CN2637505Y - Temperature gradient method growth device for large-area crystal - Google Patents

Temperature gradient method growth device for large-area crystal Download PDF

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Publication number
CN2637505Y
CN2637505Y CN 03256323 CN03256323U CN2637505Y CN 2637505 Y CN2637505 Y CN 2637505Y CN 03256323 CN03256323 CN 03256323 CN 03256323 U CN03256323 U CN 03256323U CN 2637505 Y CN2637505 Y CN 2637505Y
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heating element
crucible
crystal
main heating
temperature
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CN 03256323
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周国清
徐军
司继良
赵广军
邓佩珍
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Abstract

The device comprises a bell-jar vacuum resistance furnace, wherein the inner structure of the furnace body comprises a crucible and a heating body, the crucible is arranged at the central position in the furnace body, the crucible is a conical crucible with a seed crystal groove at the center of the bottom, the heating body is composed of a cylindrical graphite main heating body and a conical special-shaped auxiliary heating body, a vacuum system, a UPS (uninterrupted power supply), 2 sets of silicon controlled trigger circuits and 2 sets of intelligent temperature controllers are additionally attached outside the furnace body, are respectively used as heating power supplies of the main heating body and the auxiliary heating body, independently control the temperature, and are respectively provided with thermocouples for testing the temperatures of the main heating body and the auxiliary heating body. The utility model discloses the device can dynamic adjustment temperature gradient at the crystal growth in-process, and the crystal normal position annealing is realized to the growth later stage. The utility model discloses can grow out the complete crystal that does not split that the diameter is greater than 5 inches to the easy fracture crystal, like calcium fluoride crystal, yttrium aluminate crystal, garnet crystal and sapphire crystal etc..

Description

The terraced method growing apparatus of big area crystalline temperature
Technical field
The utility model relates to the growing crystal method and the device thereof of vertical temperature gradient condensation-crystallization method (VGF), and the terraced method growing apparatus of particularly a kind of big area crystalline temperature utilizes this device to crystal easy to crack, as calcium fluoride crystal (CaF 2), yttrium aluminate crystal (YAlO 3), garnet crystal (Y 3Al 5O 12) and sapphire crystal (Al 2O 3) wait and can grow diameter greater than complete indehiscent crystal of 5 inches.
Background technology
(the Crystal Systems Inc. of U.S. Crystal Syst in 1970, CSI) scientist F.Schmid, D.J.Viechnicki American Ceramic Society's proceedings the 53rd on the 9th phase of volume (J.Am.Ceramic Society53 (9) 528 (1970)) delivered " gradient method growing sapphire crystal sheet " literary composition (Growth of SapphireDisks from the Melt by a Gradient Furnace Technique "; propose first that (Heat Exchanger Method; HEM) grow diameter and reach 230mm, weight reaches the Al that 20kg has higher optical quality with heat-exchanging method 2O 3Crystal.Heat-exchanging method is actually in check directional freeze crystallization process, the graphite heater heat arrives heat exchanger by melt, crystal, take away by helium (He) stream, set up by the crucible inwall, temperature gradient field through melt seed crystal center at the bottom of the crucible, it comprises a kind of solid heat exchanger and flat crucible that is made of tungsten cover, graphite heater and water-cooled copper base, places the heat exchange crystal growing apparatus of seed crystal at the crucible bottom center.The appearance of heat-exchanging method growing technology is the quantum jump on the growing method, especially can grow high-melting-point, large-size crystals in crystal growing process, can be set up and the attemperation gradient by the mobile helium, and, realize the crystal in-situ annealing in the crystal growth later stage limitedly.But still there is shortcoming in this device: in process of growth, need a large amount of helium that flow to set up the temperature ladder, device is complicated, cost is high.
People such as Chinese science Cui man wind post in 1980, Zhou Yongzong propose with " the warm terraced method (TGT) that leads growth high-quality sapphire single-crystal ", be published in " silicate journal " Vol.8, on the No.2109 (1980), growing diameter is 54mm, and thickness is the sapphire crystal of 45mm.Patent " a kind of resistant to elevated temperatures tgt crystal growth device " (patent No.: 85100534.9 of Chinese science man Zhou Yongzong application in 1985,1988.11.24 authorize), further described this technology growth device, and the successful diameter of growing is 75mm, length is 105mm, weighs the Nd:YAG crystal of 2080 grams.(the U.S. happiness in Yamamoto is male according to the Tammann-Bridgman crystallization principle for this method, " crystal engineering Ha Application De Block Star Network ", 497 (1971)), a kind of opposite with universal gravity constant direction temperature and melt relative system immobilized mechanism have been selected for use and with the method for the seed crystal crystallographic orientation warm terraced method that promptly leads, the temperature ladder is obtained by special heating element and attemperator in the crystallizer vacuum resistance furnace, stove.The advantage of this method is the shortcoming that has overcome heat-exchanging method, and equipment is simple, easy to operate, cost is low, and helium need not flow.Shortcoming be the growth special high-melting-point size greater than the above crystal of  120mm (as Al 2O 32050 ℃ of fusing points) time, upper and lower temperature difference reaches about 200~350 ℃ in the stove, and top temperature reaches about 2350 ℃, and used crucible and the heat protection screen Mo softening temperature under carbon containing (C) atmosphere is about 2200 ℃, to make crucible and heat protection screen damage, can not growing crystal.In addition, because this method thermograde basic fixed in process of growth can not dynamically be adjusted thermograde, when growing more the big area crystal, cracking easily, calcium fluoride crystal (CaF particularly grows 2) and yttrium aluminate crystal (YAlO 3) time, crystal seriously ftractures, and perhaps has a large amount of pattern structures in the crystal.
Summary of the invention
The purpose of this utility model is in order to overcome the shortcoming of the terraced method growing crystal of above-mentioned temperature, provide a kind of improved big area crystalline temperature terraced method growing apparatus, for growing large-area high-quality monocrystalline provides good growth temperature field and annealing temperature field, as far as possible simplified apparatus just can growing single-crystal simultaneously, particularly to crystal easy to crack, as calcium fluoride crystal (CaF 2), yttrium aluminate crystal (YAlO 3), garnet crystal (Y 3Al 5O 12) and sapphire crystal (Al 2O 3) wait and can grow diameter greater than complete indehiscent crystal of 5 inches.
Technical conceive of the present utility model is: the terraced method growing apparatus of a kind of big area crystalline temperature, its gordian technique are that it comprises 2 cover heating elements.Heating element is the wavy strip type graphite cylinder of rectangle, be divided into inside and outside 2 covers, the internal heat generation body is auxilliary heating element, outer heating element is a main heating element, and independent temperature control forms stable temperature field in stove respectively, simultaneously in crystal growing process, can dynamically adjust thermograde, and, realize the crystal in-situ annealing in the crystal growth later stage.So be called the vertical gradient furnace of two heating again.
Melt is before crystallization finishes, and by regulating main heating element and auxilliary heating element, independent temperature control forms stable, suitable thermal field (as bigger thermograde) respectively, is beneficial to the crystalline crystallization.After crystal structure finishes, re-adjustment main heating element and auxilliary heating element, the independent temperature control of difference, after in stove, forming lesser temps gradient even thermal field near the zero-temperature coefficient gradient, press set heating-cooling program by 2 cover intelligent temperature controllers, realize the crystal in-situ annealing, finish crystalline growth whole process automatically.Can form suitable thermograde at the crystal growth initial stage like this, be beneficial to release, the crystalline crystallization of crystal structure latent heat, avoid the crystal growth later stage again, made crystal cleavage owing to thermograde is excessive.
The concrete technical solution of the utility model is:
The terraced method growing apparatus of a kind of big area crystalline temperature, comprise the bell-jar vacuum resistance furnace, the structure of body of heater inside comprises crucible and heating element, crucible places on the interior central position of body of heater, crucible is the taper crucible that bottom centre has a seed slot, it is characterized in that described heating element is to be made of garden tubular graphite main heating element and the auxilliary heating element of taper abnormity, attached vacuum system in addition outside the body of heater, the UPS voltage stabilized source, 2 cover silicon controlled rectifiers trigger circuit and 2 cover intelligent temperature controllers, respectively as the heating power supply of main heating element and auxilliary heating element, independent temperature control is respectively equipped with the thermopair of measuring auxilliary heating element and main heating element temperature.
Around the described crucible is garden tubular graphite main heating element, main heating element inside is the auxilliary heating element of taper abnormity, the outer side heat protection screen that is with of main heating element, last heat protection screen with the driving fit of side heat protection screen is arranged at the top of main heating element, the beneath of crucible is the crucible holder, the battery lead plate that links to each other with main heating element is supported by support ring, following heat protection screen is arranged in support ring, the center of passing down heat protection screen and battery lead plate reaches water coolant pole in the crucible holder, for measuring, the thermopair of the auxilliary heating element temperature of control reaches crucible bottom, for measuring, the thermopair of control main heating element temperature reaches the top of crucible from last heat protection screen.
Described main heating element and auxilliary heating element have all separated a plurality of grooves and a plurality of grooves down gone up to constitute the wavy lath power circuit of rectangle by inscribed angle etc., arrange the hole that makes different apertures or hole count according to certain rules at the lath first half of lath power circuit.
Described crucible can be made with materials processings such as graphite, molybdenum, tungsten or miramints.
Described crucible holder is made with zirconia material; Support ring is made with corundum ring; Upward, side, following heat protection screen are made with molybdenum sheet or tungsten-molybdenum sheet.
Described crucible top can have the crucible cover that a molybdenum sheet is made.
Compare with crystal technique formerly (as heat-exchanging method and the warm terraced method of guiding), the gordian technique of the terraced method growing apparatus of the utility model big area crystalline temperature is that it comprises 2 cover heating elements, it is main and auxiliary heating element, the independent temperature control of difference, in stove, form stable temperature field, in crystal growing process, can dynamically adjust thermograde and, realize the crystal in-situ annealing simultaneously in the crystal growth later stage.Like this, both overcome heat-exchanging method, and needed a large amount of helium that flow to set up the temperature ladder, the shortcoming that device is complicated, cost is high has overcome the warm terraced method that leads again and can not dynamically adjust thermograde, growing large-area crystal shortcoming easy to crack.To crystal easy to crack, as calcium fluoride crystal (CaF 2), yttrium aluminate crystal (YAlO 3), garnet crystal (Y 2Al 5O 12) and sapphire crystal (Al 2O 3) wait and can grow diameter greater than complete indehiscent crystal of 5 inches.
Description of drawings
Fig. 1 is the terraced method growing apparatus of the utility model big area crystalline temperature-gradient furnace internal structure sectional view
Fig. 2 is main heating element and auxilliary heating element plane outspread drawing
Fig. 3 is the sectional view of auxilliary heating element.
Embodiment
The terraced method growing apparatus of the utility model big area crystalline temperature is the bell-jar vacuum resistance furnace as shown in Figure 1, and the structure of body of heater inside comprises crucible, main and auxiliary heating element etc.Crucible 1 places on the interior central position of body of heater, crucible 1 is the taper crucible that bottom centre has a seed slot, on the one hand the crystallization material is fully fused and guarantee that seed crystal is not melted, produces when stoping crystal growth twin or polycrystalline, the crucible taper is easy to take out behind the crystal structure and need damage crucible on the other hand.The crucible top can have the crucible cover sealing that a molybdenum sheet is made, and can effectively suppress volatile melt such as Calcium Fluoride (Fluorspan) (CaF 2) volatilization.Around the crucible 1 is garden tubular graphite main heating element 2, main heating element 2 inside are the auxilliary heating elements 3 of the abnormal shape of band taper, the outer side heat protection screen 10 that is with of main heating element 2, last heat protection screen 9 with 10 driving fits of side heat protection screen is arranged at the top of main heating element 2, crucible holder 4 is arranged under the crucible 1, the battery lead plate 7 that links to each other with main heating element 2 has support ring 8 to support, following heat protection screen 11 is arranged in support ring 8, the center of passing down heat protection screen 11 and battery lead plate 7 reaches water coolant pole 6 in the crucible holder 4, also have for measuring, the thermopair 5 of auxilliary heating element 3 temperature of control reaches crucible 1 bottom, for measuring, the thermopair 12 of control main heating element 2 temperature reaches the top of crucible 1 from last heat protection screen 9.The material of crucible 1 can be that materials processings such as graphite, molybdenum, tungsten and miramint are made.Crucible holder 4 usefulness zirconium white (ZrO 2) material makes, support ring 8 is used corundum ring.Upward, side, following heat protection screen 9,10,11 usefulness molybdenum sheets or tungsten-molybdenum sheet are made.
Fig. 2 is main heating element 2 and auxilliary heating element 3 plane outspread drawings, and Fig. 3 is the sectional view of auxilliary heating element 3.Graphite tube main heating element 2 and auxilliary heating element 3 have all separated a plurality of groove 2-1 of going up and a plurality of groove 2-2 down to constitute the wavy lath power circuit 2-3 of rectangle by inscribed angle etc., arrange the hole 2-4 that makes different apertures or hole count according to certain rules at the lath first half of lath power circuit, its purpose is to adjust the heating resistor of lath, cause the temperature difference that is close to linearity from top to bottom after making its energising, and the temperature difference of heating element Lower Half is created by the thermal conduction of graphite heater and battery lead plate, and near the temperature field the seed crystal then also will rely on the thermal conduction with crucible pole to produce jointly.
Attached vacuum system in addition outside the body of heater, the graceful A2S1047 type of 60KW Mermithidae UPS voltage stabilized source, 2 cover silicon controlled rectifiers trigger circuit and 2 cover intelligent temperature controllers, not shown in the figures, respectively as the heating power supply of main heating element 2 and auxilliary heating element 3, independent temperature control, thermopair 5 and thermopair 12 adopt W-Re W/Re3-W/Re25 type.
Utilize the technical process of the terraced method growing apparatus of the utility model big area crystalline temperature growing crystal as follows:
<1〉in the seed slot of two heating gradient furnace crucibles 1, puts into oriented seed.
<2〉raw material (crystal block material or powder compact material) that will be used for growing crystal is put into crucible and is installed stove, and thermal exhaust reaches the vacuum tightness that requires 10 -3Pa charges into the inert protective gas reheat to given power material.
<3〉after the temperature of thermopair 5 reaches the melt melting temperature, constant temperature several hours.
<4〉by regulating main heating element and auxilliary heating element, independent temperature control respectively, form stable, suitable thermal field after, by set heating-cooling program, finish the crystal growth whole process of crystalline crystallization, in-situ annealing by 2 cover intelligent temperature controllers automatically.
<5〉treat that body of heater slowly is cooled to room temperature after, open bonnet, take out crystal.
Through on probation, adopt the utility model big area terraced method growing apparatus of crystalline temperature and above-mentioned technical process to carry out calcium fluoride crystal (CaF 2) growth, can obtain that crystal diameter reaches Φ 220mm, the 10kg that weighs, perfect crystalline, no pattern structure, do not ftracture, the crystal inner quality is apparently higher than the calcium fluoride crystal of additive method.
Graphite (C) system crucible 1 is of a size of Φ 220 * 250mm, has the taper crucible of a seed slot for bottom centre.Graphite heater 2 is a drum shape, and the heat protection screen internal layer is lined with the molybdenum tube of tungsten sheet.[111] oriented seed.With 10kg CaF 2Powder and 1kg PbF 2Powder mixes 24 hours in mixer after, 1% PbF wherein 2Powder is used 2t/cm as the deoxidation scavenging agent 2Isostatic pressure forge into piece or CaF 2The crystal block material; directly pack in the crucible 1; add the sealing of plumbago crucible lid; place gradient furnace; be warming up to while vacuumizing by 800 ℃ (thermopairs 5); charge into high-purity argon gas protective atmosphere to 1 normal atmosphere; by regulating main heating element and auxilliary heating element; the independent temperature control of difference; after forming stable, suitable thermal field, by set heating-cooling program, finish the crystal growth whole process of crystalline crystallization, in-situ annealing automatically: be warming up to melt temperature~1430 ℃ (thermopair 5) by 2 cover intelligent temperature controllers; constant temperature 3 hours was with 2.5 ℃/hr speed cooling 72 hours.Reduce to room temperature with 0.5 ℃/min speed after crystallization is finished, the growth whole process finishes.Take out CaF 2Crystal, crystal diameter reach Φ 220mm, the 10kg that weighs, and perfect crystalline, no pattern structure, do not ftracture, and the crystal inner quality is apparently higher than additive method.

Claims (6)

1, the terraced method growing apparatus of a kind of big area crystalline temperature, comprise the bell-jar vacuum resistance furnace, the structure of body of heater inside comprises crucible and heating element, crucible (1) places on the interior central position of body of heater, crucible (1) is the taper crucible that bottom centre has a seed slot, it is characterized in that described heating element is to be made of garden tubular graphite main heating element (2) and the auxilliary heating element (3) of taper abnormity, attached vacuum system in addition outside the body of heater, the UPS voltage stabilized source, 2 cover silicon controlled rectifiers trigger circuit and 2 cover intelligent temperature controllers, respectively as the heating power supply of main heating element (2) and auxilliary heating element (3), independent temperature control is respectively equipped with thermopair (5) and the thermopair (12) of measuring auxilliary heating element (3) and main heating element (2) temperature.
The terraced method growing apparatus of 2 big area crystalline temperature according to claim 1, what it is characterized in that described crucible (1) is garden tubular graphite main heating element (2) on every side, main heating element (2) inside is the auxilliary heating element (3) of taper abnormity, the outer side heat protection screen (10) that is with of main heating element (2), last heat protection screen (9) with side heat protection screen (10) driving fit is arranged at the top of main heating element (2), the beneath of crucible (1) is crucible holder (4), the battery lead plate (7) that links to each other with main heating element (2) is supported by support ring (8), following heat protection screen (11) is arranged in support ring (8), the center of passing down heat protection screen (11) and battery lead plate (7) reaches water coolant pole (6) in the crucible holder (4), reach crucible (1) bottom for the thermopair (5) of measuring auxilliary heating element (3) temperature, go up the top that heat protection screen (9) reaches crucible (1) certainly for the thermopair (12) of measuring main heating element (2) temperature.
3, the terraced method growing apparatus of big area crystalline temperature according to claim 1, it is characterized in that described main heating element (2) and auxilliary heating element (3) have all separated a plurality of grooves (2-1) and a plurality of grooves (2-2) down gone up to constitute the wavy lath power circuit (2-3) of rectangle by inscribed angle etc., arrange the hole (2-4) of different apertures of making or hole count according to certain rules at the lath first half of lath power circuit.
4, the terraced method growing apparatus of big area crystalline temperature according to claim 1 is characterized in that materials processings such as the available graphite of described crucible (1), molybdenum, tungsten or miramint make.
5, the terraced method growing apparatus of big area crystalline temperature according to claim 1 is characterized in that described crucible holder (4) makes with zirconia material; Support ring (8) is a corundum ring; Upward, side, following heat protection screen (9,10,11) are made with molybdenum sheet or tungsten-molybdenum sheet.
6, the terraced method growing apparatus of big area crystalline temperature according to claim 1 is characterized in that described crucible (1) top can have the crucible cover that a molybdenum sheet is made.
CN 03256323 2003-08-08 2003-08-08 Temperature gradient method growth device for large-area crystal Expired - Fee Related CN2637505Y (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100400720C (en) * 2006-04-21 2008-07-09 罗建国 Precise vertical temperature-difference gradient condensation single crystal growth device and method thereof
CN102191535A (en) * 2010-03-02 2011-09-21 国立大学法人信州大学 Manufacturing device for sapphire monocrystal
CN103160913A (en) * 2011-12-18 2013-06-19 洛阳金诺机械工程有限公司 Temperature gradient controlling device of crystal growth and method thereof
CN105133005A (en) * 2014-06-03 2015-12-09 长春理工大学 Crystal growth method for obtaining flat solid-liquid interface, and apparatus thereof
CN109338461A (en) * 2018-12-18 2019-02-15 北方民族大学 The auxiliary heating means and device and single crystal growing furnace of induction heating monocrystalline growth with czochralski
CN109355701A (en) * 2018-12-18 2019-02-19 北方民族大学 The meausring apparatus and single crystal growing furnace of induction heating monocrystalline growth with czochralski

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100400720C (en) * 2006-04-21 2008-07-09 罗建国 Precise vertical temperature-difference gradient condensation single crystal growth device and method thereof
CN102191535A (en) * 2010-03-02 2011-09-21 国立大学法人信州大学 Manufacturing device for sapphire monocrystal
CN102191535B (en) * 2010-03-02 2015-07-08 国立大学法人信州大学 Manufacturing device for sapphire monocrystal
CN103160913A (en) * 2011-12-18 2013-06-19 洛阳金诺机械工程有限公司 Temperature gradient controlling device of crystal growth and method thereof
CN105133005A (en) * 2014-06-03 2015-12-09 长春理工大学 Crystal growth method for obtaining flat solid-liquid interface, and apparatus thereof
CN105133005B (en) * 2014-06-03 2018-01-09 长春理工大学 Obtain the growing method and device of smooth solid liquid interface
CN109338461A (en) * 2018-12-18 2019-02-15 北方民族大学 The auxiliary heating means and device and single crystal growing furnace of induction heating monocrystalline growth with czochralski
CN109355701A (en) * 2018-12-18 2019-02-19 北方民族大学 The meausring apparatus and single crystal growing furnace of induction heating monocrystalline growth with czochralski

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