Magnesium tantalate doped with antimony, tin, bismuth / lithium scintillation luminescent material and its preparation method and application

Abstract

The present invention discloses a tantalum magnesium doped antimony, tin, bismuth / lithium scintillating luminescent material, a preparation method thereof and an application thereof. The chemical composition formula of the scintillating luminescent material is Mg4Ta2O9: x at% Sb 5+ (0 ≤ x ≤ 10); Mg4Ta2O9: y at% Sn 4+ (0 ≤ y ≤ 1.5); (Mg (1‑2z) Bi z Li z )4Ta2O9 (0 ≤ z ≤ 0.02). The preparation method is as follows: weighing raw materials according to the chemical general formula, mixing all the raw materials evenly; then pre-calcining and calcining the mixture in an air atmosphere in sequence, and then naturally cooling to room temperature and grinding. By doping Sb2O5, SnO2 and Bi2O3 / Li2CO3 into Mg4Ta2O9 in different proportions respectively, the present invention greatly shortens the decay time of the scintillator material, and can be applied in the field of X-ray and γ-ray radiation detection.

Description

Technical Field

[0001] The present invention relates to magnesium tantalate doped with antimony, tin, bismuth / lithium scintillation luminescent material and its preparation method and application, in particular to magnesium tantalate doped with antimony, tin, bismuth / lithium scintillation luminescent material for X or gamma high energy ray detection. 4 Ta 2 O 9 :x at%Sb 5+ (x=0,0.1,1,10),Mg 4 Ta 2 O 9 :y at%Sn 4+ (y=0, 0.5, 1.0, 1.5), (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 (z=0, 0.005, 0.010, 0.015, 0.020) scintillation luminescent material and preparation method belong to the field of high-performance scintillator material and high-energy ray detection technology. Background Art

[0002] Scintillator refers to a photoelectric functional material that emits ultraviolet or visible light under the action of radiation energy such as high-energy rays (X-rays, gamma rays) or high-energy particles (alpha particles, neutrons) and can be detected by photodetectors. It has been widely used in nuclear medicine imaging, astrophysics, nuclear physics, high-energy physics, security inspection, industrial material testing, radiation environment monitoring, and resource exploration. In these applications, the demand for high-density and fast-response scintillating materials is increasing. Single crystals such as chromium tungstate (CdWO) are widely used in the field of high-energy ray detection. 4 ) and cesium iodide activated by thallium ions (CsI:Tl + ), respectively, have the problems of being brittle, having low radiation stopping power or having long afterglow. In addition, Cd and Tl are highly toxic and do not meet the current environmental protection requirements during preparation and use. Therefore, it is necessary and urgent to explore scintillator materials with excellent comprehensive properties such as high light yield, low afterglow, fast decay, high density, low cost and environmental friendliness.

[0003] Mg 4 Ta 2 O 9 Belongs to the hexagonal system, space group is P The unit cell parameters are a = 0.51614nm, c = 1.40482nm. Mg 4 Ta 2 O 9 The glittering luminescence is mainly caused by (TaO 6 ) 7- The charge transfer transition of the octahedral Ta-O bond.4 Ta 2 O 9 It has excellent scintillation performance, with a light output of 16000ph. / MeV, which is higher than CdWO 4 The crystal's 14000ph. / MeV is high, not as high as CsI:Tl + The crystal has a ph. / MeV of 52000~56000; its decay time under X-ray excitation is 5.7μs, which is better than CdWO 4 The 14μs of crystal is less than that of CsI:Tl + The energy resolution of the crystal is 6.2%, which is better than that of CdWO. 4 8.3% of the crystal, less than CsI:Tl + 5.7% of crystals; Mg 4 Ta 2 O 9 The emission peak is at 360nm, CdWO 4 The luminescence peak of the crystal is at 475nm, CsI:Tl + The luminescence peak of the crystal is at 550nm, and there are commercial photomultiplier tubes with specific sensitive wavelengths to match it, and there is no distinction between good and bad. 4 Ta 2 O 9 The density of the crystal is 6.2 g / cm 3 , smaller than CdWO 4 Crystal 7.9g / cm 3 , greater than CsI:Tl + Crystalline 4.5g / cm 3 Mg 4 Ta 2 O 9 The effective atomic number of the crystal is 59.6 g / mol, which is smaller than that of CdWO 4 Crystal 64.2g / mol, greater than CsI:Tl + Crystalline 54g / mol. Mg 4 Ta 2 O 9 The attenuation distance of the crystal's 662keV gamma ray is 1.82cm, which is greater than that of CdWO 4 Crystal 1.45cm, smaller than CsI:Tl + 2.87cm of crystal; Mg 4 Ta 2 O 9 The afterglow of the crystal is 0.011% / 3ms, which is similar to CdWO 4 Crystal 0.01% / 3ms equivalent, much smaller than CsI:Tl + 2% / 2ms of the crystal. Overall, Mg 4 Ta2 O 9 The long attenuation time of the crystal is its main disadvantage, which limits its application in other high-energy ray detection fields besides security inspection, industrial material testing, radiation environment monitoring and resource exploration. Summary of the invention

[0004] The technical problem solved by the present invention is: how to reduce the scintillation luminescent material Mg 4 Ta 2 O 9 decay time.

[0005] In order to solve the above technical problems, the present invention provides a scintillation luminescent material, whose chemical composition formula is Mg 4 Ta 2 O 9 :x at%Sb 5+ Mg 4 Ta 2 O 9 :y at% Sn 4+ or (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 ; Among them, 0<x≤10, 0<y≤1.5, 0<z≤0.02.

[0006] Preferably, the scintillation luminescent material is Mg under 30keV X-ray excitation. 4 Ta 2 O 9 :x at%Sb 5+ Light output is 4800~20015ph. / MeV, decay time is 652ns~944ns; Mg 4 Ta 2 O 9 :y at% Sn 4+ The light output is 2473~14400ph. / MeV, and the decay time is 685ns~869ns; (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 The light output is 800~6791ph. / MeV, and the decay time is 631ns~802ns.

[0007] The present invention also provides a method for preparing the above-mentioned scintillation luminescent material, comprising: weighing raw materials MgO and Ta according to the chemical composition formula in a stoichiometric ratio; 2 O 5and an oxide containing a doping element, all the raw materials are mixed uniformly; then the obtained mixture is pre-sintered and calcined in an air atmosphere, and then naturally cooled to room temperature and ground; the oxide containing a doping element is Sb 2 O 5 SnO 2 Or Bi 2 O 3 and Li 2 CO 3 combination.

[0008] Preferably, the amount of MgO added should be 3at% in excess of the standard stoichiometric ratio.

[0009] Preferably, the pre-sintering temperature is 1200° C. and the time is 3 hours; the calcining temperature is 1400° C. and the time is 6 hours.

[0010] The present invention also provides the application of the above-mentioned scintillation luminescent material in high-energy ray detection.

[0011] The present invention proposes that pentavalent antimony ions, tetravalent selenium ions and trivalent bismuth ions are partially substituted (TaO 6 ) 7- 、(MgO 6 ) 10 -Octahedral Ta or Mg elements, forming part (SbO 6 ) 7- 、(SnO 6 ) 8- 、(BiO 6 ) 9- Octahedral luminescent center or sensitizing center, forming a 6 ) 7- The energy transfer mechanism of the octahedron changes (TaO 6 ) 7- The bond length and bond angle of the octahedron increase the concentration of free electrons, thereby changing the Mg 4 Ta 2 O 9 The absorption spectrum of the crystal changes the charge migration transition mechanism, shortens its luminescence decay time, and expands its application to nuclear medical imaging, astrophysics, nuclear physics, high energy physics and other fields. The present invention can provide theoretical and technical support for the design and preparation of new scintillator materials.

[0012] Compared with the prior art, the present invention has the following beneficial effects:

[0013] (1) The present invention is carried out by 4 Ta 2 O 9 Doping Sb in different proportions 2 O5 SnO 2 and Bi 2 O 3 / Li 2 CO 3 , which greatly shortens the decay time of scintillator materials and can be used in the field of X-ray and gamma-ray radiation detection;

[0014] (2)Mg 4 Ta 2 O 9 :0.1at%Sb 5+ The light yield is 20015 ph. / MeV, which is undoped with Mg 4 Ta 2 O 9 The decay time is shortened to less than microseconds, 944ns, which is 1.25 times that of undoped Mg. 4 Ta 2 O 9 The emission wavelength is 475nm, which is located in the blue light region. 4 Ta 2 O 9 It emits light at 337nm in the ultraviolet region, which is more compatible with commercial photomultiplier tubes;

[0015] (3) The scintillation luminescent material of the present invention is synthesized by a high-temperature solid-phase method, which has a simple preparation process, safe operation, and easy-to-control conditions;

[0016] (4) The density of the scintillation luminescent material of the present invention is improved to varying degrees, and the decay time is significantly shortened, which expands the Mg 4 Ta 2 O 9 Application in the radiation detection segment. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The scintillation luminescent material Mg prepared in the embodiment 4 Ta 2 O 9 :x at%Sb 5+ X-ray diffraction pattern of

[0018] Figure 2 The scintillation luminescent material Mg prepared in the embodiment 4 Ta 2 O 9 :y at% Sn 4+ X-ray diffraction pattern of

[0019] Figure 3 The scintillation luminescent material (Mg (1-2z) Bi zLi z ) 4 Ta 2 O 9 X-ray diffraction pattern of

[0020] Figure 4 Mg 4 Ta 2 O 9 :0.1at%Sb 5+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0021] Figure 5 Mg 4 Ta 2 O 9 :1at%Sb 5+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0022] Figure 6 Mg 4 Ta 2 O 9 :10at%Sb 5+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0023] Figure 7 Mg 4 Ta 2 O 9 :0.5at%Sn 4+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0024] Figure 8 Mg 4 Ta 2 O 9 :1.0at%Sn 4+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0025] Fig. 9 Mg 4 Ta 2 O 9 :1.5at%Sn 4+ Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0026] Fig.10 is (Mg 0.99 Bi 0.005 Li 0.005 ) 4 Ta 2 O 9Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0027] Fig.11 is (Mg 0.98 Bi 0.010 Li 0.010 ) 4 Ta 2 O 9 Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0028] Fig.12 is (Mg 0.97 Bi 0.015 Li 0.015 ) 4 Ta 2 O 9 Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0029] Fig.13 is (Mg 0.96 Bi 0.020 Li 0.020 ) 4 Ta 2 O 9 Emission spectra of scintillation luminescent materials measured under 30keV X-ray excitation;

[0030] Fig.14 ad is Mg 4 Ta 2 O 9 :x at%Sb 5+ Decay time graphs of scintillation luminescent materials;

[0031] Fig.15 ad is Mg 4 Ta 2 O 9 :y at%Sn 4+ Decay time graphs of scintillation luminescent materials;

[0032] Fig.16 ae is (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 Graph of decay times of scintillation luminescent materials. DETAILED DESCRIPTION

[0033] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0034] In the following examples, all the raw materials and reagents used are conventional commercially available products.

[0035] Example 1

[0036] Weigh MgO and Ta in the stoichiometric ratio of 4.120:0.999:0.001 respectively. 2 O 5 , Sb 2 O 5 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0037] The X-ray diffraction pattern of the product is Figure 1 As shown in the curve at x=0.1, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 4 As shown, x = 0.1, that is, Mg 4 Ta 2 O 9 :0.1at%Sb 5+ The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 475nm and its half-height width is 171nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 138 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 1.25 times of Mg 4 Ta 2 O 9 :0.1at%Sb 5+ The light output is 20015 ph. / MeV. Fig.14 As shown in b, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened, which is Mg 4 Ta 2 O 9 0.137 times of Mg 4 Ta 2 O 9 :0.1at%Sb5+ The decay time is 944ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1. 4 Ta 2 O 9 :0.1at%Sb 5+ The density is 6.2084g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 A slight improvement will help improve its ray stopping ability.

[0038] Table 1 Lattice constants, relative atomic numbers and theoretical densities of scintillation luminescent materials prepared in Examples 1 to 10 and Comparative Examples

[0039]

[0040] Example 2

[0041] Weigh MgO and Ta in the stoichiometric ratio of 4.12:0.99:0.01 respectively. 2 O 5 , Sb 2 O 5 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0042] The X-ray diffraction pattern of the product is Figure 1 As shown in the curve with x=1, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 5 As shown, x = 1, that is, Mg 4 Ta 2 O 9 :1at%Sb 5+ The 30k eV X-ray excitation emission spectrum shows that its emission wavelength is 352nm and its half-height width is 228nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 15 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta2 O 9 0.3 times of Mg 4 Ta 2 O 9 :1at%Sb 5+ The light output is 4800ph. / MeV. Fig.14 As shown in c, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.106 times of Mg 4 Ta 2 O 9 :1at%Sb 5+ The decay time is 731ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1. 4 Ta 2 O 9 :1at%Sb 5+ The density is 6.2315g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 A slight improvement will help improve its ray stopping ability.

[0043] Example 3

[0044] Weigh MgO and Ta in the stoichiometric ratio of 4.12:0.90:0.10 respectively. 2 O 5 , Sb 2 O 5 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0045] The X-ray diffraction pattern of the product is Figure 1 As shown in the curve with x=10, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 6 As shown, x = 10, that is, Mg 4 Ta2 O 9 :10at%Sb 5+ The 30k eV X-ray excitation emission spectrum shows that its emission wavelength is 343nm and its half-height width is 83nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 6nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.90 times of Mg 4 Ta 2 O 9 :10at%Sb 5+ The light output is 14356 ph. / MeV. Fig.14 As shown in d, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.095 times of Mg 4 Ta 2 O 9 :10at%Sb 5+ The decay time is 652ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1. 4 Ta 2 O 9 :10at%Sb 5+ The density is 6.1426 g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 Slightly lower, which is not conducive to its ray stopping ability.

[0046] Example 4

[0047] Weigh MgO and Ta in the stoichiometric ratio of 4.120:0.995:0.010 respectively. 2 O 5 , SnO 2 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0048] The X-ray diffraction pattern of the product is Figure 2As shown in the curve with y=0.5, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 7 As shown, y = 0.5, that is, Mg 4 Ta 2 O 9 :0.5at%Sn 4+ The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 345nm and its half-height width is 85nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 8nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.28 times of Mg 4 Ta 2 O 9 :0.5at%Sn 4+ The light output is 4480 ph. / MeV. Fig.15 As shown in b, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened, which is Mg 4 Ta 2 O 9 0.100 times of Mg 4 Ta 2 O 9 :0.5at%Sn 4+ The decay time is 685ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1. 4 Ta 2 O 9 :0.5at%Sn 4+ The density is 6.3055g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 The improvement is beneficial to improve its ray stopping ability.

[0049] Example 5

[0050] Weigh MgO and Ta in the stoichiometric ratio of 4.12:0.99:0.02 respectively. 2 O 5 , SnO 2The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0051] The X-ray diffraction pattern of the product is Figure 2 As shown in the y=1 curve, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 8 As shown, y = 1, that is, Mg 4 Ta 2 O 9 :1at%Sn 4+ The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 345nm and its half-height width is 87nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 2nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.14 times of Mg 4 Ta 2 O 9 :1at%Sn 4+ The light output is 2473 ph. / MeV. Fig.15 As shown in c, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.127 times of Mg 4 Ta 2 O 9 :1at%Sn 4+ The decay time is 869ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1. 4 Ta 2 O 9 :1at%Sn 4+ The density is 6.2842g / cm 3 , than Mg 4 Ta 2 O 9Density 6.2g / cm 3 The improvement is beneficial to improve its ray stopping ability.

[0052] Example 6

[0053] Weigh MgO and Ta in the stoichiometric ratio of 4.120:0.985:0.030 respectively. 2 O 5 , SnO 2 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to obtain the product.

[0054] The X-ray diffraction pattern of the product is Figure 2 As shown in the curve with y=1.5, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Fig. 9 As shown, y = 1.5, that is, Mg 4 Ta 2 O 9 :1.5at%Sn 4+ The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 342nm and its half-height width is 88nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 5 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.09 times of Mg 4 Ta 2 O 9 :1.5at%Sn 4+ The light output is 14400ph. / MeV. Fig.15 As shown in d, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.111 times of Mg 4 Ta 2 O 9 :1.5at%Sn4+ The decay time of Mg is 760ns. As shown in Table 1, 4 Ta 2 O 9 :1.5at%Sn 4+ The density is 6.2049 g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 A slight improvement will help improve its ray stopping ability.

[0055] Example 7

[0056] Weigh MgO and Ta in the stoichiometric ratio of 4.08:1.00:0.01:0.01 respectively. 2 O 5 ,Bi 2 O 3 , Li 2 CO 3 The above raw materials were ground in an agate mortar to obtain Li + Li 2 CO 3 It can be used for charge compensation. Anhydrous ethanol is added as a dispersant. After grinding evenly, it is loaded into a corundum crucible and pre-fired at 1200℃ for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out and continue to be fully ground in an agate mortar. Then, it is loaded into a corundum crucible and sintered at 1400℃ for 6 hours in an air atmosphere. After naturally cooling to room temperature, it is ground evenly to finally obtain the product.

[0057] The X-ray diffraction pattern of the product is Figure 3 As shown in the curve at z = 0.005, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Fig.10 As shown, z = 0.005, that is (Mg 0.99 Bi 0.005 Li 0.005 ) 4 Ta 2 O 9 The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 346nm and its half-height width is 86nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 9 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta2 O 9 0.42 times, it is estimated that (Mg 0.99 Bi 0.005 Li 0.005 ) 4 Ta 2 O 9 The light output is 6791 ph. / MeV. Fig.16 As shown in b, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened, which is Mg 4 Ta 2 O 9 0.117 times of (Mg 0.99 Bi 0.005 Li 0.005 ) 4 Ta 2 O 9 The decay time of (Mg 0.99 Bi 0.005 Li 0.005 ) 4 Ta 2 O 9 The density is 6.2766g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 A slight improvement will help improve its ray stopping ability.

[0058] Example 8

[0059] MgO and Ta were respectively taken according to the stoichiometric ratio of 4.04:1.00:0.02:0.02. 2 O 5 ,Bi 2 O 3 , Li 2 CO 3 The above raw materials were ground in an agate mortar to obtain Li + Li 2 CO 3 It can be used for charge compensation, and anhydrous ethanol is added as a dispersant. After grinding evenly, it is loaded into a corundum crucible and pre-fired at 1200℃ for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out and continue to be fully ground in an agate mortar. Then, it is loaded into a corundum crucible and sintered at 1400℃ for 6 hours in an air atmosphere. After naturally cooling to room temperature, it is ground evenly to finally obtain the product.

[0060] The X-ray diffraction pattern of the product is Figure 3As shown in the curve at z = 0.01, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Fig.11 As shown, z = 0.01, that is (Mg 0.98 Bi 0.01 Li 0.01 ) 4 Ta 2 O 9 The 30k eV X-ray excitation emission spectrum shows that its emission wavelength is 395nm and its half-height width is 124nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 58 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.12 times, it is estimated that (Mg 0.98 Bi 0.01 Li 0.01 ) 4 Ta 2 O 9 The light output is 1912 ph. / MeV. Fig.16 As shown in c, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.114 times of (Mg 0.98 Bi 0.01 Li 0.01 ) 4 Ta 2 O 9 The decay time of (Mg 0.98 Bi 0.01 Li 0.01 ) 4 Ta 2 O 9 The density is 6.3091g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 The improvement is beneficial to improve its ray stopping ability.

[0061] Example 9

[0062] Weigh MgO and Ta in the stoichiometric ratio of 4.00:1.00:0.03:0.03 respectively. 2 O 5 ,Bi 2 O 3 , Li 2 CO 3 The above raw materials were ground in an agate mortar to obtain Li + Li 2 CO 3 It can be used for charge compensation, and anhydrous ethanol is added as a dispersant. After grinding evenly, it is loaded into a corundum crucible and pre-fired at 1200℃ for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out and continue to be fully ground in an agate mortar. Then, it is loaded into a corundum crucible and sintered at 1400℃ for 6 hours in an air atmosphere. After naturally cooling to room temperature, it is ground evenly to finally obtain the product.

[0063] The X-ray diffraction pattern of the product is Figure 3 As shown in the curve at z = 0.015, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Fig.12 As shown, z = 0.015, that is (Mg 0.97 Bi 0.015 Li 0.015 ) 4 Ta 2 O 9 The 30k eV X-ray excitation emission spectrum shows that its emission wavelength is 394nm and its half-height width is 133nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 57 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.08 times, it is estimated that (Mg 0.97 Bi 0.015 Li 0.015 ) 4 Ta 2 O 9 The light output is 1218 ph. / MeV. Fig.16 As shown in d, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.117 times of (Mg0.97 Bi 0.015 Li 0.015 ) 4 Ta 2 O 9 The decay time of (Mg 0.97 Bi 0.015 Li 0.015 ) 4 Ta 2 O 9 The density is 6.3208g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 The improvement is beneficial to improve its ray stopping ability.

[0064] Example 10

[0065] MgO and Ta were weighed according to the stoichiometric ratio of 3.96:1.00:0.04:0.04 respectively. 2 O 5 ,Bi 2 O 3 , Li 2 CO 3 The above raw materials were ground in an agate mortar to obtain Li + Li 2 CO 3 It can be used for charge compensation, and anhydrous ethanol is added as a dispersant. After grinding evenly, it is loaded into a corundum crucible and pre-fired at 1200℃ for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out and continue to be fully ground in an agate mortar. Then, it is loaded into a corundum crucible and sintered at 1400℃ for 6 hours in an air atmosphere. After naturally cooling to room temperature, it is ground evenly to finally obtain the product.

[0066] The X-ray diffraction pattern of the product is Figure 3 As shown in the curve at z = 0.02, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Fig.13 As shown, z = 0.02, that is (Mg 0.96 Bi 0.02 Li 0.02 ) 4 Ta 2 O 9The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 414nm and its half-height width is 95nm, which is relatively 4 Ta 2 O 9 The emission wavelength is red-shifted by 77 nm, and the luminescence intensity is calculated by the luminescence peak area to be Mg 4 Ta 2 O 9 0.05 times of (Mg 0.96 Bi 0.02 Li 0.02 ) 4 Ta 2 O 9 The light output is 800ph. / MeV. Fig.16 As shown in e, when the excitation wavelength is 223 nm and the emission wavelength is 449 nm, the fluorescence decay time is greatly shortened. 4 Ta 2 O 9 0.092 times of (Mg 0.96 Bi 0.02 Li 0.02 ) 4 Ta 2 O 9 The decay time of (Mg 0.96 Bi 0.02 Li 0.02 ) 4 Ta 2 O 9 The density is 6.4557 g / cm 3 , than Mg 4 Ta 2 O 9 Density 6.2g / cm 3 The improvement is beneficial to improve its ray stopping ability.

[0067] Comparative Example

[0068] Weigh MgO and Ta in a stoichiometric ratio of 4.12:1.00 respectively. 2 O 5 The above raw materials are ground in an agate mortar, and anhydrous ethanol is added as a dispersant. After grinding evenly, they are loaded into a corundum crucible and pre-fired at 1200°C for 3 hours in an air atmosphere. After naturally cooling to room temperature, the raw materials are poured out, and further ground in an agate mortar. Then, they are loaded into a corundum crucible and sintered at 1400°C for 6 hours in an air atmosphere. After naturally cooling to room temperature, they are ground evenly to finally obtain the product.

[0069] The X-ray diffraction pattern of the product is Figure 1As shown in the curve at x=0, all diffraction peaks correspond to the standard diffraction peaks (PDF#38-1458), indicating that it has Mg 4 Ta 2 O 9 The pure phase structure of . Its unit cell parameters are obtained through XRD data, as shown in Table 1. like Figure 4 As shown, x = 0, that is, Mg 4 Ta 2 O 9 The 30keV X-ray excitation emission spectrum shows that its emission wavelength is 337nm and its half-height width is 89nm. Fig.14 As shown in a, when the excitation wavelength is 203 nm and the emission wavelength is 385 nm, the fluorescence decay time is 6867 ns. The lattice constant, relative atomic number and theoretical density of the material are shown in Table 1.

[0070] The above description is only a preferred embodiment of the present invention and is not any formal or substantial limitation of the present invention. It should be pointed out that a person skilled in the art can make several improvements and supplements without departing from the present invention, and these improvements and supplements should also be regarded as the protection scope of the present invention.

Claims

1. A scintillation luminescent material, It is characterized in that Its chemical formula is Mg 4 Ta 2 O 9 :x at%Sb 5+ Mg 4 Ta 2 O 9 :yat%Sn 4+ or (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 ; Among them, 0<x≤10, 0<y≤1.5, 0<z≤0.

02.

2. The scintillation luminescent material according to claim 1, It is characterized in that The scintillation luminescent material is excited by 30keV X-rays. 4 Ta 2 O 9 :x at%Sb 5+ Light output is 4800~20015ph. / MeV, decay time is 652ns~944ns; Mg 4 Ta 2 O 9 :y at% Sn 4+ The light output is 2473~14400ph. / MeV, and the decay time is 685ns~869ns; (Mg (1-2z) Bi z Li z ) 4 Ta 2 O 9 The light output is 800~6791ph. / MeV, and the decay time is 631ns~802ns.

3. A method for preparing the scintillation luminescent material according to claim 1 or 2, It is characterized in that include: According to the chemical composition formula, weigh the raw materials MgO and Ta in a stoichiometric ratio. 2 O 5 and an oxide containing a doping element, all the raw materials are mixed uniformly; then the obtained mixture is pre-sintered and calcined in an air atmosphere, and then naturally cooled to room temperature and ground; the oxide containing a doping element is Sb 2 O 5 SnO 2 Or Bi 2 O 3 and Li 2 CO 3 combination.

4. The method for preparing the scintillation luminescent material according to claim 3, It is characterized in that The amount of MgO added should be 3at% in excess relative to the standard stoichiometric ratio.

5. The method for preparing the scintillation luminescent material according to claim 3, It is characterized in that The pre-sintering temperature is 1200° C. and the time is 3 hours; the calcining temperature is 1400° C. and the time is 6 hours.

6. Use of the scintillation luminescent material according to claim 1 or 2 in high energy ray detection.

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