CN113818078B - Europium-doped borate laser crystal material and preparation method and application thereof - Google Patents

Europium-doped borate laser crystal material and preparation method and application thereof Download PDF

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CN113818078B
CN113818078B CN202111106058.0A CN202111106058A CN113818078B CN 113818078 B CN113818078 B CN 113818078B CN 202111106058 A CN202111106058 A CN 202111106058A CN 113818078 B CN113818078 B CN 113818078B
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europium
crystal material
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laser crystal
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CN113818078A (en
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景芳丽
李悦
吴以成
胡章贵
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Tianjin University of Technology
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    • 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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
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    • 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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    • 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
    • C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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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
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • 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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    • H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • 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
    • H01S3/16—Solid materials
    • H01S3/163—Solid materials characterised by a crystal matrix
    • H01S3/1666—Solid materials characterised by a crystal matrix borate, carbonate, arsenide

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Abstract

The invention relates to the technical field of laser materials, in particular to a europium-doped borate laser crystal material and a preparation method and application thereof. The chemical formula of the europium-doped borate laser crystal material provided by the invention is as follows: (Eu) x La 1‑x ) 2 CaB 10 O 19 Wherein, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.999. Compared with the prior art, the invention has the following advantages: after europium ions are doped in the calcium lanthanum borate crystal, the calcium lanthanum borate crystal has wide absorption and fluorescence spectrum, high-power laser output of 560-720 nm wave bands can be realized efficiently, and the material has good nonlinear optical effect and high laser damage threshold.

Description

Europium-doped borate laser crystal material and preparation method and application thereof
Technical Field
The invention relates to the technical field of laser materials, in particular to a europium-doped borate laser crystal material and a preparation method and application thereof.
Background
The 560-720 nm wave band visible laser has wide application prospect in the fields of laser processing, laser radar, laser Raman, urban landscapes, scientific research, national defense, military and the like. The main technology for realizing 560-720 nm wave band laser output at present comprises the following steps: 1. nonlinear optical frequency conversion technology: the method needs a pumping source with high coherence and a proper nonlinear optical crystal, and the device system for realizing laser output has complex structure and low cost performance, thereby limiting the application units and fields thereof; 2. semiconductor laser technology: the laser output power generated by the technology is lower, the laser output power generally has relatively wider wavelength bandwidth and high dispersion, and at the higher output power, the coherence of the output laser is not ideal enough, and the divergence angle is larger, so that the application of the laser output power in the field of high beam quality requirement is restricted. Therefore, it is important how to provide a 560-720 nm visible gain material with high beam quality.
Disclosure of Invention
The invention aims to provide a europium-doped borate laser crystal material, a preparation method and application thereof, wherein the europium-doped borate laser crystal material has high laser damage threshold and high thermal conductivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a europium-doped borate laser crystal material, which has the chemical formula: (Eu) x La 1-x ) 2 CaB 10 O 19 ，
Wherein, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.999.
Preferably, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.50.
Preferably, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.25.
The invention also provides a preparation method of the europium-doped borate laser crystal material, which comprises the following steps:
mixing a europium source, a lanthanum source, a calcium source and a boron source according to the proportion of each element in the europium-doped borate laser crystal material to obtain a mixture;
and treating the mixture by adopting a hydrothermal method, a crucible descending method, a pulling method, a fluxing agent method, a floating zone method or a kyropoulos method to obtain the europium-doped borate laser crystal material.
Preferably, when the mixture is treated by a flux method, the method comprises the following steps:
grinding and sintering the mixture in sequence to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain a molten material;
and (3) carrying out single crystal growth from the melt by adopting a top seed crystal method to obtain the europium-doped borate laser crystal material.
Preferably, the sintering temperature is 200-1200 ℃, and the heat preservation time is 0.1-240 h.
Preferably, the temperature rising rate of the sintering temperature is 0.01-20 ℃/min.
Preferably, the melting temperature is 900-1200 ℃.
Preferably, the cooling rate of the top seed crystal method is 0.001-20 ℃/24h, and the rotation rate of the seed crystal is 0.001-100 r/min.
The invention also provides an application of the europium-doped borate laser crystal material prepared by the technical scheme or the europium-doped borate laser crystal material prepared by the preparation method in an all-solid-state laser.
The invention provides a europium-doped borate laser crystal material, which has the chemical formula: (Eu) x La 1-x ) 2 CaB 10 O 19 Wherein, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.999. The invention utilizes that lanthanum ions in calcium borate lanthanum crystal are easily replaced by rare earth ions, and calcium ions and rare earth ions have similar radiuses and are easily replaced by rare earth ions; and by using a transition with 4f electrons of europium ions 5 D 0 → 7 F 0 ， 5 D 0 → 7 F 1 ， 5 D 0 → 7 F 2 ， 5 D 0 → 7 F 3 ， 5 D 0 → 7 F 4 The transition mode of the fluorescent material can generate the characteristic of 560-720 nm-band red-yellow visible laser, europium ions are doped into calcium lanthanum borate matrix crystals to serve as activating ions to replace part of lanthanum ions and calcium ions, so that the fluorescent material emits 560-720 nm emission light after absorbing 350-570 nm wavelength light. The broad absorption spectrum increases the wavelength of the alternative pump light source, and the broad fluorescence spectrum is suitable for developing the broadband visible laser material.
Compared with the prior art, the invention has the following advantages:
after europium ions are doped in the calcium lanthanum borate crystal, the calcium lanthanum borate crystal has wide absorption and fluorescence spectrum, high-power laser output of 560-720 nm wave bands can be realized efficiently, and the material has good nonlinear optical effect and high laser damage threshold.
Drawings
FIG. 1 is a graph showing the absorption spectrum at room temperature of the europium-doped borate laser crystal material of example 1;
FIG. 2 is a graph showing fluorescence spectrum of the europium-doped borate laser crystal material of example 2 at an excitation wavelength of 395 nm;
FIG. 3 is a graph showing fluorescence spectra of the europium-doped borate laser crystal materials of examples 1-3 at an excitation wavelength of 395 nm;
FIG. 4 is a physical diagram of the europium-doped borate laser crystal material of example 1;
FIG. 5 is a graph showing fluorescence spectrum of the europium-doped borate laser crystal material of example 3 at an excitation wavelength of 395 nm;
fig. 6 is a schematic structural diagram of the europium-doped borate laser crystal material applied in a laser device.
Detailed Description
The invention provides a europium-doped borate laser crystal material, which has the chemical formula: (Eu) x La 1-x ) 2 CaB 10 O 19 ，
Wherein, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.999.
In the present invention, the value of x is preferably 0.001.ltoreq.x.ltoreq.0.50, more preferably 0.001.ltoreq.x.ltoreq.0.25, and most preferably 0.01.ltoreq.x.ltoreq.0.15.
The invention also provides a preparation method of the europium-doped borate laser crystal material, which comprises the following steps:
mixing a europium source, a lanthanum source, a calcium source and a boron source according to the proportion of each element in the europium-doped borate laser crystal material to obtain a mixture;
and treating the mixture by adopting a hydrothermal method, a crucible descending method, a pulling method, a fluxing agent method, a floating zone method or a kyropoulos method to obtain the europium-doped borate laser crystal material.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, when the production method employs a flux method, the production method preferably includes the steps of:
mixing a europium source, a lanthanum source, a calcium source and a boron source according to the proportion of each element in the europium-doped borate laser crystal material to obtain a mixture;
grinding and sintering the mixture in sequence to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain a molten material;
and (3) carrying out single crystal growth from the melt by adopting a top seed crystal method to obtain the europium-doped borate laser crystal material.
According to the proportion of each element in the europium-doped borate laser crystal material, a europium source, a lanthanum source, a calcium source and a boron source are mixed to obtain a mixture.
In the present invention, the europium source is preferably Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The lanthanum source is preferably La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The calcium source is preferably calcium carbonate; the boron source is preferably boric acid.
In the invention, the purities of the europium source, the lanthanum source, the calcium source and the boron source are independent and preferably more than or equal to 99.99 percent. The sources of the europium source, lanthanum source, calcium source and boron source are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the mixture is obtained, the mixture is sequentially ground and sintered to obtain the polycrystalline powder.
In the present invention, the grinding preferably includes clockwise grinding and counterclockwise grinding; the number of grinding turns of the clockwise grinding and the counterclockwise grinding are preferably the same. The time for the grinding is preferably 1 to 120 minutes, more preferably 5 to 30 minutes. In the present invention, the grinding is preferably performed in an agate mortar; the mortar is preferably cleaned before grinding, and the cleaning preferably comprises cleaning with water and alcohol in sequence, and then wiping with clean anhydrous cloth.
After the grinding, the invention also preferably comprises a process of filling the mixture obtained after the grinding. In the invention, the filling is preferably to fill the mixture obtained after grinding into a corundum crucible for compaction.
In the present invention, the sintering temperature is preferably 200 to 1200 ℃, more preferably 400 to 1000 ℃; the heat preservation time is preferably 0.1 to 240 hours, more preferably 1 to 200 hours; the rate of heating to the sintering temperature is preferably 0.01 to 20 ℃/min, more preferably 1 to 15 ℃/min, and most preferably 5 to 15 ℃/min. In the present invention, the sintering is preferably performed in an air atmosphere. In the present invention, the sintering is preferably performed in a muffle furnace.
In the present invention, performing the sintering and controlling the sintering within the above-described condition ranges can be more advantageous in obtaining a polycrystalline powder having a uniform distribution of doped ions (europium ions).
After the polycrystalline powder is obtained, the polycrystalline powder and the fluxing agent powder are mixed and melted to obtain a molten material.
In the present invention, the flux powder preferably includes one or more of a calcium source, a lithium source, a boron source, and a molybdenum source; the calcium source preferably comprises one or more of calcium oxide, calcium carbonate and calcium oxalate; the lithium source preferably comprises one or more of lithium oxide, lithium carbonate and lithium oxalate; the boron source preferably comprises boric acid and/or boron oxide; the molybdenum source preferably comprises molybdenum oxide; when the flux powder is two or more of the above specific choices, the compounding ratio of the above specific substances is not particularly limited, and the flux powder may be mixed in any compounding ratio. In a specific embodiment of the invention, the flux powder preferably comprises a mixture of calcium carbonate, lithium carbonate and boric acid in a mass ratio of 1:1.70:11.29. In the invention, the cosolvent powder has the function of reducing the melting point of the polycrystalline powder and preventing the polycrystalline powder from being decomposed in the process of melting into a glassy state.
In the present invention, the mass ratio of the polycrystal powder material to the flux powder material is preferably 1 (0.01 to 100), more preferably 1 (0.1 to 20), and most preferably 1 (0.1 to 5).
In the present invention, the mixing of the polycrystal powder material and the flux powder material preferably includes: and mixing, grinding and compacting the polycrystalline powder and the fluxing agent powder, and sintering. In the present invention, the time for the grinding is preferably 10 minutes. After the grinding, the invention also preferably comprises filling the mixture obtained after the grinding into a corundum crucible for compaction. In the present invention, the sintering temperature is preferably 200 to 1200 ℃, more preferably 400 to 1000 ℃, and most preferably 450 to 950 ℃; the heat preservation time is preferably 0.1 to 240 hours, more preferably 1 to 200 hours, and most preferably 10 to 100 hours; the heating rate to the sintering temperature is preferably 0.01 to 20 ℃/min, more preferably 1 to 15 ℃/min, and most preferably 5 to 15 ℃/min. In the invention, the sintering function is to fully react raw materials to generate europium-doped calcium lanthanum borate polycrystalline powder.
In the present invention, the melting temperature is preferably 900 to 1200 ℃. The melting is preferably batch melting; the batch melting process is not particularly limited, and may be performed by a process known to those skilled in the art. In the implementation of the invention, the molten material obtained after melting is preferably placed in a platinum crucible, and the volume of the molten material and the volume of the platinum crucible are less than or equal to 2:3. In the invention, the effect of the melting is to melt the polycrystalline powder into a glass state with smaller volume and put the glass state into a platinum crucible for single crystal growth.
After the melting material is obtained, the invention adopts a top seed crystal method to carry out single crystal growth from the melting material, and the europium-doped borate laser crystal material is obtained.
In the invention, the cooling rate of the top seed crystal method is preferably 0.001-20 ℃/24h, more preferably 0.001-15 ℃/24h; the rotation rate of the seed crystal is preferably 0.001 to 100r/min, more preferably 0.1 to 50r/min, and most preferably 1 to 30r/min.
In the present invention, after the single crystal is grown to a desired single crystal length, the temperature in the growth furnace is preferably reduced at a rate of 0.2 to 20 ℃/h, the growth furnace is closed, and the single crystal is pulled up to the growth interface.
The specific steps and equipment required for the top-seeding method are not particularly limited, and those known to those skilled in the art may be employed.
In the present invention, when the production method adopts a Czochralski method, the production method preferably comprises the steps of:
mixing a europium source, a lanthanum source, a calcium source and a boron source according to the proportion of each element in the europium-doped borate laser crystal material to obtain a mixture;
grinding and sintering the mixture in sequence to obtain polycrystalline powder;
and after the polycrystalline powder is melted, introducing seed crystals from the top, and carrying out seed crystal pulling growth to obtain the europium-doped borate laser crystal material.
According to the proportion of each element in the europium-doped borate laser crystal material, a europium source, a lanthanum source, a calcium source and a boron source are mixed to obtain a mixture.
In the present invention, the europium source is preferably Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The lanthanum source is preferably La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The calcium source is preferably calcium carbonate; the boron source is preferably boric acid.
In the invention, the purities of the europium source, the lanthanum source, the calcium source and the boron source are independent and preferably more than or equal to 99.99 percent. The sources of the europium source, lanthanum source, calcium source and boron source are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the mixture is obtained, the mixture is sequentially ground and sintered to obtain the polycrystalline powder.
The grinding process is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the sintering preferably includes presintering and final sintering; the temperature of the presintering is preferably 500 ℃ and the time is preferably 10 hours. The final firing temperature is preferably 900 ℃ and the time is preferably 48 hours.
After the polycrystalline powder is obtained, the invention introduces seed crystals from the top after the polycrystalline powder is melted, and carries out seed crystal pulling treatment to obtain the europium-doped borate laser crystal material.
In the invention, the orientation of the seed crystal is preferably in the [100] direction, and the rotation speed of the crystal in the seed crystal pulling treatment is preferably 10-25 r/min, more preferably 15-20 r/min; the pulling speed of the seed crystal pulling treatment is preferably less than or equal to 1mm/h; the axial temperature gradient near the liquid level in the seed crystal pulling treatment process is preferably 30-60 ℃/cm, more preferably 40-50 ℃/cm.
After the seed crystal pulling treatment is completed, the temperature is preferably reduced to room temperature at a temperature reduction rate of 50 ℃/h.
In the present invention, when the preparation method adopts a hydrothermal method, a crucible lowering method, a floating zone method or a kyropoulos method, the process of the hydrothermal method, the crucible lowering method, the floating zone method or the kyropoulos method is not limited in any way, and the preparation method can be performed by adopting a process well known to those skilled in the art.
The invention also provides an application of the europium-doped borate laser crystal material prepared by the technical scheme or the europium-doped borate laser crystal material prepared by the preparation method in an all-solid-state laser. In the invention, the europium-doped borate laser crystal material is preferably used as a laser gain medium or an application of a laser and frequency conversion composite device in an all-solid-state laser. The method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The europium-doped borate laser crystal materials, the preparation methods and applications thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
According to europium: lanthanum: calcium: boron=0.06:1.94:1:10, 10.56g europium oxide (purity not less than 99.99 wt%), 316.22g lanthanum oxide (purity not less than 99.99 wt%), 100.09g calcium carbonate (purity not less than 99.99 wt%) and 628g boric acid (purity not less than 99.99 wt%) are mixed to obtain a mixture;
1054.87g of the mixture is placed in an agate mortar with the diameter of 18cm, the agate mortar is respectively ground for 10min in the clockwise and anticlockwise directions with the same number of turns, the ground material is filled in a corundum crucible for compaction until the filling height reaches 15cm, and then the mixture is placed in a muffle furnace and sintered for 24h in the air atmosphere at the temperature rising rate of 1 ℃ min to 1000 ℃ to obtain 720g of polycrystalline powder;
mixing 100.09g of calcium carbonate, 169.92g of lithium carbonate and 1130.4g of boric acid according to the mass ratio of 1:1.70:11.29, mixing with 720g of polycrystalline powder, grinding for 10min, filling into a corundum crucible for compaction until the filling height reaches 15cm, placing into a muffle furnace, heating to 600 ℃ in an air atmosphere at the heating rate of 1 ℃/min, sintering for 10h, melting to a platinum crucible with the diameter of 10cm in batches at 1040 ℃, and performing operation of a top seed crystal method after melting to two thirds of the volume of the crucible: the conditions are as follows: the cooling rate is 1 ℃/24h, the rotation rate is 10r/min, after the single crystal grows to the required length, the single crystal is lifted to a growth interface, the temperature in the furnace is reduced to room temperature at the rate of 5 ℃/h, the growth furnace is closed, and then the single crystal is taken out, so that the europium-doped borate laser crystal material (marked as 3% Eu-LCB) is obtained;
FIG. 1 is a graph showing the absorption spectrum of the europium-doped borate laser crystal material at room temperature, wherein the europium-doped borate laser crystal material exhibits a strong absorption peak near 395nm due to the transition of europium ion as rare earth activated ion through its ability as shown in FIG. 1 5 D 0 → 7 F 0 , 5 D 0 → 7 F 1 , 5 D 0 → 7 F 2 , 5 D 0 → 7 F 3 , 5 D 0 → 7 F 4 ) Can produceGenerating visible yellow-red laser with 560-720 nm wave band, pumping the europium-doped calcium lanthanum borate laser element by adopting a developed GaN semiconductor laser with the laser wavelength of 395nm, wherein europium ions can effectively absorb pumping energy, so that a stronger absorption peak appears near 395nm in the europium-doped calcium lanthanum borate;
fig. 4 is a physical diagram of the europium-doped borate laser crystal material, and as can be seen from fig. 4, the crystal size is larger, the quality is better, and no obvious inclusion exists.
Example 2
According to europium: lanthanum: calcium: boron=0.14:1.86:1:10, 24.64g europium oxide (purity: 99.99 wt.%), 303.18g lanthanum oxide (purity: 99.99 wt.%), 100.09g calcium carbonate (purity: 99.99 wt.%) and 628g boric acid (purity: 99.99 wt.%), were mixed to obtain a mixture;
1055.91g of the mixture is placed in an agate mortar with the diameter of 18cm, the agate mortar is respectively ground for 10min in the clockwise and anticlockwise directions with the same number of turns, the ground material is filled in a corundum crucible for compaction until the filling height reaches 15cm, and then the mixture is placed in a muffle furnace, and is sintered for 24h in the air atmosphere at the temperature rising rate of 1 ℃ min to 1000 ℃ to obtain 720g of polycrystalline powder;
mixing 100.09g of calcium carbonate, 169.92g of lithium carbonate and 1130.4g of boric acid according to the mass ratio of 1:1.70:11.29, mixing with 720g of polycrystalline powder, grinding for 10min, filling into a corundum crucible for compaction until the filling height reaches 15cm, placing into a muffle furnace, heating to 600 ℃ in an air atmosphere at the heating rate of 1 ℃/min, sintering for 10h, melting to a platinum crucible with the diameter of 10cm in batches at 1040 ℃, and performing operation of a top seed crystal method after melting to two thirds of the volume of the crucible: the conditions are as follows: and (3) cooling at a speed of 1 ℃/24h and a rotation speed of 10r/min, after the single crystal grows to a required length, lifting the single crystal out of a growth interface, reducing the temperature in the furnace to room temperature at a speed of 5 ℃/h, closing the growth furnace, and taking out the single crystal to obtain the europium-doped borate laser crystal material (marked as 7% Eu-LCB).
Example 3
According to europium: lanthanum: calcium: boron=0.2:1.8:1:10, 35.2g europium oxide (purity: 99.99 wt.%), 293.4g lanthanum oxide (purity: 99.99 wt.%), 100.09g calcium carbonate (purity: 99.99 wt.%) and 628g boric acid (purity: 99.99 wt.%), were mixed to obtain a mixture;
1056.69g of the mixture is placed in an agate mortar with the diameter of 18cm, the agate mortar is respectively ground for 10min in the clockwise and anticlockwise directions with the same number of turns, the ground material is filled in a corundum crucible for compaction until the filling height reaches 15cm, and then the mixture is placed in a muffle furnace and sintered for 24h in the air atmosphere at the temperature rising rate of 1 ℃/min to 1000 ℃ to obtain 720g of polycrystalline powder;
mixing 100.09g of calcium carbonate, 169.92g of lithium carbonate and 1130.4g of boric acid according to the mass ratio of 1:2.3:18, mixing with about 720g of polycrystalline powder, grinding for 10min, filling into a corundum crucible for compaction until the filling height reaches 15cm, placing into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min in an air atmosphere, sintering for 10h, melting to a platinum crucible with the diameter of 10cm in batches at 1040 ℃, and carrying out the operation of a top seed crystal method until the melting accounts for two thirds of the volume of the crucible: the conditions are as follows: and (3) cooling at a speed of 1 ℃/24h and a rotation speed of 10r/min, after the single crystal grows to a required length, lifting the single crystal out of a growth interface, reducing the temperature in the furnace to room temperature at a speed of 5 ℃/h, closing the growth furnace, and taking out the single crystal to obtain the europium-doped borate laser crystal material (recorded as 10% Eu-LCB).
Test case
Cutting the europium-doped borate laser crystal material prepared in the examples 1-3 according to the I-type phase matching angle, and then using the cut europium-doped borate laser crystal material as a europium-doped calcium lanthanum borate self-frequency doubling element;
according to the structure shown in FIG. 6, the GaN semiconductor laser with 395nm is adopted to pump the europium-doped borate laser crystal material, so that the fundamental frequency light 560-720 nm can be obtained. FIG. 2 is a fluorescence spectrum diagram of the europium-doped borate laser crystal material of example 2 at an excitation wavelength of 395nm, wherein the emission peak centers of the europium-doped calcium-lanthanum borate laser element are respectively located at 575nm, 585nm, 615nm and 695nm, and a yellow-red laser output is obtained;
FIG. 3 is a fluorescence spectrum of the europium-doped borate laser crystal materials of examples 1 to 3 at an excitation wavelength of 395nm, as can be seen from FIG. 3 3+ A kind of electronic device 5 D 0 And 7 F 0 the number of emission peaks in the spectrum that observe transitions between them, which do not split in the crystal field, means Eu in the lattice 3+ The ions occupy the number of sites. FIG. 3 shows 10% Eu 3+ In the spectrum of doped LCB crystals 5 D 0 → 7 F 0 The emission peak is split into two, proving Eu 3+ The ions occupy two lattice sites in the crystal structure, namely when the content of europium reaches a certain range, europium can replace part of calcium element besides replacing part of lanthanum element in the crystal structure;
FIG. 5 is a fluorescence spectrum of the europium-doped borate laser crystal material of example 3 at an excitation wavelength of 395nm, and as can be seen from FIG. 5, the main emission wavelengths of the europium-doped borate laser crystal material are 575-590 nm, 590-630 nm and 685-702 nm;
therefore, the main production modes of the visible laser on the market at present comprise methods of crystal second harmonic generation, double-wavelength internal frequency combination, raman laser frequency multiplication, optical pump semiconductor vertical external cavity surface emitting laser, cavity frequency multiplication, raman fiber laser/amplifier, external cavity frequency multiplication and the like, but the modes basically use frequency multiplication conversion, so that the laser structure is more complex and the volume is larger, and the europium-doped borate laser crystal material can generate laser in a direct excitation mode on the wave bands of yellow light, orange light and deep red light without using a frequency multiplication conversion system.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. Application of europium-doped borate laser crystal material in all-solid-state laser, and chemistry of europium-doped borate laser crystal materialThe formula is: (Eu) x La 1-x ) 2 CaB 10 O 19 ，
Wherein, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.50.
2. The use of claim 1, wherein the range of values for x is: x is more than or equal to 0.001 and less than or equal to 0.25.
3. The use according to claim 1 or 2, wherein the preparation method of the europium-doped borate laser crystal material comprises the steps of:
mixing a europium source, a lanthanum source, a calcium source and a boron source according to the proportion of each element in the europium-doped borate laser crystal material to obtain a mixture;
and treating the mixture by adopting a hydrothermal method, a crucible descending method, a pulling method, a fluxing agent method, a floating zone method or a kyropoulos method to obtain the europium-doped borate laser crystal material.
4. A use according to claim 3, wherein the mixture, when treated by the flux method, comprises the steps of:
grinding and sintering the mixture in sequence to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain a molten material;
and (3) carrying out single crystal growth from the melt by adopting a top seed crystal method to obtain the europium-doped borate laser crystal material.
5. The method according to claim 4, wherein the sintering temperature is 200-1200 ℃ and the holding time is 0.1-240 h.
6. The use according to claim 5, wherein the rate of rise of the temperature to the sintering temperature is 0.01-20 ℃/min.
7. The use according to claim 4, wherein the melting temperature is 900 to 1200 ℃.
8. The use according to claim 4, wherein the top seed method has a cooling rate of 0.001-20 ℃/24h and a rotation rate of 0.001-100 r/min.
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