Dual-channel ratio fluorescent material, preparation method and application thereof

Abstract

This invention relates to the field of fluorescent materials and fluorescent thermometers, specifically to a dual-channel ratiometric fluorescent material, its preparation method, and its application. The dual-channel ratiometric fluorescent material is based on Bi... 3+ Tb is an indicator signal ion. 3+ As a reference signal ion, Bi 3+ and Tb 3+ The dual-channel ratiometric fluorescent material is obtained by doping into a matrix material; the expression for the dual-channel ratiometric fluorescent material is Ca2M. x Zr2Al3O 12 :aBi 3+ ,yTb 3+ Where M is Y, Gd, or Lu, x = 1 - a - y, y = 0.1 to 0.3, a = 0.005 to 0.015. This invention will utilize Bi... 3+ and Tb 3+ Co-doping in the matrix material to achieve dual channels FIR The temperature measurement technology demonstrates improved thermal stability of the luminescent center of fluorescent materials and effectively widens the temperature measurement range, solving the problems of relatively low sensitivity and narrow temperature measurement range of phosphors currently used in ratiometric fluorescent thermometers.

Description

Technical Field

[0001] This invention relates to the field of fluorescent materials and fluorescent thermometers, specifically to a dual-channel ratiometric fluorescent material, its preparation method, and its application. Background Technology

[0002] Compared with contact temperature measurement, optical temperature sensors have significant advantages such as higher sensitivity, wider temperature measurement range, immunity to electromagnetic interference, long-path monitoring, and independence from electronic devices. They are widely used in fields such as biomedicine, energy, industry and agriculture, and daily life, and are gradually becoming an indispensable and important temperature monitoring technology.

[0003] The working principle of optical temperature sensors is based on monitoring the change in emission intensity caused by temperature when a luminescent material interacts with a physical system. In practice, a phosphor with high emission intensity is selected as the temperature detector, and the measured spectrum is converted into temperature. The temperature range can be easily determined and calculated using key parameters such as luminescence intensity, effective bandwidth, spectral shape, spectral shift, and lifetime. Among these, the fluorescence intensity ratio temperature measurement technique, which uses the sensitivity of the indicator light signal's emission to changes in ambient temperature while referencing a stable light signal, is more widely used due to its advantages such as simple structure, high cost-effectiveness, high accuracy, fast response time, and excellent resolution.

[0004] However, stable and accurate measurement of minute changes over a wide temperature range remains a major challenge for this type of optical thermometer. Therefore, developing a ratiometric fluorescent thermometer with ultra-sensitive sensitivity and a wide temperature range is of great significance.

[0005] Currently, when using phosphors with high emission intensity as ratiometric fluorescent thermometers, the phenomenon of luminescence-thermal quenching of the phosphor exists. That is, the fluorescence intensity inevitably decreases as the ambient temperature increases. This limits the temperature measurement sensitivity and range of fluorescence intensity-based thermometry, resulting in existing phosphors having relatively low sensitivity and narrow temperature measurement range. For example, using S... r >1% K -1 Calculations show that existing phosphors generally only have high relative sensitivity within a temperature measurement range of 150°C, and cannot be widely used over a wider temperature measurement range. Summary of the Invention

[0006] To address the issues of low sensitivity and narrow temperature measurement range of phosphors currently used in ratiometric fluorescent thermometers, this invention provides a dual-channel ratiometric fluorescent material with an antithermal quenching reference signal, its preparation method, and its application.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows.

[0008] The first aspect of this invention provides a dual-channel ratiometric fluorescent material, which is based on Bi 3+ Tb is an indicator signal ion. 3+ As a reference signal ion, Bi 3+ and Tb 3+ The dual-channel ratiometric fluorescent material is obtained by doping into a matrix material; the expression for the dual-channel ratiometric fluorescent material is Ca2M. x Zr2Al3O 12 :aBi 3+ ,yTb 3+ Where M is Y, Gd or Lu, x=1-ay, y=0.1~0.3, a=0.005~0.015.

[0009] Preferably, the matrix material has a garnet crystal structure, belonging to the cubic crystal system. (230) Space group; the matrix material is expressed as Ca2M x Zr2Al3O 12 .

[0010] This invention utilizes the rigidity of the garnet-structured matrix material to ensure Tb at low temperatures. 3+ The emitted signal exhibits good thermal stability, meaning that thermal quenching is not significant, thereby improving the relative sensitivity at low temperatures. Simultaneously, this invention utilizes the garnet structure crystal field and charge migration state to modulate Bi... 3+ and Tb 3+ The excitation spectrum ensures that both excitations in the range of 294nm–316nm and 265nm–290nm can be co-excited.

[0011] Preferably, the dual-channel ratiometric fluorescent material generates two ratiometric signal channels in two temperature measurement zones. Each ratiometric signal channel is composed of the fluorescence intensity ratio of the indicator signal ion and the reference signal ion. The two temperature measurement zones are designated as the first temperature measurement zone and the second temperature measurement zone, respectively, and the two ratiometric signal channels are designated as the first ratiometric signal channel and the second ratiometric signal channel, respectively. When the ambient temperature is in the first temperature measurement zone, the dual-channel ratiometric fluorescent material generates the first ratiometric signal channel upon excitation at an excitation wavelength of 294 nm to 316 nm. When the ambient temperature is in the second temperature measurement zone, the dual-channel ratiometric fluorescent material generates the second ratiometric signal channel upon excitation at an excitation wavelength of 265 nm to 290 nm. The temperature range of the first temperature measurement zone is 293 K to b, and the temperature range of the second temperature measurement zone is c to 573 K; where 433 K ≤ b ≤ 493 K, and 393 K ≤ c ≤ 453 K. The first temperature measurement zone is a low-temperature zone, and the second temperature measurement zone is a high-temperature zone.

[0012] Within an ambient temperature range of 293K to 573K, the dual-channel ratiometric fluorescent material of this invention generates two ratiometric signal channels under excitation at different wavelengths. The first ratiometric signal channel indicates the low-temperature region, and the second ratiometric signal channel indicates the high-temperature region. When the temperature is measured in the low-temperature region, the indicator signal ion Bi... 3+ The luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature, while the luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature. 3+ The luminescence intensity of the ion does not decrease significantly, and its thermal stability is good. When the temperature is measured in the high-temperature range, the indicator signal ion Bi... 3+ The luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature, while the luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature. 3+ The luminescence intensity is significantly improved, indicating significant anti-thermal quenching. The dual-ratio signal channel of this invention is the main factor in achieving high sensitivity performance and widening the temperature measurement range.

[0013] This invention develops a dual-channel ratiometric fluorescent material, wherein the Bi indicating the signal... 3+ It exhibits sensitive thermal quenching, manifested as a broadband excitation spectrum and a dual-emission indication signal composed of two different emission wavelengths under different excitation spectra, while Tb serves as the reference optical signal. 3+ Based on the electron-phonon coupling phenomenon, two distinct thermal quenching characteristics—low-temperature quenching and reverse-temperature quenching—we have achieved a dual-channel ratiometric fluorescent material exhibiting characteristics in both low-temperature and high-temperature regions. The superior improvement in relative sensitivity in the low-temperature region is achieved by utilizing the rigidity of the matrix material and the simultaneous excitation of Bi by the excitation source. 3+ and Tb 3+ The luminescence is achieved through electron emission. The superior improvement in relative sensitivity in the high-temperature region is achieved by utilizing the electron-phonon coupling phenomenon to enhance the reference signal ion Tb. 3+ This is achieved by increasing the luminescence intensity at high temperatures.

[0014] The specific principle is: utilizing the broadband excitation spectrum of Bi 3+ It features a unique dual-transmission indication signal characteristic formed by A-band and D-band transmission, combined with Tb 3+ Based on the unique green luminescence parameter signal, a dual-channel ratiometric fluorescent material was designed. Simultaneously, based on the broadening and redshift characteristics of the rare-earth ion excitation spectrum associated with increased electron-phonon coupling, the Tb values ​​were modulated in both low-temperature and high-temperature regions. 3+ Different emission spectral intensities were used to design fluorescent materials with dual-channel ratios.

[0015] When the ambient temperature is in the low-temperature range, Bi is simultaneously excited using an excitation light source in the 294nm–316nm range. 3+ and Tb 3+ To achieve Bi 3 + and Tb 3+Co-luminescence forms a ratio signal channel in the low-temperature region. At this time, when the ambient temperature rises but remains within the low-temperature region, due to Bi... 3+ and Tb 3+ The thermal quenching property of Bi leads to 3+ The luminescence intensity decreased significantly, but due to the rigidity of the matrix material and the effect of the excitation source on Tb 3+ The stimulating effect of Tb 3+ The decrease is not significant. The present invention solves the problem of sensitive temperature measurement in the low-temperature region by utilizing the normal thermal quenching phenomenon of the indicator signal and the reference signal. That is, after the light source with a wavelength of around 309nm is excited, the indicator signal emits light and undergoes normal thermal quenching, while the reference light signal emits light stably and the thermal quenching phenomenon is not significant.

[0016] When the ambient temperature is in the high-temperature range, the wavelength of the excitation source is adjusted to 265nm–290nm, and Tb is induced by electron-phonon coupling. 3+ Excitation spectral broadening and redshift increase Tb 3+ The absorption intensity is adjusted to achieve an ultrasensitive signal where the intensity of the indicator signal decreases with increasing temperature, while the intensity of the reference signal increases with increasing temperature.

[0017] The excitation source of this invention consists of two ultraviolet chips. One excitation source has a wavelength around 309 nm, and the other has a wavelength around 275 nm. They operate respectively in the low-temperature and high-temperature testing regions. In the low-temperature region, the ultraviolet chip with a wavelength around 309 nm exhibits relatively high sensitivity, and at this time, the light source with a wavelength around 309 nm excites the phosphor alone. At high temperatures, the system switches to the ultraviolet chip with a wavelength of 275 nm to excite the phosphor alone.

[0018] This invention utilizes Bi 3+ and Tb 3+ Co-doping in the matrix material, utilizing Bi 3+ It features dual emission indication signals from both the A-band and D-band, enabling dual-channel ratiometric fluorescence thermometry. Simultaneously, based on the enhanced electron-phonon coupling phenomenon, it demonstrates a precise improvement in the thermal stability of the luminescent center of the fluorescent material and an effective widening of its temperature measurement range. The fluorescence intensity ratio is abbreviated as Fluorescence Intensity Ratio. FIR . FIR The Chinese name for a fluorescent thermometer is a fluorescence intensity ratio thermometer or a ratio-type fluorescent thermometer.

[0019] Further preferably, M is Y or Lu; when M is Y, the expression for the dual-channel ratiometric fluorescent material is Ca2Y. 0.99- y Zr2Al3O 12 0.01Bi3+ ,yTb 3+ y = 0.1~0.3; Alternatively, when M is Lu, the expression for the dual-channel ratiometric fluorescent material is Ca2Lu. 0.99-y Zr2Al3O 12 0.01Bi 3 + ,yTb 3+ ; y = 0.1~0.3.

[0020] A second aspect of this invention provides a method for preparing a dual-channel ratiometric fluorescent material as described in the first aspect, comprising the following steps: According to the expression of dual-channel ratiometric fluorescent materials Ca2M x Zr2Al3O 12 :aBi 3+ ,yTb 3+ By determining the stoichiometric ratio, metal ion sources corresponding to Ca, M, Zr, Al, Bi and Tb were obtained as raw materials. After grinding and mixing the raw materials, they were calcined, cooled and ground into powder to obtain a dual-channel ratiometric fluorescent material.

[0021] Addressing the shortcomings of existing fluorescent materials in production, such as low high-temperature sensitivity, high technical difficulty, complex production process, high production cost, and low production efficiency, this invention simplifies the entire production process without requiring additional manufacturing steps, eliminates the need for atmosphere protection, maximizes cost savings, and significantly promotes... FIR Applications of this type of thermometer in various fields.

[0022] Preferably, the roasting temperature is 1500℃~1600℃ and the roasting time is 5h~7h.

[0023] Preferably, the raw materials are metal oxides or metal carbonates corresponding to Ca, M, Zr, Al, Bi and Tb.

[0024] The present invention has the advantages of simple synthetic materials and wide applicability of principles.

[0025] A third aspect of the present invention provides an application of the dual-channel ratiometric fluorescent material described in the first aspect as a dual-channel ratiometric fluorescent thermometer.

[0026] Preferably, the dual-channel ratio fluorescent thermometer has two ratio signal channels, and the two ratio signal channels respectively indicate two temperature measurement zones; when the temperature measurement zone is between 293K and b, and 433K≤b≤493K, the dual-channel ratio fluorescent thermometer generates one ratio signal channel under an excitation wavelength of 294nm to 316nm; when the temperature measurement zone is between c and 573K, and 393K≤c≤453K, the dual-channel ratio fluorescent thermometer generates another ratio signal channel under an excitation wavelength of 265nm to 290nm.

[0027] Preferably, for Ca2Y 0.99-y Zr2Al3O 12 For the substrate material, when y=0.1, the temperature at which the relative sensitivity reaches its maximum is 353K when the temperature measurement range is 293K to 433K; and when the temperature measurement range is 393K to 573K, the temperature at which the relative sensitivity reaches its maximum is 473K.

[0028] For Ca2Y 0.99-y Zr2Al3O 12 For the substrate material, when y=0.3, the temperature at which the relative sensitivity reaches its maximum is 393K when the temperature measurement range is 293K to 493K; and the temperature at which the relative sensitivity reaches its maximum is 513K when the temperature measurement range is 433K to 573K.

[0029] For Ca2Lu 0.99-y Zr2Al3O 12 For the substrate material, when y=0.1, the temperature at which the relative sensitivity reaches its maximum is 333K when the temperature measurement range is 293K to 453K; and the temperature at which the relative sensitivity reaches its maximum is 533K when the temperature measurement range is 453K to 573K.

[0030] For Ca2Lu 0.99-y Zr2Al3O 12 For the substrate material, when y=0.3, the temperature at which the relative sensitivity reaches its maximum is 393K when the temperature measurement range is 293K to 493K; and the temperature at which the relative sensitivity reaches its maximum is 473K when the temperature measurement range is 433K to 573K.

[0031] Preferably, within the two temperature measurement zones FIR The relative sensitivity of all thermometers is >1%K -1 In this invention, the temperature range of the two temperature measurement zones is based on a relative sensitivity >1%K. -1 get.

[0032] The beneficial effects of this invention are: 1. This invention will utilize Bi 3+ and Tb 3+Dual-channel ratiometric fluorescent materials were prepared by co-doping in a matrix material. This was achieved using Bi... 3+ It features dual-transmission indication signals in both A-band and D-band, enabling dual-channel operation. FIR Temperature measurement technology. Simultaneously, based on the phenomenon of enhanced electron-phonon coupling, it demonstrates a precise improvement in the thermal stability of the luminescent center of fluorescent materials and an effective widening of their temperature measurement range, solving the problems of relatively low sensitivity and narrow temperature measurement range currently found in phosphors used in ratiometric fluorescent thermometers.

[0033] 2. The dual-channel ratiometric fluorescent material of the present invention uses dual-channel indication signals. The two temperature measurement ranges can be combined to cover 293K to 573K. Compared with other ratiometric fluorescent materials, it has a wider temperature measurement range and takes into account the need for sensitive temperature measurement in both high-temperature and low-temperature ranges.

[0034] 3. The dual-channel ratiometric fluorescent material of the present invention, as a ratiometric fluorescent thermometer, has dual ratio signal channels to indicate two temperature measurement zones, thereby achieving high temperature measurement sensitivity and effectively widening the temperature measurement range. Attached Figure Description

[0035] Figure 1 The Ca2Y prepared in Example 1 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ Temperature-dependent emission spectra of phosphors. Among them, (a) is the temperature-dependent emission spectrum excited at 309 nm; (b) is the temperature-dependent emission spectrum excited at 275 nm.

[0036] Figure 2 The Ca2Y prepared in Example 1 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ Phosphor at monitoring wavelength λ em Fluorescence excitation spectrum at 545 nm at temperatures ranging from 293 K to 573 K.

[0037] Figure 3 The Ca2Y prepared in Example 1 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ The absolute and relative sensitivity of the phosphor at temperatures ranging from 293 K to 573 K. Where (a) is the sensitivity at the excitation wavelength λ. ex (a) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; (b) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; exAbsolute and relative sensitivity at 275nm excitation.

[0038] Figure 4 The Ca2Y prepared in Example 2 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ Temperature-dependent emission spectra of phosphors. Among them, (a) is the temperature-dependent emission spectrum excited at 309 nm; (b) is the temperature-dependent emission spectrum excited at 275 nm.

[0039] Figure 5 The Ca2Y prepared in Example 2 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ Phosphor at monitoring wavelength λ em Fluorescence excitation spectrum at 545 nm at temperatures ranging from 293 K to 573 K.

[0040] Figure 6 The Ca2Y prepared in Example 2 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ The absolute and relative sensitivity of the phosphor at temperatures ranging from 293 K to 573 K. Where (a) is the sensitivity at the excitation wavelength λ. ex (a) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; (b) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; ex Absolute and relative sensitivity at 275nm excitation.

[0041] Figure 7 It is the Ca2Lu prepared in Example 3 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ Temperature-dependent emission spectra of phosphors. Among them, (a) is the temperature-dependent emission spectrum excited at 309 nm; (b) is the temperature-dependent emission spectrum excited at 275 nm.

[0042] Figure 8 It is the Ca2Lu prepared in Example 3 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ Phosphor at monitoring wavelength λ em Fluorescence excitation spectrum at 545 nm at temperatures ranging from 293 K to 573 K.

[0043] Figure 9 It is the Ca2Lu prepared in Example 3 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ The absolute and relative sensitivity of the phosphor at temperatures ranging from 293 K to 573 K. Where (a) is the sensitivity at the excitation wavelength λ. ex (a) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; (b) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; ex Absolute and relative sensitivity at 275nm excitation.

[0044] Figure 10 It is the Ca2Lu prepared in Example 4 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ Temperature-dependent emission spectra of phosphors. Among them, (a) is the temperature-dependent emission spectrum excited at 309 nm; (b) is the temperature-dependent emission spectrum excited at 275 nm.

[0045] Figure 11 It is the Ca2Lu prepared in Example 4 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ Phosphor at monitoring wavelength λ em Fluorescence excitation spectrum at 545 nm at temperatures ranging from 293 K to 573 K.

[0046] Figure 12 It is the Ca2Lu prepared in Example 4 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ The absolute and relative sensitivity of the phosphor at temperatures ranging from 293 K to 573 K. Among them, (a) represents the sensitivity at the excitation wavelength λ. ex (a) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; (b) Absolute and relative sensitivity at excitation wavelength λ = 309 nm; ex Absolute and relative sensitivity at 275nm excitation.

[0047] Figure 13 This is a schematic diagram of the crystal structure model of the dual-channel ratiometric fluorescent material provided in an embodiment of the present invention.

[0048] Figure 14These are X-ray diffraction patterns of the dual-channel ratiometric fluorescent materials prepared in Examples 1 to 4. Specifically, (a) is the X-ray diffraction pattern of the dual-channel ratiometric fluorescent materials prepared in Examples 1 to 2; (b) is the X-ray diffraction pattern of the dual-channel ratiometric fluorescent materials prepared in Examples 3 to 4; and (c) is the X-ray diffraction pattern of Ca2Gd... 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ X-ray diffraction pattern of phosphor, y=0.1 or 0.3. Detailed Implementation

[0049] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0050] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] Due to the luminescence quenching phenomenon of existing phosphors, they suffer from relatively low sensitivity and narrow temperature measurement range. Therefore, finding an efficient strategy that can accurately control the thermal stability of the luminescence center signal has become the key to promoting the application of optical thermometry in fluorescent materials.

[0052] Based on existing technologies, there are currently two main approaches to improving the temperature sensitivity of fluorescent materials: finding two fluorescent indicator signals and a reference signal with diametrically opposed temperature responses, where the indicator signal intensity decreases with increasing temperature, while the reference signal intensity increases with increasing temperature, thus achieving a change in the ratio of reference signal intensity to indicator signal intensity caused by temperature changes. Therefore, the main solutions to address the poor thermal stability of activator ions in fluorescent materials include defect engineering strategies and negative thermal expansion strategies.

[0053] Defect engineering strategy involves artificially creating defect energy levels to store electrons, and then activating the electrons in the trap energy levels to provide compensatory luminescence when heated, thereby enhancing the luminescence intensity of the indicator signal luminescence center ions when heated.

[0054] The negative thermal expansion strategy utilizes the contraction / transformation of the crystal lattice during heating to enhance the symmetry of the crystal, suppress lattice vibrations to reduce nonradiative transitions of electrons, thereby improving the thermal stability of fluorescent material luminescence at high temperatures and avoiding the occurrence of thermal quenching of the reference signal.

[0055] Both of the above strategies can reduce the non-radiative energy transitions caused by heating, and have the advantages of maintaining stable luminescence. Thus, they still have efficient luminescence performance in high-temperature environments and can be used to make fluorescent materials with variable temperature or high-temperature working requirements.

[0056] However, current experimental techniques for defect engineering strategies are insufficient to fully understand and determine the exact properties of defect states. Therefore, it is impossible to control the number of introduced defect states and their distribution in fluorescent materials, often leading to contradictory experimental results. Introducing defect states into fluorescent materials through defect engineering strategies also causes lattice distortion, affecting the overall structural stability of the material. Furthermore, precisely introducing or manipulating specific types of defect states is technically challenging and easily introduces unintended impurities, negatively impacting the luminescence performance of the fluorescent material.

[0057] Currently, very few fluorescent materials are suitable for the negative thermal expansion strategy, and a thorough understanding of how the shrinkage of the crystal structure during heating affects the detailed process of electronic transitions remains lacking. The technology for using negative thermal expansion to improve the thermal stability of luminescent ions in fluorescent materials is far from mature, and it is impossible to achieve completely precise artificial control over the thermal expansion coefficient of negative thermal expansion inorganic phosphors. Therefore, matching the thermal expansion coefficient of negative thermal expansion phosphors with that of the matrix material remains a critical issue.

[0058] The two strategies mentioned above have revealed fatal flaws in terms of high production technology difficulty, complex production process, high production cost and low production efficiency under market demand, which seriously hinders the entry of fluorescent materials into various fields.

[0059] Addressing the shortcomings of existing fluorescent materials in production, such as low high-temperature sensitivity, high technical difficulty, complex production process, high production cost, and low production efficiency, this invention simplifies the entire production process without requiring additional manufacturing steps, eliminates the need for atmosphere protection, maximizes cost savings, and significantly promotes... FIR Applications of this type of thermometer in various fields.

[0060] Within an ambient temperature range of 293K to 573K, the dual-channel ratiometric fluorescent material of this invention generates two ratiometric signal channels under excitation at different wavelengths. The first ratiometric signal channel indicates the low-temperature region, and the second ratiometric signal channel indicates the high-temperature region. When the temperature is measured in the low-temperature region, the indicator signal ion Bi... 3+ The luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature, while the luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature. 3+ The luminescence intensity of the ion does not decrease significantly, and its thermal stability is good. When the temperature is measured in the high-temperature range, the indicator signal ion Bi... 3+ The luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature, while the luminescence intensity of the reference signal ion Tb decreases significantly with increasing temperature. 3+The luminescence intensity is significantly improved, indicating significant anti-thermal quenching. The dual-ratio signal channel of this invention is the main factor in achieving high sensitivity performance and widening the temperature measurement range.

[0061] Current methods cannot extend the temperature measurement range. This invention employs a dual-ratio signal channel strategy, covering two temperature ranges. When the two temperature measurement ranges are combined, they can cover 293K to 573K, providing a wider temperature measurement range compared to other ratio fluorescent materials, while also meeting the needs for sensitive temperature measurement in both high and low temperature ranges.

[0062] This invention utilizes Bi 3+ Broadband excitation spectra, combined with electron-phonon coupling mechanisms to promote Tb 3+ It exhibits anti-thermal quenching luminescence, thereby enhancing relative sensitivity at high temperatures.

[0063] Furthermore, this invention utilizes the rigidity of the garnet-structured matrix material to ensure Tb at low temperatures. 3+ The emitted signal exhibits good thermal stability, meaning that thermal quenching is not significant, thereby improving relative sensitivity at low temperatures. Simultaneously, this invention utilizes the garnet structure to modulate Bi... 3+ and Tb 3+ The excitation spectrum ensures that excitation light in the 294nm–316nm and 265nm–290nm ranges can be used to co-excite both.

[0064] In the following embodiments, the matrix material is a compound with a garnet crystal structure, belonging to the cubic crystal system. (230) Space group, mineral model structure formula is A3B2C3O 12 This material possesses excellent structural rigidity due to its stable polyhedral framework structure and has a low phonon vibration frequency, resulting in superior thermal quenching resistance in the fluorescent materials prepared after doping. The crystal structure model of the dual-channel ratiometric fluorescent material of this invention is as follows: Figure 13 As shown, in the matrix material of the present invention, Ca 2+ M 3+ Bi 3+ and Tb 3+ The ions are all located at the Wyckoff site at 24c, forming a distorted dodecahedron of [AO8]; M 3+ For Y 3+ Gd 3+ Or Lu 3+ And Zr 4+ And Al 3+ The ions are distributed at the Wyckoff sites at 16a and 24d, respectively, forming [BO6] octahedrons and [CO4] tetrahedrons.

[0065] In the following embodiments, the expression for the dual-channel ratiometric fluorescent material is Ca2M. x Zr2Al3O 12 :aBi 3+ ,yTb 3+ Where M is Y, Gd, or Lu, x = 1 - ay, y = 0.1 to 0.3, and a = 0.005 to 0.015. The value of a can vary within the range of 0.005 to 0.015. To explain the technical solution of the present invention, the following uses a = 0.001 as an example to further illustrate the technical solution of the present invention through specific embodiments.

[0066] In the following embodiments, unless otherwise specified, the methods described are conventional methods; and unless otherwise specified, the reagents and materials described are commercially available.

[0067] In the following examples, CaCO3, Al2O3, and ZrO2 were all of analytical grade; Y2O3, Tb4O7, and Lu2O3 were all of 99.99% purity; and Bi2O3 was of 99.9% purity.

[0068] Example 1 A method for preparing a dual-channel ratiometric fluorescent material includes the following steps: According to the phosphor Ca2Y 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ The stoichiometric ratio was determined, where y = 0.1. 2 mol of CaCO3, 1.5 mol of Al2O3, 0.445 mol of Y2O3, 2 mol of ZrO2, 0.005 mol of Bi2O3, and 0.025 mol of Tb4O7 were weighed as raw materials. The weighed raw materials were poured into an agate mortar, and an appropriate amount of absolute ethanol was added and mixed thoroughly. The mixture was stirred for 30 minutes and then placed in an alumina crucible. The alumina crucible containing the raw materials was then placed stably into an alumina tube furnace and sintered at 1550℃ for 6 hours. Afterward, it was naturally cooled to room temperature and ground into powder to obtain the fluorescent powder Ca2Y. 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ It is used as a dual-channel ratio fluorescent thermometer.

[0069] Example 2 A method for preparing a dual-channel ratiometric fluorescent material includes the following steps: According to the phosphor Ca2Y 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb3+ The stoichiometric ratio was determined, where y = 0.3. 2 mol of CaCO3, 1.5 mol of Al2O3, 0.345 mol of Y2O3, 2 mol of ZrO2, 0.005 mol of Bi2O3, and 0.075 mol of Tb4O7 were weighed as raw materials. The weighed raw materials were poured into an agate mortar, and an appropriate amount of absolute ethanol was added and mixed thoroughly. The mixture was stirred for 30 minutes and then placed in an alumina crucible. The alumina crucible containing the raw materials was then placed stably in an alumina tube furnace and sintered at 1550℃ for 6 hours. Afterward, it was naturally cooled to room temperature and ground into powder to obtain the fluorescent powder Ca2Y. 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ It is used as a dual-channel ratio fluorescent thermometer.

[0070] Table 1. Y-values ​​and phosphors of Examples 1-2 Note: The value ranges for the low-temperature and high-temperature regions are based on the relative sensitivity Sr > 1%K. -1 Obtained as a benchmark.

[0071] The formula for the dual-channel ratiometric fluorescent material in Examples 1 and 2 is Ca2Y. 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ ; y = 0.1~0.3.

[0072] Examples 1 and 2 use Ca2Y 0.99-y Zr2Al3O 12 The substrate, abbreviated as CYZA substrate, is based on Bi. 3+ and Tb 3+ The luminescence properties of ions on the CYZA substrate were studied, and a series of Ca2Y phosphors were designed accordingly. 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ Where y = 0.10 or 0.30. For ease of description, Ca2Y 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ Abbreviation CYZA:0.01Bi 3+ ,yTb 3 + The series of fluorescent powders CYZA:0.01Bi 3+ ,yTb 3+As a dual-channel ratiometric fluorescent thermometer, dual-channel ratiometric temperature measurement was achieved under excitation at 309 nm and 275 nm.

[0073] Figure 1 The variable-temperature PL spectra are shown respectively under the strategy of Embodiment 1 of the present invention. The variable-temperature PL spectrum represents the variable-temperature emission spectrum. (Using dual channels...) FIR A comparison of temperature measurement schemes, showing the implementation of only Bi 3+ Luminous intensity reduction strategy FIR The effect of improving temperature measurement sensitivity, and the implementation of Bi 3+ Achieving Tb while reducing luminous intensity 3+ Strategies to increase luminescence intensity FIR Improved temperature measurement sensitivity.

[0074] Figure 1 Figure (a) shows that, at 309 nm excitation, Bi 3+ and Tb 3+ All exhibit thermal quenching characteristics, with the luminescence intensity of Bi3+ decreasing significantly with increasing temperature, indicating severe thermal quenching. Furthermore, due to the rigidity of the matrix material and the influence of the excitation source on Tb... 3+ The stimulating effect of Tb 3+ The decline was not significant.

[0075] Figure 1 Figure (b) shows that when excited at 275 nm, Bi is achieved. 3+ While the intensity of ion emission decreases rapidly with increasing ambient temperature, Tb 3+ Ions accepting Bi 3+ The ion energy absorbs the energy from the 275nm light source, causing its luminescence intensity to show a single increasing trend with rising ambient temperature, while simultaneously indicating the signal ion Bi. 3+ The luminous intensity gradually decreases.

[0076] Figure 2 This visually demonstrates how the degree of electron-phonon coupling can be used to modulate Tb. 3+ A strategy to enhance the intensity of the luminescent signal, using phosphor CYZA:0.01Bi. 3+ 0.10Tb 3+ At the monitoring wavelength λ em At 545 nm, the increase in ambient temperature enhances electron-phonon coupling, resulting in Tb 3+ The excitation peak exhibits an increase in FWHM and a redshift, gradually covering the optimal excitation peak position of 275 nm, thus achieving the reference signal ion Tb. 3+ It absorbs at a wavelength of 275 nm, and the absorption intensity shows a single upward trend.

[0077] FIR Temperature measurement sensitivity is mainly expressed in terms of absolute sensitivity and relative sensitivity; FIR The expression for temperature sensitivity is as follows: ; ; in, S a Indicates absolute sensitivity; S r Indicates relative sensitivity; FIR The fluorescence intensity ratio represents the ratio of the intensities of two fluorescence emission peaks at different wavelengths. T It represents Kelvin temperature.

[0078] Figure 3 Demonstration through FIR The absolute and relative sensitivities calculated by fitting the expression for temperature sensitivity, with dual-channel sensitivity at 309 nm excitation. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.034K -1 , S r（max） =1.64%K -1 The temperature at this point is 353K. Dual-channel excitation at 275nm. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.2784K -1 , S r（max） =2.14%K -1 The temperature at this time is 473K.

[0079] Figure 4 The variable-temperature PL spectra under the strategy of Embodiment 2 of the present invention are displayed separately, through dual channels. FIR A comparison of temperature measurement schemes, showing the implementation of only Bi 3+ Luminous intensity reduction strategy FIR The effect of improving temperature measurement sensitivity, and the implementation of Bi 3+ Achieving Tb while reducing luminous intensity 3+ Strategies to increase luminescence intensity FIR Improved temperature measurement sensitivity.

[0080] Figure 4 Figure (a) shows that, at 309 nm excitation, Bi 3+ and Tb 3+ All exhibit thermal quenching characteristics, among which Bi 3+ The luminescence intensity decreases significantly with increasing temperature, indicating severe thermal quenching. Furthermore, the rigidity of the matrix material and the effect of the excitation source on Tb...3+ The stimulating effect of Tb 3+ The decline was not significant.

[0081] Figure 4 Figure (b) shows that when excited at 275 nm, Bi is achieved. 3+ While the intensity of ion emission decreases rapidly with increasing ambient temperature, Tb 3+ Ions accepting Bi 3+ The ion energy absorbs the energy from the 275nm light source, causing its luminescence intensity to show a single increasing trend with rising ambient temperature, while simultaneously indicating the signal ion Bi. 3+ The luminous intensity gradually decreases.

[0082] Figure 5 This visually demonstrates how the degree of electron-phonon coupling can be used to modulate Tb. 3+ A strategy to enhance the intensity of the luminescent signal, using phosphor CYZA:0.01Bi. 3+ 0.30Tb 3+ At the monitoring wavelength λ em At 545 nm, the increase in ambient temperature enhances electron-phonon coupling, resulting in Tb 3+ The excitation peak exhibits an increase in FWHM and a redshift, gradually covering the optimal excitation peak position of 275 nm, thus achieving the reference signal ion Tb. 3+ It absorbs at a wavelength of 275 nm, and the absorption intensity shows a single upward trend.

[0083] Figure 6 Demonstration through FIR The absolute and relative sensitivities calculated by fitting the expression for temperature sensitivity, with dual-channel sensitivity at 309 nm excitation. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.401K -1 , S r（max） =2.05%K -1 The temperature at this point is 393K. Dual-channel excitation at 275nm. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =2.34K -1 , S r（max） =1.64%K -1 The temperature at this time is 513K.

[0084] The results in summary show that the ratiometric fluorescent thermometer, after implementing the strategy of the embodiments of the present invention, achieves high temperature sensitivity and effectively broadens the temperature measurement range of the ratiometric fluorescent thermometer.

[0085] Example 3 A method for preparing a dual-channel ratiometric fluorescent material includes the following steps: According to the phosphor Ca2Lu 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ The stoichiometric ratio, where y = 0.10, was used to weigh CaCO3, Al2O3, Lu2O3, ZrO2, Tb4O7, and Bi2O3 as raw materials. These raw materials were poured into an agate mortar, and an appropriate amount of absolute ethanol was added and mixed thoroughly. The mixture was stirred for 30 minutes and then placed in an alumina crucible. The alumina crucible containing the raw materials was then placed stably into an alumina tube furnace and sintered at 1550℃ for 6 hours. Afterward, it was allowed to cool naturally to room temperature and ground into powder to obtain the phosphor Ca2Lu. 0.89 Zr2Al3O 12 0.01Bi 3+ 0.10Tb 3+ It is used as a dual-channel ratio fluorescent thermometer.

[0086] Example 4 A method for preparing a dual-channel ratiometric fluorescent material includes the following steps: According to the phosphor Ca2Lu 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ The stoichiometric ratio, where y = 0.30, was used to weigh CaCO3, Al2O3, Lu2O3, ZrO2, Tb4O7, and Bi2O3 as raw materials. These raw materials were poured into an agate mortar, and an appropriate amount of absolute ethanol was added and mixed thoroughly. The mixture was stirred for 30 minutes and then placed in an alumina crucible. The alumina crucible containing the raw materials was then placed stably into an alumina tube furnace and sintered at 1550℃ for 6 hours. Afterward, it was allowed to cool naturally to room temperature and ground into powder to obtain the phosphor Ca2Lu. 0.69 Zr2Al3O 12 0.01Bi 3+ 0.30Tb 3+ It is used as a dual-channel ratio fluorescent thermometer.

[0087] Table 2. Y-values ​​and phosphor temperature measurement ranges for Examples 3-4 Note: The value ranges for the low-temperature and high-temperature regions are based on the relative sensitivity Sr > 1%K. -1 Obtained as a benchmark.

[0088] The formula for the dual-channel ratiometric fluorescent materials in Examples 3 and 4 is Ca2Lu. 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ ; y = 0.1~0.3.

[0089] Examples 3 and 4 use Ca2Lu 0.99-y Zr2Al3O 12 The substrate, abbreviated as CLZA substrate, is based on Bi. 3+ and Tb 3+ The luminescence properties of ions on CLZA substrates were studied, and a series of phosphors, Ca2Lu, were designed accordingly. 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ Where y = 0.10 or 0.30. For ease of description, Ca2Lu 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ Abbreviation CLZA:0.01Bi 3+ ,yTb 3+ The series of phosphors CLZA:0.01Bi 3+ ,yTb 3+ As a dual-channel ratiometric fluorescent thermometer, temperature measurement was achieved under excitation at 309 nm and 275 nm, respectively.

[0090] Figure 7 The variable-temperature PL spectra are shown respectively under the strategies implemented in the embodiments of the present invention. The variable-temperature PL spectrum represents the variable-temperature emission spectrum. This is achieved through a dual-channel... FIR A comparison of temperature measurement schemes, showing the implementation of only Bi 3+ Luminous intensity reduction strategy FIR The effect of improving temperature measurement sensitivity, and the implementation of Bi 3+ Achieving Tb while reducing luminous intensity 3+ Strategies to increase luminescence intensity FIR Improved temperature measurement sensitivity.

[0091] Figure 7 Figure (a) shows that, at 309 nm excitation, Bi 3+ and T b3+ All exhibit thermal quenching characteristics, among which Bi 3+ The luminescence intensity decreases significantly with increasing temperature, indicating severe thermal quenching. Furthermore, the rigidity of the matrix material and the effect of the excitation source on Tb... 3+ The stimulating effect of Tb 3+ The decline was not significant.

[0092] Figure 7 Figure (b) shows that when excited at 275 nm, Bi is achieved. 3+ While the intensity of ion emission decreases rapidly with increasing ambient temperature, Tb 3+ Ions accepting Bi 3+ The ion energy absorbs the energy from the 275nm light source, causing its luminescence intensity to show a single increasing trend with rising ambient temperature, while simultaneously indicating the signal ion Bi. 3+ The luminous intensity gradually decreases.

[0093] Figure 8 This visually demonstrates how the degree of electron-phonon coupling can be used to modulate Tb. 3+ A strategy to enhance the intensity of luminescent signal, using phosphor CLZA:0.01Bi. 3+ 0.10Tb 3+ At the monitoring wavelength λ em At 545 nm, the increase in ambient temperature enhances electron-phonon coupling, resulting in Tb 3+ The excitation peak exhibits an increase in FWHM and a redshift, gradually covering the optimal excitation peak position of 275 nm, thus achieving the reference signal ion Tb. 3+ It absorbs at a wavelength of 275 nm, and the absorption intensity shows a single upward trend.

[0094] Figure 9 Demonstration through FIR The absolute and relative sensitivities calculated by fitting the expression for temperature sensitivity, with dual-channel sensitivity at 309 nm excitation. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.029K -1 , S r（max） =1.77%K -1 The temperature at this point is 333K. Dual-channel excitation at 275nm. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.174K -1 , S r（max） =2.04%K -1 The temperature at this time is 533K.

[0095] Figure 10 The variable-temperature PL spectra under the strategies implemented in the embodiments of the present invention are displayed separately, through dual channels. FIR A comparison of temperature measurement schemes, showing the implementation of only Bi 3+ Luminous intensity reduction strategy FIRThe effect of improving temperature measurement sensitivity, and the implementation of Bi 3+ Achieving Tb while reducing luminous intensity 3+ Strategies to increase luminescence intensity FIR Improved temperature measurement sensitivity.

[0096] Figure 10 Figure (a) shows that, at 309 nm excitation, Bi 3+ and Tb 3+ All exhibit thermal quenching characteristics, among which Bi 3+ The luminescence intensity decreases significantly with increasing temperature, indicating severe thermal quenching. Furthermore, the rigidity of the matrix material and the effect of the excitation source on Tb... 3+ The stimulating effect of Tb 3+ The decline was not significant.

[0097] Figure 10 Figure (b) shows that when excited at 275 nm, Bi is achieved. 3+ While the intensity of ion emission decreases rapidly with increasing ambient temperature, Tb 3+ Ions accepting Bi 3+ The ion energy absorbs the energy from the 275nm light source, causing its luminescence intensity to show a single increasing trend with rising ambient temperature, while simultaneously indicating the signal ion Bi. 3+ The luminous intensity gradually decreases.

[0098] Figure 11 This visually demonstrates how the degree of electron-phonon coupling can be used to modulate Tb. 3+ A strategy to enhance the intensity of luminescent signal, using phosphor CLZA:0.01Bi. 3+ 0.30Tb 3+ At the monitoring wavelength λ em At 545 nm, the increase in ambient temperature enhances electron-phonon coupling, resulting in Tb 3+ The excitation peak exhibits an increase in FWHM and a redshift, gradually covering the optimal excitation peak position of 275 nm, thus achieving the reference signal ion Tb. 3+ It absorbs at a wavelength of 275 nm, and the absorption intensity shows a single upward trend.

[0099] Figure 12 Demonstration through FIR The absolute and relative sensitivities calculated by fitting the expression for temperature sensitivity, with dual-channel sensitivity at 309 nm excitation. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =0.323K -1 , S r（max） =1.79%K-1 The temperature at this point is 393K. Dual-channel excitation at 275nm. FIR The temperature measurement sensitivity of the temperature measurement scheme is S a（max） =1.48K -1 , S r（max） =1.62%K -1 The temperature at this time is 473K.

[0100] The results in summary demonstrate that the ratiometric fluorescent thermometer, after implementing the strategy of the embodiments of the present invention, achieves high temperature sensitivity and effectively expands the temperature measurement range of the ratiometric fluorescent thermometer.

[0101] Comparative Example 1 CaYGaO4:Bi was prepared according to the method described in reference 1: doi.org / 10.1016 / j.optmat.2023.114245. 3+ ,Tb 3+ Fluorescent powder.

[0102] CaYGaO4: Bi 3+ , Tb 3+ The phosphor was tested in a temperature range of 303K to 483K, with a maximum relative sensitivity of Sr = 0.61% K. -1 (303K), compared with Embodiment 2 of the present invention, the maximum value of Sr does not exceed 1% K. -1 Meanwhile, the temperature measurement coverage of Comparative Example 1 is 100°C smaller than the temperature measurement coverage (293K~573K) of Example 2 of the present invention.

[0103] Comparative Example 2 LaNbO4:Bi was prepared according to the method in reference 2: doi.org / 10.1016 / j.cej.2021.128977. 3+ , Tb 3+ Fluorescent powder.

[0104] Comparative Example 2: LaNbO4: Bi 3+ , Tb 3+ The testing temperature range for phosphors is 323K to 483K (with Sr > 1%). -1 (Calculated), maximum Sr = 1.47% K -1 (383K). The maximum Sr value in Example 2 of this invention is 2.14% K. -1 (Extreme value of 473K in the high-temperature region), and 1.64% K -1(Extreme value of 353K in the low temperature region). The maximum value of Sr in Comparative Example 2 is about 33% different from the maximum value of Sr in Example 2 of the present invention. The temperature range covered by Example 2 of the present invention is 293K to 573K. The temperature measurement coverage range of Comparative Example 2 is 120℃ smaller than that of Example 2 of the present invention.

[0105] Comparative Example 3 LaNbO4:Bi was prepared according to the method in reference 3: doi.org / 10.1016 / j.cej.2024.148717. 3+, Tb 3+ Fluorescent powder.

[0106] Comparative Example 3: LaNbO4: Bi 3+, Tb 3+ The testing temperature range for phosphors is 313K to 473K, with a maximum S0. r =0.93%K -1 Compared with Embodiment 2 of the present invention, the maximum value of Sr in each embodiment did not exceed 1% K. -1 Meanwhile, its temperature measurement coverage range is 120°C smaller than that of 293K~573K in Embodiment 2 of the present invention.

[0107] Figure 14 These are X-ray diffraction patterns of the dual-channel ratiometric fluorescent materials prepared in Examples 1 to 4. Specifically, (a) is the X-ray diffraction pattern of the dual-channel ratiometric fluorescent materials prepared in Examples 1 to 2; (b) is the X-ray diffraction pattern of the dual-channel ratiometric fluorescent materials prepared in Examples 3 to 4; and (c) is the X-ray diffraction pattern of Ca2Gd... 0.99-y Zr2Al3O 12 0.01Bi 3+ ,yTb 3+ X-ray diffraction pattern of phosphor, y=0.1 or 0.3.

[0108] Figure 14 (a) indicates that Ca2Y 1-a-y Zr2Al3O 12 :aBi 3+ yTb 3+ The X-ray diffraction (XRD) pattern of the phosphor matched well with the JCPDS#75-0553 standard card, confirming that garnet-structured Ca2Y can be obtained under the synthesis conditions of this embodiment. 1-a-y Zr2Al3O 12 :aBi 3+ yTb 3+ Fluorescent powder.

[0109] Figure 14 (b) indicates that Ca2Lu 1-a-y Zr2Al3O12 :aBi 3+ yTb 3+ The X-ray diffraction (XRD) pattern of the phosphor matched well with the JCPDS #25-1178 standard card, confirming that the garnet-structured Ca2Lu can be obtained under the synthesis conditions of the embodiments of the present invention. 1-a-y Zr2Al3O 12 :aBi 3+ yTb 3+ Fluorescent powder.

[0110] Figure 14 (c) indicates that Ca2Gd 0.99-y Zr2Al3O 12 0.01Bi 3+ yTb 3+ The X-ray diffraction (XRD) pattern of the phosphor matched well with the COD #43387818 standard card, confirming that garnet-structured Ca2Gd can be obtained under the synthesis conditions of this embodiment. 0.99-y Zr2Al3O 12 0.01Bi 3+ yTb 3+ Phosphor. Ca2Gd 0.99-y Zr2Al3O 12 0.01Bi 3+ yTb 3+ The phosphor was prepared according to the preparation methods of Examples 1 to 4, wherein y = 0.1 or 0.3. Ca2Gd 0.99-y Zr2Al3O 12 0.01Bi 3+ yTb 3+ Abbreviated as CGZA:0.01Bi 3+ yTb 3+ .

[0111] In summary, the strategy of this invention can effectively control the thermal stability of the reference signal center emission according to different application environments of the fluorescent material for temperature measurement. This allows the ratiometric fluorescent thermometer to enhance or stabilize the intensity of the reference signal while the intensity of the indicated signal decreases, thus achieving high-sensitivity temperature measurement performance over a wide temperature range in practical applications. Furthermore, the strategy of this invention eliminates the dependence of high-sensitivity ratiometric fluorescent thermometers on the substrate material structure and manufacturing process, significantly reducing the production difficulty and cost of high-sensitivity ratiometric fluorescent thermometers. This will strongly promote the application of high-sensitivity ratiometric fluorescent thermometers in various fields.

[0112] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An application of a dual-channel ratiometric fluorescent material as a dual-channel ratiometric fluorescent thermometer, characterized in that, The dual-channel ratiometric fluorescent material is based on Bi 3+ Tb is an indicator signal ion. 3+ As a reference signal ion, Bi 3+ and Tb 3+ Obtained by doping into a matrix material; The expression for the dual-channel ratiometric fluorescent material is Ca2M x Zr2Al3O 12 :aBi 3+ ,yTb 3+ Where M is Y, Gd, or Lu, x = 1 - ay, y = 0.1 to 0.3, and a = 0.005 to 0.015; The dual-channel ratio fluorescent thermometer has two ratio signal channels, and the two ratio signal channels respectively indicate two temperature measurement zones; When the temperature measurement zone is between 293K and b, and 433K≤b≤493K, the dual-channel ratio fluorescent thermometer generates a ratio signal channel when the excitation wavelength is between 294nm and 316nm. When the temperature measurement zone is between c and 573K, and 393K≤c≤453K, the dual-channel ratio fluorescent thermometer generates another ratio signal channel when the excitation wavelength is between 265nm and 290nm.

2. The application according to claim 1, characterized in that, The matrix material has a garnet crystal structure, belonging to the cubic crystal system. (230) Space group; the matrix material is expressed as Ca2M x Zr2Al3O 12 .

3. The application according to claim 1, characterized in that, The preparation method of dual-channel ratiometric fluorescent materials includes the following steps: According to the expression of dual-channel ratiometric fluorescent materials Ca2M x Zr2Al3O 12 :aBi 3+ ,yTb 3+ By determining the stoichiometric ratio, metal ion sources corresponding to Ca, M, Zr, Al, Bi and Tb were obtained as raw materials. After grinding and mixing the raw materials, they were calcined, cooled and ground into powder to obtain a dual-channel ratiometric fluorescent material.

4. The application according to claim 3, characterized in that, The roasting temperature is 1500℃~1600℃, and the roasting time is 5h~7h.

5. The application according to claim 3, characterized in that, The raw materials are metal oxides or metal carbonates corresponding to Ca, M, Zr, Al, Bi and Tb.

6. The application according to claim 1, characterized in that, The relative sensitivity of both temperature measurement zones is >1%K -1 .

Images