CN117552106A - Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof - Google Patents
Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN117552106A CN117552106A CN202410034956.7A CN202410034956A CN117552106A CN 117552106 A CN117552106 A CN 117552106A CN 202410034956 A CN202410034956 A CN 202410034956A CN 117552106 A CN117552106 A CN 117552106A
- Authority
- CN
- China
- Prior art keywords
- crucible
- rare earth
- equal
- single crystal
- crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004820 halides Chemical class 0.000 title claims abstract description 103
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 194
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 238000002059 diagnostic imaging Methods 0.000 claims abstract description 10
- 238000007689 inspection Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 54
- 239000010453 quartz Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000001816 cooling Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 230000005251 gamma ray Effects 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000003384 imaging method Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000003746 solid phase reaction Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 230000005855 radiation Effects 0.000 abstract description 9
- 239000010949 copper Substances 0.000 description 127
- 229910052693 Europium Inorganic materials 0.000 description 48
- -1 rare earth ion Chemical class 0.000 description 34
- 238000004020 luminiscence type Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000306 component Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052769 Ytterbium Inorganic materials 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000010899 nucleation Methods 0.000 description 8
- 229910052706 scandium Inorganic materials 0.000 description 8
- 229910052777 Praseodymium Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052765 Lutetium Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 238000009206 nuclear medicine Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 239000008358 core component Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- JTCLRWIPWYKOTF-UHFFFAOYSA-N [Sc].[Y].[La] Chemical compound [Sc].[Y].[La] JTCLRWIPWYKOTF-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
- G01T1/2023—Selection of materials
Abstract
The application belongs to the technical field of radiation detection, relates to a rare earth-based zero-dimensional perovskite halide scintillation single crystal, a preparation method and application thereof, and provides a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal, which has the following composition general formula: (Cs) 1‑x A x ) 3 (Cu 1‑ y B y ) 2 (I 1‑z X z ) 5 :mat% RE, wherein: a combination of one or more of a= Rb, K, na, tl and In; b=one or a combination of Ag and Li; x=one or a combination of Cl and Br; RE is a rare earth ion selected from the group consisting of: eu (Eu) 2+ 、Yb 2+ 、Sc 3+ 、Y 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ And Tb 3+ The method comprises the steps of carrying out a first treatment on the surface of the And x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0 and less than or equal to 5. The scintillation single crystal has the performance advantages of low preparation cost, high stability, high light yield, high energy resolution and the like, and has great application prospects in the fields of medical imaging, safety inspection, high-energy physics and the like.
Description
Technical Field
The application belongs to the technical field of radiation detection, relates to a composition, a preparation method and application of a novel rare earth ion doped low-dimensional halide scintillation single crystal, and in particular relates to a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal and a preparation method and application thereof.
Background
Scintillator crystals are capable of converting high-energy ionizing radiation into low-energy luminescence, which is widely used in many fields as a core component of radiation detectors. In nuclear medicine imaging, a high-performance scintillation crystal is a core component for realizing high-resolution imaging; in the fields of homeland and social security, scintillation crystals are widely used in dangerous nuclide identification and public security inspection equipment; high energy physical and deep space detection applications also require a large number of scintillation crystals to detect high energy rays and particles. With the continuous increase of application space and the rapid improvement of technical requirements, further optimization of key parameters such as light yield, energy resolution, scintillation decay time and stability of the scintillation crystal has attracted a great deal of attention.
Recently, metal halide materials having a low-dimensional molecular structure have been widely focused on the existence of strong quantum confinement effects. As a scintillation or light-emitting material, these low-dimensional halides achieve strong electroacoustic coupling action by confinement effect while reducing the probability of trapping carriers by defects, thereby having light-emitting characteristics of low self-absorption and high quantum efficiency. In addition, these low-dimensional metal halides also tend to achieve lower melting points and better stability, which is of great importance for low-cost production and application. Among them, copper-based low-dimensional halides are an excellent scintillation crystal with efficient confinement exciton luminescence. Cs in zero dimension 3 Cu 2 I 5 For example, it has no deliquescence, low self-absorption, low melting point, high light yield (28,000 ph./MeV) and high energy resolution (4.8% @662 keV), and has been found to be Tl ion dopedCan obviously optimize light yield (87,000 ph/MeV) and energy resolution (3.4% @662 keV), and has great application prospect.
On the other hand, rare earth ion activator luminescence is the main luminescence form of the high-performance scintillation crystal at present. The diverse and efficient luminescence characteristics of rare earth ions provide a variety of scintillation crystals for radiation detection applications, but at the same time face a variety of problems. For example, srI 2 Eu, liI Eu, eu plasma (Eu) 2+ ) Doped scintillation crystals can achieve extremely high light yields and superior energy resolution due to 5d-4f allowed transitions, but suffer from severe degradation in performance with size amplification due to strong self-absorption of luminescence. Cerium ions (Ce) 3+ ) Doped scintillation crystals, e.g. LaBr 3 Ce, LYSO, ce and the like can have the advantages of high light yield, rapid decay and the like, but the performance of the crystal is bottleneck because free carriers can be captured by defects.
In addition, ytterbium ions (Yb 2+ ) Doped CsPbI 3 Perovskite scintillators have also recently been found to produce extremely high light yields through quantum clipping effects; samarium ion (Sm) 2+ ) The luminescent wavelength can be converted to a near infrared band to match a silicon-based photodetector with high detection efficiency; scandium yttrium lanthanum plasma (Sc) with non-luminous center 3+ 、Y 3+ 、La 3+ Etc.) doping can also increase the luminous efficiency of the scintillation crystal or obtain faster scintillation decay time through defect regulation. However, to date, no scintillation detection material has been proposed in the art that can meet the higher performance requirements in the fields of medical imaging, security inspection, high energy physics, etc.
Therefore, there is a need in the art to develop new high performance scintillation materials to overcome the above-mentioned drawbacks of the prior art, so as to meet the higher performance requirements of scintillation detection materials in the fields of medical imaging, security inspection, high energy physics, etc.
Disclosure of Invention
The application provides a rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal and a preparation method thereof, which can be widely applied to X-ray, gamma-ray, neutron detection and imaging, so that the problems in the prior art are solved.
According to a first aspect of the present application, there is provided a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal having the following compositional formula:
(Cs 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE, wherein:
a combination of one or more of a= Rb, K, na, tl and In;
b=one or a combination of Ag and Li;
x=one or a combination of Cl and Br;
RE is a rare earth ion selected from the group consisting of: eu (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+ The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with
X is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.25, z is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0 and less than or equal to 5.
In a preferred embodiment, x=y=z=0 and re=eu 2+ Cs, i.e 3 Cu 2 I 5 :mat%Eu 2+ 。
In another preferred embodiment, a=tl, y=z=0 and re=eu 2+ I.e. (Cs) 1-x Tl x ) 3 Cu 2 I 5 :mat%Eu 2+ 。
According to a second aspect of the present application, there is provided a method for preparing the above rare earth ion doped zero-dimensional perovskite halide scintillation single crystal, the method comprising the steps of:
the halide with the purity of more than or equal to 99.9 percent is used as a raw material, a target component is prepared according to the molar ratio of the composition formula, the raw material is filled into a sealed container, a compound meeting the composition formula is obtained by a solid phase reaction method or a molten salt cooling method, and then the target rare earth ion doped zero-dimensional perovskite halide scintillation single crystal is obtained by a Bridgman descent method or a horizontal directional solidification method.
In a preferred embodiment, the method comprises the steps of:
(1) Weighing various raw materials according to a composition formula;
(2) Placing the mixed raw materials in a crucible with a capillary bottom in an inert environment, vacuumizing and sealing the crucible, and obtaining a compound meeting the composition general formula by a solid-phase reaction method or a molten salt cooling method;
(3) Vertically placing the sealed crucible in the middle of a crystal growth furnace; heating the crystal growth furnace until the raw materials are completely melted and uniformly mixed; regulating the position and the furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value, then enabling the crucible to descend in the furnace body, and enabling crystals to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
In another preferred embodiment, the method comprises the steps of:
(1) Weighing various raw materials according to a composition formula;
(2) Placing the mixed raw materials in a crucible with a capillary bottom in an inert environment, vacuumizing and sealing the crucible, and obtaining a compound meeting the composition general formula by a solid-phase reaction method or a molten salt cooling method;
(3) Horizontally placing the sealed crucible in the middle of a horizontal directional growth furnace; heating the horizontal directional growth furnace until the raw materials are completely melted and uniformly mixed; adjusting the position and the furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value, enabling the crucible to move horizontally in the furnace body at a constant speed, and enabling crystals to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
In another preferred embodiment, in step (2), the inert environment comprises 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 ℃; the temperature of the bottom of the crucible is 330-400 ℃.
According to a third aspect of the present application there is provided the use of the rare earth ion doped zero-dimensional perovskite halide scintillation single crystal described above in X-ray, gamma ray and neutron detection and imaging, wherein the use includes use in medical imaging, security inspection and high energy physics.
The beneficial effects are that: the rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal has the advantages of low raw material cost, higher chemical stability, low melting point and easiness in preparation, meanwhile, high-efficiency scintillation luminescence is obtained through rare earth ion doping or optimization improvement, higher detection efficiency is realized, and the rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal can be used for X-ray, gamma-ray and neutron detection and imaging and has important application prospects in the fields of medical imaging, safety inspection, high-energy physics and the like.
These and other features and advantages will become apparent upon reading the following detailed description and upon reference to the associated drawings. It is to be understood that both the foregoing general description and the following detailed description are explanatory only and are not restrictive of aspects as claimed.
Drawings
FIG. 1 shows a halide scintillation single crystal Cs obtained in example 1 of the present application 3 Cu 2 I 5 :0.5%Eu 2+ Halide scintillation single crystal Cs obtained in example 2 3 Cu 2 I 5 :0.5%Pr 3+ And Cs 3 Cu 2 I 5 :0.5%Yb 2+ Photograph of sample under natural light.
FIG. 2 shows a halide scintillation single crystal (Cs) obtained in example 3 of the present application 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ Photograph of sample under natural light.
FIG. 3 shows a halide scintillation single crystal (Cs) obtained in example 4 of the present application 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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3 + Photograph of sample under natural light.
FIG. 4 shows a halide scintillation single crystal Cs obtained in example 5 of the present application 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ And the halide scintillation single crystal (Cs) obtained in example 6 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ Photograph of sample under natural light.
FIG. 5 shows a halide scintillation single crystal Cs obtained in example 1 of the present application 3 Cu 2 I 5 :0.5%Eu 2+ Is provided.
FIG. 6 shows a halide scintillation single crystal (Cs) obtained in example 3 of the present application 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ Is provided.
FIG. 7 shows a halide scintillation single crystal (Cs) obtained in example 4 of the present application 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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3 + Is compared with undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 Crystals).
FIG. 8 shows a halide scintillation single crystal Cs obtained in example 1 of the present application 3 Cu 2 I 5 :0.5%Eu 2+ And the halide scintillation single crystal SrI obtained in comparative example 2 2 :Eu 2+ Is a fluorescent spectrum of (a).
FIG. 9 shows a halide scintillation single crystal Cs obtained in example 1 of the present application 3 Cu 2 I 5 :0.5%Eu 2+ And the halide scintillation single crystal Cs obtained in comparative example 1 3 Cu 2 I 5 Gamma-ray energy spectrum of (c).
FIG. 10 shows a halide scintillation single crystal (Cs) obtained in example 4 of the present application 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Sc 3 + Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Y 3+ Gamma-ray energy spectrum of (c).
FIG. 11 shows a halide scintillation single crystal Cs obtained in example 1 of the present application 3 Cu 2 I 5 :0.5%Eu 2+ Is a flicker decay curve of (a).
FIG. 12 shows a halide scintillation single crystal Cs obtained in example 2 of the present application 3 Cu 2 I 5 :0.5%Pr 3+ And Cs 3 Cu 2 I 5 :0.5%Yb 2+ Is a flicker decay curve of (a).
Fig. 13 shows a schematic diagram of a scintillation single crystal coupled photodetector in accordance with a preferred embodiment of the present application.
Detailed Description
The features of the present application will be more fully apparent from the following detailed description, taken in conjunction with the accompanying drawings.
The "ranges" disclosed herein are defined as lower and upper limits, with the given ranges being defined by selecting a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular ranges. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, 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 are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
In this application, all embodiments and preferred embodiments mentioned herein can be combined with each other to form new solutions, unless specifically stated otherwise. In the present application, all technical features mentioned herein as well as preferred features may be combined with each other to form new solutions, if not specifically stated.
In the present application, references herein to "comprising" and "including" mean open, and may be closed, unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the description herein, unless otherwise indicated, the term "or" is inclusive. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
Aiming at the defects that the existing low-dimensional structure halide scintillation crystal has limitations in carrier utilization efficiency and scintillation efficiency and the traditional rare earth ion doped halide scintillation crystal has stability, self-absorption, radioactivity background and the like, the further application of the low-dimensional structure halide scintillation crystal in the fields of nuclear medicine imaging, homeland and social security, high-energy physics, deep space detection and the like is limited, and no solution exists in the prior art.
Cs from zero-dimensional structure 3 Cu 2 I 5 The crystal starts, the luminescence mechanism is self-trapping exciton composite luminescence provided by strong quantum confinement effect, and theoretically, high light yield of 150,000 ph/MeV can be obtained, but non-radiative quenching caused by the interaction between excitons can not obtain ideal performance. Eu in Eu 2+ The ion represents luminescent ion doping, and provides a new rare earth ion related radiation luminescent channel in the crystal, thereby improving the carrier utilization rate generated by ionization. From the characteristics of rare earth luminescent ions, the energy relaxation provided by the low-dimensional structure and the soft crystal lattice can improve the self-absorption effect of luminescence, and meanwhile, the domain-limiting effect can reduce the probability of capturing hot carriers by defects in the process of transporting the hot carriers to a luminescent center in the crystal lattice. Instead of luminescent central ions such as Y 3+ The ion doping can add new defect energy level between the energy levels of the finite field excitons, temporarily store carriers lost in the non-radiative process to shallow defect energy level, and quickly reenter the finite field exciton state to participate in scintillation luminescence.
The high quantum confinement effect of the low-dimensional metal halide scintillation crystal is combined with the high-efficiency diversified luminescence of the rare earth doped scintillation crystal, so that the novel scintillation crystal with the combined performances of low self-absorption, low defect capture probability, high luminous efficiency and the like is hopeful to be obtained. Compared with the existing low-dimensional structure halide scintillation crystal, the high-stability low-self-absorption low-radioactivity halide scintillation crystal has the advantages of being capable of obtaining higher carrier utilization efficiency and scintillation efficiency, and being higher in stability, low in self-absorption and low in radioactivity background compared with the traditional rare earth ion doped halide scintillation crystal. The rare earth ion doped low-dimensional halide scintillation crystal can provide a better scintillation crystal candidate scheme for the fields of nuclear medicine images, national and social security, high-energy physics, deep space exploration and the like.
The application provides a novel rare earth ion doped zero-dimensional perovskite halide scintillation single crystal and a preparation method thereof, and the halide scintillation single crystal can be widely applied to X-ray, gamma-ray and neutron detection and imaging, so that the problems in the prior art are solved.
The invention is characterized by providing a novel strategy of low-dimensional structure halide scintillation crystal doped with rare earth ions, and combining low-dimensional halide materials and rare earth ion doping advantagesPotential of the material. A rare earth ion doped low dimensional structure halide scintillation crystal (Cs) is provided 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mComposition of at% RE, preparation method and application. Most importantly, a rare earth doping optimization Cs is provided 3 Cu 2 I 5 Strategies based on scintillation crystal performance.
In a first aspect of the present application, there is provided a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal having the following compositional formula:
(Cs 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% (at%) RE, wherein:
a = Rb, K, na, tl, in;
b=one or a combination of Ag and Li;
x=one or a combination of Cl and Br;
RE is 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+ Plasma rare earth ion, and
0≤x≤0.1、0≤y≤0.25、0≤z≤1、0<m≤5。
in this application, the rare earth ion doped zero-dimensional perovskite halide scintillation single crystal has the following two preferred compositions: cs (cells) 3 Cu 2 I 5 :mat%Eu 2+ Sum (Cs) 1-x Tl x ) 3 Cu 2 I 5 :mat%Eu 2+ Wherein: x is more than or equal to 0 and less than or equal to 0.1, m is more than or equal to 0 and less than or equal to 5.
In a second aspect of the present application, there is provided a method for preparing a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal, the method comprising the steps of:
the method comprises the steps of taking high-purity halide with purity (more than or equal to 99.9%) as a raw material, proportioning target components according to a composition formula in a molar ratio, filling the target components into a sealed container, obtaining a compound meeting the composition formula by a solid-phase reaction method or a molten salt cooling method, and obtaining the target rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal by a Bridgman descent method or a horizontal directional solidification method.
In this application, the method comprises the steps of:
(1) According to the above general formula (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mWeighing various raw materials at%;
(2) Placing the mixed raw materials into a quartz crucible with a capillary bottom or a crucible made of other materials in an inert environment (such as a glove box filled with inert gas), and vacuumizing and sealing the crucible;
(3) Placing the sealed crucible in a tube furnace or other heating furnaces; the solid phase reaction method or the molten salt cooling method (the method increases the temperature to be higher than the melting point of the compound meeting the composition general formula, such as 400-600 ℃ to obtain higher product uniformity and reaction efficiency) is utilized to fully react the raw materials to synthesize the target component polycrystal; then placing the mixture into a Bridgman growth furnace; regulating the position and furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value (for example, 330-400 ℃), then enabling the crucible to descend in the furnace body, and enabling crystals to start to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
In this application, the method comprises the steps of:
(1) According to the above general formula (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mWeighing various raw materials at%;
(2) Placing the mixed raw materials into a quartz crucible with a capillary bottom or a crucible made of other materials in an inert environment (such as a glove box filled with inert gas), and vacuumizing and sealing the crucible;
(3) Placing the sealed crucible in a tube furnace or other heating furnaces; the solid phase reaction method or the molten salt cooling method (the method increases the temperature to be higher than the melting point of the compound meeting the composition general formula, such as 400-600 ℃ to obtain higher product uniformity and reaction efficiency) is utilized to fully react the raw materials to synthesize the target component polycrystal; then horizontally placing the mixture into a horizontal directional growth furnace; adjusting the position and the furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value (for example, 330-400 ℃), enabling the crucible to move horizontally in the furnace body at a constant speed, and enabling crystals to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
In a third aspect of the present application, there is provided the use of the rare earth ion doped zero-dimensional perovskite halide scintillation single crystal described above in X-ray, gamma ray and neutron detection and imaging, wherein the use includes use in medical imaging, security inspection and high energy physics.
In the application, the monocrystalline material prepared by the method can be directly coupled with a photoelectric device for high-energy ionization radiation detection after being subjected to cutting, grinding and polishing treatment, is most typically applied to gamma energy spectrum detection, and is also suitable for being applied to the fields of medical imaging, homeland security, physical research and the like through detection of X-rays, alpha particles, beta particles, neutrons and the like according to specific requirements.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1: the zero-dimensional perovskite halide scintillation single crystal proposed in the present example 1 has the composition chemical formula Cs 3 Cu 2 I 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0, y=0, z=0, m=0.5, re=eu 2+ The above halide flashThe scintillation single crystal is prepared by a Bridgman descent method, and the preparation process comprises the following operations: intrinsic halide scintillation single crystal composition formula Cs prepared on demand 3 Cu 2 I 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with argon; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 550 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 350 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 7 ℃ per hour until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and subjected to cutting processing.
Testing the radiant luminescence spectrum and the photoluminescence excitation and emission spectrum of the scintillation single crystal, and besides intrinsic self-limiting exciton luminescence, a new Eu exists 2+ And a light-emitting center. Coupling to photomultiplier tube to test Cs 3 Cu 2 I 5 :0.5%Eu 2+ The light yield of the crystals was 60,000 ph/MeV and the energy resolution was 4.0%. Compared with undoped Cs 3 Cu 2 I 5 The crystal has 1.1 times of light yield and 0.8 percent of energy resolution optimized. SrI of non-low dimensional structure 2 :Eu 2+ Eu in crystal 2+ The ion luminescence has strong self-absorption effect, and Cs with low-dimensional crystal structure 3 Cu 2 I 5 :0.5%Eu 2+ Eu in crystal 2+ The self-absorption phenomenon of the ion luminescence is obviously optimized.
Comparative example 1: the chemical composition formula is Cs 3 Cu 2 I 5 The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) Intrinsic halide scintillator composition on demand formula Cs 3 Cu 2 I 5 Weighing the raw materials; b) Placing each raw material in a glove box filled with argon and provided with a capillary bottomIs arranged in the quartz crucible; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 550 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 350 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 7 ℃ per hour until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and subjected to cutting processing.
Coupling to photomultiplier tube to test Cs 3 Cu 2 I 5 The light yield of the crystals was 28,000 ph/MeV and the energy resolution was 4.8%.
Comparative example 2: the chemical composition formula is SrI 2 :Eu 2+ The scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) On-demand intrinsic halide scintillator composition formula SrI 2 :Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with argon; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growing furnace to about 600 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 530 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 7 ℃ per hour until the temperature is reduced to the room temperature; finally, the prepared halide scintillator is taken out of the quartz crucible in a dry environment and subjected to cutting processing.
The above scintillation crystal was tested for photoluminescence excitation and emission spectra and found to have severe self-absorption.
Example 2: the four zero-dimensional perovskite halide scintillation single crystals proposed in this example 2 have a composition chemical formula 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+ I.e. in (Cs) 1- x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0, y=0, z=0, m=0.5, re=pr 3+ 、Yb 2+ 、Sm 2+ And Ce (Ce) 3+ The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) Intrinsic halide scintillation single crystal composition formula Cs prepared on demand 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+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 550 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 350 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 0.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 7 ℃ per hour until the temperature is reduced to the room temperature; finally, the prepared crystal is taken out from the quartz crucible.
Coupling to photomultiplier tube to test Cs 3 Cu 2 I 5 :0.5%Pr 3+ And Cs 3 Cu 2 I 5 :0.5%Yb 2+ Light yield of crystals compared to undoped Cs 3 Cu 2 I 5 The crystals were all lifted at 40,000 ph/MeV and 45,000 ph/MeV, respectively; the energy resolution was 4.2% and 4.5%, respectively. Compared with undoped Cs 3 Cu 2 I 5 Decay time of Cs 3 Cu 2 I 5 :0.5%Ce 3+ The scintillation decay time of the crystal is 561 ns, which is accelerated by about 40%.
Example 3: the zero-dimensional perovskite halide scintillation single crystal proposed in this example 3 has a composition formula (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0.01, y=0, z=0, m=0.5, a=tl, re=eu 2+ The halide scintillation single crystal is prepared by adopting a horizontal directional solidification method, and the preparation process comprises the following operations: a) The intrinsic halide scintillator composition formula (Cs) as prepared on demand 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then the crucible is vacuumized and sealed; c) Horizontally placing the sealed quartz crucible in the middle of a horizontal directional growth furnace; heating the crystal growing furnace to about 600 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the capillary temperature of the crucible to about 360 ℃, and then enabling the quartz crucible to horizontally move at a constant speed in the furnace body at a moving speed of 0.7 mm/h, wherein crystals start to nucleate and grow from the capillary position of the crucible until the melt is completely solidified; then cooling at a rate of 10 ℃ per hour until the temperature is reduced to room temperature; finally, the prepared crystal is taken out from the quartz crucible.
Testing the radiation luminescence spectrum and photoluminescence excitation and emission spectrum of the scintillation crystal, and besides intrinsic self-limiting exciton luminescence and Tl ion binding exciton luminescence, a new Eu exists 2+ And a light-emitting center. Is coupled to a photomultiplier tube to obtain (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ The light yield of the crystals was 93,000 ph/MeV and the energy resolution was 3.3%. Compared with undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 The crystal has improved light yield by 7%, and excellent energy resolution0.1 percentage points are normalized.
Example 4: the four zero-dimensional perovskite halide scintillation single crystals proposed in this example 4 have a composition 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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0.01, y=0, z=0, m=0.5, a=tl, re=sc 3+ 、Y 3+ 、La 3+ And Lu 3+ The halide scintillation single crystal is prepared by adopting a horizontal directional solidification method, and the preparation process comprises the following operations: a) An intrinsic halide scintillation single crystal composition formula (Cs) prepared on demand 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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then the crucible is vacuumized and sealed; c) Horizontally placing the sealed quartz crucible in the middle of a horizontal directional growth furnace; heating the crystal growing furnace to about 600 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the capillary temperature of the crucible to about 360 ℃, and then enabling the quartz crucible to horizontally move at a constant speed in the furnace body at a moving speed of 0.8 mm/h, wherein crystals start to nucleate and grow from the capillary position of the crucible until the melt is completely solidified; then cooling at a rate of 10 ℃ per hour until the temperature is reduced to room temperature; finally, the prepared crystal is taken out from the quartz crucible。
Coupled to photomultiplier tube test (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Y 3+ The light yield of the crystals was 90,000 ph/MeV. Compared with undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 The crystal and the light yield are improved by 3 percent. (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Sc 3+ The decay time of (a) is 750ns, compared to undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 The crystal is accelerated by about 20 percent.
Example 5: the zero-dimensional perovskite halide scintillation single crystal proposed in this example 5 has a composition chemical formula of Cs 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0, y=0, z=0.2, m=0.5, x=br, re=eu 2+ . The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) Intrinsic halide scintillation single crystal composition formula Cs prepared on demand 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with nitrogen; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growing furnace to about 600 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 370 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 1.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a rate of 12 ℃ per hour until the temperature is reduced to room temperature; finally, the prepared crystal is taken out from the quartz crucible.
The resulting Cs 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ The crystal has good crystallinity, no deliquescence and small self absorption, can grow single crystals with good crystal quality at a faster descending speed and a cooling speed, and has obvious advantages for large-size crystal growth. Coupling to photomultiplier tube to test Cs 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ The crystals had a light yield of 60,000 ph/MeV and an energy resolution of 4.2% compared to undoped Cs 3 Cu 2 I 5 The crystal has 40% raised light yield and optimized energy resolution of 0.6% point.
Example 6: the zero-dimensional perovskite halide scintillation single crystal of example 6 has a composition formula (Cs 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0.01, y=0, z=0.2, m=0.5, a=tl, b=br, re=eu 2+ . The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) An intrinsic halide scintillation single crystal composition formula (Cs) prepared on demand 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with argon; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 550 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 370 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 1.5 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a rate of 12 ℃ per hour until the temperature is reduced to room temperature; finally, the prepared crystal is taken out from the quartz crucible.
The resulting (Cs) 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ The crystal has good crystallinity, no deliquescence and small self absorption, can grow single crystals with good crystal quality at a faster descending speed and a cooling speed, and has obvious advantages for large-size crystal growth. Is coupled to a photomultiplier tube to obtain (Cs 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ The crystals had a light yield of 110,000 ph/MeV and an energy resolution of 3.2% compared to undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 The crystal has 26% raised light yield and optimized energy resolution of 0.2% point.
Example 7: the zero-dimensional perovskite halide scintillation single crystal proposed in this example 7 has a composition formula (Cs 0.9 Rb 0.1 ) 3 Cu 2 I 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the general formula x=0.1, y=0, z=0, m=0.5, a=rb, re=eu 2+ . The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) An intrinsic halide scintillation single crystal composition formula (Cs) prepared on demand 0.9 Rb 0.1 ) 3 Cu 2 I 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with argon; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growing furnace to about 600 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 370 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 1.0 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at a rate of 10 ℃ per hour until the temperature is reduced to room temperature; finally, taking out the quartz crucible to finish the preparationIs a crystal of (a).
The gamma ray and X ray energy spectrum test result shows that (Cs) 0.9 Rb 0.1 ) 3 Cu 2 I 5 :0.5%Eu 2+ The scintillation single crystal has the radiation detection performance, 137 gamma-ray energy spectrum under Cs irradiation shows (Cs 0.9 Rb 0.1 ) 3 Cu 2 I 5 :0.5%Eu 2+ The energy resolution is better and the energy of the light source is better, 137 the scintillation decay curve under Cs irradiation shows (Cs 0.9 Rb 0.1 ) 3 Cu 2 I 5 :0.5%Eu 2+ The attenuation time is faster, and the method can be applied to the fields of medical imaging, safety inspection, high-energy physics and the like.
Example 8: the zero-dimensional perovskite halide scintillation single crystal of the embodiment 8 has the chemical formula Cs 3 (Cu 0.9 Ag 0.1 ) 2 I 5 :0.5%Eu 2+ I.e. in (Cs) 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE is of the formula x=0, y=0.1, z=0, m=0.5, b=ag, re=eu 2+ . The halide scintillation single crystal is prepared by adopting a Bridgman descent method, and the preparation process comprises the following operations: a) Intrinsic halide scintillation single crystal composition formula Cs prepared on demand 3 (Cu 0.9 Ag 0.1 ) 2 I 5 :0.5%Eu 2+ Weighing the raw materials; b) Placing the raw materials into a quartz crucible with a capillary bottom in a glove box filled with argon; then the crucible is vacuumized and sealed; c) Vertically placing the sealed quartz crucible in the middle of a crystal growth furnace; heating the crystal growth furnace to reach 550 ℃ until the raw materials are completely melted and uniformly mixed; regulating the position and furnace temperature of the crucible, reducing the temperature of the bottom of the crucible to about 350 ℃, then reducing the quartz crucible in the furnace body at the reducing speed of 1.0 mm/h, and starting nucleation and growth of crystals from the capillary bottom of the crucible until the melt is completely solidified; then cooling at the speed of 7 ℃ per hour until the temperature is reduced to the room temperature; finally, the prepared crystal is taken out from the quartz crucible.
Gamma-ray and X-ray energy spectrumThe test results show that Cs 3 (Cu 0.9 Ag 0.1 ) 2 I 5 :0.5%Eu 2+ The scintillation single crystal has the radiation detection performance, 137 the gamma-ray energy spectrum under Cs irradiation shows Cs 3 (Cu 0.9 Ag 0.1 ) 2 I 5 :0.5%Eu 2+ The energy resolution is better and the energy of the light source is better, 137 the scintillation decay curve under Cs irradiation indicates Cs 3 (Cu 0.9 Ag 0.1 ) 2 I 5 :0.5%Eu 2+ The attenuation time is faster, and the method can be applied to the fields of medical imaging, safety inspection, high-energy physics and the like.
FIG. 1 shows a photograph of a sample of the halide scintillation single crystal obtained in examples 1-2 of the present application under natural light. As shown in FIG. 1, the resulting Cs 3 Cu 2 I 5 :0.5%Eu 2+ 、Cs 3 Cu 2 I 5 :0.5%Pr 3+ And Cs 3 Cu 2 I 5 :0.5%Yb 2+ The monocrystal is transparent and has no inclusion.
FIG. 2 is a photograph showing a sample of a halide scintillation single crystal obtained in example 3 of the present application under natural light. As shown in FIG. 2, the resulting (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ The monocrystal is transparent and has no inclusion.
FIG. 3 is a photograph showing a sample of the halide scintillation single crystal obtained in example 4 of the present application under natural light. As shown in FIG. 3, the resulting (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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3+ The monocrystal is transparent and has no inclusion.
FIG. 4 shows photographs of samples of halide scintillation single crystals obtained in examples 5 to 6 of the present application under natural light. As shown in FIG. 4, the resulting Cs 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 (I 0.8 Br 0.2 ) 5 :0.5%Eu 2+ The monocrystal is transparent and has no inclusion.
Fig. 5 shows the radiant emission spectrum of the halide scintillation single crystal obtained in example 1 of the present application. As shown in FIG. 5, the resulting Cs 3 Cu 2 I 5 :0.5%Eu 2+ The single crystal has an emission peak of 450 nm and 560 nm at X-ray excitation.
Fig. 6 shows the radiant emission spectrum of the halide scintillation single crystal obtained in example 3 of the present application. As shown in FIG. 6, the resulting (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Eu 2+ The single crystal has an emission peak of 510 and nm under X-ray excitation.
Fig. 7 shows the radiant emission spectrum of the halide scintillation single crystal obtained in example 4 of the present application. As shown in fig. 7, compared with undoped (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 Crystals, the resulting (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+ Sum (Cs) 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Lu 3+ The emission peak of the single crystal under X-ray excitation was not significantly changed, both at 510 and nm.
Fig. 8 shows fluorescence spectra of halide scintillation single crystals obtained in example 1 and comparative example 2 of the present application. As shown in fig. 8, compared with SrI 2 Eu crystal, cs obtained 3 Cu 2 I 5 :0.5%Eu 2+ The single crystal has little self-absorption.
Fig. 9 shows gamma ray energy spectra of the halide scintillation single crystals obtained in example 1 and comparative example 1 of the present application. As shown in FIG. 9, compared to undoped Cs 3 Cu 2 I 5 Crystals, the resulting Cs 3 Cu 2 I 5 :0.5%Eu 2+ Light yield and single crystalThe energy resolution is optimized.
Fig. 10 shows a gamma ray energy spectrum of a halide scintillation single crystal obtained in example 4 of the present application. As shown in FIG. 10, the resulting (Cs 0.99 Tl 0.01 ) 3 Cu 2 I 5 :0.5%Y 3+ The energy resolution and light yield of the single crystal are optimized.
Fig. 11 shows a scintillation decay curve of the halide scintillation single crystal obtained in example 1 of the present application. As shown in FIG. 11, the resulting Cs 3 Cu 2 I 5 :0.5%Eu 2+ The scintillation decay time of the single crystal has a fast component of 152 ns and a slow component of 995 ns, respectively.
Fig. 12 shows a scintillation decay curve of the halide scintillation single crystal obtained in example 2 of the present application. As shown in FIG. 12, the resulting Cs 3 Cu 2 I 5 :0.5%Pr 3+ The scintillation decay time of the single crystal, there is a fast component of 170 ns and a slow component of 995 ns, respectively; the resulting Cs 3 Cu 2 I 5 :0.5%Yb 2+ The scintillation decay time of the single crystal has a fast component of 195 ns and a slow component of 1000 ns, respectively.
Fig. 13 shows a schematic diagram of a scintillation single crystal coupled photodetector in accordance with a preferred embodiment of the present application. As shown in fig. 13, the scintillation crystal 1 converts incident high-energy rays (including γ rays, and other high-energy rays such as β or neutrons) into ultraviolet light or visible light, and collects the scintillation light into the photomultiplier tube 3 through the reflection layer 2 as much as possible, converts an optical signal into an electrical signal (digital signal) through photoelectric conversion, and finally outputs the signal after processing by the electronics 4.
Finally, what is necessary here is: the above embodiments are only for further detailed description of the technical solutions of the present invention, and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments made by those skilled in the art from the above disclosure are all within the scope of the present invention.
Claims (8)
1. A rare earth ion doped zero-dimensional perovskite halide scintillation single crystal is characterized by having the following composition general formula:
(Cs 1-x A x ) 3 (Cu 1-y B y ) 2 (I 1-z X z ) 5 :mat% RE, wherein:
a combination of one or more of a= Rb, K, na, tl and In;
b=one or a combination of Ag and Li;
x=one or a combination of Cl and Br;
RE is a rare earth ion selected from the group consisting of: eu (Eu) 2+ 、Yb 2+ 、Sc 3+ 、Y 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ And Tb 3 + The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with
X is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 1 and m is more than or equal to 0 and less than or equal to 5, wherein x, y and z are not 0 at the same time.
2. A method for preparing the rare earth ion doped zero-dimensional perovskite halide scintillation single crystal as recited in claim 1, comprising the steps of:
the halide with the purity of more than or equal to 99.9 percent is used as a raw material, a target component is prepared according to the molar ratio of the composition formula, the raw material is filled into a sealed container, a compound meeting the composition formula is obtained by a solid phase reaction method or a molten salt cooling method, and then the target rare earth ion doped zero-dimensional perovskite halide scintillation single crystal is obtained by a Bridgman descent method or a horizontal directional solidification method.
3. A method as claimed in claim 2, characterized in that the method comprises the steps of:
(1) Weighing various raw materials according to a composition formula;
(2) Placing the mixed raw materials in a crucible with a capillary bottom in an inert environment, vacuumizing and sealing the crucible, and obtaining a compound meeting the composition general formula by a solid-phase reaction method or a molten salt cooling method;
(3) Vertically placing the sealed crucible in the middle of a crystal growth furnace; heating the crystal growth furnace until the raw materials are completely melted and uniformly mixed; regulating the position and the furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value, then enabling the crucible to descend in the furnace body, and enabling crystals to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
4. A method as claimed in claim 2, characterized in that the method comprises the steps of:
(1) Weighing various raw materials according to a composition formula;
(2) Placing the mixed raw materials in a crucible with a capillary bottom in an inert environment, vacuumizing and sealing the crucible, and obtaining a compound meeting the composition general formula by a solid-phase reaction method or a molten salt cooling method;
(3) Horizontally placing the sealed crucible in the middle of a horizontal directional growth furnace; heating the horizontal directional growth furnace until the raw materials are completely melted and uniformly mixed; adjusting the position and the furnace temperature of the crucible, enabling the temperature of the bottom of the crucible to reach a preset value, enabling the crucible to move horizontally in the furnace body at a constant speed, and enabling crystals to nucleate and grow from the capillary bottom of the crucible until the melt is completely crystallized; then cooling until the temperature is reduced to room temperature;
(4) And taking out the prepared rare earth ion doped zero-dimensional perovskite halide scintillation monocrystal from the crucible in a dry environment.
5. The method of claim 3 or 4, wherein in step (2), the inert environment comprises a glove box.
6. The method of claim 3 or 4, wherein in step (2), the crucible comprises a quartz crucible.
7. The method according to claim 3 or 4, wherein in step (3), the crystal growth furnace or the horizontally oriented growth furnace is heated to 400 to 600 ℃; the temperature of the bottom of the crucible is 330-400 ℃.
8. Use of a rare earth ion doped zero-dimensional perovskite halide scintillation single crystal as defined in claim 1 in X-ray, gamma ray and neutron detection and imaging, including medical imaging, security inspection and high energy physics.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202410034956.7A CN117552106B (en) | 2024-01-10 | 2024-01-10 | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202410034956.7A CN117552106B (en) | 2024-01-10 | 2024-01-10 | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117552106A true CN117552106A (en) | 2024-02-13 |
CN117552106B CN117552106B (en) | 2024-04-05 |
Family
ID=89813109
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202410034956.7A Active CN117552106B (en) | 2024-01-10 | 2024-01-10 | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117552106B (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
CN110606505A (en) * | 2019-10-21 | 2019-12-24 | 江苏科技大学 | Zero-dimensional halogen perovskite structure material Cs4PbBr6Preparation and use of |
CN113136203A (en) * | 2021-03-26 | 2021-07-20 | 南京理工大学 | Thallium-doped Cs with high luminous yield3Cu2I5Nanocrystalline scintillator |
CN113373501A (en) * | 2021-06-10 | 2021-09-10 | 天津理工大学 | EuCl3Helper Cs3Cu2X5Method for growing perovskite single crystal |
CN113529168A (en) * | 2021-07-01 | 2021-10-22 | 中国计量大学 | Li+Zero-dimensional perovskite structure doped metal halide scintillation crystal and preparation method and application thereof |
CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
CN113957525A (en) * | 2021-08-03 | 2022-01-21 | 中国计量大学 | Li for neutron/gamma retort+Halide-doped scintillation crystal and preparation method thereof |
CN114276802A (en) * | 2021-12-27 | 2022-04-05 | 南京理工大学 | Preparation method of thallium-doped cesium-copper-iodine scintillator film for inhibiting oxidation and precipitation of iodide ions |
CN114411252A (en) * | 2022-01-24 | 2022-04-29 | 中国科学院上海硅酸盐研究所 | Novel perovskite-like structure scintillator for neutron detection and preparation method and application thereof |
CN115565712A (en) * | 2022-09-20 | 2023-01-03 | 西北核技术研究所 | Long-life alpha-type photovoltaic isotope battery |
CN116855750A (en) * | 2023-05-22 | 2023-10-10 | 山东大学 | High light yield, ultrafast scintillation attenuation and low cost Cs 3 Cu 2 I 5 Mn monocrystal scintillator, preparation and application thereof |
-
2024
- 2024-01-10 CN CN202410034956.7A patent/CN117552106B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
CN110606505A (en) * | 2019-10-21 | 2019-12-24 | 江苏科技大学 | Zero-dimensional halogen perovskite structure material Cs4PbBr6Preparation and use of |
CN113897666A (en) * | 2020-06-22 | 2022-01-07 | 中国科学院上海硅酸盐研究所 | Intrinsically luminous halide scintillation crystal and preparation method and application thereof |
CN113136203A (en) * | 2021-03-26 | 2021-07-20 | 南京理工大学 | Thallium-doped Cs with high luminous yield3Cu2I5Nanocrystalline scintillator |
CN113373501A (en) * | 2021-06-10 | 2021-09-10 | 天津理工大学 | EuCl3Helper Cs3Cu2X5Method for growing perovskite single crystal |
CN113529168A (en) * | 2021-07-01 | 2021-10-22 | 中国计量大学 | Li+Zero-dimensional perovskite structure doped metal halide scintillation crystal and preparation method and application thereof |
CN113957525A (en) * | 2021-08-03 | 2022-01-21 | 中国计量大学 | Li for neutron/gamma retort+Halide-doped scintillation crystal and preparation method thereof |
CN114276802A (en) * | 2021-12-27 | 2022-04-05 | 南京理工大学 | Preparation method of thallium-doped cesium-copper-iodine scintillator film for inhibiting oxidation and precipitation of iodide ions |
CN114411252A (en) * | 2022-01-24 | 2022-04-29 | 中国科学院上海硅酸盐研究所 | Novel perovskite-like structure scintillator for neutron detection and preparation method and application thereof |
CN115565712A (en) * | 2022-09-20 | 2023-01-03 | 西北核技术研究所 | Long-life alpha-type photovoltaic isotope battery |
CN116855750A (en) * | 2023-05-22 | 2023-10-10 | 山东大学 | High light yield, ultrafast scintillation attenuation and low cost Cs 3 Cu 2 I 5 Mn monocrystal scintillator, preparation and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN117552106B (en) | 2024-04-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5389328B2 (en) | Single crystal for scintillator containing Pr, its manufacturing method, radiation detector and inspection apparatus | |
US20230235219A1 (en) | Low-dimensional perovskite-structured metal halide and preparation method and application thereof | |
US20230002927A1 (en) | Li+ doped metal halide scintillation crystal with zero-dimensional perovskite structure, preparation method and use thereof | |
He et al. | Scintillation Properties of $\beta $-Ga 2 O 3 Single Crystal Excited by $\alpha $-Ray | |
CN105332056A (en) | Divalent metal cation and cerium co-doped lutetium aluminum garnet crystal for laser illumination and preparation method thereof | |
Dickens et al. | Increased luminescence and improved decay kinetics in lithium and cerium co-doped yttrium aluminum garnet scintillators grown by the Czochralski method | |
CN114411252B (en) | Novel perovskite-like structure scintillator for neutron detection, and preparation method and application thereof | |
CN113897666A (en) | Intrinsically luminous halide scintillation crystal and preparation method and application thereof | |
CN106048725B (en) | Silicon ytterbium ion is co-doped with YAG fast flashing crystal and preparation method thereof | |
CN105908257B (en) | Calcium ytterbium ion is co-doped with YAG fast flashing crystal and preparation method thereof | |
CN108441960A (en) | Divalent metal is co-doped with lutetium aluminum carbuncle crystal preparation method with cerium | |
US7347956B2 (en) | Luminous material for scintillator comprising single crystal of Yb mixed crystal oxide | |
Wu et al. | A homogeneity study on (Ce, Gd) 3 Ga 2 Al 3 O 12 crystal scintillators grown by an optical floating zone method and a traveling solvent floating zone method | |
CN117552106B (en) | Rare earth-based zero-dimensional perovskite halide scintillation monocrystal as well as preparation method and application thereof | |
CN106048724B (en) | Sodium barium ytterbium ion is co-doped with YAG fast flashing crystal and preparation method thereof | |
CN112390278B (en) | Strong electron-withdrawing element doped rare earth orthosilicate scintillation material and preparation method and application thereof | |
CN108893779A (en) | A kind of calcium ions and magnesium ions and cerium co-doped yttrium aluminium garnet scintillation crystal and preparation method thereof | |
CN115506007A (en) | Near-infrared luminous metal halide scintillation crystal and preparation method and application thereof | |
Nikl et al. | Single-crystal scintillation materials | |
CN105297136A (en) | Cerium-doped gadolinium lutecium aluminate garnet crystal for laser illumination and preparation method thereof | |
CN113512757A (en) | Large-block high-quality scintillation crystal and preparation method and application thereof | |
Barbaran et al. | Growth and spectral properties of Ce 3: YAG single crystal | |
CN117304933B (en) | Rare earth cluster reinforced low-dimensional halide scintillation material and preparation method and application thereof | |
CN108505117A (en) | Sodium calcium ytterbium ion is co-doped with YAG fast flashing crystal and preparation method thereof | |
CN110004485A (en) | A kind of scintillation crystal and preparation method thereof of rare earth element cerium dopping |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |