CN113818078A - 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 PDFInfo
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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 europium-doped borate laser crystal material provided by the invention has the chemical formula as follows: (Eu)xLa1‑x)2CaB10O19Wherein, the value range of x is as follows: 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: europium ions are doped in the calcium lanthanum borate crystal, so that the calcium lanthanum borate crystal has wide absorption and fluorescence spectrum, high-efficiency high-power laser output in a 560-720 nm wave band can be realized, and the material has a good nonlinear optical effect and a high laser damage threshold.
Description
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 band visible laser has wide application prospect in the fields of laser processing, laser radar, laser Raman, urban landscape, scientific research, national defense and 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 high-coherence pump source and a proper nonlinear optical crystal, and the device for realizing laser output has a complex system structure and low cost performance, thereby limiting the application units and the field; 2. semiconductor laser technology: the laser generated by the technology has low output power, relatively wide wavelength bandwidth and high phase dispersion, and the coherence of the output laser is not ideal and the divergence angle is large at high output power, so that the application of the laser in the field with high light beam quality is limited. Therefore, how to provide the 560-720 nm visible gain material with high beam quality is of great significance.
Disclosure of Invention
The invention aims to provide a europium-doped borate laser crystal material, and a preparation method and application thereof.
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 as follows: (Eu)xLa1-x)2CaB10O19，
Wherein, the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.999.
Preferably, the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.50.
Preferably, the value range of x is as follows: 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 Bridgman-Stockbarge method, a Czochralski 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 processed by a flux method, the method comprises the following steps:
sequentially grinding and sintering the mixture to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain molten material;
and performing single crystal growth from the molten material 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 heating rate of heating to 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 the application of the europium-doped borate laser crystal material in the technical scheme or the europium-doped borate laser crystal material prepared by the preparation method in the technical scheme in an all-solid-state laser.
The invention provides a europium-doped borate laser crystal material, which has the chemical formula as follows: (Eu)xLa1-x)2CaB10O19Wherein, the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.999. The invention utilizes the advantages that lanthanum ions in the calcium lanthanum borate crystal are easily replaced by rare earth ions, and calcium ions with similar radiuses to the rare earth ions are also easily replaced by the rare earth ions; and utilizing the transition of europium ions with 4f electrons5D0→7F0，5D0→7F1，5D0→7F2，5D0→7F3，5D0→7F4The transition mode of the method can generate the characteristics of red-yellow visible laser with the wave band of 560-720 nm, europium ions are doped in the calcium lanthanum borate matrix crystal to be used as active ions to replace partial lanthanum ions and calcium ions, and after the lanthanum borate matrix crystal absorbs light with the wavelength of 350-570 nm, 560-720 nm emitted light is emitted. The wide absorption spectrum increases the wavelength of the alternative pump light source, and the wide fluorescence spectrum is suitable for developing wide-band visible laser materials.
Compared with the prior art, the invention has the following advantages:
europium ions are doped in the calcium lanthanum borate crystal, so that the calcium lanthanum borate crystal has wide absorption and fluorescence spectrum, high-efficiency high-power laser output in a 560-720 nm wave band can be realized, and the material has a good nonlinear optical effect and a high laser damage threshold.
Drawings
FIG. 1 is a graph showing the room temperature absorption spectrum of the europium-doped borate laser crystal material of example 1;
FIG. 2 is a fluorescence spectrum of the europium-doped borate laser crystal material of example 2 at an excitation wavelength of 395 nm;
FIG. 3 is a fluorescence spectrum of the europium-doped borate laser crystal material of examples 1 to 3 at an excitation wavelength of 395 nm;
FIG. 4 is a schematic representation of the europium-doped borate laser crystal material of example 1;
FIG. 5 is a 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 an application of the europium-doped borate laser crystal material in a laser device.
Detailed Description
The invention provides a europium-doped borate laser crystal material, which has the chemical formula as follows: (Eu)xLa1-x)2CaB10O19，
Wherein, the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.999.
In the invention, the value range of x is preferably 0.001-0.50, more preferably 0.001-0.25, and most preferably 0.01-0.15.
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 Bridgman-Stockbarge method, a Czochralski 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 starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
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;
sequentially grinding and sintering the mixture to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain molten material;
and performing single crystal growth from the molten material 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 Eu2O3(ii) a The lanthanum source is preferably La2O3(ii) a The calcium source is preferably calcium carbonate; the boron source is preferably boric acid.
In the invention, the purity of the europium source, the lanthanum source, the calcium source and the boron source is preferably equal to or greater than 99.99% independently. 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 method known to those skilled in the art.
After the mixture is obtained, the mixture is sequentially ground and sintered to obtain 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 is preferably the same. The grinding time is preferably 1-120 min, and more preferably 5-30 min. In the present invention, the grinding is preferably carried out in an agate mortar; before grinding, the mortar is preferably cleaned, and the cleaning preferably comprises cleaning with water and alcohol in sequence and then wiping with a clean and anhydrous cloth.
After the grinding, the invention also preferably comprises a process of filling the mixture obtained after the grinding. In the present invention, the filling is preferably performed by filling the mixture obtained after grinding into a corundum crucible and compacting the mixture.
In the invention, the sintering temperature is preferably 200-1200 ℃, and more preferably 400-1000 ℃; the heat preservation time is preferably 0.1-240 hours, and more preferably 1-200 hours; the heating rate for 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-mentioned condition range may be more advantageous to obtain polycrystalline powder having a uniform distribution of dopant ions (europium ions).
After the polycrystalline powder is obtained, the polycrystalline powder and the fluxing agent powder are mixed and melted to obtain molten material.
In the invention, the fluxing agent powder preferably comprises 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 fluxing agent powder is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In a specific embodiment of the present invention, the flux powder preferably includes 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 decomposing in the process of melting into a glass state.
In the present invention, the mass ratio of the polycrystalline powder to the flux powder 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 polycrystalline powder and the flux powder preferably comprises: and mixing and grinding the polycrystalline powder and the fluxing agent powder, compacting, and sintering. In the present invention, the time for the grinding is preferably 10 min. After the grinding, the invention also preferably comprises filling the mixture obtained after the grinding into a corundum crucible and compacting. In the invention, the sintering temperature is preferably 200-1200 ℃, more preferably 400-1000 ℃, and most preferably 450-950 ℃; the heat preservation time is preferably 0.1-240 hours, more preferably 1-200 hours, and most preferably 10-100 hours; the heating rate for heating to the sintering temperature is preferably 0.01-20 ℃/min, more preferably 1-15 ℃/min, and most preferably 5-15 ℃/min. In the invention, the sintering function is to enable the raw materials to fully react to generate europium-doped calcium lanthanum borate polycrystalline powder.
In the invention, the melting temperature is preferably 900-1200 ℃. The melting is preferably batch melting; the batch melting process of the present invention is not particularly limited, and may be carried out by a process known to those skilled in the art. In the specific 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 melting function is to melt the polycrystalline powder into a glass state with smaller volume, and the glass state is placed in a platinum crucible used for single crystal growth.
After obtaining the molten material, the invention adopts a top seed crystal method to carry out single crystal growth from the molten 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, and more preferably 0.001-15 ℃/24 h; 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 30 r/min.
In the invention, after the single crystal grows to the actual required length of the single crystal, the temperature in the growth furnace is preferably reduced at the speed of 0.2-20 ℃/h, the growth furnace is closed, and the pulling is continuously carried out to pull the single crystal out of a growth interface.
The present invention is not limited to any particular process steps and equipment required for the top-seeded process, and may be practiced using process steps and equipment well known to those skilled in the art.
In the present invention, when the preparation method employs a pulling method, the preparation 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;
sequentially grinding and sintering the mixture 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 Eu2O3(ii) a The lanthanum source is preferably La2O3(ii) a The calcium source is preferably calcium carbonate; the boron source is preferably boric acid.
In the invention, the purity of the europium source, the lanthanum source, the calcium source and the boron source is preferably equal to or greater than 99.99% independently. 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 method known to those skilled in the art.
After the mixture is obtained, the mixture is sequentially ground and sintered to obtain polycrystalline powder.
The grinding process is not particularly limited, and may be performed by a method known to those skilled in the art.
In the present invention, the sintering preferably includes pre-firing and final firing; the temperature of the pre-burning is preferably 500 ℃, and the time is preferably 10 hours. The temperature of the final burning is preferably 900 ℃, and the time is preferably 48 hours.
After obtaining the polycrystalline powder, the invention melts the polycrystalline powder, introduces seed crystal from the top, 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 direction of [100], and the crystal rotation speed of the seed crystal pulling treatment is preferably 10-25 r/min, and more preferably 15-20 r/min; the pulling speed of the seed crystal pulling treatment is preferably less than or equal to 1 mm/h; the axial temperature gradient close to the liquid surface in the seed crystal pulling treatment process is preferably 30-60 ℃/cm, and more preferably 40-50 ℃/cm.
After the seed crystal pulling treatment is finished, the temperature is preferably reduced to room temperature at a cooling rate of 50 ℃/h.
In the present invention, when the preparation method adopts a hydrothermal method, a Bridgman method, a float zone method or a kyropoulos method, the process of the hydrothermal method, the Bridgman method, the float zone method or the kyropoulos method is not limited in any way, and can be performed by a process known to those skilled in the art.
The invention also provides the application of the europium-doped borate laser crystal material in the technical scheme or the europium-doped borate laser crystal material prepared by the preparation method in the technical scheme 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 the method may be performed by a method known to those skilled in the art.
The europium-doped borate laser crystal material and the preparation method and application thereof provided by the invention are described in detail with reference to the following examples, but the materials should not be construed as limiting the scope of the invention.
Example 1
According to the europium: lanthanum: calcium: mixing 10.56g of europium oxide (with the purity being more than or equal to 99.99 wt%), 316.22g of lanthanum oxide (with the purity being more than or equal to 99.99 wt%), 100.09g of calcium carbonate (with the purity being more than or equal to 99.99 wt%) and 628g of boric acid (with the purity being more than or equal to 99.99 wt%) to obtain a mixture;
placing 1054.87g of the mixture into an agate mortar with the diameter of 18cm, grinding for 10min in the clockwise and anticlockwise directions with the same number of turns, filling the ground material into a corundum crucible, compacting until the filling height reaches 15cm, placing the corundum crucible into a muffle furnace, and heating to 1000 ℃ at the heating rate of 1 ℃ min in the air atmosphere for sintering for 24h 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 the mixture into a corundum crucible, compacting until the filling height reaches 15cm, placing the mixture into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min in the air atmosphere, sintering for 10h, melting to a platinum crucible with the diameter of 10cm in batches at 1040 ℃, and performing the top seed crystal method operation after the molten material occupies 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 out of a growth interface, the temperature in the furnace is reduced to the 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 room temperature absorption spectrum of the europium-doped borate laser crystal material, and it can be seen from FIG. 1 that the europium-doped borate laser crystal material shows a strong absorption peak near 395nm due to the capability transition of europium ions as rare earth active ions through europium ions (II)5D0→7F0,5D0→7F1,5D0→7F2,5D0→7F3,5D0→7F4) Visible yellow-red laser with a wave band of 560-720 nm can be generated, a developed GaN semiconductor laser with a laser wavelength of 395nm is adopted to pump the europium-doped calcium lanthanum borate laser element, europium ions can effectively absorb pumping energy, and the europium-doped calcium lanthanum borate has a strong absorption peak near 395 nm;
fig. 4 is a diagram of an object of the europium-doped borate laser crystal material, and as can be seen from fig. 4, the crystal has a large size, good quality and no obvious inclusion.
Example 2
According to the europium: lanthanum: calcium: mixing 24.64g of europium oxide (with the purity being more than or equal to 99.99 wt%), 303.18g of lanthanum oxide (with the purity being more than or equal to 99.99 wt%), 100.09g of calcium carbonate (with the purity being more than or equal to 99.99 wt%) and 628g of boric acid (with the purity being more than or equal to 99.99 wt%) to obtain a mixture;
placing 1055.91g of the mixture into an agate mortar with the diameter of 18cm, grinding for 10min in the clockwise and anticlockwise directions with the same number of turns, filling the ground material into a corundum crucible, compacting until the filling height reaches 15cm, placing the corundum crucible into a muffle furnace, and heating to 1000 ℃ at the heating rate of 1 ℃ min in the air atmosphere for sintering for 24h 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 the mixture into a corundum crucible, compacting until the filling height reaches 15cm, placing the mixture into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min in the air atmosphere, sintering for 10h, melting to a platinum crucible with the diameter of 10cm in batches at 1040 ℃, and performing the top seed crystal method operation after the molten material occupies 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 out of the growth interface, the temperature in the furnace is reduced to the 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 7% Eu-LCB) is obtained.
Example 3
According to the europium: lanthanum: calcium: mixing 35.2g of europium oxide (with the purity being more than or equal to 99.99 wt%), 293.4g of lanthanum oxide (with the purity being more than or equal to 99.99 wt%), 100.09g of calcium carbonate (with the purity being more than or equal to 99.99 wt%) and 628g of boric acid (with the purity being more than or equal to 99.99 wt%) to obtain a mixture;
placing 1056.69g of the mixture into an agate mortar with the diameter of 18cm, grinding for 10min in the clockwise and anticlockwise directions with the same number of turns, filling the ground material into a corundum crucible, compacting until the filling height reaches 15cm, placing the corundum crucible into a muffle furnace, and heating to 1000 ℃ at the heating rate of 1 ℃/min in the air atmosphere for sintering for 24h 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 720g of polycrystalline powder, grinding for 10min, filling the mixture into a corundum crucible, compacting until the filling height reaches 15cm, placing the mixture into a muffle furnace, heating to 600 ℃ at the heating rate of 1 ℃/min in the air atmosphere, sintering for 10h, melting the mixture to a platinum crucible with the diameter of 10cm in batches at 1040 ℃ until the molten material occupies two thirds of the volume of the crucible, and then carrying out the operation of a top seed crystal method: 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 out of the growth interface, the temperature in the furnace is reduced to the 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 10% Eu-LCB) is obtained.
Test example
Cutting the europium-doped borate laser crystal material prepared in the embodiment 1-3 according to a class I phase matching angle, and 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, a 395nm GaN semiconductor laser is used for pumping the europium-doped borate laser crystal material, so that 560-720 nm fundamental frequency light can be obtained. Wherein, fig. 2 is a fluorescence spectrum of the europium-doped borate laser crystal material of embodiment 2 at an excitation wavelength of 395nm, and the centers of emission peaks of the europium-doped calcium lanthanum borate laser elements are respectively located at 575nm, 585nm, 615nm and 695nm, so as to obtain yellow-red laser output;
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, and it can be seen from FIG. 3 that Eu3+Is/are as follows5D0And7F0the number of emission peaks observed in the spectrum as transitions between them without splitting in the crystal field means Eu in the crystal lattice3+The number of sites occupied by ions. 10% Eu in FIG. 33+Spectrum of doped LCB crystal5D0→7F0The emission peak is split into two, proving that Eu3+The ions occupy two lattice sites in the crystal structure, namely, when the content of europium reaches a certain range, the europium replaces part of lanthanum element and also replaces part of calcium 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 it can be seen from FIG. 5 that the europium-doped borate laser crystal material has main emission wavelengths of 575 to 590nm, 590 to 630nm and 685 to 702 nm;
therefore, the main production modes of visible laser in the market at present comprise methods such as crystal second harmonic generation, dual-wavelength internal frequency combination, Raman laser frequency multiplication, optical pump semiconductor vertical external cavity surface emitting laser, intracavity frequency multiplication, Raman fiber laser/amplifier and external cavity frequency multiplication, but the modes basically use frequency multiplication conversion, so that the laser structure is more complex and the size is larger.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A europium-doped borate laser crystal material is characterized by having a chemical formula as follows: (Eu)xLa1-x)2CaB10O19，
Wherein, the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.999.
2. The europium-doped borate laser crystal material of claim 1, wherein x has a value in the range: x is more than or equal to 0.001 and less than or equal to 0.50.
3. The europium-doped borate laser crystal material of claim 1, wherein x has a value in the range: x is more than or equal to 0.001 and less than or equal to 0.25.
4. The method for preparing the europium-doped borate laser crystal material of any one of claims 1 to 3, comprising 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 Bridgman-Stockbarge method, a Czochralski method, a fluxing agent method, a floating zone method or a kyropoulos method to obtain the europium-doped borate laser crystal material.
5. The method of claim 4, wherein when the mixture is processed by a flux method, the method comprises the steps of:
sequentially grinding and sintering the mixture to obtain polycrystalline powder;
mixing the polycrystalline powder and the fluxing agent powder, and melting to obtain molten material;
and performing single crystal growth from the molten material by adopting a top seed crystal method to obtain the europium-doped borate laser crystal material.
6. The preparation method according to claim 5, wherein the sintering temperature is 200-1200 ℃ and the holding time is 0.1-240 h.
7. The method according to claim 6, wherein a temperature rise rate at which the temperature is raised to the sintering temperature is 0.01 to 20 ℃/min.
8. The method of claim 5, wherein the melting temperature is 900 to 1200 ℃.
9. The preparation method according to claim 5, wherein 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.
10. Use of the europium-doped borate laser crystal material of any one of claims 1 to 3 or the europium-doped borate laser crystal material prepared by the preparation method of any one of claims 4 to 9 in an all-solid-state laser.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
| CN1786297A (en) * | 2004-12-10 | 2006-06-14 | 中国科学院理化技术研究所 | R2CaB10O19Flux growth method of single crystal |
| CN101514489A (en) * | 2008-02-22 | 2009-08-26 | 中国科学院理化技术研究所 | Fluoborate containing rare earth ions, crystal, growth method and application of crystal |
| CN102021641A (en) * | 2009-09-14 | 2011-04-20 | 中国科学院理化技术研究所 | R2CaB10O19Directional seed crystal growth method of single crystal |
| CN112662399A (en) * | 2020-12-23 | 2021-04-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Fluorescent powder excited by cathode ray to emit light and preparation method thereof |
-
2021
- 2021-09-22 CN CN202111106058.0A patent/CN113818078B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
| CN1786297A (en) * | 2004-12-10 | 2006-06-14 | 中国科学院理化技术研究所 | R2CaB10O19Flux growth method of single crystal |
| CN101514489A (en) * | 2008-02-22 | 2009-08-26 | 中国科学院理化技术研究所 | Fluoborate containing rare earth ions, crystal, growth method and application of crystal |
| CN102021641A (en) * | 2009-09-14 | 2011-04-20 | 中国科学院理化技术研究所 | R2CaB10O19Directional seed crystal growth method of single crystal |
| CN112662399A (en) * | 2020-12-23 | 2021-04-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Fluorescent powder excited by cathode ray to emit light and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| LIN HUIHONG，ET AL.: "Luminescence and site occupancies of Eu3+ in La2CaB10O19", 《DALTON TRANSACTIONS》 * |
| PAZIK, ROBERT，ET AL.: "Temperature induced emission quenching processes in Eu3+-doped La2CaB10O19", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| RUI GUO，ET AL.: "Optical transition probabilities of Er3+ ions in La2CaB10O19 crystal", 《CHEMICAL PHYSICS LETTERS》 * |
| XIONG, H. H.，ET AL.: "Rare earth doped lanthanum calcium borate polycrystalline red phosphors", 《ADVANCES IN MATERIALS SCIENCE AND ENGINEERING》 * |
| 李岚: "溶胶-凝胶法合成掺铕硼酸镧钙荧光粉及其表征", 《广东化工》 * |
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