CN112928586A - Erbium ion self-activated laser crystal and preparation method and application thereof - Google Patents
Erbium ion self-activated laser crystal and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an erbium ion self-activated laser crystal and a preparation method and application thereof, and relates to the technical field of laser crystal gain materials. The main feature of self-activating laser crystals is that the luminescent ion is an integral part of the crystal matrix. In the crystal, erbium ions can emit light in a 3-micron mid-infrared band as active light-emitting ions, and meanwhile erbium ions can be used as part of a matrix crystal to realize high-concentration doping. The self-activating crystal of the present invention incorporates europium ions as deactivating ions to suppress the self-terminating "bottleneck" reaction of erbium ions at 3 micron emission. The crystal can be grown by a pulling method or a molten salt growth method. The self-activated laser crystal is used as a gain medium, and a commercial laser pump with the central emission wavelength of 760-820 nm or 940-980 nm is utilized, so that the high-efficiency mid-infrared laser output of a wave band near 3 microns can be realized, and the self-activated laser crystal has important application prospects in the fields of laser medical treatment, scientific research, national defense, military and the like.
Description
Technical Field
The invention relates to the technical field of laser crystal gain materials, in particular to an erbium ion self-activated laser crystal and a preparation method and application thereof.
Background
The laser with the wave band near 3 microns has wide application prospect in the fields of communication, environmental monitoring, sensing, biomedical treatment, engineering control, remote sensing detection, laser radar, space scientific research and the like. The rare earth ions which are reported at present and can realize 2.7-3.0 micron mid-infrared band laser by direct transition have erbium ions (Er)3+):4I11/2→4I13/2Holmium ion (Ho)3+):5I6→5I7And dysprosium ion (Dy)3+):6H13/2→6H15/2And the like. Erbium ion is one of the effective ions for realizing laser output in a band around 3 microns, and is a very popular active ion due to its abundant energy level. Visible light can be emitted through4S3/2→4I15/2Transition, 1.5 micron Near Infrared (NIR) emission vs4I13/2→4I15/2Transition, 3 micron mid-infrared (MIR) emission mapping4I11/2→4I13/2And (4) transition. Furthermore, unlike commercial high power laser pumps where the holmium and dysprosium ions lack intrinsic absorption matching with the rare earth ions, erbium ions have two favorable absorption bands with peaks at about 980nm and 808 nm, corresponding to 980nm and 808 nm, respectively4I15/2→4I11/2And4I15/2→4I9/2transition, this can be pumped with a commercial 980nm or 808 nm laser. Pump light from ground state4I15/2Absorbed energy transition to4I9/2Energy level or4I11/2Energy levelThen at4I9/2The erbium ions of the energy level will make radiationless transition to4I11/2Two radiative transitions then occur:4I11/2→4I13/2and4I13/2→4I15/2the corresponding luminescence bands were 3 microns and 1.5 microns. Up-conversion process Er in which the amount of Er ions present is transferred3+:4I13/2+4I13/2→4I9/2+4I15/2Can reduce4I13/2Population of energy levels, thereby shortening4I13/2Fluorescence lifetime of the energy level, reducing the emission by 1.5 microns. At the same time at4I9/2The erbium ions of the energy level will make radiationless transition to4I11/2Increase of4I11/2Population of energy level, formation4I11/2、4I13/2Population inversion between upper and lower levels, thereby enhancing4I11/2→4I13/23 micron fluorescence emission transition. It can be seen that the energy transfer up-conversion process helps achieve an enhancement of the 3 micron mid-ir emission and a reduction of the 1.5 micron near-ir emission, and that the intensity of the 3 micron mid-ir emission increases with increasing erbium ion concentration.
The high doping concentration of the erbium ions in the self-activated laser crystal can effectively solve the problem of low pumping absorption efficiency of the erbium ions, and improve the absorption efficiency of the erbium ions near 808 nm or 980 nm. Erbium ion in4I11/2→4I13/2The problem of the self-terminating "bottleneck" effect present in the emission process of (a) is another problem with erbium ions. It is not favorable to form population inversion, which may be due to the upper layer4I11/2Energy level to life ratio of lower layer4I13/2The short service life of the energy level limits the application of the erbium ion doped laser crystal material in the aspect of the mid-infrared laser. The high doping concentration characteristic of erbium ions in the self-activated laser crystal can effectively overcome the self-termination bottleneck effect of erbium ions in a 3-micron wave band.
Disclosure of Invention
The main feature of self-activating laser crystals is that the luminescent ion is an integral part of the crystal matrix. In a general doped crystal, when the concentration of the activated luminescent ion is increased to a certain extent, concentration quenching effect is generated to reduce the fluorescence lifetime, and doping with too high ion concentration may make it difficult to obtain a crystal with high optical quality. However, in the self-excited laser crystal, although the content of the doped ions is high, the fluorescence lifetime is not significantly reduced. It can be seen that the self-activated laser crystal has high doping concentration on one hand and does not have serious fluorescence concentration quenching phenomenon on the other hand.
The energy transfer up-conversion process of erbium ions in the presence of high doping concentration in self-activated laser crystals is advantageous for formation4I11/2、4I13/2The population of the upper and lower levels is reversed. To overcome the negative effects of self-terminating "bottlenecks" and to more effectively shorten4I13/2Life of energy level, formation4I11/2、4I13/2Upper and lower level population inversion, we can refer to deactivation ions to reduce4I13/2Lifetime of the energy level. Research shows that europium ion (Eu)3+) Can be effectively used as a deactivation ion of erbium ions, and can inhibit the self-termination bottleneck effect existing in the erbium ions. We can use europium ions as deactivating ions, with Er3+:4I13/2→Eu3 +:7F6The energy transfer can be effectively reduced4I13/2Life of energy level to increase4I11/2、4I13/2The lifetime ratio between the two energy levels suppresses the self-terminating bottleneck effect of the presence of erbium ions.
In the erbium ion self-activated laser crystal, erbium ions have double functions and can be used as activated luminescent ions and also can be used as a part of a matrix crystal, namely the luminescent ions are a component of a crystal matrix. The erbium ion self-activated laser crystal can avoid the phenomenon of fluorescence concentration quenching, thereby greatly improving the doping concentration of erbium ions. High concentration doping of erbium ions is beneficial to increasing erbium contentThe pump absorption efficiency of the ions at about 980nm or 808 nm is improved, so that the mid-infrared fluorescence emission of the erbium ions as active luminescent ions at a wave band of 3 microns is enhanced. The high-concentration doping of erbium ions can obtain quite high laser gain under the action of proper pumping, and is beneficial to reducing the laser threshold of 3-micron luminescence and improving the laser efficiency. The high-concentration doping of erbium ions is beneficial to the formation of an energy transfer up-conversion process and realizes4I11/2、4I13/2The population inversion of the upper and lower energy levels inhibits the self-termination 'bottleneck' effect of the erbium ions in a 3-micron wave band, enhances the 3-micron mid-infrared emission and reduces the 1.5-micron near-infrared emission, and the 3-micron mid-infrared emission intensity is enhanced along with the increase of the concentration of the erbium ions. The purpose is realized by adopting the following technical scheme:
an erbium ion self-activated laser crystal, the chemical formula of which is Eu4x:Na2Er4(1-x)(WO4)7Wherein x is 0.1-5 mol%, and x is the mole percentage of europium ion in erbium ion in the matrix.
Europium ions in the self-activated laser crystal can be used as deactivation ions to inhibit self-termination bottleneck reaction of erbium ions in 3-micron emission, and mid-infrared emission of a 3-micron accessory wave band is enhanced, wherein the doping concentration of the erbium ions is 0.1-5 at.%.
The self-activating laser crystal is a single crystal. The crystal is suitable for laser pumping with the center wavelength of 980nm or 808 nm. The erbium ion self-activated laser crystal is used as a laser gain material, and a commercial laser pump with the central emission wavelength of 760-820 nm or 940-980 nm is utilized, so that high-efficiency full-solid-state infrared laser output near 3 microns can be realized.
Another aspect of the present invention provides a method for preparing the erbium ion self-activated laser crystal, which may adopt a czochralski method or a molten salt method. Specifically, the preparation method of the erbium ion self-activated laser crystal at least comprises the following steps:
1) selecting Na2CO3、Eu2O3、Er2O3、WO3Is original toThe raw materials are mixed according to the following chemical equation:
Na2CO3+2xEu2O3+2(1-x)Er2O3+7WO3→Eu4x:Na2Er4(1-x)(WO4)7+CO2↑;
2) uniformly mixing the raw materials prepared in the step 1), pressing the raw materials into blocks, and calcining the blocks to obtain a sintered material;
3) adopting a pulling method or a molten salt method to carry out crystal growth:
a. when the crystal growth is carried out by adopting the pulling method, the operation is as follows: placing the sintered material obtained in the step 2) in a reactor, heating to a temperature higher than a melting point to completely melt the sintered material, carrying out constant temperature treatment, and then carrying out crystal growth; after the crystal growth is finished, cooling to room temperature, and taking out the crystal to obtain a target product;
b. when the molten salt method is adopted for crystal growth, the operation is as follows: and (3) placing the sintering material and the cosolvent obtained in the step 2) into a reactor, heating to a temperature above the melting point to completely melt the sintering material and the cosolvent, carrying out constant temperature treatment, and then cooling to carry out crystal growth, thus obtaining the target product.
Preferably, in the step 1), the purity of all raw materials reaches 99.999 percent in order to improve the crystal quality. Calculating the mass required by each raw material according to the proportion of the self-activating laser crystal, accurately weighing, and adding excessive WO in the weighing process3Compensating the volatilization of tungsten, wherein the compensation amount is generally 3-10 wt.% of the total weight; preferably 5 wt.%.
Preferably, in step 2), the calcination conditions are set as follows: the sintering temperature is 500-900 ℃, and the sintering time is 4-24 hours.
Preferably, in the step 3) a, the temperature is increased to be higher than the melting point, specifically, the temperature is increased to be higher than the melting point by 60-90 ℃; the melting point temperature was 1252 ℃.
Preferably, in the step 3) a, the constant temperature treatment time is 1-12 hours.
Preferably, in the step 3) a, in the crystal growth process, the pulling speed is 0.2-5.0 mm/h, and the rotating speed is 5-50 rpm.
Preferably, in the step 3) a, the annealing rate is 8-16 ℃/h in the cooling process.
Preferably, in step 3) b, the fluxing agent is Na2W2O7According to the chemical equation: na (Na)2CO3+2WO3→Na2W2O7+CO2And ≈ @.
Preferably, in the step 3) b, the temperature is raised to be higher than the melting point, specifically, the temperature is raised to be higher than the melting point by 60-90 ℃.
Preferably, in the step 3) b, the constant temperature treatment time is 1-12 hours.
Preferably, in the step 3) b, in the crystal growth process, the cooling speed is 8-16 ℃/h, and the rotating speed is 5-50 rpm.
The invention also provides the application of the erbium ion self-activated laser crystal in preparing a solid laser.
The solid laser adopts the erbium ion self-activated laser crystal as a laser working substance and adopts a flash lamp or a Laser Diode (LD) as a pumping source.
The solid laser outputs laser with wave band of 760-820 nm and/or wave band of 940-980 nm.
In a final aspect, the invention provides applications of the erbium ion self-activated laser crystal or the solid-state laser, including applications in the fields of spectroscopy, biochemistry, medical treatment, military, national defense and the like.
Compared with the prior art, the invention has the following advantages and effects:
at present, no erbium ion self-activated laser crystal Eu with wave band near 3 microns exists at home and abroad4x:Na2Er4(1-x)(WO4)7The report of (1).
The erbium ion self-activated laser crystal provided by the invention can realize high-efficiency laser output of a wave band near 3 microns, and has important application prospects in the fields of laser medical treatment, scientific research, national defense, military and the like.
Drawings
FIG. 1 shows an erbium ion self-activated laser crystal Eu according to the present invention4x:Na2Er4(1-x)(WO4)7The erbium ion self-activation and europium ion deactivation mechanism is shown in the diagram.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 erbium ion self-activated laser crystal Eux:Na2Er4-x(WO4)7
This example discloses an erbium ion self-activated laser crystal Eux:Na2Er4-x(WO4)7Wherein x is 0.1-5 mol%, and x is the mole percentage of europium ion in erbium ion in the matrix. In the self-activated laser crystal, erbium ions have double functions, on one hand, the self-activated laser crystal can be used as activated luminescent ions, and on the other hand, the self-activated laser crystal can be used as a part of a matrix crystal, so that the phenomenon of fluorescence concentration quenching can be avoided, and the doping concentration of the erbium ions is greatly improved. The high-concentration doping of the erbium ions is beneficial to improving the pumping absorption efficiency of the erbium ions near 980nm or 808 nm, so that the mid-infrared fluorescence emission of the erbium ions as active luminescent ions in a 3-micron wave band is enhanced. The erbium ion self-activated laser crystal can be grown by a pulling method or a molten salt growth method. The crystal is used as a gain medium, and a laser pump with the central emission wavelength of 760-820 nm or 940-980 nm is utilized, so that high-efficiency infrared laser output near 3 microns can be realized, and the crystal has important application prospects in the fields of laser medical treatment, scientific research, national defense, military and the like.
Example 2 erbium ion self-activated laser crystal Eu0.02:Na2Er3.98(WO4)7By Czochralski method
Mixing Na2CO3(99.999%)、Eu2O3(99.999%)、Er2O3(99.999%)、WO3(99.999%) the required mass of each raw material was calculated according to the proportioning chemical equation and accurately weighed. And then putting the prepared raw materials into a mixer to be uniformly mixed, pressing the uniformly mixed samples into blocks and placing the blocks into a crucible. Then the sample is placed in a muffle furnace for calcination, and the sintering temperature is highThe temperature is 600 ℃, and the sintering time is 8 hours, thus obtaining the sintering material. And putting the obtained sintered material into a pulling furnace, heating to 60 ℃ above the melting point, completely melting the sintered material, keeping the temperature for 4 hours, and then slowly cooling to the crystallization point to perform crystal growth, wherein the pulling speed is 1mm/h, and the rotating speed is 10 rpm. When the growth process is complete, the crystal is pulled out of the melt and cooled to room temperature at an annealing rate of 12 ℃/h, and then the crystal is removed.
Example 3 erbium ion self-activated laser crystal Eu0.04:Na2Er3.96(WO4)7Preparation by molten salt growth
Mixing Na2CO3(99.999%)、Eu2O3(99.999%)、Er2O3(99.999%)、WO3(99.999%) the required mass of each raw material was calculated according to the proportioning chemical equation and accurately weighed. And then putting the prepared raw materials into a mixer to be uniformly mixed, pressing the uniformly mixed samples into blocks and placing the blocks into a crucible. And then, placing the sample in a muffle furnace for calcining, wherein the sintering temperature is set to be 600 ℃, and the sintering time is 8 hours, so that the sintered material can be obtained. Placing the obtained sintering material in a fluxing agent growth furnace, wherein the fluxing agent is Na2W2O7. In the process of crystal growth, the temperature is raised to 60 ℃ above the melting point, the crystal is completely melted and is kept at the constant temperature for 4 hours, then the crystal is cooled and crystallized to grow, the cooling speed is 12 ℃/h, the rotating speed is 5rpm, and the crystal can be taken out after the growth and cooling are finished.
Example 4 erbium ion self-activated laser crystal Eu0.08:Na2Er3.92(WO4)7By Czochralski method
Mixing Na2CO3(99.999%)、Eu2O3(99.999%)、Er2O3(99.999%)、WO3(99.999%) the required mass of each raw material was calculated according to the proportioning chemical equation and accurately weighed. And then putting the prepared raw materials into a mixer to be uniformly mixed, pressing the uniformly mixed samples into blocks and placing the blocks into a crucible. The sample was then placed in a muffle furnace for calcination,the sintering temperature is 800 ℃, and the sintering time is 6 hours, thus obtaining the sintering material. And putting the obtained sintered material into a pulling furnace, heating to 70 ℃ above the melting point, completely melting the sintered material, keeping the temperature for 6 hours, and then slowly cooling to the crystallization point to perform crystal growth, wherein the pulling speed is 1mm/h, and the rotating speed is 10 rpm. When the growth process is complete, the crystal is pulled out of the melt and cooled to room temperature at an annealing rate of 12 ℃/h, and then the crystal is removed.
Example 5 erbium ion self-activating laser crystal Eu0.12:Na2Er3.88(WO4)7Preparation by molten salt growth
A sintered material obtained as described in example 4 was placed in a flux growth furnace in the case of crystal growth by the molten salt method, and Na was used as a flux2W2O7. And setting the temperature to rise to 70 ℃ above the melting point in the crystal growth process, completely melting the crystal, keeping the temperature for 6 hours, then carrying out crystal temperature reduction crystallization growth, wherein the temperature reduction speed is 12 ℃/h, the rotation speed is 5rpm, and taking out the crystal after the growth and temperature reduction are finished.
Example 6 erbium ion self-activating laser crystal Eu0.16:Na2Er3.84(WO4)7By Czochralski method
Mixing Na2CO3(99.999%)、Eu2O3(99.999%)、Er2O3(99.999%)、WO3(99.999%) the required mass of each raw material was calculated according to the proportioning chemical equation and accurately weighed. And then putting the prepared raw materials into a mixer to be uniformly mixed, pressing the uniformly mixed samples into blocks and placing the blocks into a crucible. And then, placing the sample in a muffle furnace for calcining at the sintering temperature of 900 ℃ for 6 hours to obtain a sintered material. And placing the obtained sintered material in a pulling furnace, heating to the temperature of 80 ℃ above the melting point, completely melting the sintered material, keeping the temperature for 6 hours, and then slowly cooling to the crystallization point to perform crystal growth, wherein the pulling speed is 1mm/h, and the rotating speed is 10 rpm. When the growth process is complete, the crystal is pulled out of the melt and annealed at a rate of 12 ℃/hCooled to room temperature and then the crystals were taken out.
Example 7 erbium ion self-activating laser crystal Eu0.2:Na2Er3.8(WO4)7Preparation by molten salt growth
A sintered material obtained as described in example 6 was placed in a flux growth furnace in the case of crystal growth by the molten salt method, and Na was used as a flux2W2O7. And (3) setting the temperature to rise to 50 ℃ above the melting point in the crystal growth process, completely melting the crystal, keeping the temperature for 8 hours, then carrying out crystal temperature reduction crystallization growth, wherein the temperature reduction speed is 12 ℃/h, the rotation speed is 8rpm, and taking out the crystal after the growth and temperature reduction are finished.
The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit of the present invention are intended to be equivalent replacements within the scope of the present invention.
Claims (10)
1. An erbium ion self-activated laser crystal characterized by: the chemical formula of the erbium ion self-activated laser crystal is Eu4x:Na2Er4(1-x)(WO4)7Wherein x is 0.1-5 mol%, and x is the mole percentage of europium ion in erbium ion in the matrix.
2. A method for producing an erbium ion self-activated laser crystal according to claim 1, wherein: the erbium ion self-activated laser crystal grows by adopting a pulling method or a molten salt growth method, and comprises the following steps:
1) selecting Na2CO3、Eu2O3、Er2O3、WO3The raw materials are prepared according to the following chemical formula:
Na2CO3+2xEu2O3+2(1-x)Er2O3+7WO3→Eu4x:Na2Er4(1-x)(WO4)7+CO2↑;
2) uniformly mixing the raw materials prepared in the step 1), pressing the raw materials into blocks, and calcining the blocks to obtain a sintered material;
3) adopting a pulling method or a molten salt method to carry out crystal growth:
a. when the crystal growth is carried out by adopting the pulling method, the operation is as follows: placing the sintered material obtained in the step 2) in a reactor, heating to a temperature higher than a melting point to completely melt the sintered material, carrying out constant temperature treatment, and then carrying out crystal growth; after the crystal growth is finished, cooling to room temperature, and taking out the crystal to obtain a target product;
b. when the molten salt method is adopted for crystal growth, the operation is as follows: and (3) placing the sintering material and the cosolvent obtained in the step 2) into a reactor, heating to a temperature above the melting point to completely melt the sintering material and the cosolvent, carrying out constant temperature treatment, and then cooling to carry out crystal growth, thus obtaining the target product.
3. A method for producing an erbium ion self-activated laser crystal according to claim 2, wherein:
in step 2), the calcining conditions are set as follows: the sintering temperature is 500-900 ℃, and the sintering time is 4-24 hours.
4. A method for producing an erbium ion self-activated laser crystal according to claim 2, wherein:
in the step 3), a, heating to a temperature higher than the melting point, specifically heating to a temperature 60-90 ℃ higher than the melting point; the melting point temperature is 1252 ℃;
in the step 3), a, the constant temperature treatment time is 1-12 hours;
in the step 3), in the crystal growth process, the pulling speed is 0.2-5.0 mm/h, and the rotating speed is 5-50 rpm;
in the step 3) a, the annealing speed is 8-16 ℃/h in the cooling process.
5. A method for producing an erbium ion self-activated laser crystal according to claim 2, wherein:
in the step 3) b, the fluxing agent is Na2W2O7According to the chemical equation: na (Na)2CO3+2WO3→Na2W2O7+CO2≈ @;
in the step 3) b, heating to a temperature higher than the melting point, specifically heating to a temperature 60-90 ℃ higher than the melting point;
in the step 3) b, the constant temperature treatment time is 1-12 hours;
in the step 3) b, in the crystal growth process, the cooling speed is 8-16 ℃/h, and the rotating speed is 5-50 rpm.
6. A method for producing an erbium ion self-activated laser crystal according to claim 2, wherein:
in the step 1), the purity of all raw materials reaches 99.999 percent; excess WO is added during weighing3To compensate the volatilization of tungsten in an amount of 3 to 10 wt.% based on the total weight.
7. Use of the erbium ion self-activating laser crystal according to claim 1 for the preparation of solid-state lasers.
8. A solid state laser characterized by: the erbium ion self-activated laser crystal according to claim 1 is used as a laser working substance, and a flash lamp or a laser diode is used as a pumping source.
9. The solid state laser of claim 8, wherein:
the solid laser outputs laser with wave band of 760-820 nm and/or wave band of 940-980 nm.
10. Use of an erbium ion self-activating laser crystal according to claim 1 or a solid-state laser according to any one of claims 8 to 9, wherein: the application is in the fields of spectroscopy, biochemistry, medical treatment, military, national defense and the like.
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CN116742463A (en) * | 2023-08-15 | 2023-09-12 | 长春理工大学 | Intermediate infrared laser of dual-wavelength pumping bonding crystal |
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