A neodymium doped butylamine lead bromide single crystal with differentiable adjustment of luminescence decay time under gamma / alpha ray excitation

Abstract

The application relates to a neodymium-doped butylamine lead bromide monocrystal with differentiable adjustment of light-emitting decay time under gamma / alpha ray excitation, and solves the technical problem that the existing two-dimensional perovskite performance regulation method cannot realize differentiable regulation of responses to different radiation rays. The neodymium-doped butylamine lead bromide monocrystal with differentiable adjustment of light-emitting decay time under gamma / alpha ray excitation is prepared by the following method: 1) weighing; butylamine hydrobromide, lead bromide and neodymium bromide are weighed and placed in a glass bottle; the concentration ratio of the butylamine hydrobromide, the lead bromide and the neodymium bromide is 2:1:(0.2-0.7); 2) obtaining a precursor solution; 3) obtaining a crystal; the precursor solution is filtered and then placed in a glass beaker for crystallization, so that the neodymium-doped butylamine lead bromide monocrystal is obtained, and the decay time of the two-dimensional perovskite to the gamma / alpha ray response can be differentially adjusted.

Description

Technical Field

[0001] Specifically, this invention relates to a neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation. Background Technology

[0002] Scintillators are a key component of indirect radiation detection systems, and their response time is one of the key technical indicators of scintillators, directly affecting the temporal resolution of the detection system. Furthermore, the differences in the response characteristics of scintillators to different radiation rays are a necessary condition for ray waveform discrimination, making response time another important performance indicator of scintillators.

[0003] Two-dimensional perovskite materials possess a natural quantum well structure and a large exciton binding energy, thus they can emit light upon excitation by ionizing radiation at room temperature, making them suitable scintillators. Their luminescence decay time is shorter than that of commercially available scintillators such as NaI, BGO, and LYSO, and their fabrication process is simple and cost-effective, giving them significant application potential in the field of ultrafast radiation detection.

[0004] Existing two-dimensional perovskites show little difference in response time to different rays, and their ability to distinguish ray waveforms is limited. Methods to regulate the decay time of luminescence in two-dimensional perovskites include partial or complete substitution of halogen atoms, doping with heterovalent ions, and modification with organic amine ions, but no schemes have been found to differentiate the regulation for different radiation rays. Summary of the Invention

[0005] The purpose of this invention is to solve the technical problem that existing two-dimensional perovskite performance control methods are difficult to achieve differentiated control of the response to different radiation rays, and to provide a neodymium-doped butylamine lead bromide single crystal with differentiated adjustment of luminescence decay time under γ / α ray excitation.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation is characterized by being prepared by the following method:

[0008] 1) Weighing;

[0009] Weigh out butylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the concentration ratio of butylamine hydrobromide, lead bromide, and neodymium bromide is 2:1:(0.2-0.7);

[0010] 2) Obtain the precursor solution;

[0011] Add N,N-dimethylformamide to a glass bottle, heat and stir until completely dissolved to obtain a precursor solution;

[0012] 3) Obtain the crystal;

[0013] After filtering the precursor solution, it was placed in a glass beaker for crystallization to obtain neodymium-doped butylamine lead bromide single crystals.

[0014] The amount of neodymium in neodymium-doped butylamine lead bromide single crystals is 0.4% to 0.8% of the amount of lead.

[0015] Furthermore, in step 2), the purity of butylamine hydrobromide, neodymium bromide, and lead bromide in the precursor solution is greater than 98%.

[0016] Further, in step 2), the N,N-dimethylformamide is anhydrous N,N-dimethylformamide with a purity greater than 99.5%.

[0017] Furthermore, step 3) specifically involves:

[0018] After filtering the precursor solution, it is placed in a glass beaker and crystallized by solvent evaporation, cooling crystallization, or antisolvent crystallization to obtain neodymium-doped butylamine lead bromide single crystals.

[0019] Furthermore, in step 3), the filtration uses a nylon filter head with a pore size of 0.45 micrometers.

[0020] Furthermore, it also includes step 4):

[0021] The neodymium-doped butylamine lead bromide single crystal was removed, the surface solution was dried, and it was cleaned with an anti-solvent and then vacuum dried at room temperature to obtain a neodymium-doped butylamine lead bromide single crystal scintillator.

[0022] Further, in step 4), the antisolvent is cyclohexane or chlorobenzene.

[0023] The beneficial effects of this invention are:

[0024] 1. This invention discloses a neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation. The neodymium-doped butylamine lead bromide single crystal is obtained by doping raw materials (i.e., butylamine hydrobromide and lead bromide) with a high concentration of neodymium. The neodymium-doped butylamine lead bromide single crystal lattice, through bandgap modulation, constrains the movement of carriers generated by radiation, accelerating the radiative recombination rate of carriers. Simultaneously, by utilizing the neodymium constraint on carrier movement, the proportion of Auger recombination (one of the important non-radiative recombination mechanisms under high ionization density) induced by γ / α rays in carrier recombination is differentially adjusted, thereby differentially adjusting the non-radiative recombination rate of carriers, and ultimately differentially adjusting the decay time of the two-dimensional perovskite response to γ / α rays.

[0025] 2. The present invention provides a neodymium-doped butylamine lead bromide single crystal with differentially adjustable emission decay time under γ / α ray excitation. This can increase the difference in response time of γ / α rays to this two-dimensional perovskite, butylamine lead bromide single crystal, and provide a reference for the development of perovskite scintillators with ray discrimination capability. Attached Figure Description

[0026] Figure 1 The neodymium-doped butylamine lead-bromine single-crystal scintillator in Example 1 of this invention was subjected to... 137 Cs produces gamma rays and 241 Decay time diagram of luminescence excited by α rays generated by Am;

[0027] Figure 2 In Example 2 of this invention, the neodymium-doped butylamine lead-bromine single-crystal scintillator was subjected to... 137 Cs produces gamma rays and 241 Decay time diagram of luminescence excited by α rays generated by Am;

[0028] Figure 3 To compare the effects of undoped neodymium scintillators on... 137 Cs produces gamma rays and 241 Decay time diagram of alpha-ray excitation luminescence generated by Am. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1

[0031] This invention provides a method for preparing neodymium-doped butylamine lead bromide single crystals with differentially adjustable luminescence decay time under γ / α ray excitation, comprising the following steps:

[0032] 20 mmol of butylamine hydrobromide (BABr), 10 mmol of lead bromide (PbBr2), and 2 mmol of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 7.4 mL of N,N-dimethylformamide (DMF) was added, and the mixture was heated and stirred until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. Neodymium-doped butylamine lead bromide single crystals were prepared by solvent evaporation. The NdBr3 single crystals were removed with tweezers, the surface solution was blotted dry with filter paper, rinsed with cyclohexane, and vacuum dried for 24 h before storage. Testing showed that the molar amount of neodymium in the NdBr3 single crystal was 0.48% of that of lead.

[0033] like Figure 1 As shown, using 137 Cs produces gamma rays and 241 The luminescence decay time diagram of neodymium-doped phenylethylamine lead bromide scintillators excited by α rays generated by Am is shown, with time on the horizontal axis and luminescence intensity on the vertical axis. Figure 1 It can be seen that after doping with 0.48% neodymium (as a percentage of lead), the decay time of both γ and α rays is shortened to a certain extent, with the decay time of α rays being shortened more significantly.

[0034] Example 2

[0035] 10 mmol of butylamine hydrobromide (BABr), 5 mmol of lead bromide (PbBr2), and 3.5 mmol of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 4.85 mL of N,N-dimethylformamide (DMF) was added, and the mixture was heated and stirred with a magnetic stirrer until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 50 mL glass beaker. Neodymium-doped butylamine lead bromide single crystals were prepared by anti-solvent evaporation crystallization. The NdBr3 single crystals were removed with tweezers, and the surface solution was blotted dry with filter paper. After washing with chlorobenzene, the crystals were vacuum dried for 24 h before storage. Testing showed that the amount of neodymium in the NdBr3 single crystals was 0.8% of the amount of lead.

[0036] like Figure 2 As shown, using 137 Cs produces gamma rays and 241 The luminescence decay time diagram of neodymium-doped butylamine lead-bromine single-crystal scintillators excited by α rays generated by Am is shown, with time on the horizontal axis and luminescence intensity on the vertical axis. Figure 2 It can be seen that after doping with 0.8% neodymium (as a percentage of lead), the decay time of alpha ray emission is significantly shortened, while the decay time of γ ray emission is not significantly shortened.

[0037] Comparative Example

[0038] Weigh 20 mmol BABr (4.0500 g) and 10 mmol PbBr2 (3.6700 g) into a glass reagent bottle, add 7.695 mL DMF, heat and stir until completely dissolved, filter the solution using a 0.45 μm nylon filter and transfer to a 100 mL glass beaker, and prepare butylamine lead bromide single crystals by solvent evaporation. Remove the neodymium-doped butylamine lead bromide single crystals with tweezers, blot dry the surface solution with filter paper, wash with chlorobenzene, vacuum dry for 24 h, and then store.

[0039] like Figure 3 As shown, using 137 Cs produces gamma rays and 241The luminescence decay time diagram of an undoped butylamine lead-bromine single-crystal scintillator excited by α rays generated by Am is shown, with time on the horizontal axis and luminescence intensity on the vertical axis. Figure 3 As can be seen, there is a certain difference in the emission decay time of γ / α rays, with α rays exhibiting a faster emission decay time. Compared to the emission decay times of γ / α rays in Example 1 and Example 2, the difference in emission decay times of γ / α rays from the undoped butylamine lead bromide single crystal is even smaller.

[0040] Example 3

[0041] 20 mmol of butylamine hydrobromide (BABr), 10 mmol of lead bromide (PbBr2), and 4 mmol of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 7.7 mL of N,N-dimethylformamide (DMF) was added, and the mixture was heated and stirred until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. Neodymium-doped butylamine lead bromide single crystals were prepared by solvent evaporation. The NdBr3 single crystals were removed with tweezers, the surface solution was blotted dry with filter paper, rinsed with cyclohexane, and then vacuum-dried for 24 h before storage. Testing showed that the molar amount of neodymium in the NdBr3 single crystal was 0.56% of that of lead.

[0042] Example 4

[0043] 20 mmol of butylamine hydrobromide (BABr), 10 mmol of lead bromide (PbBr2), and 5 mmol of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 8 mL of N,N-dimethylformamide (DMF) was added, and the solution was heated and stirred with a magnetic stirrer until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. Neodymium-doped butylamine lead bromide single crystals were prepared by solvent evaporation. The NdBr3 single crystals were removed with tweezers, the surface solution was blotted dry with filter paper, rinsed with cyclohexane, and then vacuum-dried for 24 h before storage. The molar amount of neodymium in the NdBr3 single crystals was determined to be 0.63% of the lead content.

[0044] Example 5

[0045] 20 mmol of butylamine hydrobromide (BABr), 10 mmol of lead bromide (PbBr2), and 6 mmol of neodymium bromide (NdBr3) were weighed into a glass reagent bottle. 8.5 mL of N,N-dimethylformamide (DMF) was added, and the mixture was heated and stirred until completely dissolved. The solution was filtered through a 0.45 μm nylon filter and transferred to a 100 mL glass beaker. Neodymium-doped butylamine lead bromide single crystals were prepared by solvent evaporation. The NdBr3 single crystals were removed with tweezers, the surface solution was blotted dry with filter paper, rinsed with cyclohexane, and then vacuum-dried for 24 h before storage. The molar amount of neodymium in the NdBr3 single crystals was determined to be 0.72% of the lead content.

[0046] 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 should be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation, characterized in that, Prepared using the following method: 1) Weighing; Weigh out butylamine hydrobromide, lead bromide, and neodymium bromide and place them in a glass bottle; the concentration ratio of butylamine hydrobromide, lead bromide, and neodymium bromide is 2:1:(0.2-0.7); 2) Obtain the precursor solution; Add N,N-dimethylformamide to a glass bottle, heat and stir until completely dissolved to obtain a precursor solution; 3) Obtain the crystal; After filtering the precursor solution, it was placed in a glass beaker for crystallization to obtain neodymium-doped butylamine lead bromide single crystals. The amount of neodymium in the neodymium-doped butylamine lead bromide single crystal is 0.4% to 0.8% of the amount of lead.

2. The neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 1, characterized in that: In step 2), the purity of butylamine hydrobromide, neodymium bromide, and lead bromide in the precursor solution is greater than 98%.

3. The neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 1, characterized in that: In step 2), the N,N-dimethylformamide is anhydrous N,N-dimethylformamide with a purity greater than 99.5%.

4. A neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 2 or 3, characterized in that, Step 3) specifically refers to: After filtering the precursor solution, it is placed in a glass beaker and crystallized by solvent evaporation, cooling crystallization, or antisolvent crystallization to obtain neodymium-doped butylamine lead bromide single crystals.

5. The neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 4, characterized in that: In step 3), the filtration uses a nylon filter head with a pore size of 0.45 micrometers.

6. The neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 5, characterized in that, It also includes step 4): The neodymium-doped butylamine lead bromide single crystal was removed, the surface solution was dried, and it was cleaned with an anti-solvent and then vacuum dried at room temperature to obtain a neodymium-doped butylamine lead bromide single crystal scintillator.

7. The neodymium-doped butylamine lead bromide single crystal with differentially adjustable luminescence decay time under γ / α ray excitation as described in claim 6, characterized in that: In step 4), the antisolvent is cyclohexane or chlorobenzene.

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