Eu < 3 + > and Sm < 3 + > co-doped sesquioxide-based red light scintillation crystal material as well as preparation method and application thereof

Abstract

The invention discloses a sesquioxide-based red light scintillation crystal material co-doped with Eu < 3 + > and Sm < 3 + >, and a preparation method and application thereof, and belongs to the technical field of artificial crystal growth. The chemical formula is (SmxEuyR1-x-y) 2O3, x is greater than or equal to 0.01 and less than or equal to 0.08, y is greater than or equal to 0.01 and less than or equal to 0.06, and R is selected from any one of Lu, Sc and Y. And when R is Lu, the crystal has more excellent performance, and has more advantages when being used for high-energy ray detection in an extreme environment. When R is Lu, the crystal is transparent and good in appearance, has microsecond-level decay time and high light yield, and has excellent scintillation performance and extreme environment resistance; the scintillation material can be effectively combined with photoelectric detection equipment, can be used in a nuclear radiation detection use environment with extreme temperature and intense radiation, widens the application range of the scintillation material, makes up the application blank of the traditional scintillation material in the extreme use environment, and meets the development requirements of science and technology such as nuclear detection.

Description

Technical Field

[0001] The invention belongs to the technical field of artificial crystal growth, and specifically relates to a co-doped Eu 3+ 、Sm 3+ The invention discloses a sesquioxide-based red light scintillation crystal material and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Scintillator crystal is an energy conversion material that can convert ionizing radiation of high-energy rays (X-rays, gamma rays, etc.) or high-energy particles (alpha particles, beta particles, protons, etc.) into ultraviolet / visible light under the action of high-energy radiation. Detectors made of scintillator crystals play an irreplaceable role in medical diagnostic imaging, radioactive detection, geological exploration, environmental monitoring and other fields.

[0004] Among them, in the field of extreme environment service, such as nuclear reactors, deep space and deep sea environments, due to their extreme temperatures, strong radiation and other characteristics, extremely stringent requirements are placed on scintillating materials. First of all, as far as nuclear reactors are concerned, they have ultra-high temperatures exceeding 1000°C, requiring scintillating crystals to have a higher melting point. Because there is high-energy radiation around nuclear reactors, scintillators need to have good radiation hardness. Secondly, scintillators also need to have good pressure and temperature stability to adapt to the high temperature and high pressure conditions that may exist in the nuclear reactor environment to ensure long-term performance stability. For deep space environments, extreme temperature differences and strong radiation (solar particle events, galactic cosmic rays, captured radiation belts and blackbody surface radiation) also require scintillators to have high physical and chemical stability and radiation hardness. In addition to high pressure and low temperature, the deep-sea environment also has high humidity and corrosiveness, which places higher requirements on the corrosion resistance and deliquesce resistance of scintillating materials. Traditional scintillating crystals LaBr 3 Although Ce and NaI(Tl) have high luminous efficiency, they have the disadvantages of being easy to deliquesce, corrode and have low radiation hardness. Bismuth germanate crystal (BGO) as an oxide has good physical and chemical properties, but its light output is low and it is difficult to meet the needs of detection applications in extreme working environments with extreme temperatures and strong radiation.

[0005] Rare earth sesquioxides (lutetium oxide, yttrium oxide, scandium oxide, etc.) have extremely high chemical stability, which enables them to maintain their structure and properties unchanged under extreme conditions such as high temperature and high pressure. They are potential scintillation crystal materials for use in extreme environments.

[0006] Samarium doped rare earth sesquioxide crystal R 2 O 3:Sm can achieve efficient red light scintillation luminescence, but single-doped Sm 3+ crystals generally have low light yields and poor energy resolutions, severely restricting the application of rare earth sesquioxide crystals in extreme environment detection fields such as nuclear reactors.

[0007] Therefore, there is an urgent need to invent a red light scintillation crystal material that can be applied to extreme service environments and has high light yields and high energy resolutions. Summary of the Invention

[0008] To solve the deficiencies of the prior art, the purpose of the present invention is to provide a sesquioxide-based red light scintillation crystal material co-doped with Eu 3+ , Sm 3+ , and its preparation method and application. Aiming at the problems that traditional scintillation crystals cannot meet the requirements of extreme service environments and the scintillation performance of samarium-doped rare earth sesquioxide crystals is poor, Eu 3+ and Sm 3+ are co-doped in rare earth sesquioxides. Through the energy transfer of Eu 3+ -Sm 3+ , Eu 3+ acts as a sensitizer and Sm 3+ is the luminescence center to achieve efficient red light emission, enabling the R 2 O 3 :Sm crystal to have a high light yield and excellent energy resolution greatly improved on the premise of maintaining the ability to withstand high temperature and strong radiation in nuclear radiation detection service environments.

[0009] To achieve the above purpose, the technical solution of the present invention is as follows:

[0010] In the first aspect of the present invention, a sesquioxide-based red light scintillation crystal material co-doped with Eu 3+ , Sm 3+ is provided, and its chemical formula is (Sm x Eu y R 1-x-y ) 2 O 3 , where 0.01 ≤ x ≤ 0.08, 0.01 ≤ y ≤ 0.06, and R is selected from any one of Lu, Sc, and Y.

[0011] Lutetium oxide (Lu 2 O 3 ) has an extremely high density (9.42 g / cm 3 ), and it is the matrix material with the second highest density among currently known scintillators, only slightly lower than hafnium oxide crystal HfO 2 (9.68 g / cm 3), which makes it have a very high ability to stop all kinds of rays (X-rays, gamma rays). In addition, the melting point of lutetium oxide is as high as 2450℃, and the temperature resistance can reach 2400℃, which is much higher than that of ordinary oxide scintillating materials. Lutetium oxide has excellent physical and chemical properties such as high hardness, high strength, high toughness, and stable chemical properties (chemical corrosion resistance), so it is a very potential scintillating crystal material for extreme environments. And because the density of lutetium oxide is greater than that of scandium oxide and yttrium oxide, it has a stronger ability to stop all kinds of rays, so the R is preferably Lu, co-doped with Eu 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material is preferably co-doped with Eu 3+ 、Sm 3+ Lutetium oxide-based red light scintillation crystal material, its chemical formula is (Sm x Eu y Lu 1-x-y ) 2 O 3 , where 0.01≤x≤0.08,0.01≤y≤0.06.

[0012] The co-doped Eu provided by the present invention 3+ 、Sm 3+ The lutetium oxide-based red light scintillation crystal material has the characteristics of crystal transparency, good external light, excellent scintillation performance and resistance to extreme environments. It has stable performance in extreme nuclear detection service environments. It can be effectively combined with photoelectric detection equipment, broadening the application scope of scintillation materials, filling the application gap of traditional scintillation materials in extreme service environments, and meeting the needs of scientific and technological development such as nuclear detection.

[0013] The second aspect of the present invention provides a co-doped Eu 3+ 、Sm 3+ The method for preparing a sesquioxide-based red light scintillation crystal material comprises:

[0014] Sm 2 O 3 、Eu 2 O 3 , R 2 O 3 According to the chemical formula (Sm x Eu y R 1-x-y ) 2 O 3 The ingredients are mixed and pressed into rods; wherein 0.01≤x≤0.08, 0.01≤y≤0.06, and R is selected from any one of Lu, Sc, and Y;

[0015] The material rod is sintered in an air atmosphere to obtain a polycrystalline material, and then a melt method is used to grow crystals to obtain a co-doped Eu 3+ 、Sm3+ Lutetium-based red light scintillation crystal material.

[0016] Preferably, the Sm 2 O 3 , Eu 2 O 3 , R 2 O 3 (R is any one selected from Lu, Sc, and Y) are all high-purity powders, and the purity reaches 99.999%. Using high-purity raw materials is crucial for preparing high-quality crystal materials, which can reduce impurities, improve performance, ensure test reproducibility, avoid side reactions, meet application requirements, and improve growth efficiency.

[0017] In some embodiments of the present invention, the pressing is carried out by isostatic pressing at 150 - 250 MPa for 100 - 150 s.

[0018] It should be noted that using the isostatic pressing method to prepare the rod can efficiently compress the raw material powder and reduce waste; during the pressing process, the raw material powder is uniformly pressed in all directions, so as to obtain a rod with high and uniform density, reduce the density gradient, avoid defects during crystal growth, and improve the crystal quality; it can effectively eliminate internal defects such as pores and cracks, improve the densification and mechanical strength of the rod, and provide a better basis for subsequent crystal growth.

[0019] To further increase the density of the obtained rod and improve the crystal quality, it is preferably pressed at 170 - 220 MPa for 100 - 140 s, and more preferably pressed at 190 - 210 MPa for 110 - 130 s.

[0020] In some embodiments of the present invention, the sintering is carried out at 1100 - 1300 °C for 20 - 30 h.

[0021] Sm 2 O 3 , Eu 2 O 3 and R 2 O 3 (R is any one selected from Lu, Sc, and Y) have relatively high melting points (exceeding 2000 °C), but they have good thermal stability and sintering activity at medium and low temperatures (1100 - 1300 °C). In the range of 1100 - 1300 °C, these oxides can undergo solid-phase diffusion and densification without decomposition or volatilization, ensuring the stability of the sintering process. And this temperature range is sufficient to make Sm 2 O 3 , Eu 2 O 3 and R 2 O 3(R is selected from any one of Lu, Sc, and Y) Solid phase reaction occurs between particles to form a uniform sintered body, while avoiding excessive grain growth caused by excessive temperature. This temperature range can achieve a balance between densification and grain growth, ensuring a moderate grain size, thereby obtaining high-quality crystalline materials.

[0022] In order to obtain high-quality crystalline materials, it is preferred to sinter at 1200-1300° C. for 22-26 h; further preferred is sintering at 1240-1260° C. for 23-25 ​​h.

[0023] The crystal growth temperature depends on the crystal growth method used. The present invention adopts a melt method for crystal growth, and the temperature needs to reach or be slightly higher than the melting point of the sesquioxide.

[0024] The melting point of lutetium oxide is about 2490°C, so the melt method needs to be carried out at a temperature close to or slightly higher than the melting point, and the crystal growth temperature is 2400-2500°C. Preferably, the crystal growth temperature is 2450°C.

[0025] Likewise, the melting point of scandium oxide is about 2400° C., and its crystal growth temperature is 2390-2450° C., preferably 2400° C. The melting point of yttrium oxide is about 2410° C., and its crystal growth temperature is 2410-2450° C., preferably 2410° C.

[0026] In some embodiments of the present invention, after the crystal growth is completed, it is taken out and annealed at 1600° C. for 48 hours in an air atmosphere to obtain a co-doped Eu 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material. Annealing treatment can eliminate internal stress, reduce crystal defects, optimize crystal structure, improve crystal performance and stabilize crystal composition.

[0027] In some embodiments of the present invention, the melt method includes a Czochralski method, a guided mold method, a temperature gradient method, and a crucible descent method.

[0028] In some embodiments of the present invention, when the crystal is grown by the Czochralski method, the crystal growth atmosphere is Ar and H 2 The mixed atmosphere, the seed crystal is pure R 2 O 3 The seed crystal has a pulling speed of 0.5-5 mm / h and a rotation speed of 10-30 rpm; R is selected from any one of Lu, Sc, and Y.

[0029] Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

[0030] In some embodiments of the present invention, when the guided mode method is used for crystal growth, the crystal growth atmosphere is Ar and H 2The mixed atmosphere, the seed crystal is pure R 2 O 3 The seed crystal has a pulling speed of 0.3-6 mm / h and a rotation speed of 8-38 rpm; R is selected from any one of Lu, Sc, and Y.

[0031] Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

[0032] In some embodiments of the present invention, when the temperature gradient method is used for crystal growth, the crystal growth atmosphere is Ar and H 2 The mixed atmosphere is cooled at a cooling rate of 25-30℃ / h and crystals are grown.

[0033] Preferably, when the temperature gradient method is used for crystal growth, no seed crystal is placed at the bottom, or pure R 2 O 3 The seed crystal is induced to crystallize by a top seed crystal method; R is selected from any one of Lu, Sc, and Y.

[0034] Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

[0035] In some embodiments of the present invention, when the crucible descent method is used for crystal growth, the crystal growth atmosphere is Ar and H 2 The mixed atmosphere, the seed crystal is pure R 2 O 3 Seed crystal, the crucible descent rate is 0.1~1.5mm / h.

[0036] Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

[0037] The third aspect of the present invention provides a co-doped Eu 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material or the co-doped Eu prepared by the above preparation method 3+ 、Sm 3+ Application of sesquioxide-based red light scintillation crystal materials in high-energy ray detection in extreme environments.

[0038] Preferably, the extreme environment includes a nuclear reactor environment, a deep space environment and a deep sea environment.

[0039] The fourth aspect of the present invention provides Eu 3+ In improving Lu 2 O 3 :Application of Sm crystal scintillation properties.

[0040] Preferably, the scintillation performance comprises light yield.

[0041] The beneficial effects of the present invention are as follows:

[0042] The present invention provides a sesquioxide-based red light scintillation crystal material co-doped with Eu 3+ , Sm 3+ . Its chemical formula is (Sm x Eu y R 1-x-y ) 2 O 3 , where 0.01 ≤ x ≤ 0.08, 0.01 ≤ y ≤ 0.06, and R is selected from any one of Lu, Sc, and Y. Among them, when R is Lu, the sesquioxide-based red light scintillation crystal material co-doped with Eu 3+ , Sm 3+ (Sm x Eu y Lu 1-x-y ) 2 O 3 has the most excellent performance, where 0.01 ≤ x ≤ 0.08, 0.01 ≤ y ≤ 0.06. The crystal is transparent with good appearance, has a microsecond-level decay time and a high light yield, and has excellent scintillation performance and extreme environment resistance. (Sm x Eu y Lu 1-x-y ) 2 O 3 can be effectively combined with optoelectronic detection devices, can be used in nuclear radiation detection use environments with extreme temperatures and strong radiation, broadens the application range of scintillation materials, makes up for the application blank of traditional scintillation materials in extreme service environments, and meets the needs of the development of science and technology such as nuclear detection.

[0043] The lutetium oxide scintillation crystal matrix of the present invention has an extremely high density and a very high stopping power for various rays (X-rays, γ-rays), and has extremely high radiation resistance; in addition, lutetium oxide has good physical, chemical and mechanical properties, and its melting point is as high as 2450 °C. Eu 3+ doping makes the crystal have a high light yield and excellent energy resolution. Therefore, through Eu 3+ -Sm 3+ co-doped lutetium oxide, the disadvantages of low light yield and poor energy resolution of Lu 2 O 3 :Sm crystals can be overcome, and efficient red light scintillation luminescence can be obtained through transformation. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The accompanying drawings forming a part of this specification are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0045] Figure 1(Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Fluorescence emission spectrum of red scintillation crystal materials;

[0046] Figure 2 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 、(Sm 0.01 Lu 0.99 ) 2 O 3 X-ray excitation emission spectra of BGO scintillating materials;

[0047] Figure 3 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Force-displacement curve of red scintillation crystal material against compression;

[0048] Figure 4 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 TG-DTA curve of red scintillation crystal material.

[0049] It should be noted that Figure 1 , 2 、3 in Sm,Eu:Lu 2 O 3 (Sm prepared in Example 1 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Red light flashes crystals, Figure 2 Sm:Lu 2 O 3 Sm 0.01 Lu 0.99 ) 2 O 3 Red light flashes crystals, Figure 2 The BGO in the glass is bismuth germanate crystal. DETAILED DESCRIPTION

[0050] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0051] Since the density of lutetium oxide is much greater than that of scandium oxide and yttrium oxide, it is more advantageous for detecting high-energy rays in extreme environments. 3+ 、Sm 3+ Lutetium oxide-based red light scintillation crystals.

[0052] Example 1: Czochralski growth (Sm 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Red flashing crystal

[0053] Select commercially purchased 5N grade Lu 2 O 3 、5N grade Sm 2 O 3 and 5N grade Eu 2 O 3 Powder, according to (Sm 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 The ingredients are prepared according to the chemical formula, and after being mixed evenly, the material is pressed for 120 seconds at a pressure of 200MPa by isostatic pressing to form a material rod. After the material rod is taken out, it is sintered in a muffle furnace for 24 hours at a sintering temperature of 1250℃ and an air atmosphere to obtain a polycrystalline material. The material block is taken out and placed in a rhenium crucible and grown by the Czochralski method (Sm 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Red light flashing crystal. Zirconia is used as insulation material, and the observation port is sealed with gemstone. The seed crystal is <111> Direction of pure road 2 O 3 Seed crystal, size 5mm×5mm×35mm, crystal growth in high purity Ar and H 2 The crystal was pulled at a speed of 3 mm / h, the rotation speed was 10-30 rpm, the crystal convex interface growth was controlled, and the growth temperature was 2450°C. The crystal growth process included furnace loading, vacuuming, argon filling, heating and material processing, seed baking, seeding, necking, shoulder release, equal diameter growth, lifting and cooling. The entire growth cycle was about 6 days. Transparent (Sm) with a size of Ф30×45 mm was grown. 0.01 Eu 0.01 Lu 0.98 ) 2 O 3After the crystal is taken out, it can be annealed at 1600℃ in air for 48h.

[0054] Figure 1 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 Fluorescence emission spectrum of red scintillation crystal. Figure 1 It can be seen that (Sm 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 The fluorescence emission spectrum of the red light scintillation crystal has an emission peak near 615nm, indicating that it has red light scintillation properties.

[0055] Figure 2 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 X-ray excitation emission spectrum of red scintillation crystals. Figure 2 It can be seen that, with bismuth germanate crystal (BGO) as the standard sample, (Sm 0.01 Lu 0.99 ) 2 O 3 For comparison, (Sm 0.01 Lu 0.99 ) 2 O 3 The light output is 15520ph. / MeV, (Sm 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 The light output is 32400ph. / MeV, and the scintillation performance is greatly improved.

[0056] It should be noted that (Sm 0.01 Lu 0.99 ) 2 O 3 The difference between the preparation method of Example 1 and that of Example 1 is that commercially purchased Lu with a purity of 5N grade is selected. 2 O 3 and 5N grade Sm 2 O 3 Powder according to (Sm 0.01 Lu 0.99 ) 2 O 3 The remaining steps are the same as those in Example 1.

[0057] Figure 3 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 The force-displacement curve of the red light scintillation crystal material against compression. In this embodiment 1, the size of the 3 The crystal is a compression test sample with a compressive strength of 753.33167MPa. It has very high compressive strength and excellent mechanical properties and can withstand extreme environments with higher pressures.

[0058] Figure 4 (Sm prepared in Example 1 of the present invention 0.01 Eu 0.01 Lu 0.98 ) 2 O 3 TG-DTA curve of red scintillation crystal material. Figure 4 It can be seen that it has good thermal stability and can withstand extreme environments with higher temperatures.

[0059] Example 2: Guided Mode Growth (Sm 0.02 Eu 0.03 Lu 0.95 ) 2 O 3 Red flashing crystal

[0060] Select commercially purchased 5N grade Lu 2 O 3 、5N grade Sm 2 O 3 and 5N grade Eu 2 O 3 Powder, according to (Sm 0.02 Eu 0.03 Lu 0.95 ) 2 O 3 The ingredients are prepared according to the chemical formula. After being mixed evenly, the materials are pressed into rods by isostatic pressing at a pressure of 200 MPa for 120 seconds. After the rods are taken out, they are sintered in a muffle furnace for 24 hours at a sintering temperature of 1250°C and an air atmosphere to obtain polycrystalline materials. The material blocks are taken out and placed in a rhenium crucible with pure lutetium oxide crystals as seed crystals with a size of 5 mm × 5 mm × 35 mm. High-purity Ar and H are filled in. 2A mixed gas is used as a protective atmosphere. After heating and melting, keep it for 3 hours to fully melt the raw materials, lower the seed crystal to the surface of the mold, and continue to lower it to contact the mold after contacting the melt. After the mass signal stabilizes, start pulling. The pulling speed is 4mm / h and the rotation speed is 20rpm. During the pulling process, the melt will gradually cover the entire mold surface, and then enter the equal-diameter growth process. During the growth process, the heating power and pulling speed of the medium frequency power supply are adjusted by observing the mass change curve over time. After the growth is completed, the crystal is removed and then slowly cooled to room temperature at a cooling rate of 30℃ / h. A transparent (Sm) with a size of Ф25×30mm is grown. 0.02 Eu 0.03 Lu 0.95 ) 2 O 3 After the crystal is taken out, it can be annealed at 1600℃ in air for 48h.

[0061] Example 3: Temperature Gradient Growth (Sm 0.03 Eu 0.02 Lu 0.95 ) 2 O 3 Red flashing crystal

[0062] Select commercially purchased 5N grade Lu 2 O 3 、5N grade Sm 2 O 3 and 5N grade Eu 2 O 3 Powder, according to (Sm 0.03 Eu 0.02 Lu 0.95 ) 2 O 3 The ingredients are prepared according to the chemical formula, and after being mixed evenly, the material is pressed by isostatic pressing at a pressure of 200 MPa for 120 seconds to form a material rod. After the material rod is taken out, it is sintered in a muffle furnace for 24 hours at a sintering temperature of 1250°C and an air atmosphere to obtain a polycrystalline material. The material block is taken out and placed in a rhenium crucible and vacuumed to 6×10 -4 Pa, Ar and H 2 The mixed gas was used as the protective atmosphere, and after heating and melting, the temperature was kept for 6 hours to fully melt the raw materials, and the temperature was lowered at a rate of 30°C / h to obtain (Sm 0.03 Eu 0.02 Lu 0.95 ) 2 O 3 After the crystal is taken out, it can be annealed at 1600℃ in air for 48h.

[0063] Example 4: Temperature Gradient Growth (Sm 0.07 Eu 0.05 Lu0.88 ) 2 O 3 Red flashing crystal

[0064] Select commercially purchased 5N grade Lu 2 O 3 、5N grade Sm 2 O 3 and 5N grade Eu 2 O 3 Powder, according to (Sm 0.07 Eu 0.05 Lu 0.88 ) 2 O 3 The ingredients are prepared according to the chemical formula, and after being mixed evenly, the material is pressed by isostatic pressing at a pressure of 200 MPa for 120 seconds to form a material rod. After the material rod is taken out, it is sintered in a muffle furnace for 24 hours at a sintering temperature of 1250°C and an air atmosphere to obtain a polycrystalline material. The material block is taken out and placed in a rhenium crucible and vacuumed to 6×10 -4 Pa, Ar and H 2 The mixed gas was used as the protective atmosphere, and the temperature was raised and melted, and then kept warm for 6 hours. After the raw materials were fully melted, the seed crystal was lowered to the surface of the melt, and then the temperature was slowly lowered at a cooling rate of 30℃ / h to induce crystallization to obtain (Sm 0.07 Eu 0.05 Lu 0.88 ) 2 O 3 After the crystal is taken out, it can be annealed at 1600℃ in air for 48h.

[0065] Example 5: Crucible Descent Growth (Sm 0.08 Eu 0.06 Lu 0.86 ) 2 O 3 Red flashing crystal

[0066] Select commercially purchased 5N grade Lu 2 O 3 、5N grade Sm 2 O 3 and 5N grade Eu 2 O 3 Powder, according to (Sm 0.08 Eu 0.06 Lu 0.86 ) 2 O 3 The ingredients are prepared according to the chemical formula, and after being mixed evenly, the material is pressed for 120 seconds at a pressure of 200 MPa by isostatic pressing to form a material rod. After the material rod is taken out, it is sintered in a muffle furnace for 24 hours at a sintering temperature of 1250°C and an air atmosphere to obtain a polycrystalline material. The material block is taken out and placed in a rhenium crucible, and the descent method is used to grow (Sm0.08 Eu 0.06 Lu 0.86 ) 2 O 3 Red scintillation crystal, seed crystal is <111> or <100> Pure lutetium oxide seed crystals are grown in high purity Ar and H 2 The mixture was carried out in a mixed gas atmosphere with a crucible descending rate of 0.75 mm / h. Transparent (Sm) with a size of Ф40×50 mm was grown. 0.08 Eu 0.06 Lu 0.86 ) 2 O 3 After the crystal is taken out, it can be annealed at 1600℃ in air for 48h.

[0067] After testing, the red scintillation crystals prepared in Examples 2, 3, 4, and 5 have the same properties as the red scintillation crystal prepared in Example 1, and all have red light scintillation performance, high light yield, high compressive strength, and excellent thermal stability.

[0068] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A co-doped Eu 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material is characterized in that: Its chemical formula is (Sm x Eu y R 1-x-y )2O3, wherein 0.01≤x≤0.08, 0.01≤y≤0.06, and R is selected from any one of Lu, Sc, and Y.

2. The co-doped Eu as claimed in claim 1 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material is characterized in that: The co-doped Eu 3+ 、Sm 3+ The chemical formula of the sesquioxide-based red light scintillation crystal material is (Sm x Eu y Lu 1-x-y )2O3, where 0.01≤x≤0.08, 0.01≤y≤0.

06.

3. A co-doped Eu as claimed in claim 1 or 2 3+ 、Sm 3+ A method for preparing a sesquioxide-based red light scintillation crystal material, characterized in that: include: Sm2O3, Eu2O3, R2O3 are mixed according to the chemical formula (Sm x Eu y R 1-x-y )2O3 is mixed and pressed into rods; wherein 0.01≤x≤0.08, 0.01≤y≤0.06; The material rod is sintered in an air atmosphere to obtain a polycrystalline material, and then a melt method is used to grow crystals to obtain a co-doped Eu 3+ 、Sm 3+ Sesquioxide-based red light scintillation crystal material.

4. The preparation method according to claim 3, characterized in that: The pressing is performed by isostatic pressing at 150-250 MPa for 100-150 seconds; preferably, at 170-220 MPa for 100-140 seconds; further preferably, at 190-210 MPa for 110-130 seconds; Preferably, the sintering is performed at 1100-1300° C. for 20-30 h; preferably, the sintering is performed at 1200-1300° C. for 22-26 h; further preferably, the sintering is performed at 1240-1260° C. for 23-25 ​​h.

5. The preparation method according to claim 3, characterized in that: The melt method includes the Czochralski method, the guided mold method, the temperature gradient method and the crucible descent method; Preferably, the crystal growth temperature is 2400-2500°C; Preferably, after the crystal growth is completed, it is taken out and annealed at 1600°C in air for 48 hours to obtain the co-doped Eu 3+ 、Sm 3+ Sesquioxide-based red light scintillation crystal material.

6. The preparation method according to claim 5, characterized in that: When the crystal is grown by the pulling method, the crystal growth atmosphere is a mixed atmosphere of Ar and H2, the seed crystal is a pure R2O3 seed crystal, the pulling speed is 0.5-5mm / h, and the rotation speed is 10-30rpm; R is selected from any one of Lu, Sc, and Y; Preferably, when R is Lu, the seed crystal is <111> or <100> Direction of pure lutetium oxide seed crystals.

7. The preparation method according to claim 5, characterized in that: When the guided mold method is used for crystal growth, the crystal growth atmosphere is a mixed atmosphere of Ar and H2, the seed crystal is a pure R2O3 seed crystal, the pulling speed is 0.3-6 mm / h, and the rotation speed is 8-38 rpm; R is selected from any one of Lu, Sc, and Y; Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

8. The preparation method according to claim 5, characterized in that: When the temperature gradient method is used for crystal growth, the crystal growth atmosphere is a mixed atmosphere of Ar and H2, and the temperature is reduced and the crystal is grown at a cooling rate of 25-30°C / h; Preferably, when the temperature gradient method is used for crystal growth, no seed crystal is placed at the bottom, or pure R2O3 seed crystal is placed to induce crystallization by the top seed method; R is selected from any one of Lu, Sc, and Y; Preferably, when R is Lu, the seed crystal is <111> or <100> Direction of pure lutetium oxide seed crystals; Or, when the crucible descent method is used for crystal growth, the crystal growth atmosphere is a mixed atmosphere of Ar and H2, the seed crystal is a pure R2O3 seed crystal, and the crucible descent rate is 0.1 to 1.5 mm / h; Preferably, when R is Lu, the seed crystal is <111> or <100> Pure lutetium oxide seed crystals in the direction of.

9. A co-doped Eu as claimed in claim 1 3+ 、Sm 3+ The sesquioxide-based red light scintillation crystal material or the co-doped Eu prepared by any preparation method described in claim 2-8 3+ 、Sm 3+ Application of sesquioxide-based red light scintillation crystal materials in high-energy ray detection in extreme environments; Preferably, the extreme environment includes a nuclear reactor environment, a deep space environment and a deep sea environment. 10.Eu 3+ Application in improving the scintillation performance of Lu2O3:Sm crystals; Preferably, the scintillation performance comprises light yield.

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