CN100434573C - Method for developing aluminum nitride crystal in large size through flow of plasma flame - Google Patents
Method for developing aluminum nitride crystal in large size through flow of plasma flame Download PDFInfo
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- CN100434573C CN100434573C CNB2006100712923A CN200610071292A CN100434573C CN 100434573 C CN100434573 C CN 100434573C CN B2006100712923 A CNB2006100712923 A CN B2006100712923A CN 200610071292 A CN200610071292 A CN 200610071292A CN 100434573 C CN100434573 C CN 100434573C
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Abstract
This invention discloses a method for growing AlN single crystal by heating raw materials with plasma flow. The method comprises: utilizing plasma flow as the heating source, and AlN micropowder or high-purity Al micropowder and N2 as the raw materials, sending the raw materials into plasma flow by using carrier gas, utilizing AlN single crystal as the crystal seed or AlN polycrystal as the matrix material for self-nucleating growth, heating the crystal seed or matrix material by plasma flow or other methods to the temperature need for crystallization, and growing in the growth chamber with N2 as the growth environmental gas. The powder delivery rate is adjustable. The stage for supporting the crystal seed or matrix material can be elevated and rotated with controllable speed. The pressure of N2 is adjustable. This invention also shows the figure for depicting the reaction apparatus for growing AlN single crystal by heating raw materials with plasma flow.
Description
Technical field
The present invention relates to be used for preparation, especially the growing aluminum nitride crystal preparation methods of the high temperature semiconductors monocrystal material of electronics and photoelectronic industry.Compact ultraviolet source and the high density data storage numerous areas such as short wavelength laser that use of aluminum nitride crystal material in compact Analytical equipment that all solid state white-light illuminating, sterilization and sterilization device, biotechnology and pharmacopedics are used, biotechnological formulation detection system, covert-channel is with a wide range of applications, in addition, it is as the substrate material of making nitride compound semiconductor device, high power RF device, millimetric wave device and microwave device, and also the utmost point has prospect.
Background technology
Can at first go out aluminium nitride whisker in prepared in laboratory in 1956 from people such as Kohn to aluminum-nitride single crystal bulk-growth Study on Technology in the world reviews.From G.A.Slack and T.F.McNelly (" Growth of High Purity AlNCrystals ", J.Cryst.Growth 34,263 (1976) and " AlN Single Crystals ", J.Cryst.Growth 42,560 (1977)) grow block aluminium nitride material with distillation recrystallize method, caused since the common concern and research interest of people to aluminum nitride crystal, in the aluminum nitride crystal growth history of four more than ten years, the various countries investigator has almost attempted all possible research method, comprises distillation crystallization process (claiming the physical vapor transport method again), vapor phase process is (as Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, hydride vapour phase epitaxy method, aluminum vapor Xiang Fa etc.), melting method and the hot method of ammonia etc.
Distillation crystallization process (" Report on the growth of bulk aluminum nitride and subsequentsubstrate preparation ", J.Cryst.Growth, 231 (2001) 317-321 and " Growth of AlN bulkcrystals by sublimation sandwich method ", Mater.Sci.Forum, 433-436 (2003) 979-982) is considered to the most promising method of present growing large-size aluminum nitride crystal, be not resolved but remain, such as raw material continues a lot of problems such as conveying and growing crystal crucible life weak point in a lot of problems; Hydride vapour phase epitaxy method (" Growth of thick AlN layers by hydride vapor-phase epitaxy ", J.Cryst.Growth, 281 (2005) 62-67) wafer (Wafer) of having grown and being of a size of 30 * 30 millimeters, but because underlayer temperature is lower, thereby defect concentration is very big; Other are as several aluminum nitride crystal growth methods such as Metalorganic Chemical Vapor Deposition, molecular beam epitaxy, aluminum vapor phase method, melting method, the hot methods of ammonia, from growth mechanism owing to there is very strong anisotropic growth trend (cold zones below 2100 ℃), so be difficult to the growth of realization large-size crystals.
Anatomizing and studying through and present situation historical to aluminum nitride crystal growth, we recognize: because aluminium nitride need could form the high-quality crystallization near 2200 ℃ of temperature, and aluminium nitride has had the distillation phenomenon when this temperature, therefore adopt vapor phase process (to comprise the distillation crystallization process, also claim the physical vapor transport method) be the unique valid approach of growing aluminum nitride crystal, liquid phase process or additive method may, also can't grow large-sized aluminum nitride crystal hardly.And in the vapor phase process growth method, the distillation crystallization process is the best method of growing aluminum nitride single crystal at present.The experimental study of many decades has also proved these conclusions both at home and abroad.Yet we see, although the American Studies scholar has expended huge fund in 40 years, best result is only for growing the about 12 millimeters single crystal of diameter up to now.Before this result is reported in two to three years, do not see obvious progress over the past two years as yet.Let alone this laboratory level achievement in research also can't realize industrialization production, also can't satisfy each Application Areas to aluminum nitride crystal demand quantitatively.The basic reason that faces above predicament is that originally there is certain limitation in the distillation crystallization process of aluminum nitride crystal on principle, be embodied in: what the crystallization process that 1. distils adopted is a material sealing or semiclosed system, be difficult to realize the lasting conveying of material in the process of growth, crystal can't continue to grow up; 2. the raw material in the system the deactivated phenomenon of raw material can occur at all after dates of several temperature fluctuations of experience, causes the powder caking, and the total system rate of sublimation diminishes; 3. crystal growth rate is difficult to control, particularly at the crystal growth initial stage.Crystalline growth velocity can be controlled by parameters such as the temperature of the distillation district of growth room and crystallizing field and thermograde are regulated and control on the principle, but be to be difficult to operation to the accurate measurement and the control of high-temperature area temperature in fact; 4. the subliming method aluminum nitride crystal growth needs crucible, can make crucible be subjected to serious destruction but at high temperature decompose the aluminum vapor that produces.Crucible material that screening is fit to and raising pot life are insoluble for a long time difficult problems.
In the face of the difficulty of distillation crystallization process on realization large size aluminum nitride crystal growth, be necessary to find new outlets from changing growing principle and method, break through.
Summary of the invention
The present invention proposes the method for using plasma flame stream growing aluminum nitride crystal.The characteristics of plasma flame stream are extreme temperatures, contain a large amount of various types of charged ions, neutral particle and electronics isoreactivity species in the flame.Plasma flame stream is used widely in fields such as the energy, chemical industry, material, environment, country and space flight as a kind of thermal source.Thermal plasma flame stream temperature can reach 3 * 10
3～3 * 10
4K, utilize plasma flame stream can carry out thermospray and surface Hardening Treatment, Germany Metaplas Ionon company (" Performance of new Al TiN coatings indry and high speed cutting ", Surface and Coatings Technology 163-164 (2003) 674-680) adopts the AlTiN coating of metal fine powder material preparation to have anti-mechanical wear, resistance to chemical attack or changes the effect of surface property.Print auspicious forever (" plasma method prepares the research of superfine powder aluminium nitride ", New Chemical Materials, the 32nd the 7th phase of volume, 8-10) and Yang Bangchao (" plasma method prepares the research of aluminum nitride powder powder stock " (2004), silicate journal, the 30th volume supplementary issue, (2002) 96-97) etc. be raw material with high-purity aluminium powder and nitrogen, adopt the DC arc plasma method to prepare the very high aluminium nitride ultra-fine micropowder of purity, contain the whisker of part submicron in the micro mist.Motohiro Yamada (" Nitridation of aluminum particles and formation process of aluminum nitride coatingsby reactive RF plasma spraying ", Thin Solid Films, In Press, Accepted Manuscript, Available online 6March 2006) etc. people nitrogen plasma flame district that high-purity aluminium powder is produced by radio frequency and with the nitrogen reaction, at the bottom of the stainless steel lining, prepared aluminium nitride coating.These studies show that aluminium nitride can generate in reaction in thermal plasma flame stream, therefore, using plasma flame stream method growing aluminum nitride crystal is feasible in principle.M.Breiter (" Diamond synthesis with a DC plasma jet:control of the substrate temperature ", Diamond and Related Materials 9 (2000) 333-336) and Li Huiqi (" plasma jet method gas-phase grown diamond ", coal-mining industry is published, nineteen ninety-five, the 1st edition) etc. using plasma spray vapor phase process and prepare the fine diamond thin, because the plasma physical efficiency is enhanced the particle activity that participates in reaction, thereby has higher growth velocity than additive method.These researchs show simultaneously uses the plasma flame flow growing aluminum nitride crystal not only can avoid out a difficult problem in the distillation crystallization process, also has some other advantage.
Particular content of the present invention is: the using plasma flame flows as heating raw thermal source in the crystal growing process, and the means that produce plasma flame stream can be electric arc, radio frequency or microwave method; With aluminium nitride micro mist or rafifinal micro mist raw material as the aluminium atom; Select for use nitrogen as carrier gas, aluminium nitride micro mist or rafifinal powder material are sent into the plasma flame flow district with carrier gas; Regulate the growth velocity of the powder feeding rate control aluminum nitride crystal of raw material by powder feeding mechanism; With nitrogen or other nitrogenous gas as the working gas that produces plasma body, in the plasma flame stream nitrogen ion as the ion that participates in reaction and near the nitrogen ion the additional crystal plane to improve crystal structure speed; Use aluminum-nitride single crystal body is as crystal seed or use the base material of aluminium nitride polycrystal as spontaneous nucleation growth; Crystal seed or substrate saddle are placed on the support with lifting and spinfunction, and it is temperature required that crystal seed or substrate are heated to crystal structure by flame stream thermal field; Adopt nitrogen can to adjust and control in the growth room as growing environment gas and pressure; By the elevation rate and the swinging strut of control bracket, keep the optimum position of crystal growth crystal plane and the homogeneity of crystal growth; Adopt the protective gas growth atmosphere to keep the optimal growth condition of aluminum nitride crystal.
The inventive method growing aluminum nitride crystal has following characteristics: (1) can realize the continual conveying of raw material, and raw material can not lose activity yet simultaneously; (2) can control the crystalline growth speed of aluminium nitride by the powder feeding rate of adjusting raw material, guarantee crystalline quality; (3) utilize characteristics such as plasma flame stream temperature height, energy is big and can control, the starting material of heating and sublimation-grown aluminium nitride, owing to need not use the crucible heating, thereby can in crystal growing process, newly not introduce impurity; (4) adopt the operation material of suitable nitrogen atom gas as plasma body, because of containing more nitrogen ion, to promoting near the crystallization of aluminium nitride growth interface, it is highly beneficial to improve crystal growth rate in the plasma flame; (5) can on crystal seed, realize the growth of no crucible, avoid problems such as the crucible material selection that must face and solve in the present high-temperature ammonolysis aluminium crystal technique and work-ing life.Employing the inventive method can break through the restrictions of the most difficulties that run in the present large size aluminum-nitride single crystal bulk-growth technology, is a kind of novel method of up-and-coming growing aluminum nitride crystal.
Description of drawings
Fig. 1 is a kind of original reason experiment device synoptic diagram of plasma flame stream growing aluminum nitride crystal.
Embodiment
Embodiment 1:
Adopt original reason experiment device shown in Figure 1 to carry out the growth of aluminum-nitride single crystal.This principle arrangement comprises the shell 1 that the metalloid material by stainless steel constitutes, and assemble a DC arc plasma flame flow device 2, powder rate control device 3 under the raw material, sample table 4 with lifting and spinfunction, vacuum extractor and pressure control system 5, and crystal seed support and substrate holder 6.The power supply of plasma flame flow device and airing system and carrier gas airing system do not draw in the diagram.
As heating raw thermal source in the crystal growing process, high-purity aluminium powder is as the source material of aluminium atom with DC arc plasma flame stream 2, and the aluminum-nitride single crystal body that crystal seed selects for use additive method to grow uses nitrogen as shielding gas in the growth room.Before the crystal growth, reaction chamber is vacuumized, remove foreign gases such as oxygen, charge into nitrogen then.By pressure control system 5 growth room's internal pressure is maintained a certain appropriate value scope in the process of growth.When aluminum nitride crystal growth begins, at first open plasma flame stream, and the parameters that will produce plasma body is adjusted to the suitable parameters of aluminum nitride crystal growth, to be placed on the flame below again with the crystal seed support 6 of crystal seed, adjust sample table 4 height location, make crystal seed be in " molten kind " humidity province, this temperature is greatly near 2250 ℃, send into rafifinal raw material micro mist by powder rate control device 3 under the raw material with suitable speed in plasma flame then, nitrogen is selected in the powder feeding carrier gas for use.The raw material micro mist is heated ionization and generates aluminium nitride with nitrogen ionic reaction in the plasma flame in the process by plasma flame, after aluminium nitride arrives the cold zone of flame lower end by plasma flame, and crystallization on aln seed crystal.Along with the crystalline growth of aluminium nitride on crystal seed, slowly move down sample table, make crystal plane remain on certain fixed appropriate location.The rotation of sample table 4 can make crystal have more uniform crystalline quality diametrically.
Embodiment 2:
Present embodiment is same to adopt original reason experiment device shown in Figure 1 to carry out the growth of aluminum-nitride single crystal.With DC arc plasma flame stream 2 thermals source as heating raw in the crystal growing process; suitably the aluminium nitride micro mist of granularity is as the source material of aluminium atom; the aluminum-nitride single crystal body that crystal seed selects for use additive method to grow uses nitrogen as shielding gas in the growth room.Before the crystal growth, reaction chamber is vacuumized, remove foreign gases such as oxygen, charge into nitrogen then.By pressure control system 5 growth room's internal pressure is maintained near a certain appropriate value in the process of growth.When aluminum nitride crystal growth begins, at first open plasma flame stream, and the parameters that will produce plasma body is adjusted to the suitable parameters of aluminum nitride crystal growth, to be placed on the flame below again with the crystal seed support 6 of crystal seed, adjust sample table 4 height location, make crystal seed be in " molten kind " humidity province, this temperature is greatly near 2250 ℃, send into rafifinal raw material micro mist by powder rate control device 3 under the raw material with suitable speed in plasma flame then, nitrogen is selected in the powder feeding carrier gas for use.The aluminium nitride micro mist is heated ionization in the process by plasma flame, nitrogen ion and aluminum ion after arriving the cold zone of flame lower end by plasma flame, crystallization on aln seed crystal.Nitrogen ion in the plasma flame can replenish near the nitrogen ionic concentration the crystal plane, to improve the crystallization rate of aluminium nitride.Along with the crystalline growth of aluminium nitride on crystal seed, slowly move down sample table, make crystal plane remain on certain fixed appropriate location.The rotation of sample table 4 can make crystal have more uniform crystalline quality diametrically.
Claims (3)
1, a kind of method that adopts plasma flame flow heating raw materials growing aluminum nitride single crystal, comprise: the using plasma flame flows as heating source, starting material use aluminium nitride micro mist or rafifinal micro mist and nitrogen, and send into by carrier gas, following powder speed can be adjusted and control, use aluminum-nitride single crystal body is as crystal seed or use the base material of aluminium nitride polycrystal as spontaneous nucleation growth, crystal seed or substrate saddle have the lifting and the spinfunction of may command speed, it is temperature required that crystal seed or substrate are heated to crystal structure by flame stream thermal field, and employing nitrogen can be adjusted and be controlled as growing environment gas and pressure the growth room in.
According to the method for claim 1, it is characterized in that 2, the means that produce plasma flame stream can be electric arc, radio frequency or microwave method.
3, according to the method for claim 1, it is characterized in that a large amount of various types of charged ions, neutral particle and electronically active species in the plasma flame stream.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103539086B (en) * | 2012-07-17 | 2016-06-15 | 深圳大学 | A kind of processing method preparing non-polar surface aluminum nitride material |
| CN108238801B (en) * | 2016-12-27 | 2021-03-02 | 中天科技精密材料有限公司 | Preparation method of aluminum nitride |
| CN109161960B (en) * | 2018-11-07 | 2023-06-30 | 沈阳工程学院 | Numerical control crystal growth furnace by plasma method |
| CN111514604B (en) * | 2020-04-17 | 2022-05-31 | 深圳大学 | Method for preparing high-purity crystal by fractional evaporation crystallization |
| CN115028459B (en) * | 2022-07-22 | 2023-07-04 | 成都物熙科技有限公司 | Method and device for preparing high-purity superfine aluminum nitride powder by using plasma |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1434482A (en) * | 2003-02-18 | 2003-08-06 | 华南师范大学 | Method for making gallium nitride crystal |
| EP1405936A1 (en) * | 2001-06-06 | 2004-04-07 | AMMONO Sp.z o.o. | Method and equipment for manufacturing aluminum nitride bulk single crystal |
| CN1704330A (en) * | 2004-05-26 | 2005-12-07 | 中国科学院金属研究所 | Process for preparing low-dimensional aluminium nitride nano materials |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1405936A1 (en) * | 2001-06-06 | 2004-04-07 | AMMONO Sp.z o.o. | Method and equipment for manufacturing aluminum nitride bulk single crystal |
| CN1434482A (en) * | 2003-02-18 | 2003-08-06 | 华南师范大学 | Method for making gallium nitride crystal |
| CN1704330A (en) * | 2004-05-26 | 2005-12-07 | 中国科学院金属研究所 | Process for preparing low-dimensional aluminium nitride nano materials |
Non-Patent Citations (6)
| Title |
|---|
| Diamond synthesis with a DC plasma jet: control of thesubstrate temperature. M. Breiter.Diamond and Related Materials,No.9. 2000 |
| Diamond synthesis with a DC plasma jet: control of thesubstrate temperature. M. Breiter.Diamond and Related Materials,No.9. 2000 * |
| 氮化铝晶体的生长惯习面和晶体形态. 傅仁利等.人工晶体学报，第33卷第3期. 2004 |
| 氮化铝晶体的生长惯习面和晶体形态. 傅仁利等.人工晶体学报，第33卷第3期. 2004 * |
| 等离子体法制备超细粉体氮化铝的研究. 尚书勇等.化工新型材料，第32卷第7期. 2004 |
| 等离子体法制备超细粉体氮化铝的研究. 尚书勇等.化工新型材料，第32卷第7期. 2004 * |
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