CN106746621B - erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof - Google Patents

erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof Download PDF

Info

Publication number
CN106746621B
CN106746621B CN201611115573.4A CN201611115573A CN106746621B CN 106746621 B CN106746621 B CN 106746621B CN 201611115573 A CN201611115573 A CN 201611115573A CN 106746621 B CN106746621 B CN 106746621B
Authority
CN
China
Prior art keywords
glass
temperature
erbium
ytterbium
optical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611115573.4A
Other languages
Chinese (zh)
Other versions
CN106746621A (en
Inventor
田颖
井绪峰
李兵朋
黄飞飞
徐时清
张军杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Metrology
Original Assignee
China University of Metrology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Metrology filed Critical China University of Metrology
Priority to CN201611115573.4A priority Critical patent/CN106746621B/en
Publication of CN106746621A publication Critical patent/CN106746621A/en
Application granted granted Critical
Publication of CN106746621B publication Critical patent/CN106746621B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/04—Compositions for glass with special properties for photosensitive glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/253—Silica-free oxide glass compositions containing germanium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7775—Germanates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses erbium-ytterbium co-doped lead-free fluorine germanate glass for high-temperature optical sensing, which is characterized in that erbium ions and ytterbium ions are added into the fluorine germanate glass, the erbium ions and ytterbium ions can be highly doped in the fluorine germanate glass, the pumping energy utilization rate and the luminous efficiency can be further improved, high-sensitivity temperature sensing can be realized in a shorter optical fiber, and the practicability of a temperature sensor is improved. Compared with the prior erbium-doped optical glass sensing material, the erbium-ytterbium co-doped lead-free fluorine germanate glass overcomes the inherent defects of fluoride sulfide glass and silicate (borate) glass as the optical sensing material, has higher working upper limit temperature and temperature measurement sensitivity, and can be made into optical fibers to be widely applied to the field of microwave heating temperature measurement.

Description

Erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof
Technical Field
the invention relates to an optical sensing material, in particular to erbium-ytterbium co-doped lead-free fluorine germanate glass of a high-temperature optical sensing material and a preparation method thereof, which are suitable for the field of microwave heating temperature measurement.
background
The microwave heating has the characteristics of high efficiency, high speed, heating of materials through self dielectric loss and the like, and is widely applied to the fields of food processing, material drying, medicine disinfection, household cooking and the like. But due to the presence of strong electromagnetic fields. The temperature measurement in the microwave field is a technical problem, so that most of the existing microwave heating equipment is lack of an effective and low-cost temperature detection component, the microwave heating is difficult to control the temperature, the phenomenon of overheating or insufficient heating is caused, and the effect of the microwave heating is influenced.
Because the optical fiber resists electromagnetic interference, the body is small, the weight is light, the bending is easy, and the optical fiber is suitable for being used in the severe environments of flammability, explosiveness, strict space limitation, strong electromagnetic interference and the like. Therefore, the optical fiber temperature sensing technology based on the fluorescence intensity ratio technology measures the intensity of two light beams emitted between adjacent energy levels of rare earth ions of the same sensing material related to the temperature, has high accuracy, lower cost and simple detection, well overcomes the interference of the environment by utilizing a relative ratio, and remarkably improves the measurement sensitivity and the upper limit temperature. And the proper rare earth doped sensing material becomes a key problem for restricting the optical temperature sensor.
At present, great progress is made on optical temperature sensors based on erbium-doped fluoride and sulfide glass materials, but the highest working temperature of the optical temperature sensors is lower than 523K due to the poor physicochemical properties of fluorides and sulfides. In recent years, erbium-doped silicate or borosilicate glass also shows potential as an optical temperature sensing material, the physical and chemical properties of the erbium-doped silicate or borosilicate glass are superior to those of fluoride and sulfide systems, the measurement upper limit temperature is expected to be improved, but due to the fact that the phonon energy of the erbium-doped silicate or borosilicate glass is high, the up-conversion luminous efficiency is low, and the measurement sensitivity is limited. Therefore, the development of a proper environment-friendly erbium-doped glass optical fiber material is urgently needed, so that the working temperature range and the luminous efficiency of the optical temperature sensor component are improved, and the erbium-doped glass optical fiber material is suitable for the microwave heating fields of food processing, material drying, medicine disinfection, household cooking and the like.
Disclosure of Invention
The invention aims to overcome the technical defects and provides erbium-ytterbium co-doped lead-free fluorine germanate glass for high-temperature optical sensing materials and a preparation method thereof.
The fluorine germanate glass fuses the advantages of germanate and fluoride glass, has moderate phonon energy, good glass forming performance and easy preparation, can realize high doping in the fluorine germanate glass by adding ytterbium ions, erbium and ytterbium ions, can further improve the pumping energy utilization rate and the luminous efficiency, can realize high-sensitivity temperature sensing in shorter optical fibers, and improves the practicability of a temperature sensor. Compared with the prior erbium-doped optical glass sensing material, the material overcomes the inherent defects of fluoride sulfide glass (poor thermal stability and low upper limit temperature of heat sensing work) and silicate (borate) glass (higher phonon energy, low luminous efficiency and low temperature measurement sensitivity) as the optical sensing material, and provides a suitable matrix material for an optical temperature sensor.
Erbium ytterbium co-doped lead-free fluorine germanate glass
The specific technical solution of the invention is as follows:
The erbium-ytterbium co-doped lead-free fluorine germanate glass for the high-temperature optical sensing material comprises the following components in percentage by mole:
Wherein R is a combination of at least one of Ga and Y, Gd;
Preferably, R is2O3medium Ga2O3the raw materials account for 6-16 mol percent.
preferably, the R is Ga, Y, Gd, 6, 5 and 4 (molar ratio).
The actions of the respective components and the reasons why the above composition ranges are preferable will be described below.
GeO2Is an important essential component which functions as a glass network structure former. In order to ensure the physicochemical stability of the glass, GeO is added2The content of (A) is higher than 46%. GeO, on the other hand2When the content is too high, the melting temperature is increased firstly, the preparation difficulty is increased, in addition, the total amount of other components is too small, the glass is unstable, the actual preparation of large-size germanate glass is not facilitated, and large snowflake-shaped crystallization and GeO crystallization are easy to occur2The content should be less than or equal to 54%.
R2O3wherein R represents Ga, and at least one of Y and Gd, which have high refractive index, can keep low dispersion of the glass and improve the refractive index. Ga. The introduction of Gd and Y reduces the reflection loss of the glass, is beneficial to enhancing the absorption of the material to the pump light, and improves the pumping efficiency. By introducing the combination of Ga and at least one of Y or Gd, the thermal stability parameter (the difference between the initial crystallization temperature and the glass transition temperature) of the glass is improved, so that the glass has a wider operation range in the optical fiber drawing process, and the glass is increasedThe difficulty of crystallization is favorable for drawing optical fiber. Further, the multicomponent glass has an effect of improving stability by introducing a plurality of components of Ga, Y and Gd, but it is not preferable to introduce the components excessively. The excessive introduction causes incomplete melting of the glass components and unstable and devitrified glass.
The Ba ions mainly have the effects of improving the stability of the glass and the hardness and the refractive index of the glass, but the balance of the Ba ions and other components is damaged by excessive introduction, so that 10-20 mol% of the Ba ions are introduced.
The Li ions mainly serve to lower the viscosity of the glass, the glass transition temperature, and make the glass easier to manufacture, but excessive introduction may result in a decrease in the stability of the glass. In the alkali metals, the effect of improving the stability of lithium ions is the largest, and the introduction of excessive alkali metals is not beneficial to the stability of the glass, so that only 10-20 mol% of lithium ions are selectively introduced.
R3+，Ba2+，Li+And rare earth ions are introduced in a fluoride form, and the existence of the fluoride ions can further reduce the melting temperature of the glass, so that the preparation of the glass is more facilitated. On the other hand, the introduction of the fluoride can reduce the phonon energy of the glass and improve the luminous efficiency of the rare earth ions in a visible wave band.
Er ion as a light-emitting ion due to its structure2H11/2And4S3/2The energy level interval of the energy level is moderate, belongs to thermal coupling energy level, when the temperature is increased,4S3/2Particles at energy levels are advantageously excited to2H11/2the energy level of the energy is,2H11/2And4S3/2the fluorescence intensities of the two energy levels are respectively represented by IHAnd ISExpressed, the ratio satisfies the following relationship
wherein C is a constant, k is Boltzmann's constant, T is temperature, and Δ E is2H11/2And4S3/2The energy gap size of the two energy levels.
Logarithmic form of distortion
the sensitivity (S) of the optical temperature sensor can be obtained by differentiating the above formula
After the rare earth Yb ions are introduced, the pumping energy and the luminous efficiency of erbium ions can be further improved, and the erbium ytterbium ions can realize high doping in the fluorine germanate glass, so that high-sensitivity temperature sensing can be realized in a shorter optical fiber, and the practicability of the temperature sensor is improved.
For fluorogermanate glass, the selected oxides and fluorides have different contributions to performance parameters such as refractive index, temperature refractive index coefficient and the like, the oxides are positive temperature refractive index coefficients, and the fluorides are negative temperature refractive index coefficients. The excessive introduction of fluoride can cause the change of the physical and chemical properties of the glass, and the crucible can be corroded and the stripes are generated due to the large volatilization of fluorine in the preparation process, so that the industrial production of the optical fiber is not facilitated. The content of fluoride and oxide of the fluorine germanate glass is designed and optimized to be adjusted through the components, so that the stable fluorine germanate glass optical fiber material with extremely low optical distortion coefficient can be controllably prepared.
The preparation method of the erbium-ytterbium co-doped fluorine germanate lead-free glass comprises the following steps:
Uniformly mixing the components to obtain a mixture, putting the mixture into a covered platinum crucible, putting the crucible into a silicon-carbon rod electric furnace, heating along with the furnace, setting the heating rate to be 25K/min, continuously melting for 40-50 minutes when the furnace temperature reaches 1300-1400 ℃ to obtain molten glass liquid, and introducing high-purity oxygen to remove water all the time in the melting process;
Homogenizing and clarifying the dewatered glass liquid, quickly pouring the glass liquid onto a mold preheated to 500-520 ℃, putting the mold into a muffle furnace heated to 530-560 ℃ of the glass transition temperature of the glass liquid, preserving heat for 2-3 hours, cooling to 90-100 ℃ at the speed of 9-11 ℃/hour, closing the muffle furnace, and cooling to room temperature.
has the advantages that:
(1) The erbium ytterbium co-doped lead-free fluorine germanate glass has good chemical stability and high temperature resistance, is used as an optical temperature sensing material, has a working range of 293K-750K, and has a working upper limit temperature superior to that of common glass.
(2) the erbium-ytterbium co-doped lead-free fluorine germanate glass is used as an optical temperature sensing material, has high optical sensitivity, and the sensitivity can reach 0.0024K-1The lowest can reach 0.0017K-1。
(3) since ytterbium ions can absorb more pump energy than erbium (Yb) singly doped materials2F5/2Energy level effective to transfer pump energy to erbium (Er) ions4I11/2The energy level further improves the up-conversion luminous efficiency of the erbium ions, and is beneficial to improving the sensitivity of the erbium ions as optical sensing materials.
(4) The erbium-ytterbium co-doped lead-free fluorine germanate glass does not contain toxic and harmful substance lead, avoids harm to human and environment, and is a novel high-temperature optical sensing material with great market potential.
(5) The erbium-ytterbium co-doped lead-free fluorine germanate glass has simple manufacturing process and lower production cost. The erbium ytterbium co-doped lead-free fluorine germanate glass preform can be directly drawn into an optical fiber with excellent up-conversion luminescence property. The erbium-ytterbium co-doped lead-free fluorine germanate short glass fiber is used as a probe material of the temperature sensor, has high strength, good toughness, high-voltage insulation and electromagnetic interference resistance, can timely master the temperature rise change trend at a joint, accurately judges the temperature condition of the external environment, and is small, exquisite, flexible and easy to install and maintain.
drawings
FIG. 1 is a Raman spectrum of example 1.
FIG. 2 is the upconversion fluorescence spectra of 500-600nm erbium tested in example 1 with 980nm wavelength laser diode pumping in the temperature range 300-750K. Drawing (A)The curve of the relationship between the fluorescence of the optical temperature sensing material and the temperature under the condition of 300K at middle ■, the curve of the relationship between the fluorescence of the optical temperature sensing material and the temperature under the condition of 350K at ●, the curve of the relationship between the fluorescence of the optical temperature sensing material and the temperature under the condition of 400K at T, the curve of the relationship between the fluorescence of the optical temperature sensing material and the temperature under the condition of 450K at T, and the curve of the relationship between the fluorescence of the optical temperature sensing material and the temperature under the condition of 500K at T,the change curve of the fluorescence of the optical temperature sensing material with the temperature under the condition of 550K,The change curve of the fluorescence of the optical temperature sensing material with the temperature under the condition of 600K,a curve showing the change of fluorescence with temperature of the optical temperature sensing material under 650K, a curve showing the change of fluorescence with temperature of the optical temperature sensing material under 700K,the curve of the change of the fluorescence of the optical temperature sensing material with the temperature under the condition of 750K,
FIG. 3 is a graph of temperature sensitivity curve versus temperature obtained in example 1.
Detailed Description
Table 1:
Example 1:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate to be 25K/min, putting the mixture into a covered platinum crucible, heating the mixture to 1300 ℃ along with the furnace, melting the mixture in a silicon-carbon rod electric furnace for 40 minutes to obtain molten glass, and introducing high-purity oxygen (the purity is higher than 99.995%) all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass. Homogenizing and clarifying the glass liquid with water removed, quickly pouring the glass liquid into a mold preheated to 500 ℃, quickly putting the mold into a muffle furnace heated to 540 ℃, and preserving heat for 2 hours; and reducing the temperature of the muffle furnace to 90 ℃ at the speed of 10 ℃/h, then closing the muffle furnace, and reducing the temperature to room temperature to obtain the annealed erbium-ytterbium co-doped lead-free fluorine germanate glass.
The annealed erbium ytterbium co-doped lead-free fluorogermanate glass was processed into 10 × 20 × 1 mm glass slides and polished for spectroscopic testing. Moderate glass phonon energy can effectively promote the up-conversion luminescence of rare earth ions. Through Raman spectrum testing, as shown in FIG. 1, the maximum phonon energy of example 1 is about 900 wave numbers, which is smaller than silicate glass and quartz glass (about 1100 wave numbers), and the substrate is beneficial to obtaining high-efficiency up-conversion luminescence, does not need high-power laser pumping, and reduces the cost of the sensor. The upconversion fluorescence spectrum of the 980nm semiconductor laser with the power of 300mW and the wavelength band of 500-600nm erbium in the temperature range of 300-750K is tested. As shown in FIG. 2, the erbium ytterbium co-doped lead-free fluoro-germanate glass obtained in this example can emit lights with center wavelengths of 528nm and 546 nm. From the measured up-conversion fluorescence spectra, the fluorescence intensity ratio at 528nm to 546nm at different temperatures was calculated (R ═ I528/I546). The fluorescence intensity ratio and the sensitivity (S) of the optical temperature sensor satisfy the following relationship
FIG. 3 shows the temperature dependence of the optical temperature sensing sensitivity of example 1 in the range of 300-750K, which can reach 0.0022K-1minimum 0.0018K-1It can be used as high-temperature optical temperature sensing material.
Example 2:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate to be 25K/min, putting the mixture into a covered platinum crucible, heating to 1400 ℃ along with the furnace, melting for 50 minutes in a silicon-carbon rod electric furnace to obtain molten glass liquid, and introducing high-purity oxygen all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass liquid. Homogenizing and clarifying the glass liquid with the water removed, quickly pouring the glass liquid into a mold preheated to 520 ℃, quickly placing the mold into a muffle furnace heated to 550 ℃, preserving the temperature for 3 hours, reducing the temperature to 90 ℃ at the speed of 11 ℃/hour, closing the muffle furnace, and reducing the temperature to room temperature to obtain the annealed erbium-ytterbium co-doped lead-free fluogermanate glass.
The erbium-ytterbium co-doped lead-free fluorine germanate glass prepared in the embodiment is transparent, the annealed glass is processed into a glass sheet with the size of 10 multiplied by 20 multiplied by 1 mm and polished, and the up-conversion fluorescence spectrum of erbium with the wave band of 500-600nm within the temperature range of 300-750K is tested under the pumping of a 980nm semiconductor laser. By the result of the up-conversion of the fluorescence spectrum, the fluorescence intensity ratio of 528nm to 546nm at different temperatures is calculated, and by utilizing the relation between the fluorescence intensity ratio and the sensitivity (S) of optical temperature sensing, the temperature range of 300-750K and the optical sensitivity range of 0.0019-0.0021K of example 3 are respectively controlled-1it can be used as optical temperature sensing material.
Example 3:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate at 25K/min, putting the mixture into a covered platinum crucible, heating to 1350 ℃ along with the furnace, melting for 45 minutes in a silicon-carbon rod electric furnace to obtain molten glass, and introducing high-purity oxygen all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass. Homogenizing and clarifying the glass liquid with the water removed, quickly pouring the glass liquid into a mold preheated to 510 ℃, quickly placing the glass liquid into a muffle furnace heated to 545 ℃, preserving the heat for 2.5 hours, reducing the temperature to 95 ℃ at the speed of 10 ℃/hour, closing the muffle furnace, and reducing the temperature to the room temperature to obtain the annealed ytterbium-erbium co-doped lead-free fluogermanate glass.
The erbium-ytterbium co-doped lead-free fluorine germanate glass prepared in the embodiment is transparent, the annealed glass is processed into a glass sheet with the size of 10 multiplied by 20 multiplied by 1 mm and polished, and the up-conversion fluorescence spectrum of erbium with the wave band of 500-600nm within the temperature range of 300-750K is tested under the pumping of a 980nm semiconductor laser. The fluorescence intensity ratio of 528nm to 546nm at different temperatures is calculated by up-conversion fluorescence spectrum, and the optical sensitivity range of the embodiment 3 is 0.0019-0.0021K within the temperature range of 300-750K by using the relation of the fluorescence intensity ratio and the sensitivity (S) of optical temperature sensing-1It can be used as optical temperature sensing material.
Example 4:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate at 25K/min, putting the mixture into a covered platinum crucible, heating to 1380 ℃ along with the furnace, melting for 48 minutes in a silicon-carbon rod electric furnace to obtain molten glass liquid, and introducing high-purity oxygen all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass liquid. Homogenizing and clarifying the glass liquid with the water removed, quickly pouring the glass liquid into a mold preheated to 515 ℃, quickly placing the mold into a muffle furnace heated to 560 ℃, preserving the temperature for 3 hours, reducing the temperature to 95 ℃ at the speed of 11 ℃/hour, closing the muffle furnace, and reducing the temperature to room temperature to obtain the annealed erbium-ytterbium co-doped lead-free fluogermanate glass.
the erbium-ytterbium co-doped lead-free fluorine germanate glass prepared in the embodiment is transparent, the annealed glass is processed into a glass sheet with the size of 10 multiplied by 20 multiplied by 1 mm and polished, and the up-conversion fluorescence spectrum of erbium with the wave band of 500-600nm within the temperature range of 300-750K is tested under the pumping of a 980nm semiconductor laser. The fluorescence intensity ratio of 528nm to 546nm at different temperatures is calculated by up-conversion fluorescence spectrum, and the optical sensitivity range of example 4 is 0.0018-0.0023K within the temperature range of 300-750K by using the relation of the fluorescence intensity ratio and the sensitivity (S) of optical temperature sensing-1It can be used as optical temperature sensing material.
Example 5:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate to be 25K/min, putting the mixture into a covered platinum crucible, heating the mixture to 1310 ℃ along with the furnace, melting the mixture for 42 minutes in a silicon-carbon rod electric furnace to obtain molten glass, and introducing high-purity oxygen all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass. Homogenizing and clarifying the glass liquid with the water removed, quickly pouring the glass liquid into a mold preheated to 505 ℃, quickly placing the glass liquid into a muffle furnace heated to 530 ℃, preserving the heat for 2.2 hours, reducing the temperature to 90 ℃ at the speed of 10 ℃/hour, closing the muffle furnace, and reducing the temperature to the room temperature to obtain the annealed ytterbium-erbium co-doped lead-free fluogermanate glass.
The erbium-ytterbium co-doped lead-free fluorine germanate glass prepared in the embodiment is transparent, the annealed glass is processed into a glass sheet with the size of 10 multiplied by 20 multiplied by 1 mm and polished, and the up-conversion fluorescence spectrum of erbium with the wave band of 500-600nm within the temperature range of 300-750K is tested under the pumping of a 980nm semiconductor laser. The fluorescence intensity ratio of 528nm to 546nm at different temperatures is calculated by up-conversion fluorescence spectrum, and the optical sensitivity range of example 5 is 0.0017-0.0024K within the temperature range of 300-750K by using the relation of the fluorescence intensity ratio and the sensitivity (S) of optical temperature sensing-1It can be used as optical temperature sensing material.
Example 6:
Calculating the weight of each corresponding component according to the formula in the table 1, weighing each raw material and uniformly mixing; setting the heating rate at 25K/min, putting the mixture into a covered platinum crucible, heating to 1350 ℃ along with the furnace, melting for 45 minutes in a silicon-carbon rod electric furnace to obtain molten glass, and introducing high-purity oxygen all the time in the glass melting process to carry out atmosphere protection so as to remove moisture in the glass. Homogenizing and clarifying the glass liquid with the water removed, quickly pouring the glass liquid into a mold preheated to 515 ℃, quickly placing the mold into a muffle furnace heated to 535 ℃, preserving the temperature for 2.5 hours, reducing the temperature to 90 ℃ at the speed of 10 ℃/hour, closing the muffle furnace, and reducing the temperature to the room temperature to obtain the annealed ytterbium-erbium co-doped lead-free fluogermanate glass.
erbium ytterbium codoped leadless fluorine germanate prepared by the embodimentThe glass is transparent, the annealed glass is processed into a glass sheet with the thickness of 10 multiplied by 20 multiplied by 1 mm and polished, and the upconversion fluorescence spectrum of erbium with the wave band of 500-600nm in the temperature range of 300-750K is tested under the pump of a 980nm semiconductor laser. The fluorescence intensity ratio of 528nm to 546nm at different temperatures is calculated by up-conversion fluorescence spectrum, and the optical sensitivity range of example 6 is 0.0017-0.0021K at 300-750K temperature range by using the relation between the fluorescence intensity ratio and the sensitivity (S) of optical temperature sensing-1It can be used as optical temperature sensing material.
The erbium-ytterbium co-doped lead-free fluorine germanate glass prepared by the invention has transparent glass, moderate phonon energy, up-conversion luminous intensity within the temperature range of 293K-750K and optical sensitivity within the range of 0.0017K-1-0.0024K-1The high-sensitivity high-working-limit temperature sensor has high sensitivity and high working upper limit temperature, and can be used as a novel high-temperature optical sensing material.

Claims (3)

1. The erbium-ytterbium co-doped lead-free fluorine germanate glass for the high-temperature optical sensing material is characterized by comprising the following raw materials in percentage by mole:
GeO2 46~54 mol%
R2O3 15~20 mol%
BaF2 10~20 mol%
LiF 10~20 mol%
ErF3 2~4 mol%
YbF3 2~4 mol%
Said R2O3Wherein R is the combination of Ga, Y and Gd, and the molar ratio of Ga to Y to Gd is 6 to 5 to 4.
2. a method for preparing the erbium ytterbium co-doped lead-free fluoro-germanate glass as claimed in claim 1, wherein the method comprises the following steps:
Uniformly mixing the raw material components as claimed in claim 1 to obtain a mixture, putting the mixture into a covered platinum crucible, putting the crucible into a silicon-carbon rod electric furnace, heating along with the furnace, setting the heating rate to be 25K/min, continuously melting for 40-50 minutes when the furnace temperature reaches 1300-1400 ℃ to obtain molten glass liquid, and introducing high-purity oxygen to remove water in the melting process;
Homogenizing and clarifying the glass liquid after water removal, then quickly pouring the glass liquid onto a mold preheated to 500-520 ℃, putting the mold into a muffle furnace heated to 530-560 ℃ of the glass transition temperature of the glass liquid, preserving the heat for 2-3 hours, then cooling to 90-100 ℃ at the speed of 9-11 ℃/hour, then closing the muffle furnace, and cooling to room temperature to obtain the erbium-ytterbium co-doped lead-free fluorine germanate glass.
3. The erbium ytterbium co-doped lead-free fluorine germanate glass as claimed in claim 1 for use in optical fiber.
CN201611115573.4A 2016-12-07 2016-12-07 erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof Active CN106746621B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611115573.4A CN106746621B (en) 2016-12-07 2016-12-07 erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611115573.4A CN106746621B (en) 2016-12-07 2016-12-07 erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106746621A CN106746621A (en) 2017-05-31
CN106746621B true CN106746621B (en) 2019-12-13

Family

ID=58881197

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611115573.4A Active CN106746621B (en) 2016-12-07 2016-12-07 erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106746621B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112410032A (en) * 2020-11-20 2021-02-26 浙江大学 Erbium silicate for realizing sensitized luminescence based on energy transfer among particles and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54127911A (en) * 1978-03-29 1979-10-04 Fujitsu Ltd Optical glass
CN102211873A (en) * 2011-03-23 2011-10-12 中国科学院上海光学精密机械研究所 3mu m luminous rare-earth ion-doped fluogermanate laser glass and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54127911A (en) * 1978-03-29 1979-10-04 Fujitsu Ltd Optical glass
CN102211873A (en) * 2011-03-23 2011-10-12 中国科学院上海光学精密机械研究所 3mu m luminous rare-earth ion-doped fluogermanate laser glass and preparation method thereof

Also Published As

Publication number Publication date
CN106746621A (en) 2017-05-31

Similar Documents

Publication Publication Date Title
Maheshvaran et al. Concentration dependent Eu3+ doped boro-tellurite glasses—Structural and optical investigations
Stambouli et al. Optical and spectroscopic properties of Eu-doped tellurite glasses and glass ceramics
Vijayakumar et al. Structural and optical studies on Dy3+: Tb3+ co-doped zinc leadfluoro-borophosphate glasses for white light applications
Linganna et al. 1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses
Shinozaki et al. High quantum yield and low concentration quenching of Eu3+ emission in oxyfluoride glass with high BaF2 and Al2O3 contents
CN110407462B (en) Rare earth doped silicate glass and preparation method and application thereof
CN102659313B (en) Near-infrared broadband luminescence erbium and thulium-co-doped bismuthate laser glass and preparation method thereof
Dantas et al. High quantum efficiency of Nd 3+ ions in a phosphate glass system using the Judd–Ofelt theory
Yanmin et al. Thermal stability and spectroscopic properties of Ho3+ doped tellurite-borate glasses
Effendy et al. Characterization and optical properties of erbium oxide doped ZnO–SLS glass for potential optical and optoelectronic materials
Pisarski et al. Towards lead-free oxyfluoride germanate glasses singly doped with Er3+ for long-lived near-infrared luminescence
Mariselvam et al. A novel Er3+ ions doped zirconium magnesium borate glass with very high quantum efficiency for green laser and optical amplifier applications
Liang et al. Er3+/Yb3+ co-doped SiO2-Al2O3-CaO-CaF2 glass: Structure, JO analysis and fluorescent properties
Vijayakumar et al. Influence of Zn2+ concentration on the luminescence properties of Dy3+ ions doped zinc strontium alumino-telluroborate glasses for light emitting applications
CN106746621B (en) erbium-ytterbium co-doped lead-free fluorine germanate glass of high-temperature optical sensing material and preparation method thereof
Luewarasirikul et al. Spectroscopic properties and Judd-Ofelt analysis of Sm3+ ions in barium sodium borate glasses
Jiménez de Castro et al. Infrared luminescence of erbium-doped sodium lead germanate glass
Liang et al. Study of concentration and temperature-dependent photoluminescence properties in DyF3-doped fluorophosphate glasses for thermal stable photonic device
Mohan et al. Optical properties of alkali and alkaline-earth lead borate glasses doped with Nd 3+ Ions
CN112194365A (en) Erbium-ytterbium co-doped oxyfluoride tellurate glass and preparation method thereof
CN108892375B (en) Silicon silicate glass and preparation method thereof
CN109354402A (en) A kind of ytterbium erbium Codoped Phosphate Glass and preparation method thereof and purposes
CN112110648B (en) Holmium-ytterbium co-doped oxyhalide system mid-infrared glass and preparation method thereof
Koçyiğit et al. The impact of heat treatment on the luminescence properties of Dy/Ag co-doped sodium alumina borate glasses
Yung et al. Concentration effect of Yb3+ on the thermal and optical properties of Er3+/Yb3+-codoped ZnF2–Al2O3–P2O5 glasses

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant