirred until completely dissolved to obtain a precursor solution; 3) obtaining a crystal; the precursor solution is filtered and placed in a glass beaker for crystallization to obtain a neodymium doped phenethylamine lead bromide monocrystal; through adjustment of the crystal band structure by neodymium, the radiation recombination rate is improved.

Description

Technical Field

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

[0002] Scintillators are key components of indirect radiation detection systems. Their light yield and decay time directly impact the system's detection sensitivity, signal-to-noise ratio, and temporal resolution. Improving the light yield of scintillators and shortening their luminescence decay time have long been requirements for ultrafast radiation detection, but achieving both simultaneously is difficult. Among existing commercial scintillators, LYSO has a higher light yield and a decay time faster than NaI, but still approximately 46 ns. BaF2, CsCl, and ZnO:Ga have response times of 0.8 ns, 0.9 ns, and 0.7 ns, respectively, but all have light yields below 1500 / MeV and are relatively expensive.

[0003] As a representative example of two-dimensional perovskite materials, phenylethylamine lead bromide (PEA2PbBr4) exhibits high light yield (>11,000 / MeV), rapid luminescence decay, simple preparation, and highly customizable performance. Further improving its light yield and shortening its decay time are key approaches to enhancing its performance as a scintillator. However, achieving both improvements is difficult. Summary of the Invention

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

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

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

[0007] 1) Weighing;

[0008] Weigh phenylethylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the molar ratio of phenylethylamine 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 was 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] Furthermore, 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 was taken out, the surface solution was dried, the crystal was 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] 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. By adjusting the energy band structure of the crystal by neodymium, the radiation recombination rate is improved.

[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 simultaneously 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 regulating the luminescence properties of two-dimensional perovskites. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 To utilize 137 The pulse height spectra of the gamma rays generated by Cs respectively exciting 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 utilize 241 The pulse height spectra of the α-rays generated by Am respectively exciting 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 utilize 137 The luminescence decay curves of the γ-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 utilize 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 clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0031] Example 1

[0032] The present invention is a trace neodymium-doped phenylethylamine lead bromide single crystal that can simultaneously enhance light yield and shorten decay time. The single crystal is prepared by the following method:

[0033] 20 mmol (4.0500 g) of phenylethylamine hydrobromide (PEABr), 10 mmol (3.6700 g) of lead bromide (PbBr2), and 0.5 mmol (0.1921 g) of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 7.695 mL of N,N-dimethylformamide (DMF) was added and heated with stirring until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. The beaker was sealed with tin foil and transferred to a constant temperature and low humidity environment at 25°C. Two 1 mm holes were punched in the tin foil to control the solvent evaporation rate. Neodymium-doped phenylethylamine lead bromide single crystals were prepared by the solvent evaporation method. The neodymium-doped phenylethylamine lead bromide single crystals were removed with tweezers, and the surface solution was blotted with filter paper. The crystals were then rinsed with cyclohexane and dried under vacuum for 24 h before storage. According to the test, the amount of neodymium in the neodymium-doped single crystal is 0.04% of that of lead.

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

[0035] Comparative Example

[0036] Weigh 20 mmol of PEABr (4.0500 g) and 10 mmol of PbBr2 (3.6700 g) into a glass reagent bottle, add 7.695 mL of DMF, and heat and stir to completely dissolve to form a 1.3 mol / L solution. Filter the solution and transfer it to a 100 mL glass beaker. Prepare phenylethylamine lead bromide single crystals by solvent evaporation. Remove the crystal with tweezers, absorb the surface solution with filter paper, rinse with cyclohexane, and vacuum dry for 24 hours before storage.

[0037] like Figure 1 As shown, using 137 The pulse height spectra of the gamma rays generated by Cs excite 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. Figure 1 It can be seen that the three crystals were measured 137 The full energy peak of the gamma rays generated by Cs is 480 for the undoped Nd-doped phenylethylamine lead bromide single crystal, 507 for the trace Nd-doped phenylethylamine lead bromide single crystal, and 184 for the commercial scintillator BGO. The peak positions of the undoped Nd-doped phenylethylamine lead bromide single crystal and the trace Nd-doped phenylethylamine lead bromide single crystal are both higher than those of the commercial scintillator BGO, indicating that the crystals have a higher light yield under gamma-ray excitation. In addition, the peak position of the trace Nd-doped 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 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, respectively. Figure 2 It can be seen that all three crystals have measured full-energy peaks of α rays. The full-energy peak address of the undoped Nd phenylethylamine lead bromide single crystal is 1226, the full-energy peak address of the trace Nd phenylethylamine lead bromide single crystal is 1567, and the full-energy peak address of the commercial scintillator LYSO is 746. Among them, the peak position addresses of the undoped Nd phenylethylamine lead bromide single crystal and the trace Nd phenylethylamine lead bromide single crystal are higher than those of the commercial scintillator LYSO, indicating that the crystal has a higher light yield under α ray excitation. In addition, the peak position address of the trace Nd phenylethylamine lead bromide single crystal is 27.8% higher than that of the undoped crystal, indicating that trace Nd doping increases 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. Figure 3 It can be seen that after doping with a trace amount of neodymium, the luminescence decay of the phenylethylamine lead bromide single crystal under γ-ray excitation becomes faster.

[0040] like Figure 4 As shown, using 241 The α-rays generated by Am respectively 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. Figure 4 It can be seen that after doping with a trace amount of neodymium, the luminescence decay of the phenylethylamine lead bromide single crystal under α-ray excitation becomes significantly faster.

[0041] Example 2

[0042] 20 mmol (4.0500 g) of phenylethylamine hydrobromide (PEABr), 10 mmol (3.6700 g) of lead bromide (PbBr2), and 0.3 mmol (0.1153 g) of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 6.665 mL of N,N-dimethylformamide (DMF) was added and heated to 60°C. Stirring was performed until the mixture was completely dissolved. The solution was filtered hot through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. The beaker was sealed with tin foil and transferred to a forced air drying oven. The mixture was kept at 50°C for 0.5 h and then cooled to room temperature at a rate of 2°C / day to obtain a neodymium-doped phenylethylamine lead bromide single crystal. The neodymium-doped phenylethylamine lead bromide single crystal was removed with tweezers, the surface solution was blotted off with filter paper, and the crystal was then rinsed with cyclohexane and vacuum dried for 24 h before storage. According to tests, the amount of neodymium in the neodymium-doped single crystal is 0.03% of that of lead.

[0043] Example 3

[0044] 20 mmol (4.0500 g) of phenylethylamine hydrobromide (PEABr), 10 mmol (3.6700 g) of lead bromide (PbBr2), and 0.2 mmol (0.0768 g) of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 7.695 mL of N,N-dimethylformamide (DMF) was added and heated with stirring to dissolve completely. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. The beaker was sealed with tin foil, and two 1 mm holes were punched in the foil. The solution was then transferred to a large beaker filled with chlorobenzene and sealed. Neodymium-doped phenylethylamine lead bromide single crystals were prepared by antisolvent evaporation. The neodymium-doped phenylethylamine lead bromide single crystals were removed with tweezers, and the surface solution was blotted off with filter paper. The crystals were then rinsed with chlorobenzene and vacuum-dried for 24 h before storage. According to tests, the amount of neodymium in the neodymium-doped single crystal is 0.02% of that of lead.

[0045] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions within the technical scope disclosed in the present invention shall be covered by the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of protection 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 phenylethylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the molar ratio of phenylethylamine 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 was 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 as follows: 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 was taken out, the surface solution was dried, the crystal was 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 according to any one of claims 1 to 5, which can simultaneously enhance light yield and shorten decay time, in ionizing radiation detection.

7. Use of a trace amount of neodymium-doped phenylethylamine lead bromide single crystal capable of simultaneously enhancing light yield and shortening decay time as claimed in any one of claims 1 to 5 in γ / α ray detection.

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