CN117552106B - Rare earth-based zero-dimensional perovskite halide scintillating single crystal and preparation method and application thereof - Google Patents

Abstract

The present application belongs to the field of radiation detection technology, relates to a rare earth-based zero-dimensional perovskite halide scintillating single crystal and a preparation method and application thereof, and provides a rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal having the following general composition formula: ( _{Cs1- xAx} ) ₃ ( _{Cu1 -yBy} ) ₂ ( _{I1-zXz ) 5} :mat _% RE, wherein: A=a combination of one or more of Rb, K, Na, Tl and In; B=a combination of one or more of Ag and Li; X=a combination of one or more of Cl and Br; RE is a rare earth ion selected from the group consisting of Eu2 ⁺ , Yb2 ⁺ , Sc3 ⁺ , ^Y3 +, La3 ⁺ , Ce3 ⁺ , Pr3 ⁺ , Nd3 ⁺ , Sm3 ⁺ , Eu3 ⁺ , Gd3 ⁺ and Tb3 ⁺ ; and 0≤x≤0.1, 0≤y≤0.25, 0≤z≤1 and 0＜m≤5. The scintillation single crystal has the advantages of low preparation cost, high stability, high light yield, high energy resolution and other performances, and has great application prospects in the fields of medical imaging, security inspection, high energy physics and so on.

Description

Rare earth-based zero-dimensional perovskite halide scintillating single crystal and preparation method and application thereof

Technical Field

The present application belongs to the field of radiation detection technology, and relates to the composition, preparation method and application of a new type of rare earth ion-doped low-dimensional halide scintillating single crystal, and specifically to a rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal and its preparation method and application.

Background technique

Scintillator crystals can convert high-energy ionizing radiation into low-energy luminescence. As the core component of radiation detectors, they are widely used in many fields. In nuclear medicine imaging, high-performance scintillator crystals are the core components for achieving high-resolution imaging; in the field of land and social security, scintillator crystals are widely used in dangerous nuclide identification and public security inspection equipment; high-energy physics and deep space exploration applications also require a large number of scintillator crystals to detect high-energy rays and particles. With the continuous growth of application space and the rapid improvement of technical requirements, the further optimization of key parameters such as light yield, energy resolution, scintillation decay time and stability of scintillator crystals has attracted widespread attention.

Recently, metal halide materials with low-dimensional molecular structures have attracted extensive attention due to their strong quantum confinement effect. As scintillation or luminescent materials, these low-dimensional halides obtain strong electron-phonon coupling through the confinement effect, while reducing the probability of defect capture of carriers, thus having the luminescence characteristics of low self-absorption and high quantum efficiency. In addition, these low-dimensional metal halides can also often obtain lower melting points and better stability, which is of great significance for low-cost production and application. Among them, copper-based low-dimensional halides are a class of excellent scintillating crystals with efficient confined exciton luminescence. Taking zero-dimensional Cs ₃ Cu ₂ I ₅ as an example, it has non-deliquescent, low self-absorption, low melting point, high light yield (28,000 ph./MeV) and high energy resolution (4.8%@662 keV), and it has been found that Tl ion doping can significantly optimize the light yield (87,000 ph./MeV) and energy resolution (3.4%@662 keV), which has great application prospects.

On the other hand, rare earth ion activator luminescence is the main luminescence form of high-performance scintillation crystals. The diverse and efficient luminescence properties of rare earth ions provide a variety of scintillation crystals for radiation detection applications, but they also face a variety of problems. For example, europium ion (Eu ²⁺ ) doped scintillation crystals such as SrI ₂ :Eu and LiI:Eu can obtain extremely high light yield and excellent energy resolution due to the 5d-4f allowed transition, but due to the strong self-absorption of luminescence, there is a serious degradation of performance with the size enlargement. Cerium ion (Ce ³⁺ ) doped scintillation crystals, such as LaBr ₃ :Ce and LYSO:Ce, can have the advantages of high light yield and fast decay, but because free carriers will be captured by defects, the performance of the crystal has a bottleneck.

In addition, ytterbium ion (Yb ²⁺ ) doped CsPbI ₃ perovskite scintillator has recently been found to produce extremely high light yields through quantum tailoring effects; samarium ion (Sm ²⁺ ) can convert the luminescence wavelength to the near-infrared band to match the high detection efficiency of silicon-based photodetectors; doping with scandium yttrium lanthanum ions (Sc ³⁺ , Y ³⁺ , La ³⁺ , etc.) in non-luminescent centers can also improve the luminescence efficiency of scintillating crystals or obtain faster scintillation decay time through defect regulation. However, to date, this field has not yet proposed scintillation detection materials that can meet the higher performance requirements of medical imaging, security inspection, high-energy physics and other fields.

Therefore, there is an urgent need to develop new high-performance scintillation materials in this field to overcome the defects of the above-mentioned existing technologies and meet the higher performance requirements for scintillation detection materials in the fields of medical imaging, security inspection, high-energy physics, etc.

Summary of the invention

The present application provides a rare earth ion doped zero-dimensional perovskite halide scintillating single crystal and a preparation method thereof which can be widely used in X-ray, gamma ray and neutron detection and imaging, thereby solving the problems existing in the prior art.

According to the first aspect of the present application, a rare earth ion doped zero-dimensional perovskite halide scintillating single crystal is provided, having the following general composition formula:

(Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE, where:

A = a combination of one or more of Rb, K, Na, Tl and In;

B = Ag and Li or a combination thereof;

X = one of Cl and Br or a combination thereof;

RE is a rare earth ion selected from the group consisting of Eu ²⁺ , Yb ²⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ^{3+ ,} Gd ³⁺ , Tb ³⁺ and Lu ³⁺ ; and

0≤x≤0.1, 0≤y≤0.25, 0≤z≤1 and 0＜m≤5.

In a preferred embodiment, x = y = z = 0 and RE = Eu ²⁺ , ie Cs ₃ Cu ₂ I ₅ : m at% Eu ²⁺ .

In another preferred embodiment, A = Tl, y = z = 0 and RE = Eu ²⁺ , ie (Cs _1-x Tl _x ) ₃ Cu ₂ I ₅ : m at% Eu ²⁺ .

According to the second aspect of the present application, a method for preparing the above-mentioned rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal is provided, the method comprising the following steps:

Using a halide with a purity of ≥99.9% as a raw material, the target components are molar-proportioned according to the general composition formula and loaded into a sealed container, and a compound satisfying the general composition formula is obtained by a solid-phase reaction method or a molten salt cooling method. Then, a Bridgman descent method or a horizontal directional solidification method is used to obtain a target rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal.

In a preferred embodiment, the method comprises the following steps:

(1) Weigh various raw materials according to the general composition formula;

(2) In an inert environment, the mixed raw materials are placed in a crucible with a capillary bottom, and then the crucible is evacuated to a vacuum and sealed with welding, and a compound satisfying the general composition formula is obtained by a solid phase reaction method or a molten salt cooling method;

(3) placing the sealed crucible vertically in the middle of the crystal growth furnace; heating the crystal growth furnace until the raw materials are completely melted and mixed evenly; adjusting the crucible position and furnace temperature so that the temperature at the bottom of the crucible reaches a predetermined value, and then lowering the crucible in the furnace body, so that the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling down until it reaches room temperature;

(4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment.

In another preferred embodiment, the method comprises the following steps:

(1) Weigh various raw materials according to the general composition formula;

(2) In an inert environment, the mixed raw materials are placed in a crucible with a capillary bottom, and then the crucible is evacuated to a vacuum and sealed with welding, and a compound satisfying the general composition formula is obtained by a solid phase reaction method or a molten salt cooling method;

(3) placing the sealed crucible horizontally in the middle of a horizontal directional growth furnace; heating the horizontal directional growth furnace until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature so that the temperature at the bottom of the crucible reaches a predetermined value, and then moving the crucible horizontally at a uniform speed in the furnace body, so that the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; and then cooling down until it reaches room temperature;

(4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment.

In another preferred embodiment, in step (2), the inert environment includes a glove box.

In another preferred embodiment, in step (2), the crucible comprises a quartz crucible.

In another preferred embodiment, in step (3), the temperature is raised to 400-600°C; and the temperature of the bottom of the crucible reaches 330-400°C.

According to the third aspect of the present application, there is provided an application of the above-mentioned rare earth ion doped zero-dimensional perovskite halide scintillating single crystal in X-ray, gamma ray and neutron detection and imaging, wherein the application includes application in medical imaging, security inspection and high energy physics.

Beneficial effects: The rare earth ion doped zero-dimensional perovskite halide scintillating single crystal of the present application has the advantages of low raw material cost, high chemical stability, low melting point, and easy preparation. At the same time, efficient scintillation luminescence is obtained through rare earth ion doping or optimization and improvement, achieving higher detection efficiency, and can be used for X-ray, gamma ray and neutron detection and imaging, and has important application prospects in medical imaging, security inspection and high-energy physics.

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 as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 shows sample photographs of the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 1 of the present application and the halide scintillating single crystals Cs ₃ Cu ₂ I ₅ :0.5%Pr ³⁺ and Cs ₃ Cu ₂ I ₅ :0.5%Yb ²⁺ obtained in Example 2 under natural light.

FIG2 shows a sample photo of the halide scintillating single crystal (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 3 of the present application under natural light.

3 shows sample photographs of the halide scintillating single crystals (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Sc ^{3 +} , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Y ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%La ³⁺ , and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Lu ^{3 +} obtained in Example 4 of the present application under natural light.

4 shows sample photographs of the halide scintillating single crystal Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ obtained in Example 5 of the present application and the halide scintillating single crystal (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ obtained in Example 6 under natural light.

FIG5 shows the radiative luminescence spectrum of the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 1 of the present application.

FIG6 shows the radioluminescence spectrum of the halide scintillating single crystal (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 3 of the present application.

Figure 7 shows the radioluminescence spectra of the halide scintillating single crystals (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Sc ^{3 +} , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Y ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%La ³⁺ and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Lu ^{3 +} obtained in Example 4 of the present application (compared to the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal).

FIG8 shows the fluorescence spectra of the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 1 of the present application and the halide scintillating single crystal SrI ₂ :Eu ²⁺ obtained in Comparative Example 2. FIG.

FIG. 9 shows the gamma-ray energy spectra of the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 1 of the present application and the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ obtained in Comparative Example 1. FIG.

FIG. 10 shows the γ-ray energy spectra of the halide scintillating single crystals (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5% Sc ^{3 +} and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5% Y ³⁺ obtained in Example 4 of the present application.

FIG. 11 shows the scintillation decay curve of the halide scintillating single crystal Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ obtained in Example 1 of the present application.

FIG. 12 shows the scintillation decay curves of the halide scintillating single crystals Cs ₃ Cu ₂ I ₅ :0.5% Pr ³⁺ and Cs ₃ Cu ₂ I ₅ :0.5% Yb ²⁺ obtained in Example 2 of the present application.

FIG13 shows a schematic diagram of a scintillation single crystal coupled photodetector according to a preferred embodiment of the present application.

Detailed ways

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.

"Range" 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 range defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if the range of 60-120 and 80-110 is listed for a particular parameter, it is understood that the range 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 ranges 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 "a-b" 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" represents that all real numbers between "0-5" have been fully listed herein, and "0-5" is just the 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.

In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution. In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

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.

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).

There is no solution in the existing technology to the defects of existing low-dimensional structured halide scintillator crystals in carrier utilization efficiency and scintillation efficiency, and the limitations of traditional rare earth ion-doped halide scintillator crystals in stability, self-absorption and radioactive background, which restrict their further application in the fields of nuclear medicine imaging, homeland and social security, high energy physics and deep space exploration.

Starting from the zero-dimensional structure of Cs ₃ Cu ₂ I ₅ crystal, its luminescence mechanism is the self-trapped exciton recombination luminescence provided by the strong quantum confinement effect. Theoretically, a high light yield of ~150,000 ph./MeV can be obtained, but the non-radiative quenching caused by the interaction between excitons fails to achieve ideal performance. Luminescent ion doping represented by Eu ²⁺ ions provides a new rare earth ion-related radiative luminescence channel in the crystal, thereby improving the utilization rate of carriers generated by ionization. Starting from the characteristics of rare earth luminescent ions, the energy relaxation provided by the low-dimensional structure and soft lattice can improve the self-absorption effect of luminescence, and the confinement effect can reduce the probability of hot carriers being captured by defects during the process of transporting to the luminescent center in the lattice. Doping with non-luminescent center ions such as Y ³⁺ ions can add new defect energy levels between the confined exciton energy levels, "temporarily store" the carriers lost in the non-radiative process in the shallow defect energy level, and quickly re-enter the confined exciton state to participate in the flashing luminescence.

Combining the strong quantum confinement effect of low-dimensional metal halide scintillating crystals with the high-efficiency and diverse luminescence of rare earth-doped scintillating crystals, it is expected that a new type of scintillating crystal with low self-absorption, low defect capture probability, and high luminescence efficiency can be obtained. Compared with existing low-dimensional structured halide scintillating crystals, it can achieve higher carrier utilization efficiency and scintillation efficiency. Compared with traditional rare earth ion-doped halide scintillating crystals, it has the characteristics of higher stability, low self-absorption and low radioactive background. Rare earth ion-doped low-dimensional halide scintillating crystals can provide better scintillating crystal candidate solutions for nuclear medical imaging, homeland and social security, high energy physics, and deep space exploration.

The present application provides a novel rare earth ion doped zero-dimensional perovskite halide scintillating single crystal and a preparation method thereof. The halide scintillating single crystal can be widely used in X-ray, gamma ray and neutron detection and imaging, thereby solving the problems existing in the prior art.

The invention is characterized in that a novel rare earth ion doped low-dimensional structure halide scintillating crystal strategy is proposed, which combines the advantages of low-dimensional halide materials and rare earth ion doping. A rare earth ion doped low-dimensional structure halide scintillating crystal (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE composition, preparation method and application are provided. Most importantly, a rare earth doping strategy is proposed to optimize the performance of Cs ₃ Cu ₂ I ₅ -based scintillating crystals.

In the first aspect of the present application, a rare earth ion doped zero-dimensional perovskite halide scintillating single crystal is provided, having the following general composition formula:

(Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at% (atomic %) RE, where:

A = a combination of one or more of Rb, K, Na, Tl, In;

B = Ag and Li or a combination thereof;

X = one of Cl and Br or a combination thereof;

RE is a rare earth ion such as Eu ²⁺ , Yb ²⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Lu ³⁺ , and

0≤x≤0.1, 0≤y≤0.25, 0≤z≤1, 0＜m≤5.

In the present application, the rare earth ion doped zero-dimensional perovskite halide scintillating single crystal has the following two preferred compositions: Cs ₃ Cu ₂ I ₅ : m at% Eu ²⁺ and (Cs _1-x Tl _x ) ₃ Cu ₂ I ₅ : m at% Eu ²⁺ , wherein: 0≤x≤0.1, 0＜m≤5.

In a second aspect of the present application, a method for preparing a rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal is provided, the method comprising the following steps:

Using high-purity halide with a purity of (≥99.9%) as raw material, the target components are molar-proportioned according to the general composition formula and loaded into a sealed container, and the compound satisfying the general composition formula is obtained by solid-phase reaction method or molten salt cooling method, and then the target rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal is obtained by Bridgman descent method or horizontal directional solidification method.

In the present application, the method comprises the following steps:

(1) Weigh various raw materials according to the above general composition formula (Cs1 _{-xAx ) 3} (Cu1 _{-yBy ) 2} (I1 _{-zXz ) 5} : mat %RE;

(2) In an inert environment (e.g., a glove box filled with inert gas), place the mixed raw materials in a quartz crucible with a capillary bottom or a crucible made of other materials, then evacuate the crucible and seal it with welding;

(3) placing the sealed crucible in a tubular furnace or other heating furnace; using a solid phase reaction method or a molten salt cooling method (this method raises the temperature to above the melting point of the compound satisfying the general composition formula, such as 400-600°C, to obtain higher product uniformity and reaction efficiency) to allow the raw materials to fully react and synthesize the target component polycrystal; then placing it in a Bridgman growth furnace; adjusting the crucible position and furnace temperature so that the crucible bottom temperature reaches a predetermined value (such as 330-400°C), and then lowering the crucible in the furnace body, and the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling it down to room temperature;

(4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment.

In the present application, the method comprises the following steps:

(1) Weigh various raw materials according to the above general composition formula (Cs1 _{-xAx ) 3} (Cu1 _{-yBy ) 2} (I1 _{-zXz ) 5} : mat %RE;

(2) In an inert environment (e.g., a glove box filled with inert gas), place the mixed raw materials in a quartz crucible with a capillary bottom or a crucible made of other materials, then evacuate the crucible and seal it with welding;

(3) Place the sealed crucible in a tubular furnace or other heating furnace; use a solid phase reaction method or a molten salt cooling method (this method raises the temperature to above the melting point of the compound that meets the general composition formula, such as 400-600°C, to obtain higher product uniformity and reaction efficiency) to allow the raw materials to fully react and synthesize the target component polycrystal; then place it horizontally in a horizontal directional growth furnace; adjust the crucible position and furnace temperature so that the crucible bottom temperature reaches a predetermined value (such as 330-400°C), and then move the crucible horizontally at a uniform speed in the furnace body, and the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cool it down until it reaches room temperature;

(4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment.

In the third aspect of the present application, there is provided an application of the above-mentioned rare earth ion doped zero-dimensional perovskite halide scintillating single crystal in X-ray, gamma ray and neutron detection and imaging, wherein the application includes application in medical imaging, security inspection and high energy physics.

In the present application, the single crystal material prepared by the above method can be directly coupled to optoelectronic devices for high-energy ionizing radiation detection after cutting, grinding and polishing. The most typical application is gamma spectrum detection. It is also suitable for application in medical imaging, homeland security, physical research and other fields through detection of X-rays, alpha particles, beta particles, neutrons, etc. according to specific needs.

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.

Example 1: A zero-dimensional perovskite halide scintillating single crystal proposed in Example 1 has a composition chemical formula of Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, x = 0, y = 0, z = 0, m = 0.5, RE = Eu ²⁺ , and the above halide scintillating single crystal is prepared by the Bridgman descent method, and the preparation process includes the following operations: a) weighing each raw material of the intrinsic halide scintillating single crystal with the composition chemical formula Cs 3 Cu ₂ I 5 :0.5%Eu 2+ prepared as required; b) preparing a scintillating single crystal of the intrinsic halide scintillating single crystal with the composition chemical formula Cs ₃ Cu 2 I ₅ :0.5%Eu ²⁺ ; In a glove box filled with argon, each raw material is placed in a quartz crucible with a capillary bottom; then the crucible is evacuated to a vacuum and sealed with welding; c) the sealed quartz crucible is placed vertically in the middle position of a crystal growth furnace; the crystal growth furnace is heated to about 550°C until the raw materials are completely melted and mixed evenly; the crucible position and furnace temperature are adjusted to reduce the temperature of the bottom of the crucible to about 350°C, and then the quartz crucible is lowered in the furnace body at a descending speed of 0.5 mm/h, and the crystal begins to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified; then the temperature is lowered at a rate of 7°C/h until it reaches room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and cut and processed.

The radiative luminescence spectrum and photoluminescence excitation and emission spectrum of the above-mentioned scintillating single crystals were tested. In addition to the intrinsic self-limited exciton luminescence, there is a new Eu ²⁺ luminescence center. The light yield of the Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ crystal coupled to a photomultiplier tube was 60,000 ph./MeV, and the energy resolution was 4.0%. Compared with the undoped Cs ₃ Cu ₂ I ₅ crystal, the light yield increased by 1.1 times, and the energy resolution was optimized by 0.8 percentage points. The luminescence of Eu ²⁺ ions in the non-low-dimensional SrI ₂ :Eu ²⁺ crystal has a strong self-absorption effect, while the self-absorption of Eu ²⁺ ion luminescence in the low-dimensional Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ crystal is significantly optimized.

Comparative Example 1: A halide scintillator single crystal with a chemical formula of Cs ₃ Cu ₂ I ₅ was prepared by a Bridgman descent method, and the preparation process includes the following operations: a) weighing each raw material according to the intrinsic halide scintillator with a chemical formula of Cs ₃ Cu ₂ I ₅ prepared as required; b) placing each raw material in a quartz crucible with a capillary bottom in a glove box filled with argon; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 550°C until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature to reduce the crucible bottom temperature to about 350°C, and then heating the crucible at 0.5 The quartz crucible is lowered in the furnace at a descending speed of 0.1777 W/h. Crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 7°C/h until it reaches room temperature. Finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and cut.

The light yield of Cs ₃ Cu ₂ I ₅ crystal coupled to a photomultiplier tube was 28,000 ph./MeV, and the energy resolution was 4.8%.

Comparative Example 2: A scintillating single crystal with a chemical formula of SrI ₂ :Eu ²⁺ was prepared by the Bridgman descent method, and the preparation process included the following operations: a) weighing each raw material according to the intrinsic halide scintillator with a chemical formula of SrI ₂ :Eu ²⁺ prepared as required; b) placing each raw material in a quartz crucible with a capillary bottom in a glove box filled with argon; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 600°C until the raw materials were completely melted and mixed evenly; adjusting the crucible position and furnace temperature to reduce the crucible bottom temperature to about 530°C, and then heating the crucible at 0.5 The quartz crucible is lowered in the furnace at a descending speed of 0.1777 W/h. Crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 7°C/h until it reaches room temperature. Finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and cut.

The photoluminescence excitation and emission spectra of the scintillation crystal were tested and it was found that it had severe self-absorption.

Example 2: The four zero-dimensional perovskite halide scintillating single crystals proposed in Example 2 have the chemical formulas of Cs ₃ Cu ₂ I ₅ :0.5%Pr ³⁺ , Cs ₃ Cu ₂ I ₅ :0.5%Yb ²⁺ , Cs ₃ Cu ₂ I ₅ :0.5%Sm ²⁺ and Cs ₃ Cu ₂ I ₅ :0.5%Ce ³⁺ , that is, (Cs _{1- x} A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1- z X _z ) ₅ : m at%RE as the general formula, x = 0, y = 0, z = 0, m = 0.5, RE = Pr ³⁺ , Yb ²⁺ , Sm ²⁺ and Ce ³⁺ , and the above halide scintillating single crystals are prepared by the Bridgman descent method, and the preparation process includes the following operations: a) The intrinsic halide scintillating single crystal prepared on demand has the chemical formula Cs ₃ Cu ₂ I ₅ :0.5% Pr ³⁺ , Cs ₃ Cu ₂ I ₅ :0.5% Yb ²⁺ , Cs ₃ Cu ₂ I ₅ :0.5% Sm ²⁺ and Cs ₃ Cu ₂ I ₅ :0.5% Ce ^3+. a) Weigh each raw material; b) Place each raw material in a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then evacuate the crucible and seal it with welding; c) Place the sealed quartz crucible vertically in the middle of a crystal growth furnace; Heat the crystal growth furnace to about 550°C until the raw materials are completely melted and mixed evenly; Adjust the position of the crucible and the furnace temperature to reduce the temperature of the bottom of the crucible to about 350°C, and then heat it at 0.5 The quartz crucible is lowered in the furnace at a descending speed of 0.1777 W/h. The crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 7°C/h until it reaches room temperature. Finally, the prepared crystals are taken out of the quartz crucible.

The light yields of Cs ₃ Cu ₂ I ₅ :0.5%Pr ³⁺ and Cs ₃ Cu ₂ I ₅ :0.5%Yb ²⁺ crystals were measured by coupling to a photomultiplier tube, which were 40,000 ph./MeV and 45,000 ph./MeV respectively, compared with the undoped Cs ₃ Cu ₂ I ₅ crystal. The energy resolutions were 4.2% and 4.5% respectively. Compared with the decay time of undoped Cs ₃ Cu ₂ I ₅ , the scintillation decay time of Cs ₃ Cu ₂ I ₅ :0.5%Ce ³⁺ crystal was 561 ns, which was nearly 40% faster.

Embodiment 3: A zero-dimensional perovskite halide scintillating single crystal proposed in Embodiment 3 has a composition chemical formula of (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as a general formula, x = 0.01, y = 0, z = 0, m = 0.5, A = Tl, RE = Eu ²⁺ , and the above halide scintillating single crystal is prepared by horizontal directional solidification method, and the preparation process comprises the following operations: a) weighing the raw materials of the intrinsic halide scintillator composition chemical formula (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ prepared as required; b) In a glove box filled with nitrogen, each raw material is placed in a quartz crucible with a capillary bottom; then the crucible is evacuated and sealed by welding; c) the sealed quartz crucible is placed horizontally in the middle of a horizontal directional growth furnace; the crystal growth furnace is heated to about 600°C until the raw materials are completely melted and mixed evenly; the crucible position and furnace temperature are adjusted to reduce the capillary temperature of the crucible to about 360°C, and then the quartz crucible is moved horizontally at a uniform speed of 0.7 mm/h in the furnace body, and the crystal begins to nucleate and grow from the capillary of the crucible until the melt is completely solidified; then the temperature is lowered at a rate of 10°C/h until it reaches room temperature; finally, the prepared crystal is taken out from the quartz crucible.

The radiative luminescence spectrum and photoluminescence excitation and emission spectrum of the above scintillating crystals were tested. In addition to the intrinsic self-limited exciton luminescence and the bound exciton luminescence of Tl ions, there is a new Eu ²⁺ luminescence center. The light yield of the (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ crystal was 93,000 ph./MeV and the energy resolution was 3.3% when coupled to a photomultiplier tube. Compared with the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal, the light yield increased by 7% and the energy resolution was optimized by 0.1 percentage point.

Example 4: The four zero-dimensional perovskite halide scintillating single crystals proposed in Example 4 have the following compositional formulas: (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Sc ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Y ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%La ³⁺ , and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Lu ³⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, with x = 0.01, y = 0, z = 0, m = 0.5, A = Tl, RE = Sc ³⁺ , Y ³⁺ , La ³⁺ and Lu ³⁺ , the above halide scintillating single crystal is prepared by horizontal directional solidification method, and the preparation process comprises the following operations: a) weighing the raw materials of the intrinsic halide scintillating single crystal composition chemical formula (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Sc ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Y ³⁺ , (Cs _{0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%La 3+ and (Cs 0.99 Tl 0.01 ) 3 Cu} ² _{I 5 : 0.5 %} Lu ³⁺ prepared on demand; b) In a glove box filled with nitrogen, each raw material is placed in a quartz crucible with a capillary bottom; then the crucible is evacuated and sealed with welding; c) the sealed quartz crucible is placed horizontally in the middle of a horizontal directional growth furnace; the crystal growth furnace is heated to about 600°C until the raw materials are completely melted and mixed evenly; the crucible position and furnace temperature are adjusted to reduce the capillary temperature of the crucible to about 360°C, and then the quartz crucible is moved horizontally at a uniform speed of 0.8 mm/h in the furnace body, and the crystal begins to nucleate and grow from the capillary of the crucible until the melt is completely solidified; then the temperature is lowered at a rate of 10°C/h until it reaches room temperature; finally, the prepared crystal is taken out from the quartz crucible.

The light yield of (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Y ³⁺ crystal coupled to a photomultiplier tube is 90,000 ph./MeV. Compared with the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal, the light yield is increased by 3%. The decay time of (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Sc ³⁺ is 750ns, which is about 20% faster than that of the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal.

Example 5: A zero-dimensional perovskite halide scintillating single crystal proposed in Example 5 has a composition chemical formula of Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, x = 0, y = 0, z = 0.2, m = 0.5, X = Br, RE = Eu ²⁺ . The halide scintillating single crystal is prepared by the Bridgman descent method, and the preparation process includes the following operations: a) weighing various raw materials according to the intrinsic halide scintillating single crystal composition chemical formula Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ prepared on demand; b) placing various raw materials in a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 600°C until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature to reduce the crucible bottom temperature to about 370°C, and then heating the crucible at 1.5 The quartz crucible is lowered in the furnace at a descending speed of 1.50 mm/h. The crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 12°C/h until it reaches room temperature. Finally, the prepared crystals are taken out of the quartz crucible.

The obtained Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ crystal has good crystallinity, no deliquesce, low self-absorption, and can grow single crystals with good crystal quality at a faster descent rate and cooling rate, which has obvious advantages for the growth of large-sized crystals. The light yield of Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ crystal coupled to the photomultiplier tube test was 60,000ph./MeV, and the energy resolution was 4.2%. Compared with the undoped Cs ₃ Cu ₂ I ₅ crystal, the light yield increased by 40% and the energy resolution was optimized by 0.6 percentage points.

Example 6: A zero-dimensional perovskite halide scintillating single crystal proposed in Example 6 has a composition chemical formula of (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, x = 0.01, y = 0, z = 0.2, m = 0.5, A = Tl, B = Br, RE = Eu ²⁺ . The halide scintillating single crystal is prepared by the Bridgman descent method, and the preparation process includes the following operations: a) weighing various raw materials according to the composition formula of the intrinsic halide scintillating single crystal prepared on demand (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ ; b) placing various raw materials in a quartz crucible with a capillary bottom in a glove box filled with argon; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 550°C until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature to reduce the temperature of the bottom of the crucible to about 370°C, and then heating the crucible at 1.5 The quartz crucible is lowered in the furnace at a descending speed of 1.50 mm/h. The crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 12°C/h until it reaches room temperature. Finally, the prepared crystals are taken out of the quartz crucible.

The obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ crystal has good crystallinity, no deliquesce, low self-absorption, and can grow single crystals with good crystal quality at a faster descent rate and cooling rate, which has obvious advantages for the growth of large-sized crystals. The light yield of (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ crystal was 110,000 ph./MeV and the energy resolution was 3.2% when coupled to a photomultiplier tube. Compared with the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal, the light yield increased by 26% and the energy resolution was optimized by 0.2 percentage points.

Example 7: A zero-dimensional perovskite halide scintillating single crystal proposed in Example 7 has a composition chemical formula of (Cs _0.9 Rb _0.1 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, x = 0.1, y = 0, z = 0, m = 0.5, A = Rb, RE = Eu ²⁺ . The halide scintillating single crystal is prepared by the Bridgman descent method, and the preparation process includes the following operations: a) weighing each raw material according to the composition formula of the intrinsic halide scintillating single crystal prepared on demand (Cs _0.9 Rb _0.1 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ ; b) placing each raw material in a quartz crucible with a capillary bottom in a glove box filled with argon; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 600°C until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature to reduce the crucible bottom temperature to about 370°C, and then heating the crucible at 1.0 The quartz crucible is lowered in the furnace at a descending speed of 1.5 mm/h. The crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 10°C/h until it reaches room temperature. Finally, the prepared crystals are taken out of the quartz crucible.

The test results of γ-ray and X-ray energy spectra show that the (Cs _0.9 Rb _0.1 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ scintillation single crystal has radiation detection performance. The γ-ray energy spectrum under ¹³⁷ Cs irradiation shows that (Cs _0.9 Rb _0.1 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ has good energy resolution. The scintillation decay curve under ¹³⁷ Cs irradiation shows that (Cs _0.9 Rb _0.1 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ has a fast decay time, which can be used in medical imaging, security inspection, high energy physics and other fields.

Example 8: A zero-dimensional perovskite halide scintillating single crystal proposed in Example 8 has a composition chemical formula of Cs ₃ (Cu _0.9 Ag _0.1 ) ₂ I ₅ :0.5%Eu ²⁺ , that is, (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE as the general formula, x = 0, y = 0.1, z = 0, m = 0.5, B = Ag, RE = Eu ²⁺ . The halide scintillating single crystal is prepared by the Bridgman descent method, and the preparation process includes the following operations: a) weighing various raw materials according to the composition formula of the intrinsic halide scintillating single crystal prepared on demand Cs ₃ (Cu _0.9 Ag _0.1 ) ₂ I ₅ :0.5%Eu ²⁺ ; b) placing various raw materials in a quartz crucible with a capillary bottom in a glove box filled with argon; then evacuating the crucible to a vacuum and sealing it with welding; c) vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to about 550°C until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature to reduce the crucible bottom temperature to about 350°C, and then heating the crucible at 1.0 The quartz crucible is lowered in the furnace at a descending speed of 0.1777 W/h. The crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely solidified. The temperature is then lowered at a rate of 7°C/h until it reaches room temperature. Finally, the prepared crystals are taken out of the quartz crucible.

The test results of γ-ray and X-ray energy spectra show that the Cs ₃ (Cu _0.9 Ag _0.1 ) ₂ I ₅ :0.5%Eu ²⁺ scintillating single crystal has radiation detection performance. The γ-ray energy spectrum under ¹³⁷ Cs irradiation shows that Cs ₃ (Cu _0.9 Ag _0.1 ) ₂ I ₅ :0.5%Eu ²⁺ has good energy resolution. The scintillation decay curve under ¹³⁷ Cs irradiation shows that Cs ₃ (Cu _0.9 Ag _0.1 ) ₂ I ₅ :0.5%Eu ²⁺ has a fast decay time, which can be used in medical imaging, security inspection, high energy physics and other fields.

Figure 1 shows a sample photo of the _halide scintillating single crystals obtained in Examples 1-2 of the present application under natural light. As shown in Figure 1, the obtained _Cs3Cu2I5 : _0.5 %Eu2 ⁺ , _Cs3Cu2I5 : _0.5 %Pr3 ⁺ and _Cs3Cu2I5 : _0.5 % _Yb2 ⁺ single crystals are transparent _and free of inclusions.

Figure 2 shows a sample photo of the halide scintillating single crystal obtained in Example 3 of the present application under natural light. As shown in Figure 2, the obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ single crystal is transparent and has no inclusions.

Fig. 3 shows a sample photo of the halide scintillating single crystal obtained in Example 4 of the present application under natural light. As shown in Fig. 3, the obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Sc ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Y ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%La ³⁺ and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ : 0.5%Lu ³⁺ single crystals are transparent and free of inclusions.

Figure 4 shows a sample photo of the halide scintillating single crystals obtained in Examples 5-6 of the present application under natural light. As shown in Figure 4, the obtained Cs ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ (I _0.8 Br _0.2 ) ₅ :0.5%Eu ²⁺ single crystals are transparent and free of inclusions.

Figure 5 shows the radiant luminescence spectrum of the halide scintillating single crystal obtained in Example 1 of the present application. As shown in Figure 5, the obtained Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ single crystal has an emission peak at 450 nm and 560 nm under X-ray excitation.

Figure 6 shows the radiant luminescence spectrum of the halide scintillating single crystal obtained in Example 3 of the present application. As shown in Figure 6, the obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ single crystal has an emission peak of 510 nm under X-ray excitation.

Fig. 7 shows the radioluminescence spectrum of the halide scintillating single crystal obtained in Example 4 of the present application. As shown in Fig. 7, compared with the undoped (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ crystal, the emission peaks of the obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Sc ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Y ³⁺ , (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%La ³⁺ and (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5%Lu ³⁺ single crystals under X-ray excitation have no obvious change, and are all at 510 nm.

Figure 8 shows the fluorescence spectra of the halide scintillating _single crystals obtained in Example 1 and Comparative Example 2. As shown in Figure 8, compared with _SrI2 :Eu crystal, the obtained _Cs3Cu2I5 : _0.5 %Eu2 ⁺ single crystal has almost no self-absorption.

Figure 9 shows the gamma-ray energy spectra of the halide scintillating _single crystals obtained in Example 1 and Comparative Example 1. As shown in Figure 9, compared with the undoped _Cs3Cu2I5 crystal, the light yield and energy resolution of the _{obtained Cs3Cu2I5} :0.5% _Eu2 ⁺ _single crystal are optimized.

Figure 10 shows the gamma-ray energy spectrum of the halide scintillating single crystal obtained in Example 4 of the present application. As shown in Figure 10, the energy resolution and light yield of the obtained (Cs _0.99 Tl _0.01 ) ₃ Cu ₂ I ₅ :0.5% Y ³⁺ single crystal are optimized.

Figure 11 shows the scintillation decay curve of the halide scintillating single crystal obtained in Example 1 of the present application. As shown in Figure 11, the scintillation decay time of the obtained Cs ₃ Cu ₂ I ₅ :0.5%Eu ²⁺ single crystal has a fast component of 152 ns and a slow component of 995 ns.

Figure 12 shows the scintillation decay curve of the halide scintillating single crystal obtained in Example 2 of the present application. As shown in Figure 12, the scintillation decay time of the obtained Cs ₃ Cu ₂ I ₅ :0.5% Pr ³⁺ single crystal has a fast component of 170 ns and a slow component of 995 ns; the scintillation decay time of the obtained Cs ₃ Cu ₂ I ₅ :0.5% Yb ²⁺ single crystal has a fast component of 195 ns and a slow component of 1000 ns.

Fig. 13 shows a schematic diagram of a scintillation single crystal coupled photodetector according to a preferred embodiment of the present application. As shown in Fig. 13, the scintillation crystal 1 converts the incident high-energy rays (including gamma rays, and other high-energy rays such as beta or neutrons) into ultraviolet light or visible light, and collects the scintillation light as much as possible into the photomultiplier tube 3 through the reflective layer 2, converts the optical signal into an electrical signal (digital signal) through photoelectric conversion, and finally the electronic device 4 processes the signal and outputs it.

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

Claims (8)

1. A rare earth ion doped zero-dimensional perovskite halide scintillating single crystal, characterized in that it has the following general composition formula: (Cs _1-x A _x ) ₃ (Cu _1-y B _y ) ₂ (I _1-z X _z ) ₅ : m at%RE, where: A = one of Rb, K, Na and Tl; B = Ag; X = one of Cl and Br or a combination thereof; RE is a rare earth ion selected from the group consisting of Eu ²⁺ , Yb ²⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ and Pr ³⁺ ; and 0≤x≤0.1, 0≤y≤0.25, 0≤z≤1, and 0＜m≤5, wherein x and y are not 0 at the same time. 2. A method for preparing the rare earth ion doped zero-dimensional perovskite halide scintillating single crystal as claimed in claim 1, the method comprising the following steps: Using a halide with a purity of ≥99.9% as a raw material, the target components are molar-proportioned according to the general composition formula and loaded into a sealed container, and a compound satisfying the general composition formula is obtained by a solid-phase reaction method or a molten salt cooling method. Then, a Bridgman descent method or a horizontal directional solidification method is used to obtain a target rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal. 3. The method according to claim 2, characterized in that the method comprises the following steps: (1) Weigh various raw materials according to the general composition formula; (2) In an inert environment, the mixed raw materials are placed in a crucible with a capillary bottom, and then the crucible is evacuated to a vacuum and sealed with welding, and a compound satisfying the general composition formula is obtained by a solid phase reaction method or a molten salt cooling method; (3) placing the sealed crucible vertically in the middle of the crystal growth furnace; heating the crystal growth furnace until the raw materials are completely melted and mixed evenly; adjusting the crucible position and furnace temperature so that the temperature at the bottom of the crucible reaches a predetermined value, and then lowering the crucible in the furnace body, so that the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling down until it reaches room temperature; (4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment. 4. The method according to claim 2, characterized in that the method comprises the following steps: (1) Weigh various raw materials according to the general composition formula; (2) In an inert environment, the mixed raw materials are placed in a crucible with a capillary bottom, and then the crucible is evacuated to a vacuum and sealed with welding, and a compound satisfying the general composition formula is obtained by a solid phase reaction method or a molten salt cooling method; (3) placing the sealed crucible horizontally in the middle of a horizontal directional growth furnace; heating the horizontal directional growth furnace until the raw materials are completely melted and evenly mixed; adjusting the crucible position and furnace temperature so that the temperature at the bottom of the crucible reaches a predetermined value, and then moving the crucible horizontally at a uniform speed in the furnace body, so that the crystals begin to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; and then cooling down until it reaches room temperature; (4) Taking out the prepared rare earth ion-doped zero-dimensional perovskite halide scintillating single crystal from the crucible in a dry environment. 5. The method according to claim 3 or 4, characterized in that, in step (2), the inert environment comprises a glove box. 6. The method according to claim 3 or 4, characterized in that in step (2), the crucible comprises a quartz crucible. 7. The method according to claim 3 or 4, characterized in that in step (3), the crystal growth furnace or the horizontal directional growth furnace is heated to 400-600°C; and the temperature of the bottom of the crucible reaches 330-400°C. 8. An application of the rare earth ion doped zero-dimensional perovskite halide scintillating single crystal as claimed in claim 1 in X-ray, gamma ray and neutron detection and imaging, characterized in that the application includes application in medical imaging, security inspection and high energy physics.