CN1865533A - 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
- Publication number
- CN1865533A CN1865533A CN 200610025643 CN200610025643A CN1865533A CN 1865533 A CN1865533 A CN 1865533A CN 200610025643 CN200610025643 CN 200610025643 CN 200610025643 A CN200610025643 A CN 200610025643A CN 1865533 A CN1865533 A CN 1865533A
- Authority
- CN
- China
- Prior art keywords
- crystal
- stay
- warm case
- high temperature
- volatility
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a thermal insulation case of high-temperature volatile crystal through sash growth method, which comprises the following parts: insulating layer to support copple, insulating case with cavity on the copple and insulating layer, insulating case lid and feed-through on the center of lid, wherein one outside wall of insulating case integrates observing window; the observing window hole is opened on the cavity from observing window and insulating case; one sealing transparent window plate is set on the outlet of observing window; the vertical pore is opened on the observing window bulk to connect observing window hole. The invention can inhibit the volatilization of each component to produce large-size high-quality lithium aluminate crystal, which improves the growing quality of crystal.
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-LiAlO
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 LiGaO of GaN base device substrate
2Crystal also is faced with the volatilization problem of serious component Li and Ga when crystal growth.
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 the local convection path 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-solution.
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 (3)
1, a kind of stay-warm case of 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 that one transparent and high temperature resistant, corrosion-resistant material is made.
3, the stay-warm case of used in Czochralski method growth of crystal with volatility at high temperature according to claim 2 is characterized in that described sealing window (9) is white stone wafer or titanium jewel wafer or YAG wafer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100256437A CN100398702C (en) | 2006-04-12 | 2006-04-12 | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100256437A CN100398702C (en) | 2006-04-12 | 2006-04-12 | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1865533A true CN1865533A (en) | 2006-11-22 |
CN100398702C CN100398702C (en) | 2008-07-02 |
Family
ID=37424673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2006100256437A Expired - Fee Related CN100398702C (en) | 2006-04-12 | 2006-04-12 | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100398702C (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
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 |
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 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1084398C (en) * | 1999-12-16 | 2002-05-08 | 上海中科嘉浦光电子材料有限公司 | Equipment for growing high-temp oxide crystal |
CN1256470C (en) * | 2004-03-04 | 2006-05-17 | 上海交通大学 | Growing process of thulium doped yttrium aluminate laser crystal |
-
2006
- 2006-04-12 CN CNB2006100256437A patent/CN100398702C/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN100398702C (en) | 2008-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111348674B (en) | Cs3Cu2X5Preparation method of (X ═ Cl, Br and I) nanocrystal and product | |
CN1865533A (en) | Thermal-insulating cover used in Czochralski method growth of crystal with volatility at high temperature | |
CN102803583B (en) | The cultural method of group III metal nitride single crystal and the reaction vessel for the method | |
US8486190B2 (en) | Process for producing single crystal | |
JPWO2007108338A1 (en) | Method and apparatus for producing nitride single crystal | |
CN1772972A (en) | Process for growing gallium nitride single crystal utilizing new flux molten-salt growth method | |
CN114672309B (en) | Manganese ion activated red fluorescent powder and preparation method thereof | |
CN101701355A (en) | Pulling growth method of neodymium-doped yttrium-calcium aluminate laser crystal | |
CN102766906B (en) | Erbium ion activated 3 micron waveband gallate laser crystals and preparation method thereof | |
CN1587447A (en) | Process for preparing high temperature cerium blended lutetium pyrosilicate scintillation monocrystal | |
CN103469306A (en) | Method for growing Ce: YAG monocrystal fluorescent material | |
JP2009013028A (en) | Aluminum oxide-gallium oxide solid solution and method for producing the same | |
CN100356642C (en) | C-MgxZn1-xO/MgO multi-quantum sink heterogeneous structural materials and producing process thereof | |
CN1277000C (en) | Method for preparing double tungstate crystal with stoichiometric ratio | |
CN1477239A (en) | Method for growing compound laser crystal | |
CN1314831C (en) | Cryogenic technique for preparing cube phase, wide forbidden band MgZnO crystal thin film | |
US8288022B2 (en) | Perovskite phosphor film | |
CN1206392C (en) | Method for growing neodymium-doped yttrium vanadate and yttrium vanadate composite laser crystal | |
CN109868502B (en) | Rare earth doped niobate monocrystal up-conversion luminescent material and preparation method thereof | |
CN1777708A (en) | Apparatus for producing fluoride crystal | |
CN100340703C (en) | Neodymium-doped lanthanum strontium aluminate tantalate laser crystal and process for preparing the same | |
CN1837419A (en) | Ytterbium doped Y0.8LaCa4O(BO3)3 laser crystal, its preparation method and use | |
CN1292107C (en) | Growth method of neodymium-doped gadolinium gallium garnet laser crystal | |
CN1313650C (en) | Growing method of rare-earth thiooxide crystal | |
CN100390327C (en) | Method for growing lead lanthanum zirconate stannate titanate single-crystal utilizing composite fluxing agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080702 Termination date: 20120412 |