A divalent manganese-based optical pressure measuring fluorescent material, a preparation method and application thereof
The preparation of divalent manganese-doped Zn2GeO4 fluorescent materials by DC arc method solves the problems of long synthesis time and insufficient sensitivity of existing Zn2GeO4-based materials, and achieves high-sensitivity pressure monitoring effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BOHAI UNIV
- Filing Date
- 2026-03-09
- Publication Date
- 2026-06-09
AI Technical Summary
Existing methods for synthesizing Zn2GeO4-based fluorescent materials are time-consuming and environmentally unfriendly, making it difficult to meet the requirements of low cost and convenient operation. At the same time, traditional materials lack sufficient sensitivity in pressure monitoring.
Divalent manganese-doped Zn2GeO4 fluorescent materials were prepared by DC arc method. By controlling the doping concentration and arc furnace conditions, a rhombohedral Zn2GeO4:xMn2+ structure was prepared, and the pressure was monitored by the ratio of fluorescence emission peak intensity.
It achieves high-sensitivity pressure monitoring, with an absolute pressure sensitivity of up to 651.19%/GPa and a relative pressure sensitivity of up to 308.25%/GPa, which is significantly higher than other optical pressure measuring materials. Moreover, the synthesis method is simple and environmentally friendly.
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Figure CN122168283A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of pressure sensing applications of fluorescent materials, and more particularly to divalent manganese-based fluorescent materials and high-sensitivity optical pressure measurement applications based on these materials. Background Technology
[0002] Fluorescence pressure measurement is based on the correlation between a material's fluorescence properties and pressure. It indirectly and accurately measures pressure by monitoring the dynamic changes in fluorescence parameters over pressure in real time. This method is applicable to extreme pressure conditions such as deep-sea environments, planetary interiors, and the interiors of super-heavy structures, enabling visualized, non-contact pressure monitoring. Common trivalent lanthanide ions (Ln...) 3+ The electrons in the f orbitals of 4f electrons are shielded by outer electrons (such as 5s and 5p). This shielding effect makes the 4f electrons minimally affected by the crystal field, resulting in high energy level structure stability and poor sensitivity to pressure changes. In contrast, divalent transition metal ions like Mn... 2+ With unique 3D 5 With its electronic structure lacking the shielding of outer orbitals, the 3d electrons are directly exposed to the crystal field, and its single broadband green light emission is extremely sensitive to external environmental pressure. Therefore, divalent manganese-based fluorescent materials are ideal materials for pressure monitoring.
[0003] Zn₂GeO₄ is a typical n-type semiconductor with high thermal / mechanical stability, a wide bandgap (4.68 eV), and high exciton binding energy, making it an ideal fluorescent matrix material. Doped Zn₂GeO₄ exhibits broad application prospects in numerous fields due to its tunable fluorescence properties and long afterglow characteristics. 2+ Ion-doped Zn₂GeO₄ exhibits highly efficient green fluorescence under ultraviolet light or low-voltage electron beam excitation, with excellent chromaticity and suitable luminescence intensity. Traditionally, the synthesis methods for Zn₂GeO₄-based fluorescent materials mainly include hydrothermal, solvothermal, and high-temperature solid-state methods. However, these methods often require the use of hazardous chemicals and organic solvents in practice, resulting in high energy consumption and lengthy reaction times, making it difficult to meet the requirements of low cost, convenient operation, and green synthesis. Summary of the Invention
[0004] To address existing problems, this invention discloses a method for preparing a fluorescent material of divalent manganese-doped Zn₂GeO₄ and its application in optical pressure measurement. The synthesis method of this material is simple and rapid, and as a pressure sensing material, its pressure sensitivity is higher than that of most optical pressure measuring materials, thus having wider application value. The technical solution adopted in this invention is as follows: A divalent manganese-based optical pressure-measuring fluorescent material with a rhombohedral structure and the general chemical formula: Zn₂GeO₄:xMn 2+, where x is the molar percentage of doped divalent manganese ions, and satisfies 0.002≤x≤0.030.
[0005] Preferably, x = 0.002, 0.015, or 0.030.
[0006] Another objective of this invention is to provide a method for preparing the fluorescent material described in the above technical solution, which employs a direct current arc method and includes the following steps: (1) weighing ZnO, GeO2 and metallic manganese powder in a molar ratio of 2:1:x, wherein 0.002≤x≤0.030; after thoroughly grinding and mixing the raw materials, pre-pressing them into sheets, and finally placing the resulting raw material sheets into a graphite crucible in a direct current arc furnace; (2) Evacuate the electric arc furnace cavity and introduce nitrogen as a protective gas; (3) Set the DC arc discharge conditions as follows: voltage range 10-14V, current 40-50A, reaction time 5-10s; (4) After the temperature of the graphite crucible in the electric arc furnace drops to room temperature, collect the Zn2GeO4 material doped with divalent manganese in the crucible.
[0007] As a preferred value, x = 0.002, 0.015, or 0.030.
[0008] Another objective of this invention is to provide an application of the fluorescent material based on the above-described technical solution in extreme environmental pressure scenarios. The application method involves recording the normalized spectral intensity I at 10 nm intervals on both the long-wavelength and short-wavelength sides of the fluorescence emission peak at 533 nm. y and I z Ratio. Where, I y The spectral intensity is on the long-wavelength side of the center of the fluorescence emission peak, where y is a multiple of ten between 560 and 590, and I... z The intensity of the fluorescence emission peak is the spectral intensity on the short-wave side of the center, and z is a multiple of ten between 510 and 530. The ambient pressure P is monitored based on the third-order polynomial function relationship between the ratio and the pressure P.
[0009] Preferably, this application is suitable for an environmental pressure range of 10. -4 ~3.5 GPa.
[0010] This invention is based on Mn 2+ The application method of the intensity ratio of the long-wave side to the short-wave side of the broadband single peak yielded an absolute pressure sensitivity of up to 651.19% / GPa and a relative pressure sensitivity of up to 308.25% / GPa, which is significantly higher than other known optical pressure measuring materials. Attached Figure Description
[0011] Figure 1This is a schematic diagram of the electric arc furnace device used in this invention. Figure 2 The Zn2GeO4:0.002Mn synthesized in Example 1 2+ Comparison of the X-ray diffraction pattern of the sample with the X-ray diffraction pattern and normalized diffraction data of pure phase Zn2GeO4 Figure 3 The Zn2GeO4:0.002Mn synthesized in Example 1 2+ Fluorescence spectrum of the sample under 325nm laser excitation Figure 4 The Zn2GeO4:0.015Mn synthesized in Example 2 2+ Comparison of the X-ray diffraction pattern of the sample with the X-ray diffraction pattern and normalized diffraction data of pure phase Zn2GeO4 Figure 5 The Zn2GeO4:0.015Mn synthesized in Example 2 2+ Fluorescence spectrum of the sample under 325nm laser excitation Figure 6 The Zn2GeO4:0.030Mn synthesized in Example 3 2+ Comparison of the X-ray diffraction pattern of the sample with the X-ray diffraction pattern and normalized diffraction data of pure phase Zn2GeO4 Figure 7 The Zn2GeO4:0.030Mn synthesized in Example 3 2+ Fluorescence spectrum of the sample under 325nm laser excitation Figure 8 The image shows the Zn2GeO4:0.002Mn prepared in Example 1. 2+ Normalized high-pressure fluorescence spectrum of the sample Figure 9 As shown Figure 8 The relationship between normalized spectral intensity data of the 533 nm fluorescence emission peak center on the long-wavelength and short-wavelength sides and pressure. Figure 10 For I y with I 510 In 10 -4 Data on the ratio variation with pressure in the range of ~2.02 GPa, where y is a multiple of ten between 560 and 590. Figure 11 According to Figure 10 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~2.02 GPa a picture Figure 12 According to Figure 10The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~2.02 GPa r picture Figure 13 For I y with I 520 In 10 -4 Data on the ratio variation with pressure in the range of ~2.61 GPa, where y is a multiple of ten between 560 and 590. Figure 14 According to Figure 13 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~2.61 GPa a picture Figure 15 According to Figure 13 The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~2.61 GPa r picture Figure 16 For I y with I 520 In 10 -4 Data on the ratio variation with pressure in the range of ~2.61 GPa, where y is a multiple of ten between 560 and 590. Figure 17 According to Figure 16 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~2.61 GPa a picture Figure 18 According to Figure 16 The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~2.61 GPa r picture Figure 19 The image shows the Zn2GeO4:0.015Mn prepared in Example 2. 2+ Normalized high-pressure fluorescence spectrum of the sample Figure 20 As shown Figure 19 The relationship between normalized spectral intensity data of the 533 nm fluorescence emission peak center on the long-wavelength and short-wavelength sides and pressure. Figure 21 For I y with I 510 In 10 -4 Data on the ratio variation with pressure within the range of ~3.5 GPa, where y is a multiple of ten between 560 and 590. Figure 22 According to Figure 21 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~3.5 GPa a picture Figure 23 According to Figure 21 The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~3.5 GPa r picture Figure 24 For I y with I 520 In 10 -4 Data on the ratio variation with pressure within the range of ~3.5 GPa, where y is a multiple of ten between 560 and 590. Figure 25 According to Figure 24 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~3.5 GPa a picture Figure 26 According to Figure 24 The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~3.5 GPa r picture Figure 27 For I y with I 530 In 10 -4 Data on the ratio variation with pressure within the range of ~3.5 GPa, where y is a multiple of ten between 560 and 590. Figure 28 According to Figure 27 The intensity ratio obtained from the fitted line calculation in 10 -4 Absolute pressure sensitivity S in the range of ~3.5 GPa a picture Figure 29 According to Figure 27 The intensity ratio obtained from the fitted line calculation in 10 -4 Relative pressure sensitivity S in the range of ~3.5 GPa r picture Figure 30 The image shows the Zn2GeO4:0.030Mn prepared in Example 3. 2+ Normalized high-pressure fluorescence spectrum of the sample Figure 31 As shown Figure 30 The relationship between normalized spectral intensity data of the 533 nm fluorescence emission peak center on the long-wavelength and short-wavelength sides and pressure. Figure 32 According to I y with I 510 In 10 -4 The absolute pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~1.92 GPa. a The graph shows that y is a multiple of ten between 560 and 590. Figure 33 According to I y with I 510 In 10 -4 The relative pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~1.92 GPa. r The graph shows that y is a multiple of ten between 560 and 590. Figure 34 According to I y with I 520 In 10 -4 The absolute pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~2.34 GPa. a The graph shows that y is a multiple of ten between 560 and 590. Figure 35 According to I y with I 520 In 10 -4 The relative pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~2.34 GPa. r The graph shows that y is a multiple of ten between 560 and 590. Figure 36 According to I y with I 530 In 10 -4 The absolute pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~2.34 GPa. a The graph shows that y is a multiple of ten between 560 and 590. Figure 37 According to I y with I 530 In 10 -4 The relative pressure sensitivity S is calculated from the intensity ratio fitting line in the range of ~2.34 GPa. r The graph shows that y is a multiple of ten between 560 and 590. Detailed Implementation
[0012] To make the objectives, technical solutions, and advantages of this invention clearer and more accurate, the invention will be described in more detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments described herein are only a part of the many embodiments of this invention and do not cover all of them. Based on the embodiments provided by this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the protection scope defined by this invention.
[0013] Figure 1 An electric arc furnace reactor apparatus was demonstrated. The apparatus consists of a glass enclosure 1, an internal cooling wall 2, a tungsten cathode 3, and a graphite anode 5. The reactants 4 are pre-pressed into sheets and placed inside the graphite anode 5. The graphite anode 5 is connected to a copper base 6. Before the reaction, the reactor apparatus is evacuated. The reaction chamber is purged with nitrogen through the inlet 7 and vent 8, using nitrogen as a protective gas to prevent oxygen from participating in the reaction.
[0014] Circulating water needs to be introduced into the condenser wall 2 and the copper base 6 through the inlet 9 and outlet 10 to absorb the heat generated during the reaction. During the experiment, the vertical position of the copper base 6 is adjusted to control the distance between the tungsten cathode 3 and the graphite anode 5, thereby inducing a high-temperature plasma discharge. The resulting high temperature causes the reactants 4 to undergo a chemical reaction. After the reaction is complete and the apparatus cools to room temperature, the reaction products can be collected inside the graphite anode 5.
[0015] Example 1 In this embodiment, divalent manganese-doped Zn₂GeO₄ fluorescent material was prepared. The preparation process is as follows: ZnO, GeO2, and manganese powder were weighed separately in a molar ratio of 2:1:0.002. They were thoroughly ground for half an hour to ensure uniform mixing, and then pre-pressed into raw material sheets 4 with a diameter of 20 mm and a thickness of 2 mm using a tablet press. The resulting raw material sheets 4 were then placed in a graphite crucible 5 inside a DC electric arc furnace. A tungsten rod cathode 3 was then fixed above the raw material sheets 4, ensuring that the tungsten rod cathode 3, raw material sheets 4, graphite crucible 5, and copper base 6 were aligned. Before the formal experiment, the furnace cavity was evacuated and repeatedly flushed with nitrogen to remove air. Finally, the cavity was filled with nitrogen as a protective gas, maintaining a pressure of 10 kPa within the cavity. The circulating water system was turned on to ensure the water cooling systems of the metal cover 2 and copper base 6 were functioning properly.
[0016] In the experiment, the copper base 6 was slowly raised to create a high-temperature electric arc discharge between the tungsten rod cathode 3 and the graphite crucible 5, initiating the reaction. During the reaction, the voltage was maintained at 10–14 V, the current at 40–50 A, and the reaction time at 5–10 s. After the reaction, the graphite crucible in the arc furnace was allowed to cool to room temperature, and the product in the crucible was collected; this product was divalent manganese-doped Zn₂GeO₄ material.
[0017] from Figure 2 The X-ray diffraction pattern shows that all diffraction peaks correspond to the rhombohedral phase of Zn₂GeO₄, and the normalized diffraction data card number is 11-0687. The absence of impurity peaks in the pattern indicates that the obtained Zn₂GeO₄ sample has high purity.
[0018] from Figure 3 The emission spectrum shows a broad fluorescence emission peak at approximately 533 nm, originating from Mn. 2+ of 4 T1( 4 G) to 6 A1( 6 S) energy level transition. This indicates that manganese ions have been successfully doped into the Zn2GeO4 lattice.
[0019] Example 2 In this embodiment, divalent manganese-doped Zn₂GeO₄ fluorescent material was prepared. The preparation process is as follows: ZnO, GeO2, and manganese powder were weighed separately in a molar ratio of 2:1:0.015. They were thoroughly ground for half an hour to ensure uniform mixing, and then pre-pressed into raw material sheets 4 with a diameter of 20 mm and a thickness of 2 mm using a tablet press. The resulting raw material sheets 4 were then placed in a graphite crucible 5 inside a DC electric arc furnace. A tungsten rod cathode 3 was then fixed above the raw material sheets 4, ensuring that the tungsten rod cathode 3, raw material sheets 4, graphite crucible 5, and copper base 6 were aligned. Before the formal experiment, the furnace cavity was evacuated and repeatedly flushed with nitrogen to remove air. Finally, the cavity was filled with nitrogen as a protective gas, maintaining a pressure of 10 kPa within the cavity. The circulating water system was turned on to ensure the water cooling systems of the metal cover 2 and copper base 6 were functioning properly.
[0020] In the experiment, the copper base 6 was slowly raised to create a high-temperature electric arc discharge between the tungsten rod cathode 3 and the graphite crucible 5, initiating the reaction. During the reaction, the voltage was maintained at 10–14 V, the current at 40–50 A, and the reaction time at 5–10 s. After the reaction, the graphite crucible in the arc furnace was allowed to cool to room temperature, and the product in the crucible was collected; this product was divalent manganese-doped Zn₂GeO₄ material.
[0021] from Figure 4The X-ray diffraction pattern shows that all diffraction peaks correspond to the rhombohedral phase of Zn₂GeO₄, and the normalized diffraction data card number is 11-0687. The absence of impurity peaks in the pattern indicates that the obtained Zn₂GeO₄ sample has high purity.
[0022] from Figure 5 The emission spectrum shows a broad fluorescence emission peak at approximately 533 nm, originating from Mn. 2+ of 4 T1( 4 G) to 6 A1( 6 S) energy level transition. This indicates that manganese ions have been successfully doped into the Zn2GeO4 lattice.
[0023] Example 3 In this embodiment, divalent manganese-doped Zn₂GeO₄ fluorescent material was prepared. The preparation process is as follows: ZnO, GeO2, and manganese powder were weighed separately in a molar ratio of 2:1:0.030. They were thoroughly ground for half an hour to ensure uniform mixing, and then pre-pressed into raw material sheets 4 with a diameter of 20 mm and a thickness of 2 mm using a tablet press. The resulting raw material sheets 4 were then placed in a graphite crucible 5 inside a DC electric arc furnace. A tungsten rod cathode 3 was then fixed above the raw material sheets 4, ensuring that the tungsten rod cathode 3, raw material sheets 4, graphite crucible 5, and copper base 6 were aligned. Before the formal experiment, the furnace cavity was evacuated and repeatedly flushed with nitrogen to remove air. Finally, the cavity was filled with nitrogen as a protective gas, maintaining a pressure of 10 kPa within the cavity. The circulating water system was turned on to ensure the water cooling systems of the metal cover 2 and copper base 6 were functioning properly.
[0024] In the experiment, the copper base 6 was slowly raised to create a high-temperature electric arc discharge between the tungsten rod cathode 3 and the graphite crucible 5, initiating the reaction. During the reaction, the voltage was maintained at 10–14 V, the current at 40–50 A, and the reaction time at 5–10 s. After the reaction, the graphite crucible in the arc furnace was allowed to cool to room temperature, and the product in the crucible was collected; this product was divalent manganese-doped Zn₂GeO₄ material.
[0025] from Figure 6 The X-ray diffraction pattern shows that all diffraction peaks correspond to the rhombohedral phase of Zn₂GeO₄, and the normalized diffraction data card number is 11-0687. The absence of impurity peaks in the pattern indicates that the obtained Zn₂GeO₄ sample has high purity.
[0026] from Figure 7 The emission spectrum shows a broad fluorescence emission peak at approximately 533 nm, originating from Mn. 2+ of 4 T1( 4G) to 6 A1( 6 S) energy level transition. This indicates that manganese ions have been successfully doped into the Zn2GeO4 lattice.
[0027] The above results demonstrate that manganese ions can be successfully doped into the Zn2GeO4 lattice using the preparation method of the present invention.
[0028] Figure 8 Zn2GeO4:0.002Mn 2+ Normalized high-pressure fluorescence spectrum, Mn 2+ The broad fluorescence emission peak broadens and redshifts with increasing pressure. The intensity on the long-wavelength side of the 533nm fluorescence emission peak center increases with increasing pressure, while the intensity on the short-wavelength side decreases with increasing pressure.
[0029] Figure 9 As shown Figure 8 The normalized data of spectral intensity on the long-wavelength and short-wavelength sides of the emission center in the image are related to pressure, where the data normalization is based on a 10⁻⁶ ohmmeter. -4 The intensity at GPa is used as a reference. The normalized intensity on the long-wavelength side increases with increasing pressure, while the normalized intensity on the short-wavelength side decreases with increasing pressure. Low-doped Mn 2+ The fluorescence emission intensity is weak, while the relative intensity of fluorescence emission from the matrix in the low-wavelength region increases under high-pressure conditions. This has an impact on Mn. 2+ The intensity on the shorter wavelength side of the fluorescence emission center has an impact. Therefore, at pressures of 2.25 GPa and 2.61 GPa, I 510 The intensity values were not statistically analyzed.
[0030] Depend on Figure 10 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 510 =-0.522P 3 +2.181P 2 +3.475P+1.520; I 570 / I 510 =-0.236P 3 +1.672P 2 +2.409P +0.946; I 580 / I 510 =-0.029P 3 +1.099P 2 +1.576P +0.545; I 590 / I510 =0.048P 3 +0.700P 2 +0.924P +0.304; Where P represents ambient pressure.
[0031] Depend on Figure 11 absolute pressure sensitivity S a The changes are visible, S a (I 560 / I 510 The values for the absolute pressure sensitivity first increase and then decrease with increasing pressure, while the other values for absolute pressure sensitivity increase with increasing pressure. a (I 560 / I 510 ), S a (I 570 / I 510 ), S a (I 580 / I 510 ) and S a (I 590 / I 510 The maximum values were 651.19% / GPa, 627.40% / GPa, 564.80% / GPa, and 431.23% / GPa at 1.41GPa, 2.02GPa, 2.02GPa, and 2.02GPa, respectively.
[0032] Depend on Figure 12 The relative pressure sensitivity S in r The changes are visible, S r The value decreases as pressure increases, reaching 10... -4 At GPa, the relative pressure sensitivity value is the highest, S r (I 560 / I 510 ), S r (I 570 / I 510 ), S r (I 580 / I 510 ) and S r (I 590 / I 510 The maximum values were 231.57% / GPa, 258.33% / GPa, 293.32% / GPa, and 308.25% / GPa, respectively.
[0033] Depend on Figure 13 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 520 =-0.186P3 +0.936P 2 +0.460P +0.789; I 570 / I 520 =-0.109P 3 +0.766P 2 +0.268P +0.503; I 580 / I 520 =-0.013P 3 +0.444P 2 +0.223P +0.294; I 590 / I 520 =0.058P 3 +0.154P 2 +0.208P +0.162; Where P represents ambient pressure.
[0034] Depend on Figure 14 absolute pressure sensitivity S a The changes are visible, S a (I 560 / I 520 ) and S a (I 570 / I 520 The value of S initially increases and then decreases with increasing pressure. a (I 580 / I 520 ) and S a (I 590 / I 520 The value increases with increasing pressure. Absolute pressure sensitivity S a (I 560 / I 520 ), S a (I 570 / I 520 ), S a (I 580 / I 520 ) and S a (I 590 / I 520 The maximum values were 203.24% / GPa, 206.45% / GPa, 226.90% / GPa, and 217.68% / GPa, respectively, at 1.66GPa, 2.32GPa, 2.61GPa, and 2.61GPa.
[0035] Depend on Figure 15 The relative pressure sensitivity S in r The changes are visible, S r (I560 / I 520 ), S r (I 570 / I 520 ), S r (I 580 / I 520 ) and S r (I 590 / I 520 The value initially increases and then decreases with increasing pressure. (S) r (I 560 / I 520 ), S r (I 570 / I 520 ), S r (I 580 / I 520 ) and S r (I 590 / I 520 The maximum values were 102.22% / GPa, 117.06% / GPa, 127.77% / GPa, and 131.69% / GPa at 0.50GPa, 0.55GPa, 0.50GPa, and 0.29GPa, respectively.
[0036] Depend on Figure 16 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 530 =0.027P 3 +0.019P 2 +0.466P +0.564; I 570 / I 530 =0.040P 3 +0.014P 2 +0.360P +0.355; I 580 / I 530 =0.062P 3 -0.051P 2 +0.296P +0.205; I 590 / I 530 =0.073P 3 -0.104P 2 +0.234P +0.112; Where P represents ambient pressure.
[0037] Depend on Figure 17 absolute pressure sensitivity S aThe changes are visible, S a (I 560 / I 530 ) and S a (I 570 / I 530 The value increases with increasing pressure, S a (I 580 / I 530 ) and S a (I 590 / I 530 The value of the absolute pressure sensitivity (S) initially decreases and then increases with increasing pressure. a (I 560 / I 530 ), S a (I 570 / I 530 ), S a (I 580 / I 530 ) and S a (I 590 / I 530 The maximum values were 110.17% / GPa, 125.11% / GPa, 128.00% / GPa, and 116.77% / GPa, respectively, at 2.61 GPa, 2.61 GPa, 2.61 GPa, and 2.61 GPa.
[0038] Depend on Figure 18 The relative pressure sensitivity S in r The changes are visible, S r (I 560 / I 530 ) and S r (I 570 / I 530 The value decreases as pressure increases, S r (I 580 / I 530 ) and S r (I 590 / I 530 The value initially decreases and then increases with increasing pressure. (S) r (I 560 / I 520 ), S r (I 570 / I 520 ), S r (I 580 / I 520 ) and S r (I 590 / I 520 ) respectively in 10 -4 GPa, 10 -4GPa, 10 -4 GPa and 10 -4 The maximum values for GPa are 82.74% / GPa, 101.55% / GPa, 143.95% / GPa, and 205.17% / GPa.
[0039] Figure 19 Zn2GeO4:0.015Mn 2+ Normalized high-pressure fluorescence spectrum, Mn 2+ The broad fluorescence emission peak broadens and redshifts with increasing pressure. The intensity on the long-wavelength side of the 533nm fluorescence emission peak center increases with increasing pressure, while the intensity on the short-wavelength side decreases with increasing pressure.
[0040] Figure 20 As shown Figure 19 The normalized data of spectral intensity on the long-wavelength and short-wavelength sides of the emission center in the image are related to pressure, where the data normalization is based on a 10⁻⁶ ohmmeter. -4 The intensity at GPa is used as a reference. The normalized intensity on the long-wave side increases with increasing pressure, while the normalized intensity on the short-wave side decreases with increasing pressure.
[0041] Depend on Figure 21 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 510 =0.165P 3 -1.188P 2 +2.907P +1.598; I 570 / I 510 =0.124P 3 -0.838P 2 +2.253P +1.024; I 580 / I 510 =0.052P 3 -0.370P 2 +1.431P +0.619; I 590 / I 510 =0.005P 3 -0.058P 2 +0.792P +0.370; Where P represents ambient pressure.
[0042] Depend on Figure 22 absolute pressure sensitivity S a The changes are visible, S a The value initially decreases and then increases with increasing pressure, reaching a maximum at 10...-4 At GPa, the absolute pressure sensitivity value is the highest, S a (I 560 / I 510 ), S a (I 570 / I 510 ), S a (I 580 / I 510 ) and S a (I 590 / I 510 The maximum values were 286.56% / GPa, 222.40% / GPa, 141.78% / GPa, and 79.04% / GPa, respectively.
[0043] Depend on Figure 23 The relative pressure sensitivity S in r The changes are visible, S r (I 560 / I 510 ), S r (I 570 / I 510 ), S r (I 580 / I 510 The value of S first decreases and then increases with increasing pressure. r (I 590 / I 510 The value decreases as pressure increases. At 10... -4 At GPa, the relative pressure sensitivity values are all at their maximum, S r (I 560 / I 510 ), S r (I 570 / I 510 ), S r (I 580 / I 510 ) and S r (I 590 / I 510 The maximum values were 179.2% / GPa, 217.11% / GPa, 229.05% / GPa, and 213.57% / GPa, respectively.
[0044] Depend on Figure 24 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 520 =0.009P 3 -0.095P 2 +0.775P +0.782; I570 / I 520 =-0.011P 3 +0.050P 2 +0.527P +0.507; I 580 / I 520 =-0.020P 3 +0.127P 2 +0.311P +0.308; I 590 / I 520 =-0.025P 3 +0.168P 2 +0.137P +0.185; Where P represents ambient pressure.
[0045] Depend on Figure 25 absolute pressure sensitivity S a The changes are visible, S a (I 560 / I 520 The value gradually decreases with increasing pressure, S a (I 570 / I 520 ), S a (I 580 / I 520 ) and S a (I 590 / I 520 The value initially increases and then decreases with increasing pressure. Absolute pressure sensitivity S a (I 560 / I 520 ) in 10 -4 The maximum value of GPa is 77.14% / GPa, S a (I 570 / I 520 ), S a (I 580 / I 520 ) and S a (I 590 / I 520 The maximum values were 60.16% / GPa, 58.18% / GPa, and 51.69% / GPa at 1.52GPa, 2.12GPa, and 2.26GPa, respectively.
[0046] Depend on Figure 26 The relative pressure sensitivity S in r The changes are visible, S r (I 560 / I 520 ), S r (I570 / I 520 ) and S r (I 580 / I 520 The value of S decreases as pressure increases. r (I 590 / I 520 The value initially increases and then decreases with increasing pressure. (S) r (I 560 / I 520 ), S r (I 570 / I 520 ) and S r (I 580 / I 520 ) in 10 -4 The relative pressure sensitivity at GPa was taken as the maximum values of 98.60% / GPa, 104.31% / GPa, and 102.40% / GPa; S r (I 590 / I 520 The relative pressure sensitivity is taken as the maximum value of 98.05% / GPa at 0.46GPa.
[0047] Depend on Figure 27 As can be seen, the fluorescence intensity ratio shown in the figure increases monotonically with increasing pressure, and the ratio satisfies the following equation: I 560 / I 530 =-0.006P 3 +0.015P 2 +0.351P +0.588; I 570 / I 530 =-0.015P 3 +0.083P 2 +0.243P +0.381; I 580 / I 530 =-0.018P 3 +0.114P 2 +0.140P +0.232; I 590 / I 530 =-0.019P 3 +0.128P 2 +0.051P +0.139; Where P represents ambient pressure.
[0048] Depend on Figure 28 absolute pressure sensitivity S a The changes are visible, S a (I560 / I 530 ), S a (I 570 / I 530 ), S a (I 580 / I 530 ) and S a (I 590 / I 530 The value initially increases and then decreases with increasing pressure. Absolute pressure sensitivity S a (I 560 / I 530 ), S a (I 570 / I 530 ), S a (I 580 / I 530 ) and S a (I 590 / I 530 The maximum values were 36.31% / GPa, 39.22% / GPa, 37.98% / GPa, and 33.55% / GPa at 0.81GPa, 1.80GPa, 2.09GPa, and 2.19GPa, respectively.
[0049] Depend on Figure 29 The relative pressure sensitivity S in r The changes are visible, S r (I 560 / I 530 ) and S r (I 570 / I 530 The value of S decreases as pressure increases. r (I 580 / I 530 ) and S r (I 590 / I 530 The value initially increases and then decreases with increasing pressure. (S) r (I 560 / I 530 ) and S r (I 570 / I 530 ) in 10 -4 The relative pressure sensitivity at GPa was taken as the maximum values of 59.87% / GPa and 64.45% / GPa; S r (I 580 / I 530 ) and S r (I 590 / I 530The relative pressure sensitivity was set to its maximum values of 73.24% / GPa and 87.50% / GPa at 0.49GPa and 0.71GPa, respectively.
[0050] Figure 30 Zn2GeO4:0.030Mn 2+ Normalized high-pressure fluorescence spectrum, Mn 2+ The broad fluorescence emission peak broadens and redshifts with increasing pressure. The intensity on the long-wavelength side of the 533nm fluorescence emission peak center increases with increasing pressure, while the intensity on the short-wavelength side decreases with increasing pressure.
[0051] Figure 31 As shown Figure 30 The normalized data of spectral intensity on the long-wavelength and short-wavelength sides of the emission center in the image are related to pressure, where the data normalization is based on a 10⁻⁶ ohmmeter. -4 The intensity at GPa is used as a reference. The normalized intensity on the long-wave side increases with increasing pressure, while the normalized intensity on the short-wave side decreases with increasing pressure. Therefore, the ratio of the intensity on the long-wave side to that on the short-wave side shows a similar trend with increasing pressure. Figure 10 , Figure 13 , Figure 16 , Figure 21 , Figure 24 and Figure 27 The monotonically increasing trend in Mn can be fitted using a third-order polynomial (not shown). High-doped Mn 2+ Fluorescence emission intensity decreases due to fluorescence quenching, while the relative intensity of fluorescence emission from the matrix in the low-wavelength region increases under high-pressure conditions. This has an impact on Mn. 2+ The intensity on the shorter wavelength side of the fluorescence emission center has an impact. Therefore, at a pressure of 2.34 GPa, I 510 The intensity values were not statistically analyzed.
[0052] Depend on Figure 32 As shown, the absolute pressure sensitivity value S a (I 560 / I 510 ), S a (I 570 / I 510 ), S a (I 580 / I 510 ) and S a (I 590 / I 510 ) respectively in 10 -4 GPa, 10 -4 GPa, 10 -4The maximum values for GPa and 1.57GPa are 352.40% / GPa, 239.40% / GPa, 164.93% / GPa, and 122.95% / GPa, respectively.
[0053] Depend on Figure 33 As shown, the relative pressure sensitivity value S r (I 560 / I 510 ), S r (I 570 / I 510 ), S r (I 580 / I 510 ) and S r (I 590 / I 510 ) respectively in 10 -4 GPa, 10 -4 GPa, 10 -4 GPa and 10 -4 The maximum values for GPa are 209.53% / GPa, 217.40% / GPa, 252.86% / GPa, and 256.64% / GPa.
[0054] Depend on Figure 34 As shown, the absolute pressure sensitivity value S a (I 560 / I 520 ), S a (I 570 / I 520 ), S a (I 580 / I 520 ) and S a (I 590 / I 520 The maximum values were 154.27% / GPa, 170.09% / GPa, 173.01% / GPa, and 163.03% / GPa, respectively, at 2.34 GPa, 2.34 GPa, 2.34 GPa, and 2.34 GPa.
[0055] Depend on Figure 35 As shown, the relative pressure sensitivity value S r (I 560 / I 520 ), S r (I 570 / I 520 ), S r (I 580 / I 520 ) and S r (I 590 / I 520 ) respectively in 10 -4GPa, 10 -4 GPa, 10 -4 GPa and 10 -4 The maximum values for GPa are 117.80% / GPa, 121.28% / GPa, 148.08% / GPa, and 214.81% / GPa.
[0056] Depend on Figure 36 As shown, the absolute pressure sensitivity value S a (I 560 / I 530 ), S a (I 570 / I 530 ), S a (I 580 / I 530 ) and S a (I 590 / I 530 The maximum values were 155.96% / GPa, 153.72% / GPa, 142.43% / GPa, and 124.75% / GPa, respectively, at 2.34 GPa, 2.34 GPa, 2.34 GPa, and 2.34 GPa.
[0057] Depend on Figure 37 As shown, the relative pressure sensitivity value S r (I 560 / I 530 ), S r (I 570 / I 530 ), S r (I 580 / I 530 ) and S r (I 590 / I 530 ) respectively in 10 -4 GPa, 10 -4 GPa, 10 -4 GPa and 10 -4 The maximum values for GPa are 115.08% / GPa, 134.21% / GPa, 179.06% / GPa, and 260.77% / GPa.
[0058] The absolute and relative pressure sensitivity values obtained from the application method of the divalent manganese-based optical pressure-measuring fluorescent material described in this invention are listed in Table 1. The highest pressure sensitivity based on the strength-to-pressure-measuring parameters of this material is several to tens of times higher than the highest sensitivity values of previously reported optical pressure-measuring materials with the same or different pressure-measuring parameters. It should be particularly emphasized that the Zn₂GeO₄:0.002Mn prepared in this invention… 2+The intensity ratio calculated using the pressure measurement parameters yields the highest absolute and relative pressure sensitivity values, which are the previously reported values for Zn₂GeO₄:0.006Mn. 2+ The highest sensitivity values based on chromaticity coordinates x / y are ~81.4 / ~93.0 times and ~10.5 / ~29.9 times, respectively; while Zn2GeO4:0.015Mn 2+ The corresponding sensitivity values are ~35.8 / ~40.9 times and ~7.8 / ~22.2 times, respectively; Zn2GeO4:0.030Mn 2+ The corresponding sensitivity values are ~44.1 / ~50.3 times and ~8.9 / ~25.3 times, respectively. Furthermore, the moderately doped Zn₂GeO₄:0.015Mn 2+ The fluorescent material exhibits a wider pressure tolerance range than the other two fluorescent materials with different doping concentrations in this invention.
[0059] The preparation method of the divalent manganese-based fluorescent material described in this invention is low-cost, convenient to operate, and also features green synthesis. Based on the intensity ratio of the single fluorescence emission peak of this material, the pressure measurement method exhibits extremely high pressure sensitivity, which makes it have wider application value.
[0060] Table 1 Comparison of pressure sensitivity properties of pressure gauge materials The above description is merely a specific example of the present invention, intended to illustrate the technical solution of the present invention, and is not intended to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solution of the present invention. As long as these modifications or substitutions do not depart from the core scope of the technical solution of the present invention, they should be included within the protection scope of the claims of the present invention.
Claims
1. A divalent manganese-based optical pressure-measuring fluorescent material, characterized in that, The material is a zincite structure with a general chemical formula of Zn2GeO4:xMn 2+ where x is the mole percentage of doped divalent manganese ions and satisfies 0.002≤x≤0.
030.
2. The divalent manganese-based optical pressure-measuring fluorescent material according to claim 1, characterized in that, The x = 0.002 or 0.015 or 0.
030.
3. The divalent manganese-based optical pressure-measuring fluorescent material according to claim 1 or 2, characterized in that, The fluorescent material exhibits a single broad peak fluorescent emission characteristic at 533 nm under 325 nm laser excitation. 2+ The fluorescent material exhibits a single broad peak fluorescent emission characteristic at 533 nm under 325 nm laser excitation.
4. The method for preparing the divalent manganese-based optical pressure-measuring fluorescent material according to claim 1, characterized in that, The steps include: (1) Weighing ZnO, GeO2 and manganese metal powder in a molar ratio of 2:1:x, where 0.002≤x≤0.030; After grinding and mixing the raw materials thoroughly, pre-pressing them into sheets, and finally placing the resulting raw material sheets into a graphite crucible in a DC arc furnace; (2) Evacuate the electric arc furnace cavity and introduce nitrogen as a protective gas; (3) Set the DC arc discharge conditions as follows: voltage range 10-14V, current 40-50A, reaction time 5-10s; (4) After the temperature of the graphite crucible in the electric arc furnace drops to room temperature, collect the Zn2GeO4 material doped with divalent manganese in the crucible.
5. The method for preparing the divalent manganese-based optical pressure-measuring fluorescent material according to claim 4, characterized in that, x = 0.002 or 0.015 or 0.
030.
6. The application of the divalent manganese-based fluorescent material according to claim 1 in extreme environmental pressure scenarios.
7. The application according to claim 6, characterized in that, The pressure range of the environment where the fluorescent material is located is between 10 -4 ~ 3.5 GPa.