A doped zinc germanate crystal, a preparation method and application thereof

Abstract

This application discloses a doped zinc germanate crystal, its preparation method, and its application. The molecular formula of the doped zinc germanate crystal is Zn. 2‑x GeO4:xMn, where Mn is divalent manganese with a valence of 0 ≤ x ≤ 0.5, is a series of crystals prepared as polycrystalline powders using a high-temperature solid-state method. Large crystals are grown using methods such as the Bridgman process, molten salt method, and Czochralski method, but not limited to these methods. This series of crystals exhibits steady-state luminescence characteristics, high light output, excellent radiation stability, and a low detection limit. Furthermore, due to the stable structure of the crystals, they can achieve long-term stable operation under X-ray irradiation. They can be used in many fields such as flawless inspection of electronic components, radiation imaging, and security inspection.

Description

Technical Field

[0001] This application relates to a doped zinc germanate crystal, its preparation method, and its application, belonging to the field of crystals. Background Technology

[0002] Scintillators are functional materials used for radiation detection. They can convert incident ionizing radiation (X-rays, gamma rays, etc.) or high-energy particles (thermal neutrons, etc.) into ultraviolet or visible light.

[0003] Scintillation materials are mainly classified into organic scintillators, inorganic scintillators, and organic-inorganic hybrid scintillators. Inorganic scintillators include scintillating crystals, scintillating glasses, and scintillating ceramics. Each inorganic scintillator has its own advantages and disadvantages. Compared to scintillating ceramics, scintillating crystals offer advantages such as high transmittance, high light output, and high spatial resolution. Compared to glass scintillators, they exhibit high temperature resistance. Compared to gas scintillators, they offer advantages such as high light output, low afterglow, resistance to corrosion damage, strong processability, and low manufacturing cost. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a novel scintillation crystal material, its preparation method, and its application, resulting in a new scintillation crystal applicable to 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, where Mn is divalent manganese, 0≤x≤0.5.

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

[0007] Optionally, x is independently selected from any value or a range of values ​​between 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, and 0.5.

[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 includes one of the following: high-temperature solid-state method, Bridgman process, molten salt process, and Czochralski process.

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

[0011] S1, ZnO, GeO2 and Mn-containing... 2+ The raw materials for the compound were weighed according to their chemical formulas, Zn 2-x GeO4:xMn, 0≤x≤0.5;

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

[0013] S3. Heat up the polycrystalline powder to melt it in preparation for growth. During the crystal growth process, the crystal descends at a rate of 0.2-1 mm / h. After the crystal growth is complete, slowly lower it to room temperature and remove the crystal.

[0014] Specifically, it includes the following steps:

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

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

[0017] S3. Place the raw material processed in step two into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 2-x GeO4:xMn polycrystalline powder.

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

[0019] Optionally, the calcination temperature is independently selected from any value or a range between 900℃, 950℃, 1000℃, 1050℃, 1100℃, 1150℃, 1200℃, 1250℃, and 1300℃.

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

[0021] Optionally, the descent speed is independently selected from any value or a range between any two of 0.2 mm / h, 0.3 mm / h, 0.4 mm / h, 0.5 mm / h, 0.6 mm / h, 0.7 mm / h, 0.8 mm / h, 0.9 mm / h, and 1 mm / h.

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

[0023] The above-described application of doped zinc germanate crystals as scintillation crystals.

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

[0025] Zn 2-x GeO4:xMn scintillation crystals exhibit structural stability and excellent radiative luminescence properties, enabling long-term stable operation under X-ray irradiation. They can be used in numerous fields, including flawless inspection of electronic components, radiation imaging, and security detection.

[0026] The beneficial effects that this application can produce include:

[0027] The scintillation crystal material proposed in this application utilizes a high-temperature solid-state method to mass-produce polycrystalline powder materials and employs methods such as the Bridgman process, molten salt method, and Czochralski method to prepare large-size crystal materials. This scintillation crystal material exhibits steady-state luminescence characteristics, uniform light output, high light yield, excellent irradiation stability, and a low detection limit. Compared to existing scintillation materials on the market, its performance is significantly improved. Furthermore, due to the structural stability of the scintillation crystal material, it can achieve long-term stable operation under X-ray irradiation. It can be used in numerous fields such as flawless inspection of electronic components, radiation imaging, and security detection. Attached Figure Description

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

[0029] Figure 2 Zn prepared in Examples 2-5 2-x XEL radiation spectrum of GeO4:xMn polycrystalline powder;

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

[0031] Figure 4 This is a crystal photograph of Example 3. Detailed Implementation

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

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

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

[0035] The samples were subjected to XRD tests using a Miniflex 600 powder diffractometer.

[0036] X-ray excitation emission spectroscopy analysis was performed using the Zolihan 980 spectrometer.

[0037] Stability tests were conducted using a Zolihan 980 spectrometer.

[0038] Example 1: Zn 1.995 The specific steps for preparing GeO4:0.005Mn crystals are as follows:

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

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

[0041] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.995 GeO4:0.005Mn polycrystalline powder.

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

[0043] Example 2: Zn 1.994 The specific steps for preparing GeO4:0.006Mn crystals are as follows:

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

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

[0046] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.994GeO4:0.006Mn polycrystalline powder.

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

[0048] Example 3: Zn 1.992 The specific steps for preparing GeO4:0.008Mn crystals are as follows:

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

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

[0051] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.9922 GeO4:0.008Mn polycrystalline powder.

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

[0053] Example 4: Zn 1.99 The specific steps for preparing GeO4:0.01Mn crystals are as follows:

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

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

[0056] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.99 GeO4:0.01Mn polycrystalline powder.

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

[0058] Example 5: Zn 1.974 The specific steps for preparing GeO4:0.026Mn crystals are as follows:

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

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

[0061] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.974 GeO4:0.026Mn polycrystalline powder.

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

[0063] Example 6: Zn 1.97 The specific steps for preparing GeO4:0.03Mn crystals are as follows:

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

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

[0066] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.97 GeO4:0.03Mn polycrystalline powder.

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

[0068] Example 7: Zn 1.95 The specific steps for preparing GeO4:0.05Mn crystals are as follows:

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

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

[0071] Step 3: Place the raw material processed in Step 2 into a corundum crucible and calcine it in a muffle furnace at 900-1300℃ for 10-15 hours to obtain Zn. 1.95 GeO4:0.05Mn polycrystalline powder.

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

[0073] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content 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, where Mn is divalent manganese, 0 <x≤0.5; The preparation method of the doped zinc germanate crystal includes one of the Bridgman process, molten salt process and Czochralski process; Mn 2+ Replace Zn 2+ Grid position.

2. The method for preparing doped zinc germanate crystals according to claim 1, characterized in that, The preparation method includes the following steps: S1, ZnO, GeO2 and Mn-containing... 2+ The raw materials for the compound were weighed according to their chemical formulas, Zn 2-x GeO4:xMn, 0 <x≤0.5; S2. Mix the raw materials evenly and calcine them at 900-1300℃ for 10-15 hours to obtain Zn. 2-x GeO4:xMn polycrystalline powder; S3. Heat up the polycrystalline powder to melt it in preparation for growth. During the crystal growth process, the crystal descends at a rate of 0.2-1 mm / h. After the crystal growth is complete, slowly lower it to room temperature and remove the crystal.

3. The preparation method according to claim 2, characterized in that, Raw material purity ≥ 99.99%.

4. The application of the doped zinc germanate crystal according to claim 1 as a scintillation crystal.

5. The application of the doped zinc germanate crystal according to claim 1 in the field of radiation detection.

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