CN111763987A - Tm (Tm)3+Self-activated laser crystal and preparation method thereof - Google Patents
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- CN111763987A CN111763987A CN202010638544.6A CN202010638544A CN111763987A CN 111763987 A CN111763987 A CN 111763987A CN 202010638544 A CN202010638544 A CN 202010638544A CN 111763987 A CN111763987 A CN 111763987A
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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
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- C30B29/10—Inorganic compounds or compositions
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- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition
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- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
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- H01S3/1601—Solid materials characterised by an active (lasing) ion
- H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
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Abstract
The invention discloses a Tm3+A self-activated laser crystal and a preparation method thereof relate to the field of infrared laser gain materials, and the chemical general formula of the laser crystal is ATm (MoO)4)2Wherein A is at least one element selected from Li, Na and K. In the crystal, Tm3+The ions have a dual role, on the one hand, as activating luminescent ions and, on the other hand, as part of the crystal matrix, thus greatly increasing their concentration, favoring Tm3+2 micron fluorescence emission of ions reduces laser threshold and improves laser efficiency. The crystal can be grown by a pulling method or a molten salt growth method. The crystal is used as a gain medium, and a half with central emission wavelength of 760-820 nm is utilizedThe laser pumping of the conductor laser can realize the high-efficiency infrared laser output near 2 microns, and has important application prospect in the fields of medical treatment, scientific research, military and the like.
Description
Technical Field
The invention relates to the technical field of laser crystal gain materials, in particular to a Tm3+A self-activated laser crystal and a method for preparing the same.
Background
The laser with the wave band of 2 microns has wide application prospect in the civil and military fields of communication, atmospheric pollution monitoring, sensing, medical treatment, engineering control, remote sensing, laser radar and the like. Among the numerous luminescent ions, the thulium ion (Tm)3+) Is one of effective ions for realizing laser output in a wave band near 2 microns. Tm is3+Rich ion energy level, ground state3H6Tm on energy level3+Ion absorbs pumping light with wavelength of about 800nm and then transits to3H4Energy level at3H4Tm of energy level3+Ion and Tm adjacent to the ground state3+The ions interact, a process called cross-relaxation, which is expressed as: tm is3+(3H4)+Tm3+(3H6)→2Tm3+(3F4) Then Tm3+Ion from3F4When the energy level transits to the ground state, fluorescence of a 2-micron wavelength band is emitted. It can be seen that this cross relaxation favors Tm3+2 micron fluorescence emission of the ions.
The laser crystal with stoichiometric ratio is also called self-activated laser crystal, and the luminescent ion in the self-activated laser crystal is a component of the crystal matrix, and has high doping concentration on one hand and no serious fluorescence concentration quenching phenomenon on the other hand, so the self-activated laser crystal is a promising crystal gain material of microchip laser. However, further practical applications of such laser crystals are limited due to the difficulty in obtaining high quality self-activating laser crystals in the growth process.
Tm3+Self-activating laser crystal ATm (MoO)4)2Wherein A is at least one element selected from Li, Na and K, and a pulling method or a molten salt method can be adopted to grow high-quality single crystals. Due to Tm3+The ions are used as both luminescent ions and part of the matrix material, so that on one hand, the pumping absorption efficiency can be effectively increased, and on the other hand, the Tm can be greatly improved3+The doping concentration of the ions is beneficial to improving the fluorescence emission efficiency of 2 microns.
Thus the Tm for 2 micron all solid state lasers is studied3+Self-activating laser crystal ATm (MoO)4)2Wherein A is selected from at least one of Li, Na and K elements, and has important significance for developing laser output of 2 microns. At present, Tm is not seen at home and abroad3+Self-activating laser crystal ATm (MoO)4)2Wherein A is selected from at least one of Li, Na and K elements, and is used as a report related to 2-micron infrared laser crystals.
Disclosure of Invention
It is an object of the present invention to provide a Tm3+The self-activated laser crystal and the preparation method thereof can realize high-efficiency laser output of 2 micron wave band, and have important application prospect in the fields of communication, medical treatment, scientific research, military and the like.
In one aspect of the invention, a Tm is provided3+Self-activating laser crystal having the chemical formula of ATm (MoO)4)2Wherein A is at least one element selected from Li, Na and K.
Further, Tm is3+The ions have a dual role, on the one hand, as activating luminescent ions and, on the other hand, as part of the crystal matrix, thus greatly increasing their concentration, favoring Tm3+2 micron fluorescence emission of ions reduces laser threshold and improves laser efficiency.
Further, the laser crystal is a single crystal.
Further, pumping by using a semiconductor laser with central emission wavelength of 760-820 nm or 940-980 nm, and allowing laser to pass through Tm3+Self-activated laser crystal for realizing high-efficiency all-solid-state red near 2 micronsAnd (4) outputting external laser.
Another aspect of the present invention provides the above Tm3+A method for preparing a self-activating laser crystal, the method comprising the steps of:
s1, uniformly mixing the mixture containing the raw material A, the raw material Tm and the raw material Mo in a mixer for not less than 2 hours to obtain a uniformly mixed mixture;
s2, sintering the uniformly mixed mixture at a temperature of not less than 500 ℃ for not less than 8 hours to obtain a sintered material;
s3, when crystal growth is carried out by adopting a pulling method, the sintered material is placed in a pulling furnace, the temperature is raised to be at least 100 ℃ above the melting point, the sintered material is completely melted, the temperature is kept constant for at least 1 hour, then crystal growth is carried out, the pulling speed is 0.2-5.0 mm/h, and the rotating speed is 5-50 rpm;
when the molten salt method is adopted for crystal growth, the sintering material is placed in a fluxing agent growth furnace, and Li is taken as the fluxing agent2MoO4-MoO3And heating to reach the melting point of at least 50 ℃, completely melting the mixture, keeping the temperature for at least 1 hour, and then carrying out crystal growth at the cooling speed of 0.2-2.0 ℃/day and the rotation speed of 0.6-5 rpm for 1-4 weeks.
Further, the raw material A is selected from carbonate of A or nitrate of A;
the Tm raw material is selected from oxide of Tm or nitrate of Tm;
the Mo raw material is selected from Mo oxide or molybdic acid.
Further, in the mixture containing the raw material A, the raw material Tm and the raw material Mo, the molar ratio of the raw material A to the raw material Tm to the raw material Mo is as follows:
A:Tm:Mo=1:1:2~2.5;
wherein the mole number of the raw material A is calculated by the mole number of the element A contained in the raw material A; the number of moles of the Tm raw material is calculated by the number of moles of a Tm element contained in the Tm raw material; the number of moles of the Mo raw material is based on the number of moles of the Mo element contained in the Mo raw material.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention discloses a Tm3+Self-activating laser crystal in which Tm is3+The ions have a dual role, on the one hand, as activating luminescent ions and, on the other hand, as part of the crystal matrix, thus greatly increasing their concentration, favoring Tm3+2 micron fluorescence emission of ions reduces laser threshold and improves laser efficiency.
(2) The crystal can be grown by a pulling method or a molten salt growth method. The crystal is used as a gain medium, and a semiconductor laser pump with the central emission wavelength of 760-820 nm is utilized, so that high-efficiency infrared laser output near 2 microns can be realized, and the crystal has important application prospects in the fields of medical treatment, scientific research, military affairs and the like.
Drawings
FIG. 1 is a Tm disclosed in an embodiment of the present invention3+A flow chart of a method for preparing a self-activating laser crystal.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
This example discloses a Tm3+Self-activating laser crystal ATm (MoO)4)2Wherein A is at least one element selected from Li, Na and K, and Tm3+The ions have a dual role, on the one hand, as activating luminescent ions and, on the other hand, as part of the crystal matrix, thus greatly increasing their concentration, favoring Tm3+2 micron fluorescence emission of ions reduces laser threshold and improves laser efficiency. The crystal can be grown by a pulling method or a molten salt growth method. The crystal is used as a gain medium, and a semiconductor laser pump with central emission wavelength of 760-810 nm is utilizedThe high-efficiency infrared laser output of 2 microns or so can be realized, and the method has important application prospect in the fields of medical treatment, scientific research, military affairs and the like.
Example two
This example discloses a LiTm (MoO)4)2Self-activated laser crystal and its pulling method.
Mixing high-purity Li2CO3,Tm2O3,MoO3Raw materials are mixed according to a molar ratio of Li: tm: mo is 1: 1: 2.1, preparing materials to form a mixture, placing the mixture on a mixer for mixing for 12 hours to form uniform powder, pressing the mixture into a cylindrical material block with the diameter of 50mm under the pressure of 3GPa, then placing the material block into a muffle furnace for sintering at the sintering temperature of 500 ℃ for 25 hours, then placing the sintered material block into a platinum crucible with the diameter of 60mm and placing the platinum crucible into a pulling furnace for crystal growth, heating the platinum crucible to the temperature higher than the melting point by 50 ℃, keeping the temperature for 2 hours to completely melt the material block, then keeping the temperature for 3 hours, keeping the temperature constant in a constant field, slowly lowering the seed crystal into the melt, starting crystal growth, finishing the crystal growth through seeding, necking down, shouldering, equal diameter and ending processes, wherein the pulling speed during the crystal growth is 1mm/h, the rotating speed is 12rpm, and finally lowering the temperature to room temperature at the cooling rate of 35 ℃/h, taking out the LiTm (MoO)4)2And (4) crystals.
EXAMPLE III
This example discloses a NaTm (MoO)4)2Self-activated laser crystal and its pulling method.
Mixing high-purity Na2CO3,Tm2O3,MoO3Raw materials are mixed according to a molar ratio of Na: tm: mo is 1: 1: 2.2 preparing materials to form a mixture, placing the mixture on a mixer for mixing for 15 hours to form uniform powder, pressing the powder into a cylindrical material block with the diameter of 50mm under the pressure of 4GPa, then placing the material block into a muffle furnace for sintering at the sintering temperature of 520 ℃ for 30 hours, then placing the sintered material block into a platinum crucible with the diameter of 60mm and placing the platinum crucible into a pulling furnace for crystal growth, and heating to a melting point to obtain the crystalKeeping the temperature at 50 ℃ for 1 hour to completely melt the lump material, keeping the temperature for 2 hours again, keeping the temperature field constant, then slowly lowering the seed crystal into the melt to start crystal growth, completing the crystal growth through the processes of seeding, necking, shouldering, isometric and ending, wherein the pulling speed during the crystal growth is 1.5mm/h, the rotating speed is 15rpm, finally, lowering the temperature to the room temperature at the cooling rate of 40 ℃/h, and taking out the NaTm (MoO)4)2And (4) crystals.
Example four
This example discloses KTm (MoO)4)2Self-activated laser crystal and its pulling method.
Mixing high-purity K2CO3,Tm2O3,MoO3Raw materials are mixed according to a molar ratio K: tm: mo is 1: 1: 2.5, preparing materials to form a mixture, placing the mixture on a mixer for mixing for 15 hours to form uniform powder, pressing the powder into a cylindrical material block with the diameter of 50mm under the pressure of 6GPa, then placing the material block into a muffle furnace for sintering, wherein the sintering temperature is 530 ℃ and the sintering time is 35 hours, then placing the sintered material block into a platinum crucible with the diameter of 60mm and placing the platinum crucible into a pulling furnace for crystal growth, heating the material block to 60 ℃ above the melting point, keeping the temperature for 2 hours to completely melt the material block, then keeping the temperature for 4 hours, keeping the temperature constant, slowly cooling the seed crystal to the molten liquid, starting crystal growth, finishing the crystal growth through seeding, necking, shouldering, equal diameter and ending processes, wherein the pulling speed during the crystal growth is 1.8mm/h, the rotating speed is 18rpm, and finally cooling the material to room temperature at the cooling rate of 30 ℃/h, take out KTm (MoO)4)2And (4) crystals.
EXAMPLE five
This example discloses a LiTm (MoO)4)2Self-activated laser crystal and its molten salt growth.
Mixing high-purity Li2CO3,Tm(NO3)3,MoO3Raw materials are mixed according to a molar ratio of Li: tm: mo is 1: 1: 2.3 batching to form a mixture, placing the mixture on a mixer for mixing for 18 hours to form uniform powder, 4GpaPressing under pressure to obtain cylindrical material block with diameter of 50mm, sintering at 550 deg.C for 30 hr in a muffle furnace, placing the sintered material block into a platinum crucible with diameter of 60mm, and loading into a molten salt furnace for crystal growth, wherein the fluxing agent is Li2MoO4-MoO3Heating to 50 deg.C above the melting point, completely melting, holding the temperature for 2 hr, growing crystal at 0.2 deg.C/day speed and 0.6rpm for 4 weeks, cooling to room temperature at 30 deg.C/h, and taking out LiTm (MoO)4)2And (4) crystals.
EXAMPLE six
This example discloses a NaTm (MoO)4)2Self-activated laser crystal and its molten salt growth.
Mixing high-purity Na2CO3,Tm(NO3)3,MoO3Raw materials are mixed according to a molar ratio of Na: tm: mo is 1: 1: 2.2 mixing materials to form a mixture, placing the mixture on a mixer for mixing materials for 18 hours to form uniform powder, pressing the powder into a cylindrical material block with the diameter of 50mm under the pressure of 3Gpa, then placing the material block into a muffle furnace for sintering at the sintering temperature of 555 ℃ for 35 hours, then placing the sintered material block into a platinum crucible with the diameter of 60mm and placing the platinum crucible into a molten salt furnace for crystal growth, wherein the fluxing agent is Na2MoO4-MoO3Heating to 40 ℃ above the melting point, completely melting, keeping the temperature constant for 3 hours, then performing crystal growth at a cooling speed of 0.6 ℃/day and a rotation speed of 1.0rpm for 3 weeks, finally cooling to room temperature at a cooling rate of 35 ℃/h, and taking out the NaTm (MoO)4)2And (4) crystals.
EXAMPLE seven
This example discloses KTm (MoO)4)2Self-activated laser crystal and its molten salt growth.
Mixing high-purity K2CO3,Tm(NO3)3,MoO3Raw materials are mixed according to a molar ratio K: tm: mo is 1: 1: 2.4, the materials are mixed,forming a mixture, placing the mixture on a mixer for mixing for 18 hours to form uniform powder, pressing the uniform powder into a cylindrical material block with the diameter of 50mm under the pressure of 4Gpa, then placing the material block into a muffle furnace for sintering at the sintering temperature of 545 ℃ for 38 hours, then placing the sintered material block into a platinum crucible with the diameter of 60mm and placing the platinum crucible into a molten salt furnace for crystal growth, wherein the fluxing agent is K2MoO4-MoO3Heating to 45 deg.C above the melting point, completely melting, maintaining the temperature for 4 hr, growing crystal at 1.0 deg.C/day speed and 3.0rpm for 2 weeks, cooling to room temperature at 25 deg.C/h, and taking out KTm (MoO)4)2And (4) crystals.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. Tm (Tm)3+Self-activating laser crystal, characterized in that the chemical formula of the laser crystal is ATm (MoO)4)2Wherein A is at least one element selected from Li, Na and K.
2. The Tm of claim 13+Self-activating laser crystal, characterized by Tm3+The ions have a dual role, on the one hand, as activating luminescent ions and, on the other hand, as part of the crystal matrix.
3. The Tm of claim 13+A self-activating laser crystal, wherein the laser crystal is monocrystalline.
4. The Tm of claim 13+The self-activated laser crystal is characterized in that the central emission wavelength is 760-820 nm or less940-980 nm semiconductor laser pumping, laser passing through the Tm3+The self-activated laser crystal realizes high-efficiency all-solid-state infrared laser output near 2 microns.
5. The Tm of any one of claims 1 to 43+The preparation method of the self-activated laser crystal is characterized by comprising the following steps of:
s1, uniformly mixing the mixture containing the raw material A, the raw material Tm and the raw material Mo in a mixer for not less than 2 hours to obtain a uniformly mixed mixture;
s2, sintering the uniformly mixed mixture at a temperature of not less than 500 ℃ for not less than 8 hours to obtain a sintered material;
s3, when crystal growth is carried out by adopting a pulling method, the sintered material is placed in a pulling furnace, the temperature is raised to be at least 100 ℃ above the melting point, the sintered material is completely melted, the temperature is kept constant for at least 1 hour, then crystal growth is carried out, the pulling speed is 0.2-5.0 mm/h, and the rotating speed is 5-50 rpm;
when the molten salt method is adopted for crystal growth, the sintering material is placed in a fluxing agent growth furnace, and Li is taken as the fluxing agent2MoO4-MoO3And heating to reach the melting point of at least 50 ℃, completely melting the mixture, keeping the temperature for at least 1 hour, and then carrying out crystal growth at the cooling speed of 0.2-2.0 ℃/day and the rotation speed of 0.6-5 rpm for 1-4 weeks.
6. The Tm of claim 53+The preparation method of the self-activated laser crystal is characterized in that the raw material A is selected from carbonate of A or nitrate of A;
the Tm raw material is selected from oxide of Tm or nitrate of Tm;
the Mo raw material is selected from Mo oxide or molybdic acid.
7. The Tm of claim 53+A method for producing a self-activating laser crystal, characterized in that the crystal comprises a raw material A, a raw material Tm, and MoIn the mixture of the raw materials, the molar ratio of the A raw material, the Tm raw material and the Mo raw material is as follows:
A:Tm:Mo=1:1:2~2.5;
wherein the mole number of the raw material A is calculated by the mole number of the element A contained in the raw material A; the number of moles of the Tm raw material is calculated by the number of moles of a Tm element contained in the Tm raw material; the number of moles of the Mo raw material is based on the number of moles of the Mo element contained in the Mo raw material.
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