CN103436960A - Technology for growth of rare earth element-doped Ta2O5 crystals through optical floating zone method - Google Patents
Technology for growth of rare earth element-doped Ta2O5 crystals through optical floating zone method Download PDFInfo
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Abstract
The invention relates to a technology for the growth of rare earth element-doped Ta2O5 crystals through an optical floating zone method, and belongs to the crystal growth field. The technology comprises the following steps: 1, mixing Ta2O5 powder with rare earth element oxide powder according to a stoichiometric ratio needed by the crystal growth; 2, carrying out ball milling, drying, pre-burning, grinding and sieving of a mixture obtained in step 1, filling obtained powder to an elongated balloon, sealing, evacuating, and carrying out isostatic pressing to make material rods; 3, sintering the made material rods to obtain polycrystalline rods; 4, putting the polycrystalline rods in a floating zone furnace, heating according to a heating rate of 30-60DEG C/min until the polycrystalline rods and seed crystals are fused, adjusting the rotation speeds and rotation directions of the polycrystalline rods and the seed crystals, and inoculating; 5, setting a crystal growth speed, and allowing the crystals to grow; and 6, setting a cooling time, and cooling the crystals to room temperature after growth ending. The method has the advantages of no pollution, short period, high efficiency, and rapid growth to the rare earth element-doped Ta2O5 crystals having the advantages of centimeter magnitude, no macroscopic defects and high quality.
Description
Technical field
The invention belongs to field of crystal growth, relate to floating zone method growth doped rare earth element Ta
2o
5the method of crystal.
Background technology
Floating zone method is to obtain in recent years a kind of growing method developed rapidly, and its range of application is also more and more extensive.Floating zone method provides a kind of new research method and approach for research many body system, high-melting-point, synthetic difficult Crystal study.At first, floating zone method, without crucible, pollution-free, fast growth, can make intracrystalline doping very even, crystal that can growing high-quality, be convenient to control component, some be difficult to growth or the growth of the crystal that easily pollutes aspect, demonstrate very large superiority.In addition, the floating zone method wide application, can be used for the multiclass materials such as oxide compound, semi-conductor, intermetallic compound, and raw material melts and the crystal growth almost completes simultaneously, especially is particularly suitable for the strong crystalline material of fusant reaction.Therefore, we should give full play to, and the floating zone method crystalline growth velocity is fast, restricted condition is few, implant uniformity is high, effectively suppress the advantage of fractional condensation, in scientific research is explored, is applied.
The high-k dielectric material that the research performance is good, cost is suitable, be beneficial to large-scale production is one of focus of microelectronics research from now on.Ta
2o
5because it has higher specific inductivity, low leakage current density, high voltage breakdown and with the current silicon technology advantage such as compatible mutually, be considered to SiO always
2one of best substitute.Ta
2o
5be also a kind of candidate material of the photon crystal wave-guide device got a good chance of, its specific refractory power is greater than 2, in wide wavelength region, has low absorption characteristic, large third-order non-linear feature, and light injury threshold is large and photosensitivity is remarkable.Rare earth ion has great optical transition, rear-earth-doped Ta
2o
5be expected to be widely used in the communications field as laser emitting source or amplifier, high specific refractory power is for providing possibility at the tiny area integrated waveguide, create condition for the detection of non-linear effect under low threshold value Laser emission and low power, made low-loss these technological difficulties in optical waveguides field be solved.At present, only have with the hot pedestal pulling method of the LASER HEATING Eu:Ta that grown
2o
5crystal, but the crystal diameter of this method growth is restricted, and can only reach 2.2mm, and size is difficult to meet the application needs.Therefore we adopt floating zone method to realize more large size doped rare earth element Ta
2o
5the crystal growth.
Summary of the invention
The objective of the invention is to overcome existing large size doped rare earth element Ta
2o
5the blank existed in crystal technique, provide that a kind of to grow diameter with floating zone method be centimetre-sized, without the doped rare earth element Ta of macroscopic defects
2o
5the method of crystal growth.
A kind of doped rare earth element Ta of floating zone method growth centimetre magnitude diameter
2o
5the method of crystal, comprise the steps:
(1) batching: by Ta
2o
5with rare earth oxide, according to crystal composition ratio batching, wherein, the molar mass percentage range of rare earth oxide is 0.2mol%～1mol%, Ta
2o
5the molar mass percentage range be 99.8mol%～99.0mol%;
(2) preparation of charge bar: the compound made in step (1) is sieved through ball milling, oven dry, 200 orders; Pre-burning under 1300～1400 ℃ of insulation 12～24h conditions, again grind, 200 orders sieve, and in the long strip shape balloon of then powder being packed into, seal, vacuumize, 60～70MPa etc. make charge bar under static pressure;
(3) sintering: the charge bar that step (2) is made is 1350～1500 ℃ in sintering temperature, and sintering under the condition that sintering time is 12～24 hours obtains fine and close polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, optics floating region with platinum wire, and pure Ta is used in experiment
2o
5crystal, as seed crystal, is fixed on seed crystal support with platinum filament, is arranged on lower end, install and seal with silica tube afterwards, then temperature rise rate be set be 30～60 ℃/minute and start to melt to polycrystalline rod and seed crystal, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, be incubated 5～10 minutes after inoculation; Then crystalline growth velocity is set is that 3～8mm/h carries out the crystal growth;
(5) cooling: the crystal growth finishes laggard row cooling, and it is 1.5～5 hours that temperature fall time is set, and crystal is cooled to room temperature.
In the technology of the present invention preferably the raw material in described step (1) be Ta
2o
5, rare earth oxide.
In the technology of the present invention preferably in described step (2) Ball-milling Time of compound be 12～24 hours, drying time is 8～15 hours.
Preferably grind compound after sieving in the technology of the present invention in described step (2) and pack in the long strip shape balloon and seal, then vacuum pump vacuumizes 5～10 minutes.
In the technology of the present invention, preferably in described step (4) in crystal growing process, the sense of rotation of polycrystalline rod and seed crystal be reverse, and speed of rotation is 20～30rmp.
Compared with the prior art, the obvious advantage of technique of the present invention:
1, realized mixing the Ta of various rare earth elements
2o
5the growth of crystal, realize utilizing floating zone method growing large-size (centimetre magnitude), first without the doped rare earth element Ta of macroscopic defects
2o
5crystal.
2, in air, can grow, growing method is simple to operate, and cost is relatively low, repeatable strong.
3, the doped rare earth element Ta of this technique growth
2o
5crystal does not have the macroscopic defectss such as bubble, cloud layer, inclusion, crack.The powder x-ray diffraction peak is very sharp-pointed, shows that the crystal growth quality is fine.
The accompanying drawing explanation
Fig. 1 mixes 1at%Er
2o
3ta
2o
5the shape appearance figure of crystal;
Fig. 2 mixes 0.5at%Er
2o
3ta
2o
5the XRD powdery diffractometry image of crystal;
Fig. 3 mixes 0.5at%Eu
2o
3ta
2o
5the XRD powdery diffractometry image of crystal;
Fig. 4 mixes 0.5at%La
2o
3ta
2o
5the XRD powdery diffractometry image of crystal;
Fig. 5 mixes 0.5at%Er
2o
3, Eu
2o
3, La
2o
3ta
2o
5the shape appearance figure of crystal.
Embodiment
Further describe technical scheme of the present invention below by specific embodiment.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.
Float-zone method growing large-size doped rare earth element Ta of the present invention
2o
5the growing apparatus of crystal---the four ellipsoid optics stove (Crystal Systems Co., 10000H-HR-I-VPO-PC) that flips.
Embodiment 1
(1) batching: the Ta that is 99.9999% by purity
2o
5and Er
2o
3raw material is according to molar mass per-cent 99.8at%Ta
2o
5+ 0.2at%Er
2o
3mixed;
(2) preparation of charge bar: the compound made in step (1) is put into to the ball mill ball milling 12 hours, then put into baking oven 15 hours, bake out temperature is 80 ℃.Then compound is sieved, the powder crucible of packing into is put into to the retort furnace pre-burning 12 hours, calcined temperature is 1350 ℃, after taking-up, again grinds and sieves.Powder is packed in the long strip shape balloon and sealed, with vacuum pump, vacuumize 10 minutes, with waiting static pressure to be pressed into bar-shaped charge bar under the pressure of 70Mpa;
(3) sintering: the charge bar that step (2) is made is put into high temperature sintering furnace, and sintering temperature is 1350 ℃, and sintering time is 24 hours, obtains polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, floating region with platinum wire, seed crystal is fixed on seed crystal support with platinum filament, be arranged on lower end, install and seal with silica tube afterwards, then be set to starting to melt to charge bar and seed crystal 1 hour heating-up time, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, speed of rotation is respectively 25rpm, be incubated and inoculate after stablizing melting in 5 minutes, form the solubilized stable district; By the movement of manual operation condensing lens, or the mobile ，Shi Rong district of rod descends away from focus point ，Shi Rong district temperature up and down, thereby realizes crystallization, and then crystalline growth velocity is set is that 8mm/h carries out the crystal growth;
(5) cooling: it is 1.5h that temperature fall time is set, and is cooled to room temperature.Its XRD powdery diffractometry image and Fig. 2 are similar.
(1) batching: the Ta that is 99.9999% by purity
2o
5and Er
2o
3raw material is according to molar mass per-cent 99.5at%Ta
2o
5+ 0.5at%Er
2o
3mixed;
(2) preparation of charge bar: the compound made in step (1) is put into to the ball mill ball milling 15 hours, then put into baking oven 12 hours, bake out temperature is 80 ℃.Then compound is sieved, the powder crucible of packing into is put into to the retort furnace pre-burning 15 hours, calcined temperature is 1350 ℃, after taking-up, again grinds and sieves.Powder is packed in the long strip shape balloon and sealed, with vacuum pump, vacuumize 8 minutes, with waiting static pressure to be pressed into bar-shaped charge bar under the pressure of 68Mpa;
(3) sintering: the charge bar that step (2) is made is put into high temperature sintering furnace, and sintering temperature is 1400 ℃, and sintering time is 15 hours, obtains polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, floating region with platinum wire, seed crystal is fixed on seed crystal support with platinum filament, be arranged on lower end, install and seal with silica tube afterwards, then be set to starting to melt to charge bar and seed crystal 1 hour heating-up time, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, speed of rotation is respectively 20rpm, be incubated and inoculate after stablizing melting in 6 minutes, form the solubilized stable district; By the movement of manual operation condensing lens, or the mobile ，Shi Rong district of rod descends away from focus point ，Shi Rong district temperature up and down, thereby realizes crystallization, and then crystalline growth velocity is set is that 5mm/h carries out the crystal growth;
(5) cooling: it is 3h that temperature fall time is set, and is cooled to room temperature.Its XRD powdery diffractometry image and Fig. 2 are similar.
(1) batching: the Ta that is 99.9999% by purity
2o
5and Er
2o
3raw material is according to molar mass per-cent 99.0at%Ta
2o
5+ 1at%Er
2o
3mixed;
(2) preparation of charge bar: the compound made in step (1) is put into to the ball mill ball milling 24 hours, then put into baking oven 8 hours, bake out temperature is 80 ℃.Then compound is sieved, the powder crucible of packing into is put into to the retort furnace pre-burning 24 hours, calcined temperature is 1350 ℃, after taking-up, again grinds and sieves.Powder is packed in the long strip shape balloon and sealed, with vacuum pump, vacuumize 5 minutes, with waiting static pressure to be pressed into bar-shaped charge bar under the pressure of 60Mpa;
(3) sintering: the charge bar that step (2) is made is put into high temperature sintering furnace, and sintering temperature is 1500 ℃, and sintering time is 12 hours, obtains polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, floating region with platinum wire, seed crystal is fixed on seed crystal support with platinum filament, be arranged on lower end, install and seal with silica tube afterwards, then be set to starting to melt to charge bar and seed crystal 1 hour heating-up time, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, speed of rotation is respectively 30rpm, be incubated and inoculate after stablizing melting in 10 minutes, form the solubilized stable district; By the movement of manual operation condensing lens, or the mobile ，Shi Rong district of rod descends away from focus point ，Shi Rong district temperature up and down, thereby realizes crystallization, and then crystalline growth velocity is set is that 3mm/h carries out the crystal growth;
(5) cooling: it is 5h that temperature fall time is set, and is cooled to room temperature.
Embodiment 4
(1) batching: the Ta that is 99.9999% by purity
2o
5and Eu
2o
3raw material is according to molar mass per-cent 99.5at%Ta
2o
5+ 0.5at%Eu
2o
3mixed;
(2) preparation of charge bar: the compound made in step (1) is put into to the ball mill ball milling 18 hours, then put into baking oven 15 hours, bake out temperature is 80 ℃.Then compound is sieved, the powder crucible of packing into is put into to the retort furnace pre-burning 15 hours, calcined temperature is 1350 ℃, after taking-up, again grinds and sieves.Powder is packed in the long strip shape balloon and sealed, with vacuum pump, vacuumize 10 minutes, with waiting static pressure to be pressed into bar-shaped charge bar under the pressure of 68Mpa;
(3) sintering: the charge bar that step (2) is made is put into high temperature sintering furnace, and sintering temperature is 1400 ℃, and sintering time is 20 hours, obtains polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, floating region with platinum wire, seed crystal is fixed on seed crystal support with platinum filament, be arranged on lower end, install and seal with silica tube afterwards, then be set to starting to melt to charge bar and seed crystal 1 hour heating-up time, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, speed of rotation is respectively 25rpm, be incubated and inoculate after stablizing melting in 7 minutes, form the solubilized stable district; By the movement of manual operation condensing lens, or the mobile ，Shi Rong district of rod descends away from focus point ，Shi Rong district temperature up and down, thereby realizes crystallization, and then crystalline growth velocity is set is that 4mm/h carries out the crystal growth;
(5) cooling: it is 3h that temperature fall time is set, and is cooled to room temperature.
Embodiment 5
(1) batching: the Ta that is 99.9999% by purity
2o
5and La
2o
3raw material is according to molar mass per-cent 99.5mol%Ta
2o
5+ 0.5mol%La
2o
3mixed;
(2) preparation of charge bar: the compound made in step (1) is put into to the ball mill ball milling 15 hours, then put into baking oven 10 hours, bake out temperature is 80 ℃.Then compound is sieved, the powder crucible of packing into is put into to the retort furnace pre-burning 10 hours, calcined temperature is 1350 ℃, after taking-up, again grinds and sieves.Powder is packed in the long strip shape balloon and sealed, with vacuum pump, vacuumize 8 minutes, with waiting static pressure to be pressed into bar-shaped charge bar under the pressure of 65Mpa;
(3) sintering: the charge bar that step (2) is made is put into high temperature sintering furnace, and sintering temperature is 1400 ℃, and sintering time is 15 hours, obtains polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, floating region with platinum wire, seed crystal is fixed on seed crystal support with platinum filament, be arranged on lower end, install and seal with silica tube afterwards, then be set to starting to melt to charge bar and seed crystal 1 hour heating-up time, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, speed of rotation is respectively 30rpm, be incubated and inoculate after stablizing melting in 5 minutes, form the solubilized stable district; By the movement of manual operation condensing lens, or the mobile ，Shi Rong district of rod descends away from focus point ，Shi Rong district temperature up and down, thereby realizes crystallization, and then crystalline growth velocity is set is that 5mm/h carries out the crystal growth;
(5) cooling: it is 2h that temperature fall time is set, and is cooled to room temperature.
Above-described embodiment all can growing large-size (centimetre magnitude), without the doped rare earth element Ta of macroscopic defects
2o
5crystal.
Claims (4)
1. floating zone method growth doped rare earth element Ta
2o
5the method of crystal, is characterized in that, comprises the following steps:
(1) batching: by Ta
2o
5make compound with rare earth oxide according to crystal composition ratio batching, wherein, the molar mass percentage range of rare earth oxide is 0.2mol%～1mol%, Ta
2o
5the molar mass percentage range be 99.8mol%～99.0mol%;
(2) preparation of charge bar: the compound made in step (1) is sieved through ball milling, oven dry, 200 orders; Under 1300～1400 ℃ of insulation 12～24h conditions, after pre-burning, again grind, 200 orders sieve, and in the long strip shape balloon of then powder being packed into, seal, vacuumize, 60～70MPa etc. make charge bar under static pressure;
(3) sintering: the charge bar that step (2) is made is 1350～1500 ℃ in sintering temperature, and sintering under the condition that sintering time is 12～24 hours obtains fine and close polycrystalline rod;
(4) crystal growth: polycrystalline rod is hung over to Lu upper end, optics floating region with platinum wire, and pure Ta is used in experiment
2o
5crystal, as seed crystal, is fixed on seed crystal support with platinum filament, is arranged on lower end, install and seal with silica tube afterwards, then temperature rise rate be set be 30～60 ℃/minute and start to melt to polycrystalline rod and seed crystal, adjust speed of rotation and the sense of rotation of polycrystalline rod and seed crystal, be incubated 5～10 minutes after inoculation; Then crystalline growth velocity is set is that 3～8mm/h carries out the crystal growth;
(5) cooling: the crystal growth finishes laggard row cooling, and it is 1.5～5 hours that temperature fall time is set, and crystal is cooled to room temperature.
2. according to the method for claim 1, it is characterized in that, in step (2), the Ball-milling Time of compound is 12～24 hours, and drying time is 8～15 hours.
3. according to the method for claim 1, it is characterized in that, step (2) the intermediate pump pumpdown time is 5～10 minutes.
4. according to the method for claim 1, it is characterized in that, in step (4), in crystal growing process, the sense of rotation of polycrystalline rod and seed crystal is that oppositely speed of rotation is 20～30rmp.
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| CN106255778A (en) * | 2014-04-25 | 2016-12-21 | 保利斯科有限公司 | Crystalline material, Its Preparation Method And Use |
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Application publication date: 20131211 |