CN102534798A - High-temperature high-pressure crystal growth equipment - Google Patents
High-temperature high-pressure crystal growth equipment Download PDFInfo
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- CN102534798A CN102534798A CN2012100039093A CN201210003909A CN102534798A CN 102534798 A CN102534798 A CN 102534798A CN 2012100039093 A CN2012100039093 A CN 2012100039093A CN 201210003909 A CN201210003909 A CN 201210003909A CN 102534798 A CN102534798 A CN 102534798A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
- B30B11/001—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses using a flexible element, e.g. diaphragm, urged by fluid pressure; Isostatic presses
- B30B11/002—Isostatic press chambers; Press stands therefor
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Abstract
The invention provides high-temperature high-pressure crystal growth equipment, and in particular relates to high-temperature high-pressure flux-Bridgman-Stockbarger growth equipment capable of growing large-size GaN bulk single crystals. The equipment comprises a lifting device, a base (6), a pressure tank (1), a heating furnace (18) and a descending device (5), wherein the lifting device is arranged on the top of a shell of the pressure tank (1); the base (6) is used for supporting the pressure tank (1); the heating furnace (18) and the descending device (5) are arranged in the pressure tank (1); a lower furnace mouth of the heating furnace (18) is communicated with the pressure tank (1); the descending device (5) is arranged below the heating furnace (18); and a material which is heated by the heating furnace (18) and used for generating high-temperature high-pressure crystals is placed on the descending device (5). The equipment has a simple structure, is convenient to operate, is widely applied, can be used for growing a large-size GaN bulk single crystal material and growing various functional crystal materials in a high steam pressure melt, and can be used for the hot isostatic pressing or sintering of certain substances in atmosphere, and the like.
Description
Technical field:
The invention belongs to crystalline material particularly semiconductor material and the relevant field of thermal engineering of crystal growth, be specifically related to a kind of semiconductor crystal, i.e. gallium nitride crystal growth equipment.
Background technology:
GaN is the Wideband semiconductor material of development high-voltage, high frequency, superpower and high temperature microelectronic device, opto-electronic device, is described as third generation semiconductor material.The research of GaN body material and mould material is the forward position and the focus of present global semiconductor material and device research with using.At present, the GaN material because to lack the homogeneity substrate be main with heteroepitaxy method still, mainly contains hydride gas-phase epitaxy (HVPE), metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE) etc. in growth.Substrate material mainly adopts sapphire, and the SiC of employing or Si etc. are also arranged.Though the method for growth impact plies can partly reduce defect concentration earlier between substrate and epitaxial film; But on the whole; This hetero epitaxy always unavoidably exists than Macrolattice mismatch (like GaN/ sapphire=15%) and thermal mismatching (GaN/ sapphire=25.5%), causes epitaxial film to have higher dislocation desity, forms defective and unrelieved stress; And this lattice imperfection can directly influence the photoelectric properties (like life-span and efficient) of device, has limited the further raising of device performance.
Therefore, give play to the broadband characteristics of GaN semiconductor material fully, further improve the device photoelectric performance, epitaxial substrate preferably adopts GaN body monocrystalline self-supporting substrate (free-standing substrate), carries out isoepitaxial growth.The advantage of iso-epitaxy has:
1) owing to do not have lattice mismatch and thermal mismatching, compare with hetero epitaxy, defective can reduce greatly in the device;
2) can save steps such as surfaces nitrided, nucleating layer and buffer growth, realize two-dimensional growth;
3) can overcome the nonconducting shortcoming of sapphire, realize vertical device structure, thereby simplified device making technics greatly.
At present the main method of preparation GaN monocrystal material and separately characteristics see table 1.Vapor phase process is representative with HVPE, and the crystal mass that obtains is not high, and defective is more, but the speed of growth is very fast, existing commodity selling, and also equipment is simple relatively.In three kinds of solution methods, the required pressure of high pressure nitrogen solution method is the highest, and the hot method of ammonia is taken second place, and flux method is minimum; And with regard to temperature, it is the highest to remain the high pressure nitrogen solution method, and flux method takes second place, and the hot method of ammonia is minimum.It is thus clear that comparatively speaking, the flux method growth conditions is comparatively gentle, the speed of growth is very fast, so cost is relatively low.The crystal mass that the high pressure nitrogen solution method obtains is better, but wants further increased in size difficulty very big; The crystal mass that flux method obtains is also better.The defect concentrations in crystals that the hot method of ammonia obtains is maximum, and the difficulty that improves the speed of growth is very big.Flux method has reached 2 inches, several millimeters thickness through the crystalline size that introducing large-size seed crystal obtains.Behind restriction nucleation or control oriented growth, the flux method single crystal growing then has more potentiality.Obviously, flux method might develop into industrial growing technology.But regardless of which kind of growth method, the size of GaN body monocrystal material is confined to 2 inch diameters mostly at present.And, because the big cost of crystal growth technique difficulty is high, GaN homogeneity substrate fetch long price; Limited the industrial application of GaN material, pressed for the development process advanced technology, operated simple and easy; Industrial growing technology with low cost, the present invention design i.e. purpose and forming for this reason.
The main method of table 1 preparation GaN monocrystal material
In addition, in the existing growing method, falling crucible method (claiming the Bridgman-Stockbarger method again) is one of main method wherein.Its principal feature is following:
(1) is fit to large size, the growth of most amount crystalline.
(2) can add seed crystal oriented growth monocrystalline, also can natural nucleation, according to the principle growing single-crystals of eliminating for how much.
(3) can adopt the crucible of sealing to grow, prevent that component deviation and doping content that the volatilization owing to melt, admixture causes from descending, and can avoid the pollution of objectionable impurities surrounding environment.
(4) the crystalline shape can be decided with the shape of crucible, is fit to special-shaped crystalline growth.
(5) operating procedure is fairly simple, is easy to realize sequencing, robotization.
Therefore falling crucible method is incorporated into the GaN body monocrystal material that is expected to grow large-size in the flux method.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of HTHP crystal growth equipment, especially a kind of HTHP flux-Bridgman-Stockbarge method for growing equipment of ability growing large-size GaN body monocrystalline.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of HTHP crystal growth equipment comprises hanging apparatus, base, pressure-pot, process furnace, lowering means; Hanging apparatus is installed in the top of pressure-pot shell; Base is used for the abutment pressure jar; Place process furnace and lowering means in the pressure-pot, fire door communicates with the interior furnace chamber of pressure-pot under the process furnace; Lowering means is installed in the process furnace below, places the crucible that is heated the stove heating on it, places in the crucible to be used to generate HTHP crystalline material.
Described pressure-pot comprises Stainless Steel Shell, is installed in the spiral coil cooling tube of outside, the connection terminal of supplied heated stove power; Said process furnace comprises the heat-insulating and sealing plug at lagging material, furnace chamber and the fire door place of inner Heating element, outside; Said lowering means comprises carrier table, worm and gear, timing gear wheels, slow speed motor, pointer and the graduated scale of placing crucible; Lowering means is positioned on the inner support platform that is fixedly linked with pressure-pot of pressure-pot.
The pressure-pot Stainless Steel Shell is divided into upper and lower two parts, through flange plate bolt connect or fast-open type from robust sealed.Pressure-pot keeps vacuum through being attached thereto vacuum apparatus.The process furnace Heating element is made up of one or more in graphite, Fe/Cr/Al alloy, Ni/Cr alloy, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, platinum, silit, the molybdenum silicide.
Process furnace (18) is heated to said furnace chamber～and 2000 ℃.Process furnace comprises at least two TPs, is used to measure the temperature of at least two positions of said furnace chamber; Said TP is to be selected from two or more in thermopair, its any combination of thermistor; One of them is used to control the furnace chamber temperature, and other are used to indicate furnace chamber different positions temperature.
Lagging material is one or more of the fire-resistant cotton of pure aluminium silicate, polycrystalline alumina fiber, graphite, common carbon felt, carbon laydown felt.Spiral coil cooling tube (4) is wrapped in the pressure-pot outside; The cooling water tank of the outer tape splicing water pump of spiral coil cooling tube.The output of said transmitter is introduced by the connection terminal on the pressure-pot, and safety output under 10MPa air pressure.
Characteristics of the present invention are that falling crucible method and flux method are combined, and are expected under controlled temperature, pressure condition, to grow the GaN body monocrystal material of large-size.
In a word, the present invention is simple in structure, and is easy to operate; Of many uses; Can be used for outside the growing large-size GaN body monocrystal material, also can be used for the various functional crystal materials of from the high-vapor-pressure melt, growing, can also be used for some materials hip treatment or sintering under atmosphere etc.
Description of drawings:
Fig. 1 is a kind of HTHP crystal growth equipment main part structural representation.
Fig. 2 is a HTHP GaN bulk growth stove whole plant work synoptic diagram.
Embodiment:
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment one:
With reference to accompanying drawing 1, this kind HTHP crystal growth equipment main part comprises pressure-pot 1, process furnace 18, lowering means 5.
The material of said pressure-pot 1 is 0Cr18Ni9 in the present embodiment, wall thickness 20mm, outer wall welding spiral coil cooling tube 4.Pressure-pot 1 is to be to produce high nitrogen pressure ring border in the jar, makes to be in inside and outside the process furnace 18 etc. in the static pressure environment.The high-temperature furnace body of placing in the pressure-pot 1 18, following fire door communicates with pressure-pot, and all the other oven body part are equipped with lagging material 2.Process furnace is under 1000 ℃ of long time continuous working situation, and for guaranteeing effective operation of electromechanical device in the pressure-pot 1, the cooling infrastructure of pressure-pot guarantees that a jar inner wall temperature is lower than 50 ℃.Cooling infrastructure adopts spiral coil cooling tube 4, logical recirculated cooling water in promptly the semicircle pipe twines along outer wall.
Said process furnace 18 comprises the sealing heat-insulating and sealing plug 15 at heating element 3, lagging material 2, furnace chamber and fire door place.The process furnace heating element is the Ni-Cr silk, also can be in molybdenum filament, graphite, Fe/Cr/Al alloy, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, platinum, the silit.Process furnace is provided with the vertical-type furnace chamber, and internal diameter is 80mm, total length 250mm.
Said lowering means 5 comprises carrier table, worm and gear, timing gear wheels, slow speed motor, pointer and graduated scale.The minimum 0.1mm/day that reaches of fall off rate reaches as high as 100mm/day in the present embodiment
Lowering means is positioned on the support platform 7, and for letting line related line and thermopair pass through smoothly, platform has some apertures.This platform is used to support process furnace and other relevant devices, adopts removably to fix, to make things convenient for the installation and the maintenance of its underpart wiring etc.
The concrete working process of said HTHP crystal growth equipment (seeing accompanying drawing 2): at first, the crucible 12 of packing into after correlative prepares in glove box is put into the support component 13 of process furnace 18 furnace chambers; Then, put down pressure-pot 1 top with hanging apparatus, good seal pressure-pot 1 back vacuumizes with vacuum pump 22, when to preset value, stop to vacuumize, by gas cylinder 19 after HPP 20 boosts with in the reactant gases oxide gas charged pressure jar 1; Connect recirculated cooling water case 17 power supplys then, let recirculated water in spiral coil cooling tube 4, begin to circulate, connect process furnace 18 power supplys, make it by specific temperature program work.After stove 18 to be heated is warming up to preset temperature, the insulation some time; Connect lowering means 5 work drive motors then, make crucible begin at the uniform velocity to descend; Single crystal growing finishes after dropping to predetermined distance, the process furnace cooling; Open the pressure release of pressure-pot pressure release valve, treat that pressure release is accomplished after, open pressure-pot, take out crucible and material with the hanging apparatus pressure-pot top of slinging.So far, reactors whole plant working process finishes.
Embodiment two:
With reference to embodiment one, in the glove box that fills nitrogen or argon filling, respectively 5g sodium Metal 99.5 and 5g gallium (mol ratio is: 24.9: 75.1) are put into BN crucible (or Al
2O
3Crucible), then it is transferred in the furnace chamber in the pressure-pot 1, WP 7MPa, 800 ℃ of furnace temperature, growth 96h working time can obtain the GaN body monocrystalline of mm level size under the sporadic nucleation condition.
Embodiment three:
With reference to embodiment one, in the glove box that fills nitrogen or argon filling, respectively 5g sodium and 5g gallium are put into the BN crucible, then it is transferred in the furnace chamber in the pressure-pot 1; WP 7MPa; 950 ℃ of furnace temperature, growth 300h working time can obtain the GaN body monocrystalline of a large amount of mm level sizes.
Claims (10)
1. a HTHP crystal growth equipment comprises hanging apparatus, base (6), pressure-pot (1), process furnace (18), lowering means (5); It is characterized in that: hanging apparatus is installed in the top of pressure-pot (1) shell; Base (6) is used for abutment pressure jar (1); Place process furnace (18) and lowering means (5) in the pressure-pot (1), process furnace (18) fire door down communicates with the interior furnace chamber of pressure-pot (1); Lowering means (5) is installed in process furnace (18) below, places the crucible that is heated stove (18) heating on it, places in the crucible to be used to generate HTHP crystalline material.
2. a kind of HTHP crystal growth equipment as claimed in claim 1 is characterized in that: described pressure-pot (1) comprises Stainless Steel Shell, is installed in the spiral coil cooling tube (4) of outside, the connection terminal (16) of supplied heated stove power; Said process furnace (18) comprises the heat-insulating and sealing plug (15) at lagging material (2), furnace chamber and the fire door place of inner Heating element (3), outside; Said lowering means (5) comprises carrier table, worm and gear, timing gear wheels, slow speed motor, pointer and the graduated scale of placing crucible; Lowering means (5) is positioned on the inner support platform (7) that is fixedly linked with pressure-pot of pressure-pot.
3. a kind of HTHP crystal growth equipment as claimed in claim 2 is characterized in that: the pressure-pot Stainless Steel Shell is divided into upper and lower two parts, through flange plate bolt fit sealing or fast-open type from fastening sealing.
4. according to claim 1 or claim 2 a kind of HTHP crystal growth equipment is characterized in that: pressure-pot guarantees the pure of gas in the pressure-pot or keeps vacuum through the vacuum apparatus (22) that is attached thereto.
5. a kind of HTHP crystal growth equipment as claimed in claim 2 is characterized in that: process furnace Heating element (3) is made up of one or more in graphite, Fe/Cr/Al alloy, Ni/Cr alloy, niobium, titanium, tantalum, molybdenum, tungsten, rhenium, platinum, silit, the molybdenum silicide.
6. like claim 1,2,3,5 each described a kind of HTHP crystal growth equipments is characterized in that: process furnace (18) can be heated to said furnace chamber～and 2000 ℃.
7. like claim 1,2,3,5 each described a kind of HTHP crystal growth equipments, it is characterized in that: process furnace (18) comprises at least two TPs (10,11), is used to measure the temperature of at least two positions of said furnace chamber; Said TP is to be selected from two or more in thermopair, its any combination of thermistor; One of them is used to control the furnace chamber temperature, and other are used to indicate furnace chamber different positions temperature.
8. a kind of HTHP crystal growth equipment as claimed in claim 2 is characterized in that: lagging material (2) is one or more of the fire-resistant cotton of pure aluminium silicate, polycrystalline alumina fiber, graphite, common carbon felt, carbon laydown felt.
9. a kind of HTHP crystal growth equipment as claimed in claim 2 is characterized in that: spiral coil cooling tube (4) is wrapped in the pressure-pot outside; The cooling water tank of the outer tape splicing water pump of spiral coil cooling tube (4).
10. a kind of HTHP crystal growth equipment as claimed in claim 7 is characterized in that: the output of said transmitter is introduced by the connection terminal on the pressure-pot (16), and safety output under 10MPa air pressure; The power of process furnace is also introduced by connection terminal (16) by the power on the pressure-pot, and safety transmission of electricity under 10MPa air pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100039093A CN102534798A (en) | 2012-01-06 | 2012-01-06 | High-temperature high-pressure crystal growth equipment |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100039093A CN102534798A (en) | 2012-01-06 | 2012-01-06 | High-temperature high-pressure crystal growth equipment |
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| CN102534798A true CN102534798A (en) | 2012-07-04 |
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| CN2012100039093A Pending CN102534798A (en) | 2012-01-06 | 2012-01-06 | High-temperature high-pressure crystal growth equipment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305903A (en) * | 2013-05-16 | 2013-09-18 | 西安交通大学 | Method for preparing GaN crystal by high-nitrogen pressure flux-crucible descending process |
| CN103614765A (en) * | 2013-10-31 | 2014-03-05 | 中国科学院上海光学精密机械研究所 | Method of heating graphite to grow sapphire crystal |
| CN104357908A (en) * | 2014-10-28 | 2015-02-18 | 西安建筑科技大学 | Crystal growing device and application thereof for being used as fluoro boron beryllium acid potassium crystal growing device |
| CN107649686A (en) * | 2013-03-13 | 2018-02-02 | 昆特斯技术公司 | The method of the pressure setting and compacting of fan and injector cooling with combination |
| WO2020151832A1 (en) * | 2019-01-25 | 2020-07-30 | Quintus Technologies Ab | A method in a pressing arrangement |
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| US5698029A (en) * | 1995-06-06 | 1997-12-16 | Kabushiki Kaisha Kobe Sekio Sho | Vertical furnace for the growth of single crystals |
-
2012
- 2012-01-06 CN CN2012100039093A patent/CN102534798A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5698029A (en) * | 1995-06-06 | 1997-12-16 | Kabushiki Kaisha Kobe Sekio Sho | Vertical furnace for the growth of single crystals |
Non-Patent Citations (1)
| Title |
|---|
| S.POROWSKI ET AL: "Thermodynamical properties of III-V nitrides and crystal growth of GaN at high N2 pressure", 《JOURNAL OF CRYSTAL GROWTH》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649686A (en) * | 2013-03-13 | 2018-02-02 | 昆特斯技术公司 | The method of the pressure setting and compacting of fan and injector cooling with combination |
| US10458711B2 (en) | 2013-03-13 | 2019-10-29 | Quintus Technologies Ab | Combined fan and ejector cooling |
| CN107649686B (en) * | 2013-03-13 | 2020-01-17 | 昆特斯技术公司 | Press with combined fan and ejector cooling and method of pressing |
| CN103305903A (en) * | 2013-05-16 | 2013-09-18 | 西安交通大学 | Method for preparing GaN crystal by high-nitrogen pressure flux-crucible descending process |
| CN103305903B (en) * | 2013-05-16 | 2016-01-13 | 西安交通大学 | A kind of high nitrogen pressure fusing assistant-falling crucible method prepares the method for GaN crystal |
| CN103614765A (en) * | 2013-10-31 | 2014-03-05 | 中国科学院上海光学精密机械研究所 | Method of heating graphite to grow sapphire crystal |
| CN104357908A (en) * | 2014-10-28 | 2015-02-18 | 西安建筑科技大学 | Crystal growing device and application thereof for being used as fluoro boron beryllium acid potassium crystal growing device |
| CN104357908B (en) * | 2014-10-28 | 2017-07-28 | 西安建筑科技大学 | Crystal growth equipment and its application as fluoro boron potassjum beryllate crystal growth equipment |
| WO2020151832A1 (en) * | 2019-01-25 | 2020-07-30 | Quintus Technologies Ab | A method in a pressing arrangement |
| JP7476209B2 (en) | 2019-01-25 | 2024-04-30 | キンタス・テクノロジーズ・エービー | Method in a press |
| US11969798B2 (en) | 2019-01-25 | 2024-04-30 | Quintus Technologies Ab | Method in a pressing arrangement |
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Application publication date: 20120704 |