CN108977882B - Sesquioxide single crystal optical fiber and preparation method and application thereof - Google Patents
Sesquioxide single crystal optical fiber and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/32—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres
- G01K11/3206—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres at discrete locations in the fibre, e.g. using Bragg scattering
- G01K11/3213—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres at discrete locations in the fibre, e.g. using Bragg scattering using changes in luminescence, e.g. at the distal end of the fibres
Abstract
The invention relates to a sesquioxide single crystal optical fiber and a preparation method and application thereof, wherein the chemical composition of the optical fiber is lutetium oxide single crystal doped with fluorescent ions, and the fluorescent ions are Tm3+、Yb3+Or Ho3+. The diameter range is 0.7-2.0mm, the length>10 cm. The invention adopts a laser heating pedestal method to grow lutetium oxide single crystal optical fiber, and the melting point of the lutetium oxide single crystal optical fiber is up to 2510 ℃. Inventive doping of Tm3+、Yb3+、Ho3+The lutetium oxide single crystal optical fiber combines the excellent physical and chemical properties of high thermal conductivity, high hardness, high strength, high toughness and stable chemical property of the single crystal optical fiber and Tm3+、Yb3+、Ho3+The fluorescence doped ion has the advantages of high sensitivity, wide frequency band width and the like, and can be used for preparing novel high-temperature fluorescence detection materials.
Description
Technical Field
The invention relates to a novel single crystal optical fiber and a preparation method and application thereof, in particular to a sesquioxide (lutetium oxide, yttrium oxide and scandium oxide) single crystal optical fiber and a preparation method and application thereof, belonging to the technical field of crystals and devices.
Background
High temperature detection plays a key role in many fields such as metallurgy, materials, energy, chemical engineering, aerospace, weapon tests and the like. At present, temperature measurement is mainly realized through a thermocouple, the temperature measurement needs to be in contact with a measured object, and the temperature measurement range is narrow. However, with the technical requirements, some special working environments need to be measured, such as: jet turbines, rocket engines, gas centrifuges, gas turbines, which operate internally. The traditional temperature measurement mode can not meet the requirements of the current life and science and technology, and high-melting point sesquioxide is needed to carry out high-temperature fluorescence temperature detection.
Currently, the commonly used high-temperature detection material mainly comprises Eu3+Doped YAG and ceramic film plated sapphireA single crystal silica optical fiber. Since Eu is used3+The fluorescence high temperature measurement has the phenomenon of high temperature quenching, the fluorescence conversion efficiency is low, and the measurement range of the high temperature fluorescence ratio is limited. The sapphire high-temperature optical fiber is adopted for high-temperature detection, the signal-to-noise ratio of a test result is not ideal, and the test temperature can reach about 2000 ℃. Temperature measurement for higher temperature environments has not been applicable.
Chinese patent document CN106908168A (application number: 201710088470.1) discloses a high-sensitivity temperature sensing method based on neodymium ion near-infrared fluorescence: incorporation of Nd in phosphate3+And Yb3+Ion testing the photoluminescence spectra of the materials at different temperatures to obtain a standard curve of the fluorescence intensity ratio changing along with the ambient temperature; and comparing the fluorescence intensity ratio at the temperature to be measured with the standard curve to obtain the measured value of the environmental temperature to be measured. The invention improves the signal-to-noise ratio of the system and the high-temperature fluorescence intensity. However, the rare earth doped phosphate glass has a narrow measurement range, and only the measurement in a medium and low temperature region can be realized.
The high-temperature fluorescence temperature measurement is to mix powder into a measured system or smear the powder on the surface of a measured object to be used as a fluorescence temperature probe, a transient temperature field is generated by irradiating pulse laser of a heat source on the measured system or the measured object, the temperature is represented according to the change relation of a fluorescence intensity ratio along with the temperature, and the interference of external factors, such as the loss of optical fibers, the noise of a pumping light source and the like, can be effectively overcome due to the fact that the fluorescence intensity ratio is detected, and therefore the measurement accuracy is improved. In some high-temperature measurement, such as an aerospace engine, a rocket engine, a gas turbine and the like, the high-temperature measurement becomes a long-bedevided technical problem due to high temperature, severe environment and a plurality of influence factors. Therefore, developing a probe material with a higher temperature and improving the measurement accuracy and stability become technical problems to be solved in the field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a sesquioxide single crystal optical fiber, a preparation method and application thereof, in particular to a lutetium oxide doped single crystal optical fiber which can be used as a high-temperature measuring material.
The technical scheme of the invention is as follows:
a fluorescence ion doped lutetium oxide single crystal optical fiber comprises a fluorescence ion doped lutetium oxide single crystal as a chemical composition, wherein Tm is the fluorescence ion3+、Yb3+Or Ho3+。
According to the present invention, preferably, the doping molar ratios of the fluorescent ions based on the molar content of the total raw materials are respectively: tm is2O3 3％-7％、Yb2O3 4％-8％、Ho2O3 0.05％-0.2％。
According to the present invention, preferably, the optical fiber has a circular cross section.
According to the present invention, it is preferred that the optical fiber has a diameter of 0.7 to 1.5mm, further preferably 0.75 to 1 mm;
preferably, the length of the optical fiber is more than or equal to 15 cm.
According to the present invention, the aspect ratio (length to diameter ratio) of the optical fiber is preferably greater than or equal to 100: 1.
According to the invention, preferably, the lutetium oxide single crystal is a cubic crystal system, the melting point is 2510 ℃, and the density is 9.42g/cm3Thermal conductivity (12.2) w/(m.K), refractive index @1050nm (1.91), light transmission range (140-.
The lutetium oxide single crystal fiber doped with fluorescent ions can be grown by a Laser Heating Pedestal (LHPG) method.
According to the invention, the preparation method of the fluorescent ion doped lutetium oxide single crystal optical fiber comprises the following steps:
preparing lutetium oxide doped seed crystals and source rods;
laser melting of the doped lutetium oxide source rod;
and (3) collecting the neck, shouldering, growing in an equal diameter and extracting and removing the doped lutetium oxide seed crystal in the doped lutetium oxide molten material.
According to the method for manufacturing an optical fiber of the present invention, preferably, the crystal extraction step further includes a high temperature annealing step.
According to the preparation method of the optical fiber, the preferable preparation steps of the lutetium oxide doped seed crystal and the source rod are as follows:
uniformly mixing a lutetium oxide raw material and a fluorescent ion raw material to prepare a round rod serving as a seed crystal and a source rod;
preferably, the length of the round rod is 40-120mm, and the diameter of the round rod is 2-5 mm;
further preferably, the raw materials are mixed and pressed into a round rod, and then high-temperature sintering is carried out, wherein the sintering temperature is 1250-1600 ℃, and the sintering time is kept for 12-45h, so as to obtain seed crystals and source rods.
According to the preparation method of the optical fiber, preferably, in the step of laser melting of the doped lutetium oxide source rod, the center of the source rod is placed at the center of laser for melting;
preferably, the power of the laser is 270-.
According to the preparation method of the optical fiber, the neck power is preferably 210- & lt 300 & gt. Shoulder setting, equal diameter growth power of 200-. The selection can be made according to the diameter of the polycrystalline material, the pulling speed and the concentration of doped ions.
Preferably, when the diameter of the seed crystal is narrowed to 0.5-0.7mm in the neck narrowing process, shoulder setting and equal-diameter growth are carried out;
preferably, in the process of isometric growth, the pulling speed is 0.2-1.0 mm/min;
preferably, the lutetium oxide doped source rod is fed simultaneously in the process of constant diameter growth, and the feeding speed is 0.07-0.6 mm/min.
According to the preparation method of the optical fiber, preferably, when the crystal grows to the required size in an equal diameter mode, the power of the laser is increased to 280-320W, and the crystal is extracted.
According to the preparation method of the optical fiber, preferably, in the high-temperature annealing step, the crystal is subjected to medium-high temperature annealing treatment in the air, the annealing temperature is 1100-1600 ℃, the constant temperature time is 30-48h, and the temperature is reduced at the speed of (1-1.5) ° c/min after the annealing is finished, so that the thermal stress and the defects in the crystal are eliminated, and the quality of the crystal is improved.
According to the preparation method of the optical fiber, a preferable scheme comprises the following steps:
(1) at high purity Tm2O3、Ho2O3、Lu2O3、Yb2O3The powder material is used as raw material, and the fluorescent ion powder material and lutetium oxide powder material are mixed, Lu2O384.8-92.95% of molar ratio and Tm2O33 to 7 percent of Yb2O34 to 8 percent of molar ratio and Ho2O3The molar ratio is 0.05-0.2%, and the materials are mixed for 24 hours by a mixer to be uniformly mixed; simultaneously preparing a cylindrical die with the diameter of 2-4mm and a balloon with a corresponding size; placing the balloon into a cylindrical mold, inserting a funnel into the top of the balloon, filling the raw materials into the balloon along the funnel, and compacting by using a glass rod; repeating the filling step until the length of the material rod reaches 8-10cm, and stopping filling; after the balloon is taken out of the cylindrical mold, vacuumizing the raw materials in the balloon; filling cotton from the top end of the balloon, pumping vacuum by using a vacuum pump, keeping the shape of a source rod, keeping the vacuum treatment process for 8-12min, vertically putting the balloon into an equal-diameter press after the treatment is finished, boosting the pressure to 190MPa, maintaining the pressure for 1min, and improving the uniformity of the diameter; taking out the round rods with uniform diameter, and sintering at 1250-1600 ℃ for 12-45h in a sintering furnace to obtain seed crystals and source rods with uniformly distributed fluorescent ions;
the sintering temperature and the holding time in the step can be adjusted according to the material and the doping ion species and concentration of the source rod and the size of the raw material rod, and the aim is to obtain high-quality seed crystals and source rods with uniform diameter and uniformly distributed doping.
(2) Crystal growth
a. Cleaning the furnace chamber and the laser reflector, modulating the light path uniformly, fixing the prepared source rod on the feeding device, and fixing the prepared seed crystal on the upper pulling device; increasing the power of the laser to enable the focal point of the laser to fall on the center of the source rod, uniformly heating the source rod to form a melting zone with a stable shape, and keeping the temperature for 6-8 minutes;
b. adjusting the position of the seed crystal to enable the seed crystal to be in contact with the melting zone and be positioned in the center of the melting zone, adjusting the heating power parameter to enable the melting zone and the growth interface to be stable, starting the pulling device, gradually increasing the power, and performing neck collection; when the diameter of the seed crystal is narrowed to 0.5-0.7mm, shoulder setting and equal-diameter growth are carried out; upper pulling speed in the growth process: 0.1-2.0mm/min, lower feed rate: 0.05-0.5 mm/min; the crystal has stable diameter and proper length. Closing the feeding device, and continuing pulling to pull off the crystal;
c. after the crystal growth is finished, reducing the laser power at the rate of 5-40W/min, turning off the laser, and then opening the growth furnace after flowing a flowing atmosphere for 5-12 min;
d. after the growth is finished, the crystal is taken down from the upper pulling device, and medium-high temperature annealing treatment is carried out in the air, so that the thermal stress in the crystal is eliminated, and the cracking is prevented.
The lutetium oxide single crystal optical fiber doped with fluorescent ions has the melting point as high as 2510 ℃, has a cubic crystal system, has higher strength, hardness, wear resistance and corrosion resistance, and is an ideal material for ultrahigh temperature measurement.
According to the invention, the lutetium oxide single crystal fiber doped with fluorescent ions is used as an ultrahigh temperature measuring material.
Compared with the traditional temperature measurement method, the method adopts high-temperature fluorescence temperature measurement, has simple theory, non-contact, long distance, high accuracy and wider temperature measurement range, can realize single-point temperature measurement, can realize the temperature measurement of the surface area of the whole object, can also measure the temperature in static state, steady state and high-speed dynamic state, and meets the requirements of different conditions. The sesquioxide lutetium oxide material has a high melting point (over 2400 ℃), so that the material has a great application prospect in high-temperature environments. And Tm is3+/Yb3+/Ho3+The doped fluorescent ions have good fluorescence temperature characteristics: high luminous intensity, long fluorescence lifetime, high up-conversion efficiency and the like.
The invention has the following characteristics and beneficial effects:
1. the invention utilizes the laser heating base technology to obtain the lutetium oxide single crystal optical fiber doped with fluorescent ions, the diameter of the optical fiber is within the range of 0.7-1.5mm, the length of the optical fiber reaches more than 15cm, the optical fiber has a great aspect ratio, the crystal diameter is uniform, the surface is smooth, the crystal is transparent, the doped ions are uniformly distributed, and the crystal quality is high. Is a brand new high-temperature detection material with excellent performance.
2. Compared with other materials, the fluorescent ion doped lutetium oxide single crystal optical fiber has the following advantages: the melting point is up to 2510 ℃, and the high-temperature measurement of 2000-2500 ℃ can be carried out; has excellent physical and chemical properties such as high thermal conductivity, high hardness, high strength, high toughness, stable chemical property (chemical corrosion resistance) and the like, and can work in severe environments such as high temperature, corrosive atmosphere and the like.
3. In the preparation process of the fluorescent ion doped lutetium oxide single crystal optical fiber, the crystal temperature which can be grown by a laser heating pedestal method is very high, and the doped Lu is achieved2O3The melting point temperature of (2) solves the problem that the growth cannot be realized due to the over-high melting point of the compound. Meanwhile, a stable melting zone and a growth interface are obtained by adjusting the laser power and a proper pulling ratio, and the high-quality fluorescent ion-doped lutetium oxide single crystal optical fiber with the required diameter, good uniformity, transparent crystal and uniformly distributed doped ions is obtained.
4. The present invention utilizes Tm2O3(molar ratio 3% -7%) and Yb2O3(molar ratio of 4-8 percent) and Ho2O3(the mol ratio is 0.05% -0.2%) as fluorescent ions, the fluorescent material has good fluorescence temperature characteristics: the advantages of high luminous intensity, long fluorescence lifetime, high up-conversion efficiency and the like are combined with Lu2O3High melting point and wide application in high temperature fluorescent detection.
Drawings
FIG. 1 is a photograph of a seed crystal and a source rod having a uniform distribution of fluorescent ions according to the present invention.
FIG. 2 shows a cubic phase Yb obtained in example 1 of the present invention2O3A photograph of the lutetium oxide single crystal optical fiber of (1).
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The source rod and the seed crystal described in the examples were prepared as follows:
at high purity Tm2O3、Ho2O3、Lu2O3、Yb2O3The powder material is used as raw material, and the fluorescent ion powder material and lutetium oxide powder material are mixed, Lu2O384.8-92.95% of molar ratio and Tm2O33 to 7 percent of Yb2O34 to 8 percent of molar ratio and Ho2O3The molar ratio is 0.05-0.2%, and the materials are mixed for 24 hours by a mixer to be uniformly mixed; simultaneously preparing a cylindrical die with the diameter of 2-4mm and a balloon with a corresponding size; placing the balloon into a cylindrical mold, inserting a funnel into the top of the balloon, filling the raw materials into the balloon along the funnel, and compacting by using a glass rod; repeating the filling step until the length of the material rod reaches 8-10cm, and stopping filling; after the balloon is taken out of the cylindrical mold, vacuumizing the raw materials in the balloon; filling cotton from the top end of the balloon, pumping vacuum by using a vacuum pump, keeping the shape of a source rod, keeping the vacuum treatment process for 8-12min, vertically putting the balloon into an equal-diameter press after the treatment is finished, boosting the pressure to 190MPa, maintaining the pressure for 1min, and improving the uniformity of the diameter; and taking out the pressed round rods with uniform diameters, and sintering at 1250-1600 ℃ for 12-45h in a sintering furnace to obtain seed crystals and source rods with uniformly distributed fluorescent ions.
Example 1
Yb-doped2O3The preparation method of the lutetium oxide single crystal optical fiber comprises the following steps:
(1) selection and treatment of source rods and seed crystals
Preparing doped Lu with the diameter of 2.5mm2O3(Yb2O3The molar ratio is 5 percent) of the material rod is used as a raw material and seed crystal, and the material rod is fixed on the Al with the groove by high-temperature ceramic glue2O3Dried on the rod for 6h at 70 ℃.
(2) Crystal growth
a, cleaning a furnace chamber and a laser reflector, and uniformly modulating a light path. The prepared source rod is fixed on the feeding device, and the prepared seed crystal is fixed on the upper pulling device. Increasing the power of a laser to 170W to melt the material rod, enabling the focal point of the laser to fall on the center of the material rod to obtain uniform heating, continuously increasing the power to 200W to form a stable hemispherical melting zone, and keeping the temperature constant for 8 min;
b, adjusting the position of the seed crystal to enable the seed crystal to be in contact with the melting zone and be positioned at the center of the melting zone, adjusting the heating power until the interface size is stable, starting the pulling device, gradually increasing the power to 210W, and performing neck collection. When the diameter of the seed crystal is narrowed to 0.7mm, the power is adjusted to 200W for shouldering and equal-diameter growth. Upper pulling speed in the growth process: 0.6mm/min, lower feed rate: 0.2 mm/min. When the crystal grows to the required size, the power is gradually increased to 250W, and the crystal is extracted.
c, after the crystal growth is finished, reducing the laser power at the speed of 25W/min, closing the laser, and then opening the furnace after flowing a flowing atmosphere for 10 min.
d, after the growth is finished, carrying out medium-high temperature annealing treatment on the crystal in the air to eliminate the thermal stress in the crystal and prevent cracking. The specific annealing procedure is as follows: doped Lu obtained by growth2O3The single crystal optical fiber is heated to 1600 ℃ in a sintering furnace and is kept at the constant temperature for 40 hours, and then the temperature is slowly reduced to the room temperature for 40 hours.
Example 2
Doped Tm2O3The preparation method of the lutetium oxide single crystal optical fiber comprises the following steps:
(1) selection and treatment of source rods and seed crystals
Mixing prepared doped Lu with the diameter of 2.5mm2O3(Tm2O3The mol ratio is 5%) of the material rods are mostly used as raw materials and seed crystals, and the raw materials and the seed crystals are fixed on the Al with the groove by high-temperature ceramic glue2O3Dried on the rod at room temperature for 24 h.
(2) Crystal growth
a, cleaning a furnace chamber and a laser reflector, and uniformly modulating a light path. The prepared source rod is fixed on the feeding device, and the prepared seed crystal is fixed on the upper pulling device. Increasing the power of a laser to 170W to melt the material rod, enabling the focal point of the laser to fall on the center of the material rod to obtain uniform heating, continuously increasing the power to 200W to form a stable hemispherical melting zone, and keeping the temperature constant for 8 min;
b, adjusting the position of the seed crystal to enable the seed crystal to be in contact with the melting zone and be positioned at the center of the melting zone, adjusting the heating power until the interface size is stable, starting the pulling device, gradually increasing the power to 210W, and performing neck collection. When the diameter of the seed crystal is narrowed to 0.5mm, the power is adjusted to 200W for shouldering and equal-diameter growth. Upper pulling speed in the growth process: 1.0mm/min, lower feed rate: 0.2 mm/min. When the crystal grows to the required size, the power is gradually increased to 250W, and the crystal is extracted.
And c, after the crystal growth is finished, reducing the laser power at the speed of 15W/min, closing the laser, and then opening the furnace after flowing a flowing atmosphere for 15 min.
d, after the growth is finished, carrying out medium-high temperature annealing treatment on the crystal in the air to eliminate the thermal stress in the crystal and prevent cracking. The specific annealing procedure is as follows: doped Lu obtained by growth2O3The temperature of the single crystal optical fiber is raised to 1300 ℃ in a sintering furnace and kept constant for 48 hours, and then the temperature is slowly reduced to the room temperature for 24 hours.
Example 3:
doped Ho2O3The preparation method of the lutetium oxide single crystal optical fiber comprises the following steps:
(1) selection and treatment of source rods and seed crystals
Mixing prepared doped Lu with the diameter of 2.5mm2O3(Ho2O3The mol ratio of 0.1%) of the material rods are mostly used as raw materials and seed crystals, and the material rods are fixed on the Al with the grooves by high-temperature ceramic glue2O3Dried on a rod at 70 ℃ for 6 hours.
(2) Crystal growth
a, cleaning the furnace chamber and the laser reflector, and adjusting the light path to be uniform. The prepared source rod is fixed on the feeding device, and the prepared seed crystal is fixed on the upper pulling device. Increasing the power of a laser to 170W to melt the material rod, enabling the focal point of the laser to fall on the center of the material rod to obtain uniform heating, continuously increasing the power to 200W to form a stable hemispherical melting zone, and keeping the temperature constant for 8 min;
b, adjusting the position of the seed crystal to enable the seed crystal to be in contact with the melting zone and be positioned at the center of the melting zone, adjusting the heating power until the interface size is stable, starting the pulling device, gradually increasing the power to 210W, and performing neck collection. When the diameter of the seed crystal is narrowed to 0.7mm, the power is adjusted to 200W for shouldering and equal-diameter growth. Upper pulling speed in the growth process: 0.6mm/min, lower feed rate: 0.2 mm/min. When the crystal grows to the required size, the power is gradually increased to 250W, and the crystal is extracted.
c, after the crystal growth is finished, reducing the laser power at the rate of 25W/min, turning off the laser, and then opening the furnace after flowing a flowing atmosphere for 10 min.
d, after the growth is finished, carrying out medium-high temperature annealing treatment on the crystal in the air to eliminate the thermal stress in the crystal. The specific annealing procedure is as follows: doped Lu obtained by growth2O3The temperature of the single crystal optical fiber is raised to 1600 ℃ in a sintering furnace and is kept constant for 40 hours, and then the temperature is slowly reduced to room temperature for 40 hours.
Comparative example 1
As described in example 1, except that:
step (1) the fluorescent ion only contains Yb with a molar ratio of 1%2O3Due to Yb3+The intensity and bandwidth of the absorption band also decrease as the fluorescent ions decrease.
Comparative example 2
As described in example 1, except that:
the upper part pulling speed in the growth process in the step (2) b is as follows: 1 mm/min. The pulling-feeding ratio is too large, so that a growing melting zone is unstable, and the quality of the obtained crystal optical fiber is poor.
Comparative example 3
As described in example 3, except that:
and (3) keeping the temperature of 1600 ℃ for 10h in the annealing process in the step (2), and then slowly cooling to room temperature for 10 h. The thermal stress is large, and the surface of the crystal has macrocracks, which affects the quality of the crystal.
Test example 1
The physical indexes of the products obtained in examples 1 to 3 and comparative examples 1 to 3 were measured as shown in Table 1.
TABLE 1
As can be seen from Table 1, the phosphor ion doped lutetium oxide single crystal fibers prepared in examples 1-3 of the present invention have uniform diameter, length of 10cm or more, and aspect ratio of 100:1 or more.
Comparative example 1 reduced the doping of Yb fluorescent ions so that the intensity and bandwidth of the absorption band would also be reduced. The growth parameters and the annealing temperature of the comparative example 2 and the example 3 are not properly controlled, the quality of the prepared lutetium oxide single crystal optical fiber is poor, the thermal stress is large, microcracks appear on the surface, and the length is short.
Claims (5)
1. The fluorescent ion doped lutetium oxide single crystal optical fiber is characterized in that the optical fiber comprises a fluorescent ion doped lutetium oxide single crystal in a chemical composition manner, and the fluorescent ion is Tm3+、Yb3+Or Ho3+(ii) a Based on the molar content of the total raw materials, the doping molar ratios of the fluorescent ions are respectively as follows: tm is2O3 3%-7%、Yb2O3 4%-8%、Ho2O3 0.05%-0.2%；
The diameter of the optical fiber is 0.7-1.5mm, the length of the optical fiber is more than or equal to 15cm, and the aspect ratio of the optical fiber is more than or equal to 100: 1.
2. The method for preparing a phosphor ion-doped lutetium oxide single crystal optical fiber according to claim 1, comprising:
preparing lutetium oxide doped seed crystals and source rods;
laser melting of the doped lutetium oxide source rod;
collecting the doped lutetium oxide seed crystal in the doped lutetium oxide molten material, shouldering, growing in an equal diameter mode and extracting;
in the laser melting step of the doped lutetium oxide source rod, the center of the source rod is placed at the laser center for melting, and the power of a laser is 270-;
neck power of 210-;
when the diameter of the seed crystal is narrowed to 0.5-0.7mm in the process of neck narrowing, shoulder setting and equal-diameter growth are carried out;
in the process of equal-diameter growth, the pulling speed is 0.2-1.0 mm/min;
and feeding the lutetium oxide doped source rod simultaneously in the process of isometric growth at a feeding speed of 0.07-0.6 mm/min.
3. The method of claim 2, further comprising a high temperature annealing step after the crystal is stripped.
4. The method for preparing an optical fiber according to claim 2, wherein the steps of doping lutetium oxide seed crystals and preparing source rods are as follows:
uniformly mixing a lutetium oxide raw material and a fluorescent ion raw material to prepare a round rod serving as a seed crystal and a source rod;
mixing and pressing the raw materials into a round rod, and then sintering at high temperature, wherein the sintering temperature is 1250-.
5. The method for preparing the optical fiber according to claim 3, wherein in the high temperature annealing step, the crystal is annealed at 1100-1600 ℃ for 30-48h in air at a constant temperature, and then cooled at a rate of (1-1.5) DEG C/min after the annealing is completed, so as to eliminate the thermal stress and defects in the crystal and improve the quality of the crystal.
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| CN110158150B (en) * | 2019-05-20 | 2021-04-09 | 山东大学 | ABAlO for active ion doping4Single crystal optical fiber and preparation method and application thereof |
| CN110359092A (en) * | 2019-06-24 | 2019-10-22 | 南京同溧晶体材料研究院有限公司 | A kind of scintillation crystal preparation method and application of luteium oxide matrix |
| CN110777429A (en) * | 2019-10-15 | 2020-02-11 | 山东大学 | Preparation device and method of crystal optical fiber |
| CN112281213B (en) * | 2020-10-26 | 2022-04-26 | 山东大学 | Rare earth doping (Lu)aScbYc)2O3(a + b + c = 1) single crystal optical fiber, and preparation method and application thereof |
| CN112965162A (en) * | 2021-03-04 | 2021-06-15 | 山东大学 | High-sensitivity single crystal optical fiber temperature measurement method based on single crystal optical fiber acoustic anisotropy and doping modulation |
| CN113776690A (en) * | 2021-09-16 | 2021-12-10 | 浙江大学 | End rare earth ion Sm3+Doped YAG single crystal optical fiber fluorescence temperature sensor |
| CN115182046B (en) * | 2022-07-27 | 2023-12-29 | 山东铂锐激光科技有限公司 | Method for preparing sesquioxide single crystal optical fiber cladding |
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