CN107201543B - Titanium-doped gallium oxide crystal and preparation method and application thereof - Google Patents
Titanium-doped gallium oxide crystal and preparation method and application thereof Download PDFInfo
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- CN107201543B CN107201543B CN201710440548.1A CN201710440548A CN107201543B CN 107201543 B CN107201543 B CN 107201543B CN 201710440548 A CN201710440548 A CN 201710440548A CN 107201543 B CN107201543 B CN 107201543B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
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Abstract
The invention relates to a titanium-doped gallium oxide crystal and a preparation method and application thereof. The molecular formula of the crystal is beta- (Ga)1‑xTix)2O3，0.0001<x<0.1. The invention adopts a guided mode method to grow beta- (Ga)1‑ xTix)2O3And (4) crystals. Ti is used as active ions, the fluorescence spectrum is positioned in visible and near infrared wave bands, the emission spectrum is wide, and the laser is suitable for ultrafast laser output of the wave bands and wide-band tunable laser output. Compared with the prior art, the titanium-doped gallium oxide crystal has high thermal conductivity and small lattice distortion after doping of Ti ions, and can be used as ultrafast laser and tunable laser gain medium.
Description
Technical Field
The invention relates to a novel laser crystal and a preparation method and application thereof, in particular to a titanium-doped gallium oxide crystal and a preparation method and application thereof, belonging to the technical field of crystals and devices.
Background
The ultrafast laser has the excellent characteristics of ultrashort pulse width, ultrahigh peak power and the like, can provide extreme physical conditions and advanced experimental means in various fields, and has important application value in the fields of processing, storage, medical treatment, communication, scientific research, national defense and the like.
The current common ultrafast and tunable laser crystal is Ti: Al2O3、Cr:LiSrAlF6、Cr:LiCaAlF6Wherein Cr is LiSrAlF6、Cr:LiCaAlF6The crystal has low thermal conductivity, is not suitable for high-power laser output and is appliedTo a limit. Ti of Al2O3The crystal has high thermal conductivity and wide emission spectrum, and is an ultrafast laser gain medium with excellent comprehensive performance. But Ti is Al2O3In the crystal, the difference between the radius of Ti ions and the radius of Al ions is large, and the lattice mismatch is serious, so that the growth difficulty of the crystal is large, and the crystal quality is not high. Moreover, the segregation coefficient of Ti ions is small, which easily causes the uneven distribution of ion concentration and is difficult to obtain high-doped Ti, Al and the like2O3And (4) crystals.
In view of the above, the laser crystal with wide coverage of the emission band, stable physicochemical properties, and high thermal conductivity has important application value, and has been the focus of research. Chinese patent document CN104005085A (application number: 201410263449.7) discloses an ytterbium-activated lutetium calcium borate ultrafast laser crystal, the chemical formula of which is Ca3Lu2(1-x)Yb2x(BO3)4，0<x<1，Yb3+Substitution of Lu in crystals3+. The method is characterized in that: adopts Lu with the purity of 99.99 percent2O3、Yb2O3With analytically pure H3BO3、CaCO3Yb is obtained by high-temperature solid-phase reaction as a raw material3+:Ca3Lu2(BO3)4And growing the polycrystal material by adopting a pulling method under the protection of nitrogen atmosphere to obtain high-quality crystals. However, the crystal has low thermal conductivity and narrow emission spectrum range, and has certain difficulty in obtaining ultrafast laser with higher energy and shorter pulse.
Ga2O3The crystal form has five crystal forms of alpha, beta, gamma and the like, wherein the beta structure is the most stable. beta-Ga2O3The crystal belongs to a monoclinic system, the heat conductivity can reach 28W/mK, is equivalent to sapphire and far exceeds common YAG and YVO4And the like. At present beta-Ga2O3As a new generation of ultra-wide bandgap semiconductor material, the material is widely researched in the semiconductor field, but at present, Ti doped beta-Ga is not available2O3Crystals are reported as laser gain media.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a titanium-doped gallium oxide crystal and a preparation method and application thereof, and the crystal can be used as a gain medium of ultrafast laser.
The technical scheme of the invention is as follows:
a titanium-doped gallium oxide crystal with a molecular formula of beta- (Ga)1-xTix)2O3，0.0001<x<0.1。
According to the invention, it is preferred that 0.005. ltoreq. x.ltoreq.0.05.
According to the invention, the thermal conductivity of the titanium-doped gallium oxide crystal is 13-28W/mK.
According to the invention, preferably, the emission spectrum of the titanium-doped gallium oxide crystal is in a wavelength band of 650-950nm, and the absorption spectrum is in a wavelength band of 450-650 nm.
According to the invention, the fluorescence lifetime of the titanium-doped gallium oxide crystal is preferably 100-200 μ s.
According to the invention, the preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Mixing gallium oxide and titanium oxide, drying in vacuum at 100-200 ℃ for 2-5 hours, pressing the dried raw material into a cake shape, and synthesizing the titanium-doped gallium oxide polycrystal material by adopting a solid phase sintering method;
(2) crystal growth
a. Heating and melting the titanium-doped gallium oxide polycrystal material in a protective atmosphere, continuously heating to 10-30 ℃ after the polycrystal material is completely melted, keeping the temperature for 1-2 hours, cooling to the temperature when the polycrystal material is completely melted, and keeping the temperature for 1-2 hours;
b. putting gallium oxide seed crystals at the temperature 1-5 ℃ higher than the melting point of the crystals, pulling and shrinking necks, and when the diameter of the seed crystals is thinned to 0.5-2mm, shouldering and growing in an equal diameter way; pulling rate of crystal during growth: 1-20 mm/h, when the crystal grows to the required size, heating to 5-10 ℃, keeping the temperature for 5-10 minutes, and then extracting and removing the crystal;
c. after the crystal growth is finished, cooling to room temperature at the speed of 10-50 ℃/hour to obtain the titanium-doped gallium oxide crystal.
Preparation method according to the inventionPreferably, the gallium oxide in step (1) is Ga2O3The titanium oxide is Ti2O3Or TiO2(ii) a More preferably, the purity of gallium oxide and titanium oxide is more than or equal to 99.999%.
According to the preparation method of the invention, preferably, the solid-phase sintering method in the step (1) is used for synthesizing the titanium-doped gallium oxide polycrystal material, and the steps are as follows:
sintering the cake-shaped raw material at 1350-1400 ℃ for 30-50 hours to obtain the titanium-doped gallium oxide polycrystal material.
According to the preparation method of the present invention, preferably, the protective atmosphere in the step (2) a is argon;
preferably, the titanium-doped gallium oxide polycrystal material is loaded into an iridium crucible and placed in an iridium mould, and in order to prevent gallium oxide from being violently volatilized at high temperature, an iridium upper cover is covered above the crucible for sealing, and the iridium upper cover is sealed with the upper edge of the crucible.
According to the production method of the present invention, it is preferable that the pulling rate of the crystal during growth in the step (2) b: 2-18 mm/h.
According to the preparation method of the present invention, preferably, after the crystal growth in step (2) is finished, the temperature is reduced to room temperature at a rate of 10-50 ℃/hour, and then the method further comprises step d: annealing the crystal at high temperature in an inert atmosphere or/and a hydrogen atmosphere to eliminate thermal stress in the crystal; further preferably, the inert atmosphere is argon; the preferred annealing atmosphere is hydrogen;
preferably, the specific annealing procedure is as follows: the temperature of the grown titanium-doped gallium oxide crystal is raised to 900-1350 ℃, the temperature is kept for 30-100 hours, and then the temperature is slowly reduced to the room temperature.
In the process of crystal growth, a small amount of tetravalent titanium may be generated, and the tetravalent titanium affects the performance of the crystal, so the invention anneals the grown crystal to eliminate the thermal stress in the crystal and reduce the content of the tetravalent titanium in the crystal.
According to the invention, the titanium-doped gallium oxide crystal is applied as an ultrafast laser crystal or a tunable laser crystal.
The principle and the beneficial effects of the invention are as follows:
the invention is in beta-Ga2O3Ti ions are doped into the crystal to obtain Ti-doped beta-Ga2O3The crystal is a brand new laser gain medium with excellent performance. Ti is used as active ions, the fluorescence spectrum is positioned in visible and near infrared wave bands, the emission spectrum is wide, and the laser is suitable for ultrafast laser output of the wave bands and wide-band tunable laser output. Compared with other materials, the titanium-doped gallium oxide crystal has the following advantages: on the one hand, in comparison with Al2O3Crystalline, beta-Ga2O3The radius of Ga ion in the crystal is similar to that of Ti ion (Ti)3+＝0.67nm,Ga3+＝0.62nm,Al3+0.535nm), the lattice distortion is small after Ti ion doping, high quality single crystal with large size is easy to obtain, and Ti ion doping is uniform. In another aspect, beta-Ga2O3The thermal conductivity of the crystal can reach 28W/mK and Al2O3The thermal conductivity of the crystal is equivalent to that of Cr, LiSrAlF6、Cr:LiCaAlF6The crystal has higher thermal conductivity, is beneficial to realizing high-energy laser output, and can be used as an ultrafast laser crystal of high-efficiency laser and a tunable laser gain medium.
Drawings
FIG. 1 shows Ti-doped beta-Ga obtained in example 1 of the present invention2O3Photograph of crystal sample.
FIG. 2 shows Ti-doped beta-Ga prepared in example 1 of the present invention2O3Absorption spectrum of crystal.
FIG. 3 shows Ti-doped beta-Ga prepared in example 1 of the present invention2O3Crystal emission spectrum.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1: x is 0.005, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.995Ti0.005)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Ga with the purity of 99.999 percent is weighed according to the stoichiometric ratio2O3、Ti2O3The raw materials are put into a mixer to be fully mixed for 48 hours. After the material mixing is finished, the mixed raw materials are dried for 5 hours in vacuum at the temperature of 100-200 ℃ to avoid the absorbed water from entering a growth system, and the dried raw materials are pressed into cakes by a hydraulic press. Then the material cake is put into a corundum crucible and sintered for 48 hours at 1350 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
a. And (2) putting the pressed raw materials into an iridium crucible, placing a cuboid iridium mould, wherein the upper surface of the iridium mould is rectangular and is provided with a through gap with the width of 0.5mm, and then sequentially placing an iridium upper cover, an iridium afterheater and a heat insulation material. The heat insulating material is required to be horizontally arranged and concentric with the crucible. Vacuum-pumping to 1 × 10-5Pa, filling high-purity argon to one atmosphere. The method comprises the steps of heating an iraurita crucible by medium-frequency induction, heating the raw material slowly by program heating, continuously heating to 10-30 ℃ after the raw material is completely melted, keeping the temperature for 1 hour, then cooling to the original temperature (the temperature when the raw material is completely melted), and keeping the temperature for 1-2 hours.
b. The melting point temperature of the crystal is 1740 ℃, the seeding temperature is regulated to 1740-1745 ℃, and the gallium oxide seed crystal is slowly contacted with the surface of the iridium die to be slightly melted and neck-collected. When the diameter of the seed crystal is narrowed to 1mm, shoulder setting and equal-diameter growth are carried out. The pulling rate of the crystal was 15 mm/h. When the crystal grows to the required size, the temperature is raised to 5-10 ℃, and the crystal is extracted after the constant temperature is kept for 30 minutes.
c. After the crystal growth is finished, cooling to room temperature at the speed of 30 ℃/h, and discharging.
d. After the crystal growth is finished, annealing the grown crystal at high temperature in a hydrogen atmosphere to eliminate the thermal stress in the crystal and reduce the content of tetravalent titanium in the crystal, wherein the specific annealing procedure is as follows: and heating the grown titanium-doped gallium oxide crystal to 1000 ℃ in a sintering furnace, keeping the temperature for 30 hours, and then slowly cooling to room temperature.
The photograph of the titanium-doped gallium oxide crystal sample prepared in this example is shown in FIG. 1.
The absorption spectrum and emission spectrum of the titanium-doped gallium oxide crystal prepared in this example are shown in fig. 2 and fig. 3, respectively.
As can be seen from FIG. 2, the absorption spectrum of the titanium-doped gallium oxide crystal has a main peak near 510nm and a broad absorption peak, and is suitable for pumping LD or 532nm laser.
As can be seen from FIG. 3, the emission peak of the titanium-doped gallium oxide crystal can cover the wavelength range of 650 to 950nm, the peak width can reach 300nm, and the crystal is very suitable for the output of ultrafast laser and tunable laser.
Example 2: x is 0.02, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.98Ti0.02)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Ga with the purity of 99.999 percent is weighed according to the stoichiometric ratio2O3、Ti2O3The raw materials are put into a mixer to be fully mixed for 48 hours. After the material mixing is finished, the mixed raw materials are dried for 2 hours in vacuum at the temperature of 100-200 ℃ to avoid the absorbed water from entering a growth system, and the dried raw materials are pressed into cakes by a hydraulic press. Then the material cake is put into a corundum crucible and sintered for 48 hours at 1400 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
The difference from the step (2) in example 1 is that: the pulling speed of the crystal is 5 mm/h; after the crystal growth is finished, the temperature is reduced to room temperature at the rate of 20 ℃/h.
Example 3: x is 0.02, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.98Ti0.02)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Ga with the purity of 99.999 percent is weighed according to the stoichiometric ratio2O3、Ti2O3The raw materials are put into a mixer to be fully mixed for 48 hours. After the material mixing is finished, the mixed raw materials are dried for 3 hours in vacuum at the temperature of 100-200 ℃ to avoid the absorbed water from entering a growth system, and the dried raw materials are driedPressing into cake shape with hydraulic press. Then the material cake is put into a corundum crucible and sintered for 48 hours at 1400 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
a. And (3) loading the pressed raw materials into an iraurita crucible, placing a cylindrical iraurita die, wherein a through hole with the diameter of 0.5mm penetrates through the upper part and the lower part of the die, an iraurita upper cover, an iraurita post-heater and a heat-insulating material, and the heat-insulating material is required to be placed horizontally and is concentric with the crucible. Vacuum-pumping to 1 × 10-4Pa, filling high-purity argon and hydrogen (0-100%) to one atmosphere. The method comprises the steps of heating an iraurita crucible by medium-frequency induction, heating the raw material slowly by program heating, continuously heating to 10-30 ℃ after the raw material is completely melted, keeping the temperature for 1-2 hours, then cooling to the original temperature, and keeping the temperature for 1-2 hours.
b. The melting point temperature of the crystal is 1740 ℃, the seeding temperature is regulated to 1740-1745 ℃, and the gallium oxide seed crystal is slowly descended to the surface of the iridium die, so that the seed crystal is slightly melted and the neck is collected. When the diameter of the seed crystal is narrowed to 0.5-2mm, the shoulder is placed and the growth with equal diameter is carried out. The crystal was pulled at a rate of 10 mm/h. When the crystal grows to the required size, the temperature is raised to 5-10 ℃, and the crystal is extracted after the constant temperature is kept for 30 minutes.
c. After the crystal growth is finished, cooling to room temperature at the speed of 30 ℃/h, and discharging.
d. After the crystal growth is finished, annealing the grown crystal at high temperature in an argon atmosphere to eliminate the thermal stress in the crystal and reduce the content of tetravalent titanium in the crystal; the specific annealing procedure is as follows: and heating the grown titanium-doped gallium oxide crystal to 1300 ℃ in a sintering furnace, keeping the temperature for 30 hours, and then slowly cooling to room temperature.
Example 4: x is 0.005, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.995Ti0.005)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Ga with the purity of 99.999 percent is weighed according to the stoichiometric ratio2O3、Ti2O3The raw materials are put into a mixer to be fully mixed for 48 hours. After the mixing is finished, the mixed materials are mixedThe raw materials are dried in vacuum at 100-200 ℃ for 3 hours, so that the absorbed water is prevented from entering a growth system, and the dried raw materials are pressed into cakes by a hydraulic press. Then the material cake is put into a corundum crucible and sintered for 48 hours at 1400 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
a. And (3) loading the pressed raw materials into an iridium crucible, and placing a rectangular iridium mould, an iridium upper cover, an iridium afterheater and a heat insulation material, wherein the heat insulation material is required to be placed horizontally and is concentric with the crucible. Vacuum-pumping to 1 × 10-4Pa, filling 1% of high-purity oxygen and 99% of high-purity carbon dioxide gas to one atmosphere. The method comprises the steps of heating an iraurita crucible by medium-frequency induction, heating the raw material slowly by program heating, continuously heating to 10-30 ℃ after the raw material is completely melted, keeping the temperature for 1-2 hours, then cooling to the original temperature, and keeping the temperature for 1-2 hours.
b. The melting point temperature of the crystal is 1740 ℃, the seeding temperature is regulated to 1740-1745 ℃, and the gallium oxide seed crystal is slowly fed in to slightly melt the seed crystal and shrink the neck. When the diameter of the seed crystal is narrowed to 0.5-2mm, the shoulder is placed and the growth with equal diameter is carried out. The crystal was pulled at a rate of 2 mm/h. When the crystal grows to the required size, the temperature is raised to 5-10 ℃, and the crystal is extracted after the constant temperature is kept for 30 minutes.
c. After the crystal growth is finished, cooling to room temperature at the speed of 20 ℃/h, and discharging.
d. After the crystal growth is finished, the grown crystal is annealed at high temperature in the argon atmosphere to eliminate the thermal stress in the crystal and reduce the content of tetravalent titanium in the crystal. The specific annealing procedure is as follows: and heating the grown titanium-doped gallium oxide crystal to 1350 ℃ in a sintering furnace, keeping the temperature for 40 hours, and then slowly cooling to room temperature.
Example 5: x is 0.01, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.99Ti0.01)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
Ga with the purity of 99.999 percent is weighed according to the stoichiometric ratio2O3、Ti2O3Putting the raw materials into a mixerFully mixing in a material machine for 48 hours. After the material mixing is finished, the mixed raw materials are dried for 5 hours in vacuum at the temperature of 100-200 ℃ to avoid the absorbed water from entering a growth system, and the dried raw materials are pressed into cakes by a hydraulic press. Then the material cake is put into a corundum crucible and sintered for 30 hours at 1400 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
a. And (3) loading the pressed raw materials into an iraurita crucible, placing a cylindrical iraurita die, wherein a through hole with the diameter of 0.5mm penetrates through the upper part and the lower part of the die, an iraurita upper cover, an iraurita post-heater and a heat-insulating material, and the heat-insulating material is required to be placed horizontally and is concentric with the crucible. Vacuum-pumping to 1 × 10-4Pa, filling high-purity argon and hydrogen (0-100%) to one atmosphere. The method comprises the steps of heating an iraurita crucible by medium-frequency induction, heating the raw material slowly by program heating, continuously heating to 10-30 ℃ after the raw material is completely melted, keeping the temperature for 1-2 hours, then cooling to the original temperature, and keeping the temperature for 1-2 hours.
b. The melting point temperature of the crystal is 1740 ℃, the seeding temperature is regulated to 1740-1745 ℃, and the gallium oxide seed crystal is slowly descended to the surface of the iridium die, so that the seed crystal is slightly melted and the neck is collected. When the diameter of the seed crystal is narrowed to 1mm, shoulder setting and equal-diameter growth are carried out. The crystal was pulled at a rate of 5 mm/h. When the crystal grows to the required size, the temperature is raised to 5-10 ℃, and the crystal is extracted after the constant temperature is kept for 30 minutes.
c. After the crystal growth is finished, cooling to room temperature at the speed of 40 ℃/h, and discharging.
d. After the crystal growth is finished, the grown crystal is annealed at high temperature in a hydrogen atmosphere to eliminate the thermal stress in the crystal and reduce the content of tetravalent titanium in the crystal. The specific annealing procedure is as follows: and heating the grown titanium-doped gallium oxide crystal to 900 ℃ in a sintering furnace, keeping the temperature for 100 hours, and then slowly cooling to room temperature.
Example 6: x is 0.03, and the chemical formula of the titanium-doped gallium oxide crystal is beta- (Ga)0.97Ti0.03)2O3
The preparation method of the titanium-doped gallium oxide crystal comprises the following steps:
(1) selection and treatment of raw materials
According to stoichiometric ratioGa with the purity of 99.999 percent is taken2O3、TiO2The raw materials are put into a mixer to be fully mixed for 48 hours. After the material mixing is finished, the mixed raw materials are dried for 5 hours in vacuum at the temperature of 100-200 ℃ to avoid the absorbed water from entering a growth system, and the dried raw materials are pressed into cakes by a hydraulic press. Then the material cake is put into a corundum crucible and sintered for 30 hours at 1400 ℃ to obtain the titanium-doped gallium oxide polycrystal material.
(2) Crystal growth
a. And (3) loading the pressed raw materials into an iraurita crucible, placing a cylindrical iraurita die, wherein a through hole with the diameter of 0.5mm penetrates through the upper part and the lower part of the die, an iraurita upper cover, an iraurita post-heater and a heat-insulating material, and the heat-insulating material is required to be placed horizontally and is concentric with the crucible. Vacuum-pumping to 1 × 10-4Pa, filling high-purity hydrogen to one atmosphere. The method comprises the steps of heating an iraurita crucible by medium-frequency induction, heating the raw material slowly by program heating, continuously heating to 10-30 ℃ after the raw material is completely melted, keeping the temperature for 1-2 hours, then cooling to the original temperature, and keeping the temperature for 1-2 hours.
b. The melting point temperature of the crystal is 1740 ℃, the seeding temperature is regulated to 1740-1745 ℃, and the gallium oxide seed crystal is slowly descended to the surface of the iridium die, so that the seed crystal is slightly melted and the neck is collected. When the diameter of the seed crystal is narrowed to 1mm, shoulder setting and equal-diameter growth are carried out. The crystal was pulled at a rate of 5 mm/h. When the crystal grows to the required size, the temperature is raised to 5-10 ℃, and the crystal is extracted after the constant temperature is kept for 30 minutes.
c. After the crystal growth is finished, cooling to room temperature at the speed of 35 ℃/h, and discharging.
d. After the crystal growth is finished, the grown crystal is annealed at high temperature in a hydrogen atmosphere to eliminate the thermal stress in the crystal, reduce the content of tetravalent titanium in the crystal and improve the proportion of trivalent titanium and tetravalent titanium in the crystal. The specific annealing procedure is as follows: and heating the grown titanium-doped gallium oxide crystal to 900 ℃ in a sintering furnace, keeping the temperature for 100 hours, and then slowly cooling to room temperature.
Claims (5)
1. A process for preparing ultrafast laser crystal or tunable laser crystal, which is the Ti-doped gallium oxide crystal with molecular formulaβ-(Ga1-xTix)2O3X is more than or equal to 0.005 and less than or equal to 0.05; the emission spectrum and the absorption spectrum of the titanium-doped gallium oxide crystal are respectively in 650-950nm wave bands and 450-650nm wave bands, and the fluorescence lifetime of the titanium-doped gallium oxide crystal is 200 mu s and 100-200 mu s;
the method comprises the following steps:
(1) selection and treatment of raw materials
Mixing gallium oxide and titanium oxide, drying in vacuum at 100-200 ℃ for 2-5 hours, pressing the dried raw material into a cake shape, and synthesizing the titanium-doped gallium oxide polycrystal material by adopting a solid phase sintering method;
(2) crystal growth
a. Heating and melting the titanium-doped gallium oxide polycrystal material in a protective atmosphere, continuously heating to 10-30 ℃ after the polycrystal material is completely melted, keeping the temperature for 1-2 hours, cooling to the temperature when the polycrystal material is completely melted, and keeping the temperature for 1-2 hours;
b. putting gallium oxide seed crystals at the temperature 1-5 ℃ higher than the melting point of the crystals, pulling and shrinking necks, and when the diameter of the seed crystals is thinned to 0.5-2mm, shouldering and growing in an equal diameter way; pulling rate of crystal during growth: 1-20 mm/h, when the crystal grows to the required size, heating to 5-10 ℃, keeping the temperature for 5-10 minutes, and then extracting and removing the crystal;
c. after the crystal growth is finished, cooling to room temperature at the speed of 10-50 ℃/hour;
d: annealing the crystal at high temperature in an inert atmosphere or/and a hydrogen atmosphere, wherein the specific annealing procedure is as follows: heating the grown titanium-doped gallium oxide crystal to 900-1350 ℃, keeping the temperature for 30-100 hours, and then slowly cooling to room temperature; and obtaining the titanium-doped gallium oxide crystal.
2. The method of claim 1, wherein the thermal conductivity of the annealed titanium-doped gallium oxide crystal is 13-28W/mK.
3. The method according to claim 1, wherein the gallium oxide in step (1) is Ga2O3The titanium oxide is Ti2O3Or TiO2。
4. The method according to claim 1, wherein the step of synthesizing the titanium-doped gallium oxide polycrystal material by the solid-phase sintering method in the step (1) is as follows:
sintering the cake-shaped raw material at 1350-1400 ℃ for 30-50 hours to obtain the titanium-doped gallium oxide polycrystal material.
5. The preparation method of claim 1, wherein the titanium-doped gallium oxide polycrystalline material is charged into an iraurita crucible in the step (2 a), and is placed in an iraurita mold, and an iraurita upper cover is sealed over the crucible, and the iraurita upper cover is sealed with the upper edge of the crucible, in order to prevent the gallium oxide from being violently volatilized at a high temperature.
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| CN201710440548.1A CN107201543B (en) | 2017-06-13 | 2017-06-13 | Titanium-doped gallium oxide crystal and preparation method and application thereof |
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| CN107201543B true CN107201543B (en) | 2020-10-27 |
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| CN109183150A (en) * | 2018-08-31 | 2019-01-11 | 南京同溧晶体材料研究院有限公司 | High heat conductance, codope gallium oxide crystal laser material of high conductivity and preparation method thereof |
| CN109183152A (en) * | 2018-09-20 | 2019-01-11 | 南京同溧晶体材料研究院有限公司 | Gallium oxide crystalline material and preparation method thereof based on titanium doped graphene quantum dot |
| CN109537055A (en) * | 2019-01-28 | 2019-03-29 | 山东大学 | A kind of semi-insulating gallium oxide crystal and preparation method thereof |
| CN112420936B (en) * | 2019-08-21 | 2021-12-07 | Tcl科技集团股份有限公司 | Nano material, preparation method and application thereof, and quantum dot light-emitting diode |
| WO2021141130A1 (en) * | 2020-01-10 | 2021-07-15 | 株式会社Flosfia | Conductive metal oxide film, semiconductor element, and semiconductor device |
| CN111739988B (en) * | 2020-06-29 | 2021-11-12 | 山东大学 | Vertical-structure broadband near-infrared LED and preparation method thereof |
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