CN113026108B - Double-halogen hybrid perovskite crystal material for rare earth doped radiation detector and preparation method thereof - Google Patents

Abstract

The invention disclosesA double-halogen hybridized perovskite crystal material for rare-earth doped radiation detector is disclosed, and its chemical formula is CH₃NH₃(Pb_xTm_1‑x)(Br_yI_1‑y)₃Wherein x is 0.91 and y is 0.451-1, the material has stable performance, better resistivity and lower leakage current, and the resistivity can reach 4.79 multiplied by 10⁸Omega cm, the leakage current can reach 56 nA; the invention also provides a preparation method of the crystal material, which comprises the steps of preparing a precursor solution containing bromine and iodine, mixing the precursor solution to form a mixed solution, and adding the rare earth oxide Tm₂O₃Mixing the mixture into the mixed solution, filtering, placing the mixed solution into a heating water tank to heat so as to grow crystals, and drying to obtain the crystal material.

Description

Double-halogen hybrid perovskite crystal material for rare earth doped radiation detector and preparation method thereof

Technical Field

The invention belongs to the field of materials, relates to a perovskite crystal material and a preparation method thereof, and particularly relates to a double-halogen hybrid perovskite crystal material for a rare earth doped radiation detector and a preparation method thereof.

Background

The methylamine halide lead perovskite crystal is a novel semiconductor material for a nuclear radiation detector, has smaller effective mass of electrons and holes, has higher resistivity and more proper forbidden bandwidth (1.6-3.0 eV), and has adjustable band gap, so the methylamine halide lead perovskite crystal is widely applied to the fields of solar cells, radiation detection, light-emitting diodes and the like. In the radiation detection field, the search for high-performance and low-cost radiation detection materials is one of the current major research and development directions in the field. The CdZnTe has the advantages of high response speed, good stability and the like as the current most promising semiconductor radiation detector material, but the large-scale industrial production of the material is limited by the high cost of the CdZnTe. The simple plane radiation detector can be prepared by simply processing the cubic-phase methylamine halide lead perovskite crystal structure, so the methylamine halide lead perovskite crystal becomes a radiation detection material with a very wide application prospect.

Materials for radiation detectors generally require a resistivity of 10⁸Omega cm and above, because the detector works under a certain bias voltage, in a certain voltage range, the higher the voltage is, the higher the drift velocity of the carriers is, and the probability of the carriers being recombined and captured is reduced. However, the higher the voltage, the higher the leakage current, and thus the noise of the detector increases, and the higher the resistivity, the higher the voltage that the detector can bear, so the high resistivity and the low leakage current are one of the important parameters for evaluating the quality of the material for the nuclear radiation detector. Therefore, there is a need for a perovskite material for radiation detectors that is simple to prepare, low in cost, and has high resistivity and low leakage current properties.

Disclosure of Invention

The invention aims to provide a double-halogen hybrid perovskite crystal material for a rare earth doped radiation detector, and the chemical formula of the crystal material is CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Wherein x is 0.91 and y is 0.451-1, and the material has high resistivity, low leakage current and low preparation cost.

The invention also provides a preparation method of the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector, the double-halogen hybrid perovskite crystal material is prepared by three-stage heating and temperature rise through a hydrothermal method, the method is simple, and the process is easy to control.

The technical scheme of the invention is as follows:

a double-halogen hybrid perovskite crystal material for a rare earth doped radiation detector, wherein the chemical formula of the crystal material is CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Wherein, in the step (A),x＝0.91，y＝0.451-1。

as a limitation of the present invention, when y is 0.526 to 1, the structure of the crystalline material is a simple cubic structure, and when y is 0.451 to 0.526, the structure of the crystalline material is a tetragonal structure.

In the invention, after the rare earth element is doped, because the atomic radius of the rare earth element thulium is much larger than that of lead, the addition of thulium causes lattice expansion of crystals, thereby being beneficial to increasing the scattering of electrons and improving the resistance and the resistivity; according to the Linde law, resistivity change is proportional to valence difference, and the valence difference between rare earth elements and lead is also an important factor causing resistivity increase. The higher the resistivity is, the higher the voltage the prepared detector can bear, and the smaller the leakage current during operation is. In addition, the rare earth element thulium can also enable the crystal to absorb light waves to generate certain specific transition, release excitation in a radiation form or transfer excitation energy to other ions, and further improve the on-off ratio performance of the crystal, so that the rare earth element doped with the thulium and the double halogen cooperate to improve the photoresponse and radiation detection performance of the material, improve the on-off ratio and the resistivity and reduce leakage current.

The invention also provides a preparation method of the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector, which is sequentially carried out according to the following steps:

(1) according to a molar ratio of 1: 1: 0.12-1.22: 0.12-1.22: CH was weighed in a proportion of 0.04₃NH₃Br、PbBr₂、CH₃NH₃I、PbI₂And Tm₂O₃Powder is reserved;

(2) will CH₃NH₃Br and PbBr₂Dissolving in dimethylformamide solution, marking as solution A, and adding CH₃NH₃I and PbI₂Dissolving in gamma-butyrolactone solution, and marking as solution B; mixing solution A and solution B uniformly, adding Tm₂O₃Heating the powder on a magnetic heating stirrer, stirring until the solution is clear, continuing to keep the temperature and stirring for 5 hours, and adding the antioxidant once every 1 hour in the stirring process to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

the needle tube filtered in the step and the aperture size of the needle tube have influence on the filtering effect, and the smaller aperture can filter out large impurity particles possibly introduced in the preparation process of the precursor, so that the phenomenon that the nucleation of a large amount of impurities affects the performance of the final crystal material is avoided;

(4) putting the solution D into a sealed flat-bottom beaker, putting the sealed beaker into a heating water tank, heating, and keeping the temperature for 24 hours at 90 ℃ to obtain E;

(5) and (3) drying the E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

As the limitation of the preparation method of the invention:

in the step (one), the molar concentration of the solution A is 0.8mol/L, and the molar concentration of the solution B is 1.3 mol/L.

The molar concentrations of the solution A and the solution B influence the composition uniformity of crystal nucleation, the solubility of the lead bromide methylamine in the dimethylformamide solution is gradually reduced along with the increase of the temperature, and the solubility of the lead iodide methylamine in the gamma-butyrolactone solution is also gradually reduced along with the increase of the temperature. But the maximum solubility of the lead iodide and the methylamine at the same temperature is different, and when the molar concentration ratio of the lead iodide and the methylamine is less than 8:13, lead iodide and methylamine are preferentially separated out, so that the iodine content in the crystal is higher; when the molar concentration ratio of the lead bromide to the methylamine is more than 8:13, lead bromide methylamine is preferentially separated out, and the bromine content in the separated crystal is high; because the solubility of bromine and iodine in respective solutions is reduced along with the increase of the temperature, when the concentration ratio of the bromine to the iodine is 8:13, the bromine and the iodine can be ensured to be separated out simultaneously, the component uniformity of crystal nuclei is ensured, and the performance of the prepared crystal material is further ensured.

In the step (two), the mixing volume ratio of the solution A to the solution B is 4-6.5: 0.5-3.

The volume ratio of the solution A and the solution B in the mixing process influences the content of halogen in the crystal and the crystal structure, when the volume ratio of the solution A and the solution B in the mixing process is out of the range, the crystal has higher iodine content and higher tetragonal phase structure, the oxidation of the crystal is accelerated by the higher iodine content, and more antioxidants are required to be added for keeping the performance of the crystal stable. Meanwhile, the higher iodine content can transform the crystal structure from cubic phase to tetragonal phase, and the irregular tetragonal phase structure can aggravate the manufacturing difficulty of the simple plane detector. More complicated grinding and polishing processes are needed to be carried out on the tetragonal phase crystal, new impurities and defects are introduced in the grinding and polishing process, and the quality of the crystal is reduced.

In the step (III), the heating and stirring temperature is 55 ℃, and the stirring speed is 600 rpm/min.

In the invention, the dimethylformamide solution and the gamma-butyrolactone solution are respectively used as solvents to dissolve materials, and the types of the solvents are closely related to the materials to be dissolved, which is crucial to the growth of later crystals; in the process of mixing the solution A and the solution B, the solution A and the solution B need to be heated and stirred, the solute in the solution A and the solution B needs to be fully dissolved and uniformly mixed, and when the temperature is lower than 55 ℃, the solute in the solution B can be incompletely dissolved; when the temperature is higher than 55 ℃, the solubility of the lead bromide methylamine in the dimethylformamide solution is reduced, and the solute is separated out in advance.

In the step (IV), the antioxidant is dibutyl hydroxy toluene, and the adding amount of the antioxidant is 0.02g each time.

The antioxidant is added to be dissolved in the precursor solution, and the precursor solution can be prevented from being rapidly oxidized into a colloid and the surface of the crystal is prevented from being oxidized; but the addition amount of the compound affects the quality and the performance of a final product, and when the addition amount is too large, the compound is formed by an oxidant and a perovskite solution, so that the nucleation process of perovskite is affected; when the addition amount is too small, the crystal cannot be sufficiently prevented from being oxidized, the precursor solution can be rapidly oxidized into a gel, the surface of the crystal is oxidized, and the performance of the final crystal material is influenced.

(V) in step (1), the Tm is₂O₃The powder is prepared according to the following steps: tm is₂O₃Placing in a ball millThe ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively rotates forwards for 20min and reversely for 20min, and the interval is 10 min;

tm is₂O₃Tm can be refined by ball milling₂O₃The material is better doped into a lattice structure to cause lattice expansion of the crystal, so that the scattering of electrons is increased, the resistance and the resistivity of the material are further improved, certain specific transition is finally generated after the light is absorbed by the crystal, the excitation energy is released in a radiation mode or is transferred to other ions, and the overall performance of the crystal material is improved.

In the step (4), the heating is divided into three sections, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

the three-stage heating directly influences the nucleation and growth of the crystal material, and the influence on the final quality and performance of the crystal material is very critical and mainly reflected in that: in the first stage of temperature rise, the solubility of the solute of the precursor solution is rapidly reduced, the temperature rise rate is greatly increased in the stage to reduce the time for preparing the crystal, and the temperature is kept at 70 ℃ for 5 hours to keep the precursor solution stable before the precursor solution reaches the saturation precipitation point; in the second stage of heating process, the crystal initially nucleates and grows gradually, the temperature rise rate in the stage needs to be 1 ℃/h to stabilize the crystal, the temperature rise rate in the stage needs to be slow to ensure that the nucleation and growth process are stable and uniform, and the temperature is kept at 85 ℃ for 5h to further stabilize and grow the crystal; in the third stage of heating process, the crystal continues to grow and the crystal grains are refined, the solubility is further reduced at the heating rate of 1 ℃/5h in the stage, the crystal slowly grows at the slow heating rate, the crystal is prevented from being uneven and unstable when growing, more solute and power are provided for the crystal growth in the stage, and the temperature is kept at 90 ℃ for 24h to ensure the stable precipitation of the solute and the continuous slow growth and the crystal grains refinement.

The preparation method of the invention is an organic whole, and the organic whole determine the performance of the finally prepared rare earth doped double-halogen hybrid perovskite crystal material.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:

1. the rare earth doped double-halogen hybrid perovskite crystal material prepared by the invention has better resistivity and lower dark current, and the resistivity can reach 4.79 multiplied by 10⁸Omega cm, the leakage current can reach 56 nA;

2. the preparation process of the crystal is simple, the process is easy to control, the crystal growth process is stable by a three-stage heating control method in the crystal growth process, the grown crystal has high quality and low cost.

3. By doping the rare earth oxide, the optical response and radiation detection performance of the crystal material are improved.

The rare earth doped double-halogen hybrid perovskite crystal material prepared by the invention is suitable for materials for nuclear radiation detectors.

The following description will be provided to further explain the embodiments of the present invention in detail with reference to the accompanying drawings.

Drawings

FIG. 1 is a graph comparing the samples prepared in examples 1 and 2, which were left in air for 1 h;

FIG. 2 is a comparative XRD pattern of samples prepared in example 1, example 2 and example 3;

FIG. 3 is a graph comparing the I-T curves for samples prepared in examples 2 and 3;

FIG. 4 is a pictorial representation of crystalline materials prepared in examples 3 to 9 of the present invention;

FIG. 5 is an XRD pattern of crystalline materials prepared in examples 3 to 9 of the present invention;

FIG. 6 is a graph comparing voltage-current (I-V) curves of-100V to +100V for crystalline materials prepared in examples 3 to 8 of the present invention;

FIG. 7 is a scanning electron micrograph of a crystalline powder prepared according to example 7 of the present invention;

FIG. 8 is a graph comparing voltage-current (I-V) curves of-100V to +100V for crystalline materials prepared in examples 9 and 11 of the present invention.

Detailed Description

In the following examples, commercially available reagents were used as the reagents unless otherwise specified, and conventional experimental methods and detection methods were used as the following experimental methods and detection methods unless otherwise specified.

Example 1 preparation method of lead bromide methylamine monohalogen perovskite crystal material for radiation detector

The embodiment is a preparation method of a lead bromide methylamine monohalogen perovskite crystal material for a radiation detector, which is sequentially carried out according to the following steps:

(1) according to a molar ratio of 1: 1.0.63 g CH are weighed out₃NH₃Br and 2.1g PbBr₂Powder is reserved;

(2) will CH₃NH₃Br and PbBr₂Dissolving in 7mL of dimethylformamide solution, marking as solution A, heating and stirring on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, and then continuing to stir for 5 hours under heat preservation;

(3) filtering the solution A by using a 10mL disposable needle tube and an organic filter head with the aperture of 0.22 mu m to form a solution B after filtering;

(4) putting the solution B into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal C;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal C in a drying oven at 90 ℃ for 2h to obtain the lead bromide methylamine monohalogen perovskite crystal material.

Embodiment 2 preparation method of lead bromide methylamine monohalogen perovskite crystal material for radiation detector

This example is a preparation method of lead bromide methylamine monohalogen perovskite crystal material for radiation detector, the preparation steps are similar to those of example 1, and the difference is only that: in the process of dissolving the raw material powder, namely step (2), adding an antioxidant of dibutyl hydroxy toluene into the precursor solution, wherein the specific preparation process is carried out in sequence according to the following steps:

(1) according to a molar ratio of 1: 1.0.63 g CH are weighed out₃NH₃Br and 2.1g PbBr₂Powder is reserved;

(2) will CH₃NH₃Br and PbBr₂Dissolving in 7mL of dimethylformamide solution, marking as solution A, heating and stirring on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing stirring for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain solution B;

(3) filtering the solution B by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution C after filtering;

(4) putting the solution C into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal D;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the D in a drying oven at 90 ℃ for 2h to obtain the lead bromide methylamine monohalogen perovskite crystal material.

FIG. 1 is a comparison of the samples prepared in example 1 and example 2, which were left to stand in air for 1h, and it can be seen that the crystals prepared in example 1 were significantly more oxidized than those prepared in example 2, which indicates that the addition of the antioxidant dibutylhydroxytoluene slowed the oxidation of the crystal surface, which is important for maintaining the photoelectric properties of the crystals.

In this embodiment, a comparative test is also performed on whether an antioxidant dibutyl hydroxytoluene is added into a precursor solution of a lead methylamine bromide monohalogen (iodine) perovskite crystal material in a raw material powder dissolving process, and the preparation processes of the two are similar, except that: and (4) whether the antioxidant dibutyl hydroxy toluene is added into the precursor solution in the raw material powder dissolving process. The results show that: the lead bromide methylamine monohalogen (iodine) perovskite crystal material prepared by adding the antioxidant dibutyl hydroxy toluene into the precursor solution in the process of dissolving the raw material powder has strong oxidation resistance on the surface, and the material prepared by adding the antioxidant dibutyl hydroxy toluene has more obvious oxidation resistance along with the larger iodine content in the crystal material.

Embodiment 3 preparation method of lead bromide thulium methylamine monohalogen perovskite crystal material for rare earth doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)Br₃Crystal, x ═ 0.91, and the preparation procedure was similar to example 2 except that Tm containing a rare earth element was added to the precursor solution during the dissolution of the raw material powder₂O₃The specific preparation process of the powder is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 0.63g CH was weighed out in a proportion of 0.04₃NH₃Br、2.1g PbBr₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball milling in inert atmosphereIn each period, positively rotating for 20min, reversely rotating for 20min, and intermitting for 10min to obtain the final product;

(2) will CH₃NH₃Br and PbBr₂Dissolving the powder in 7mL of dimethylformamide solution, marking as solution A, the molar concentration of which is 0.8M, adding Tm after uniformly stirring₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution B;

(3) filtering the solution B by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution C after filtering;

(4) putting the solution C into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal D;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the D in a drying oven at 90 ℃ for 2h to obtain the lead bromide thulium methylamine monohalogen perovskite crystal material for the rare earth doped radiation detector.

FIG. 2 is a comparative XRD pattern of samples prepared in examples 1, 2 and 3, and it can be seen that the addition of the antioxidants dibutylhydroxytoluene and rare earth elements during the preparation process does not change the crystal phase structure of the crystals.

Fig. 3 is an I-T diagram of samples prepared in examples 2 and 3, and it can be seen from the figure that the on-off ratio performance of the material prepared in example 3 after adding rare earth element in the preparation process is superior to that of example 2, which indicates that the rare earth element Tm is important for the performance improvement of the prepared material, and the doping of the rare earth element Tm enables a certain transition to occur after the crystal absorbs a light wave, so that the excitation energy is released in the form of radiation or transferred to other ions, thereby improving the on-off ratio performance.

Example 4 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

The material prepared in this example was CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃The crystal, x is 0.91, y is 0.891, and the preparation process is carried out according to the following steps:

(1) according to a molar ratio of 1: 1: 0.12: 0.12: 0.5824g of CH were weighed out at a ratio of 0.04₃NH₃Br、1.9084g PbBr₂、0.1034g CH₃NH₃I、0.2996g PbI₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 6.5mL of dimethylformamide, record as solution A, at a molar concentration of 0.8M, add CH₃NH₃I and PbI₂Dissolving the mixture in 0.5mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

Example 5 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Crystal, x is 0.91 and y is 0.787

The preparation process is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 0.27: 0.27: 0.5376g of CH were weighed out at a ratio of 0.04₃NH₃Br、1.7616g PbBr₂、0.2066g CH₃NH₃I、0.5993g PbI₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 6mL dimethylformamide, record as solution A, at a molar concentration of 0.8M, add CH₃NH₃I and PbI₂Dissolving the mixture in 1mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

Example 6 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Crystal, x is 0.91 and y is 0.693

The preparation steps are carried out in sequence according to the following steps:

(1) according to a molar ratio of 1: 1: 0.44: 0.44: 0.4928g of CH were weighed out at a ratio of 0.04₃NH₃Br、1.6148g PbBr₂、0.3099g CH₃NH₃I、0.8989g PbI₂And 0.086Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 5.5mL of dimethylformamide, record as solution A, at a molar concentration of 0.8M, and add CH₃NH₃I and PbI₂Dissolving the mixture in 1.5mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

Example 7 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Crystal, x is 0.91 and y is 0.606

The preparation process is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 0.65: 0.65: 0.448g of CH were weighed out in a proportion of 0.04₃NH₃Br、1.468g PbBr₂、0.4131g CH₃NH₃I、1.1986g PbI₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 5mL dimethylformamide, record as solution A, at a molar concentration of 0.8M, add CH₃NH₃I and PbI₂Dissolving the mixture in 2mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

FIG. 7 is a scanning electron microscope image of the powder of the crystal prepared in example 7, wherein the particle size of the crystal material is 150-250nm, and the morphology is spherical.

Example 8 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃The crystal, x is 0.91, y is 0.526, and the preparation process is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 0.9: 0.9: 0.4032g of CH were weighed out at a ratio of 0.04₃NH₃Br、1.3212g PbBr₂、0.5168g CH₃NH₃I、1.4983g PbI₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 4.5mL of dimethylformamide, record as solution A, at a molar concentration of 0.8M, and add CH₃NH₃I and PbI₂Dissolving the mixture in 2.5mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

Example 9 preparation method of double-halogen hybrid perovskite crystal material for rare earth-doped radiation detector

This example prepares CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Crystal, x is 0.91 and y is 0.451

The preparation process is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 1.22: 1.22: 0.3584g of CH were weighed out at a ratio of 0.04₃NH₃Br、1.1744g PbBr₂、0.6201g CH₃NH₃I、1.7979g PbI₂And 0.086g Tm₂O₃Powder is reserved;

Tm₂O₃the powder is prepared according to the following steps in advance: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 4mL dimethylformamide, record as solution A, at a molar concentration of 0.8M, add CH₃NH₃I and PbI₂Dissolving the mixture in 3mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to stir for 5 hours at a constant temperature, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

As shown in fig. 5, the crystal morphology prepared in this example is polyhedral and it is a tetragonal structure by XRD test.

FIG. 4 shows CH prepared in examples 3 to 9 of the present invention₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃A crystal entity diagram; as can be seen from the figure, the crystals prepared in examples 3 to 9 were obtained in the order from left to right.

FIG. 5 is CH of examples 3 to 9 of the present invention₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃XRD patterns of the crystals, from which it can be seen that the crystals prepared in examples 3 to 8The structural phase of the crystal is cubic. And the structural phase of the crystal prepared in example 9 is a tetragonal phase structure.

The following table is a comparative table of resistivity of cubic phase crystalline materials prepared in examples 3 to 8 of the present invention fitted by a voltage-current (I-V) curve at-0.1V to + 0.1V. The crystalline materials prepared in examples 4 to 8 had higher resistivity than that of the crystalline material prepared in example 3, in which the crystalline material prepared in example 7 had the highest resistivity.

Examples	Composition of crystal component	Resistivity (omega cm)
			3	x＝0.91，y＝1	1.32×108
4	x＝0.91，y＝0.891	1.45×108
			5	x＝0.91，y＝787	2.16×108
6	x＝0.91，y＝693	2.63×108
			7	x＝0.91，y＝606	4.79×108
8	x＝0.91，y＝526	3.65×108

FIG. 6 is a graph comparing voltage-current (I-V) curves at-100V to +100V for cubic phase crystalline materials prepared in examples 3 to 8 of the present invention. The crystal material prepared in example 7 has the lowest leakage current of 56nA during operation, and as can be seen from the table and fig. 6, the crystal material prepared in example 5 has the highest resistivity, the lowest leakage current and the best performance.

Example 10 Effect of the ball milling Process on the Properties of the Bihalogen hybrid perovskite Crystal Material for rare-earth doped radiation Detector

In the process of preparing the crystal material, Tm is required to be added into the precursor liquid₂O₃Powder, which requires ball milling pretreatment. The ball milling process may be such that Tm is₂O₃The grain size is thinned, so that the crystal is fully dissolved in the solution, the crystal can be better doped into a lattice structure in the nucleation growth process, lattice expansion of the crystal is caused, scattering of electrons is increased, and resistance and resistivity are further improved.

The following preparation of a double-halogen hybrid perovskite crystal material for a rare earth-doped radiation detector was carried out in a similar manner to example 9 except that: ball milling Tm₂O₃The preparation process of the powder is different, and specifically comprises the following steps:

group A: the ball milling process was the same as in example 9;

group B: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for one period under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

group C: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for two periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

group D: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for four periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

group E: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 10: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

and F group: tm is₂O₃Placing the mixture in a ball mill, wherein the ball material ratio is 30: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min;

group G: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 30min, negative rotation for 30min and intermittent rotation for 10 min;

group H: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 10min, negative rotation for 10min and intermittent rotation for 10 min.

The performance test of the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector prepared by the A-H groups is carried out, and the test results of the crystal material under the conditions of the resistivity of the crystal material fitted by a voltage-current (I-V) curve of-0.1V to +0.1V and the voltage-current (I-V) of-100V to +100V are shown in the following table:

group of	Leakage current (nA)	Resistivity (omega cm)
			Group A	89	2.98×108
Group B	121	2.41×108
			Group C	98	2.65×108
Group D	95	2.78×108
			Group E	113	2.49×108
Group F	94	2.81×108
			Group G	91	2.86×108
Group H	132	2.32×108

Example 11 preparation method of Bihalogen hybrid perovskite crystal Material for radiation Detector

This example prepares CH₃NH₃Pb(Br_yI_1-y)₃The crystal, y is 0.451, and the preparation process is carried out according to the following steps in sequence:

(1) according to a molar ratio of 1: 1: 1.22: 1.22 0.3584g of CH were weighed out separately₃NH₃Br、1.1744g PbBr₂、0.6201g CH₃NH₃I、1.7979g PbI₂Standby;

(2) will CH₃NH₃Br and PbBr₂Dissolve in 4mL dimethylformamide, record as solution A, at a molar concentration of 0.8M, add CH₃NH₃I and PbI₂Dissolving the mixture in 3mL of gamma-butyrolactone solution, marking as solution B, wherein the molar concentration of the solution B is 1.3M; uniformly mixing the solution A and the solution B, heating and stirring the mixture on a magnetic heating stirrer until the solution is clear, wherein the heating and stirring temperature is 55 ℃, the stirring speed is 600rpm/min, then continuing to keep the temperature and stir for 5 hours, and adding the antioxidant dibutyl hydroxy toluene once every 1 hour in the stirring process, wherein the adding amount of each time is 0.02g, so as to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, and putting the sealed beaker into a heating water tank for heating to obtain a crystal E;

the heating in the step is divided into three sections of heating, and the heating is carried out in sequence according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h;

(5) and (3) drying the crystal E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the radiation detector.

To the sameThe performance test of the radiation detector prepared by the embodiment by using the double-halogen hybrid perovskite crystal material shows that: the resistivity of the crystal material is 2.79 multiplied by 10 through the voltage-current (I-V) curve fitting between-0.1V and +0.1V⁸Omega cm, and the leakage current of the crystal material tested under the voltage-current (I-V) of-100V to +100V is 112nA, which is shown in figure 8. Compared with the example 9, the rare earth element is doped in the preparation process of the example 9, the rare earth element Tm plays an important role in improving the performance of the crystal material, and the rare earth element Tm can be used for improving the resistivity of the crystal and reducing the leakage current of the crystal by cooperating with the double halogen.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims (9)

1. A double-halogen hybrid perovskite crystal material for a rare earth doped radiation detector is characterized in that the chemical formula of the crystal material is CH₃NH₃(Pb_xTm_1-x)(Br_yI_1-y)₃Wherein x is 0.91 and y is 0.451-1.

2. The double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 1, wherein the structure of the crystal material is a simple cubic structure when y is more than or equal to 0.526 and less than or equal to 1, and the structure of the crystal material is a tetragonal structure when y is more than or equal to 0.451 and less than 0.526.

3. The preparation method of the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 1, which is characterized by sequentially carrying out the following steps:

(1) according to a molar ratio of 1: 1: 0.12-1.22: 0.12-1.22: CH was weighed in a proportion of 0.04₃NH₃Br、PbBr₂、CH₃NH₃I、PbI₂And Tm₂O₃Powder is reserved;

(2) will CH₃NH₃Br and PbBr₂Dissolving in dimethylformamide solution, marking as solution A, and adding CH₃NH₃I and PbI₂Dissolving in gamma-butyrolactone solution, and marking as solution B; mixing solution A and solution B uniformly, adding Tm₂O₃Heating and stirring the powder on a magnetic heating stirrer until the solution is clear, continuing to keep the temperature and stirring for 5 hours, and adding the antioxidant once every 1 hour in the stirring process to obtain a solution C;

(3) filtering the solution C by using a 10mL disposable needle tube and an organic filter head with the pore diameter of 0.22 mu m to form a solution D after filtering;

(4) putting the solution D into a sealed flat-bottom beaker, putting the sealed beaker into a heating water tank for heating, and keeping the temperature at 90 ℃ for 24 hours to obtain E;

(5) and (3) drying the E in a drying oven at 90 ℃ for 2h to obtain the double-halogen hybrid perovskite crystal material for the rare earth doped radiation detector.

4. The method for preparing the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 3, wherein in the step (2), the molar concentration of the solution A is 0.8mol/L, and the molar concentration of the solution B is 1.3 mol/L.

5. The method for preparing the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 3, wherein in the step (2), the volume ratio of the solution A to the solution B is 4-6.5: 0.5-3.

6. The preparation method of the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 3, wherein in the step (2), the heating and stirring temperature is 55 ℃ and the stirring speed is 600 rpm/min.

7. The method for preparing the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 3, wherein in the step (2), the antioxidant is dibutyl hydroxy toluene, and the addition amount of the dibutyl hydroxy toluene is 0.02g each time.

8. The method for preparing the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in claim 3, wherein in the step (1), the Tm is₂O₃The powder is prepared according to the following steps: tm is₂O₃Placing the mixture in a ball mill, wherein the ball-material ratio is 20: 1, ball-milling for three periods under inert atmosphere, wherein each period respectively comprises positive rotation for 20min, negative rotation for 20min and intermittent rotation for 10 min.

9. The method for preparing the double-halogen hybrid perovskite crystal material for the rare earth-doped radiation detector as claimed in any one of claims 3 to 8, wherein in the step (4), the heating is divided into three sections, and the three sections are sequentially heated according to the following steps:

in the first temperature rise stage, the temperature is raised from room temperature to 70 ℃ at the temperature rise rate of 5 ℃/h, and the temperature is kept for 5 h;

in the second temperature rise stage, the temperature is raised from 70 ℃ to 85 ℃ at the temperature rise rate of 1 ℃/h, and the temperature is kept for 5 h;

in the third temperature rise stage, the temperature is raised from 85 ℃ to 90 ℃ at the temperature rise rate of 1 ℃/5h, and the temperature is kept for 24 h.

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