CN102851737A - Carbon-doped titanium sapphire crystal and its growing method and application - Google Patents
Carbon-doped titanium sapphire crystal and its growing method and application Download PDFInfo
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- CN102851737A CN102851737A CN2011101749945A CN201110174994A CN102851737A CN 102851737 A CN102851737 A CN 102851737A CN 2011101749945 A CN2011101749945 A CN 2011101749945A CN 201110174994 A CN201110174994 A CN 201110174994A CN 102851737 A CN102851737 A CN 102851737A
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Abstract
The invention relates to a carbon-doped titanium sapphire crystal and its growing method and application. The growing method includes adding 1,000-10,000 ppm graphite powder in the titanium sapphire raw material, performing growth of the carbon-doped titanium sapphire crystal by Bridgman-Stockbarger method, and performing in situ annealing on the grown crystal at 1,700-1,900 DEG C. for 40-56 h; and cooling the crystal after annealing at a slow rate of 15-30 DEG C./h to room temperature. The inventive carbon-doped titanium sapphire crystal has residual infrared absorption coefficient reduced to 0.01-0.001 cm<-1> at normal temperature of 25 DEG C., quality factor FOM of more than 200, and high optical uniformity, and is applied to solid tunable laser.
Description
Technical field
The present invention relates to the titanium gem crystal growing technology in the laserable material field, particularly carbon dope titanium gem crystal and the growth method thereof of a kind of low residual Infrared Absorption coefficient, high quality factor.
Background technology
Early eighties, the solid-state tunable laser development is swift and violent, and the tunable laser such as titanium jewel, chrysoberyl successively occur, and wherein particularly outstanding is the research of titanium jewel.
Titanium jewel (Ti:Al
2O
3) crystal is a kind of tunable laser crystal material of excellent performance, has widely purposes.Titanium gem crystal is the larger a kind of laser crystal material of impact after NbYAG.Ti sapphire laser has that tuning range is wide, efficiency of conversion is high, the life-span is long and have the characteristics 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 generally attention of various countries scientist and the military.But, because the titanium atom in the titanium gem crystal appraises at the current rate, can form Ti in process of growth
+, Ti
2+, Ti
3+And Ti
4+, and to laser Ti advantageously
3+So, in the growing crystal process, should make great efforts to improve Ti
3+Content.Because Ti
4+Ionic radius less than Ti
3+Ionic radius, therefore, Ti
4+Than Ti
3+Easily replace Al
3+Form substitutional ion.So the determinacy of titanium gem crystal growth valence state just becomes the key of the excellent titanium gem crystal of preparation.
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 form Ti
+, Ti
2+, Ti
3+And Ti
4+Plasma, active ions only have Ti
3+(3d
1) and Ti
2+(3d
2).For laser crystals, Ti importantly
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 that overcomes laser wavelength, improves quality factor FOM value.The residual Infrared Absorption of titanium gem crystal then derives from the Ti that exists in the crystal
4+, because Ti
3+-Ti
4+Ion pair will produce additional absorption.The method that addresses this problem is to suppress Ti
4+Growth and promote Ti
4+Change into Ti
3+
Domestic research to the titanium jewel never stops, because titanium gem crystal exists laser wavelength very wide absorption problem to occur, be called residual Infrared Absorption, affect laser, workers conduct extensive research its root and elimination way, and research discovery residual Infrared Absorption originates from and has Ti in the crystal
3+-Ti
4+The model of ion pair is because Ti
3+The 3d electronics of ion is at Ti
4+The impact of the coulomb field in ion and Al room is lower, becomes can absorb infrared photon and excite, and be exactly 4 valency ion Ti in the titanium jewel so eliminate the principle of residual Infrared Absorption
4+Become 3 valency ion Ti fully
3+
Yet will be with the Ti of remnants
4+Ion is reduced into Ti
3+Ion is than Ti
3+Ion-oxygen changes into Ti
4+The ion difficulty is a lot.Based on this difficult problem people several different methods has been proposed, such as patent EP0241614, its technology point is, in the inert atmosphere of common titanium jewel growth, add a small amount of reducing gas, such as hydrogen or carbon monoxide, come the reductibility of growth regulation atmosphere or the valence state that oxygen partial pressure is controlled titanium ion, also improve the optical quality of titanium jewel simultaneously.But subsequently, the contriver of patent EP0241614 finds, the effect of controlling in this way titanium ion valence state or raising titanium jewel quality factor is very limited, the quality factor FOM that can reach mostly is 60-80, than the titanium gem crystal quality factor height of growing under the inertia growth atmosphere condition not what, far do not reach the requirement (more than 150) of actual use, therefore the titanium jewel that adopts this method to grow out, still the same with the titanium jewel that grows out from inertia growth atmosphere condition, could use after must in stronger reducing atmosphere, annealing.
In fact, under the temperature of titanium jewel growth, alumina melt is to be in a kind of oxidation-reduction equilibrium state, can produce more immediate influence to the state of oxidation of titanium, and the valence state of titanium can not be controlled by growth atmosphere simply fully.Therefore grow low remaining uptake factor, the Ti doped saphire of high quality factor still is a technical barrier.
Based on above-mentioned background, still need at present a kind of low remaining uptake factor, method of the Ti doped saphire of high quality factor of growing.
Summary of the invention
The object of the present invention is to provide a kind of low remaining uptake factor, the carbon dope titanium gem crystal of high quality factor.Be 0.01-0.001cm under 25 ℃ of normal temperature of the residual Infrared Absorption coefficient of described carbon dope titanium gem crystal
-1, quality factor FOM more than 200, reaches as high as 250.
Used " residual Infrared Absorption coefficient " refers to the residual Infrared Absorption factor alpha of 800nm under 25 ℃ of normal temperature among the present invention
800
Used " quality factor FOM " refers to that crystal under 25 ℃ of normal temperature is at the ratio of the uptake factor at the uptake factor at 490nm place and 800nm place among the present invention.Quality factor FOM reaction Ti ion existence and concentration are a kind of important indicators of titanium gemological quality.
Herein, when not indicating in addition, 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, graphite composite powder by doping 1000-10000ppm in the titanium raw material for gem, and the grow titanium gem crystal of carbon dope of the monocrystal growing furnace that adopts graphite heater and argon gas atmosphere, the strong reducing property of the carbon in the matrix under melt temperature improved Ti in the titanium jewel greatly
4+To Ti
3+Transformation, thereby reduced Ti
4+Content, overcome Ti in the titanium gem crystal
4+Too high and the shortcoming that causes thus residual Infrared Absorption of ion content, thereby solve the difficult problem of remaining its laser activity of inhalation effects of titanium jewel, adopt simultaneously the in-situ annealing technology, further improve the titanium gem crystal quality, realize low remaining uptake factor, high quality factor, the growth of high optical homogeneity titanium gem crystal.
For this reason, another object of the present invention provides the growth method of carbon dope titanium gem crystal.The method comprises, adds the 1000-10000ppm graphite composite powder in the titanium raw material for gem, adopts Bridgman-Stockbarge method for growing carbon dope titanium gem crystal; Crystal after the growth carries out the in-situ annealing of 1700-1900 ℃ and 40-56 hour; Crystal after the annealing is down to room temperature with the slow speed of 15-30 ℃/h.
Preferably, the growth method of a kind of carbon dope titanium gem crystal of the present invention comprises:
In the titanium raw material for gem, add the 1000-10000ppm graphite composite powder, 10
-3-10
-4Pa vacuum and 1700-1800 ℃ is carried out presintering, at 1-3t/cm
2Pack into behind the isostatic pressing and be equipped with in the crucible of seed crystal;
Monocrystal growing furnace growing crystal under graphite heater and inert ambient environment.
Among the present invention, preferred titanium raw material for gem 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, the directed white stone seed crystal of a axle (110) direction more preferably, 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, the growing crystal process comprises: the powder in the crucible of packing into after with isostatic pressing under graphite heater and inert ambient environment continues to be warming up to melt temperature 2050-2080 ℃, constant temperature 2-5 hour, finish fusing and after seed crystal finishes inoculation until raw material, start the crucible lowering means and carry out the crystal growth, the temperature gradient of solid-liquid interface of crystal growth is set in the 15-35 ℃/cm scope, and the crucible fall off rate is controlled in the 0.1-2.0mm/h scope.
Preferably, after the crystal growth finishes, with the speed of 20-45 ℃/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, puts into the directed white stone seed crystal of a axle (110) direction;
(2) choosing mass ratio is 100: high purity aluminium oxide (0.1-1.5) (99.99%) and High Purity Titanium Sesquioxide (99.99%) powder, and 10
-3-10
-4Pa vacuum and 1700-1800 ℃ is carried out presintering, at 1-3t/cm
2Behind the isostatic pressing, in the crucible of packing into, place together on the tripod of decline stove;
(3) system sealing is evacuated to 10
-3-10
-4Pa is warming up to 1500-1700 ℃, 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 ℃, constant temperature 2-5 hour, finish fusing and after seed crystal finishes inoculation until raw material, start the crucible lowering means and carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set in the 15-35 ℃/cm scope, and the crucible fall off rate is controlled in the 0.1-2.0mm/h scope;
(5) after the crystal growth finishes, with the speed of 20-45 ℃/h furnace temperature is down to room temperature;
(6) crystal with growth carries out in-situ annealing, annealing temperature is 1700-1900 ℃, is incubated after 40-56 hour, so that the titanium gem crystal internal stress is released and subdues crystal structure defects, then slowly be down to room temperature with the speed of 15-30 ℃/h, take out crystal.
In the growth method of carbon dope titanium gem crystal of the present invention, preferably, seed crystal is by the directed white stone of the high quality of Bridgman-Stoekbarger Technique self-growth preparation, in the descent method for growing technology, the titanium jewel is beneficial to the stable growth of crystal at a face, therefore, the more preferably directed white stone seed crystal of a axle (110) direction.
In the growth method of carbon dope titanium gem crystal of the present invention, the titanium raw material for gem is made 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 titanium jewel 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, the mass ratio of high purity aluminium oxide and High Purity Titanium Sesquioxide is 100 among the present invention: (0.1-1.5).
In the growth method of carbon dope titanium gem crystal of the present invention, the addition of graphite composite powder is controlled at 1000-10000ppm, if the graphite composite powder addition less than 1000ppm, the Ti in the crystal then
4+Can not fully be reduced into Ti
3+If the graphite composite powder addition is greater than 10000ppm, then excess carbon can cause the optical property of crystal to descend.
In the present invention, the solid-liquid interface temperature ladder of crystal growth is set in the 15-35 ℃/cm scope, and too small thermograde namely is unfavorable for the stable growth of crystal less than 15 ℃/cm if the temperature of setting is terraced, does not also meet the principle of economic growth; If the temperature ladder of setting is greater than 35 ℃/cm, then excessive thermograde can cause the titanium gem crystal process of growth cracking phenomena to occur.
Among the present invention, the crucible fall off rate is controlled in the 0.1-2.0mm/h scope, if fall off rate is less than 0.1mm/h, though then be conducive to the stable growth of crystal, still a kind of waste of energy; If fall off rate, then can cause the stress cracking of crystal in process of growth greater than 2.0mm/h.Therefore, the result who considers, the crucible fall off rate is controlled in the 0.1-2.0mm/h scope as well among the present invention.
Among the present invention, after the crystal growth finishes, with the speed of 20-45 ℃/h furnace temperature is down to room temperature, if rate of temperature fall, then causes the waste of the energy and the loss of equipment less than 20 ℃/h, if rate of temperature fall, then causes the stress cracking of crystal greater than 45 ℃/h.
In the present invention, by the crystal after the growth is carried out in-situ annealing, subdue the uniformity coefficient of matter crystal internal defect, raising crystal, improve the optical property of carbon dope titanium gem crystal.Annealing temperature is 1700-1900 ℃, is incubated after 40-56 hour, slowly is down to room temperature with the speed of 15-30 ℃/h, takes out crystal.Do not subdue the needed energy of defective and do not reach the annealing effect if annealing temperature, does not then possess crystals less than 1700 ℃, if annealing temperature, then can cause the softening even melting of titanium gem crystal greater than 1900 ℃.
The present invention is by adding the graphite composite powder of trace in the titanium raw material for gem, thereby utilize the strong reducing property characteristics of graphite carbon under melt temperature in the matrix, do auxiliary with the reduction atmosphere of the inert atmosphere manufacturing of graphite heater, reach the purpose of control titanium valence state, adopt simultaneously the in-situ annealing method, improve the annealing effect of titanium jewel.Annealing is mainly manifested in 3 points to the effect of crystal: the one, and, annealing can be subdued the point-line-surface defective of crystals.Because Ti ratio of ionic radii Al ionic radius large 26%, in process of growth, exist part Ti ion not enter case fully, reduced anneal can provide thermodynamic power for the Ti ion enters normal case, annealing can also be subdued the crystal Dislocations, the subsurface defects such as low angle boundary reduce scattering and remaining absorbent core in the titanium gem crystal; The 2nd,, annealing can discharge crystal in the thermal stresses of process of growth, improves the optical homogeneity of crystal; The 3rd,, reduced anneal can be further so that Ti
4+Be converted into Ti
3+, improve Ti
3+Content, improve main uptake factor.The specification of quality of the low remaining uptake factor of realization Ti doped saphire, high quality factor, high optical homogeneity.
Description of drawings
Fig. 1 is the structural representation of growth titanium gem crystal decline stove.
Embodiment
By the following description of the embodiments, will be clearer to characteristics of the present invention and advantage, but should be appreciated that the present invention is not limited only to these embodiment.Without departing from the inventive concept of the premise, more changeableization or improved other embodiment can also be arranged, and these changes and improvements all should belong to scope of the present invention.
Take as shown in Figure 1 decline stove as example, some embodiment of the high quality factor titanium gem crystal of descent method for growing carbon dope are described.
As shown in Figure 1, the 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 the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning that takes by weighing aluminum oxide and titanium sesquioxide is 100: 1 powder 3000 grams, add high purity graphite (99.99%) powder of 1000ppm, after evenly mixing, use 2t/cm
2The static pressure that waits of (ton/square centimeter) forges into piece, in the molybdenum crucible 2 of packing into after 1700 ℃ of presintering in a vacuum, places together on the tripod 3 of decline stove, regulates the distance of molybdenum crucible 2 and graphite heater 1, guarantees center superposition.After system is airtight, be evacuated to 4 * 10
-4Pa is warming up to 1600 ℃.Being filled with high-purity argon gas to pressure is 15KPa, continue to be warming up to 2050 ℃ of melt temperatures, constant temperature 5 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 35 ℃/cm, and the crucible fall off rate is controlled to be 0.6mm/h, after the crystal growth finishes, speed with 40 ℃/h is down to room temperature with furnace temperature, the implementation in-situ annealing is processed, and annealing temperature is 1850 ℃, is incubated 40 hours, slowly be down to room temperature with the speed of 25 ℃/h again, take out titanium gem crystal.The optical property of the carbon dope titanium gem crystal that employing JASCO V-570 UV/VIS/NIR spectrophotometric determination obtains, residual Infrared Absorption factor alpha under 25 ℃ of normal temperature
800Be 0.01cm
-1, quality factor FOM reaches 205.
Embodiment 2
In the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, take by weighing powder 3000 grams of 100: 1 titanium sesquioxide quality of aluminum oxide proportioning, add high purity graphite (99.99%) powder of 3000ppm, after evenly mixing, use 2t/cm
2The static pressure that waits forge into piece, in the molybdenum crucible 2 of packing into after 1700 ℃ of pre-burnings in a vacuum, place together on the tripod 3 of decline stove, regulate the distance of molybdenum crucible 2 and graphite heater 1, guarantee center superposition, system is airtight, is evacuated to 3 * 10
-4Pa is warming up to 1550 ℃.Being filled with high-purity argon gas to pressure is malleation 20KPa, continue to be warming up to 2060 ℃ of melt temperatures, constant temperature 4.5 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 30 ℃/cm, fall off rate is controlled to be 0.5mm/h, after the crystal growth finishes, with the speed of 35 ℃/h furnace temperature is down to room temperature, carries out in-situ annealing and process, annealing temperature is 1800 ℃, be incubated 45 hours, slowly be down to room temperature with 20 ℃/h again, take out titanium gem crystal, the Ti doped saphire optical quality that adopts the test of JASCO V-570UV/VIS/NIR spectrophotometer to obtain, residual Infrared Absorption factor alpha under 25 ℃ of normal temperature
800Reduce to 0.008cm
-1, quality factor FOM reaches 210.
Embodiment 3
In the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning that takes by weighing aluminum oxide and titanium sesquioxide is 100: 1 powder 3000 grams, add high purity graphite (99.99%) powder of 6000ppm, after evenly mixing, use 2t/cm
2The static pressure that waits of (ton/square centimeter) forges into piece, in the molybdenum crucible 2 of packing into after 1700 ℃ of pre-burnings in a vacuum, places together on the tripod 3 of decline stove, regulates the distance of molybdenum crucible 2 and graphite heater 1, guarantees center superposition, and system is airtight, is evacuated to 2 * 10
-4Pa is warming up to 1500 ℃.Being filled with high-purity argon gas to pressure is malleation 25KPa, continue to be warming up to 2070 ℃ of melt temperatures, constant temperature 4 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 25 ℃/cm, and the crucible fall off rate is controlled to be 0.4mm/h, after the crystal growth finishes, speed with 35 ℃/h is down to room temperature with furnace temperature, the implementation in-situ annealing is processed, and annealing temperature is 1750 ℃, is incubated 48 hours, slowly be down to room temperature with the speed of 20 ℃/h again, take out titanium gem crystal.The optical quality that adopts JASCO V-570UV/VIS/NIR spectrophotometer to test the Ti doped saphire that obtains, residual Infrared Absorption factor alpha under 25 ℃ of normal temperature
800Reduce to 0.006cm
-1, quality factor FOM reaches 218.
Embodiment 4
In the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning that takes by weighing aluminum oxide and titanium sesquioxide is 100: 1 powder 3000 grams, add high purity graphite (99.99%) powder of 9000ppm, after evenly mixing, use 2t/cm
2The static pressure that waits of (ton/square centimeter) forges into piece, in the molybdenum crucible 2 of packing into after 1700 ℃ of pre-burnings in a vacuum, places together on the tripod 3 of decline stove, regulates the distance of molybdenum crucible 2 and graphite heater 1, guarantees center superposition, and system is airtight, is evacuated to 1 * 10
-4Pa is warming up to 1600 ℃.Being filled with high-purity argon gas to pressure is malleation 30kpa, continue to be warming up to 2080 ℃ of melt temperatures, constant temperature 3.5 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 20 ℃/cm, and the crucible fall off rate is controlled to be 0.3mm/h, after the crystal growth finishes, speed with 30 ℃/h is down to room temperature with furnace temperature, the implementation in-situ annealing is processed, and annealing temperature is 1750 ℃, is incubated 56 hours, slowly be down to room temperature with the speed of 20 ℃/h again, take out titanium gem crystal.The optical quality that adopts JASCO V-570 UV/VIS/NIR spectrophotometer to test the Ti doped saphire that obtains, residual Infrared Absorption factor alpha under 25 ℃ of normal temperature
800Reduce to 0.004cm
-1, quality factor FOM reaches 220.
Embodiment 5
In the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning that takes by weighing aluminum oxide and titanium sesquioxide is 100: 0.5 powder 3000 grams, add high purity graphite (99.99%) powder of 6000ppm, after evenly mixing, use 1t/cm
2The static pressure that waits of (ton/square centimeter) forges into piece, in the molybdenum crucible 2 of packing into after 1800 ℃ of pre-burnings in a vacuum, places together on the tripod 3 of decline stove, regulates the distance of molybdenum crucible 2 and graphite heater 1, guarantees center superposition, and system is airtight, is evacuated to 2 * 10
-4Pa is warming up to 1500 ℃.Being filled with high-purity argon gas to pressure is malleation 25KPa, continue to be warming up to 2070 ℃ of melt temperatures, constant temperature 4 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 25 ℃/cm, and the crucible fall off rate is controlled to be 0.4mm/h, after the crystal growth finishes, speed with 35 ℃/h is down to room temperature with furnace temperature, the implementation in-situ annealing is processed, and annealing temperature is 1800 ℃, is incubated 48 hours, slowly be down to room temperature with the speed of 20 ℃/h again, take out titanium gem crystal.The optical quality that adopts JASCO V-570 UV/VIS/NIR spectrophotometer to test the Ti doped saphire that obtains, residual Infrared Absorption factor alpha under 25 ℃ of normal temperature
800Reduce to 0.005cm
-1, quality factor FOM reaches 205.
Embodiment 6
In the decline stove, put into the directed white stone seed crystal of a axle (110) direction in the seed slot of molybdenum crucible 2.The titanium raw material for gem adopts high purity aluminium oxide (99.99%) powder and titanium sesquioxide (99.99%) powder, the quality proportioning that takes by weighing aluminum oxide and titanium sesquioxide is 100: 1.5 powder 3000 grams, add high purity graphite (99.99%) powder of 6000ppm, after evenly mixing, use 3t/cm
2The static pressure that waits of (ton/square centimeter) forges into piece, in the molybdenum crucible 2 of packing into after 1800 ℃ of pre-burnings in a vacuum, places together on the tripod 3 of decline stove, regulates the distance of molybdenum crucible 2 and graphite heater 1, guarantees center superposition, and system is airtight, is evacuated to 2 * 10
-4Pa is warming up to 1500 ℃.Being filled with high-purity argon gas to pressure is malleation 25kpa, continue to be warming up to 2070 ℃ of melt temperatures, constant temperature 4 hours, finish fusing and after seed crystal finishes inoculation until raw material, start crucible lowering means 4, namely carry out the crystal growth, the solid-liquid interface temperature ladder of crystal growth is set as 25 ℃/cm, and the crucible fall off rate is controlled to be 0.4mm/h, after the crystal growth finishes, speed with 35 ℃/h is down to room temperature with furnace temperature, the implementation in-situ annealing is processed, and annealing temperature is 1800 ℃, is incubated 48 hours, slowly be down to room temperature with the speed of 20 ℃/h again, take out titanium gem crystal.The optical quality that adopts JASCO V-570 UV/VIS/NIR spectrophotometer to test the Ti doped saphire that obtains, residual Infrared Absorption factor alpha under 25 ℃ 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, its residual Infrared Absorption coefficient is 0.01-0.001cm under 25 ℃ of normal temperature
-1, quality factor FOM more than 200, is up to 250.
2. the manufacture method of carbon dope titanium gem crystal as claimed in claim 1, comprise: in the titanium raw material for gem, add the 1000-10000ppm graphite composite powder, adopt Bridgman-Stockbarge method for growing carbon dope titanium gem crystal, the crystal after the growth carries out the in-situ annealing of 1700-1900 ℃ and 40-56 hour; Crystal after the annealing is down to room temperature with the slow speed of 15-30 ℃/h.
3. method as claimed in claim 2 is characterized in that, the descent method for growing process comprises:
In the titanium raw material for gem, add the 1000-10000ppm graphite composite powder, carry out presintering vacuum and 1700-1800 ℃, at 1-3t/cm
2Pack into behind the isostatic pressing and be 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 is characterized in that, the vacuum tightness of presintering is 10
-3-10
-4Pa.
5. such as the arbitrary described method of claim 2-4, it is characterized in that the titanium raw material for gem is the mixture of aluminum oxide and titanium sesquioxide, its weight ratio is 100: (0.1-1.5).
6. method as claimed in claim 5 is characterized in that, the purity of aluminum oxide and titanium sesquioxide is more than 99.99%.
7. such as the arbitrary described method of claim 2-6, it is characterized in that selected seed crystal is directed white stone seed crystal.
8. method as claimed in claim 7 is characterized in that, directed white stone seed crystal is the directed white stone seed crystal of a axle (110) direction.
9. such as claim 7 or 8 described methods, it is characterized in that directed white stone seed crystal passes through Bridgman-Stockbarge method for growing.
10. such as the described method of claim 2-9, it is characterized in that rare gas element is argon gas.
11., it is characterized in that inert atmosphere pressure is 15-30KPa such as the arbitrary described method of claim 2-10.
12. such as the arbitrary described method of claim 2-11, it is characterized in that crystal growing process comprises:
The powder of packing into after with isostatic pressing under graphite heater and inert ambient environment in the crucible continues to be warming up to melt temperature 2050-2080 ℃, and constant temperature 2-5 hour, raw material fusing and seed crystal inoculation;
Finish fusing and after seed crystal finishes inoculation, start the crucible lowering means and carry out the crystal growth until raw material, wherein, the temperature gradient of solid-liquid interface of crystal growth is set in the 15-35 ℃/cm scope, the crucible fall off rate is controlled in the 0.1-2.0mm/h scope.
13. the growth method of carbon dope titanium gem crystal as claimed in claim 12 is characterized in that, after the crystal growth finishes, with the speed of 20-45 ℃/h furnace temperature is down to room temperature.
14. the growth method of a carbon dope titanium gem crystal comprises the steps:
(1) in the seed slot of decline stove molybdenum crucible, puts into the directed white stone seed crystal of a axle (110) direction;
(2) with 100: weight ratio (0.1-1.5) is prepared the powder of 99.99% high purity aluminium oxide and 99.99% High Purity Titanium Sesquioxide, 10
-3-10
-4Pa vacuum and 1700-1800 ℃ is carried out presintering, at 1-3t/cm
2Isostatic pressing in the above-mentioned crucible of then packing into, places crucible on the tripod of decline stove;
(3) system sealing is evacuated to 10
-3-10
-4Pa is warming up to 1500-1700 ℃, 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 ℃, constant temperature 2-5 hour, finish fusing and after seed crystal finishes inoculation until raw material, start the crucible lowering means and carry out the crystal growth, the temperature gradient of solid-liquid interface of crystal growth is set in the 15-35 ℃/cm scope, and the crucible fall off rate is controlled in the 0.1-2.0mm/h scope;
(5) after the crystal growth finishes, with the speed of 20-45 ℃/h furnace temperature is down to room temperature;
(6) crystal with growth carries out in-situ annealing, and annealing temperature is 1700-1900 ℃, is incubated after 40-56 hour, is down to room temperature with the slow speed of 15-30 ℃/h, takes out crystal.
15. method as claimed in claim 14 is characterized in that, the purity of pure argon is 99.9%-99.99%.
16. such as the carbon dope titanium gem crystal that the arbitrary described method of claim 2-15 is made, its residual Infrared Absorption coefficient is 0.01-0.001cm under 25 ℃ of normal temperature
-1, quality factor FOM more than 200, is up to 250.
17. carbon dope titanium gem crystal as claimed in claim 16 can be applicable to solid-state tunable laser.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103046137A (en) * | 2013-01-04 | 2013-04-17 | 中国科学院上海硅酸盐研究所 | Sapphire crystal with high mechanical property and fabrication method thereof |
| CN103060911A (en) * | 2013-01-04 | 2013-04-24 | 中国科学院上海硅酸盐研究所 | Large-size and high-quality factor carbon-doped titanium gem laser crystal and preparation method thereof |
| CN103695995A (en) * | 2013-12-26 | 2014-04-02 | 贵州省高新光电材料及器件研究院有限公司 | Growing method of carbon-doped sapphire crystals |
| CN107937983A (en) * | 2018-01-04 | 2018-04-20 | 河北工业大学 | A kind of sapphire material of multicomponent doping and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005043398A1 (en) * | 2005-09-08 | 2007-03-15 | Forschungsverbund Berlin E.V. | Manufacturing a titanium sapphire laser crystal using a mixture of carbon monoxide and an inert gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102005043398A1 (en) * | 2005-09-08 | 2007-03-15 | Forschungsverbund Berlin E.V. | Manufacturing a titanium sapphire laser crystal using a mixture of carbon monoxide and an inert gas |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103046137A (en) * | 2013-01-04 | 2013-04-17 | 中国科学院上海硅酸盐研究所 | Sapphire crystal with high mechanical property and fabrication method thereof |
| CN103060911A (en) * | 2013-01-04 | 2013-04-24 | 中国科学院上海硅酸盐研究所 | Large-size and high-quality factor carbon-doped titanium gem laser crystal and preparation method thereof |
| CN103695995A (en) * | 2013-12-26 | 2014-04-02 | 贵州省高新光电材料及器件研究院有限公司 | Growing method of carbon-doped sapphire crystals |
| CN103695995B (en) * | 2013-12-26 | 2015-11-25 | 贵州省高新光电材料及器件研究院有限公司 | A kind of growth method of carbon-doped sapphire crystal |
| CN107937983A (en) * | 2018-01-04 | 2018-04-20 | 河北工业大学 | A kind of sapphire material of multicomponent doping and its preparation method and application |
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