Yb3+ / Er3 + co-doped glass material for measuring temperature based on fluorescence intensity ratio as well as preparation method and application of Yb3+ / Er3 + co-doped glass material

Abstract

The invention provides a Yb < 3 + > / Er < 3 + > co-doped glass material based on fluorescence intensity ratio temperature measurement. The Yb < 3 + > / Er < 3 + > co-doped glass material comprises 20.00 to 25.00 wt% of SiO2, 6.00 to 7.00 wt% of AlF3, 28.00 to 35.00 wt% of BaF2, 6.00 to 13.00 wt% of BaO, 18.00 to 24.00 wt% of Gd2O3, 0.50 to 3.00 wt% of Er2O3 and 3.00 to 5.00 wt% of Yb2O3, and the sum of the components is 100 wt%. The co-doped glass material can effectively inhibit concentration quenching and improve the luminous efficiency, and the glass matrix and doped rare earth elements can synergistically optimize the physical properties of the glass material and significantly improve the luminous intensity, efficiency and stability of Er < 3 + >.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of luminescent materials, and particularly relates to a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement. BACKGROUND

[0002] Temperature, as the most basic thermodynamic parameter and an important indicator for characterizing the progress of chemical reactions, is widely used in industrial production, scientific research, pharmaceutical chemistry, national defense construction and other fields. Therefore, improving the accuracy and precision of temperature measurement has great practical significance for the progress of science and technology and the development of society.

[0003] Traditional temperature sensors mostly convert temperature into electronic signals that can be recognized by computers through thermal devices to read temperature. However, traditional temperature sensors mostly use a contact method to measure temperature, and at the same time, the electrical signal also has certain requirements for the working environment. With the development of the times, the increasingly complex working environment and stringent testing requirements pose great challenges to traditional temperature measurement platforms.

[0004] Compared with the thermal devices mentioned above, optical fiber sensing technology has the advantages of non-contact measurement, wide temperature measurement range, high sensitivity, corrosion resistance, anti-electromagnetic interference, and economical and durable temperature measurement system, which meets the measurement requirements of fast response and real-time detection, and can safely and effectively measure temperature in harsh environments.

[0005] At present, optical fiber temperature sensors can be divided into four categories according to the sensing method: distributed optical fiber temperature sensors, interference optical fiber temperature sensors, fluorescent optical fiber temperature sensors, and optical fiber grating temperature sensors. Among the above classifications, fluorescent optical fiber temperature sensors have gradually become the mainstream research direction in the field of temperature sensing in recent years due to their high stability, wide temperature measurement range, anti-electromagnetic interference, low system construction cost, and ability to realize absolute temperature measurement.

[0006] In order to realize temperature detection in various occasions and even harsh environments, researchers use optical fibers to transmit light and take advantage of the temperature sensitivity of fluorescent substances. By combining optical fiber technology with fluorescent sensing technology, a fluorescent optical fiber temperature sensing technology with strong anti-interference, remote detection and real-time monitoring capabilities is obtained.

[0007] According to different properties of fluorescence change of luminescent materials, fluorescence fiber sensors can be divided into three types of fluorescence intensity type, fluorescence lifetime type and fluorescence intensity ratio type. The three types of sensors are based on the change of physical quantity to change the fluorescence spectrum of luminescent materials to perceive the external environment. However, single measurement of fluorescence lifetime or fluorescence intensity for temperature sensing is easily affected by external interference, such as fluctuation of pump light source, bending loss and the like, resulting in measurement error, and the measurement accuracy is not enough. Research shows that temperature measurement using the fluorescence intensity ratio of two energy levels of rare earth ions can well eliminate external interference, maximize the stability, accuracy and reliability of the sensor. At the same time, by selecting appropriate rare earth elements and fiber matrix, it is hoped to prepare high-precision and wide-range temperature sensor. In addition, the coupling relationship between the fluorescence intensity ratio (FIR, Fluorescence Intensity Ratio) of the luminescent peak of the fluorescence material and the temperature can greatly simplify the detection and processing of the fluorescence signal, and the whole fiber sensing system finally obtained has the advantages of low cost, simple operation, high sensitivity, high accuracy and long service life.

[0008] In summary, the all-fiber temperature sensor based on the fluorescence intensity ratio type has unique advantages, and has become the focus of research on temperature detection innovation and development. SUMMARY

[0009] To solve the technical problems in the background art, the present application provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement, the composition of the co-doped glass material includes SiO2: 20.00-25.00wt%, AlF3: 6.00-7.00wt%, BaF2: 28.00-35.00wt%, BaO: 6.00-13.00wt%, Gd2O3: 18.00-24.00wt%, Er2O3: 0.50-3.00wt%, Yb2O3: 3.00-5.00wt%, the total of the composition is 100wt%;

[0010] Preferably, the Er2O3 concentration is 0.50-1.00wt%;

[0011] Preferably, the Yb2O3 concentration is 4.00-5.00wt%.

[0012] In the present application, the optimal Er 3+ doping concentration range effectively suppresses concentration quenching and improves luminescent efficiency; Yb 3+ In the low to moderate concentration range, the trend of continuously enhancing Er 3+ luminescence provides a basis for ratio optimization.

[0013] This invention also proposes a Yb thermometry method based on fluorescence intensity ratio. 3+ / Er 3+ The preparation method of co-doped glass materials is to mix the raw materials, calcine them, and then anneal them.

[0014] Preferably, the calcination temperature is 1200-1800℃;

[0015] More preferably, the calcination temperature is 1500°C.

[0016] Preferably, the calcination time is 20-60 min;

[0017] More preferably, the calcination time is 30 minutes.

[0018] Preferably, the annealing temperature is 500-800℃;

[0019] More preferably, the annealing temperature is 600°C.

[0020] This invention also proposes a Yb thermometry method based on fluorescence intensity ratio. 3+ / Er 3+ Yb based on fluorescence intensity ratio thermometry prepared by co-doped glass materials or the above preparation methods 3+ / Er 3+ Application of co-doped glass materials in temperature testing;

[0021] Preferably, the co-doped glass material is ground into powder, mixed with UV-curable adhesive, impregnated onto the end face of a multimode optical fiber, and then cured.

[0022] Preferably, the curing time is 2-10 minutes.

[0023] Beneficial effects of this invention:

[0024] (1) This invention prepares a fluorescent material with high luminous efficiency, low background noise, and high temperature sensing properties—SABG:Er 3+ / Yb 3+ Co-doped glass, combined with temperature-sensitive fluorescent materials and fiber optic probes, and using optical fiber as the signal transmission medium, enables the device for receiving and processing fluorescent signals to have high resolution, high response, and electromagnetic resistance compared to traditional temperature sensors, and can be used in harsh environments such as strong electric fields.

[0025] (2) Compared with fluorescence lifetime signals, which are more complex to measure and process, and fluorescence intensity methods, which are more dependent on measurement conditions, FIR technology can eliminate interference from other non-temperature factors (strain, environmental medium, light source fluctuations, etc.), effectively eliminating any fluctuations in fluorescence signals and pump sources, thereby simplifying the measurement process. Attached Figure Description

[0026] Figure 1 Figure 1 is a photograph of a sensing probe;

[0027] Figure 2 Figure 2 is a photograph of a stainless steel capillary packaged probe;

[0028] Figure 3 Figure 3 is a photograph of an all-fiber temperature measurement system;

[0029] Figure 4 Figure 4 is a graph of the exponential fit of FIR versus temperature in a calibration experiment;

[0030] Figure 5 Figure 5 is a graph of the upconversion luminescence intensity versus Er2O3 concentration in Examples 1-4;

[0031] Figure 6 Figure 6 is a graph of the upconversion luminescence intensity versus Yb2O3 concentration in Examples 5-8;

[0032] Figure 7 Figure 7 is a graph of the upconversion luminescence intensity versus Gd2O3 concentration in Example 9 and Comparative Example 1;

[0033] Figure 8 Figure 8 is a graph of the upconversion luminescence intensity versus BaF2 concentration in Example 10 and Comparative Example 2. DETAILED DESCRIPTION

[0034] In order to facilitate the understanding of the present application, a more complete description of the present application will be provided below in conjunction with specific examples. However, the present application can be realized in many different forms and is not limited to the embodiments described herein. Rather, the purpose of the embodiments is to make the disclosure of the present application more thorough and complete.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0036] Below, the technical solutions of the present application will be described more clearly and completely in conjunction with specific examples and comparative examples.

[0037] Example 1

[0038] This example presents a Yb 3+ / Er 3+ co-doped glass material, the composition of which includes:

[0039] SiO2: 23.50wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 20.00wt%, Er2O3: 0.50wt%, Yb2O3: 4.00wt%;

[0040] The embodiment provides a Yb 3+ / Er 3+ A preparation method of the co-doped glass material.

[0041] The mass of the raw materials is calculated according to the molar ratio of the above composition, wherein barium oxide is introduced by using raw material barium carbonate, the raw materials are weighed by using a high-precision electronic analytical balance, the weighed raw materials are uniformly ground in a same direction in an agate mortar, so that the raw materials are fully mixed, the uniformly mixed raw materials are transferred into an alumina crucible, the alumina crucible is covered and then placed in a pit furnace, the pit furnace is heated at a rate of 5 DEG C / min to 1500 DEG C under an air atmosphere, the pit furnace is kept at 1500 DEG C for 30 minutes, the powder is completely reacted into a transparent glass liquid, the glass liquid is taken out and cast on a preheated copper plate (the temperature of the copper plate is 550 DEG C) to be formed, and then the glass is quickly transferred into a muffle furnace at 600 DEG C to be annealed and kept for 2 hours, and the glass is ground into powder after being cooled to room temperature along with the furnace.

[0042] Example 2

[0043] The embodiment provides a Yb 3+ / Er 3+ The co-doped glass material comprises the following components:

[0044] SiO2: 23.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%,

[0045] Gd2O3: 20.00wt%, Er2O3: 1.00wt%, Yb2O3: 4.00wt%;

[0046] The embodiment provides a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that in the embodiment 1.

[0047] Example 3

[0048] The embodiment provides a Yb 3+ / Er 3+ The co-doped glass material comprises the following components:

[0049] SiO2: 22.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 20.00wt%, Er2O3: 2.00wt%, Yb2O3: 4.00wt%;

[0050] The embodiment provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0051] Embodiment 4

[0052] The embodiment provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0053] SiO2: 21.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 20.00wt%, Er2O3: 3.00wt%, Yb2O3: 4.00wt%;

[0054] The embodiment provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0055] Embodiment 5

[0056] The embodiment provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0057] SiO2: 25.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 22.50wt%, Er2O3: 0.50wt%, Yb2O3: 0.00wt%;

[0058] The embodiment provides a Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0059] Embodiment 6

[0060] The embodiment provides a Yb 3 + / Er 3+ co-doped glass material based on fluorescence intensity ratio temperature measurement.

[0061] SiO2: 22.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 22.50wt%, Er2O3: 0.50wt%, Yb2O3: 3.00wt%;

[0062] The embodiment proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0063] Embodiment 7

[0064] The embodiment proposes a Yb 3+ / Er 3+ The co-doped glass material comprises the following components:

[0065] SiO2: 22.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 22.50wt%, Er2O3: 0.50wt%, Yb2O3: 3.00wt%;

[0066] The embodiment proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0067] Embodiment 8

[0068] The embodiment proposes a Yb 3+ / Er 3+ The co-doped glass material comprises the following components:

[0069] SiO2: 22.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 22.50wt%, Er2O3: 0.50wt%, Yb2O3: 3.00wt%;

[0070] The embodiment proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0071] Embodiment 9

[0072] The embodiment proposes a Yb 3+ / Er3+ A co-doped glass material, the composition of which comprises:

[0073] SiO2: 22.00wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 22.50wt%, Er2O3: 0.50wt%, Yb2O3: 3.00wt%;

[0074] The embodiment proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0075] Embodiment 10

[0076] The embodiment proposes a Yb 3+ / Er 3+ A co-doped glass material, the composition of which comprises:

[0077] SiO2: 21.50wt%, AlF3: 7.00wt%, BaF2: 33.00wt%, BaO: 12.00wt%, Gd2O3: 23.00wt%, Er2O3: 0.50wt%, Yb2O3: 3.00wt%;

[0078] The embodiment proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0079] Comparative Example 1

[0080] The comparative example proposes a Yb 3+ / Er 3+ A co-doped glass material, the composition of which is the same as that of Embodiment 9, except that the composition does not contain Gd2O3;

[0081] The comparative example proposes a Yb 3+ / Er 3+ The preparation method of the co-doped glass material is the same as that of Embodiment 1.

[0082] Comparative Example 2

[0083] The comparative example proposes a Yb 3+ / Er 3+ A co-doped glass material, the composition of which is the same as that of Embodiment 10, except that the composition does not contain BaF2;

[0084] A Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio for temperature measurement was prepared according to the following method.

[0085] Performance test and application

[0086] The Yb 3+ / Er 3+ co-doped glass material powders prepared in Examples 1-10 and Comparative Examples 1-2 were weighed respectively, and then the powders and the UV curing glue were uniformly mixed (powder: UV curing glue = 0.5 g: 1 mL), and then slowly immersed on the flat end face of the multimode optical fiber, and the probe was excited with a 980 nm laser, and the position of the glass powder wrapped on the end face of the optical fiber was adjusted according to the upconversion luminescence intensity of the probe, and then the UV lamp was irradiated for 5 min to cure the UV glue, and the sensing probe was obtained after curing (see Figure 1 ), and the sensing probe was packaged with a stainless steel capillary with a diameter of 2 mm to ensure the overall mechanical strength, sealing performance and temperature measurement accuracy of the probe, and the stainless steel capillary packaged probe (see Figure 2 ) was obtained.

[0087] A 980 nm laser, a constant temperature heating table, an optical fiber spectrometer, a thermocouple temperature meter, a filter, an optical fiber splitter, an optical power meter, an aluminum block, a flange, an optical fiber and an optical fiber sensing probe (the glass powder on the probe was from Example 1) were assembled into an all-fiber temperature measurement system, see Figure 3 ;

[0088] The all-fiber temperature measurement system was used to calibrate the optical fiber temperature measurement sensor, and the constant temperature heating table was used to control the experimental temperature, and the temperature test range was 30-130℃, and the resolution was 0.01℃; the thermocouple thermometer was bound with the probe to serve as the actual value of the temperature, and the FIR value corresponding to the temperature was recorded (five samples were taken at each temperature point, the average value was taken, and the standard deviation was calculated), to complete the temperature calibration and sensing; the measured FIR and temperature were exponentially fitted, and the fitting result is shown in Figure 4 , and the error bar in the figure is almost negligible, that is, the Yb 3+ / Er 3+ co-doped glass material based on fluorescence intensity ratio for temperature measurement has high stability and reliable temperature data.

[0089] The calibrated all-fiber temperature measurement system was used for performance test, and the upconversion luminescence intensity of Examples 1-10 and Comparative Examples 1-2 was tested under the excitation of a 980 nm laser.

[0090] Figure 5The graph shows the change in upconversion luminescence intensity with Er₂O₃ concentration while keeping other component concentrations constant. The Er₂O₃ concentration increases from 0.5 wt% to 3.00 wt%. Curves 1-4 correspond to Examples 1-4. As can be seen from the graph, the upconversion luminescence intensity gradually decreases with increasing Er₂O₃ concentration. This is because when Er₂O₃ concentration increases... 3+ As concentration increases, the average distance between ions shortens, increasing the probability of cross relaxation and energy migration to non-radiative traps, leading to a significant concentration quenching effect; FIR thermometry depends on Er. 3+ ion 2H 11 The thermal equilibrium population state between the / 2 and 4S3 / 2 energy levels; a high signal strength can significantly improve the signal-to-noise ratio of the emission peaks of the two energy levels, thereby improving temperature resolution. Excessively high Er... 3+ Concentration will reduce the intensity of the two peaks, causing the slope of the FIR curve to decrease and the sensitivity to drop; therefore, the optimal Er 3+ The concentration range is 0.50–1.00 wt%, within which both luminescence intensity and energy transfer efficiency can be balanced.

[0091] Figure 6 This is a comparison graph showing the change in upconversion luminescence intensity with Yb₂O₃ concentration while keeping other component concentrations constant. The Yb₂O₃ concentration increases from 0 wt% to 5.00 wt%. Curves 5-8 correspond to Examples 5-8. As shown in the graph, the upconversion luminescence intensity increases with Yb₂O₃ concentration. 3+ The effect is significantly enhanced with increasing concentration; this is because of Yb 3+ It has a large absorption cross-section and a wide absorption band, which can efficiently absorb pump light and direct it to Er 3+ Energy transfer is performed, thereby improving the overall luminous efficiency; a stronger upconversion luminous signal enables 2H 11 The improved measurement accuracy of the / 2 and 4S3 / 2 emission peaks reduces random noise errors in temperature calculations, thereby enhancing temperature measurement sensitivity and repeatability.

[0092] Figure 7 This is a comparison chart showing the change in upconversion luminescence intensity with Gd₂O₃ concentration while keeping the concentrations of other components constant. Figure 7 Curve S1 corresponds to Example 9, and Gd2O3:0% corresponds to Comparative Example 1. As shown in the figure, the luminescence intensity of the sample containing Gd2O3 under 980nm excitation is significantly higher than that of the sample without Gd2O3, with an increase exceeding 85%. Without Gd2O3, the proportion of high-frequency vibrational groups in the glass increases, and the multiphonon relaxation rate accelerates, leading to an increase in Er... 3+The excited state lifetime is shortened, and the luminescence quantum efficiency is reduced; the sample containing Gd2O3 is superior to the sample without Gd2O3 in the aspect of heat treatment stability; the lower luminescence intensity leads to the signal attenuation of the FIR temperature measurement curve, and the signal noise ratio is reduced more obviously in the high temperature region, and the temperature measurement resolution is reduced; the addition of Gd2O3 can ensure that the signal noise ratio of the temperature measurement curve remains stable in the whole temperature region.

[0093] Figure 8 For the case that the concentrations of other components are unchanged, the contrast graph of the up-conversion luminescence intensity changing with the BaF2 concentration is as follows, Figure 8 The curve S1 in the graph corresponds to Example 10, and BaF2: 0% corresponds to Comparative Example 2. As can be seen from the graph, the glass viscosity of the sample without BaF2 is significantly increased, the melt flowability is reduced, and the forming difficulty in the preparation process is large; the Er 3+ The luminescence intensity is obviously reduced, it is speculated that the introduction of BaF2 reduces the phonon energy of the glass matrix, reduces the non-radiation loss; the optical uniformity and the transparency of the finished product of the sample containing BaF2 are superior to those of the sample without BaF2; reducing the phonon energy can prolong the lifetime of the upper energy level, enhance the emission peak intensity of the two thermal coupling energy levels, make the temperature fitting curve smoother and reduce the error. 3+ The above described, only for the preferred specific embodiments of the present application, but the protection scope of the present application is not limited to this, any skilled in the art of the technical personnel in the technical range disclosed by the present application, according to the technical scheme of the present application and the invention concept to equivalent replacement or change, should be covered in the protection scope of the present application.

[0094] The above described, only for the preferred specific embodiments of the present application, but the protection scope of the present application is not limited to this, any skilled in the art of the technical personnel in the technical range disclosed by the present application, according to the technical scheme of the present application and the invention concept to equivalent replacement or change, should be covered in the protection scope of the present application.

Claims

1. A Yb 3+ / Er 3+ co-doped glass material for measuring temperature based on fluorescence intensity ratio, characterized in that, The composition of the co-doped glass material comprises SiO2: 20.00-25.00wt%, AlF3: 6.00-7.00wt%, BaF2: 28.00-35.00wt%, BaO: 6.00-13.00wt%, Gd2O3: 18.00-24.00wt%, Er2O3: 0.50-3.00wt%, Yb2O3: 3.00-5.00wt%, and the total of the composition is 100wt%.

2. The Yb 3+ / Er 3+ co-doped glass material according to claim 1, characterized in that The concentration of Er2O3 is 0.50-1.00wt%.

3. The Yb3+-Er3+co-doped glass material for measuring temperature based on fluorescence intensity ratio according to claim 1 or 2, wherein the glass material is a fluoride glass material. 3+ / Er 3+ co-doped glass material, characterized in that, The concentration of Yb2O3 is 4.00-5.00wt%.

4. A Yb 3+ / Er 3+ co-doped glass material for measuring temperature based on fluorescence intensity ratio according to any one of claims 1 to 3, wherein the glass material is a glass-ceramic material. After mixing the raw materials, calcination and annealing are performed. ​​ 5. The Yb 3+ / Er 3+ glass material according to claim 4, wherein the glass material is a glass material for a fiber amplifier. The calcination temperature is 1200-1800℃. Preferably, the calcination temperature is 1500℃.

6. The Yb 3+ / Er 3+ co-doped glass material according to claim 4 or 5, wherein the glass material is a glass-ceramic material. The calcination time is 20-60min. Preferably, the calcination time is 30min.

7. The Yb 3+ / Er 3+ glass material according to any one of claims 4 to 6, wherein the glass material is a glass material for measuring a temperature based on a fluorescence intensity ratio. The annealing temperature is 500-800℃. Preferably, the annealing temperature is 600℃.

8. A Yb / Er co-doped glass material for temperature measurement based on fluorescence intensity ratio according to any one of claims 1 to 3. 3+ / Er 3+ co-doped glass material or a Yb / Er co-doped glass material prepared by the method according to any one of claims 4 to 7. 3+ / Er 3+ application of a Yb / Er co-doped glass material in temperature measurement.

9. The Yb 3+ / Er 3+ co-doped glass material for use in temperature testing, characterized in that The co-doped glass material is ground into powder, mixed with ultraviolet curing glue, and then immersed in the end face of a multimode optical fiber for curing.

10. The Yb 3+ / Er 3+ co-doped glass material for use in temperature testing, characterized in that The curing time is 2-10min.

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