阅读说明：本技术 一种阴离子掺杂石榴石闪烁体及其制备方法与应用 (Anion-doped garnet scintillator and preparation method and application thereof ) 是由 丁栋舟 祁强 赵书文 杨帆 孟猛 施俊杰 袁晨 任国浩 于 2020-12-24 设计创作，主要内容包括：本发明涉及一种阴离子掺杂石榴石闪烁体及其制备方法与应用,该阴离子掺杂石榴石闪烁体的化学式为：(RE-(1-a-b)A-aB-b)-3(C-(1-d)D-d)-5(O-(1-ne)E-e)-(12),式中0＜a≤0.05,0≤b≤0.05,0≤d≤1,0＜e≤0.1,n=0.5或1.5；E离子取代O离子格位；所述RE选自镧La、钆Gd、镥Lu、钇Y中至少一种；所述E选自氟F、氯Cl、氮N中至少一种。(The invention relates to an anion-doped garnet scintillator and a preparation method and application thereof, wherein the anion-doped garnet scintillator has the chemical formula: (RE) 1‑a‑b A a B b ) 3 (C 1‑d D d ) 5 (O 1‑ne E e ) 12 Wherein a is more than 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, d is more than or equal to 0 and less than or equal to 1, e is more than 0 and less than or equal to 0.1, and n =0.5 or 1.5; e ions replace O ion lattice sites; the RE is at least one of La, Gd, Lu and Y; and E is selected from at least one of fluorine F, chlorine Cl and nitrogen N.)

1. An anion-doped garnet scintillation material, characterized in that the anion-doped garnet scintillation material has the chemical formula: (RE)_1-a-bA_aB_b)₃(C_1-dD_d)₅(O_1-neE_e)₁₂Wherein a is more than 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, d is more than or equal to 0 and less than or equal to 1, e is more than 0 and less than or equal to 0.1, and n =0.5 or 1.5; e ions replace O ion lattice sites;

the RE is at least one of La, Gd, Lu and Y; and E is selected from at least one of fluorine F, chlorine Cl and nitrogen N.

2. The anion doped garnet scintillation material as claimed in claim 1, characterized in that a is selected from at least one of cerium Ce, praseodymium Pr, neodymium Nd, europium Eu, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb;

b is selected from at least one of Li, Na, K, Mg, Ca, Sr, Cu, Zn, Ti, V, Mn and Sc;

c is selected from at least one of scandium Sc, aluminum Al and gallium Ga;

and D is selected from at least one of Zn, Ti, V V, Fe Fe, Cr, Mn, Co, Cu, Pb, Zr, W and In.

3. The anion-doped garnet scintillation material as claimed in claim 1 or 2, characterized in that when E is at least one of fluorine F, chlorine Cl, 0.0001 < E ≦ 0.1, preferably 0.0005 ≦ E ≦ 0.1;

and when E is N, 0.0005 is less than or equal to E is less than or equal to 0.05.

4. The anion doped garnet scintillation material of any of claims 1 to 3, wherein the anion doped garnet scintillation material is an anion doped garnet scintillation polycrystalline powder, an anion doped garnet scintillation ceramic, or an anion doped garnet scintillation single crystal.

5. A method for preparing anion-doped garnet scintillating polycrystalline powder, which is characterized by comprising the following steps:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) and carrying out solid phase reaction on the obtained mixed powder at 1000-1850 ℃ for 5-100 hours to obtain the anion-doped garnet scintillation polycrystalline powder.

6. A preparation method of anion-doped garnet scintillating ceramic is characterized by comprising the following steps:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) and pressing and molding the mixed powder, and carrying out solid-phase reaction for 5-100 hours at 1000-1850 ℃ to obtain the anion-doped garnet scintillating ceramic.

7. The method according to claim 6, wherein the compression molding is dry compression molding or/and cold isostatic pressing; preferably, the pressure of the dry pressing is 20-35 MPa, and the pressure of the cold isostatic pressing is 200-300 MPa.

8. The preparation method of claim 6 or 7, wherein the obtained anion-doped garnet scintillation ceramic is subjected to hot isostatic pressing and annealing treatment to obtain an anion-doped garnet transparent scintillation ceramic;

the hot isostatic pressing treatment atmosphere is inert atmosphere, the temperature is 1400-1450 ℃, the hot isostatic pressure is 160-250 MPa, the time is 2-3 hours, and the preferred inert atmosphere is argon atmosphere;

the annealing treatment atmosphere is air atmosphere, the temperature is 1000-1300 ℃, and the time is 10-30 hours.

9. A method for preparing an anion-doped garnet scintillation single crystal, comprising:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) heating the mixed powder or the anion-doped garnet scintillation polycrystalline powder to be molten, and growing the anion-doped garnet scintillation single crystal by adopting a pulling method, a Bridgman method, a temperature gradient method, a heat exchange method, a kyropoulos method, a top seed crystal method, a fluxing agent crystal growth method or a micro-pulling method.

10. Use of the anion-doped garnet scintillation material of any one of claims 1 to 4 in the fields of high-energy physical detection and particle discrimination and fast nuclear medical imaging.

Technical Field

The invention relates to an anion-doped garnet scintillator (or anion-doped garnet scintillating material) and a preparation method and application thereof, belonging to the technical field of scintillating materials.

Background

An inorganic scintillator is an energy conversion medium that converts high-energy rays (X-rays, gamma rays) or high-energy particles (alpha particles, beta particles, etc.) into ultraviolet-visible light. Detectors made of inorganic scintillating crystals have been widely used in the fields of high-energy physics, nuclear medicine imaging (XCT, PET), security inspection, nondestructive inspection, geological exploration, environmental monitoring, and the like. With the rapid development of nuclear medicine imaging and related technologies, scintillation crystals with higher performance are required, so that the scintillation crystals such as nai (tl), BGO, PWO and the like in the current market cannot meet the application requirements, and the aluminate crystals of the new generation gradually become research hotspots due to the characteristics of high light output, rapid attenuation and the like.

The garnet structure belongs to a cubic crystal system, has the highest symmetry and has higher density. With rare earth ions Ce³⁺As an activator, use is made of Ce³⁺The 5d → 4f parity of (c) allows transitions to achieve fast decay luminescence, such as: ce YAG, LuAG, Ce, GAGG, Ce, etc. are emerging as a new flashScintillating materials, particularly GAGG: Ce, have been the focus of research. In order to more accurately detect high-energy rays, researchers have proposed time-of-flight (TOF) techniques, with scintillators having fast decay times and high light yields being the key to providing accurate TOF information.

The difference of ion radius between ions leads to the change of crystal lattice constant and the disordered distribution of ions, and the crystal field can be finely adjusted by adjusting the crystal components. For Ce ion doped garnet scintillation systems, the relevant literature focuses on co-doping ions to optimize the scintillation properties of the crystal. Patent 1(CN106048725A) discloses a silicon ytterbium ion codoped YAG ultrafast scintillation crystal and a preparation method thereof, wherein ytterbium ions replace yttrium ion lattice sites, silicon ions replace aluminum ion lattice sites, and the prepared YAG crystal codoped with silicon and ytterbium ions has the advantages of fast decay time, strong irradiation damage resistance and the like, but the light yield is only 2800 ph/MeV. Patent 2(CN108218417A) relates to the chemical formula (Lu)_1-x-yCe_xMe_y)₃Al₅O₁₂Me is Ca²⁺、Ba²⁺、Zn²⁺X is more than 0 and less than or equal to 0.05, and y is more than 0 and less than or equal to 0.1; when LuAG is 0.3% Ce, 0.3% Li, LuAG is 0.3% Ce, 0.1% Mg decay time is obviously reduced. WANG et al (nucleic Instruments and Methods in Physics Research A,2016,820:8-13) found that in GYGAG, the Gd to Y ratio was adjusted in (Gd)₂Y₁)Ga_2.7Al_2.3O₁₂1 at.% has the highest scintillation efficiency. Patent 3(WO2017059832A1) discloses a method for shortening the scintillation response of luminescence centers, Nd-doped GAGG: Ce in radioisotopes²²The decay time accelerates from 91ns to 54ns under excitation by gamma radiation with 511keV photon energy of Na, but the decay time is still longer. In order to meet the requirements of high-energy physics, TOF technology application and the like, a scintillator having better scintillation performance is required. The existing patents basically study the doping at each cationic site, but do not study the effect of anionic doping on time.

Disclosure of Invention

According to the practical application needs, the invention aims to provide an anion-doped garnet scintillation material and a preparation method thereof, which can better meet the requirements of the application in the fields of high-energy physical detection, particle discrimination and nuclear medicine imaging (X-CT and TOF-PET).

In a first aspect, the present invention provides an anion-doped garnet scintillation material having the formula: (RE)_1-a-bA_aB_b)₃(C_1-dD_d)₅(O_1-neE_e)₁₂In the formula, a is more than 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, d is more than or equal to 0 and less than or equal to 1, e is more than 0 and less than or equal to 0.1, and n is 0.5 or 1.5; e ions replace O ion lattice sites;

the RE is at least one of La, Gd, Lu and Y; and E is selected from at least one of fluorine F, chlorine Cl and nitrogen N.

In the present disclosure, the substitution behavior of E dopant ions in crystals depends mainly on the number of charges, ionic radius, electronegativity, and coordination environment. D ions are in a regular tetrahedron formed by enclosing 4 oxygen ions or in a regular octahedron formed by enclosing 6 oxygen ions; the point defect structure of the crystal is changed by changing the charge compensation mechanism of the material or influencing the vacancy defect concentration in the material, thereby influencing the scintillation property of the material.

Preferably, A is selected from at least one of cerium Ce, praseodymium Pr, neodymium Nd, europium Eu, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm and ytterbium Yb;

b is selected from at least one of Li, Na, K, Mg, Ca, Sr, Cu, Zn, Ti, V, Mn and Sc;

c is selected from at least one of scandium Sc, aluminum Al and gallium Ga;

and D is at least one selected from Zn, Ti, V V, Fe Fe, Cr, Mn, Co, Cu, Pb, Zr, Si, W and In.

Preferably, when E is at least one of F and Cl, 0.0001 < e.ltoreq.0.1, preferably 0.0005. ltoreq.e.ltoreq.0.1.

Preferably, when E is N, 0.0005. ltoreq. e.ltoreq.0.05.

Preferably, the anion-doped garnet scintillation material is anion-doped garnet scintillation polycrystalline powder, anion-doped garnet scintillation ceramic or anion-doped garnet scintillation single crystal.

In a second aspect, the present invention provides a method for preparing an anion-doped garnet scintillating polycrystalline powder, comprising:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) and carrying out solid phase reaction on the obtained mixed powder at 1000-1850 ℃ for 5-100 hours to obtain the anion-doped garnet scintillation polycrystalline powder.

In a third aspect, the present invention provides a method for preparing an anion-doped garnet scintillating ceramic, comprising:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) and pressing and molding the mixed powder, and carrying out solid-phase reaction for 5-100 hours at 1000-1850 ℃ to obtain the anion-doped garnet scintillating ceramic.

Preferably, the compression molding mode is dry compression molding or/and cold isostatic pressing; preferably, the pressure of the dry pressing is 20-30 MPa, and the pressure of the cold isostatic pressing is 200-300 MPa.

Preferably, the anion-doped garnet scintillating ceramic is subjected to hot isostatic pressing treatment and annealing treatment to obtain anion-doped garnet transparent scintillating ceramic;

the hot isostatic pressing treatment atmosphere is inert atmosphere, the temperature is 1400-1450 ℃, the hot isostatic pressure is 160-250 MPa, the time is 2-3 hours, and the preferred inert atmosphere is argon atmosphere;

the annealing treatment atmosphere is air atmosphere, the temperature is 1000-1300 ℃, and the time is 10-30 hours.

In a fourth aspect, the present invention provides a method for preparing an anion-doped garnet scintillation single crystal, comprising:

(1) weighing CeF according to the chemical formula of anion-doped garnet scintillation material₃、CeCl₃、YF₃、GdF₃And at least one of GaN, an oxide of RE, an oxide of A, an oxide of B, an oxide of C and an oxide of D, and mixing to obtain mixed powder;

(2) heating the mixed powder or the anion-doped garnet scintillation polycrystalline powder to be molten, and growing the anion-doped garnet scintillation single crystal by adopting a pulling method, a Bridgman method, a temperature gradient method, a heat exchange method, a kyropoulos method, a top seed crystal method, a fluxing agent crystal growth method or a micro-pulling method.

In a fifth aspect, the invention provides an application of an anion-doped garnet scintillation material in the fields of high-energy physical detection and particle discrimination and fast nuclear medical imaging.

Has the advantages that:

1. the patent proposes that oxygen lattice site anion doping of an anion co-doped garnet scintillation crystal improves the luminescence performance of the material, and comprises that the scintillation rise time or decay time is shortened, the scintillation light output/light yield is improved, and the energy resolution is improved;

2. the ceramic or single crystal prepared from the component material can be applied to high-energy physical detection and particle discrimination and nuclear medicine imaging (X-CT, TOF-PET), and can effectively improve the time resolution of detection;

3. in the invention, the research on the oxygen site doping part anions of the garnet scintillation material is significant, and a novel component material with excellent performance is obtained so as to meet one or more specific requirements in different applications.

Drawings

FIG. 1 is a scintillation decay time profile and fitting results for anion doped garnet scintillators of examples 14 and 16;

FIG. 2 is a scintillation rise time profile of anion-doped garnet scintillators of examples 14 and 16;

FIG. 3 is a scintillation decay time profile and fitting results for anion doped garnet scintillators of examples 14 and 18;

FIG. 4 is a scintillation rise time profile for anion-doped garnet scintillators of examples 14 and 18.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the present disclosure, partial oxygen sites of garnet scintillation materials are replaced by anions to improve the luminescence properties of the materials, including ultra-fast time performance (reduced scintillation rise time or decay time), increased scintillation light yield/light yield; at least one of a decrease in energy resolution, an increase in fluorescence emission intensity, or an increase in X-ray excitation emission intensity is also accompanied.

In the present disclosure, an anion co-doped garnet scintillation material belongs to the cubic crystal system, and its chemical formula may be: (RE)_{1-a- b}A_aB_b)₃(C_1-dD_d)₅(O_1-neE_e)₁₂In the formula, a is more than 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, d is more than or equal to 0 and less than or equal to 1, e is more than 0 and less than or equal to 0.1, and n is 0.5 or 1.5; e ions replace O ion sites. The E ion specifically comprises at least one of fluorine F, chlorine Cl and nitrogen N. The value of E is in the range of 0 < E.ltoreq.0.1 (fluorine F or chlorine Cl is preferably 0.0005. ltoreq.e.ltoreq.0.1; nitrogen N is preferably 0.0005. ltoreq.e.ltoreq.0.05 (in this preferred range, the decay time performance is more excellent)). When the E ion is at least one of fluorine F and chlorine Cl, n is 0.5. When the E ion is specifically nitrogen N, N is 1.5.

The A ions specifically comprise at least one of cerium (Ce), praseodymium (Pr), neodymium (Nd), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb). Preferably 0.002 < a.ltoreq.0.03 (in this preferred range, the decay time property is more excellent).

Wherein, the B ions specifically comprise at least one of lithium Li, sodium Na, potassium K, magnesium Mg, calcium Ca, strontium Sr, copper Cu, zinc Zn, titanium Ti, vanadium V, manganese Mn and scandium (Sc). Preferably 0.001. ltoreq. b.ltoreq.0.03 (in this preferable range, the decay time property is more excellent).

Wherein the RE ions specifically include at least one of lanthanum (La), gadolinium (Gd), lutetium (Lu), and yttrium (Y).

Wherein the C ions specifically include at least one of scandium (Sc), aluminum (Al) and gallium (Ga).

Wherein the D ions specifically comprise at least one of Zn, Ti, V V, Fe Fe, Cr, Mn, Co, Cu, Pb, Zr, Si, W and In. Preferably 0. ltoreq. d.ltoreq.0.1 (in this preferred range, the decay time property is more excellent).

In an alternative embodiment, a ═ Ce, doped simultaneously with E, helps to shorten at least one of the scintillation decay time, the rise time of the anion-doped garnet scintillation material.

In the present invention, the anionic co-doped garnet scintillation material may be a polycrystalline powder, a ceramic (including transparent and non-transparent ceramics), or a single crystal. The following is an exemplary description of the method of making an anion-doped garnet scintillation material.

Using oxides (including A, B, C, D, etc.) and CeF₃、CeCl₃、YF₃、GdF₃And at least one of GaN and the like is used as a raw material, and the raw materials are mixed according to the molar weight of the chemical formula of the raw materials and are fully and uniformly mixed to obtain mixed powder (or called mixed powder). The purity of the used raw materials is more than 99.99 percent (4N).

Preparation of anion co-doped garnet ultrafast scintillation polycrystalline powder: the mixed powder can be directly calcined at the temperature of 1000-1850 ℃ for 5-100h to generate solid phase reaction to obtain polycrystalline powder. Preferably, the solid phase reaction temperature is 1100-1850 ℃ and the time is 10-50 h.

Preparation of aluminum anion co-doped garnet ultrafast scintillating ceramic: pressing the mixed powder into blocks, and sintering at the temperature of 1000-1850 ℃ for 5-100h to obtain the ceramic. Preferably, the solid phase reaction temperature is 1100-1850 ℃ and the time is 10-50 h. The compression molding mode is dry compression molding or/and cold isostatic pressing; preferably, the pressure of the dry pressing is 20-30 MPa, and the pressure of the cold isostatic pressing is 200-300 MPa.

Preparing the anion co-doped garnet ultrafast flickering transparent ceramic: and (4) preparing the transparent ceramic by regulating and controlling a sintering process. Preferably, the solid phase reaction temperature is 1100-1850 ℃ and the time is 10-50 h. The compression molding mode is dry compression molding or/and cold isostatic pressing; preferably, the pressure of the dry pressing is 20-30 MPa, and the pressure of the cold isostatic pressing is 200-300 MPa. And after the solid-phase reaction is finished, hot isostatic pressing treatment and annealing treatment are carried out.

Preparation of anion co-doped garnet ultrafast scintillation single crystal: the mixed powder, the polycrystalline powder or the ceramic block is put into a container to be melted by heating (resistance or electromagnetic induction or light and the like), and the single crystal is prepared by slowly crystallizing from the melt, wherein the specific method comprises a pulling method, a crucible descending method, a temperature gradient method, a heat exchange method, a kyropoulos method, a top seed crystal method, a fluxing agent crystal growth method and a micro-pulling-down method (mu-PD).

Wherein, the container can be a graphite crucible, an iridium crucible, a molybdenum crucible, a tungsten molybdenum crucible, a rhenium crucible, a tantalum crucible, an alumina crucible, a zirconia crucible, etc.

The atmosphere for single crystal growth can be one or a mixture of air, argon, nitrogen, carbon dioxide and carbon monoxide.

In an optional embodiment, the crystal is grown by a pulling method, a container is an iridium crucible, induction heating is adopted, high-purity nitrogen is adopted in the growth atmosphere, pulling is carried out while rotating, the pulling speed is 0.7-6.0 mm/h, and the rotating speed is 3-20 r/min.

In an alternative embodiment, the resulting ceramic and single crystal may also be ground into a polycrystalline powder by crushing.

In the disclosure, the obtained anion co-doped garnet ultrafast scintillation material can be used in the fields of high-energy physical detection and particle discrimination, and nuclear medicine imaging (X-CT, TOF-PET).

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1 (growth (Y)_0.988Ce_0.01Mg_0.002)₃Al₅(O_0.99625F_0.0075)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Y₂O₃:Al₂O₃:CeF₃MgO (1.482: 2.5:0.03: 0.006) through proportional mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing single crystals with preset sizes from a melt to obtain (Y)_0.988Ce_0.01Mg_0.002)₃Al₅(O_0.99625F_0.0075)₁₂And (3) single crystal.

Example 2 (preparation (Y)_0.993Ce_0.005Mg_0.002)₃Al₅(O_0.998125F_0.00375)₁₂Polycrystalline powder body

According to molar weight ratio Y₂O₃:Al₂O₃:CeF₃The materials including 1.4895, 2.5, 0.03 and 0.006 are mixed homogeneously. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Y)_0.993Ce_0.005Mg_0.002)₃Al₅(O_0.998125F_0.00375)₁₂A polycrystalline powder.

Example 3 (growth (Y)_0.99Ce_0.01)₃(Al_0.97Mn_0.03)₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Y₂O₃:Al₂O₃:CeO₂:MnO₂:YF₃The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 1.385:2.425:0.03:0.15: 0.2. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing single crystals with preset sizes from a melt to obtain (Y)_0.99Ce_0.01)₃(Al_0.97Mn_0.03)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 4 (preparation (Y)_0.995Ce_0.005)₃(Al_0.97Mn_0.03)₅(O_0.975F_0.05)₁₂Polycrystalline powder body

According to molar weight ratio Y₂O₃:Al₂O₃:CeO₂:MnO₂:YF₃The ingredients are mixed fully and evenly, wherein the ratio of the ingredients is 1.3925:2.425:0.03:0.15: 0.2. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Y)_0.995Ce_0.005)₃(Al_0.97Mn_0.03)₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Example 5 (growth (Y)_0.99Yb_0.01)₃(Al_0.94Sc_0.06)₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Y₂O₃:Al₂O₃:Yb₂O₃:Sc₂O₃:YF₃The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 1.385:2.35:0.015:0.15: 0.2. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, and adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen content is 1-5%, and the method comprises the steps ofInduction heating and full melting, controlling crystal growth in real time by PID, automatically adjusting pulling speed and rotation speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min, and slowly pulling and growing single crystal with preset size from the melt to obtain (Y)_0.99Yb_0.01)₃(Al_0.94Sc_0.06)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 6 (preparation (Y)_0.99Yb_0.01)₃(Al_0.94Sc_0.06)₅(O_0.975F_0.05)₁₂Polycrystalline powder body

According to molar weight ratio Y₂O₃:Al₂O₃:Yb₂O₃:Sc₂O₃:YF₃The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 1.385:2.35:0.015:0.15: 0.2. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Y)_0.99Yb_0.01)₃(Al_0.94Sc_0.06)₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Example 7 (growth (Lu)_0.988Ce_0.01Ca_0.002)₃Al₅(O_0.99625Cl_0.0075)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Lu₂O₃:Al₂O₃:CeCl₃CaO in the ratio of 1.482:2.5:0.03:0.006, and mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing single crystals with preset sizes from a melt to obtain the (Lu)_0.988Ce_0.01Ca_0.002)₃Al₅(O_0.99625Cl_0.0075)₁₂And (3) single crystal.

Example 8 (preparation ((Lu)_0.993Ce_0.005Ca_0.002)₃Al₅(O₉₉₈₁₂₅Cl_0.00375)₁₂Polycrystalline powder body

According to molar weight ratio Lu₂O₃:Al₂O₃:CeF₃CaO (1.4895), 2.5, 0.015 and 0.006, and fully and uniformly mixing. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining at 1850 ℃ for 10 hours to perform solid phase reaction to obtain the (Lu)_0.993Ce_0.005Ca_0.002)₃Al₅(O₉₉₈₁₂₅Cl_0.00375)₁₂A polycrystalline powder.

Example 9 (growth (Lu)_0.9233Ce_0.01Y_0.0667)₃(Al_0.95Cr_0.05)₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Lu₂O₃:Al₂O₃:CeO₂:YF₃:Cr₂O₃The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 1.385:2.375:0.03:0.2: 0.25. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing single crystals with preset sizes from a melt to obtain the (Lu)_0.9233Ce_0.01Y_0.0667)₃(Al_0.95Cr_0.05)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 10 (preparation (Lu)_0.9283Ce_0.005Y_0.0667)₃(Al_0.95Cr_0.05)₅(O_0.975F_0.05)₁₂Ceramic material)

Non-transparent state: according to molar weight ratio Lu₂O₃:Al₂O₃:CeO₂:YF₃:Cr₂O₃Materials are added according to the ratio of 1.3925:2.375:0.03:0.2:0.25, and the materials are fully and uniformly mixed to obtain a mixture. Pressing the obtained mixture into blocks by a tablet machine, wherein the pressure is 30Mpa, then carrying out cold isostatic pressing, the cold isostatic pressing is 200-300Mpa, putting the blocks into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature for 4 hours at 800 ℃ to remove organic matters and volatile impurities in the powder, calcining the corundum crucible at the temperature of 1400-1850 ℃ for 10 hours to carry out solid phase reaction to obtain the (Lu)_0.9283Ce_0.005Y_0.0667)₃(Al_0.95Cr_0.05)₅(O_0.975F_0.05)₁₂A non-transparent ceramic. Transparent: according to molar weight ratio Lu₂O₃:Al₂O₃:CeO₂:YF₃:Cr₂O₃Materials are added according to the ratio of 1.3925:2.375:0.03:0.2:0.25, and the materials are fully and uniformly mixed to obtain a mixture. And pressing the obtained mixture into blocks by a tablet machine, wherein the pressure is 30Mpa, and then carrying out cold isostatic pressing, and the cold isostatic pressure is 200-300Mpa to obtain the blocks. Putting the block into a corundum crucible, putting the corundum crucible into a muffle furnace, and preserving heat for 4 hours at 800 ℃ to remove organic matters and volatile impurities in the powder; placing the sample into a vacuum tube furnace, introducing oxygen, calcining at the temperature of 1400-1850 ℃ for 10h to generate a solid phase reaction, and then carrying out hot isostatic pressing treatment on the sintered sample, wherein the hot isothermal temperature is 1400-1450 ℃, the isothermal pressure is 200MPa in an argon atmosphere, and the temperature is kept for 2-3 h. Finally, annealing the sample at 1200 ℃, and carrying out air atmosphere for 10-30h to obtain (Lu)_0.9283Ce_0.005Y_0.0667)₃(Al_0.95Cr_0.05)₅(O_0.975F_0.05)₁₂A transparent scintillating ceramic.

Example 11 (growth (Lu)_0.9213Pr_0.01Y_0.0667Mg_0.002)₃Al₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. According to molar weight ratio Lu₂O₃:Al₂O₃:Pr₆O₁₁:YF₃MgO (1.382: 2.5:0.005:0.2: 0.006), and mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressing, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, performing induction heating and full melting, performing PID real-time control on crystal growth, automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing single crystals with preset sizes from a melt to obtain the (Lu)_0.9213Pr_0.01Y_0.0667Mg_0.002)₃Al₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 12 (preparation (Lu)_0.9263Pr_0.005Y_0.0667Mg_0.002)₃Al₅(O_0.975F_0.05)₁₂Polycrystalline powder body

According to molar weight ratio Lu₂O₃:Al₂O₃:Pr₆O₁₁:YF₃The materials with the ratio of MgO to 1.3895:2.5:0.0025:0.2:0.006 are mixed fully and evenly. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining at 1850 ℃ for 10 hours to perform solid phase reaction to obtain the (Lu)_0.9263Pr_0.005Y_0.0667Mg_0.002)₃Al₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Example 13 (preparation (Gd)_0.66Ce_0.01Y_0.33)₃(Ga_0.54Al_0.46)₅O₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Y₂O₃:Ga₂O₃:Al₂O₃:CeO₂The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 0.99:0.495:1.35:1.15: 0.03. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1% -5%, heating by induction and melting fully, and introducingControlling the crystal growth in real time by PID, automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, and slowly pulling and growing a single crystal with a preset size from the melt to obtain (Gd)_0.66Ce_0.01Y_0.33)₃(Ga_0.54Al_0.46)₅O₁₂And (3) single crystal.

Example 14 (preparation of Gd)_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O₁₂Non-transparent ceramics)

Gd is proportioned according to molar weight₂O₃:Y₂O₃:Ga₂O₃:Al₂O₃:CeO₂The materials are mixed fully and uniformly to obtain a mixture, wherein the ratio of the materials is 0.995:0.4975:1.35:1.15: 0.015. And pressing the obtained mixture into blocks by a tablet press, wherein the pressure is 30Mpa, then carrying out cold isostatic pressing, the cold isostatic pressure is 200-300Mpa, putting the blocks into a corundum crucible, putting the corundum crucible into a muffle furnace, and keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder. Placing the mixture into a vacuum tube furnace, introducing oxygen, calcining the mixture for 10 hours at 1400-1600 ℃ to perform solid phase reaction to obtain Gd_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O₁₂A non-transparent ceramic.

Example 15 (growth (Gd)_0.99Ce_0.01)₃(Ga_0.6Al_0.4)₅(O_0.99625Cl_0.0075)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:Ce Cl₃Mixing the materials in the ratio of 1.485 to 1.5 to 1 to 0.03, and fully and uniformly mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.99Ce_0.01)₃(Ga_0.6Al_0.4)₅(O_0.99625Cl_0.0075)₁₂And (3) single crystal.

EXAMPLE 16 preparation of Gd_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O_11.955Cl_0.045Non-transparent ceramics

Gd is proportioned according to molar weight₂O₃:Y₂O₃:Ga₂O₃:Al₂O₃:CeCl₃The materials are mixed fully and evenly, wherein the ratio of the materials is 0.995:0.49:1.35:1.15: 0.015. And pressing the obtained mixture into blocks by a tablet press, wherein the pressure is 30Mpa, then carrying out cold isostatic pressing, the cold isostatic pressing is 200-300Mpa, and placing the blocks into a corundum crucible, placing the corundum crucible into a muffle furnace, and keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder. Placing the mixture into a vacuum tube furnace, introducing oxygen, calcining the mixture for 10 hours at 1400-1600 ℃ to perform solid phase reaction to obtain Gd_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O_11.955Cl_0.045A non-transparent ceramic.

Example 17 (growth (Gd)_0.66Y_0.33Ce_0.01)₃(Ga_0.54Al_0.46)₅(O_1-0.5eF_e)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃Mixing the materials at 0.99:1.35:1.15:0.03:12e (e is 0.005, 0.01, 0.03, 0.05, 0.10), and mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.66Y_0.33Ce_0.01)₃(Ga_0.54Al_0.46)₅(O_1-0.5eF_e)₁₂And (3) single crystal.

EXAMPLE 18 preparation of Gd_1.99Y_0.995Ce_0.015Ga_2.7Al_2.3O_12(1-0.5e)F_12eNon-transparent ceramics)

Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃Mixing the raw materials (e is 0.005, 0.01, 0.03, 0.05 and 0.1) at 0.995:1.35:1.15:0.015:12e, and mixing well. And pressing the obtained mixture into blocks by a tablet press, wherein the pressure is 30Mpa, then carrying out cold isostatic pressing, the cold isostatic pressing is 200-300Mpa, and placing the blocks into a corundum crucible, placing the corundum crucible into a muffle furnace, and keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder. Placing the mixture into a vacuum tube furnace, introducing oxygen, calcining the mixture for 10 hours at 1400-1600 ℃ to perform solid phase reaction to obtain Gd_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O_11.955Cl_0.045A non-transparent ceramic.

Example 19 (growth (Gd)_0.9203Ce_0.01Y_0.0667Yb_0.003)₃(Ga_0.54Al_0.4Sc_0.06)₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃:Yb₂O₃:Sc₂O₃Materials are added according to the ratio of 1.3805:1.35:1:0.03:0.2:0.0045:0.3, and the materials are fully and uniformly mixed. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.9203Ce_0.01Y_0.0667Yb_0.003)₃(Ga_0.54Al_0.4Sc_0.06)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 20 (preparation (Gd)_0.9253Ce_0.005Y_0.0667Yb_0.003)₃(Ga_0.54Al_0.4Sc_0.06)₅(O_0.975F_0.05)₁₂Polycrystalline powder body

Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃:Yb₂O₃:Sc₂O₃The ingredients are mixed according to the ratio of 1.388:1.35:1:0.03:0.2:0.0045:0.3 and fully and uniformly mixed. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Gd)_0.9253Ce_0.005Y_0.0667Yb_0.003)₃(Ga_0.54Al_0.4Sc_0.06)₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Example 21 (preparation (Gd)_0.99Ce_0.01)₃(Ga_0.54Al_0.46)₅(O_0.99625Cl_0.0075)₁₂Polycrystalline powder body

Gd is proportioned according to molar weight₂O₃:Ga₂O₃:Al₂O₃:CeCl₃The materials are mixed according to the ratio of 1.485:1.35:1.15:0.03, and the mixture is fully and evenly mixed. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Gd)_0.99Ce_0.01)₃(Ga_0.54Al_0.46)₅(O_0.99625Cl_0.0075)₁₂A polycrystalline powder.

Example 22 (growth (Gd)_0.79Lu_0.2Ce_0.01)₃(Ga_0.6Al_0.38Ti_0.02)₅(O_0.99625Cl_0.0075)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Lu₂O₃:Ga₂O₃:Al₂O₃:CeCl₃:TiO₂The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 1.185:0.3:1.5:0.95:0.03: 0.1. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.79Lu_0.2Ce_0.01)₃(Ga_0.6Al_0.38Ti_0.02)₅(O_0.99625Cl_0.0075)₁₂And (3) single crystal.

Example 23 (preparation (Gd)_0.795Lu_0.2Ce_0.005)₃(Ga_0.6Al_0.38Ti_0.02)₅(O_0.99625Cl_0.0075)₁₂Polycrystalline powder body

Gd is proportioned according to molar weight₂O₃:Lu₂O₃:Ga₂O₃:Al₂O₃:CeCl₃:TiO₂The ingredients are added according to the ratio of 1.1925:0.3:1.5:0.95:0.03:0.1, and the mixture is fully and uniformly mixed. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Gd)_0.795Lu_0.2Ce_0.005)₃(Ga_0.6Al_0.38Ti_0.02)₅(O_0.99625Cl_0.0075)₁₂A polycrystalline powder.

Example 24 (growth (Gd)_0.7233Lu_0.2Ce_0.01Y_0.0667)₃(Ga_0.6Al_0.4)₅(O_0.975F_0.05)₁₂Single crystal)

Adopting a Czochralski method to grow the sheetAnd (4) crystallizing. Gd is proportioned according to molar weight₂O₃:Lu₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃Materials are mixed according to the ratio of 1.085:0.3:1.5:1:0.03:0.2, and the mixture is fully and evenly mixed. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.7233Lu_0.2Ce_0.01Y_0.0667)₃(Ga_0.6Al_0.4)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 25 (preparation (Gd)_0.7283Lu_0.2Ce_0.005Y_0.0667)₃(Ga_0.6Al_0.4)₅(O_0.975F_0.05)₁₂Polycrystalline powder body

Gd is proportioned according to molar weight₂O₃:Lu₂O₃:Ga₂O₃:Al₂O₃:CeO₂:YF₃The ingredients are mixed according to the ratio of 1.0925:0.3:1.5:1:0.015:0.2, and the mixture is fully and uniformly mixed. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Gd)_0.7283Lu_0.2Ce_0.005Y_0.0667)₃(Ga_0.6Al_0.4)₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Example 26 (growth (Gd)_0.66Y_0.33Ce_0.01)₃(Ga_0.54Al_0.42Co_0.04)₅(O_0.975F_0.05)₁₂Single crystal)

A Czochralski method is adopted to grow single crystals. Gd is proportioned according to molar weight₂O₃:Y₂O₃:Ga₂O₃:Al₂O₃:CeO₂:Co₂O₃:YF₃0.99:0.395:1.35:1.05:0.03:0.2:0.6, and fully and uniformly mixing. Pressing the mixture into blocks under 2500MPa cold isostatic pressure, placing the blocks into an iridium crucible, adopting high-purity nitrogen-oxygen mixed gas as growth atmosphere, wherein the volume fraction of oxygen is 1-5%, fully melting the blocks through induction heating, controlling the crystal growth in real time through PID (proportion integration differentiation), automatically adjusting the pulling speed and the rotating speed within the ranges of 0.7-6.0 mm/h and 3-12 r/min respectively, slowly pulling and growing a single crystal with a preset size from a melt to obtain the Gd (Gd)_0.66Y_0.33Ce_0.01)₃(Ga_0.54Al_0.42Co_0.04)₅(O_0.975F_0.05)₁₂And (3) single crystal.

Example 27 (preparation (Gd)_0.663Y_0.332Ce_0.005)₃(Ga_0.54Al_0.42Co_0.04)₅(O_0.975F_0.05)₁₂Polycrystalline powder body

Gd is proportioned according to molar weight₂O₃:Y₂O₃:Ga₂O₃:Al₂O₃:CeO₂:Co₂O₃:YF₃The ingredients are mixed fully and uniformly, wherein the ratio of the ingredients is 0.9945:0.398:1.35:1.05:0.03:0.2: 0.6. Putting the powder mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, keeping the temperature at 800 ℃ for 4 hours to remove organic matters and volatile impurities in the powder, putting the corundum crucible into a vacuum tube furnace, introducing oxygen, calcining the corundum crucible at 1600 ℃ for 10 hours to perform solid phase reaction to obtain (Gd)_0.663Y_0.332Ce_0.005)₃(Ga_0.54Al_0.42Co_0.04)₅(O_0.975F_0.05)₁₂A polycrystalline powder.

Table 1 shows Gd prepared in example 14_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O₁₂Scintillating Material and Gd prepared in example 16_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O_11.955Cl_{0.045(12e＝0.045，e＝0.00375)}Scintillation decay time of the scintillation material:

sample (I)	τ1	I1	τ2	I2
					GYGAG:Ce	64	72％	311	28％
GYGAG:Ce，Cl，e＝0.375at.％	52	74％	359	26％

。

Table 2 shows Gd prepared in example 14_1.99Ce_0.015Y_0.995Ga_2.7Al_2.3O₁₂And Gd prepared in example 18_1.99Y_{0.99 5}Ce_0.015Ga_2.7Al_2.3O_12(1-0.5e)F_12e(e＝0.005、0.01、0.03、0.05, 0.1) scintillation decay time:

sample (I)	τ1	I1	τ2	I2
					GYGAG:Ce	64	72％	311	28％
GYGAG:Ce，F，e＝0.5at.％	51	80％	339	20％
					GYGAG:Ce，F，e＝1at.％	59	67％	350	33％
GYGAG:Ce，F，e＝3at.％	62	77％	360	23％
					GYGAG:Ce，F，e＝5at.％	54	67％	357	33％
GYGAG:Ce，F，e＝10at.％	69	79％	535	21％

。

The above examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations of the present invention by those skilled in the art based on the foregoing descriptions are within the scope of the present invention.