CN113512757B - Large-block high-quality scintillation crystal and preparation method and application thereof - Google Patents

Large-block high-quality scintillation crystal and preparation method and application thereof Download PDF

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CN113512757B
CN113512757B CN202110468167.0A CN202110468167A CN113512757B CN 113512757 B CN113512757 B CN 113512757B CN 202110468167 A CN202110468167 A CN 202110468167A CN 113512757 B CN113512757 B CN 113512757B
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CN113512757A (en
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李静
温航
王彪
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Abstract

The invention relates to a high-quality flash blockScintillation crystal and preparation method and application thereof, wherein the scintillation crystal is CsMgX 3 The crystal is a substrate, and is doped or not doped with rare earth elements and/or alkali metals; the rare earth element is one of Eu and Pr; the alkali metal is 6 Li, the bulk, high quality, crack-free single crystals were first grown using the Bridgman method. The scintillation crystal obtained by the invention is a novel all-inorganic halogen perovskite block crystal, and the scintillation crystal is a novel all-inorganic halogen perovskite block crystal, and has the advantages of large block crystal size, crystal diameter of 10-25mm, good crystal quality, high transmittance and small refractive index. The decay time is very short, only a few nanoseconds, the scintillation crystal with the luminescence can realize double detection of neutrons and gamma rays, has high atomic number and smaller band gap, and is a scintillation crystal with great application prospect.

Description

Large-block high-quality scintillation crystal and preparation method and application thereof
Technical Field
The invention relates to a large-block high-quality scintillation crystal and a preparation method and application thereof, belonging to the technical field of crystal growth.
Background
Scintillators are a class of materials capable of emitting visible light after absorbing high-energy particles or rays, and play an important role in the field of radiation detection. Under the irradiation of high-energy rays, visible light emitted by the scintillator is converted into an electrical signal through a photomultiplier tube, a photodiode, an avalanche photodiode and the like, so that high-energy particles or rays are detected or imaged. In medicine, a scintillator is a core component of a nuclear medicine imaging apparatus, and through it, a lesion of each organ of a human body, the size and the position of a tumor tissue can be rapidly diagnosed. Plays an irreplaceable role in the fields of baggage security inspection, nondestructive inspection, radioactive detection and the like. Meanwhile, the scintillator is an important material for manufacturing electromagnetic energy measuring devices in various colliders, can capture information of various particles generated after nuclear reaction, and is an important tool for exploring the mystery of the microcosmic world and the universe. Ultrafast scintillating material refers to materials having response times less than 4ns (10) -9 s) scintillator material. The material plays a supporting role in Pulsed radiation detection (Pulsed radiation detection), solar neutrino detection, reaction kinetics, inertial confinement nuclear fusion and cosmic ray research.
Although different applications may impose different requirements on the scintillator, the scintillator is used for detecting ionizing radiation in most applications, so that the scintillator is required to have high capability of blocking ionizing radiation, i.e. the scintillator is required to have high density and contain elements with large atomic number.
The currently commonly used scintillating materials can be divided into three categories, namely organic scintillators, inorganic scintillators and composite scintillators according to material characteristics, the organic scintillators have good energy resolution but low radiation resistance intensity and are not beneficial to long-time use, and the inorganic scintillators have the characteristics of high light yield, high response speed, short attenuation time, good stability and the like. The composite scintillator is a novel scintillator prepared by dispersing an inorganic scintillator serving as a solute in an organic scintillator.
Inorganic scintillators are classified into oxide scintillators and halide scintillators according to different compositions, and oxide scintillators have the advantages of large effective atomic number, stable physicochemical properties, larger band gap, generally lower light yield and poor energy resolution, so that the halide scintillators become the research hotspot as novel scintillating materials with high light yield and high energy resolution at present.
The halide scintillation crystal has the advantages of high light yield, good energy resolution and simple components, and with the development of ABX3 type perovskite compounds, perovskite scintillation crystal materials with scintillation property are gradually discovered, and the regulation and control of crystal band gaps can be realized by substituting halogen at X position in A BX3, so that the application under different conditions is met, and the halogen perovskite materials rapidly become the next generation novel luminescent materials by structural diversity and excellent photoelectric properties.
Disclosure of Invention
Aiming at the advantages of high light yield, excellent energy resolution and rapid decay time of the existing halogen perovskite scintillation crystal, the invention provides a large-block high-quality scintillation crystal and a preparation method and application thereof. The scintillation crystal obtained by the invention is a novel all-inorganic halogen perovskite bulk crystal, has large bulk crystal size and CVL luminescence, and meets the requirements of medical imaging on fast attenuation.
The invention grows the large-block high-quality crack-free single crystal for the first time by improving the process and using the Bridgman method.
The technical scheme of the invention is as follows:
a large-block high-quality scintillation crystal is CsMgX 3 The crystal is a matrix, doped or not with rare earth elements andor an alkali metal.
According to the present invention, preferably, the rare earth element may be one of Eu and Pr.
Preferably, the rare earth element is Eu.
Eu ions have 5d-4f transition, 5d orbits are completely exposed, the influence of the environment is large, the scintillation response capability is favorably improved, and the Eu ions can be substituted with Mg in an equivalent manner, so that the Eu ions are the most preferable.
Preferably, the alkali metal is 6 Li。
6 The presence of Li will react with neutrons:
Figure BDA0003044883130000021
the reaction allows the crystal to achieve detection of thermal neutrons.
The rare earth element is Eu, and the alkali metal is 6 Further preferred on the basis of Li are:
the chemical formula of the scintillation crystal is as follows:
Cs x 6 Li 1-x Mg y Eu 1-y X 3 (ii) a Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and X is selected from one of I, br and Cl.
The crystal is a perovskite crystal, and the change of the X-site elements (I, br, cl) can affect the band gap of the crystal, thereby affecting other properties of the crystal.
When X is selected from I, the perovskite crystal doped with the rare earth element is Cs x 6 Li 1-x Mg y Eu 1-y I 3 . The crystal has a smaller band gap, is expected to have high light yield and low energy resolution, and is a scintillation crystal with very potential.
When X is selected from Br, the perovskite crystal doped with the rare earth element is Cs x 6 Li 1-x Mg y Eu 1-y Br 3 。
When X is Cl, the perovskite crystal doped with the rare earth element is Cs x 6 Li 1-x Mg y Eu 1-y Cl 3 。
Preferably, according to the invention, the scintillation crystal is a rare earth element doped perovskite crystal when x =1,0 < y < 1.
Preferably according to the present invention, when x =1,0 < y < 1, the rare earth element doped perovskite crystal is selected from one of the following: csMg y I 3 :Eu 1-y 、CsMg y Br 3 :Eu 1-y 、CsMg y Cl 3 :Eu 1-y 。
Preferably, according to the invention, when 0 < x < 1,y =1, the scintillation crystal is an alkali metal doped perovskite crystal.
When X is selected from I, the perovskite crystal doped with alkali metal is Cs x MgI 3 : 6 Li 1-x 。
When X is selected from Br, the perovskite crystal doped with alkali metal is Cs x MgBr 3 : 6 Li 1-x 。
When X is selected from Cl, the perovskite crystal doped with alkali metal is Cs x MgCl 3 : 6 Li 1-x 。
CsMgCl 3 The light emitting diode has CVL light emission and extremely fast decay time. Incorporation of 6 After Li, the double detection of gamma rays and neutrons can be realized.
Preferably according to the invention, when 0 < x < 1,y =1, the rare earth element-doped perovskite crystal is selected from one of the following: cs x MgI 3 : 6 Li 1-x 、Cs x MgBr 3 : 6 Li 1-x 、Cs x MgCl 3 : 6 Li 1-x 。
Preferably, according to the invention, when x =1,y =1, the scintillation crystal is CsMgX 3 And X is selected from one of I, br and Cl.
According to the invention, it is preferred that when x is 0. Ltoreq. X.ltoreq.1, y is 0. Ltoreq. Y.ltoreq.1, x.noteq.1, y.noteq.1, the scintillation crystal Cs x 6 Li 1-x Mg y Eu 1-y X 3 The crystal is a co-doped crystal of rare earth elements and alkali metals, can emit light under the irradiation of neutrons and gamma rays, and realizes dual detection of the neutrons and the gamma rays.
The second purpose of the invention is to provide a method for preparing a large-block high-quality scintillation crystal.
Aiming at the problems that the existing scintillation crystal has strong deliquescence and is easy to crack periodically along a vertical growth surface, the invention firstly grows a large block of high-quality crack-free single crystal by using a Bridgman method through an improved process.
A method for preparing a large-block high-quality scintillation crystal comprises the following steps:
1) CsX and MgX were mixed in a stoichiometric ratio in a glovebox 2 Mixing uniformly, with or without adding 6 LiX and/or EuX 2 Filling the mixed material into a quartz tube, vacuumizing and sealing;
2) Placing the sealed quartz tube into a resistance furnace, circulating for three times in a heating-cooling-heating mode, keeping the temperature at 400-680 ℃ for 8-15 hours, and cooling to room temperature to obtain a polycrystalline material;
3) Putting a quartz tube containing polycrystalline materials into a crucible descending furnace, heating to 300-680 ℃, preserving heat for 8-15 hours, adjusting the position of the quartz tube to ensure that the temperature of a spontaneous nucleation area or an inoculation area at the bottom of the quartz tube is 1-5 ℃ higher than a melting point, the temperature gradient in a single crystal growth furnace is 5-15 ℃/cm, then slowly descending the quartz tube at the speed of 0.03-0.05mm/h, keeping the growth temperature unchanged, after the growth is finished, cooling the growth furnace to 180-220 ℃, and then naturally cooling to room temperature to obtain the large-block high-quality scintillation crystal.
Preferably, in step 1), the degree of vacuum after evacuation is 10 –6 mbar。
According to the present invention, in step 2), the heating-cooling-heating manner is specifically: firstly heating to 400-650 deg.C at a rate of 50-100 deg.C/h, then cooling to 100-150 deg.C at a rate of 30-50 deg.C/h, then heating to 500-650 deg.C at a rate of 50-100 deg.C/h, and circulating for three times. The reaction is fully carried out, and the components of the polycrystalline material are ensured to be uniform.
Preferably, in step 2), the cooling rate of the temperature to room temperature is 1-15 ℃/h.
The preparation method of the invention obtains the bulk single crystal with the diameter of 10-20mm, no crack and no deliquescence.
The application of large-block high-quality scintillation crystal is used for implementing neutron detection or neutron and gamma ray double detection in the fields of national defense, medical treatment, security inspection and nuclear non-diffusion, etc.
The novel all-inorganic halogen perovskite bulk crystal luminescence principle of the invention is as follows:
when excited by external gamma rays, the CsMgI3 crystal generates electron transition, the electron transits from a valence band to a conduction band and absorbs the energy of the gamma rays, the electron after the transition belongs to a high-energy electron and is in an unstable state, the electrons are subjected to excitation reversion to the valence band, and the energy is released in the form of photons, and the process is the scintillation process of the crystal. The analysis of gamma rays can be performed based on the analysis of photons emitted by this process.
CsMgI 3 : the Eu ions in the Eu crystal enter to form a new impurity energy level between the valence band and the conduction band of the crystal, so that the crystal can jump to the impurity energy level with lower energy when being excited, more electrons are excited by the same energy, more photons are emitted when being de-excited, the light yield of the crystal is higher, the scintillation efficiency is higher, and the response capability is better.
The CsMgCl3 crystal has the electron transition from the core band to the valence band in addition to the transition between the conduction bands of the electron valence band as in the CsMgI3 crystal, the process also generates the absorption and emission of energy, and the time is extremely short because the occurring region is between the core band and the valence band, and the process is the CVL luminescence process of the CsMgCl3 crystal.
When the crystal is 6 Li xCs 1-xmcg 3, the presence of 6Li allows the crystal to nucleate with thermal neutrons: :
Figure BDA0003044883130000041
the reaction converts the energy of the neutron into the energy of the electron and emits the photon in the subsequent de-excitation process, and because the process involves more steps and generally has a time span longer than that of the CVL, the separation of the neutron/gamma signals can be realized by the time analysis of the two signals, so that the neutron/gamma signals can be distinguishedThereby realizing neutron/gamma double detection.
The invention has the advantages and technical characteristics that:
1. the scintillation crystal is a novel all-inorganic halogen perovskite block crystal, the size of the block crystal is large, the diameter of the crystal is 10-25mm, the quality of the crystal is good, the transmittance is high, and the refractive index is small.
2. The scintillation crystal has core valence luminescence, the attenuation time is extremely short and is only a few nanoseconds, and the scintillation crystal with the luminescence can realize double detection of neutrons and gamma rays.
3. The scintillation crystal of the invention contains heavy ions, has high atomic number and smaller band gap, and is a scintillation crystal with great application prospect.
Drawings
FIG. 1 shows CsMg with a diameter of 15mm obtained in example 1 0.99 Eu 0.01 I 3 Photographs of crystal and cross-sectional slices, a being CsMg 0.99 Eu 0.01 I 3 B is a photograph of the wafer after cutting;
FIG. 2 is CsMg with a diameter of 15mm obtained in example 1 0.99 Eu 0.01 I 3 Grinding the crystal into powder to obtain a powder XRD pattern;
FIG. 3 shows CsMg with a diameter of 15mm obtained in example 1 0.99 Eu 0.01 I 3 Crystalline 1% photoluminescence spectrum;
FIG. 4 is CsMg obtained in example 2 0.95 Eu 0.05 Cl 3 A crystal photograph;
FIG. 5 shows CsMg obtained in example 2 0.95 Eu 0.05 Cl 3 A crystalline photoluminescence spectrum;
FIG. 6 is CsMgCl with a diameter of 12mm obtained in example 3 3 A crystal photograph;
FIG. 7 shows CsMgCl with a diameter of 12mm obtained in example 3 3 Grinding the crystal into powder to obtain a powder XRD pattern;
FIG. 8 shows Cs obtained in example 4 0.99 6 Li 0.01 MgI 3 Scintillation crystal photographs.
Detailed Description
The present invention will be further described with reference to the following examples and accompanying drawings.
Example 1
CsMg 0.99 Eu 0.01 I 3 Preparation of bulk crystals, the procedure was as follows:
1) CsI, mgI in glove box 2 And EuI 2 Mixing at stoichiometric ratio, sealing in quartz tube with vacuum degree of 10 –6 mbar。
2) Putting the sealed quartz tube into a resistance furnace, heating to 450 ℃ at the speed of 100 ℃/h, then cooling to 100 ℃ at the speed of 50 ℃/h, heating to 450 ℃ at the speed of 100 ℃/h, circulating for three times, keeping the temperature at 450 ℃ for 10 hours, then cooling to 25 ℃ at the speed of 15 ℃/h to obtain CsMg 0.99 Eu 0.01 I 3 Polycrystal;
3) Will contain CsMg 0.99 Eu 0.01 I 3 Putting the polycrystalline quartz tube into a crucible descending furnace, heating to 420 ℃, preserving heat for 10 hours, adjusting the position of the quartz tube to ensure that the temperature of a spontaneous nucleation area or an inoculation area at the bottom of the quartz tube is 1-5 ℃ higher than a melting point, the temperature gradient in the single crystal growth furnace is 5 ℃/cm, then slowly reducing the quartz tube at the speed of 0.3mm/h, and simultaneously keeping the growth temperature unchanged. After the growth is finished, the temperature of the growth furnace is reduced to 200 ℃ at a speed of 15 ℃/h, and then the growth furnace is naturally cooled to 30 ℃.
Taking out the quartz tube, and cutting the tube wall with a wire cutting machine to obtain high-quality CsMg with a diameter of 15mm 0.99 Eu 0.01 I 3 And (6) scintillation crystals.
CsMg prepared in example 1 0.99 Eu 0.01 I 3 The crystal and cross-sectional slice photographs are shown in FIG. 1. It can be seen from the photographs that the crystals obtained by the present invention are bulk crystals and large in size.
The results of powder XRD diffraction by grinding the resulting crystals into powder are shown in FIG. 2.
The photoluminescence spectrum of the crystal is shown in FIG. 3, and it can be seen from FIG. 3 that Eu represents a peak around 560nm 2+ Ion 5d-4f transition.
Example 2
CsMg 0.95 Eu 0.05 Cl 3 Bulk crystals were prepared by the following steps:
1) CsCl, mgCl2 and EuCl2 are mixed in stoichiometric ratio in a glove box, sealed in a quartz tube and vacuum degree of 10 -6 mbar。
2) Putting the sealed quartz tube into a resistance furnace, heating to 650 ℃ at the speed of 100 ℃/h, then cooling to 100 ℃ at the speed of 50 ℃/h, heating to 650 ℃ at the speed of 100 ℃/h, circulating for three times, keeping the temperature at 650 ℃ for 10 hours, then cooling to 25 ℃ at the speed of 15 ℃/h to obtain CsMg 0.95 Eu 0.05 Cl 3 Polycrystal;
3) Will contain CsMg 0.95 Eu 0.05 Cl 3 Putting the polycrystalline quartz tube into a crucible descending furnace, heating to 615 ℃, preserving the temperature for 10 hours, adjusting the position of the quartz tube to ensure that the temperature of a spontaneous nucleation area or an inoculation area at the bottom of the quartz tube is 1-5 ℃ higher than a melting point, the temperature gradient in the single crystal growth furnace is 5 ℃/cm, then slowly reducing the quartz tube at the speed of 0.3mm/h, and simultaneously keeping the growth temperature unchanged. After the growth is finished, the temperature of the growth furnace is reduced to 200 ℃ at a speed of 15 ℃/h, and then the growth furnace is naturally cooled to 30 ℃.
4) Taking out the quartz tube, and cutting the tube wall with a wire cutting machine to obtain high-quality CsMg with diameter of 15mm 0.95 Eu 0.05 Cl 3 A scintillation crystal;
CsMg prepared in example 2 0.95 Eu 0.05 Cl 3 The crystal photograph is shown in FIG. 4.
CsMg 0.95 Eu 0.05 Cl 3 The photoluminescence spectrum of the crystal is shown in FIG. 5, from which it can be seen that CsMg 0.95 Eu 0.05 Cl 3 Only one luminescence peak is positioned at about 480nm and is typical Eu 2+ Ion luminescence peak.
Example 3
CsMgCl 3 Preparation of bulk crystals, the procedure was as follows:
1) Mixing CsCl and MgCl2 in a glove box at stoichiometric ratio, sealing in a quartz tube at vacuum degree of 10 –6 mbar。
2) Placing the sealed quartz tube into a resistance furnace, heating to 650 ℃ at the speed of 100 ℃/h, then cooling to 100 ℃ at the speed of 50 ℃/h, heating to 650 ℃ at the speed of 100 ℃/h, circulating for three times, keeping the temperature at 650 ℃ for 10 hours, and then cooling to 25 ℃ at the speed of 15 ℃/h to obtain CsMgCl3 polycrystal;
3) Putting a CsMgCl3 polycrystal-containing quartz tube into a crucible descending furnace, heating to 615 ℃, preserving heat for 10 hours, adjusting the position of the quartz tube to ensure that the temperature of a spontaneous nucleation area or an inoculation area at the bottom of the quartz tube is 1-5 ℃ higher than a melting point, the temperature gradient in a single crystal growth furnace is 5 ℃/cm, then slowly reducing the quartz tube at a speed of 0.3mm/h, and simultaneously keeping the growth temperature unchanged. After the growth is finished, the temperature of the growth furnace is reduced to 200 ℃ at a speed of 15 ℃/h, and then the growth furnace is naturally cooled to 30 ℃.
4) Taking out the quartz tube, and cutting the tube wall by using a wire cutting machine to obtain a CsMgCl3 scintillation crystal with the diameter of 15mm and high quality;
the photograph of the CsMgCl3 scintillation crystal prepared in example 3 is shown in FIG. 6.
The result of powder XRD diffraction by grinding the crystals into powder is shown in FIG. 7.
Example 4
Cs 0.99 6 Li 0.01 Mg 0.99 Eu 0.01 I 3 Bulk crystals were prepared by the following steps:
1) CsI, mgI2, euI2 and 6LiI are mixed uniformly according to the stoichiometric ratio in a glove box, and the mixture is filled into a quartz tube and sealed, and the vacuum degree reaches 10-6mbar.
2) Putting the sealed quartz tube into a resistance furnace, heating to 600-650 ℃ at the speed of 50-100 ℃/h, then cooling to 100-150 ℃ at the speed of 30-50 ℃/h, heating to 600-650 ℃ at the speed of 50-100 ℃/h, circulating for three times, keeping the temperature at 600-650 ℃ for 10 hours, then cooling to 25 ℃ at the speed of 1-15 ℃/h to obtain Cs 0.99 6 Li 0.01 Mg 0.99 Eu 0.01 I 3 Polycrystal;
3) Will contain Cs 0.99 6 Li 0.01 Mg 0.99 Eu 0.01 I 3 Putting the polycrystalline quartz tube into a crucible descending furnace, heating to 450-650 ℃, preserving heat for 10 hours, adjusting the position of the quartz tube to ensure that the spontaneous nucleation temperature or the inoculation temperature at the bottom of the quartz tube is near the melting point, the temperature gradient is 5-15 ℃/cm, then slowly reducing the quartz tube at the speed of 0.3-0.5mm/h, and simultaneously keeping the growth temperature unchanged. After the growth is finished, the temperature of the growth furnace is reduced to 200 ℃ at a speed of 15 ℃/h, and then the growth furnace is naturally cooled to 30 ℃.
4) Taking out the quartz tube, and cutting the tube wall with a wire cutting machine to obtain high-quality Cs with diameter of 10-20mm 0.99 6 Li 0.01 Mg 0.99 Eu 0.01 I 3 And (4) scintillation crystals.
Cs obtained in example 4 0.99 6 Li 0.01 Mg 0.99 Eu 0.01 I 3 The scintillation crystal photograph is shown in fig. 8.

Claims (1)

1. A method for preparing a large-block high-quality scintillation crystal comprises the following steps:
1) CsX and MgX were mixed in a stoichiometric ratio in a glovebox 2 Mixing uniformly, and mixing 6 LiX and EuX 2 Filling the mixed material into a quartz tube, and then vacuumizing and sealing; the vacuum degree after vacuum pumping is 10 –6 mbar；
2) Placing the sealed quartz tube into a resistance furnace, circulating for three times in a heating-cooling-heating mode, keeping the temperature at 400-680 ℃ for 8-15 hours, and cooling to room temperature to obtain a polycrystalline material; the heating-cooling-heating mode comprises the following specific steps: heating to 500-650 deg.C at a rate of 50-100 deg.C/h, cooling to 100-150 deg.C at a rate of 30-50 deg.C/h, heating to 500-650 deg.C at a rate of 50-100 deg.C/h, and circulating for three times; the cooling rate of cooling to room temperature is 1-15 ℃/h; obtaining a quartz tube containing a polycrystalline material;
3) Putting a quartz tube containing polycrystalline materials into a crucible descending furnace, heating to 300-680 ℃, preserving heat for 8-15 hours, adjusting the position of the quartz tube, enabling the temperature of a spontaneous nucleation area or an inoculation area at the bottom of the quartz tube to be 1-5 ℃ higher than a melting point, enabling the temperature gradient in a single crystal growth furnace to be 5-15 ℃/cm, then slowly descending the quartz tube at the speed of 0.03-0.05mm/h, keeping the growth temperature unchanged, after the growth is finished, cooling the temperature of the growth furnace to 180-220 ℃, and then naturally cooling to room temperature to obtain a large block of high-quality scintillation crystals;
the scintillation crystal has the chemical formula:
Cs x 6 Li 1-x Mg y Eu 1-y X 3 (ii) a Wherein 0<x<1，0<y<1, X is selected from one of I, br and Cl, and can realize double detection of neutron signals and gamma rays.
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