Rare-earth-doped alkaline earth lithium silicate microcrystalline glass for high-energy radiation detection as well as preparation method and application of rare-earth-doped alkaline earth lithium silicate microcrystalline glass

Abstract

The invention belongs to the field of radiation detection, and discloses rare earth doped alkaline earth lithium silicate microcrystalline glass for high-energy radiation detection as well as a preparation method and application of the rare earth doped alkaline earth lithium silicate microcrystalline glass. The rare earth doped alkaline earth lithium silicate glass ceramic comprises 0.01-2 mol% of rare earth ions, the rare earth ions are at least one of Eu < 3 + >, Sm < 3 + > and Ce < 3 + >, and a crystal phase separated from the glass ceramic is at least one of Li2CaSiO4, Li2Ca2Si2O7, Li2SrSiO4 or Li2BaSiO4. The preparation method comprises the following steps: weighing raw materials according to the molar percentage, fully grinding, melting to obtain molten glass, cooling and forming to obtain a transparent glass block, annealing to obtain precursor glass, heating, preserving heat, cooling, and taking out to obtain the microcrystalline glass. The rare earth doped alkaline earth lithium silicate microcrystalline glass has excellent optical performance and high-energy ray, high-energy particle and neutron detection performance, and can be used in the related fields of radiation imaging, energy exploration, environment monitoring and the like.

Description

Technical Field

[0001] The present invention relates to the field of radiation detection, and in particular to a rare earth-doped alkaline earth lithium silicate glass-ceramic for high-energy radiation detection, and a preparation method and application thereof. Background Art

[0002] Radiation detection is widely used in fields such as security inspection, oil exploration, medical radiography, and high-energy physics. Currently, indirect radiation detection based on scintillators is the primary method in these applications. Scintillators offer excellent radiation resistance and enable high-throughput signal acquisition and processing. The performance of the scintillator directly determines the effectiveness of the detection system.

[0003] Currently, commonly used scintillator materials are mainly divided into scintillating single crystals, scintillating ceramics, and scintillating glass. Scintillating single crystals and ceramics have excellent scintillation properties, but problems in their preparation, processing, and storage severely restrict their application potential. Specifically, single crystals and ceramics require demanding growth conditions and cycles; at the same time, due to their strict reliance on container processing, large-scale samples are difficult to obtain. Most single crystals and ceramics have poor mechanical properties and lack processability after crystal growth and formation. Halide single crystals and ceramics also face stability issues such as oxidative deliquescence, which limits their long-term use.

[0004] As an alternative to scintillation single crystals and ceramics, scintillating glass has excellent machinability and can obtain samples of specific shapes, sizes, and even fiber-optic samples while being robust. However, the progress of scintillating glass has been slow, mainly due to the large number of defects in its molding process, which makes the high-energy electrons generated by its interaction with rays have a very short range, and the energy cannot be effectively transferred to the luminescence center, resulting in low efficiency. Microcrystalline glass scintillators obtained by in-situ crystallization of glass can combine the advantages of crystals and glass. It not only inherits the high optical transmittance and easy processing and preparation advantages of glass, but also reduces the number of defects inside the glass and improves the chemical environment around the luminescence center. It is considered to be the most likely way to solve the low scintillation performance of glass. However, the scintillation performance of microcrystalline glass scintillators currently reported has been improved compared to scintillating glass, but there is still a large gap with scintillating crystals. The GdBr3 glass-ceramic scintillator reported by Dai et al. can achieve neutron detection, but the light output is only 43% of that of neutron detection GS20 glass, which is much lower than scintillation crystals (Dai W., Marcacci H., Lynch B., et al. Rare-earth activated glass and glass-ceramic for neutron detection [J]. MRS Proceedings, 2012, 1471: 92-97.). The CaF2 glass-ceramic scintillator reported by Struebing et al. can achieve a light output of 70% of commercial neutron detection GS20 glass, about 5600 photons / neutron, which is still much lower than scintillation crystals (Struebing C., Chong J., Lee G., et al. Aneutron scintillator based on transparent nanocrystalline CaF 2:Eu glass ceramic [J]. Applied Physics Letters, 2016, 108 (15): 153106.). In addition, there is no microcrystalline glass scintillator that can simultaneously detect high-energy rays, high-energy particles and neutrons. The main problems are two points: (1) Microcrystalline glass lacks high neutron capture cross-section isotopes, making it difficult to detect neutrons. (2) Microcrystalline glass has a relatively low crystallinity, a low crystalline phase content, and poor scintillation performance, making it impossible to detect high-energy rays, high-energy particles and neutrons. For example, the microcrystalline glass scintillator reported in the existing patent CN118894650A has a lower radiation luminescence intensity than BGO scintillating crystals, making it difficult to detect gamma rays and high-energy particles, and does not contain high neutron capture cross-section elements, making it impossible to detect neutrons. The integrated intensity of the radiant luminescence produced by the perovskite (CsPbX3, X=Cl and Br) nanocrystalline glass reported by Wang et al. is only 1 / 18 of that of the commercial BGO scintillating crystal, and no gamma-ray, high-energy particle and neutron signals were detected (Wang C., Lin H., Zhang Z., et al. X-ray excited CsPb(Cl,Br)3perovskite quantum dots-glass composite with long-lifetime[J]. Journal of the European Ceramic Society, 2020, 40(5): 2234-2238). The BaCl2:Eu 2+ The photoluminescence quantum efficiency of nano-crystal glass can reach 80.41%, and the integrated intensity of radioluminescence is 132% higher than that of commercial BGO scintillating crystals. However, it still has not detected gamma rays, high-energy particles and neutron signals (Liu Q., Ran P., Chen W., et al. Bright transparent scintillators with high fraction BaCl2:Eu 2+ nanocrystals precipitation: an linic-covalenthybrid network strategy toward superior X-ray imaging glass-ceramics[J]. Advanced Science, 2023, 10(34): 2304889.).

[0005] In summary, the scintillation performance of currently available glass-ceramics scintillators is relatively poor, far inferior to that of scintillating single crystals and ceramics. Furthermore, there is no glass-ceramic scintillator that can simultaneously detect high-energy radiation, high-energy particles, and neutrons. Developing glass-ceramics scintillators with high scintillation performance that can detect high-energy radiation, high-energy particles, and neutrons is of great significance. Summary of the Invention

[0006] In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a rare earth-doped alkaline earth lithium silicate glass-ceramics for high-energy radiation detection. The rare earth-doped alkaline earth lithium silicate glass-ceramics of the present invention has excellent high-energy ray, high-energy particle and neutron detection performance, and can be used as a radiation detector in energy exploration, environmental monitoring, medical imaging and other related fields.

[0007] Another object of the present invention is to provide a method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics.

[0008] Another object of the present invention is to provide an application of the rare earth-doped alkaline earth lithium silicate glass-ceramics in the field of radiation detection.

[0009] Another object of the present invention is to provide a detector, specifically a high-energy ray detector, a high-energy particle detector and a neutron detector.

[0010] The purpose of the present invention is achieved through the following technical solutions:

[0011] A rare earth doped alkaline earth lithium silicate glass-ceramics, wherein the raw materials of the rare earth doped alkaline earth lithium silicate glass-ceramics include 0.01-2 mol% of rare earth ions.

[0012] Preferably, the rare earth-doped alkaline earth lithium silicate glass-ceramics includes 0.1 to 1 mol % of rare earth ions.

[0013] Preferably, the rare earth ion is Eu 3+ 、Sm 3+ or Ce 3+ At least one of .

[0014] Preferably, the crystalline phase precipitated from the rare earth-doped alkaline earth lithium silicate glass-ceramics is at least one of Li2CaSiO4, Li2Ca2Si2O7, Li2SrSiO4 and Li2BaSiO4.

[0015] Preferably, the rare earth-doped alkaline earth lithium silicate glass-ceramics generates radiant luminescence of 300 to 1100 nm under X-ray excitation.

[0016] Preferably, the rare earth ion is Eu 3+ When , the main emission peak is located at 400~600nm;

[0017] Preferably, the rare earth ion is Sm 3+ When , the main emission peak is located at 800~1100nm;

[0018] Preferably, the rare earth ion is Ce 3+ When , the main emission peak is located at 300 ~ 550nm.

[0019] Preferably, the components and their molar percentages of the rare earth-doped alkaline earth lithium silicate glass-ceramics are:

[0020] Li2O: 10-50%;

[0021] Alkaline earth metal oxides: 10-50%;

[0022] SiO2: 25-60%;

[0023] Al2O3: 0~5%;

[0024] Rare earth compounds: 0.01~2%.

[0025] Preferably, the composition and molar percentage of the rare earth-doped alkaline earth lithium silicate glass-ceramics are:

[0026] Li2O: 15-40%;

[0027] Alkaline earth metal oxide: 20-45%, more preferably 23-42%;

[0028] SiO2: 30-45%, more preferably 33-42%;

[0029] Al2O3: 1-2%;

[0030] Rare earth compound: 0.05 to 1%, more preferably 0.05 to 0.5%.

[0031] Preferably, the rare earth compound is a rare earth oxide and / or a rare earth fluoride;

[0032] The rare earth oxide is at least one of Eu2O3, Sm2O3 or CeO2;

[0033] The rare earth fluoride is at least one of EuF3, SmF3 or CeF3;

[0034] The alkaline earth metal is at least one of Mg, Ca, Sr or Ba.

[0035] The rare earth-doped alkaline earth lithium silicate glass-ceramics has excellent high-energy ray, high-energy particle and neutron detection performance, and can simultaneously achieve accurate detection of the above radiation.

[0036] A method for preparing rare earth-doped alkaline earth lithium calcium glass-ceramics is provided. The method is a melting and cooling method, in which the raw materials are ground, melted, cooled, annealed and kept warm to obtain the glass-ceramics.

[0037] Preferably, the preparation method comprises the following specific steps:

[0038] The raw materials are weighed according to molar percentage, fully ground and then melted to obtain glass liquid, the glass liquid is cooled and formed into a transparent glass block, annealed to obtain precursor glass, and then taken out after heat preservation and cooling to obtain the product.

[0039] Preferably, the method specifically includes the following steps:

[0040] (1) weighing raw materials by mole percentage, grinding and then melting to obtain glass liquid;

[0041] (2) pouring the glass liquid onto a stainless steel plate and cooling it to form a glass block;

[0042] (3) annealing the glass block to obtain precursor glass;

[0043] (4) The precursor glass is kept warm for a period of time, cooled to room temperature, and then taken out to prepare rare earth-doped alkaline earth lithium silicate microcrystalline glass.

[0044] Preferably, the raw materials and their molar percentages are:

[0045] Li2CO3 or Li2O: 10-50%;

[0046] Alkaline earth metal compounds: 10-50%;

[0047] SiO2: 25-60%;

[0048] Al2O3: 0~5%;

[0049] Rare earth compounds: 0.01-2%;

[0050] The alkaline earth metal compound is an alkaline earth metal oxide or an alkaline earth metal carbonate; the alkaline earth metal oxide is selected from at least one of MgO, CaO, SrO or BaO; the alkaline earth metal carbonate is selected from at least one of MgCO3, CaCO3, SrCO3 or BaCO3.

[0051] Preferably, the time for fully grinding in step (1) is not less than 15 minutes.

[0052] Preferably, the melting conditions in step (1) are 1100-1650° C. for 5-120 min, and the melting atmosphere is air atmosphere or reducing atmosphere;

[0053] More preferably, cerium-doped alkaline earth lithium silicate glass-ceramics need to be melted in a reducing atmosphere, and europium-doped and samarium-doped alkaline earth lithium silicate glass-ceramics need to be melted in a reducing atmosphere or an air atmosphere, wherein the reducing atmosphere is a H2 / N2 mixed atmosphere or a CO atmosphere.

[0054] Preferably, the annealing condition in step (3) is annealing at 400-500° C. for 4-96 hours.

[0055] Preferably, the holding temperature in step (4) is the crystallization temperature, and the specific holding conditions are holding at 550-800° C. for 1-10 hours, and the cooling rate is 1-5° C. / min.

[0056] The above rare earth doped alkaline earth lithium silicate glass-ceramics are used in the fields of radiation detection, energy exploration, environmental monitoring and medical imaging.

[0057] Preferably, the rare earth doped alkaline earth lithium silicate glass-ceramics is used in the detection of high energy rays, high energy particles and neutrons.

[0058] Preferably, the high-energy rays are X-rays and / or gamma rays; and the high-energy particles are at least one of alpha particles, beta particles or protons.

[0059] A radiation detector comprises the rare earth-doped alkaline earth lithium silicate glass-ceramics.

[0060] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0061] (1) The rare earth-doped alkaline earth lithium silicate glass-ceramics prepared by the present invention has easy-to-adjust composition and a simple preparation method. Large-sized samples can be prepared with low cost and are easy to industrialize and mass-produce.

[0062] (2) The rare earth-doped alkaline earth lithium silicate glass-ceramics prepared by the present invention has a high degree of crystallinity, which helps to achieve efficient radiation detection.

[0063] (3) The rare earth-doped alkaline earth silicate glass-ceramics prepared by the present invention has excellent environmental stability and can be used stably in many harsh environments.

[0064] (4) The rare earth-doped alkaline earth lithium silicate glass-ceramics prepared by the present invention can realize the detection of high-energy rays, high-energy particles and neutrons. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 XRD pattern of europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0066] Figure 2The optical transmission spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0067] Figure 3 This is a photoluminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0068] Figure 4 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0069] Figure 5 The gamma ray ( 137 Cs) Excitation pulse height spectrum.

[0070] Figure 6 α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0071] Figure 7 Neutron excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 1;

[0072] Figure 8 XRD pattern of europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics prepared in Example 2;

[0073] Figure 9 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics prepared in Example 2;

[0074] Figure 10 γ-ray ( 137 Cs) excitation pulse height spectrum;

[0075] Figure 11 α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics prepared in Example 2;

[0076] Figure 12 Neutron excitation pulse height spectrum of europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics prepared in Example 2;

[0077] Figure 13 XRD pattern of europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics prepared in Example 3;

[0078] Figure 14 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics prepared in Example 3;

[0079] Figure 15 γ-ray ( 137 Cs) excitation pulse height spectrum;

[0080] Figure 16 α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics prepared in Example 3;

[0081] Figure 17 Neutron excitation pulse height spectrum of europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics prepared in Example 3;

[0082] Figure 18 The XRD pattern of the cerium-doped alkaline earth lithium silicate (Li2Ca2Si2O7) glass-ceramics prepared in Example 4;

[0083] Figure 19 This is the X-ray excited radiation luminescence spectrum of the cerium-doped alkaline earth lithium silicate (Li2Ca2Si2O7) glass-ceramics prepared in Example 4;

[0084] Figure 20 The γ-ray ( 137 Cs) excitation pulse height spectrum;

[0085] Figure 21 α-particle excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate (Li2Ca2Si2O7) glass-ceramics prepared in Example 4;

[0086] Figure 22 Neutron excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate (Li2Ca2Si2O7) glass-ceramics prepared in Example 4;

[0087] Figure 23 This is the X-ray excited radiation luminescence spectrum of the cerium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 5;

[0088] Figure 24 The γ-ray ( 137 Cs) excitation pulse height spectrum;

[0089] Figure 25α-particle excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 5;

[0090] Figure 26 This is the neutron excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 5;

[0091] Figure 27 This is the X-ray excited radiation luminescence spectrum of the samarium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 6;

[0092] Figure 28 The γ-ray ( 137 Cs) excitation pulse height spectrum;

[0093] Figure 29 α-particle excitation pulse height spectrum of samarium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 6;

[0094] Figure 30 This is the neutron excitation pulse height spectrum of the samarium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 6;

[0095] Figure 31 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics prepared in Example 7;

[0096] Figure 32 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics prepared in Example 8;

[0097] Figure 33 This is the X-ray excited radiation luminescence spectrum of the europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics prepared in Example 9;

[0098] Figure 34 This is the X-ray excited radiation luminescence spectrum of the cerium-doped alkaline earth lithium silicate (Li2Ca2Si2O7) glass-ceramics prepared in Example 10;

[0099] Figure 35 This is the neutron pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Comparative Example 1;

[0100] Figure 36 This is the neutron pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Comparative Example 3. DETAILED DESCRIPTION

[0101] The present invention will be further described in detail below with reference to the examples and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0102] The alkaline earth lithium silicate glass-ceramics containing CeO2 or CeF3 in Examples 4, 5 and 10 need to be melted in a reducing atmosphere, and the alkaline earth lithium silicate glass-ceramics in other Examples and Comparative Examples can be melted in a reducing atmosphere or an air atmosphere.

[0103] Example 1

[0104] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0105] Li2CO3, CaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0106] Li2CO3: 36%

[0107] CaO: 25.5%

[0108] SiO2: 37.4%

[0109] Al2O3: 1%

[0110] Eu2O3: 0.1%

[0111] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 5 minutes to obtain a glass liquid;

[0112] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0113] (3) annealing the transparent glass block obtained in (2) at 500° C. for 4 h to obtain a precursor glass;

[0114] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 1 hour, cooled to room temperature at a rate of 1°C / min, and then taken out to prepare the europium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-CaO-SiO2-Al2O3-Eu2O3.

[0115] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 1The XRD spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1 shows a perfect match with the standard Li2CaSiO4 crystal phase PDF card (PDF#27-0290), and has a high diffraction peak intensity. It is difficult to see the glass characteristic signal, which proves that the glass-ceramics prepared in Example 1 has a high degree of crystallinity. Figure 2 The optical transmittance spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1 shows that the transmittance is 60% at 500 nm, which proves that it has high optical transmittance. High optical transmittance is beneficial to radiation detection performance. Figure 3 This is the photoluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1, in which obvious blue fluorescence emission centered at 480 nm can be seen. Figure 4 This is the radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1. It can be seen that there is obvious blue fluorescence emission centered at 480 nm, which is similar to photoluminescence. Figure 5 The γ-ray excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1 shows that its γ-ray full energy peak is clearly visible and clearly distinguishable from the noise signal. Figure 6 The α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1 shows that the α-particle full energy peak is clearly visible and has a high counting rate, indicating that the glass-ceramics has a high sensitivity to α-particles. Figure 7 The neutron pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 1 shows a clear full-energy peak for the neutron signal and a high count rate, indicating high neutron detection efficiency. Example 1 demonstrates that europium-doped alkaline earth lithium silicate (Li2CaSiO4) glass-ceramics have excellent scintillation properties, enabling the detection of high-energy radiation, high-energy particles, and neutrons.

[0116] Example 2

[0117] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0118] Li2CO3, SrCO3, SiO2 and EuF3 with a purity of 99.99% were selected, and the raw materials were calculated according to the following molar ratio:

[0119] Li2CO3: 38%

[0120] SrCO3: 24%

[0121] SiO2: 37.5%

[0122] EuF3: 0.5%

[0123] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1450°C for 20 minutes to obtain a glass liquid;

[0124] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0125] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0126] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 680°C for 2 hours, cooled to room temperature at a rate of 2°C / min, and then taken out after cooling to room temperature, thereby preparing the europium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-SrO-SiO2-Eu2F3.

[0127] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 8 The XRD spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2 shows that the XRD spectrum contains Li2SrSiO4 (PDF#00-055-0217) crystal phase and has a high diffraction peak intensity. It is difficult to see the glass characteristic signal, which proves that the glass-ceramics prepared in Example 2 has a high degree of crystallinity. Figure 9 This is the radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2, in which obvious yellow fluorescence emission centered at 585 nm can be seen. Figure 10 The γ-ray excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2 shows that its γ-ray full-energy peak is clearly visible, which is obviously different from the noise signal, and the full-energy peak address is lower than that in Example 1. Figure 11 The α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2 shows that the α-particle full-energy peak is clearly visible, and the full-energy peak address is also lower than that in Example 1. Figure 12 The neutron pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2 shows a clear full-energy peak of the neutron signal, and the full-energy peak address is also lower than that in Example 1. Example 2 demonstrates that europium-doped alkaline earth lithium silicate (Li2SrSiO4) glass-ceramics have excellent scintillation properties, enabling the detection of high-energy rays, high-energy particles, and neutrons. In addition, the scintillation performance of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 2 is lower than that in Example 1. This is due to the different precipitated crystal phases.

[0128] Example 3

[0129] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0130] Li2CO3, BaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0131] Li2CO3: 35%

[0132] BaO: 25%

[0133] SiO2: 37.9%

[0134] Al2O3: 2%

[0135] Eu2O3: 0.1%

[0136] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1450°C for 120 minutes to obtain a glass liquid;

[0137] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0138] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0139] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 660°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to obtain the europium-doped alkaline earth lithium silicate glass-ceramics having a composition of Li2O-BaO-SiO2-Al2O3-Eu2O3.

[0140] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 13 The XRD spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3 shows a perfect match with the standard Li2BaSiO4 crystal phase PDF card (PDF#96-201-7069), and has a high diffraction peak intensity. It is difficult to see the glass characteristic signal, which proves that the glass-ceramics prepared in Example 3 has a high degree of crystallinity. Figure 14 This is the radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3, in which obvious green fluorescence emission centered at 506 nm can be seen. Figure 15 The γ-ray excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3 shows that its γ-ray full-energy peak is clearly visible and clearly distinguished from the noise signal. The full-energy peak address is higher than that in Example 2 and slightly lower than that in Example 1. Figure 16 The α-particle excitation pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3 shows that the α-particle full-energy peak is clearly visible, and the full-energy peak address is also higher than that of Example 2 and slightly lower than that of Example 1. Figure 17The neutron pulse height spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3 shows a clear full-energy peak of the neutron signal, and the full-energy peak address is also higher than that of Example 2 and slightly lower than that of Example 1. Example 3 demonstrates that europium-doped alkaline earth lithium silicate (Li2BaSiO4) glass-ceramics have excellent scintillation performance, enabling the detection of high-energy rays, high-energy particles, and neutrons. Furthermore, the scintillation performance of Example 3 is higher than that of Example 2 and slightly lower than that of Example 1. This is primarily due to the different precipitated crystal phases, and also has a certain influence on the transparency and luminescence peak position of the glass-ceramics.

[0141] Example 4

[0142] This embodiment provides a method for preparing cerium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0143] Li2CO3, CaO, SiO2, Al2O3 and CeO2 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0144] Li2CO3: 19.9%

[0145] CaO: 40%

[0146] SiO2: 39.9%

[0147] Al2O3: 0.1%

[0148] CeO2: 0.1%

[0149] (1) After being fully ground, the product is placed in a platinum crucible and kept at 1350°C for 20 minutes in a reducing atmosphere (H2 / N2 mixed gas or CO atmosphere) to melt the product to obtain a glass liquid;

[0150] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0151] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0152] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 750°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out after cooling to room temperature, thereby preparing the cerium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-CaO-SiO2-Al2O3-CeO2.

[0153] The prepared cerium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 18The XRD spectrum of the cerium-doped alkaline earth lithium silicate microcrystalline glass prepared in Example 4 can be seen to perfectly match the standard Li2Ca2Si2O7 crystal phase PDF card (PDF#00-031-0712), and at the same time has a high diffraction peak intensity, and it is difficult to see the glass characteristic signal, which proves that the microcrystalline glass prepared in Example 4 has a high degree of crystallinity. Figure 19 This is the radiative luminescence spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 4, in which an obvious blue fluorescent emission centered at 424 nm can be seen. Figure 20 The γ-ray excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 4 shows that its γ-ray full-energy peak is clearly visible, which is obviously different from the noise signal, and the full-energy peak address is slightly lower than that in Example 1. Figure 21 The α-particle excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 4 shows that the α-particle full-energy peak is clearly visible, and the full-energy peak address is also slightly lower than that in Example 1. Figure 22 The neutron pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 3 shows a clear full-energy peak of the neutron signal, and the full-energy peak address is also slightly lower than that in Example 1. Example 4 shows that cerium-doped alkaline earth lithium silicate glass-ceramics can also realize the detection of high-energy rays, high-energy particles and neutrons.

[0154] Example 5

[0155] This embodiment provides a method for preparing cerium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0156] Li2CO3, CaO, SiO2, Al2O3 and CeF3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0157] Li2CO3: 36%

[0158] CaO: 25%

[0159] SiO2: 37%

[0160] Al2O3: 1%

[0161] CeF3: 1%

[0162] (1) After being fully ground, the product is placed in a platinum crucible and kept at 1350°C for 20 minutes in a reducing atmosphere (H2 / N2 mixed gas or CO atmosphere) to melt the product to obtain a glass liquid;

[0163] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0164] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0165] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C and kept warm for 10 hours, and then cooled to room temperature at a rate of 5°C / min. After cooling to room temperature, the precursor glass is taken out to prepare the cerium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-CaO-SiO2-Al2O3-CeF3.

[0166] The prepared cerium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 23 The radiative luminescence spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 5 shows obvious blue fluorescence emission centered at 410 nm, which proves that the cerium-doped alkaline earth lithium silicate glass-ceramics also has efficient radiative luminescence. Figure 24 From the γ-ray excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 5, it can be seen that its γ-ray full energy peak is clearly visible, which is obviously different from the noise signal, and the full energy peak address is slightly lower than that in Example 4. Figure 25 This is the α-particle excitation pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 5. It can be seen that the α-particle full energy peak is clearly visible. Figure 26 The neutron pulse height spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 5 shows a clearly visible full-energy peak of the neutron signal, and the full-energy peak address is also slightly lower than that in Example 4. Example 5 demonstrates that the scintillation performance of cerium-doped Li2CaSiO4 crystalline alkaline earth lithium silicate glass-ceramics is slightly lower than that of cerium-doped Li2Ca2Si2O7 crystalline alkaline earth lithium silicate glass-ceramics. It also demonstrates that rare earth fluorides can also be used to prepare alkaline earth lithium silicate glass-ceramics.

[0167] Example 6

[0168] This embodiment provides a method for preparing samarium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0169] Li2CO3, CaO, SiO2, Al2O3 and Sm2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0170] Li2CO3: 36%

[0171] CaO: 25%

[0172] SiO2: 37.9%

[0173] Al2O3: 1%

[0174] Sm2O3: 0.1%

[0175] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 120 minutes to obtain a glass liquid;

[0176] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0177] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0178] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to obtain the samarium-doped alkaline earth lithium silicate glass-ceramics having a composition of Li2O-CaO-SiO2-Al2O3-Sm2O3.

[0179] The prepared samarium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 27 The radioluminescence spectrum of the samarium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 6 shows fluorescence emission centered at 900 nm, which proves that the samarium-doped alkaline earth lithium silicate glass-ceramics also has efficient radioluminescence. Figure 28 From the γ-ray excitation pulse height spectrum of the samarium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 6, it can be seen that its γ-ray full energy peak is clearly visible and clearly distinguishable from the noise signal. Figure 29 The α-particle excitation pulse height spectrum of the samarium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 6 shows that the α-particle full energy peak is clearly visible. Figure 30 The neutron pulse height spectrum of the samarium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 6 shows a clear full-energy peak of the neutron signal. Example 6 demonstrates that samarium-doped Li2CaSiO4 crystalline alkaline earth lithium silicate glass-ceramics can also detect high-energy rays, high-energy particles, and neutrons.

[0180] Example 7

[0181] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0182] Li2CO3, CaO, SrO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0183] Li2CO3: 35%

[0184] CaO: 23%

[0185] SrO: 2%

[0186] SiO2: 37.9%

[0187] Al2O3: 2%

[0188] Eu2O3: 0.1%

[0189] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 10 minutes to obtain a glass liquid;

[0190] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0191] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0192] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to prepare the europium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-CaO--SrO-SiO2-Al2O3-Eu2O3.

[0193] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 31 The radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 7 shows a clear blue fluorescence emission centered at 480 nm, consistent with the results of Example 1. Example 7 demonstrates that mixed alkaline earth metal oxides of Ca and Sr can also achieve efficient radiation detection and can be used for the detection of high-energy rays, high-energy particles, and neutrons.

[0194] Example 8

[0195] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0196] Li2CO3, SrCO3, BaCO3, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0197] Li2CO3: 34%

[0198] SrCO3: 24.5%

[0199] BaCO3: 1.5%

[0200] SiO2: 37.5%

[0201] Al2O3: 2%

[0202] Eu2O3: 0.5%

[0203] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 10 minutes to obtain a glass liquid;

[0204] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0205] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0206] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to prepare the europium-doped alkaline earth lithium silicate microcrystalline glass having a composition of Li2O-CaO-BaO-SiO2-Al2O3-Eu2O3.

[0207] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 32 The radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 8 shows a distinct yellow fluorescence emission centered at 585 nm, consistent with the results of Example 2. Example 8 demonstrates that Sr and Ba mixed alkaline earth metal carbonates can also achieve efficient radiation detection and can be used for the detection of high-energy rays, high-energy particles, and neutrons.

[0208] Example 9

[0209] This embodiment provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0210] Li2CO3, CaO, BaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0211] Li2CO3: 35.5%

[0212] CaO: 2%

[0213] BaO: 24.5%

[0214] SiO2: 37.8%

[0215] Al2O3: 0.1%

[0216] Eu2O3:0.1%

[0217] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 10 minutes to obtain a glass liquid;

[0218] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0219] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0220] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to obtain the europium-doped alkaline earth lithium silicate glass-ceramics.

[0221] The prepared europium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 33 The radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 9 shows a clear blue fluorescence emission centered at 506 nm, consistent with the results of Example 3. Example 9 demonstrates that mixed alkaline earth metal oxides of Ca and Ba can also achieve efficient radiation detection and can be used for the detection of high-energy rays, high-energy particles, and neutrons.

[0222] Example 10

[0223] This embodiment provides a method for preparing cerium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0224] Li2CO3, CaO, SrO, MgO, BaO, SiO2, Al2O3 and CeO2 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0225] Li2CO3: 19.9%

[0226] CaO: 36%

[0227] MgO: 1%

[0228] SrO: 2%

[0229] BaO: 3%

[0230] SiO2: 38.9%

[0231] Al2O3: 0.1%

[0232] CeO2: 0.1%

[0233] (1) After being fully ground, the product is placed in a platinum crucible and kept at 1350°C for 20 minutes to be melted in a reducing atmosphere (H2 / N2 mixed gas or CO atmosphere) to obtain a glass liquid;

[0234] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0235] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0236] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 750°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to obtain the cerium-doped alkaline earth lithium silicate glass-ceramics having a composition of Li2O-CaO-MgO-SrO-BaO-SiO2-Al2O3-CeO2.

[0237] The prepared cerium-doped alkaline earth lithium silicate glass-ceramics were characterized. Figure 34 The radioluminescence spectrum of the cerium-doped alkaline earth lithium silicate glass-ceramics prepared in Example 10 shows a clear blue fluorescence emission centered at 424 nm, consistent with the results of Example 4. Example 10 demonstrates that mixed alkaline earth metal oxides of Mg, Ca, Sr, and Ba can also achieve efficient radiation detection and can be used for the detection of high-energy rays, high-energy particles, and neutrons.

[0238] Comparative Example 1

[0239] This comparative example provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0240] Li2CO3, CaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0241] Li2CO3: 5%

[0242] CaO: 42%

[0243] SiO2: 40.9%

[0244] Al2O3: 2%

[0245] Eu2O3: 0.1%

[0246] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1350°C for 60 minutes to obtain a glass liquid;

[0247] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0248] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0249] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C for 10 hours, cooled to room temperature at a rate of 5°C / min, and then taken out to obtain microcrystalline glass.

[0250] Figure 35This is the radioluminescence spectrum of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Comparative Example 1. Since the target crystal phase cannot be precipitated under this raw material composition, there is no obvious luminescence signal.

[0251] Comparative Example 2

[0252] This comparative example provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0253] Li2CO3, CaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0254] Li2CO3: 50%

[0255] CaO: 25%

[0256] SiO2: 24%

[0257] Al2O3: 0.9%

[0258] Eu2O3: 0.1%

[0259] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1050°C for 60 minutes to obtain a glass liquid;

[0260] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a devitrified glass block;

[0261] The glass sample prepared in Comparative Example 2 has lost its clarity. This raw material component cannot form glass and cannot be further characterized and tested.

[0262] Comparative Example 3

[0263] This comparative example provides a method for preparing europium-doped alkaline earth lithium silicate glass-ceramics, comprising the following steps:

[0264] Li2CO3, CaO, SiO2, Al2O3 and Eu2O3 with a purity of 99.99% are selected, and the raw materials are calculated according to the following molar ratio:

[0265] Li2CO3: 35%

[0266] CaO: 25%

[0267] SiO2: 37.9%

[0268] Al2O3: 2%

[0269] Eu2O3: 0.1%

[0270] (1) After being fully ground, the mixture is placed in a platinum crucible and melted at 1850°C for 60 minutes to obtain a glass liquid;

[0271] (2) pouring the glass liquid obtained in (1) onto a stainless steel plate and cooling it to form a transparent glass block;

[0272] (3) annealing the transparent glass block obtained in (2) at 400° C. for 96 h to obtain a precursor glass;

[0273] (4) The precursor glass obtained in (3) is placed at a crystallization temperature of 670°C and kept warm for 10 hours, then cooled to room temperature at a rate of 5°C / min and taken out to obtain microcrystalline glass.

[0274] Figure 36 The radiation luminescence spectra of the europium-doped alkaline earth lithium silicate glass-ceramics prepared in Comparative Example 3 are as follows. Since the melting temperature is too high and the raw materials are severely volatilized, the target crystal phase cannot be precipitated, so no luminescence signal can be detected.

[0275] The above embodiments are cases for implementing the present invention, but the implementation methods of the present invention are not limited to the embodiments. Any other changes, modifications, substitutions, combinations, simplifications, etc. made without departing from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A rare earth-doped alkaline earth lithium silicate glass-ceramics, characterized in that: The rare earth-doped alkaline earth lithium silicate glass-ceramics includes 0.01 to 2 mol % of rare earth ions.

2. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 1, characterized in that: The rare earth doped alkaline earth lithium silicate glass-ceramics includes 0.1 to 1 mol% of rare earth ions; The rare earth ion is Eu 3+ 、Sm 3+ or Ce 3+ At least one of .

3. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 1, characterized in that: The crystalline phase precipitated from the rare earth-doped alkaline earth lithium silicate glass-ceramics is at least one of Li2CaSiO4, Li2Ca2Si2O7, Li2SrSiO4 or Li2BaSiO4.

4. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 1, characterized in that: The components and molar percentages of the rare earth-doped alkaline earth lithium silicate glass-ceramics are: Li2O: 10-50%; Alkaline earth metal oxides: 10-50%; SiO2: 25-60%; Al2O3: 0~5%; Rare earth compounds: 0.01~2%.

5. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 4, characterized in that: The raw materials and their molar percentages of the rare earth-doped alkaline earth lithium silicate glass-ceramics are: Li2O: 15-40%; Alkaline earth metal oxides: 20-45%; SiO2: 30-45%; Al2O3: 1-2%; Rare earth compounds: 0.05-1%.

6. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 4 or 5, characterized in that: The rare earth compound is a rare earth oxide and / or a rare earth fluoride; The rare earth oxide is at least one of Eu2O3, Sm2O3 or CeO2; The rare earth fluoride is at least one of EuF3, SmF3 or CeF3; The alkaline earth metal is at least one of Mg, Ca, Sr or Ba.

7. The rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 1, characterized in that: The rare earth-doped alkaline earth lithium silicate glass-ceramics has excellent high-energy ray, high-energy particle and neutron detection performance, and can simultaneously achieve accurate detection of the above radiation.

8. A method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to any one of claims 1 to 7, characterized in that: The preparation method is a melt cooling method, in which the raw materials are ground, melted, cooled, annealed and kept warm to obtain the product.

9. The method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 8, characterized in that: The method comprises the following specific steps: (1) weighing raw materials by mole percentage, grinding and then melting to obtain glass liquid; (2) cooling the glass liquid to form a glass block; (3) annealing the glass block to obtain precursor glass; (4) The precursor glass is kept warm for a period of time, and taken out after cooling to prepare rare earth-doped alkaline earth lithium silicate microcrystalline glass.

10. The method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 9, characterized in that: The raw materials and their molar percentages are: Li2CO3 or Li2O: 10-50%; Alkaline earth metal compounds: 10-50%; SiO2: 25-60%; Al2O3: 0~5%; Rare earth compounds: 0.01-2%; The alkaline earth metal compound is an alkaline earth metal oxide or an alkaline earth metal carbonate.

11. The method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 9, characterized in that: The grinding time in step (1) is not less than 15 minutes.

12. The method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 9, wherein: The melting conditions in step (1) are: keeping warm at 1100-1650° C. for 5-120 minutes; and the melting atmosphere is air atmosphere or reducing atmosphere.

13. The method for preparing rare earth-doped alkaline earth lithium silicate glass-ceramics according to claim 9, characterized in that: The annealing condition in step (3) is annealing at 400-500° C. for 4-96 hours; The holding temperature in step (4) is the crystallization temperature, and the temperature is kept at 550-800° C. for 1-10 hours, and the cooling rate is 1-5° C. / min.

14. Application of the rare earth-doped alkaline earth lithium silicate glass-ceramics according to any one of claims 1 to 7 in the fields of radiation detection, energy exploration, environmental monitoring and medical imaging.

15. A radiation detector, characterized in that: The radiation detector comprises the rare earth-doped alkaline earth lithium silicate glass-ceramics according to any one of claims 1 to 7.

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