Doped zinc germanate crystal as well as preparation method and application thereof

Abstract

The invention discloses a doped zinc germanate crystal and a preparation method and application thereof, the molecular formula of the doped zinc germanate crystal is Zn2-xGeO4: xMn, Mn is a positive bivalent manganese element, and x is greater than or equal to 0 and less than or equal to 0.5, the series of crystals are prepared into polycrystalline powder through a high-temperature solid phase method, and large crystals are grown through a Bridgman method, a molten salt method, a Czochralski method and other methods and are not limited to the methods. The series of crystals have the characteristics of steady-state luminescence, high light output, excellent irradiation stability and low detection limit. And the structure of the crystal is stable, so that long-term stable work under ray irradiation can be realized. The method can be used in the fields of electronic component non-flaw detection, radiation imaging, safety detection and the like.

Description

Technical Field

[0001] The present application relates to a doped zinc germanate crystal and a preparation method and application thereof, belonging to the field of crystals. Background Art

[0002] Scintillator is a functional material used for radiation detection. It can convert incident ionizing radiation (X-rays, gamma rays, etc.) or high-energy particles (thermal neutrons, etc.) into ultraviolet light or visible light.

[0003] The scintillating materials mainly include organic scintillators, inorganic scintillators and organic-inorganic hybrid scintillators. Among them, inorganic scintillators include: scintillating crystals, scintillating glasses and scintillating ceramics. Inorganic scintillators each have their own advantages and disadvantages. Among them, scintillating crystals have the advantages of high transmittance, high light output and high spatial resolution compared with scintillating ceramics. Compared with glass scintillators, it has high temperature resistance. Compared with gas scintillators, it has the advantages of high light output, low afterglow, corrosion resistance, strong processability and low preparation cost. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a new scintillation crystal material and a preparation method and application thereof, thereby obtaining a new scintillation crystal for use in the field of radiation detection.

[0005] A doped zinc germanate crystal, wherein the chemical formula of the doped zinc germanate crystal is Zn 2-x GeO4:xMn, wherein Mn is a divalent manganese element, 0≤x≤0.5.

[0006] Optionally, Mn 2+ Replace Zn 2+ Grid position.

[0007] Optionally, x is independently selected from any value among 0, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.026, 0.03, 0.035, 0.04, 0.045, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or any range therebetween.

[0008] Optionally, the molecular formula of the doped zinc germanate crystal is Zn 2-x GeO4:xMn.

[0009] The preparation method of the doped zinc germanate crystal described above comprises one of a high temperature solid phase method, a Bridgman method, a molten salt method and a Czochralski method.

[0010] Optionally, the preparation method comprises the following steps:

[0011] S1, ZnO, GeO2 and Mn 2+ The raw materials of the compound are weighed according to the chemical formula, Zn 2-x GeO4:xMn, 0≤x≤0.5;

[0012] S2, mix the raw materials evenly, and calcine at 900-1300℃ for 10-15h to obtain Zn 2-x GeO4:xMn polycrystalline powder;

[0013] S3. Heat the polycrystalline powder and melt it to prepare for growth. The descent rate during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0014] Specifically, the steps include:

[0015] S1, ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 2-x GeO4:xMn, wherein Mn is a divalent manganese element 0≤x≤0.5.

[0016] S2. Mix the weighed raw materials evenly in an agate mortar.

[0017] S3, the raw materials processed in step 2 are placed in a corundum crucible, and calcined in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 2-x GeO4:xMn polycrystalline powder.

[0018] S4. Put the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0019] Optionally, the calcination temperature is independently selected from any value of 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, or any range therebetween.

[0020] Optionally, the calcination time is independently selected from any value of 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, or any range therebetween.

[0021] Optionally, the descending speed is independently selected from any value among 0.2mm / h, 0.3mm / h, 0.4mm / h, 0.5mm / h, 0.6mm / h, 0.7mm / h, 0.8mm / h, 0.9mm / h, 1mm / h, or any range therebetween.

[0022] Optionally, the raw material purity is ≥99.99%.

[0023] The above-mentioned doped zinc germanate crystal is used as a scintillation crystal.

[0024] The application of the above-mentioned doped zinc germanate crystal in the field of radiation detection.

[0025] Zn 2-x GeO4:xMn scintillator crystal has a stable structure and good radioluminescence performance, and has successfully achieved long-term stable operation under x-ray irradiation. It can be used in many fields such as electronic component non-destructive testing, radiation imaging and safety detection.

[0026] The beneficial effects of this application include:

[0027] The scintillation crystal material proposed in this application uses a high-temperature solid-phase method to prepare a large amount of polycrystalline powder material, and uses the Bridgman method, molten salt method and pulling method to prepare large-size crystal materials. The scintillation crystal material has steady-state luminescence characteristics, uniform light output, high light yield, excellent irradiation stability and low detection limit. Compared with the existing scintillation materials on the market, the performance is greatly improved. And because the structure of the scintillation crystal material is stable, it can achieve long-term stable operation under x-ray irradiation. It can be used in many fields such as non-destructive testing of electronic components, radiation imaging and safety detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Zn prepared in Example 1-7 2-x XRD pattern of GeO4:xMn polycrystalline powder;

[0029] Figure 2 Zn prepared in Example 2-5 2-x Radioluminescence spectrum (XEL) of GeO4:xMn polycrystalline powder;

[0030] Figure 3 is the radiation stability spectrum of the crystal of Example 3;

[0031] Figure 4 This is a crystal photograph of Example 3. DETAILED DESCRIPTION

[0032] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0033] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0034] The analysis methods used in the examples of this application are as follows:

[0035] The samples were tested by XRD using a powder diffractometer Miniflex 600;

[0036] X-ray excitation emission spectroscopy was performed using Zhuoli Hanguang 980 spectrometer;

[0037] Use Zhuoli Hanguang 980 spectrometer to conduct stability test;

[0038] Example 1: Zn 1.995 The preparation steps of GeO4:0.005Mn crystal are as follows:

[0039] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.995 GeO4:0.005Mn, where Mn is the positive divalent manganese element.

[0040] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0041] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.995 GeO4:0.005Mn polycrystalline powder.

[0042] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0043] Example 2: Zn 1.994 The preparation steps of GeO4:0.006Mn crystal are as follows:

[0044] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.994 GeO4:0.006Mn, where Mn is the divalent manganese element.

[0045] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0046] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.994GeO4:0.006Mn polycrystalline powder.

[0047] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0048] Example 3: Zn 1.992 The preparation steps of GeO4:0.008Mn crystal are as follows:

[0049] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.992 GeO4:0.008Mn, where Mn is the divalent manganese element.

[0050] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0051] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.9922 GeO4:0.008Mn polycrystalline powder.

[0052] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0053] Example 4: Zn 1.99 The preparation steps of GeO4:0.01Mn crystal are as follows:

[0054] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.99 GeO4:0.01Mn, where Mn is the divalent manganese element.

[0055] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0056] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.99 GeO4:0.01Mn polycrystalline powder.

[0057] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0058] Example 5: Zn 1.974 The preparation steps of GeO4:0.026Mn crystal are as follows:

[0059] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.974 GeO4: 0.026Mn, where Mn is the divalent manganese element.

[0060] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0061] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.974 GeO4:0.026Mn polycrystalline powder.

[0062] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0063] Example 6: Zn 1.97 The preparation steps of GeO4:0.03Mn crystal are as follows:

[0064] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.97 GeO4:0.03Mn, where Mn is the divalent manganese element.

[0065] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0066] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.97 GeO4:0.03Mn polycrystalline powder.

[0067] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0068] Example 7: Zn 1.95 The preparation steps of GeO4:0.05Mn crystal are as follows:

[0069] Step 1: ZnO, GeO2 and Mn 2+ The high-purity raw materials of the compound are weighed according to the chemical formula: Zn 1.95 GeO4:0.05Mn, where Mn is the divalent manganese element.

[0070] Step 2: Mix the weighed raw materials evenly in an agate mortar.

[0071] Step 3: Place the processed raw materials in step 2 into a corundum crucible and calcine them in a muffle furnace at 900-1300°C for 10-15h to obtain Zn 1.95 GeO4:0.05Mn polycrystalline powder.

[0072] Step 4: Place the polycrystalline powder in step 3 into a platinum crucible, load it into a descending furnace, and then heat it up to melt it in preparation for growth; the descending speed during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0073] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A doped zinc germanate crystal, characterized in that: The chemical formula of the doped zinc germanate crystal is Zn 2-x GeO4:xMn, wherein Mn is a divalent manganese element, 0≤x≤0.

5.

2. The doped zinc germanate crystal according to claim 1, characterized in that: Mn 2+ Replace Zn 2+ Grid position.

3. The method for preparing the doped zinc germanate crystal according to claim 1 or 2, characterized in that: The preparation method comprises one of a high temperature solid phase method, a Bridgman method, a molten salt method and a Czochralski method.

4. The preparation method according to claim 3, characterized in that: The preparation method comprises the following steps: S1, ZnO, GeO2 and Mn 2+ The raw materials of the compound are weighed according to the chemical formula, Zn 2-x GeO4:xMn, 0≤x≤0.5; S2, mix the raw materials evenly, and calcine at 900-1300℃ for 10-15h to obtain Zn 2-x GeO4:xMn polycrystalline powder; S3. Heat the polycrystalline powder and melt it to prepare for growth. The descent rate during the crystal growth process is 0.2-1mm / h. After the crystal growth is completed, slowly cool it to room temperature and take out the crystal.

5. The preparation method according to claim 4, characterized in that: Raw material purity ≥99.99%.

6. Use of the doped zinc germanate crystal according to claim 1 or 2 as a scintillation crystal.

7. Use of the doped zinc germanate crystal according to claim 1 or 2 in the field of radiation detection.

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