A high-quality factor transition metal element-doped garnet-structured aluminate scintillating material and its preparation method and application

Abstract

The present invention relates to a high quality factor transition metal element doped garnet structure aluminate scintillating material and its preparation method and application. The chemical formula of the transition metal element doped garnet structure aluminate scintillating material is: RE 3‑x‑a Ce x A a Al 5‑y‑ z D y M z O 12 ; wherein 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1; the rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb; the A is selected from at least one of Li, Mg, Ca, K, and Na; the D is selected from at least one of Ga and In; the M is a transition metal element, selected from at least one of Cr, Mn, Fe, Co, and Ni.

Description

Technical Field

[0001] The present invention relates to a method for determining the relationship between ionic radius, electronegativity and Al 3+ The invention relates to a high quality factor garnet-structured aluminate scintillating material obtained by doping similar transition metal elements, a preparation method thereof and an application thereof, and belongs to the technical field of scintillating materials. Background Art

[0002] Inorganic scintillating materials are energy converters that convert the energy of high-energy rays (X-rays, gamma rays) or particles (protons, neutrons, etc.) into ultraviolet or visible light. Coupling them with subsequent photoelectric conversion devices (photodiodes, silicon photomultipliers, photomultiplier tubes, etc.) enables effective detection of nuclear radiation. X-rays or gamma rays generated by a radioactive source are incident on the scintillator, where they are absorbed and produce scintillation light. A photodetector then converts the light signal into an electrical signal, which is then collected, stored, and displayed, enabling precise measurement of numerous physical parameters such as the energy, momentum, direction, and duration of these invisible high-energy rays or particles. Detectors made from inorganic scintillating crystals are now widely used in fields such as high-energy physics, space physics, industrial nondestructive testing, safety audits, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET). They represent the mainstream of scintillator material development and hold enormous market potential.

[0003] With the rapid development of nuclear detection and related technologies, higher requirements are placed on the performance of scintillation crystals. Traditional NaI:Tl, CsI:Tl, Bi4Ge3O 12 Scintillating crystals such as BGO (BGO), BaF2, and PbWO4 (PWO) are no longer able to meet application requirements. The development of scintillating crystals with high density, large atomic number, high light output, fast decay, and radiation resistance is our ongoing goal. The new generation of garnet-structured aluminate scintillating crystals has become a research hotspot due to their high light output, excellent energy resolution, and rapid decay.

[0004] Rare earth doped garnet aluminates can be viewed as tetrahedra and octahedra connected in space by apex oxygen ions, with the gaps formed being distorted dodecahedrons. In one unit, there are eight stoichiometric formulas [A 3+ ]3[B 3+ ]2[Y 3+ ]3O 12 The molecule Y 3+ In the tetrahedron composed of 4 oxygen ions, B 3+ In the octahedron composed of 6 oxygen ions, A 3+ It is located in the distorted dodecahedron formed by the gaps between the regular tetrahedron and the regular octahedron. 3+When doped with some trivalent rare earth ions, they generally enter the dodecahedral position. 3+ Doped gadolinium aluminum gallate scintillator crystal (Gd3Al2Ga3O 12 :Ce,GAGG:Ce) was developed in recent years under the guidance of "band gap engineering". 3+ As an activator, Ce 3+ The 5d→4f parity-allowed transition of PET allows for fast-decaying luminescence. This crystal exhibits excellent overall performance, including high light output, fast luminescence decay, a large effective atomic number, high density, no self-radiation, and no deliquescent properties, and holds great promise for future development. With the further development of PET technology, time-of-flight (TOF) technology has been proposed to improve imaging resolution, reduce patient dose, and shorten scan times. However, TOF technology requires scintillators with faster decay times and higher light yields, which translate to higher imaging resolution and positioning accuracy.

[0005] The fast component of the scintillation decay time of GAGG:Ce crystal is about 90ns. Although it is shorter than the traditional bismuth germanium oxide (Bi4Ge3O 12 , referred to as BGO), the decay time is significantly accelerated, but for practical applications, a shorter scintillation decay time is required to better play its advantages. In order to accelerate the scintillation decay speed of GAGG:Ce crystals, Patent 1 (Application Publication No. WO2014171985A3) discloses a method of improving the scintillation and optical properties of GAGG by doping rare earth sites and adjusting the Al-Ga ratio. In addition to adjusting the matrix components, ion co-doping is also the most commonly used means to regulate scintillation performance. Wu et al. co-doped Ca 2+ , through the charge balance mechanism, part of Ce 3+ Converted to Ce, which emits light faster 4+ , thus shortening the scintillation decay time of GAGG:Ce crystal, but the light yield and energy resolution have deteriorated to a certain extent (Physical Review Applied, 2014, 2(4), 044009.). Kamada et al. reported that Mg 2+ Co-doping can significantly shorten the decay time, and the effect is better than that of Ca 2+Co-doping is better (Optical Materials, 2015, 41, 63.). Patent 2 (application publication number PCT / CZ2016 / 000112) discloses a method of shortening the scintillation response time by co-doping at the rare earth lattice site, and does not explore the effect of co-doping ions at the Al site on the time. Patent 3 (China Publication No. CN115322784A) discloses an octahedral lattice site doping to improve the gadolinium aluminum gallate scintillation material and its preparation method and application. It discloses co-doping at the Al site with at least one of hafnium Hf, zirconium Zr, copper Cu, zinc Zn, tin Sn, lead Pb, titanium Ti, tellurium Te, and terbium Tb, but it mainly relies on spatial structure modification, by co-doping ions with a radius between Gd 3+ and Al 3+ The elements between the ions are preferentially distributed in the octahedral lattice around the luminescent center Ce, which inhibits the formation of antisite defects and thus accelerates the decay. This patent does not consider whether the electron arrangement outside the ion nucleus will affect the Ce in the crystal. 3+ , nor did we consider whether there is Ce 4+ After co-doping with the above ions, the quality factor is slightly improved, but the improvement effect is not obvious. Summary of the Invention

[0006] According to the actual application needs and to achieve the above-mentioned purpose, the purpose of the present invention is to provide a 3+ Similar, and the electron configuration outside the nucleus is [Ar]3d n 4s 1～2 A garnet-structured aluminate scintillating material doped with a transition metal element (n≥5), and a preparation method and application thereof.

[0007] In one aspect, the present invention provides a transition metal element doped garnet-structured aluminate scintillating material, wherein the chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x-a Ce x A a Al 5-y-z D y M z O 12 ; Wherein 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1;

[0008] The rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb;

[0009] A is selected from at least one of Li, Mg, Ca, K, and Na;

[0010] The D is selected from at least one of Ga and In;

[0011] The M is a transition metal element, selected from at least one of Cr, Mn, Fe, Co, and Ni.

[0012] In the present invention, the radius, electronegativity and Al 3+ Similar transition metal elements, compared to Gd, these transition metal elements (at least one of Cr, Mn, Fe, Co, Ni) are more preferentially occupied in the Al position, and the ionic radius, electronegativity, etc. are similar to Al. 3+ More similar, less impact on the surrounding crystal field. At the same time, the extranuclear electron configuration of these transition metal elements is [Ar]3d n 4s 1～2 (n≥5), the electron configuration of Ce atom is [Xe]4f 1 5d 1 6s 2 When the co-doped atoms and Ce atoms are close to each other, Ce has a tendency to form a stable +4 valence, thereby accelerating the scintillation decay and improving the quality factor. A faster luminescence decay rate is achieved by doping with transition metal elements, including shortening at least one of the decay times of photoluminescence or scintillation luminescence. More preferably, in addition to a faster decay time, it is also accompanied by at least one of increased light output, better energy resolution, and reduced afterglow. The present invention prepares a new scintillating material with a high quality factor and ultrafast luminescence performance, which better meets the use requirements of high-energy physics, space physics, industrial non-destructive testing, safety inspection, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET).

[0013] Preferably, 0.00001≤z≤0.05.

[0014] Preferably, 0.001<x≤0.05.

[0015] Preferably, the transition metal element doped garnet-structured aluminate scintillating material is transition metal element doped garnet-structured aluminate scintillating polycrystalline powder, transition metal element doped garnet-structured aluminate scintillating ceramic or transition metal element doped garnet-structured aluminate scintillating single crystal.

[0016] In a second aspect, the present invention provides a method for preparing a transition metal element doped garnet-structured aluminate scintillating material, wherein the chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x-a Ce x A a Al 5-y- z D y M z O 12; wherein 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1; the rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb; the A is selected from at least one of Li, Mg, Ca, K, and Na; the D is selected from at least one of Ga and In; the M is a transition metal element, selected from at least one of Cr, Mn, Fe, Co, and Ni;

[0017] The transition metal element doped garnet structure aluminate scintillating material is a transition metal element doped garnet structure aluminate scintillating polycrystalline powder, and the preparation method thereof comprises:

[0018] (1) weighing CeO2, Al2O3, RE oxide, D oxide, and M oxide as raw materials according to the chemical formula of transition metal element-doped garnet-configuration aluminate scintillating polycrystalline powder and mixing them to obtain a mixed powder;

[0019] (2) subjecting the mixed powder to a solid-phase reaction to obtain the transition metal element-doped garnet-structured aluminate scintillating polycrystalline powder.

[0020] Preferably, the raw materials are pre-fired before mixing; the pre-fired temperature is 1100° C. and the time is 20 hours; the solid phase reaction temperature is 1200-2000° C. and the time is 5-200 hours.

[0021] In a third aspect, the present invention provides a method for preparing a transition metal element doped garnet-structured aluminate scintillating material, wherein the chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x-a Ce x A a Al 5-y- z D y M z O 12 ; wherein 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1; the rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb; the A is selected from at least one of Li, Mg, Ca, K, and Na; the D is selected from at least one of Ga and In; the M is a transition metal element, selected from at least one of Cr, Mn, Fe, Co, and Ni;

[0022] The transition metal element doped garnet structure aluminate scintillation material is a transition metal element doped garnet structure aluminate scintillation ceramic, and the preparation method thereof comprises:

[0023] (1) weighing CeO2, Al2O3, RE oxide, D oxide, and M oxide as raw materials according to the chemical formula of transition metal element-doped garnet-configuration aluminate scintillating polycrystalline powder and mixing them to obtain a mixed powder;

[0024] (2) The mixed powder is formed into a green body, and then sintered to obtain the transition metal element-doped garnet-structured aluminate scintillating ceramic.

[0025] Preferably, the raw materials are pre-fired before mixing; the pre-fired temperature is 1100° C. and the time is 20 hours; the green body is formed by at least one of dry pressing and cold isostatic pressing; preferably, the dry pressing pressure is 10-35 MPa, and the cold isostatic pressing pressure is 2-5 GPa;

[0026] The sintering method is at least one of pressureless sintering, hot pressing sintering, and hot isostatic pressing sintering. Preferably, the pressureless sintering temperature is 1200-2000° C., and the time is 5-200 hours.

[0027] In a fourth aspect, the present invention provides a method for preparing a transition metal element doped garnet-structured aluminate scintillating material, wherein the chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x-a Ce x A a Al 5-y- z D y M z O 12 ; wherein 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1; the rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb; the A is selected from at least one of Li, Mg, Ca, K, and Na; the D is selected from at least one of Ga and In; the M is a transition metal element, selected from at least one of Cr, Mn, Fe, Co, and Ni;

[0028] The transition metal element doped garnet-structured aluminate scintillating material is a transition metal element doped garnet-structured aluminate scintillating single crystal, and the preparation method thereof comprises:

[0029] (1) weighing CeO2, Al2O3, RE oxide, D oxide, and M oxide as raw materials according to the chemical formula of transition metal element-doped garnet-configuration aluminate scintillating polycrystalline powder and mixing them to obtain a mixed powder;

[0030] (2) melting the mixed powder by heating to start the growth of a single crystal; the single crystal growth method includes one of a pulling method, a crucible descent method, a temperature gradient method, a heat exchange method, a kyberyzing method, a top seed crystal method, a flux crystal growth method, and a micro-pull-down method.

[0031] Preferably, the raw materials are pre-fired before mixing; the pre-fired temperature is 1100°C and the time is 20 hours; the heating method is resistance heating, electromagnetic induction heating or light heating;

[0032] The parameters of the pulling method include: required dimensional parameter design, temperature field design, PID quality control temperature, pulling speed, and rotation speed;

[0033] The parameters of the crucible descent method include: required size parameter design, temperature field design, and growth rate.

[0034] In a fifth aspect, the present invention provides an application of a transition metal element-doped garnet-structured aluminate scintillating material according to any one of claims 1 to 10 in high energy physics, space physics, industrial non-destructive testing, safety inspection, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET).

[0035] Beneficial effects of the present invention:

[0036] 1. In the present invention, the relationship between ionic radius, electronegativity and Al 3+ Similar technical solutions for doping garnet-structured aluminate scintillating materials with transition metal elements, and screening suitable doping ions based on reasonable predictions and experimental verification;

[0037] 2. In the present invention, after the garnet-structured aluminate scintillating material is doped with transition metal elements, the luminescence performance of the material is significantly improved, including but not limited to a significant increase in the quality factor (light yield / scintillation decay time) related to scintillation performance, a shortened scintillation rise time or decay time, and a significant reduction in the afterglow level;

[0038] 3. In the present invention, the scintillation material with a high quality factor obtained by doping the garnet-structured aluminate scintillation material with transition metal elements can be better applied in high-energy physics, space physics, industrial non-destructive testing, safety inspection, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET). BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the scintillation decay time spectrum of the single crystal of Example 18;

[0040] Figure 2 This is the multi-channel energy spectrum of the single crystal of Example 18;

[0041] Figure 3is the X-ray excitation spectrum of the single crystal of Example 18;

[0042] Figure 4 This is the afterglow decay spectrum of the single crystal of Example 18. DETAILED DESCRIPTION

[0043] The present invention is further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0044] In the present disclosure, the co-doping radius, ionic radius, electronegativity and Al 3+ Similar transition metal elements, such as Cr, Mn, Fe, Co, Ni, etc., are doped with elements that take up the Al position more preferentially than Gd, and their ionic radius and electronegativity are more similar to those of Al, thus having less influence on the surrounding crystal field. At the same time, the extranuclear electron configuration of these transition metal elements is [Ar]3d n 4s 1 ～2 (n≥5), the electron configuration of Ce atom is [Xe]4f 1 5d 1 6s 2 When the co-doped atoms and Ce atoms are close to each other, Ce tends to form a stable +4 valence, thereby accelerating the scintillation decay and significantly improving the quality factor. This method has universal applicability for garnet-structured aluminate scintillating materials and is expected to produce new component materials with excellent performance. This method has universal applicability for garnet-structured aluminate scintillating materials and is of great significance for improving the scintillation performance of garnet-structured aluminate scintillating materials, and is expected to produce new component materials with excellent performance.

[0045] Furthermore, in addition to significantly improving the quality factor, the present invention also achieves at least one of the following: a shortened scintillation rise time, a significantly reduced afterglow level, improved energy resolution, and enhanced fluorescence emission intensity or X-ray induced emission intensity. If the z value is too high, the quality factor, energy resolution, afterglow, fluorescence emission intensity, or X-ray induced emission intensity may degrade.

[0046] In the present disclosure, the chemical formula of the transition metal element doped garnet-structured aluminate scintillating material may be: RE 3-x- a Ce x A a Al 5-y-z D y M z O 12, where 0<x≤0.15, 0≤y≤3, 0<z≤0.1, 0≤a≤0.1. The rare earth element RE is selected from at least one of Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb; D is selected from no more than one of Ga and In; and M is a co-doping element selected from at least one of Cr, Mn, Fe, Co, and Ni. In an optional embodiment, RE may also be added. 3-x Ce x Al 5-y-z D y M z O 12 Another A element dopant is added into the rare earth RE site, and the A element specifically includes at least one of Li, Mg, Ca, K, and Na. Preferably, the transition metal element doped garnet-structured aluminate scintillating material is a polycrystalline powder, ceramic, or single crystal.

[0047] In an optional embodiment, when RE is Gd, D is Ga, and M is Cr, 0.003≤z≤0.05; when RE is Gd, D is Ga, and M is Mn, 0.0002≤z≤0.05; when RE is Gd, D is Ga, and M is Fe, 0.003≤z≤0.05; when RE is Gd, D is Ga, and M is Co, 0.003≤z≤0.05; when RE is Gd, D is Ga, and M is Ni, 0.001≤z≤0.05.

[0048] In an optional embodiment, when RE is Lu, M is Cr, 0.001≤z≤0.05; when RE is Lu, M is Mn, 0.0004≤z≤0.05; when RE is Lu, M is Fe, 0.003≤z≤0.05; when RE is Lu, M is Co, 0.001≤z≤0.05; when RE is Lu, M is Ni, 0.0006≤z≤0.05.

[0049] In an optional embodiment, when RE is Y, M is Cr, 0.003≤z≤0.05; when RE is Y, M is Mn, 0.0004≤z≤0.05; when RE is Y, M is Fe, 0.001≤z≤0.05; when RE is Y, M is Co, 0.0006≤z≤0.05; when RE is Y, M is Ni, 0.0006≤z≤0.05.

[0050] The following is an exemplary description of the preparation method of the transition metal element-doped garnet-structured aluminate scintillating material provided by the present invention. The resulting transition metal element-doped garnet-structured aluminate scintillating material is a polycrystalline powder, a ceramic, or a single crystal. The ceramic includes transparent ceramics and non-transparent ceramics.

[0051] Using CeO2, Al2O3, rare earth oxide (RE m O n ), Ga or In oxide (D2O3) as raw materials, and according to the molar ratio of raw material components RE m O n :CeO2:Al2O3:D2O3=(3-x) / m:x:(5-yz) / 2:y / 2) ingredients are prepared and thoroughly mixed to obtain a mixed powder. The purity of all raw materials used is 99.99% (4N) or above. Preferably, before preparing the ingredients, the initial raw materials are placed in a muffle furnace under an air atmosphere and calcined at 1100°C for 20 hours to remove adsorbed water, crystallized water, and some organic matter (such as residual oxalate in the rare earth raw materials).

[0052] The mixed powder can be directly calcined at 1200-2000°C for 5-200 hours to induce a solid-phase reaction, thereby obtaining a polycrystalline powder. Preferably, the solid-phase reaction temperature can be 1400-1600°C for 10-50 hours. In an optional embodiment, the preparation of garnet-configured aluminate scintillating polycrystalline powder can also be performed by crushing and grinding the resulting ceramic and single crystal into powder.

[0053] The mixed powder can be directly pressed into a block by cold isostatic pressing (at a pressure of 2-5 GPa), and then sintered at 1200-2000°C for 5-200 hours to produce a ceramic. Alternatively, the sintering process can be controlled to produce a transparent ceramic, such as by hot pressing or vacuum sintering. The pressure for pressing into a block can be 2-5 GPa. Preferably, the solid-phase reaction temperature can be 1400-1600°C, and the reaction time can be 10-50 hours.

[0054] A mixed powder or polycrystalline powder is placed in a container and melted by heating (resistance, electromagnetic induction, light, etc.), and slowly crystallized from the melt to prepare a single crystal. Specific methods include Czochralski method, crucible descent method, temperature gradient method, heat exchange method, kyropoulos method, top seed method, flux crystal growth method, and micro-pull-down method (μ-PD) for growth. The container used can be a graphite crucible, an iridium crucible, a molybdenum crucible, a tungsten-molybdenum crucible, a rhenium crucible, a tantalum crucible, an alumina crucible, or a zirconia crucible. The atmosphere for single crystal growth can be a mixture of one or more of air, argon, nitrogen, carbon dioxide, and carbon monoxide. In an optional embodiment, the single crystal is grown by Czochralski method, the container is an iridium crucible, induction heating is used, the growth atmosphere uses high-purity nitrogen, and it is pulled while rotating; more preferably, the pulling speed of the single crystal grown by Czochralski method is 0.7-6.0 mm / h, and the rotation speed is 3-15 r / min.

[0055] In the present disclosure, during the preparation of transition metal-doped garnet-structured aluminate scintillating materials, a very small amount of doping element M may be doped into the rare earth RE sites. However, due to technical limitations, conventional characterization methods are difficult to determine the exact doping content. Of course, the doping of a very small amount of doping element M into the rare earth RE sites will not substantially change the performance of the material itself. Moreover, the resulting transition metal-doped garnet-structured aluminate scintillating material has a high quality factor that can be better applied in high-energy physics, space physics, industrial non-destructive testing, safety inspections, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET).

[0056] The following examples are further given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values exemplified below.

[0057] Example 1 (Growth of Cr-doped GAGG:Ce single crystal by Czochralski method)

[0058] Single crystals were grown using the Czochralski method. The ingredients (z = 0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1) were prepared in a molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Cr2O3 = 1.485:0.03:(2.3-z) / 2:1.35:z / 2. After being thoroughly mixed, the mixture was pressed by cold isostatic pressing (pressure of 3 GPa). The pressed block is placed in an iridium crucible, and in a nitrogen atmosphere, it is fully melted by induction heating. After seeding, a single crystal of a preset size is slowly pulled out from the melt to obtain Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Cr z O 12 The parameters of the Czochralski method include: design of required dimensional parameters, temperature field design, PID quality control temperature, pulling speed of 0.7-6.0 mm / h, and rotation speed of 3-15 r / min.

[0059] Example 2 (Growth of Cr-doped GAGG:Ce single crystal by micro-pull-down method)

[0060] Single crystals were grown using a micro-pulldown method. The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Cr2O3 was 1.4925:0.015:(2.3-z) / 2:1.35:z / 2 (z = 0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1) was used. After thorough mixing, the raw materials were pre-sintered at 1450°C in a muffle furnace. The sintered raw materials were placed in an iridium crucible and fully melted by induction heating using a nitrogen atmosphere. The seed crystal is slowly pulled downward after contacting the melt to obtain Gd 2.985 Ce 0.015 Al 2.3- z Ga 2.7 Cr z O 12 The parameters of the micro-pull-down method include: design of required dimensional parameters, temperature field design, and micro-pull-down speed of 3 to 20 mm / h.

[0061] Example 3 (Preparation of Cr-doped GAGG:Ce polycrystalline powder)

[0062] The ingredients were prepared according to Example 2, mixed thoroughly and placed in a corundum crucible, and calcined in a muffle furnace at 1600°C for 10 hours to perform a sufficient solid phase reaction to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 Polycrystalline powder.

[0063] Example 4 (Preparation of Cr-doped GAGG:Ce ceramics)

[0064] Non-transparent: Prepare the ingredients according to Example 2, mix the powders thoroughly and evenly, and then press them into blocks by cold isostatic pressing (pressure is 3 GPa). The pressed blocks are placed in a corundum crucible and sintered in a muffle furnace at 1600℃ for 10 hours to fully react with the solid phase to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 Non-transparent ceramic.

[0065] Transparent: Prepare the ingredients according to Example 2, mix the powders thoroughly and evenly, press them by cold isostatic pressing (pressure is 3 GPa), and then carry out sufficient solid phase reaction in a vacuum hot press (1600 ° C, 50 h), remove bubbles and voids as much as possible, and obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 Transparent ceramic.

[0066] Example 5 (Growth of Mn-doped GAGG:Ce Single Crystal by Czochralski Method)

[0067] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Mn2O3=1.485:0.03:(2.3-z) / 2:1.35:z / 2 was used for the preparation (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Mn z O 12 Single crystal.

[0068] Example 6 (Growth of Mn-doped GAGG:Ce Single Crystal by Micro-pull-down Method)

[0069] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Mn2O3=1.4925:0.015:(2.3-z) / 2:1.35:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 Single crystal.

[0070] Example 7 (Preparation of Mn-doped GAGG:Ce polycrystalline powder)

[0071] The ingredients were prepared as in Example 6, and the subsequent steps were the same as in Example 3 to obtain Gd2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 Polycrystalline powder.

[0072] Example 8 (Preparation of Mn-doped GAGG:Ce ceramics)

[0073] The ingredients were prepared according to Example 6, and the subsequent steps were the same as those in Example 4 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 Non-transparent ceramics and transparent ceramics.

[0074] Example 9 (Growth of Fe-doped GAGG:Ce Single Crystal by Czochralski Method)

[0075] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Fe2O3=1.485:0.03:(2.3-z) / 2:1.35:z / 2 (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1) was used for the preparation, and the subsequent steps were the same as in Example 1 to obtain Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Fe z O 12 Single crystal.

[0076] Example 10 (Growth of Fe-doped GAGG:Ce Single Crystal by Micro-pull-down Method)

[0077] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Fe2O3=1.4925:0.015:(2.3-z) / 2:1.35:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Fe z O 12 Single crystal.

[0078] Example 11 (Preparation of Fe-doped GAGG:Ce polycrystalline powder)

[0079] The ingredients were prepared as in Example 10, and the subsequent steps were the same as in Example 3 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Fe z O 12 Polycrystalline powder.

[0080] Example 12 (Preparation of Fe-doped GAGG:Ce ceramics)

[0081] The ingredients were prepared according to Example 10, and the subsequent steps were the same as those in Example 4 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Fe z O 12 Non-transparent ceramics and transparent ceramics.

[0082] Example 13 (Growth of Co-doped GAGG:Ce Single Crystal by Czochralski Method)

[0083] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:CoO=1.485:0.03:(2.3-z) / 2:1.35:z (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1) was used for the preparation, and the subsequent steps were the same as in Example 1 to obtain Gd 2.97 Ce 0.03 Al 2.3- z Ga 2.7 Co z O 12 Single crystal.

[0084] Example 14 (Growth of Co-doped GAGG:Ce Single Crystal by Micro-pull-down Method)

[0085] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:CoO=1.4925:0.015:(2.3-z) / 2:1.35:z was prepared (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Co z O 12 Single crystal.

[0086] Example 15 (Preparation of Co-doped GAGG:Ce polycrystalline powder)

[0087] The ingredients were prepared as in Example 14, and the subsequent steps were the same as in Example 3 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Co z O 12 Polycrystalline powder.

[0088] Example 16 (Preparation of Co-doped GAGG:Ce ceramics)

[0089] The ingredients were prepared according to Example 14, and the subsequent steps were the same as those in Example 4 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Co z O 12 Non-transparent ceramics and transparent ceramics.

[0090] Example 17 (Growth of Ni-doped GAGG:Ce Single Crystal by Czochralski Method)

[0091] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Ni2O3=1.485:0.03:(2.3-z) / 2:1.35:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Niz O 12 Single crystal.

[0092] Example 18 (Growth of Ni-doped GAGG:Ce Single Crystal by Micro-Pull-Down Method)

[0093] The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Ni2O3=1.4925:0.015:(2.3-z) / 2:1.35:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Ni z O 12 Single crystal.

[0094] Example 19 (Preparation of Ni-doped GAGG:Ce polycrystalline powder)

[0095] The ingredients were prepared as in Example 18, and the subsequent steps were the same as in Example 3 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Ni z O 12 Polycrystalline powder.

[0096] Example 20 (Preparation of Ni-doped GAGG:Ce ceramics)

[0097] The ingredients were prepared according to Example 18, and the subsequent steps were the same as those in Example 4 to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Ni z O 12 Non-transparent ceramics and transparent ceramics.

[0098] Example 21 (Growth of Cr-doped LuAG:Ce Single Crystal by Czochralski Method)

[0099] The molar ratio of Lu2O3:CeO2:Al2O3:Cr2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Cr z O 12 Single crystal.

[0100] Example 22 (Growth of Cr-doped LuAG:Ce Single Crystal by Micro-pull-down Method)

[0101] The molar ratio of Lu2O3:CeO2:Al2O3:Cr2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Cr z O 12 Single crystal.

[0102] Example 23 (Preparation of Cr-doped LuAG:Ce polycrystalline powder)

[0103] The ingredients were prepared as in Example 22, and the subsequent steps were the same as in Example 3 to obtain Lu 2.985 Ce 0.015 Al 5-z Cr z O 12 Polycrystalline powder.

[0104] Example 24 (Preparation of Cr-doped LuAG:Ce ceramics)

[0105] The ingredients were prepared according to Example 22, and the subsequent steps were the same as those in Example 4 to obtain Lu 2.985 Ce 0.015 Al 5-z Cr z O 12 Non-transparent ceramics and transparent ceramics.

[0106] Example 25 (Growth of Mn-doped LuAG:Ce Single Crystal by Czochralski Method)

[0107] The molar ratio of Lu2O3:CeO2:Al2O3:Mn2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Mn z O 12 Single crystal.

[0108] Example 26 (Growth of Mn-doped LuAG:Ce Single Crystal by Micro-Pull-Down Method)

[0109] The molar ratio of Lu2O3:CeO2:Al2O3:Mn2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Mn z O 12 Single crystal.

[0110] Example 27 (Preparation of Mn-doped LuAG:Ce polycrystalline powder)

[0111] The ingredients were prepared as in Example 26, and the subsequent steps were the same as in Example 3 to obtain Lu 2.985 Ce 0.015 Al 5-z Mn z O 12 Polycrystalline powder.

[0112] Example 28 (Preparation of Mn-doped LuAG:Ce ceramics)

[0113] The ingredients were prepared according to Example 26, and the subsequent steps were the same as those in Example 4 to obtain Lu 2.985 Ce 0.015 Al 5-z Mn z O 12 Non-transparent ceramics and transparent ceramics.

[0114] Example 29 (Growth of Fe-doped LuAG:Ce Single Crystal by Czochralski Method)

[0115] The molar ratio of Lu2O3:CeO2:Al2O3:Fe2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Fe z O 12 Single crystal.

[0116] Example 30 (Growth of Fe-doped LuAG:Ce Single Crystal by Micro-Pull-Down Method)

[0117] The molar ratio of Lu2O3:CeO2:Al2O3:Fe2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Fe z O 12 Single crystal.

[0118] Example 31 (Preparation of Fe-doped LuAG:Ce polycrystalline powder)

[0119] The ingredients were prepared as in Example 30, and the subsequent steps were the same as in Example 3 to obtain Lu 2.985 Ce 0.015 Al 5-z Fe z O 12 Polycrystalline powder.

[0120] Example 32 (Preparation of Fe-doped LuAG:Ce ceramics)

[0121] The ingredients were prepared as in Example 30, and the subsequent steps were the same as in Example 4 to obtain Lu 2.985 Ce 0.015 Al 5-z Fe z O 12 Non-transparent ceramics and transparent ceramics.

[0122] Example 33 (Growth of Co-doped LuAG:Ce Single Crystal by Czochralski Method)

[0123] The molar ratio of Lu2O3:CeO2:Al2O3:CoO=1.485:0.03:(5-z) / 2:z was prepared (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Co z O 12 Single crystal.

[0124] Example 34 (Growth of Co-doped LuAG:Ce Single Crystal by Micro-Pull-Down Method)

[0125] The molar ratio of Lu2O3:CeO2:Al2O3:CoO=1.4925:0.015:(5-z) / 2:z was prepared (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Co z O 12 Single crystal.

[0126] Example 35 (Preparation of Co-doped LuAG:Ce polycrystalline powder)

[0127] The ingredients were prepared as in Example 34, and the subsequent steps were the same as in Example 3 to obtain Lu 2.985 Ce 0.015 Al 5-z Co z O 12 Polycrystalline powder.

[0128] Example 36 (Preparation of Co-doped LuAG:Ce ceramics)

[0129] The ingredients were prepared according to Example 34, and the subsequent steps were the same as those in Example 4 to obtain Lu 2.985 Ce 0.015 Al 5-z Co z O 12Non-transparent ceramics and transparent ceramics.

[0130] Example 37 (Growth of Ni-doped LuAG:Ce Single Crystal by Czochralski Method)

[0131] The molar ratio of Lu2O3:CeO2:Al2O3:Ni2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Ni z O 12 Single crystal.

[0132] Example 38 (Growth of Ni-doped LuAG:Ce Single Crystal by Micro-Pull-Down Method)

[0133] The molar ratio of Lu2O3:CeO2:Al2O3:Ni2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Ni z O 12 Single crystal.

[0134] Example 39 (Preparation of Ni-doped LuAG:Ce polycrystalline powder)

[0135] The ingredients were prepared as in Example 38, and the subsequent steps were the same as in Example 3 to obtain Lu 2.985 Ce 0.015 Al 5-z Ni z O 12 Polycrystalline powder.

[0136] Example 40 (Preparation of Ni-doped LuAG:Ce ceramics)

[0137] The ingredients were prepared according to Example 38, and the subsequent steps were the same as those in Example 4 to obtain Lu 2.985 Ce 0.015 Al 5-z Niz O 12 Non-transparent ceramics and transparent ceramics.

[0138] Example 41 (Growth of Cr-doped YAG:Ce Single Crystal by Czochralski Method)

[0139] The molar ratio of Y2O3:CeO2:Al2O3:Cr2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Cr z O 12 Single crystal.

[0140] Example 42 (Growth of Cr-doped YAG:Ce Single Crystal by Micro-pull-down Method)

[0141] The molar ratio of Y2O3:CeO2:Al2O3:Cr2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Cr z O 12 Single crystal.

[0142] Example 43 (Preparation of Cr-doped YAG:Ce polycrystalline powder)

[0143] The ingredients were prepared according to Example 42, and the subsequent steps were the same as in Example 3 to obtain Y 2.985 Ce 0.015 Al 5-z Cr z O 12 Polycrystalline powder.

[0144] Example 44 (Preparation of Cr-doped YAG:Ce ceramics)

[0145] According to the ingredients of Example 42, the subsequent steps are the same as those of Example 4 to obtain Y 2.985 Ce 0.015 Al5-z Cr z O 12 Non-transparent ceramics and transparent ceramics.

[0146] Example 45 (Growth of Mn-doped YAG:Ce Single Crystal by Czochralski Method)

[0147] The molar ratio of Y2O3:CeO2:Al2O3:Mn2O3=1.485:0.03:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Mn z O 12 Single crystal.

[0148] Example 46 (Growth of Mn-doped YAG:Ce Single Crystal by Micro-Pull-Down Method)

[0149] The molar ratio of Y2O3:CeO2:Al2O3:Mn2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Mn z O 12 Single crystal.

[0150] Example 47 (Preparation of Mn-doped YAG:Ce polycrystalline powder)

[0151] The ingredients were prepared according to Example 46, and the subsequent steps were the same as in Example 3 to obtain Y 2.985 Ce 0.015 Al 5-z Mn z O 12 Polycrystalline powder.

[0152] Example 48 (Preparation of Mn-doped YAG:Ce ceramics)

[0153] According to the ingredients of Example 46, the subsequent steps are the same as those of Example 4 to obtain Y 2.985 Ce0.015 Al 5-z Mn z O 12 Non-transparent ceramics and transparent ceramics.

[0154] Example 49 (Growth of Fe-doped YAG:Ce Single Crystal by Czochralski Method)

[0155] The molar ratio of Y2O3:CeO2:Al2O3:Fe2O3=1.485:0.03:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Fe z O 12 Single crystal.

[0156] Example 50 (Growth of Fe-doped YAG:Ce Single Crystal by Micro-pull-down Method)

[0157] The molar ratio of Y2O3:CeO2:Al2O3:Fe2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Fe z O 12 Single crystal.

[0158] Example 51 (Preparation of Fe-doped YAG:Ce polycrystalline powder)

[0159] The ingredients were prepared according to Example 50, and the subsequent steps were the same as Example 3 to obtain Y 2.985 Ce 0.015 Al 5-z Fe z O 12 Polycrystalline powder.

[0160] Example 52 (Preparation of Fe-doped YAG:Ce ceramics)

[0161] The ingredients were prepared according to Example 50, and the subsequent steps were the same as Example 4 to obtain Y2.985 Ce 0.015 Al 5-z Fe z O 12 Non-transparent ceramics and transparent ceramics.

[0162] Example 53 (Growth of Co-doped YAG:Ce Single Crystal by Czochralski Method)

[0163] The molar ratio of Y2O3:CeO2:Al2O3:CoO=1.485:0.03:(5-z) / 2:z was prepared (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Co z O 12 Single crystal.

[0164] Example 54 (Growth of Co-doped YAG:Ce Single Crystal by Micro-pull-down Method)

[0165] The molar ratio of Y2O3:CeO2:Al2O3:CoO=1.4925:0.015:(5-z) / 2:z was prepared (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Co z O 12 Single crystal.

[0166] Example 55 (Preparation of Co-doped YAG:Ce polycrystalline powder)

[0167] The ingredients were prepared as in Example 54, and the subsequent steps were the same as in Example 3 to obtain Y 2.985 Ce 0.015 Al 5-z Co z O 12 Polycrystalline powder.

[0168] Example 56 (Preparation of Co-doped YAG:Ce ceramics)

[0169] According to the ingredients of Example 54, the subsequent steps are the same as those of Example 4 to obtain Y2.985 Ce 0.015 Al 5-z Co z O 12 Non-transparent ceramics and transparent ceramics.

[0170] Example 57 (Growth of Ni-doped YAG:Ce Single Crystal by Czochralski Method)

[0171] The molar ratio of Y2O3:CeO2:Al2O3:Ni2O3=1.485:0.03:(5-z) / 2:z / 2 was used for mixing (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Ni z O 12 Single crystal.

[0172] Example 58 (Growth of Ni-doped YAG:Ce Single Crystal by Micro-pull-down Method)

[0173] The molar ratio of Y2O3:CeO2:Al2O3:Ni2O3=1.4925:0.015:(5-z) / 2:z / 2 was used for batching (z=0.00001, 0.00005, 0.0001, 0.0002, 0.0004, 0.0006, 0.0008, 0.001, 0.002, 0.003, 0.005, 0.007, 0.01, 0.03, 0.05, 0.07, 0.1), and the subsequent steps were the same as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Ni z O 12 Single crystal.

[0174] Example 59 (Preparation of Ni-doped YAG:Ce polycrystalline powder)

[0175] The ingredients were prepared as in Example 58, and the subsequent steps were the same as in Example 3 to obtain Y 2.985 Ce 0.015 Al 5-z Ni z O 12 Polycrystalline powder.

[0176] Example 60 (Preparation of Ni-doped YAG:Ce ceramics)

[0177] According to the ingredients of Example 58, the subsequent steps are the same as those of Example 4 to obtain Y 2.985 Ce 0.015 Al 5-z Ni z O 12 Non-transparent ceramics and transparent ceramics.

[0178] Table 1 shows the relative light yield and quality factor (light yield / scintillation decay time) of the single crystal of Example 18:

[0179] z-value Relative light output Quality Factor z＝0 100％ 227 z＝0.001 87.4％ 247 z＝0.003 81.7％ 557 z＝0.005 80.5％ 515 z＝0.007 76.7％ 490 z＝0.01 65.0％ 488 .

[0180] Table 2 shows the afterglow level of the single crystal of Example 18:

[0181]

[0182]

[0183] Table 3 shows the relative quality factors of the non-transparent ceramics of Examples 4, 8, 12, 16, and 20 (compared with the non-co-doped non-transparent ceramic sheet):

[0184]

[0185] Table 4 shows the relative quality factors of the non-transparent ceramics of Examples 24, 28, 32, 36, and 40 (compared with the non-co-doped non-transparent ceramic sheet):

[0186]

[0187] Table 5 shows the relative quality factors of the non-transparent ceramics of Examples 44, 48, 52, 56, and 60 (compared with the non-co-doped non-transparent ceramic sheet):

[0188]

[0189] In the present invention, the ionic radius, electronegativity and Al 3+ Similar transition metal elements, such as Cr, Mn, Fe, Co, Ni, etc., doping elements take up Al sites more preferentially than Gd, and their ionic radius, electronegativity, etc. are similar to Al. 3+ More similar, less impact on the surrounding crystal field. At the same time, the extranuclear electron configuration of these transition metal elements is [Ar]3d n 4s 1～2 (n≥5), the electron configuration of Ce atom is [Xe]4f 1 5d 1 6s 2When the co-doped atoms and Ce atoms are close to each other, Ce tends to form a stable +4 valence, which accelerates the scintillation decay and improves the quality factor. This method is generally applicable to garnet-structured aluminate scintillating materials and can provide guidance for the design of new components.

[0190] The above embodiments are only used to further illustrate the present invention and should not be understood as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above contents of the present invention fall within the scope of protection of the present invention.

Claims

1. A transition metal element doped garnet-structured aluminate scintillating material, characterized in that: The chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x Ce x Al 5-y-z Ga y M z O 12 ; Where 0<x≤0.05, 0≤y≤3, 0<z≤0.1; The rare earth element RE is selected from at least one of Gd and Lu; The M is a transition metal element selected from one of Co and Ni; The transition metal element doped garnet configuration aluminate scintillating material is a transition metal element doped garnet configuration aluminate scintillating ceramic or a transition metal element doped garnet configuration aluminate scintillating single crystal.

2. The transition metal element-doped garnet-structured aluminate scintillating material according to claim 1, characterized in that: 0.00001≤z≤0.05。 3. The transition metal element-doped garnet-structured aluminate scintillating material according to claim 1, characterized in that: 0.001＜x≤0.05。 4. A method for preparing a transition metal element-doped garnet-structured aluminate scintillating material, characterized in that: The chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x Ce x Al 5-y-z Ga y M z O 12 ; Wherein 0<x≤0.05, 0≤y≤3, 0<z≤0.1; the rare earth element RE is selected from at least one of Gd and Lu; the M is a transition metal element, selected from one of Co and Ni; The transition metal element doped garnet structure aluminate scintillation material is a transition metal element doped garnet structure aluminate scintillation ceramic, and the preparation method thereof comprises: (1) CeO2, Al2O3, Ga2O3, RE oxide, and M oxide are weighed as raw materials according to the chemical formula of transition metal element-doped garnet-structured aluminate scintillating polycrystalline powder and mixed to obtain a mixed powder; (2) The mixed powder is formed into a green body, and then sintered to obtain the transition metal element-doped garnet-structured aluminate scintillating ceramic.

5. The preparation method according to claim 4, wherein Before mixing, the raw materials were pre-fired at a temperature of 1100°C for 20 hours. The forming method of the green body includes at least one of dry pressing and cold isostatic pressing; the pressure of the dry pressing is 10 to 35 MPa, and the pressure of the cold isostatic pressing is 2 to 5 GPa; The sintering method is at least one of pressureless sintering, hot pressing sintering, and hot isostatic pressing sintering; the pressureless sintering temperature is 1200-2000° C., and the time is 5-200 hours.

6. A method for preparing a transition metal element-doped garnet-structured aluminate scintillating material, characterized in that: The chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is: RE 3-x Ce x Al 5-y-z Ga y M z O 12 ; Wherein 0<x≤0.05, 0≤y≤3, 0<z≤0.1; the rare earth element RE is selected from at least one of Gd and Lu; the M is a transition metal element, selected from one of Co and Ni; The transition metal element doped garnet-structured aluminate scintillation material is a transition metal element doped garnet-structured aluminate scintillation single crystal, and the preparation method thereof comprises: (1) CeO2, Al2O3, Ga2O3, RE oxide, and M oxide are weighed as raw materials according to the chemical formula of transition metal element-doped garnet-structured aluminate scintillating polycrystalline powder and mixed to obtain a mixed powder; (2) The mixed powder is melted by heating to start the growth of a single crystal; the single crystal growth method includes one of the following: a Czochralski method, a crucible descent method, a temperature gradient method, a heat exchange method, a kyberyzine method, a top seed crystal method, a flux crystal growth method, and a micro-pull-down method.

7. The preparation method according to claim 6, wherein Before mixing, the raw materials were pre-fired at a temperature of 1100°C for 20 hours. The heating method is resistance heating, electromagnetic induction heating or light heating.

8. Application of the transition metal element-doped garnet-structured aluminate scintillating material according to any one of claims 1 to 3 in high energy physics, space physics, industrial non-destructive testing, safety auditing, mineral and oil well exploration, and nuclear medicine imaging.

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