CN100398702C - Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature - Google Patents
Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature Download PDFInfo
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- CN100398702C CN100398702C CNB2006100256437A CN200610025643A CN100398702C CN 100398702 C CN100398702 C CN 100398702C CN B2006100256437 A CNB2006100256437 A CN B2006100256437A CN 200610025643 A CN200610025643 A CN 200610025643A CN 100398702 C CN100398702 C CN 100398702C
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Abstract
The present invention relates to a thermal-insulating cover for the growth of crystals with volatility at high temperature by a drawing method, which comprises a thermal-insulating layer, a thermal-insulating cover body and a top cap of the thermal-insulating cover, wherein the thermal-insulating layer is used for supporting a crucible, the thermal-insulating cover body arranged above the crucible and the thermal-insulating layer is provided with an inner cavity, and the center of the top cap is provided with a through hole. The outer wall of one side of the thermal-insulating cover body is provided with an observation window body connected with the thermal-insulating cover body into a whole, and a communicated observation window hole is arranged from the observation window body to the inner cavity of the thermal-insulating cover body, wherein an outlet of the observation window hole is provided with a sealing transparent window sheet, and the observation window body is provided with a vertical thin hole which is communicated with the observation window hole. The present invention can inhibit the volatilization of components when crystals grow, and thus, lithium aluminate crystals with large size and high quality can be successfully prepared. The thermal-insulating cover device is also suitable for the growth of other crystals with volatility at high temperature by a drawing method, such as, crystals of LiGaO 2, Gd 3 Ga5O12GGG, Ca 5 (PO4) 3F, etc., and the growth quality of crystals is enhanced.
Description
Technical field
The present invention relates to crystal growth, particularly a kind of stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature.
Background technology
At present, the research and the industrialization of GaN base wide-bandgap semiconductor material and photoelectric device thereof are like a raging fire, have obtained a series of breakthroughs at aspects such as blue light-emitting diode, short wavelength laser, ultraviolet detector and semi-conductor white-light illuminatings in succession.Aspect the GaN base device prepared, high-end and technology core was the preparation of extension chip, wherein developed self-supporting iso-epitaxy substrate material and non-polar GaN base device technology of preparing is the focus of current international research and industrialization.
Aspect nonpolar and semi-polarity GaN base device technology of preparing, at present can be with (100) γ-LiAlO
2Substrate is an original template, preparation m face GaN thick film, and the GaN base device for preparing on this non-polar m-surface GaN thick film substrate can make luminous efficiency significantly improve.
But γ-L
1AlO
2Have serious lithium volatilization during crystal growth, the large-sized crystal of high quality is difficult to obtain.How growing high-quality large size crystal with volatility at high temperature is the difficult problem of crystal growth always in fact.The another back selection material L of GaN base device substrate
1GaO
2Crystal also is faced with serious component L when crystal growth
1Volatilization problem with Ga.
In addition, at laser technology field, Nd:GGG has mechanics and chemical stability is good, thermal conductivity is high, pump absorption bandwidth, fluorescence lifetime long, can realize continuously or the pulse type laser running, has become one of preferred material of high average power solid laser device.Calcium fluorapatite doped with ytterbium (Yb:Ca
5(PO
4)
3F is designated as Yb:FAP) have low pumping threshold, the important application prospect is being arranged aspect the laser inertial confinement fusion research.But they also are faced with serious component volatilization problem when growth.
Being used for crucible that crystal pulling method (Czochralski method) carries out crystal growth has the stay-warm case of hollow circular cylinder outward, and stay-warm case generally is to use ZrO
2Make, ZrO is arranged at the stay-warm case top
2Top cover, there is a little perforate in top cover central authorities, and seed rod stretches into stay-warm case inside by this hole, lifts out crystal by seed rod lower end fixed seed crystal from melt.On the other hand, the stay-warm case outside generally has an aperture, as viewing window.The perforate of the top cover at this stay-warm case outside viewing window and stay-warm case top forms circulation flow path owing to the temperature difference, but this stay-warm case often can not solve the quality problems of the volatile high temperature crystal growth of component, how suppressing the volatilization of crystal component when high growth temperature, is the key problem in technology that obtains the high quality crystal material.
Summary of the invention
The present invention seeks in order to solve the quality problems of the volatile high temperature crystal growth of component, the stay-warm case device of a kind of crystal pulling method (Czochralski method) growth of crystal with volatility at high temperature is provided, regulate temperature field and convection current by the design of stay-warm case, the volatilization of component when suppressing crystal growth to a great extent, thus the quality of crystal growth improved.
Technical solution of the present invention is as follows:
A kind of stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature, the thermal insulation layer, one that comprises a support crucible places the insulation cover body with inner chamber of described crucible and thermal insulation layer top, one stay-warm case top cover, there is a through hole in the central authorities of this top cover, have on the described insulation cover body one side outer wall one with the observation forms that fuse of insulation cover body, be provided with an observation fenestra that is connected from these observation forms to the inner chamber that is incubated cover body, outlet at described observation fenestra has a sealed transparent window, and the vertical pore that communicates with described observation fenestra is arranged on described observation forms.
Described sealing window is that one transparent and high temperature resistant, corrosion-resistant material is made.
Described sealing window is white stone wafer or titanium jewel wafer or YAG wafer.
Described pore is vertical.
Facts have proved, the present invention is with transparent high temperature resistant and have certain corrosion resistant wafer and seal view port, on the observation forms above the viewing window, have simultaneously the pore that communicates with described observation fenestra from top to bottom, in the time of can suppressing crystal growth, crystal component volatilization problem, the seed rod through hole forms local convection directly over these vertical pores and the top cover simultaneously.
Utilize stay-warm case of the present invention system, carried out γ-LiAlO
2Crystal, LiGaO
2Crystal, GGG crystal, calcium monofluorophosphate (Ca
5(PO
4)
3F) crystal and their admixture crystalline growth test, the result shows that volatilization is obviously suppressed, crystal mass has had raising.
Description of drawings
Fig. 1 is the structural representation of the stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature of the present invention.
Among the figure: the crucible of 1-growing crystal; The thermal insulation layer that the 2-crucible is outer; 3-stay-warm case inner chamber; 4-is incubated cover body; 5-stay-warm case top cover; Perforate on the 6-stay-warm case top cover; 7-observes forms; 8-observes fenestra; The transparent sheet at 9-view port place; 10-observes the vertical pore on the forms; The 11-seed rod; The crystal of 12-growth; The 13-melt.
Embodiment
List several specific embodiment of the present invention below, but should not limit protection scope of the present invention with this.
See also Fig. 1 earlier, Fig. 1 is the structural representation of the stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature of the present invention.As seen from the figure, the stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature of the present invention, the thermal insulation layer 2 that comprises a support crucible 1, one places the insulation cover body 4 with inner chamber 3 of described crucible and thermal insulation layer top, one stay-warm case top cover 5, there is a through hole 6 in the central authorities of this top cover, have on the described insulation cover body one side outer wall one with the observation forms 7 that fuse of insulation cover body, be provided with an observation fenestra 8 that is connected from these observation forms to the inner chamber that is incubated cover body, outlet at described observation fenestra has a sealed transparent window 9, and the vertical pore 10 that communicates with described observation fenestra is arranged on described observation forms.
Described sealing window 9 is that one transparent and high temperature resistant, corrosion-resistant material is made.Described obviously sealing window 9 can be made by white stone wafer or titanium jewel wafer or YAG wafer.
Utilize apparatus of the present invention to carry out the growth of multiple crystal with volatility:
Comparative Examples: LiAlO
2Crystal growth
Do not adopt stay-warm case of the present invention system, promptly the outstanding view port in the stay-warm case outside opens wide, and does not add transparent hermetyic window, and vertical pore is not opened in outstanding observation forms top, the stay-warm case outside.Li in molar ratio
2CO
3: Al
2O
3Take by weighing high purity (greater than 99.99%) Li at=1.01: 1
2CO
3And Al
2O
3, uniform mixing, briquetting, 1000 ℃ of pre-burnings are 10 hours in retort furnace, and this pre-imitation frosted glass is put into lifting furnace, vacuumize (vacuum tightness is better than 0.1pa), charge into Ar gas or N
2Gas (purity 〉=99.99%), growing crystal, the seed crystal direction is [100] or [001], and pull rate is 3mm/h, and rotating speed is 18rpm.In process of growth, volatilization is serious, and the crystal mass that grows is poor.
Embodiment 1:LiAlO
2Crystal growth
Utilize stay-warm case device shown in Figure 1, promptly outstanding non-the opening wide of view port in the stay-warm case outside inserted transparent titanium jewel LED reverse mounting type as hermetyic window, and outstanding observation forms top, the stay-warm case outside has several vertical pores, other complete same Comparative Examples.In process of growth, the volatilization phenomenon obviously is inhibited, and can obtain transparent complete lithium aluminate crystal.
Embodiment 2:LiGaO
2Crystal growth
Adopt stay-warm case device shown in Figure 1, in molar ratio Li
2CO
3: Ga
2O
3Take by weighing high purity (greater than 99.99%) Li at=1.01: 1
2CO
3And Ga
2O
3, uniform mixing, briquetting, 1000-1200 ℃ of pre-burning is 10 hours in retort furnace, and above-mentioned sintered material is put into lifting furnace, vacuumizes (vacuum tightness is better than 0.1pa), charges into N
2Gas (purity 〉=99.99%), growing crystal, the seed crystal direction is [001], and pull rate is 1-3mm/h, and rotating speed is 15-25rpm.In process of growth, the volatilization phenomenon obviously weakens, and can obtain transparent complete lithium gallate crystal.
Embodiment 3:GGG crystal growth
Adopt stay-warm case device shown in Figure 1, in molar ratio Gd
2O
3: Ga
2O
3=3: 5.05 weighing high purity (greater than 99.99%) Gd
2O
3And Ga
2O
3, uniform mixing, briquetting, 1150 ℃ of sintering 10 hours, the lifting furnace of packing into vacuumized, and charges into 99% nitrogen and 1% oxygen, and pull rate is 3mm/h during crystal growth, and rotating speed is 16rpm.After crystal growth finishes, slowly reduce to room temperature.In crystal growth, the volatilization phenomenon weakens.
Embodiment 4:Nd:GGG crystal growth
Adopt stay-warm case device shown in Figure 1, in molar ratio Gd
2O
3: Ga
2O
3: Nd
2O
3=2.97: 5.10: 0.03 weighing high purity (greater than 99.99%) Gd
2O
3, Ga
2O
3And Nd
2O
3, uniform mixing, briquetting, 1200 ℃ of sintering 10 hours, the lifting furnace of packing into vacuumized, and charges into 99% nitrogen and 1% oxygen, and pull rate is 3mm/h during crystal growth, and rotating speed is 15rpm.After crystal growth finishes, slowly reduce to room temperature.In crystal growth, the volatilization phenomenon weakens.
Embodiment 5:FAP crystal growth
Adopt stay-warm case device shown in Figure 1, with CaHPO
4, CaCO
3, CaF
2, Yb
2O
3High pure raw material (greater than 99.9%) is according to 6: 3: 1.04 molar ratio weighing, wherein CaF
2Excessive about 4%.At first with CaHPO
4And CaCO
3By the said ratio weighing, after mechanically mixing was even, 1150 ℃ of sintering in retort furnace were removed wherein water and carbonic acid gas.Be cooled to after the room temperature weighing CaF immediately
2, together mix with the raw material that sinters, with the swager briquetting and rapidly shove charge vacuumize and fill oxygen in case deliquescence the intensification flux growth.Adopt the method for flowing nitrogen in the experiment, flow is 180ml/min.Pull rate is 3mm/h, and rotating speed is 15rpm.Behind the growth ending, slowly reduce to room temperature.In crystal growth, the volatilization phenomenon weakens.
Embodiment 6:Yb:FAP crystal growth
Adopt stay-warm case device shown in Figure 1, with CaHPO
4, CaCO
3, CaF
2, Yb
2O
3High pure raw material (greater than 99.9%) was according to 6: 3: 1.00: 0.02 molar ratio weighing, wherein CaF
2Excessive about 4%.At first with CaHPO
4, CaCO
3And Yb
2O
3By the said ratio weighing, after mechanically mixing was even, 1250 ℃ of sintering in retort furnace were removed wherein water and carbonic acid gas.Be cooled to after the room temperature weighing CaF immediately
2, together mix with the raw material that sinters, with the swager briquetting and rapidly shove charge vacuumize and fill oxygen in case deliquescence the intensification flux growth.Adopt the method for flowing nitrogen in the experiment, flow is 150ml/min.Pull rate is 2mm/h, and rotating speed is 13rpm.Behind the growth ending, slowly reduce to room temperature.In crystal growth, the volatilization phenomenon weakens.
In sum, utilize stay-warm case of the present invention, carried out γ-LiAlO
2Crystal, LiGaO
2Crystal, GGG crystal, calcium monofluorophosphate (Ca
5(PO
4)
3F) crystal and their admixture crystalline growth test, the result shows: volatilization is obviously suppressed, and crystal mass has had raising.
Claims (2)
1. the stay-warm case of a used in Czochralski method growth of crystal with volatility at high temperature, the thermal insulation layer (2) that comprises a support crucible (1), one places the insulation cover body (4) with inner chamber (3) of described crucible and thermal insulation layer top, one stay-warm case top cover (5), there is a through hole (6) in the central authorities of this top cover, have on the described insulation cover body one side outer wall one with the observation forms (7) that fuse of insulation cover body, be provided with an observation fenestra (8) that is connected from these observation forms to the inner chamber that is incubated cover body, outlet at described observation fenestra has a sealed transparent window (9), and the vertical pore (10) that communicates with described observation fenestra is arranged on described observation forms.
2. the stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature according to claim 1 is characterized in that described sealing window (9) is white stone wafer or titanium jewel wafer or YAG wafer.
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|---|---|---|---|
| CNB2006100256437A CN100398702C (en) | 2006-04-12 | 2006-04-12 | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature |
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|---|---|---|---|
| CNB2006100256437A CN100398702C (en) | 2006-04-12 | 2006-04-12 | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature |
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| CN100398702C true CN100398702C (en) | 2008-07-02 |
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|---|---|---|---|---|
| CN101649486B (en) * | 2008-08-11 | 2013-03-20 | 元亮科技有限公司 | Device and method for growing terbium gallium garnet (TGG) crystal by pulling method |
| CN101956233B (en) * | 2009-07-20 | 2012-10-03 | 上海半导体照明工程技术研究中心 | Method for preparing lithium gallate crystals |
| CN104264213A (en) * | 2014-09-30 | 2015-01-07 | 元亮科技有限公司 | EFG (edge-defined film-fed growth) device of large-size doped sapphire crystals and growth process thereof |
| CN104264214A (en) * | 2014-09-30 | 2015-01-07 | 元亮科技有限公司 | Growing device and growing process for growing of terbium gallium garnet crystals by virtue of guided mode method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257943A (en) * | 1999-12-16 | 2000-06-28 | 中国科学院上海光学精密机械研究所 | Equipment for growing high-temp oxide crystal |
| CN1560329A (en) * | 2004-03-04 | 2005-01-05 | 上海交通大学 | Growing process of thulium doped yttrium aluminate laser crystal |
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2006
- 2006-04-12 CN CNB2006100256437A patent/CN100398702C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257943A (en) * | 1999-12-16 | 2000-06-28 | 中国科学院上海光学精密机械研究所 | Equipment for growing high-temp oxide crystal |
| CN1560329A (en) * | 2004-03-04 | 2005-01-05 | 上海交通大学 | Growing process of thulium doped yttrium aluminate laser crystal |
Non-Patent Citations (2)
| Title |
|---|
| 大尺寸高质量γ－LiAlO2晶体的制备研究. 邹军等.无机材料学报，第21卷第1期. 2006 * |
| 提拉法生长大尺寸γ－LiAlO2单晶的研究. 彭观良等.人工晶体学报，第34卷第2期. 2005 * |
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