CN102851737B - A kind of carbon dope titanium gem crystal and growth method thereof and application - Google Patents
A kind of carbon dope titanium gem crystal and growth method thereof and application Download PDFInfo
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- CN102851737B CN102851737B CN201110174994.5A CN201110174994A CN102851737B CN 102851737 B CN102851737 B CN 102851737B CN 201110174994 A CN201110174994 A CN 201110174994A CN 102851737 B CN102851737 B CN 102851737B
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Abstract
The present invention relates to a kind of carbon dope titanium gem crystal, under normal temperature, its residual Infrared Absorption coefficient is 0.01-0.001cm
-1, quality factor FOM is more than 200.Its manufacture method comprises: in Ti∶Sapphire laser raw material, add 1000-10000ppm graphite composite powder, and adopt Bridgman-Stockbarge method for growing carbon dope titanium gem crystal, the crystal after growth carries out the in-situ annealing of 1700-1900 DEG C and 40-56 hour; Crystal after annealing, is down to room temperature with the slow speed of 15-30 DEG C/h.Carbon dope titanium gem crystal of the present invention, under 25 DEG C of normal temperature, its residual Infrared Absorption coefficient reduces to 0.01-0.001cm
-1, quality factor FOM is more than 200.There is high optical homogeneity, be applicable to being applied in solid-state tunable laser.
Description
Technical field
The present invention relates to the titanium gem crystal growing technology in laserable material field, particularly the carbon dope titanium gem crystal of a kind of low residual Infrared Absorption coefficient, high quality factor and growth method thereof.
Background technology
Early eighties, solid-state tunable laser development is swift and violent, and the tunable laser such as Ti∶Sapphire laser, chrysoberyl successively occurs, wherein particularly outstanding is the research of Ti∶Sapphire laser.
Ti∶Sapphire laser (Ti:Al
2o
3) crystal is a kind of tunable laser crystal material of excellent performance, tool has been widely used.Titanium gem crystal is after NbYAG, affect larger a kind of laser crystal material.Ti sapphire laser has that tuning range is wide, efficiency of conversion is high, the life-span is long and have the features such as multiple pumping source, be widely used in the fields such as environmental pollution monitoring, Military Application, transient optical state, laser spectrum, laser chemistry, laser remote sensing, lidar, be subject to the most attention of various countries scientist and the military.But, because the titanium atom in titanium gem crystal appraises at the current rate in process of growth, can Ti be formed
+, Ti
2+, Ti
3+and Ti
4+, and to laser advantageously Ti
3+, so should make great efforts to improve Ti in growing crystal process
3+content.Due to Ti
4+ionic radius be less than Ti
3+ionic radius, therefore, Ti
4+comparatively Ti
3+easy replacement Al
3+form substitutional ion.So the determinacy of titanium gem crystal growth valence state just becomes the key preparing excellent titanium gem crystal.
At Ti:Al
2o
3process of growth in, the most important thing is to solve the valence state problem of titanium ion.The electronic configuration of Ti atom is: 1s
22s
22p
63s
23p
63d
24s
2, can Ti be formed
+, Ti
2+, Ti
3+and Ti
4+plasma, active ions only have Ti
3+(3d
1) and Ti
2+(3d
2).For laser crystals, importantly Ti
3+ion, its level structure is simple, does not have excited state absorption.The key of growth titanium gem crystal is the residual Infrared Absorption overcoming laser wavelength, improves quality factor FOM value.The residual Infrared Absorption of titanium gem crystal then derives from the Ti existed in crystal
4+, because Ti
3+-Ti
4+ion pair will produce additional absorption.Solving the method for this problem, is suppress Ti
4+growth and promote Ti
4+change into Ti
3+.
The domestic research to Ti∶Sapphire laser never stops, because there is laser wavelength in titanium gem crystal occurs very wide absorption problem, be called residual Infrared Absorption, affect laser, workers conduct extensive research its root and removing measures, and research finds that residual Infrared Absorption originates from crystal and there is Ti
3+-Ti
4+the model of ion pair, due to Ti
3+the 3d electronics of ion is at Ti
4+under the coulomb field impact in ion and Al room, become and can absorb infrared photon and excite, therefore the principle eliminating residual Infrared Absorption be exactly 4 valency ion Ti in Ti∶Sapphire laser
4+become 3 valency ion Ti completely
3+.
But will by the Ti of remnants
4+ion reduction becomes Ti
3+ion is than Ti
3+ion-oxygen changes into Ti
4+ion difficulty is a lot.Multiple method is there has been proposed based on this difficult problem, as patent EP0241614, its technology point is, a small amount of reducing gas is added in the inert atmosphere that common Ti∶Sapphire laser grows, such as hydrogen or carbon monoxide, come the reductibility of growth regulation atmosphere or oxygen partial pressure to control the valence state of titanium ion, also improve the optical quality of Ti∶Sapphire laser simultaneously.But subsequently, the contriver of patent EP0241614 finds, the effect controlling titanium ion valence state or raising Ti∶Sapphire laser quality factor is in this way very limited, the quality factor FOM that can reach mostly is 60-80, more not how many than the titanium gem crystal quality factor height that grows from inertia growth atmosphere condition, far do not reach the requirement (more than 150) of actual use, therefore the Ti∶Sapphire laser grown out in this way is adopted, still the same with from inertia growth atmosphere conditioned growth Ti∶Sapphire laser out, could use after must annealing in stronger reducing atmosphere.
In fact, at the temperature of Ti∶Sapphire laser growth, alumina melt is in a kind of oxidation-reduction equilibrium state, can produce more immediate influence, the valence state of titanium can not be controlled by growth atmosphere completely simply to the state of oxidation of titanium.Therefore grow low residual absorption coefficient, the Ti doped saphire of high quality factor is still a technical barrier.
Based on above-mentioned background, one is still needed to grow low residual absorption coefficient, the method for the Ti doped saphire of high quality factor at present.
Summary of the invention
The object of the present invention is to provide a kind of low residual absorption coefficient, the carbon dope titanium gem crystal of high quality factor.Be 0.01-0.001cm under residual Infrared Absorption coefficient 25 DEG C of normal temperature of described carbon dope titanium gem crystal
-1, quality factor FOM is more than 200, reaches as high as 250.
" residual Infrared Absorption coefficient " used in the present invention refers to the residual Infrared Absorption factor alpha of 800nm under 25 DEG C of normal temperature
800.
" quality factor FOM " used in the present invention refers to the ratio of the uptake factor at uptake factor at 490nm place of crystal under 25 DEG C of normal temperature and 800nm place.Quality factor FOM reacts Ti ion existence and concentration, is a kind of important indicator of Ti∶Sapphire laser quality.
Herein, when separately not indicating, described content is weight ratio or weight percent content.
For achieving the above object, the growth method of carbon dope titanium gem crystal of the present invention, by the graphite composite powder of the 1000-10000ppm that adulterates in Ti∶Sapphire laser raw material, and adopting the monocrystal growing furnace of graphite heater and argon gas atmosphere to grow the titanium gem crystal of carbon dope, the strong reducing property of the carbon in matrix under melt temperature substantially increases Ti in Ti∶Sapphire laser
4+to Ti
3+transformation, thus reduce Ti
4+content, overcome Ti in titanium gem crystal
4+ion content is too high and cause the shortcoming of residual Infrared Absorption thus, thus solve the difficult problem that Ti∶Sapphire laser residual absorption affects its laser activity, adopt in-situ annealing technology simultaneously, further raising titanium gem crystal quality, realize low residual absorption coefficient, high quality factor, the growth of high optical homogeneity titanium gem crystal.
For this reason, another object of the present invention is to provide the growth method of carbon dope titanium gem crystal.The method comprises, and adds 1000-10000ppm graphite composite powder in Ti∶Sapphire laser raw material, adopts Bridgman-Stockbarge method for growing carbon dope titanium gem crystal; Crystal after growth carries out the in-situ annealing of 1700-1900 DEG C and 40-56 hour; Crystal after annealing, is down to room temperature with the slow speed of 15-30 DEG C/h.
Preferably, the growth method of a kind of carbon dope titanium gem crystal of the present invention, comprising:
1000-10000ppm graphite composite powder is added, 10 in Ti∶Sapphire laser raw material
-3-10
-4pa vacuum and 1700-1800 DEG C carry out presintering, at 1-3t/cm
2loading after isostatic pressing is equipped with in the crucible of seed crystal;
Monocrystal growing furnace growing crystal under graphite heater and inert ambient environment.
In the present invention, preferred Ti∶Sapphire laser raw material is aluminum oxide and titanium sesquioxide, and its weight ratio is 100: (0.1-1.5).
Preferably, the purity of aluminum oxide and titanium sesquioxide is more than 99.99% (weight).
Preferably, rare gas element is argon gas.
Preferably, seed crystal is directed white stone seed crystal, is more preferably the directed white stone seed crystal in a axle (110) direction, and most preferably seed crystal is the directed white stone seed crystal of Bridgman-Stockbarge method for growing.
Preferably, inert atmosphere pressure is 15-30KPa.
Preferably, growing crystal process comprises: under graphite heater and inert ambient environment by isostatic pressing after the powder loaded in crucible continue to be warming up to melt temperature 2050-2080 DEG C, constant temperature 2-5 hour, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means and carry out crystal growth, be set in by the temperature gradient of solid-liquid interface of crystal growth within the scope of 15-35 DEG C/cm, crucible fall off rate controls within the scope of 0.1-2.0mm/h.
Preferably, after crystal growth terminates, with the speed of 20-45 DEG C/h, furnace temperature is down to room temperature.
A preferred embodiment of the invention, the growth method of carbon dope high quality factor titanium gem crystal, can comprise the steps:
(1) in the seed slot of decline stove molybdenum crucible, put into the directed white stone seed crystal in a axle (110) direction;
(2) choosing mass ratio is 100: the high purity aluminium oxide (99.99%) of (0.1-1.5) and High Purity Titanium Sesquioxide (99.99%) powder, 10
-3-10
-4pa vacuum and 1700-1800 DEG C carry out presintering, at 1-3t/cm
2after isostatic pressing, load in crucible, be placed on the tripod of decline stove together;
(3) system sealing, is evacuated to 10
-3-10
-4pa, is warming up to 1500-1700 DEG C, is filled with high-purity argon gas as shielding gas, and being charged to pressure is 15-30Kpa;
(4) continue to be warming up to melt temperature 2050-2080 DEG C, constant temperature 2-5 hour, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means and carry out crystal growth, be set within the scope of 15-35 DEG C/cm by the solid-liquid interface temperature ladder of crystal growth, crucible fall off rate controls within the scope of 0.1-2.0mm/h;
(5), after crystal growth terminates, with the speed of 20-45 DEG C/h, furnace temperature is down to room temperature;
(6) crystal of growth is carried out in-situ annealing, annealing temperature is 1700-1900 DEG C, is incubated after 40-56 hour, makes titanium gem crystal internal stress be released and cut down crystal structure defects, then be slowly down to room temperature with the speed of 15-30 DEG C/h, take out crystal.
In the growth method of carbon dope titanium gem crystal of the present invention, preferably, seed crystal is the directed white stone of high quality prepared by Bridgman-Stoekbarger Technique self-growth, in descent method for growing technology, Ti∶Sapphire laser is beneficial to the stable growth of crystal on a face, therefore, the directed white stone seed crystal in more preferably a axle (110) direction.
In the growth method of carbon dope titanium gem crystal of the present invention, Ti∶Sapphire laser raw material is made up of high purity aluminium oxide and High Purity Titanium Sesquioxide, and wherein, " high-purity " refers to that purity reaches more than 99.99%.The mass ratio of high purity aluminium oxide and High Purity Titanium Sesquioxide is 100: (0.1-1.5), if the mass ratio of High Purity Titanium Sesquioxide is lower than lower limit, then titanium ion does not reach the required concentration requirement of Ti∶Sapphire laser bright dipping, if the mass ratio of High Purity Titanium Sesquioxide is higher than the upper limit, then the excessive meeting of titanium ion causes concentration quenching and reduces luminous efficiency, therefore, in the present invention, the mass ratio of high purity aluminium oxide and High Purity Titanium Sesquioxide is 100: (0.1-1.5).
In the growth method of carbon dope titanium gem crystal of the present invention, the addition of graphite composite powder controls at 1000-10000ppm, if graphite composite powder addition is less than 1000ppm, then and the Ti in crystal
4+fully can not be reduced into Ti
3+if graphite composite powder addition is greater than 10000ppm, then excess carbon can cause the optical property of crystal to decline.
In the present invention, the solid-liquid interface temperature ladder of crystal growth is set within the scope of 15-35 DEG C/cm, if the temperature ladder of setting is less than 15 DEG C/cm, namely too small thermograde is unfavorable for the stable growth of crystal, does not also meet the principle of economical deposition; If the temperature ladder of setting is greater than 35 DEG C/cm, then excessive thermograde can cause titanium gem crystal process of growth to occur cracking phenomena.
In the present invention, crucible fall off rate controls within the scope of 0.1-2.0mm/h, if fall off rate is less than 0.1mm/h, though be then conducive to the stable growth of crystal, but a kind of waste of energy; If fall off rate is greater than 2.0mm/h, then can cause the stress cracking of crystal in process of growth.Therefore, the result considered, in the present invention, crucible fall off rate to control within the scope of 0.1-2.0mm/h as well.
In the present invention, after crystal growth terminates, with the speed of 20-45 DEG C/h, furnace temperature is down to room temperature, if rate of temperature fall is less than 20 DEG C/h, then causes the waste of the energy and the loss of equipment, if rate of temperature fall is greater than 45 DEG C/h, then cause the stress of crystal to ftracture.
In the present invention, by carrying out in-situ annealing to the crystal after growth, the uniformity coefficient of abatement matter crystal internal defect, raising crystal, improves the optical property of carbon dope titanium gem crystal.Annealing temperature is 1700-1900 DEG C, is incubated after 40-56 hour, is slowly down to room temperature with the speed of 15-30 DEG C/h, takes out crystal.If annealing temperature is less than 1700 DEG C, does not then possess crystals and cut down the energy required for defect and do not reach annealing effect, if annealing temperature is greater than 1900 DEG C, then can cause the softening even melting of titanium gem crystal.
The present invention by adding the graphite composite powder of trace in Ti∶Sapphire laser raw material, thus utilize the strong reducing property feature of graphite carbon under melt temperature in matrix, do auxiliary with the reduction atmosphere manufactured by the inert atmosphere of graphite heater, reach the object controlling titanium valence state, adopt in-situ annealing method simultaneously, improve the annealing effect of Ti∶Sapphire laser.Annealing is mainly manifested in 3 points to the effect of crystal: one is, annealing can cut down the point-line-surface defect of crystals.Due to Ti ratio of ionic radii Al ionic radius large 26%, in process of growth, there is part Ti ion do not enter case completely, reduced anneal can provide thermodynamic power for Ti ion enters normal case, annealing can also cut down crystal Dislocations, the subsurface defects such as low angle boundary, reduce scattering and residual absorption center in titanium gem crystal; Two are, annealing can discharge the thermal stresses of crystal in process of growth, improve the optical homogeneity of crystal; Three are, reduced anneal can make Ti further
4+be converted into Ti
3+, improve Ti
3+content, improve main uptake factor.Realize the specification of quality of the low residual absorption coefficient of Ti doped saphire, high quality factor, high optical homogeneity.
Accompanying drawing explanation
Fig. 1 is the structural representation of growth titanium gem crystal decline stove.
Embodiment
By the following description of the embodiments, to the features and advantages of the invention clearly, but will should be appreciated that the present invention is not limited only to these embodiments.Without departing from the inventive concept of the premise, other embodiments of more evolutions or improvement can also be had, and these changes and improvements all should belong to scope of the present invention.
For decline stove as shown in Figure 1, some embodiments of the high quality factor titanium gem crystal of descent method for growing carbon dope are described.
As shown in Figure 1, decline stove comprises: graphite heater 1, molybdenum crucible 2, tripod 3, crucible moving device 4.
Embodiment 1: the high quality factor titanium gem crystal of Bridgman-Stockbarge method for growing carbon dope
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning taking aluminum oxide and titanium sesquioxide is the powder 3000 grams of 100: 1, add high purity graphite (99.99%) powder of 1000ppm, after Homogeneous phase mixing, use 2t/cm
2the isostatic pressed of (ton/square centimeter) forges into block, loads in molybdenum crucible 2 in a vacuum, be placed on the tripod 3 of decline stove together after 1700 DEG C of presintering, regulates the distance of molybdenum crucible 2 and graphite heater 1, ensures center superposition.After system is airtight, be evacuated to 4 × 10
-4pa, is warming up to 1600 DEG C.Being filled with high-purity argon gas to pressure is 15KPa, continue to be warming up to melt temperature 2050 DEG C, constant temperature 5 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 35 DEG C/cm, and crucible fall off rate controls as 0.6mm/h, after crystal growth terminates, with the speed of 40 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1850 DEG C, is incubated 40 hours, slowly be down to room temperature with the speed of 25 DEG C/h again, take out titanium gem crystal.The optical property of the carbon dope titanium gem crystal adopting JASCO V-570 UV/VIS/NIR spectrophotometric determination to obtain, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800for 0.01cm
-1, quality factor FOM reaches 205.
Embodiment 2
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, take the powder 3000 grams of aluminum oxide 100: 1 titanium sesquioxide quality proportioning, add high purity graphite (99.99%) powder of 3000ppm, after Homogeneous phase mixing, use 2t/cm
2isostatic pressed forge into block, load in molybdenum crucible 2 after 1700 DEG C of pre-burnings in a vacuum, be placed on the tripod 3 of decline stove together, regulate the distance of molybdenum crucible 2 and graphite heater 1, ensure center superposition, system is airtight, is evacuated to 3 × 10
-4pa, is warming up to 1550 DEG C.Being filled with high-purity argon gas to pressure is malleation 20KPa, continue to be warming up to melt temperature 2060 DEG C, constant temperature 4.5 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 30 DEG C/cm, fall off rate controls as 0.5mm/h, after crystal growth terminates, with the speed of 35 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1800 DEG C, be incubated 45 hours, slowly room temperature is down to again with 20 DEG C/h, take out titanium gem crystal, JASCO V-570UV/VIS/NIR spectrophotometer is adopted to test the Ti doped saphire optical quality obtained, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800reduce to 0.008cm
-1, quality factor FOM reaches 210.
Embodiment 3
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning taking aluminum oxide and titanium sesquioxide is the powder 3000 grams of 100: 1, add high purity graphite (99.99%) powder of 6000ppm, after Homogeneous phase mixing, use 2t/cm
2the isostatic pressed of (ton/square centimeter) forges into block, loads in molybdenum crucible 2 in a vacuum, be placed on the tripod 3 of decline stove together after 1700 DEG C of pre-burnings, regulate the distance of molybdenum crucible 2 and graphite heater 1, ensure center superposition, system is airtight, is evacuated to 2 × 10
-4pa, is warming up to 1500 DEG C.Being filled with high-purity argon gas to pressure is malleation 25KPa, continue to be warming up to melt temperature 2070 DEG C, constant temperature 4 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 25 DEG C/cm, and crucible fall off rate controls as 0.4mm/h, after crystal growth terminates, with the speed of 35 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1750 DEG C, is incubated 48 hours, slowly be down to room temperature with the speed of 20 DEG C/h again, take out titanium gem crystal.JASCO V-570UV/VIS/NIR spectrophotometer is adopted to test the optical quality of the Ti doped saphire obtained, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800reduce to 0.006cm
-1, quality factor FOM reaches 218.
Embodiment 4
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning taking aluminum oxide and titanium sesquioxide is the powder 3000 grams of 100: 1, add high purity graphite (99.99%) powder of 9000ppm, after Homogeneous phase mixing, use 2t/cm
2the isostatic pressed of (ton/square centimeter) forges into block, loads in molybdenum crucible 2 in a vacuum, be placed on the tripod 3 of decline stove together after 1700 DEG C of pre-burnings, regulate the distance of molybdenum crucible 2 and graphite heater 1, ensure center superposition, system is airtight, is evacuated to 1 × 10
-4pa, is warming up to 1600 DEG C.Being filled with high-purity argon gas to pressure is malleation 30kpa, continue to be warming up to melt temperature 2080 DEG C, constant temperature 3.5 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 20 DEG C/cm, and crucible fall off rate controls as 0.3mm/h, after crystal growth terminates, with the speed of 30 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1750 DEG C, is incubated 56 hours, slowly be down to room temperature with the speed of 20 DEG C/h again, take out titanium gem crystal.JASCO V-570 UV/VIS/NIR spectrophotometer is adopted to test the optical quality of the Ti doped saphire obtained, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800reduce to 0.004cm
-1, quality factor FOM reaches 220.
Embodiment 5
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning taking aluminum oxide and titanium sesquioxide is the powder 3000 grams of 100: 0.5, add high purity graphite (99.99%) powder of 6000ppm, after Homogeneous phase mixing, use 1t/cm
2the isostatic pressed of (ton/square centimeter) forges into block, loads in molybdenum crucible 2 in a vacuum, be placed on the tripod 3 of decline stove together after 1800 DEG C of pre-burnings, regulate the distance of molybdenum crucible 2 and graphite heater 1, ensure center superposition, system is airtight, is evacuated to 2 × 10
-4pa, is warming up to 1500 DEG C.Being filled with high-purity argon gas to pressure is malleation 25KPa, continue to be warming up to melt temperature 2070 DEG C, constant temperature 4 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 25 DEG C/cm, and crucible fall off rate controls as 0.4mm/h, after crystal growth terminates, with the speed of 35 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1800 DEG C, is incubated 48 hours, slowly be down to room temperature with the speed of 20 DEG C/h again, take out titanium gem crystal.JASCO V-570 UV/VIS/NIR spectrophotometer is adopted to test the optical quality of the Ti doped saphire obtained, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800reduce to 0.005cm
-1, quality factor FOM reaches 205.
Embodiment 6
In decline stove molybdenum crucible 2 seed slot in put into the directed white stone seed crystal in a axle (110) direction.Ti∶Sapphire laser raw material adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning taking aluminum oxide and titanium sesquioxide is the powder 3000 grams of 100: 1.5, add high purity graphite (99.99%) powder of 6000ppm, after Homogeneous phase mixing, use 3t/cm
2the isostatic pressed of (ton/square centimeter) forges into block, loads in molybdenum crucible 2 in a vacuum, be placed on the tripod 3 of decline stove together after 1800 DEG C of pre-burnings, regulate the distance of molybdenum crucible 2 and graphite heater 1, ensure center superposition, system is airtight, is evacuated to 2 × 10
-4pa, is warming up to 1500 DEG C.Being filled with high-purity argon gas to pressure is malleation 25kpa, continue to be warming up to melt temperature 2070 DEG C, constant temperature 4 hours, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means 4, namely crystal growth is carried out, the solid-liquid interface temperature ladder of crystal growth is set as 25 DEG C/cm, and crucible fall off rate controls as 0.4mm/h, after crystal growth terminates, with the speed of 35 DEG C/h, furnace temperature is down to room temperature, carry out in-situ annealing process, annealing temperature is 1800 DEG C, is incubated 48 hours, slowly be down to room temperature with the speed of 20 DEG C/h again, take out titanium gem crystal.JASCO V-570 UV/VIS/NIR spectrophotometer is adopted to test the optical quality of the Ti doped saphire obtained, residual Infrared Absorption factor alpha under 25 DEG C of normal temperature
800reduce to 0.009cm
-1, quality factor FOM reaches 201.
Claims (17)
1. a carbon dope titanium gem crystal, is characterized in that, under 25 DEG C of normal temperature, its residual Infrared Absorption coefficient is 0.01-0.001cm
-1, quality factor FOM is more than 200, is up to 250, and wherein said residual Infrared Absorption coefficient refers to the residual Infrared Absorption factor alpha of 800nm under 25 DEG C of normal temperature
800, described quality factor FOM refers to the uptake factor and 800 of crystal at 490nm place under 25 DEG C of normal temperature
nmthe ratio of the uptake factor at place.
2. the manufacture method of carbon dope titanium gem crystal as claimed in claim 1, comprise: in Ti∶Sapphire laser raw material, add 1000-10000ppm graphite composite powder, adopt Bridgman-Stockbarge method for growing carbon dope titanium gem crystal, the crystal after growth carries out the in-situ annealing of 1700-1900 DEG C and 40-56 hour; Crystal after annealing, is down to room temperature with the slow speed of 15-30 DEG C/h.
3. method as claimed in claim 2, it is characterized in that, descent method for growing process comprises:
In Ti∶Sapphire laser raw material, add 1000-10000ppm graphite composite powder, carry out presintering, at 1-3t/cm in vacuum and 1700-1800 DEG C
2loading after isostatic pressing is equipped with in the crucible of seed crystal;
Monocrystal growing furnace growing crystal under graphite heater and inert ambient environment.
4. method as claimed in claim 3, it is characterized in that, the vacuum tightness of presintering is 10
-3-10
-4pa.
5. method as claimed in claim 2, it is characterized in that, Ti∶Sapphire laser raw material is the mixture of aluminum oxide and titanium sesquioxide, and its weight ratio is 100: (0.1-1.5).
6. method as claimed in claim 5, it is characterized in that, the purity of aluminum oxide and titanium sesquioxide is more than 99.99%.
7. method as claimed in claim 3, it is characterized in that, selected seed crystal is directed white stone seed crystal.
8. method as claimed in claim 7, it is characterized in that, directed white stone seed crystal is the directed white stone seed crystal in a axle (110) direction.
9. method as claimed in claim 7, it is characterized in that, directed white stone seed crystal passes through Bridgman-Stockbarge method for growing.
10. method as claimed in claim 3, it is characterized in that, rare gas element is argon gas.
11. methods as claimed in claim 3, it is characterized in that, inert atmosphere pressure is 15-30KPa.
12. methods as claimed in claim 3, it is characterized in that, crystal growing process comprises:
Under graphite heater and inert ambient environment by isostatic pressing after the powder loaded in crucible continue to be warming up to melt temperature 2050-2080 DEG C, constant temperature 2-5 hour, melting sources and seed crystal inoculation;
After raw material completes fusing and seed crystal completes inoculation, start crucible lowering means and carry out crystal growth, wherein, be set in by the temperature gradient of solid-liquid interface of crystal growth within the scope of 15-35 DEG C/cm, crucible fall off rate controls within the scope of 0.1-2.0mm/h.
13. methods as claimed in claim 12, is characterized in that, after the growth of carbon dope titanium gem crystal terminates, with the speed of 20-45 DEG C/h, furnace temperature are down to room temperature.
The growth method of 14. 1 kinds of carbon dope titanium gem crystals, comprises the steps:
(1) in the seed slot of decline stove molybdenum crucible, put into the directed white stone seed crystal in a axle (110) direction;
(2) with 100: the weight ratio of (0.1-1.5) prepares the powder of 99.99% high purity aluminium oxide and 99.99% High Purity Titanium Sesquioxide, 10
-3-10
-4pa vacuum and 1700-1800 DEG C carry out presintering, at 1-3t/cm
2isostatic pressing, then loads in above-mentioned crucible, is placed in by crucible on the tripod of decline stove;
(3) system sealing, is evacuated to 10
-3-10
-4pa, is warming up to 1500-1700 DEG C, is filled with argon gas as shielding gas, and being charged to malleation is 15-30Kpa;
(4) continue to be warming up to melt temperature 2050-2080 DEG C, constant temperature 2-5 hour, after raw material completes fusing and seed crystal completes inoculation, start crucible lowering means and carry out crystal growth, be set in by the temperature gradient of solid-liquid interface of crystal growth within the scope of 15-35 DEG C/cm, crucible fall off rate controls within the scope of 0.1-2.0mm/h;
(5), after crystal growth terminates, with the speed of 20-45 DEG C/h, furnace temperature is down to room temperature;
(6) crystal of growth is carried out in-situ annealing, annealing temperature is 1700-1900 DEG C, is incubated after 40-56 hour, is down to room temperature with the slow speed of 15-30 DEG C/h, takes out crystal.
15. methods as claimed in claim 14, is characterized in that, the purity of argon gas is 99.9%-99.99%.
16. as arbitrary in claim 2-15 as described in method manufacture carbon dope titanium gem crystal, under 25 DEG C of normal temperature, its residual Infrared Absorption coefficient is 0.01-0.001cm
-1, quality factor FOM is more than 200, is up to 250, and wherein said residual Infrared Absorption coefficient refers to the residual Infrared Absorption factor alpha of 800nm under 25 DEG C of normal temperature
800, described quality factor FOM refers to the ratio of the uptake factor at uptake factor at 490nm place of crystal under 25 DEG C of normal temperature and 800nm place.
The purposes of 17. carbon dope titanium gem crystals as claimed in claim 16 in solid-state tunable laser.
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