Transition metal element-doped garnet-structure aluminate scintillation material with high quality factor, and its manufacturing method and use

Abstract

To provide a garnet-structured aluminate scintillating material doped with a transition metal element having an ionic radius and electronegativity similar to Al3+, and an outer electron configuration of [Ar]3dn4s1-2 (n≥5), as well as a preparation method and application thereof.SOLUTION: The chemical formula of the transition metal element doped garnet-structured aluminate scintillating material is RE3-x-aCexAaAl5-y-zDyMzO12, wherein x is 0<x≤0.15, y is 0≤y≤3, z is 0<z≤0.1, and a is 0≤a≤0.1; the rare earth element RE is at least one selected from Gd, Lu, Y, Sc, La, Nd, Eu, Tb, Dy, Ho, Er, Tm, and Yb, the A is at least one selected from Li, Mg, Ca, K, and Na, the D is at least one selected from Ga and In, and the M is a transition metal element, which is at least one selected from Cr, Mn, Fe, Co, and Ni.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] In this invention, the ionic radius and electronegativity are Al 3+ This invention relates to a garnet structure aluminate scintillation material with high quality factor obtained by doping with transition metal elements similar to those mentioned above, as well as its manufacturing method and application, which belongs to the field of scintillation material technology. [Background technology]

[0002] Inorganic scintillation materials are energy converters that can convert the energy of high-energy radiation (X-rays, gamma rays) or particles (protons, neutrons, etc.) into ultraviolet or visible light. When combined with a subsequent photoelectric conversion element (e.g., photodiode, silicon photomultiplier, photomultiplier tube), they can effectively detect radiation. X-rays or gamma rays emitted from a radiation source are incident on a scintillator, where the radiation is absorbed to produce scintillation light. The light signal is then converted into an electrical signal by a photodetector, which then collects, stores, and displays the electrical signal, enabling accurate measurement of many physical parameters, such as the energy, momentum, direction, and duration, of these invisible high-energy radiation or particles. Currently, detectors made from inorganic scintillation crystals are widely used in many fields, including high-energy physics, aerospace physics, industrial nondestructive testing, safety audits, mineral and oil exploration, and nuclear medicine imaging (X-CT, TOF-PET). These detectors represent the mainstream of scintillation material development and have enormous market potential.

[0003] With the rapid development of nuclear exploration and related technologies, higher requirements are being put forward for the performance of scintillation crystals, and the traditional NaI:Tl, CsI:Tl, Bi4Ge3O 12Scintillation crystals such as (BGO), BaF2, and PbWO4 (PWO) are no longer able to meet the requirements for use, and the development of scintillation crystals with high density, large atomic number, high light output, fast decay, and radiation resistance has been a long-standing goal. Next-generation garnet-structure aluminate scintillation crystals have gradually become the focus of research due to their high light output, excellent energy resolution, fast decay, and other properties.

[0004] Rare-earth doped garnet structure aluminates can be considered as a distorted dodecahedron in which regular tetrahedrons and regular octahedrons are spatially interconnected through oxygen ions at the apex angles, and the voids formed are connected to each other through oxygen ions at the apex angles. One unit has eight stoichiometric units, [A 3+ ]3[B 3+ ]2[Y 3+ ]3O 12 There is a molecule of Y 3+ is located within a tetrahedron of four oxygen ions, and B 3+ is located within an octahedron of six oxygen ions, and A 3+ is located in a distorted dodecahedron formed by the gap between a regular tetrahedron and a regular octahedron. Ce 3+ When doped with some trivalent rare earth ions such as Ce, they generally occupy the dodecahedral sites. 3+ Doped gadolinium aluminum gallium scintillation crystal (Gd3Al2Ga3O 12 :Ce, GAGG:Ce) has been developed under the guidance of "band gap engineering" in recent years. 3+ is used as an activator, and Ce 3+ This crystal utilizes the 5d → 4f parity allowed transition to obtain fast decay emission. This crystal has characteristics such as high light output, fast emission decay, large effective atomic number, high density, no self-radiation, and non-deliquescent, and has excellent overall performance and great prospects for development. With the further development of PET technology, the introduction of time-of-flight (TOF) technology has been proposed to improve its imaging resolution, reduce patient dose, and shorten scan times. However, TOF technology requires the scintillator to have a faster decay time and higher light yield, corresponding to higher image resolution and positioning accuracy.

[0005] The fast component of the scintillation decay time of the GAGG:Ce crystal is about 90 ns, while that of the conventional bismuth germanate (Bi4Ge3O 12 Although the decay time is significantly faster than that of GAGG:Ce (abbreviated as BGO), a shorter scintillation decay time is required for practical applications to better demonstrate its advantages. In order to accelerate the scintillation decay rate of GAGG:Ce crystals, Patent Document 1 discloses a method of doping rare earth lattice sites and adjusting the Al-Ga ratio to improve the GAGG scintillation and optical performance. In addition to adjusting the substrate components, co-doping with ions is also the most common means to adjust the scintillation performance. Wu et al. 2+ Co-doping with Ce and partially doping with Ce through a charge balancing mechanism 3 Ce emits light faster 4+ converted to Mg, thereby shortening the scintillation decay time of GAGG:Ce crystals, but the light yield and energy resolution were reduced to some extent (Non-Patent Document 1). 2+ Co-doping can significantly shorten the decay time, and the effect is 2+ reported that the scintillation response time is superior to co-doping (Non-Patent Document 2). The method of shortening the scintillation response time disclosed in Patent Document 2 is to co-dope rare earth lattice sites, and the effect of co-doping ions on the Al site has not been examined. Patent Document 3 discloses gadolinium aluminum gallium tyrration materials improved by doping octahedral lattice sites, and their manufacturing methods and applications. It discloses that the Al site is co-doped 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 this mainly depends on the change in the spatial structure, and Gd 3+ and Al 3+ By co-doping with elements with ionic radii between 0.01 and 0.1, they are preferentially distributed in the octahedral lattice sites around the luminescent center Ce, suppressing the formation of antisite defects and thereby accelerating decay. 3+ It does not consider whether Ce4+ The presence of ions was not taken into consideration. After co-doping with the above ions, the quality factor was slightly improved, but the improvement effect was not obvious. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2014 / 171985 [Patent Document 2] International Publication No. 2017 / 059832 [Patent Document 3] Chinese Patent Application Publication No. 115322784 [Non-patent literature]

[0007] [Non-Patent Document 1] Yuntao Wu, Fang Meng, Qi Li, Merry Koschan, and Charles L. Melcher, "Role of Ce4+ in the Scintillation Mechanism of Codoped Gd3Ga3Al2O12:Ce", PHYSICAL REVIEW APPLIED 2, 044009 (2014), [Non-patent document 2] Kei Kamada, Martin Nikl, Shunsuke Kurosawa, Alena Beitlerova, Aya Nagura, Yasuhiro Shoji, "Alkali earth co-doping effects on luminescence and scintillation properties of Ce doped Gd3Al2Ga3O12 scintillator", Optical Materials 41 (2015) 63-66 Summary of the Invention [Problem to be solved by the invention]

[0008] In order to achieve the practical needs and the above-mentioned objects, the object of the present invention is to provide a compound having an ionic radius and electronegativity of Al 3+ Similar to the [Ar]3d n 4s 1 ~ 2 The present invention provides a garnet-structured aluminate scintillation material doped with a transition metal element (n≧5), and a method for producing the same and its applications. [Means for solving the problem]

[0009] In one aspect, the present invention provides a transition metal element-doped garnet-structure aluminate scintillation material, the chemical formula of the transition metal element-doped garnet-structure aluminate scintillation material being RE 3-x-a Ce x A a Al 5-y-z D y M z O 12 where x is 0 <x≦0.15、yは0≦y≦3、zは0<z≦0.1、aは0≦a≦0.1であり、 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; A is selected from at least one of Li, Mg, Ca, K, and Na; D is selected from at least one of Ga and In, The M is a transition metal element and is selected from at least one of Cr, Mn, Fe, Co, and Ni.

[0010] In the present invention, the ionic radius and electronegativity are Al 3+ Compared with Gd, these transition metal elements (at least one of Cr, Mn, Fe, Co, and Ni) preferentially occupy the Al site, and their ionic radii, electronegativities, etc. are similar to those of Al. 3+At the same time, the electron configuration of these transition metal elements is similar to [Ar]3d n 4s 1 ~ 2 (n≧5) and the electron configuration of the Ce atom is [Xe]4f 1 5d 1 6s 2 When the co-doping atom and the Ce atom are close to each other, Ce tends to form a stable +4 valence, thereby accelerating the scintillation decay and improving the quality factor. Doping with a transition metal element achieves a faster luminescence decay rate, including at least one shortening of the decay time of photoluminescence or scintillation luminescence. More preferably, in addition to the faster decay time, at least one of improved light output, better energy resolution, and reduced afterglow is also achieved. The present invention produces a new scintillation material with high quality factor and ultrafast luminescence performance, which better meets the needs of high-energy physics, space physics, industrial nondestructive testing, safety audits, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET).

[0011] Preferably, z is in the range of 0.00001≦z≦0.05.

[0012] Preferably, x is 0.001 <x≦0.05である。

[0013] Preferably, the transition metal element-doped garnet structure aluminate scintillation material is a transition metal element-doped garnet structure aluminate scintillation polycrystalline powder, a transition metal element-doped garnet structure aluminate scintillation ceramic, or a transition metal element-doped garnet structure aluminate scintillation single crystal.

[0014] In a second aspect, the present invention provides a method for producing a transition metal element-doped garnet-structure aluminate scintillation material, the chemical formula of the transition metal element-doped garnet-structure aluminate scintillation material is: 3-x-a Ce x A aAl 5-y-z D y M z O 12 where x is 0 < x ≤ 0.15, y is 0 ≤ y ≤ 3, z is 0 < z ≤ 0.1, a is 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, Yb, the A is selected from at least one of Li, Mg, Ca, K, Na, the D is selected from at least one of Ga, In, and the M is a transition metal element selected from at least one of Cr, Mn, Fe, Co, Ni. When the transition metal element-doped garnet structure aluminate scintillation material is a transition metal element-doped garnet structure aluminate scintillation polycrystalline powder, its manufacturing method is as follows. (1) Weigh CeO2, Al2O3, the oxide of RE, the oxide of D, and the oxide of M as raw materials according to the chemical formula of the transition metal element-doped garnet structure aluminate scintillation polycrystalline powder, and mix them to obtain a mixed powder. (2A) Perform a solid-phase reaction on the mixed powder to obtain the transition metal element-doped garnet structure aluminate scintillation polycrystalline powder.

[0015] Preferably, before mixing, the raw materials are pre-sintered. The pre-sintering is at a temperature of 1100 °C for 20 hours. The solid-phase reaction is at a temperature of 1200 - 2000 °C for 5 - 200 hours.

[0016] In a third aspect, the present invention provides a method for manufacturing a transition metal element-doped garnet structure aluminate scintillation material. The chemical formula of the transition metal element-doped garnet structure aluminate scintillation material is RE 3-x-a Ce x A a Al 5-y-z D y M z O 12where x is 0 < x ≤ 0.15, y is 0 ≤ y ≤ 3, z is 0 < z ≤ 0.1, a is 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, Yb, the A is selected from at least one of Li, Mg, Ca, K, Na, the D is selected from at least one of Ga, In, and the M is a transition metal element selected from at least one of Cr, Mn, Fe, Co, Ni. When the transition metal element-doped garnet structure aluminate scintillation material is a transition metal element-doped garnet structure aluminate scintillation ceramic, its manufacturing method is as follows. (1) Weigh CeO2, Al2O3, the oxide of RE, the oxide of D, and the oxide of M according to the chemical formula of the transition metal element-doped garnet structure aluminate scintillation polycrystalline powder, and mix them to obtain a mixed powder. (2B) After forming the mixed powder into a compact, sinter it to obtain the transition metal element-doped garnet structure aluminate scintillation ceramic.

[0017] Preferably, before mixing, the raw materials are pre-sintered. The pre-sintering is at a temperature of 1100 °C for 20 hours. The forming method of the compact includes at least one of dry pressing and cold isostatic pressing. Preferably, the pressure of the dry pressing is 10 - 35 MPa, and the pressure of the cold isostatic pressing is 2 - 5 GPa. The sintering method is at least one of non-pressure sintering, hot pressing sintering, and hot isostatic pressing sintering. Preferably, the non-pressure sintering is at a temperature of 1200 - 2000 °C for 5 - 200 hours.

[0018] In a fourth aspect, the present invention provides a method for manufacturing a transition metal element-doped garnet structure aluminate scintillation material. The chemical formula of the transition metal element-doped garnet structure aluminate scintillation material is RE 3-x-a Cex A a Al 5-y-z D y M z O 12 where x is 0 < x ≤ 0.15, y is 0 ≤ y ≤ 3, z is 0 < z ≤ 0.1, a is 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, Yb, A is selected from at least one of Li, Mg, Ca, K, Na, D is selected from at least one of Ga, In, and M is a transition metal element selected from at least one of Cr, Mn, Fe, Co, Ni. When the transition metal element doped garnet structure aluminate scintillation material is a transition metal element doped garnet structure aluminate scintillation single crystal, its manufacturing method is as follows. (1) Weigh CeO2, Al2O3, the oxide of RE, the oxide of D, and the oxide of M as raw materials according to the chemical formula of the transition metal element doped garnet structure aluminate scintillation polycrystalline powder, and mix them to obtain a mixed powder. (2C) Melt the mixed powder by heating to initiate the growth of a single crystal. The single crystal growth method includes any one of the Czochralski method, the Bridgman method, the temperature gradient method, the heat exchange method, the kiloprocess method, the top-seed solution growth method, the flux method, and the micro-pulling method.

[0019] Preferably, before mixing, the raw materials are pre-sintered. The pre-sintering is carried out at a temperature of 1100 °C for 20 hours. The heating method is resistance heating, electromagnetic induction heating, or light heating. The parameters of the Czochralski method include parameter design of required dimensions, temperature field design, PID quality control temperature, pulling speed, and rotation speed. The parameters of the Bridgman method include parameter design of required dimensions, temperature field design, and growth rate.

[0020] In the fifth aspect, the present invention provides applications of the above-mentioned transition metal element-doped garnet-structure aluminate scintillation materials in high energy physics, space physics, industrial non-destructive testing, safety auditing, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET). [Effects of the Invention]

[0021] 1. In this invention, a technical solution for garnet structure aluminate scintillation material doped with transition metal elements whose ionic radius and electronegativity are similar to those of Al3+ is proposed, and suitable doping ions are selected based on reasonable prediction and experimental verification. 2. In the present invention, after the garnet-structure aluminate scintillation material is doped with transition metal elements, the luminescence performance of the material is significantly improved, including but not limited to the quality factor (light yield / scintillation decay time) related to the scintillation performance being significantly improved, the scintillation rise time or decay time being shortened, and the afterglow level being significantly reduced. 3. In the present invention, the scintillation material with high quality factor obtained by doping transition metal elements into the garnet structure aluminate scintillation material can be better applied in high energy physics, space physics, industrial non-destructive testing, safety auditing, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET). [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a scintillation decay time spectrum of the single crystal of Example 18. [Figure 2] FIG. 2 is a multi-channel energy spectrum of the single crystal of Example 18. [Figure 3] FIG. 3 is an X-ray excitation spectrum of the single crystal of Example 18. [Figure 4] FIG. 4 shows the afterglow decay spectrum of the single crystal of Example 18. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention will be further described below through the following embodiments. The following embodiments are provided to illustrate the present invention and are not intended to limit the present invention.

[0024] In the present disclosure, GAGG:Ce includes, for example, Cr, Mn, Fe, Co, Ni, etc., which have a radius, ionic radius, and electronegativity of Al. 3+ The doping element preferentially occupies the Al site rather than Gd, and its ionic radius, electronegativity, etc. are more similar to those of Al, so it has less influence on the surrounding crystal field. At the same time, the electron configuration of these transition metal elements is [Ar]3d n 4s 1 ~ 2 (n≧5) and the electron configuration of the Ce atom is [Xe]4f 1 5d 1 6s 2 When the co-doping atom and the Ce atom are close to each other, Ce tends to form a stable +4 valence, thereby accelerating scintillation decay and significantly improving the quality factor. This method is generally applicable to garnet-structure aluminate scintillation materials and is expected to yield novel component materials with excellent performance. This method is generally applicable to garnet-structure aluminate scintillation materials and is of great significance in improving the scintillation performance of garnet-structure aluminate scintillation materials and is expected to yield novel component materials with excellent performance.

[0025] In addition to achieving a significant improvement in the quality factor, the present invention also results in at least one of the following: a shorter scintillation rise time, a significant reduction in the afterglow level, an improvement in energy resolution, and an increase in the fluorescence intensity or X-ray excited emission intensity. If the z value is too high, performance degradation occurs in the quality factor, energy resolution, afterglow, fluorescence intensity, or X-ray excited emission intensity.

[0026] In the present disclosure, the chemical formula of the transition metal element-doped garnet-structure aluminate scintillation material is RE3-x-a Ce x A a Al 5-y-z D y M z O 12 where x is 0 < x ≤ 0.15, y is 0 ≤ y ≤ 3, z is 0 < z ≤ 0.1, and a may be 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 one of Ga and In, and M is a co-doping element and is selected from at least one of Cr, Mn, Fe, Co, and Ni. In any embodiment, RE 3-x Ce x Al 5-y-z D y M z O 12 Another A element dopant may be added to RE and incorporated into the RE lattice sites. The A element specifically includes at least one of Li, Mg, Ca, K, and Na. Preferably, the garnet-structured aluminate scintillation material improved by doping with the transition metal element is polycrystalline powder, ceramics, or a single crystal.

[0027] In any embodiment, when RE is Gd, D is Ga, and M is Cr, z is 0.003 ≤ z ≤ 0.05; when RE is Gd, D is Ga, and M is Mn, z is 0.0002 ≤ z ≤ 0.05; when RE is Gd, D is Ga, and M is Fe, z is 0.003 ≤ z ≤ 0.05; when RE is Gd, D is Ga, and M is Co, z is 0.003 ≤ z ≤ 0.05; when RE is Gd, D is Ga, and M is Ni, z is 0.001 ≤ z ≤ 0.05.

[0028] In any embodiment, when RE is Lu and M is Cr, z is 0.001 ≤ z ≤ 0.05; when RE is Lu and M is Mn, z is 0.0004 ≤ z ≤ 0.05; when RE is Lu and M is Fe, z is 0.003 ≤ z ≤ 0.05; when RE is Lu and M is Co, z is 0.001 ≤ z ≤ 0.05; when RE is Lu and M is Ni, z is 0.0006 ≤ z ≤ 0.05.

[0029] In any embodiment, when RE is Y and M is Cr, z is 0.003≦z≦0.05; when RE is Y and M is Mn, z is 0.0004≦z≦0.05; when RE is Y and M is Fe, z is 0.001≦z≦0.05; when RE is Y and M is Co, z is 0.0006≦z≦0.05; and when RE is Y and M is Ni, z is 0.0006≦z≦0.05.

[0030] The following is an exemplary method for preparing the improved garnet-structure aluminate scintillation material doped with a transition metal element provided by the present invention. The obtained transition-metal-doped garnet-structure aluminate scintillation material is a polycrystalline powder, a ceramic, or a single crystal. The ceramic includes transparent ceramics and non-transparent ceramics.

[0031] CeO2, Al2O3, rare earth oxides (RE m O n ), Ga or In oxide (D2O3) is used as raw material, and the molar ratio of raw material components is m O n The raw materials were blended according to the following formula: CeO2:Al2O3:D2O3 = (3 - x) / m:x:(5 - yz) / 2:y / 2, and thoroughly mixed to obtain a mixed powder. The purity of all raw materials used was 99.99% (4N) or higher. Preferably, before blending, the starting materials were placed in a muffle furnace under an air atmosphere and calcined at 1100°C for 20 hours to remove adsorbed water, crystallization water, and some organic matter (such as oxalate ions that may remain in the rare earth raw materials) from the raw materials.

[0032] The mixed powder may be directly fired at 1200 to 2000°C for 5 to 200 hours to cause a solid-state reaction, thereby obtaining a polycrystalline powder. Preferably, the solid-state reaction may be carried out at a temperature of 1400 to 1600°C for 10 to 50 hours. In an optional embodiment, in the production of the garnet-structure aluminate scintillation polycrystalline powder, the obtained ceramics and single crystals may be crushed into powder.

[0033] The mixed powder may be directly pressed into a block using a cold isostatic press (pressure 2-5 GPa) and sintered at 1200-2000°C for 5-200 hours to obtain ceramics. Alternatively, transparent ceramics may be produced by adjusting the sintering process, such as using hot press sintering or vacuum sintering. The pressure used to press into a block may be 2-5 GPa. Preferably, the solid-state reaction may be carried out at a temperature of 1400-1600°C for 10-50 hours.

[0034] Single crystals are produced by placing a mixed powder or polycrystalline powder in a container, melting it by heating (such as resistance heating, electromagnetic induction heating, or light heating), and slowly crystallizing it from the melt. Specific growth methods include the Czochralski method, the Bridgman method, the temperature gradient method, the heat exchange method, the Kyropoulos method, the top-seeded solution growth method, the flux method, and the micro-pulling down method (μ-PD). The container used may 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 may be one or more of air, argon, nitrogen, carbon dioxide, and carbon monoxide, or a mixture of these. In any embodiment, the single crystal is grown by the Czochralski method, the container is an iridium crucible, induction heating is used, the growth atmosphere is high-purity nitrogen, and the crystal is pulled up while rotating. More preferably, the pulling speed for growing the single crystal by the Czochralski method is 0.7 to 6.0 mm / h, and the rotation speed is 3 to 15 r / min.

[0035] In the present application, when preparing a transition metal element-doped garnet-structure aluminate scintillation material, a very small amount of doping element M is doped into the rare earth RE site. However, due to technical limitations, it is difficult to obtain an accurate doping content using conventional characterization methods. Naturally, even if a very small amount of doping element M is doped into the rare earth RE site, there is no fundamental change in the performance of the material itself. Furthermore, the obtained transition metal element-doped garnet-structure aluminate scintillation material has a high quality factor and can be better applied in high-energy physics, space physics, industrial non-destructive testing, safety audits, mineral and oil well exploration, and nuclear medicine imaging (X-CT, TOF-PET).

[0036] The present invention will be described in more detail below through examples. Similarly, the following examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention are within the scope of the present invention. The specific process variables in the following examples are merely examples within the applicable range, i.e., those skilled in the art can select them within an appropriate range based on the description of the present invention, and are not limited to the specific numerical values ​​in the following examples.

[0037] Example 1 (Growth of Cr-doped GAGG:Ce single crystals by the Czochralski method) Single crystals were grown using the Czochralski method. The molar ratios of Gd2O3:CeO2:Al2O3:Ga2O3:Cr2O3 were 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, and 0.1). After thorough mixing, the mixture was cold isostatically pressed (3 GPa). The pressed block is placed in an iridium crucible, and is then fully melted by induction heating under a protective nitrogen atmosphere. After seed crystals are inoculated, the block is slowly pulled out of the melt to grow a single crystal of the desired size. 2.97 Ce 0.03Al 2.3-z Ga 2.7 Cr z O 12 The single crystal was obtained, among which the parameters of the Czochralski method included the required size parameter design, temperature field design, PID quality control temperature, pulling speed of 0.7~6.0mm / h, and rotation speed of 3~15r / min.

[0038] Example 2 (Growth of Cr-doped GAGG:Ce single crystals by the micro-pulling-down method) Single crystals were grown using the micro-pulling down method. The molar ratios of Gd2O3:CeO2:Al2O3:Ga2O3:Cr2O3 = 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, and 0.1) were mixed thoroughly and homogeneously. The mixture was pre-sintered at 1450 °C in a muffle furnace. The sintered materials were then placed in an iridium crucible and melted thoroughly by induction heating under a nitrogen gas protective atmosphere. After the seed crystal was brought into contact with the melt, it was slowly pulled down and Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 The single crystal was obtained. The parameters of the micro-pulling down process include the required size parameter design, temperature field design, and the micro-pulling down process speed of 3-20 mm / h.

[0039] Example 3 (Preparation of Cr-doped GAGG:Ce polycrystalline powder) The mixture was prepared according to Example 2, thoroughly mixed uniformly, and then placed in an alumina crucible and fired at 1600°C for 10 hours in a muffle furnace to allow a sufficient solid-state reaction to occur, resulting in the formation of Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 A polycrystalline powder was obtained.

[0040] Example 4 (Preparation of Cr-doped GAGG:Ce ceramics) Non-transparent: The powder was mixed thoroughly and uniformly according to Example 2, and then pressed into a block by cold isostatic pressing (3 GPa pressure). The pressed block was placed in an alumina crucible and sintered at 1600 °C for 10 h in a muffle furnace to achieve a sufficient solid-state reaction, resulting in the formation of Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 Non-transparent ceramics were obtained. Transparent: The powder was mixed thoroughly and uniformly according to Example 2, and then pressed under cold isostatic pressure (3 GPa pressure). Then, a sufficient solid-state reaction was carried out in a vacuum hot press furnace (1600°C, 50 hours). Air bubbles and voids were removed as much as possible, and the Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Cr z O 12 Transparent ceramics were obtained.

[0041] Example 5 (Growth of Mn-doped GAGG:Ce single crystals by the Czochralski method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Mn2O3 was 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). The next step was the same as in Example 1, and Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Mn z O 12 A single crystal was obtained.

[0042] Example 6 (Growth of Mn-doped GAGG:Ce single crystals by the micro-pulling-down method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Mn2O3 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). The next step was the same as in Example 2, and Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 A single crystal was obtained.

[0043] Example 7 (Preparation of Mn-doped GAGG:Ce polycrystalline powder) The compounding was carried out according to Example 6, and the next step was the same as in Example 3, to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 A polycrystalline powder was obtained.

[0044] Example 8 (Preparation of Mn-doped GAGG:Ce ceramics) The compounding was carried out according to Example 6, and the next step was the same as in Example 4, to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Mn z O 12 Non-transparent and transparent ceramics were obtained.

[0045] Example 9 (Growth of Fe-doped GAGG:Ce single crystals by the Czochralski method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Fe2O3 was 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). The next step was the same as in Example 1, and Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Fe z O 12 A single crystal was obtained.

[0046] Example 10 (Growth of Fe-doped GAGG:Ce single crystals by the micro-pulling-down method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Fe2O3 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). The next step was the same as in Example 2, and Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Fe z O 12 A single crystal was obtained.

[0047] Example 11 (Preparation of Fe-doped GAGG:Ce polycrystalline powder) The compounding was carried out according to Example 10, and the next step was 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 A polycrystalline powder was obtained.

[0048] Example 12 (Preparation of Fe-doped GAGG:Ce ceramics) The compounding was carried out according to Example 10, and the next step was the same as in Example 4, to obtain Gd2.985 Ce 0.015 Al 2.3-z Ga 2.7 Fe z O 12 Non-transparent and transparent ceramics were obtained.

[0049] Example 13 (Growth of Co-doped GAGG:Ce single crystals by the Czochralski method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:CoO was 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). The next step was the same as in Example 1, and Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Co z O 12 A single crystal was obtained.

[0050] Example 14 (Growth of Co-doped GAGG:Ce single crystals by the micro-pulling-down method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:CoO was 1.4925:0.015:(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). The next step was the same as in Example 2, and Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Co z O 12 A single crystal was obtained.

[0051] Example 15 (Preparation of Co-doped GAGG:Ce polycrystalline powder) The compounding was carried out according to Example 14, and the next step was the same as in Example 3, to obtain Gd 2.985 Ce 0.015Al 2.3-z Ga 2.7 Co z O 12 A polycrystalline powder was obtained.

[0052] Example 16 (Preparation of Co-doped GAGG:Ce ceramics) The compounding was carried out according to Example 14, and the next step was the same as in Example 4, to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Co z O 12 Non-transparent and transparent ceramics were obtained.

[0053] Example 17 (Growth of Ni-doped GAGG:Ce single crystals by the Czochralski method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Ni2O3 was 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). The next step was the same as in Example 1, and Gd 2.97 Ce 0.03 Al 2.3-z Ga 2.7 Ni z O 12 A single crystal was obtained.

[0054] Example 18 (Growth of Ni-doped GAGG:Ce single crystals by the micro-pulling-down method) The molar ratio of Gd2O3:CeO2:Al2O3:Ga2O3:Ni2O3 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). The next step was the same as in Example 2, and Gd 2.985 Ce 0.015 Al 2.3-zGa 2.7 Ni z O 12 A single crystal was obtained.

[0055] Example 19 (Preparation of Ni-doped GAGG:Ce polycrystalline powder) The compounding was carried out according to Example 18, and the next step was 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 A polycrystalline powder was obtained.

[0056] Example 20 (Preparation of Ni-doped GAGG:Ce ceramics) The compounding was carried out according to Example 18, and the next step was the same as in Example 4, to obtain Gd 2.985 Ce 0.015 Al 2.3-z Ga 2.7 Ni z O 12 Non-transparent and transparent ceramics were obtained.

[0057] Example 21 (Growth of Cr-doped LuAG:Ce single crystals by the Czochralski method) The molar ratio of Lu2O3:CeO2:Al2O3:Cr2O3 was 1.485:0.03:(5-z) / 2: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). The next step was carried out in the same manner as in Example 1, to obtain Lu 2.97 Ce 0.03 Al 5-z Cr z O 12 A single crystal was obtained.

[0058] Example 22 (Growth of Cr-doped LuAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Lu2O3:CeO2:Al2O3:Cr2O3 was 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Cr z O 12 A single crystal was obtained.

[0059] Example 23 (Preparation of Cr-doped LuAG:Ce polycrystalline powder) The compounding was carried out according to Example 22, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Cr z O 12 A polycrystalline powder was obtained.

[0060] Example 24 (Preparation of Cr-doped LuAG:Ce ceramics) The compounding was carried out according to Example 22, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Cr z O 12 Non-transparent and transparent ceramics were obtained.

[0061] Example 25 (Growth of Mn-doped LuAG:Ce single crystals by the Czochralski method) The molar ratio of Lu2O3:CeO2:Al2O3:Mn2O3 was 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Mn z O12 A single crystal was obtained.

[0062] Example 26 (Growth of Mn-doped LuAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Lu2O3:CeO2:Al2O3:Mn2O3 was 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Mn z O 12 A single crystal was obtained.

[0063] Example 27 (Preparation of Mn-doped LuAG:Ce polycrystalline powder) The compounding was carried out according to Example 26, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Mn z O 12 A polycrystalline powder was obtained.

[0064] Example 28 (Preparation of Mn-doped LuAG:Ce ceramics) The compounding was carried out according to Example 26, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Mn z O 12 Non-transparent and transparent ceramics were obtained.

[0065] Example 29 (Growth of Fe-doped LuAG:Ce single crystals by the Czochralski method) The molar ratio of Lu2O3:CeO2:Al2O3:Fe2O3 was 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Fe z O 12 A single crystal was obtained.

[0066] Example 30 (Growth of Fe-doped LuAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Lu2O3:CeO2:Al2O3:Fe2O3 was 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Fe z O 12 A single crystal was obtained.

[0067] Example 31 (Preparation of Fe-doped LuAG:Ce polycrystalline powder) The compounding was carried out according to Example 30, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Fe z O 12 A polycrystalline powder was obtained.

[0068] Example 32 (Preparation of Fe-doped LuAG:Ce ceramics) The compounding was carried out according to Example 30, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Fe z O 12Non-transparent and transparent ceramics were obtained.

[0069] Example 33 (Growth of Co-doped LuAG:Ce single crystals by the Czochralski method) The molar ratio of Lu2O3:CeO2:Al2O3:CoO was 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Co z O 12 A single crystal was obtained.

[0070] Example 34 (Growth of Co-doped LuAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Lu2O3:CeO2:Al2O3:CoO was 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Lu 2.985 Ce 0.015 Al 5-z Co z O 12 A single crystal was obtained.

[0071] Example 35 (Preparation of Co-doped LuAG:Ce polycrystalline powder) The compounding was carried out according to Example 34, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Co z O 12 A polycrystalline powder was obtained.

[0072] Example 36 (Preparation of Co-doped LuAG:Ce ceramics) The compounding was carried out according to Example 34, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Co z O 12 Non-transparent and transparent ceramics were obtained.

[0073] Example 37 (Growth of Ni-doped LuAG:Ce single crystals by the Czochralski method) The molar ratio of Lu2O3:CeO2:Al2O3:Ni2O3 was 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Lu 2.97 Ce 0.03 Al 5-z Ni z O 12 A single crystal was obtained.

[0074] Example 38 (Growth of Ni-doped LuAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Lu2O3:CeO2:Al2O3:Ni2O3 was 1.4925:0.015:(5-z) / 2: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), and the next step was the same as in Example 2, to obtain Lu 2.985 Ce 0.015 Al 5-z Ni z O 12 A single crystal was obtained.

[0075] Example 39 (Preparation of Ni-doped LuAG:Ce polycrystalline powder) The compounding was carried out according to Example 38, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Niz O 12 A polycrystalline powder was obtained.

[0076] Example 40 (Preparation of Ni-doped LuAG: Preparation of Ce ceramics) The compounding was carried out according to Example 38, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Ni z O 12 Non-transparent and transparent ceramics were obtained.

[0077] Example 41 (Growth of Cr-doped YAG:Ce single crystals by the Czochralski method) The molar ratio of Y2O3:CeO2:Al2O3:Cr2O3 was 1.485:0.03:(5-z) / 2: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). The next step was the same as in Example 1, and Y 2.97 Ce 0.03 Al 5-z Cr z O 12 A single crystal was obtained.

[0078] Example 42 (Growth of Cr-doped YAG:Ce single crystals by the micro-pulling-down method) The molar ratios of Y2O3:CeO2:Al2O3:Cr2O3 were mixed in a ratio of 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Y. 2.985 Ce 0.015 Al 5-z Cr z O 12 A single crystal was obtained.

[0079] Example 43 (Production of Cr-doped YAG:Ce polycrystalline powder) The compounding was carried out according to Example 42, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Cr z O 12 A polycrystalline powder was obtained.

[0080] Example 44 (Preparation of Cr-doped YAG:Ce ceramics) The compounding was carried out according to Example 42, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Cr z O 12 Non-transparent and transparent ceramics were obtained.

[0081] Example 45 (Growth of Mn-doped YAG:Ce single crystals by the Czochralski method) The molar ratios of Y2O3:CeO2:Al2O3:Mn2O3 were mixed in a ratio of 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Mn z O 12 A single crystal was obtained.

[0082] Example 46 (Growth of Mn-doped YAG:Ce single crystals by the micro-pulling-down method) The molar ratios of Y2O3:CeO2:Al2O3:Mn2O3 were mixed in a ratio of 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Y. 2.985 Ce0.015 Al 5-z Mn z O 12 A single crystal was obtained.

[0083] Example 47 (Production of Mn-doped YAG:Ce polycrystalline powder) The compounding was carried out according to Example 46, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Mn z O 12 A polycrystalline powder was obtained.

[0084] Example 48 (Preparation of Mn-doped YAG:Ce ceramics) The compounding was carried out according to Example 46, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Mn z O 12 Non-transparent and transparent ceramics were obtained.

[0085] Example 49 (Growth of Fe-doped YAG:Ce single crystals by the Czochralski method) The molar ratio of Y2O3:CeO2:Al2O3:Fe2O3 was 1.485:0.03:(5-z) / 2: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). The next step was the same as in Example 1, and Y 2.97 Ce 0.03 Al 5-z Fe z O 12 A single crystal was obtained.

[0086] Example 50 (Growth of Fe-doped YAG:Ce single crystals by the micro-pulling-down method) The molar ratios of Y2O3:CeO2:Al2O3:Fe2O3 were mixed in a ratio of 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Fe z O 12 A single crystal was obtained.

[0087] Example 51 (Production of Fe-doped YAG:Ce polycrystalline powder) The compounding was carried out according to Example 50, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Fe z O 12 A polycrystalline powder was obtained.

[0088] Example 52 (Preparation of Fe-doped YAG:Ce ceramics) The compounding was carried out according to Example 50, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Fe z O 12 Non-transparent and transparent ceramics were obtained.

[0089] Example 53 (Growth of Co-doped YAG:Ce single crystals by the Czochralski method) The molar ratio of Y2O3:CeO2:Al2O3:CoO was 1.485:0.03:(5-z) / 2: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). The next step was the same as in Example 1, and Y 2.97 Ce 0.03 Al 5-z Co z O 12A single crystal was obtained.

[0090] Example 54 (Growth of Co-doped YAG:Ce single crystals by the micro-pulling-down method) The molar ratio of Y2O3:CeO2:Al2O3:CoO was 1.4925:0.015:(5-z) / 2: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). The next step was the same as in Example 2, and Y 2.985 Ce 0.015 Al 5-z Co z O 12 A single crystal was obtained.

[0091] Example 55 (Preparation of Co-doped YAG:Ce polycrystalline powder) The compounding was carried out according to Example 54, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Co z O 12 A polycrystalline powder was obtained.

[0092] Example 56 (Preparation of Co-doped YAG:Ce ceramics) The compounding was carried out according to Example 54, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Co z O 12 Non-transparent and transparent ceramics were obtained.

[0093] Example 57 (Growth of Ni-doped YAG:Ce single crystals by the Czochralski method) The molar ratios of Y2O3:CeO2:Al2O3:Ni2O3 were mixed in a ratio of 1.485:0.03:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 1 to obtain Y 2.97 Ce 0.03 Al 5-z Ni z O 12 A single crystal was obtained.

[0094] Example 58 (Growth of Ni-doped YAG:Ce single crystals by the micro-pulling-down method) The molar ratios of Y2O3:CeO2:Al2O3:Ni2O3 were mixed in a ratio of 1.4925:0.015:(5-z) / 2: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), and the next step was carried out in the same manner as in Example 2 to obtain Y 2.985 Ce 0.015 Al 5-z Ni z O 12 A single crystal was obtained.

[0095] Example 59 (Preparation of Ni-doped YAG:Ce polycrystalline powder) The compounding was carried out according to Example 58, and the next step was the same as in Example 3, 2.985 Ce 0.015 Al 5-z Ni z O 12 A polycrystalline powder was obtained.

[0096] Example 60 (Preparation of Ni-doped YAG:Ce ceramics) The compounding was carried out according to Example 58, and the next step was the same as in Example 4, 2.985 Ce 0.015 Al 5-z Ni z O 12Non-transparent and transparent ceramics were obtained.

[0097] Table 1 shows the relative light yield and quality factor (light yield / scintillation decay time) of the single crystal of Example 18.

[0098] [Table 1]

[0099] Table 2 shows the afterglow levels of the single crystals of Example 18.

[0100] [Table 2]

[0101] Table 3 shows the relative quality factors of the non-transparent ceramics of Examples 4, 8, 12, 16 and 20 (compared to non-codoped non-transparent ceramic sheets).

[0102] [Table 3]

[0103] Table 4 shows the relative quality factors of the non-transparent ceramics of Examples 24, 28, 32, 36 and 40 (compared to non-codoped non-transparent ceramic sheets).

[0104] [Table 4]

[0105] Table 5 shows the relative quality factors of the non-transparent ceramics of Examples 44, 48, 52, 56 and 60 (compared to non-codoped non-transparent ceramic sheets).

[0106] [Table 5]

[0107] In the present invention, GAGG:Ce has an ionic radius and electronegativity similar to Al. 3+ The doping element preferentially occupies the Al site over Gd, and the ionic radius, electronegativity, etc. are similar to those of Al. 3+ At the same time, the electron configuration of these transition metal elements is similar to [Ar]3d n 4s 1 ~ 2 (n≧5) and the electron configuration of the Ce atom is [Xe]4f 1 5d 1 6s 2 When the co-doping atom and the Ce atom are close to each other, the Ce tends to form a stable +4 valence, thereby accelerating the scintillation decay and improving the quality factor. This method is generally applicable to garnet-structured aluminate scintillation materials and can provide guidance for the design of new components.

[0108] Similarly, the above examples are for the purpose of further illustrating the present invention, and do not limit the scope of the invention. Any non-essential improvements and modifications made by those skilled in the art based on the above content of the present invention are within the scope of the invention.

Claims

1. The chemical formula is: RE ３－ｘ－ａ Ce ｘ A ａ Al ５－ｙ－ｚ D ｙ M ｚ O １２ wherein x is 0<x≦0.05, y is 0≦y≦3, z is 0.00001≦z≦0.1, and a is 0≦a≦0.1; RE is a rare earth element selected from at least one of Gd, Lu, and Y; A is selected from at least one of Li, Mg, Ca, K, and Na; D is selected from at least one of Ga and In, M is a transition metal element selected from at least one of Co and Ni, When RE is Gd, D is Ga, and M is Co, z satisfies 0.003≦z≦0.05; When RE is Gd, D is Ga, and M is Ni, z satisfies 0.001≦z≦0.05; When RE is Lu and M is Co, z satisfies 0.001≦z≦0.05; When RE is Lu and M is Ni, z satisfies 0.0006≦z≦0.05; When RE is Y and M is Co, z satisfies 0.0006≦z≦0.05; When RE is Y and M is Ni, z is 0.0006≦z≦0.

05. A garnet-structure aluminate scintillation material doped with transition metal elements.

2. 2. The transition metal element-doped garnet-structure aluminate scintillation material according to claim 1, wherein x is in the range of 0.001<x≦0.

05.

3. 3. The transition metal element-doped garnet-structure aluminate scintillation material according to claim 1 or 2, characterized in that the transition metal element-doped garnet-structure aluminate scintillation material is a transition metal element-doped garnet-structure aluminate scintillation polycrystalline powder, a transition metal element-doped garnet-structure aluminate scintillation ceramic, or a transition metal element-doped garnet-structure aluminate scintillation single crystal.

4. The chemical formula of the transition metal element-doped garnet structure aluminate scintillation material is RE ３－ｘ－ａ Ce ｘ A ａ Al ５－ｙ－ｚ D ｙ M ｚ O １２ and wherein x is 0<x≦0.05, y is 0≦y≦3, z is 0.00001≦z≦0.1, and a is 0≦a≦0.1; RE is a rare earth element selected from at least one of Gd, Lu, and Y; A is selected from at least one of Li, Mg, Ca, K, and Na; D is selected from at least one of Ga and In, M is a transition metal element selected from at least one of Co and Ni, When RE is Gd, D is Ga, and M is Co, z satisfies 0.003≦z≦0.05; When RE is Gd, D is Ga, and M is Ni, z satisfies 0.001≦z≦0.05; When RE is Lu and M is Co, z satisfies 0.001≦z≦0.05; When RE is Lu and M is Ni, z satisfies 0.0006≦z≦0.05; When RE is Y and M is Co, z satisfies 0.0006≦z≦0.05; When RE is Y and M is Ni, z satisfies 0.0006≦z≦0.05; The manufacturing method is When the transition metal element-doped garnet-structure aluminate scintillation material is a polycrystalline powder, (1) CeO according to the above chemical formula ２ , Al ２ O ３ , an oxide of RE, an oxide of D, and an oxide of M are weighed as raw materials and mixed to obtain a mixed powder; (2A) subjecting the mixed powder to a solid-state reaction to obtain the transition metal element-doped garnet-structure aluminate scintillation polycrystalline powder, wherein the solid-state reaction is carried out at a temperature of 1200-2000°C for a time of 5-200 hours; When the transition metal element-doped garnet-structure aluminate scintillation material is a ceramic, (1) CeO according to the above chemical formula ２ , Al ２ O ３ , an oxide of RE, an oxide of D, and an oxide of M are weighed as raw materials and mixed to obtain a mixed powder; (2B) forming the mixed powder into a compact and then sintering it to obtain the transition metal element-doped garnet-structure aluminate scintillation ceramics, the method for forming the compact being at least one of dry pressing and cold isostatic pressing, the pressure for the dry pressing being 10-35 MPa and the pressure for the cold isostatic pressing being 2-5 GPa, the method for sintering being at least one of pressureless sintering, hot pressure sintering and hot isostatic sintering, the temperature for the pressureless sintering being 1200-2000°C and the time being 5-200 hours; When the transition metal element-doped garnet-structure aluminate scintillation material is a single crystal, (1) CeO according to the above chemical formula ２ , Al ２ O ３ , an oxide of RE, an oxide of D, and an oxide of M are weighed as raw materials and mixed to obtain a mixed powder; (2C) melting the mixed powder by heating to initiate single crystal growth, wherein the single crystal growth method includes any one of the Czochralski method, the Bridgman method, the temperature gradient method, the heat exchange method, the Kyropoulos method, the top-seeded solution growth method, the flux method, and the micro-pulling-down method, and the heating method is resistance heating, electromagnetic induction heating, or light heating. A method for producing a transition metal element-doped garnet-structure aluminate scintillation material.

5. The method according to claim 4, wherein the raw materials are pre-fired before mixing, and the pre-fired temperature is 1100°C for 20 hours.

6. Use of the transition metal element-doped garnet-structure aluminate scintillation material according to claim 1 in high energy physics, space physics, industrial non-destructive testing, safety audits, mineral and oil well exploration, and nuclear medicine imaging.

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