Wide-spacing dual-emission optical temperature measurement fluorescent powder as well as preparation method and application thereof

Abstract

The invention discloses wide-spacing dual-emission optical temperature measurement fluorescent powder as well as a preparation method and application thereof, and the chemical formula of the fluorescent powder is Ca3Gd1-x-yAl3B4O15: xBi < 3 + >, yEu < 3 + >, the fluorescent powder disclosed by the invention can be efficiently excited by 250-300nm ultraviolet light and can generate broadband emission in a 300-450nm wave band and obtain multiple characteristic narrow-band fluorescence emission of Eu < 3 + > in a 570-20nm wave band, the emission behaviors of the broadband emission and the Eu < 3 + > are not mutually influenced, and the fluorescent powder has the characteristics of wide excitation range and wide double-peak spacing. According to the preparation method of the fluorescent powder, the fluorescent powder can be prepared through solid-phase reaction one-step sintering, and the product is high in purity, complete in crystallinity and high in luminance.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and particularly relates to a wide-spacing dual-emission optical temperature-measuring phosphor and a preparation method and application thereof. Background Art

[0002] As one of the basic thermodynamic parameters, temperature is of crucial significance in various disciplines. Non-contact temperature measurement mainly utilizes the principle of thermal radiation. The fluorescence intensity ratio (FIR) is a very important technology in non-contact temperature measurement. Its mechanism is to detect temperature through the linear relationship between the emission intensity ratio between different luminescence centers or different luminescence energy levels in the luminescent material and temperature. Traditional optical temperature-measuring materials mostly rely on a single emission peak or a narrow-spacing dual-emission system (such as the Bi 3+ / Mn 4+ system), which has the defects of large signal cross-interference and limited temperature-measuring sensitivity. Existing research shows that although co-doping with two activating ions can construct a ratio-type temperature-measuring system, due to the energy transfer effect between ions, the emission peak spacing is generally less than 150 nm, resulting in insufficient resolution of the temperature response signal. Summary of the Invention

[0003] The present invention aims to at least solve the above technical problems existing in the prior art. For this reason, the purpose of the present invention is to provide a wide-spacing dual-emission optical temperature-measuring phosphor and a preparation method and application thereof.

[0004] In order to achieve the above purpose, the technical solutions adopted by the present invention are as follows:

[0005] In the first aspect of the present invention, a phosphor is provided, and its chemical formula is: Ca3Gd 1-x-y Al3B4O 15 :xBi 3+ ,yEu 3+ , where 0.005 ≤ x ≤ 0.015, 0.005 ≤ y ≤ 0.015.

[0006] In the present invention, Bi 3+ and Eu3+ jointly replace the Gd 3+ sites in the matrix lattice. The chemical substitution compatibility of the Gd 3+ sites provides a structural basis for the co-doping of two ions, and can also effectively inhibit the energy transfer between ions, enabling Bi 3+ and Eu 3+ activators to achieve wide-spacing dual-emission characteristics in a single matrix, and the emission characteristics of the two do not affect each other, breaking through the limitation of insufficient spacing of traditional dual-emission materials.

[0007] In some embodiments of the present invention, 0.008 ≤ x ≤ 0.012, 0.008 ≤ y ≤ 0.012; 0.009 ≤ x ≤ 0.011, 0.009 ≤ y ≤ 0.011.

[0008] In some embodiments of the present invention, the chemical formula of the phosphor is Ca3Gd 0.98 Al3B4O 15 :0.009Bi 3+ ,0.011Eu 3+ 、Ca3Gd 0.98 Al3B4O 15 :0.01Bi 3+ ,0.01Eu 3+ 、Ca3Gd 0.98 Al3B4O 15 :0.011Bi 3+ ,0.009Eu 3+ 。

[0009] In a second aspect of the present invention, there is provided a method for preparing the phosphor, comprising the following steps:

[0010] According to the stoichiometric ratios of the elements in the chemical formula, a substance containing calcium element, a substance containing gadolinium element, a substance containing aluminum element, a substance containing boron element, a substance containing bismuth element and a substance containing europium element are mixed and sintered to obtain the phosphor.

[0011] In some embodiments of the present invention, the sintering is carried out in an air atmosphere at normal pressure (i.e., about 100 KPa); the sintering temperature is 900 °C to 1300 °C, such as 1000 °C to 1200 °C; the sintering time is 8 to 12 h, such as 9 to 11 h; the heating rate of the sintering is 3 °C / min to 8 °C / min, such as 4 °C / min to 7 °C / min; the sintering is one-step sintering.

[0012] In some embodiments of the present invention, the sintering is carried out in the presence of a flux, and the flux includes at least one of boric acid, borax, and calcium oxide.

[0013] In some embodiments of the present invention, the substance containing calcium element includes at least one of calcium-containing oxides, calcium-containing carbonates, calcium-containing nitrates, calcium-containing citrates, calcium-containing oxalates, and calcium-containing acetates; such as at least one of CaO, CaCO3, Ca(NO3)2, Ca(C6H5O7)2, CaC2O4, and Ca(CH3COO)2.

[0014] In some embodiments of the present invention, the gadolinium-containing substance includes at least one of a gadolinium-containing oxide, a gadolinium-containing carbonate, and a gadolinium-containing nitrate; such as at least one of Gd2O3, Gd(CO3)3, and Gd(NO3)3.

[0015] In some embodiments of the present invention, the aluminum-containing substance includes at least one of an aluminum-containing oxide, an aluminum-containing hydroxide, an aluminum-containing carbonate, an aluminum-containing nitrate, an aluminum-containing citrate, an aluminum-containing oxalate, and an aluminum-containing acetate, such as at least one of Al2O3, Al(OH)3, Al(CO3)3, Al(NO3)3, Al(C6H5O7)3, Al2(C2O4)3, and Al(CH3COO)3.

[0016] In some embodiments of the present invention, the boron-containing substance is at least one of boric acid (H3BO3), boric anhydride (B2O3), and boron powder.

[0017] In some embodiments of the present invention, the bismuth-containing substance is at least one of a bismuth oxide, a bismuth hydroxide, a bismuth halide, a bismuth oxalate, a bismuth acetate, and a bismuth nitrate, such as at least one of Bi2O3, Bi(NO3)3, and Bi(CH3COO)3.

[0018] In some embodiments of the present invention, the europium-containing substance is at least one of an europium-containing oxide, an europium-containing halide, an europium-containing carbonate, an europium-containing nitrate, an europium-containing oxalate, an europium-containing citrate, and an europium-containing acetate; such as at least one of Eu2O3, EuCl3, EuF3, EuBr3, Eu2(CO3)3, EuC2O4, Eu(NO3)3, Eu(C6H5O7)3, and Eu(CH3COO)3.

[0019] In some embodiments of the present invention, the preparation method further includes grinding the sintered product, and the grinding time is preferably 5 to 120 min, such as 10 to 100 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, and 120 min.

[0020] In a third aspect of the present invention, a fluorescence temperature measuring material is provided, including the phosphor.

[0021] In the present invention, under the excitation of ultraviolet light with a wavelength of 250-300 nm, Bi 3+ produces a broadband emission located at 300-450 nm, and Eu 3+ exhibits multiple sharp emission peaks in the wavelength range of 570-720 nm. The two form a unique spectral separation characteristic. The intensity ratio of the emission peaks of the phosphor with double emission peaks varies with temperature in the range of 303-403 K. The wide spectral spacing can effectively suppress signal cross-interference and achieve accurate fluorescence temperature measurement.

[0022] In some embodiments of the present invention, the temperature measurement includes contact temperature detection and non-contact temperature detection; the non-contact temperature detection includes temperature detection of any one of microelectronic components, the internal environment of cells, an electromagnetic interference environment, a corrosion environment, and an electrical power station.

[0023] In a fourth aspect of the present invention, there is provided a fluorescence temperature measurement device including the phosphor or the fluorescence temperature measurement material as described above.

[0024] In some embodiments of the present invention, the fluorescence temperature measurement device further includes an ultraviolet light excitation source; the ultraviolet light excitation source emits ultraviolet light with a wavelength of 250-300 nm.

[0025] In a fifth aspect of the present invention, there is provided a non-contact temperature detection method including using the phosphor or the fluorescence temperature measurement material or the fluorescence temperature measurement device as described above for temperature detection.

[0026] In some embodiments of the present invention, the non-contact temperature measurement method includes exciting the phosphor or the fluorescence temperature measurement material or the fluorescence temperature measurement device with ultraviolet light with a wavelength of 250-300 nm and then performing temperature detection.

[0027] The beneficial effects of the present invention are as follows:

[0028] The phosphor of the present invention can be efficiently excited by ultraviolet light with a wavelength of 250-300 nm and produce a broadband emission in the range of 300-450 nm and obtain multiple characteristic narrow-band fluorescence emissions of Eu in the range of 570-720 nm. The emission behaviors of the two do not affect each other, and it has the characteristics of a wide excitation range and a wide double-peak spacing. 3+ The emission behaviors of the two do not affect each other, and it has the characteristics of a wide excitation range and a wide double-peak spacing.

[0029] The preparation method of the phosphor in the present invention can be sintered in one step by a solid-phase reaction, and the product has high purity, good crystallinity, and strong luminescence brightness.

[0030] The intensity ratio of the emission peaks of the phosphor with double emission peaks of the present invention shows an exponential relationship with temperature change in the range of 303-403 K. The wide spectral spacing can effectively suppress signal cross-interference and can be used for accurate fluorescence temperature measurement. Description of the Drawings

[0031] Figure 1 X-ray diffraction pattern of the phosphor prepared in the embodiment of the present invention.

[0032] Figure 2 Emission spectrum of the phosphors prepared in Examples 2-4 of the present invention.

[0033] Figure 3 Emission spectrum of the phosphor prepared in Example 1 of the present invention.

[0034] Figure 4 Variable-temperature emission spectrum of the phosphor prepared in Example 1 of the present invention.

[0035] Figure 5 FIR temperature measurement fitting result of the phosphor prepared in Example 1 of the present invention.

[0036] Figure 6 FIR temperature measurement relative sensitivity of the phosphor prepared in Example 1 of the present invention.

[0037] Figure 7 Variable-temperature CEI value of the phosphor prepared in Example 1 of the present invention; the inset is a CIE coordinate diagram. Detailed implementation manners

[0038] The content of the present invention will be further described in detail through specific examples below. The raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial channels or by existing technical methods without special instructions. Unless otherwise specified, the test or measurement methods are conventional methods in the art.

[0039] Example 1

[0040] A phosphor was prepared in this example, and the specific process was as follows:

[0041] (1) Weigh 0.3003 g of calcium carbonate (CaCO3), 0.1776 g of gadolinium oxide (Gd2O3), 0.0023 g of bismuth oxide (Bi2O3), 0.0018 g of europium oxide (Eu2O3), 0.1529 g of aluminum oxide (Al2O3), and 0.2600 g of boric acid (H3BO3) respectively. Place the above raw materials in an agate mortar and grind for 30 minutes. After being uniform, carry out solid-phase reaction, and heat up to 1100 °C at a rate of 5 °C / min in an atmospheric air atmosphere, and keep the temperature constant at this temperature for 10 h.

[0042] (2) Transfer the mixture obtained in step (1) to a corundum crucible, and then place it in a muffle furnace and heat up to 1100 °C at a rate of 5 °C / min in an atmospheric air atmosphere, and keep the temperature constant for 10 h.

[0043] (3) After the reaction is completed, wait for it to cool to room temperature, take out the sample and grind it for 30 minutes until it is uniform, then Ca3Gd can be obtained. 0.98 Al3B4O 15 :0.01Bi 3+ ,0.01Eu 3+ Optical temperature measurement phosphor.

[0044] Example 2

[0045] This comparative example prepared a phosphor, and the specific process was as follows:

[0046] (1) Weigh 0.3003 g of calcium carbonate (CaCO3), 0.1794 g of gadolinium oxide (Gd2O3), 0.0023 g of bismuth oxide (Bi2O3), 0.1529 g of aluminum oxide (Al2O3), and 0.2600 g of boric acid (H3BO3) respectively. Place the above raw materials in an agate mortar and grind for 30 minutes. After being uniform, carry out solid-phase reaction, and heat up to 1100 °C at a rate of 5 °C / min under normal pressure air atmosphere, and keep it at this temperature for 10 h.

[0047] (2) Transfer the mixture obtained in step (1) to a corundum crucible, and then put it into a muffle furnace and heat up to 1100 °C at a rate of 5 °C / min under normal pressure air atmosphere, and keep it at this temperature for 10 h.

[0048] (3) After the reaction is completed, wait for it to cool to room temperature, take out the sample and grind it for 30 minutes until it is uniform, then Ca3Gd can be obtained. 0.99 Al3B4O 15 :0.01Bi 3+ Phosphor.

[0049] Example 3

[0050] This comparative example prepared a phosphor, and the specific process was as follows:

[0051] (1) Weigh 0.3003 g of calcium carbonate (CaCO3), 0.1803 g of gadolinium oxide (Gd2O3), 0.0012 g of bismuth oxide (Bi2O3), 0.1529 g of aluminum oxide (Al2O3), and 0.2600 g of boric acid (H3BO3) respectively. Place the above raw materials in an agate mortar and grind for 30 minutes. After being uniform, carry out solid-phase reaction, and heat up to 1100 °C at a rate of 5 °C / min under normal pressure air atmosphere, and keep it at this temperature for 10 h.

[0052] (2) Transfer the mixture obtained in step (1) to a corundum crucible, and then put it into a muffle furnace and heat up to 1100 °C at a rate of 5 °C / min under normal pressure air atmosphere, and keep it at this temperature for 10 h.

[0053] (3) After the reaction is completed, wait for it to cool to room temperature, take out the sample and grind it for 30 minutes until it is uniform, then Ca3Gd 0.995 Al3B4O 15 :0.005Bi 3+ phosphor can be obtained.

[0054] Example 4

[0055] This comparative example prepared a phosphor, and the specific process was as follows:

[0056] (1) Weigh 0.3003 g of calcium carbonate (CaCO3), 0.1785 g of gadolinium oxide (Gd2O3), 0.0035 of bismuth oxide (Bi2O3), 0.1529 g of aluminum oxide (Al2O3), and 0.2600 g of boric acid (H3BO3) respectively. Place the above raw materials in an agate mortar and grind for 30 minutes. After being uniform, carry out solid-phase reaction, and heat it to 1100 °C at a rate of 5 °C / min in an atmospheric air atmosphere, and keep it at this temperature for 10 h.

[0057] (2) Transfer the mixture obtained in step (1) to a corundum crucible, and then put it into a muffle furnace and heat it to 1100 °C at a rate of 5 °C / min in an atmospheric air atmosphere, and keep it at a constant temperature for 10 h.

[0058] (3) After the reaction is completed, wait for it to cool to room temperature, take out the sample and grind it for 30 minutes until it is uniform, then Ca3Gd 0.985 Al3B4O 15 :0.015Bi 3+ phosphor can be obtained.

[0059] Test Example

[0060] This test example characterized the performance of the phosphor, and the specific process was as follows:

[0061] The X-ray powder diffraction patterns and emission spectra of the phosphors prepared in Examples 1 to 4 are as Figures 1 to 3 shown.

[0062] It can be seen that under the excitation of 280 nm ultraviolet light, the phosphors with different doping amounts of Bi 3+ can all produce broadband emission at 300 - 450 nm, and the emission intensity is relatively high at about 385 nm. Among them, the emission intensity of the phosphor with a doping amount of 0.01 Bi 3+ is the highest.

[0063] As Figure 3 shown, under the excitation of 288 nm ultraviolet light, Ca3Gd 0.98 Al3B4O 15 :0.01Bi 3+ ,0.01Eu 3+The phosphor produces broadband emission at 385nm and obtains Eu in the 570-720nm band. 3+ Multiple characteristic narrow-band fluorescence emissions, and Eu 3+ Compare 3+ The fluorescence behavior at 300-450nm was not affected.

[0064] The phosphor prepared in Example 1 was subjected to temperature spectrum test and FIR (fluorescence intensity ratio) temperature measurement fitting. The results are as follows: Figure 4 , Figure 5 The double emission peaks of the phosphor show an exponential relationship between the emission peak intensity ratio and temperature at 303-403K (FIR = 0.06192 + 1.03633exp (-1690.35548 / T), R 2 =0.98984). The relative sensitivity of FIR temperature measurement is as follows Figure 6 As shown, the relative sensitivity Sr can reach 0.21%K -1 , effectively realizing optical temperature measurement.

[0065] The temperature-dependent CIE value (chromaticity coordinate) of the phosphor obtained in Example 1 is as follows: Figure 7 As shown, in the temperature range of 303~430K, Ca3Gd 0.98 Al3B4O 15 :0.01Bi 3+ ,0.01Eu 3+ The CIE value of the phosphor remains stable, indicating that the wide spacing between the double peaks enables independent thermal quenching of each signal peak without being affected by the adjacent signal peaks. Figure 7 The inset in the middle shows the CIE coordinate diagram, and the color temperature drift occurs when the luminescence of the phosphor is heated up. The results show that the wide spectral spacing avoids the cross relaxation and energy transfer of the double peaks, which can effectively suppress the signal cross interference.

[0066] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A fluorescent powder, characterized in that: Its chemical formula is: Ca3Gd 1-x-y Al3B4O 15 :xBi 3+ ,yEu 3+ in, 0.005≤x≤0.015, 0.005≤y≤0.

015.

2. The phosphor according to claim 1, characterized in that: The chemical formula of the phosphor is Ca3Gd 0.98 Al3B4O 15 :0.009Bi 3+ ,0.011Eu 3+ , Ca3Gd 0.98 Al3B4O 15 :0.01Bi 3+ ,0.01Eu 3+ , Ca3Gd 0.98 Al3B4O 15 :0.011Bi 3+ ,0.009Eu 3+ .

3. A method for preparing the phosphor according to claim 1 or 2, characterized in that: The following steps are involved: According to the stoichiometric ratio of each element in the chemical formula, a substance containing calcium element, a substance containing gadolinium element, a substance containing aluminum element, a substance containing boron element, a substance containing bismuth element and a substance containing europium element are mixed and sintered to obtain the phosphor.

4. The method for preparing the phosphor according to claim 3, characterized in that: The sintering temperature is 900° C. to 1300° C.; and / or, the sintering time is 8 to 12 hours; and / or, the sintering heating rate is 3° C. / min to 8° C. / min.

5. The method for preparing the phosphor according to claim 3, characterized in that: The sintering is carried out in the presence of a solvent, and the solvent comprises at least one of boric acid, borax and calcium oxide.

6. The method for preparing the phosphor according to claim 3, characterized in that: The calcium-containing substance includes at least one of an oxide containing calcium, a carbonate containing calcium, a nitrate containing calcium, a citrate containing calcium, an oxalate containing calcium and an acetate containing calcium; and / or, the gadolinium-containing substance includes at least one of an oxide containing gadolinium, a carbonate containing gadolinium and a nitrate containing gadolinium; and / or, the aluminum-containing substance includes an oxide containing aluminum, a hydroxide containing aluminum, a carbonate containing aluminum, a nitrate containing aluminum, a citrate containing aluminum, an aluminum-containing hydroxide, at least one of oxalates and acetates containing aluminum; and / or, at least one of boric acid, boric anhydride and boron powder as the substance containing boron; and / or, at least one of bismuth oxide, bismuth hydroxide, bismuth halide, bismuth oxalate, bismuth acetate and bismuth nitrate as the substance containing bismuth; and / or, at least one of europium oxide, europium halide, europium carbonate, europium nitrate, europium oxalate, europium citrate and europium acetate as the substance containing europium.

7. A fluorescent temperature measuring material, characterized in that: The invention comprises the phosphor described in claim 1 or 2.

8. A fluorescence temperature measuring device, characterized in that: It includes the fluorescent powder described in claim 1 or 2 or the fluorescent temperature measuring material described in claim 7.

9. The fluorescence temperature measuring device according to claim 8, characterized in that: The fluorescent temperature measuring device also includes an ultraviolet excitation light source; the ultraviolet excitation light source emits 250-300nm ultraviolet light.

10. A non-contact temperature detection method, comprising using the fluorescent powder according to claim 1 or 2, the fluorescent temperature measuring material according to claim 7, or the fluorescent temperature measuring device according to claim 8 or 9 to perform temperature detection.

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