CN1248957C - Unidimensional aluminium nitride nanometer structure array and its preparation method - Google Patents
Unidimensional aluminium nitride nanometer structure array and its preparation method Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 65
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- 229910052786 argon Inorganic materials 0.000 claims description 122
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- 239000010453 quartz Substances 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 69
- 239000002110 nanocone Substances 0.000 claims description 56
- 229910052710 silicon Inorganic materials 0.000 claims description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000010703 silicon Substances 0.000 claims description 53
- 239000002061 nanopillar Substances 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 40
- 239000002086 nanomaterial Substances 0.000 claims description 37
- 238000005554 pickling Methods 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 238000009415 formwork Methods 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000003491 array Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 4
- 150000004767 nitrides Chemical class 0.000 abstract description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 abstract description 2
- 238000000348 solid-phase epitaxy Methods 0.000 abstract description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 4
- 238000000407 epitaxy Methods 0.000 abstract 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
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Abstract
The present invention relates to a preparation method for arrays with one-dimensional nanometer structures by gas phase epitaxy synthetic aluminum nitride. The present invention uses anhydrous AlCl3 as an Al source, and uses NH3/N2 mixed gas with 4% to 20% of NH3 as an N source. The Al source and the N source are deposited on a substrate loaded with catalyst granules in a tubular furnace at a moderate temperature of 700 to 1000 DEG C, and AlN arrays with one-dimensional nanometer structures are obtained. The present invention is characterized in that multiple controllable AlN one-dimensional nanometer structures can be obtained by adjusting synthetic conditions such as the gasification temperature of AlCl3, the reaction temperature, the reaction time, the flow rate of the carrier gas, substrate materials, etc.; the multiple one-dimensional nanometer structures comprise nanometer cones, nanometer columns (or rods), nanometer flowers, nanometer coral clusters, etc. The present invention develops a new method for preparing arrays with AlN one-dimensional nanometer structures by the reaction of gas and solid phase epitaxy. Compared with other methods, reaction conditions of the method are mild, and patterns of products can be controlled by preparation conditions. Consequently, the present invention provides a new way for preparing one-dimensional nanometer structures of other III group of a nitride system and for the research of nanometer electronic devices.
Description
One. technical field
The present invention relates to the preparation method of novel one dimension Nano structure arrays such as aluminum nitride nanometer awl, nano-pillar (or rod), nanometer flower, nanometer coral bunch, the technology of gas-solid phase epitaxy method of a kind of usefulness and the aluminium nitride one dimension Nano structure array by the controlled growth different-shape of modulation reaction conditions, high orientation is provided especially.
Two. background technology
From 1991 Japanese carbonization scholar Iijima (S.Iijima) with high-resolution electron microscopy in the graphite arc discharge product first observed (S.Iijima Nature 354 (1991) since carbon nanotube, 56), people have carried out extensive and deep research to synthetic, structure, performance and the application etc. of carbon nanotube.Carbon nanotube has the seamless tube structure that unique one dimension hollow graphite aspect is curled into because of it, and have a series of new physico-chemical properties that are different from the conventional graphite material, chemistry and thermostability as height, (Theoretical Calculation shows high physical strength, its tensile strength is 100 times of steel, and density have only steel 1/6), special electric property (different according to caliber and helicity, can be the conductor not worse than copper, also can be semi-conductor), therefore be considered at structured material, there is wide application prospect (R.H.Baughman et al.Science 297 (2002), 787) the functional materials aspect.The research of one dimension Nano structure just grows up after carbon nanotube is found gradually.
The III group-III nitride that with GaN is representative is the important third generation semiconductor material of a class, can form 3.4eV from the 1.9eV of InN to GaN up to the ternary or the quaternary solid solution alloy system (as AlGaN, GaInN, AlGaInN) of the 6.2eV of AlN continuous variable, its corresponding direct band gap wavelength has covered the scope from red, yellow, green to UV-light.Based on its turquoise photodiode (LEDs) and laser diode (LDs) great market aspect the read-write of full color indicating meter, high definition duplicating machine, indigo plant and ultraviolet laser, high-density CDs and the DCDs shaven head promoted people seek efficient, believable and high-speed can red-emitting to the semiconductor material (F.A.Ponce et al.Nature 386 (1997), 351) of blue wave band.Adopt this semiconductor material to substitute the full color light-emitting diode display of electron tube, can make the brightness increase of single wavelength light and can cover wider wavelength.In addition, when the blue laser that uses the short wavelength replaced data on the laser and/write CDs of present widely used 780nm wavelength, only the minimizing because of LASER SPECKLE on CD just can make 4 times of present CD data of optical disk store content raisings.
AlN is a kind of important broad-band gap third generation semiconductor material, and its vertical band gap width reaches 6.2eV, can be used as the luminescent material in extreme ultraviolet light district; Its low or even negative electron affinity makes its electron emission on the scene field that the important application prospect be arranged in addition; AlN is again a kind of high thermal conductivity material simultaneously, and the room temperature thermal conductivity can reach 320W * m in theory
-1* K
-1, be 10～15 times (Y.Baik, et al.Key Eng.Mater.122-124 (1996), 553) of conventional aluminium oxide substrate material; It also have excellent electric insulating can and thermo-chemical stability, advantage such as close with the thermal expansivity of Si, be the crucible material etc. of desirable heat sink material, packaged material and the anti-molten metal attack of large-scale integrated circuit, semiconductor module circuit and high power device, extensive application prospect aspect high energy, high temperature electronics and photoelectronics.Therefore, the research of AlN is subjected to people's extensive attention.
At present, the synthetic AlN one dimension Nano structure of researchist's effort, thereby character such as the electricity of AlN excellence, photoelectricity, an emission and One-dimensional Quantum effect are combined, expand its application in microelectronics and field of nanometer technology, for example, the cutting-edge structure of AlN nano-cone array and directional property just are expected to improve greatly its field emission performance.Though the AlN whisker as far back as 1956 just by Kohn (J.A.Kohn, et al.Am.Mineralogist 41 (1956), 355) in experiment, chance on, and people (J.A.Haber such as J.A.Haber, etal.J.Am.Chem.Soc.119 (1997), 5455) pass through AlCl
3Auxiliary law: 1000 ℃ or 1100 ℃ with nano level Al powder of nitrogen nitrogenize (organo-metallic aluminum compound decomposes and get) and AlCl
3Mixture has optionally obtained nano level AlN whisker, but for synthetic, the performance of AlN one dimension Nano structure and use (W.Q.Han et al.Science277 (1997) after people such as S.S.Fan successfully make the GaN nanometer rod with carbon nanotube confinement method, 1287), just carried out widely.People such as H.Chen (H.Chen, et al.J.Cryst.Growth224 (2001), 187) adopt aluminium powder and NH
4F+NH
4Cl elder generation ball milling is again at N
2The incendiary method has been synthesized diameter at the AlN of 70～500nm nanofiber under the atmosphere; They pass through at NH (H.Chen et al.Mod.Phys.Lett.B30 (2001), 1455) subsequently
3Under the atmosphere, the AlN particle to 1500 that heating and ball-milling is crossed ℃ has obtained the AlN nano wire of the about 10-60nm of diameter; People such as S.S.Fan (C.C.Tang, et al.Chem.Phys.Lett.333 (2001), 12) adopt SiO
2Auxiliary method is with Al and NH
3Under 1100 ℃, grow the AlN nano wire of the about 100nm of diameter for raw material; It is that template is with Al and Al that people such as Y.J.Zhang (Y.J.Zhang et al.Chem.Mater.13 (2001), 3899) adopt carbon nanotube
2O
3(4: 1) and NH
3Or N
2For raw material has synthesized the controlled AlN nano wire of radius under 950 ℃-1200 ℃; People such as H.T.Cong (H.C.Tong et al.Physica B 323 (2002), 354) adopt at N
2Under the atmosphere, in 750 ℃-850 ℃ altogether hot Al and AlN nano particle mixture and obtained the AlN nano wire of the about 10-50nm of diameter; Recently, people such as Q.Wu adopt the gas-liquid-solid growth method of expansion, and the Al powder and the 4%NH of catalyzer arranged with load
3/ N
2To be raw material controlled made AlN nano wire (the Q.Wu et al.J.Mater.Chem.13 (2003) that diameter is about 15nm in 1100 ℃ to gas mixture, 2024) and caliber be the AlN nanotube (Q.Wu et al.J.Am.Chem.Soc.125 (2003), 10176) of 30-80nm.
More than these synthetic methods mostly belong to chemical Vapor deposition process and based on preparation AlN nano wire.Can be divided into two big classes substantially, a class is Vapor-Liquid-Solid (VLS) growth mechanism, and principal feature is: one, appropriate catalyst must be arranged, and catalyzer is in liquid state during nanostructure growth, so need suitable temperature.It two must have nitrogenous, aluminiferous precursor, and precursor constantly enters catalyzer by dissociating or reacting after generating the target product species on catalyzer drop surface, separates out, generates nanostructure reach supersaturation in the catalyzer drop after.Another kind of is template control growing method, for example, adopts carbon nanotube, and reactant reacts under the space constraint effect of carbon nanotube and generates specific nanostructure.
Three. summary of the invention
The novel method or the new technology path that the purpose of this invention is to provide a kind of AlN of preparation one dimension Nano structure array, and prepare the AlN nanostructure with special purpose with this comprise nanocone, nano-pillar (or rod), nanometer flower and nanometer coral bunch etc.Specifically, at middle gentle NH
3/ N
2Under the mixed atmosphere, the AlCl of the gasification that carrier gas is brought into
3In Al species and NH
3/ N
2N species in the gas mixture react down and deposit on substrate catalyzer auxiliary and obtain the AlN one-dimensional nano-array.
The object of the invention also is, by the CONTROL PROCESS condition, as AlCl
3Gasification temperature, temperature of reaction, reaction times etc., the various AlN one dimension Nano structure of acquisition that can be controlled.
The main difference of comparing with existing VLS class methods is that the present invention adopts AlCl
3Rather than traditional metal A l or Al/Al
2O
3(4: 1) mixture is as the aluminium source, thereby reaction is undertaken by the VS epitaxial growth mechanism.This just makes that the final pattern of product is determined by the reaction conditions that influences the crystal face speed of growth, rather than only depends on the kind and the yardstick of catalyzer.This difference has than VLS class methods more control means present method, can obtain the AlN one dimension Nano structure of multiple different-shape.Simultaneously, people's such as the present invention and J.A.Haber AlCl
3The maximum difference of auxiliary VS growth method is: Al of the present invention source (AlCl
3) Al-AlCl that adopts than people such as J.A.Haber
3Higher reactive behavior is arranged, can under lower temperature of reaction, (700 ℃-1000 ℃) obtain product, make synthetic condition milder, help large-scale industrial application.
The present invention is achieved through the following technical solutions:
The preparation method of AlN one dimension Nano structure and array thereof is with the AlCl of gasification
3For the Al source, with NH
3/ N
2Mixed air is a N material, under mesophilic condition, utilizes gas-solid phase reaction to have in load that deposition obtains AlN one dimension Nano structure array on the substrate of catalyzer, comprises nano-pillar, nanometer flower, nanometer coral bunch, the nanocone of AlN.Particularly, there are silicon chip, quartz plate or the porous alumina formwork substrate of iron, cobalt, ferronickel series catalysts to insert in the stove with load, under argon gas atmosphere, be warming up to 700～1000 ℃ of required temperature of growth earlier, then argon gas is switched to the NH that flow is 50～200ml/min
3/ N
2Gas mixture is with anhydrous AlCl
3Rapid heating gasifies and brings anhydrous AlCl into by the Ar carrier gas
3130～190 ℃ of the temperature of rapid heating gasification.Under constant temperature, grow then, obtain AlN one dimension Nano structure array.NH
3With N
2Volume ratio be 1: 10～24.The method of load iron, cobalt, ferronickel series catalysts substrate is by pickling process, sputtering method, vapour deposition method etc. Fe-series catalyst to be loaded on the substrate.
By regulating the AlCl of vitellarium
3Gasification temperature, temperature of reaction, reaction times regulation and control, the AlN one dimension Nano structure of the controlled various different-shapes of acquisition.
Temperature of reaction 800-900 ℃, anhydrous AlCl on control silicon chip, quartz plate, the porous alumina formwork
3Gasification temperature 170-180 ℃ of preparation AlN one-dimensional nano-array.
Temperature of reaction 700-800 ℃, gasification temperature 130-190 ℃ preparation AlN nano-cone array on control silicon chip, the quartz substrate: have the silicon substrate of Fe-series catalyst to insert in the tube furnace load, under argon gas atmosphere, temperature rise rate with 15 ℃/min rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140-145 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array, and its vertical yardstick is 20-50nm.
Temperature of reaction 800-900 ℃, gasification temperature 150-190 ℃ preparation AlN nano-pillar, nanometer coral bunch on control silicon chip, quartz plate, the porous alumina formwork: have the quartz plate of Fe-series catalyst to insert in the tube furnace load, under argon gas atmosphere, temperature rise rate with 15 ℃/min rises to 850 ℃ from room temperature, then oxygen is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 170-180 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas; Under 850 ℃ of conditions, growth 90-120min obtains the AlN nano-pillar, and its yardstick is 1-2 μ m.
Be controlled at temperature of reaction 900-1000 ℃, gasification temperature 130-190 ℃ preparation AlN nanometer flower array on silicon chip, quartz substrate, the porous alumina formwork.To there be the quartz substrate of Fe-series catalyst to insert in the tube furnace with load, under argon gas atmosphere, rise to 950 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 170-180 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas; Under 950 ℃ of conditions, growth 90-120min obtains AlN nanometer flower array, and the six prismatical yardsticks of forming the nanometer flower are 1-2 μ m.
Device required for the present invention mainly contains body of heater, gas distributing system and vacuum system three parts and forms, the relation of its each several part is as follows with effect: the reaction chamber that (1) is made by alundum tube or silica tube places in the tube furnace, load has the substrate of catalyzer to place the reaction chamber center, the temperature of vitellarium can be regulated and control, to obtain different-shape AlN one dimension Nano structure.(2) gas distributing system is made up of gas circuit and mass flowmeter, is connected to an end of growth room, utilizes it can regulate kind, flow and the proportioning of AlN nanostructure growth chamber gas.(3) vacuum system, utilize it can be before heating up in the growth room applying argon gas and vacuumizing repeatedly, get rid of the oxygen that exists in the growth room, the impurity of water vapour.
The AlN one dimension Nano structure of the present invention preparation comprises nanocone, nano-pillar (or rod), nanometer flower and nanometer coral bunch etc., and its crystalline form is h-AlN.The diameter of nanocone provided by the present invention is along direction of growth linear decrease, and its vertical yardstick is 20-50nm; Nano-pillar has the hexagon looks, and yardstick is 1～2 μ m; Nanometer flower or be that the nano-pillar of 1-2 μ m is formed by yardstick, tool sixfold symmetry, or be that the hecaprismo of 200-500nm is formed by yardstick, there is not obvious symmetry; Nanometer coral bunch is formed by nanometer hexagonal awl tight agglomeration, and the diameter of its six pyramidal main shaft is 100-200nm, is parallel to its six that each vertical-growth has thinner AlN nano-pillar on the crystal face of the direction of growth.More than these patterns all on substrate, be array distribution.
Characteristics of the present invention are the CONTROL PROCESS condition, acquisition AlN nanocone that can be controlled, nano-pillar (or rod), nanometer flower and nanometer coral cluster array.Mainly be by control AlCl
3Gasification temperature, temperature of reaction, reaction times etc., the various AlN one dimension Nano structure of acquisition that can be controlled.
The preparation method of AlN one dimension Nano structure of the present invention and array thereof is middle temperature chemical Vapor deposition process.Raw material is inexpensive, simple to operate, temperature is lower, and what obtain is the AlN one dimension Nano structure and the array thereof of different-shape, comprises nanocone, nano-pillar (or rod), nanometer flower and nanometer coral bunch.By the modulation reaction conditions can be controlled synthetic these patterns, therefore be a kind of AlN one dimension Nano structure of acquisition different-shape of economy and the effective ways of array thereof.
Characteristics of the present invention are as follows:
1 present method is with anhydrous AlCl
3Rather than traditional metal A l or Al-Al
2O
3(4: 1) mixture is as the aluminium source, thereby reaction is undertaken by the VS epitaxial growth mechanism.AlN one dimension Nano structure and array thereof that this make to change the synthetic different-shape that reaction conditions can be controlled comprise nanocone, nano-pillar (or rod), nanometer flower and nanometer coral bunch.
The technological line of 2 preparation nanostructures provided by the invention helps exploring some novel one dimension Nano structures, might obtain innovation and breakthrough at aspects such as finding new pattern, raising physico-chemical property.
3 the present invention provide new selection for the similar one dimension Nano structure for preparing other III group-III nitride systems.
Four. description of drawings
Fig. 1: the testing apparatus synoptic diagram of growing AIN one dimension Nano structure of the present invention and array thereof.
Fig. 2: with the SEM photo (embodiment 1) of the inventive method at 850 ℃ of AlN nano column arrays that deposition obtains on porous alumina formwork.
Fig. 3: with the SEM photo (embodiment 5) of the inventive method at 900 ℃ of AlN nanometer flowers that deposition obtains on porous alumina formwork.
Fig. 4: with the SEM photo (embodiment 24) of the inventive method at 900 ℃ of AlN nanometer flowers that deposition obtains on quartz substrate.
Fig. 5: with the SEM photo (embodiment 2) of the inventive method at 850 ℃ of AlN nanometer corals of obtaining of deposition bunch on the porous alumina formwork edge.
Fig. 6: with the SEM photo (embodiment 37) of the inventive method at 700 ℃ of AlN nano-cone arrays that deposition obtains on silicon substrate.
Fig. 7: with the TEM photo (embodiment 21) of the inventive method at 850 ℃ of AlN nano column arrays that deposition obtains on quartz substrate.
Fig. 8: with the TEM photo (embodiment 13) of the inventive method 750 ℃ of single AlN nanocone that deposition obtains on quartz substrate.
Fig. 9: with the TEM photo (embodiment 38) of the inventive method at 700 ℃ of AlN nano-cone arrays that deposition obtains on silicon substrate.
Figure 10: with the HRTEM photo (embodiment 13) of the inventive method 750 ℃ of AlN nanocone that deposition obtains on quartz substrate.
Five, embodiment
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 100ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 90min obtains the AlN nano column array, and AlN nano-pillar yardstick is a 1-2 μ m (see figure 2).
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 90min obtains the AlN nano column array in template central authorities, and AlN nano-pillar yardstick is 1-2 μ m; Obtain nanometer coral bunch at the edge of template and the back side, the diameter of its main shaft is 100-200nm, goes out the nano wire (see figure 5) that diameter is 50nm in its six lateral growth.
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 900 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 900 ℃ of conditions, growth 120min obtains the AlN nano column array, and AlN nano-pillar yardstick is 1-2 μ m.
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 950 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 950 ℃ of conditions, growth 90min obtains AlN nanometer flower, and the six prismatic yardsticks of forming the nanometer flower are 1-2 μ m.
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 900 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 160 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 900 ℃ of conditions, growth 120min obtains AlN nanometer flower, and the six prismatic yardsticks of forming the nanometer flower are 1-2 μ m (see figure 3).
With the 80nm aperture have the permeability alumina formwork of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 950 ℃ from room temperature with the temperature rise rate of 15 ℃/min, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 160 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 950 ℃ of conditions, growth 120min obtains AlN nanometer flower, and the six prismatic yardsticks of forming the nanometer flower are 1-2 μ m.
To insert in the tube furnace with the quartz substrate of pickling process load Fe catalyzer, under argon gas atmosphere, rise to 700 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
To insert in the tube furnace with the quartz substrate of pickling process load C o catalyzer, under argon gas atmosphere, rise to 700 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
To insert in the tube furnace with the quartz substrate of pickling process supported ni catalyst, under argon gas atmosphere, rise to 700 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
Embodiment 10 is being impregnated with 750 ℃ of temperature of reaction, NH on the Fe catalyzer quartz substrate
3/ N
2Mixed gas flow 90ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
To there be the quartz substrate of Fe catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 90ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-30nm.
Embodiment 11 is being impregnated with 750 ℃ of temperature of reaction, NH on the Fe catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, gasification temperature 140 ℃ of preparations AlN nanocone and nanometer coral bunch.
To there be the quartz substrate of Fe catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm; Obtain AlN nanometer coral bunch simultaneously, the diameter of its main shaft is 200-300nm, goes out the nano wire that diameter is 50nm in its six lateral growth.
Embodiment 12 is being impregnated with 750 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 90ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 90ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-30nm.
Embodiment 13 is being impregnated with 750 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 30-50nm (seeing Fig. 8,10).
Embodiment 14 is being impregnated with 750 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate
3/ N
2Mixed gas flow 90ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
To there be the quartz substrate of Ni catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 90ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-30nm.
Embodiment 15 is being impregnated with 750 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Ni catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 200nm.
Embodiment 16 is being impregnated with 800 ℃ of temperature of reaction, NH on the Fe catalyzer quartz substrate
3/ N
2Mixed gas flow 140ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Fe catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 800 ℃ from room temperature, then argon gas be switched to the NH that flow is 140ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and AlN nano-pillar yardstick is 0.5-1 μ m.
Embodiment 17 is being impregnated with 800 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 140ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 800 ℃ from room temperature, then argon gas be switched to the NH that flow is 140ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and AlN nano-pillar yardstick is 0.5-1 μ m.
Embodiment 18 is being impregnated with 800 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 800 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 180min obtains the AlN nano column array, and yardstick is 0.5-1 μ m.
Embodiment 19 is being impregnated with 800 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, gasification temperature 140 ℃ of preparations AlN nano column array and nanometer flower
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 800 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array in zone, substrate top, and yardstick is 1-2 μ m, obtains AlN nanometer flower in the subregion, and the six prismatic yardsticks of forming the nanometer flower are 200-500nm.
Embodiment 20 is being impregnated with 800 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate
3/ N
2Mixed gas flow 140ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Ni catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 800 ℃ from room temperature, then argon gas be switched to the NH that flow is 140ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and AlN nano-pillar yardstick is 0.5-1 μ m.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 100ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
44%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 90min obtains the AlN nano column array, and AlN nano-pillar yardstick is a 1-2 μ m (see figure 7).
Embodiment 22 is being impregnated with 850 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 180 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 90min obtains the AlN nano column array, and AlN nano-pillar yardstick is 1-2 μ m.
Embodiment 23 is being impregnated with 900 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 180 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 900 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 900 ℃ of conditions, growth 120min obtains the AlN nano column array, and AlN nano-pillar yardstick is 1-2 μ m.
Embodiment 24 is being impregnated with 900 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, gasification temperature 160 ℃ of preparations AlN nano column array and AlN nanometer flower.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 900 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 160 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 900 ℃ of conditions, growth 120min obtains AlN nano column array and AlN nanometer flower mixture; The yardstick of nano-pillar is 200-500nm; The six prismatic yardsticks of forming the nanometer flower are the 200-500nm (see figure 4).
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 950 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 180 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 950 ℃ of conditions, growth 90min obtains AlN nanometer flower, and the six prismatic yardsticks of forming the nanometer flower are 200-500nm.
Embodiment 26 is being impregnated with 950 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 160 ℃ of preparations of gasification temperature AlN nanometer flower.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 950 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 160 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 950 ℃ of conditions, growth 120min obtains AlN nanometer flower, and the six prismatic yardsticks of forming the nanometer flower are 200-500nm.
Embodiment 27 is being impregnated with 850 ℃-670 ℃ of temperature of reaction, NH on the Fe catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nanometer flower.
To there be the quartz substrate of Fe catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 670 ℃ in the 180min internal linear and obtains AlN nanometer flower subsequently, and the six prismatic yardsticks of forming the nanometer flower are 150-200nm.
Embodiment 28 is being impregnated with 850 ℃-670 ℃ of temperature of reaction, NH on the Co catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nanometer flower.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 670 ℃ in the 180min internal linear and obtains AlN nanometer flower subsequently, what form the nanometer flower is nano-pillar or nanocone, wherein the diameter of nano-pillar is 150-200nm, and the mean diameter of nano-pillar is 150nm, and the top is 20nm.
Embodiment 29 is being impregnated with 850 ℃-670 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nanometer flower.
To there be the quartz substrate of Ni catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 670 ℃ in the 180min internal linear and obtains AlN nanometer flower subsequently, what form the nanometer flower is nano-pillar or nanocone, wherein the diameter of nano-pillar is 150-200nm, and the mean diameter of nano-pillar is 150nm, and the top is 20nm.
Embodiment 30 is being impregnated with 850 ℃-700 ℃ of temperature of reaction, NH on the Fe catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 120 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Fe catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 700 ℃ in the 30min internal linear subsequently, continues reaction 150min down at 700 ℃, obtains the AlN nano column array of semi-directional, and wherein the diameter of nano-pillar is 40-200nm.
To there be the quartz substrate of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 700 ℃ in the 30min internal linear subsequently, continues reaction 150min down at 700 ℃, obtains the AlN nano column array of semi-directional, and wherein the diameter of nano-pillar is 40-200nm.
Embodiment 32 is being impregnated with 850 ℃-700 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate
3/ N
2Mixed gas flow 150ml/min, 120 ℃ of preparations of gasification temperature AlN nano column array.
To there be the quartz substrate of Ni catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 850 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 700 ℃ in the 30min internal linear subsequently, continues reaction 150min down at 700 ℃, obtains the AlN nano column array of semi-directional, and wherein the diameter of nano-pillar is 40-200nm.
Embodiment 33 is 750 ℃ of temperature of reaction, NH on the silicon chip that is impregnated with the Co catalyzer
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array
To there be the silicon chip of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains AlN nano-pillar thinned array on substrate, and diameter is 100-200nm.
Embodiment 34 is 750 ℃ of temperature of reaction, NH on the silicon chip that is impregnated with the Co catalyzer
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nanometer flower
To there be the silicon chip of Co catalyzer to insert in the tube furnace with the pickling process load, under argon gas atmosphere, rise to 750 ℃ from room temperature, then argon gas be switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
310%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains AlN nanometer flower on substrate, and it is colored that AlN nano-pillar diameter is 30-50nm to form nanometer.
Embodiment 35 has 700 ℃ of temperature of reaction, NH on the Fe catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Fe catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 700 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 30-50nm.
Embodiment 36 has 700 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 700 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 30-50nm.
Embodiment 37 has 700 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 700 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 180min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is the 20-40nm (see figure 6).
Embodiment 38 has 700 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 700 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is the 30-50nm (see figure 9).
Embodiment 39 has 700 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 700 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 700 ℃ of conditions, growth 180min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-40nm.
Embodiment 40 has 750 ℃ of temperature of reaction, NH on the Fe catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Fe catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
Embodiment 41 has 750 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
Embodiment 42 has 750 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 120 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
Embodiment 43 has 750 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-50nm.
Embodiment 44 has 750 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 90ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 90ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 200-300nm.
Embodiment 45 has 750 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 120 ℃ of preparations of gasification temperature AlN nano-cone array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array on substrate, and its diameter is along direction of growth linear decrease, and its vertical yardstick is 20-30nm.
Embodiment 46 has 800 ℃ of temperature of reaction, NH on the Fe catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Fe catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 800 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 150-300nm.
Embodiment 47 has 800 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 800 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 150-300nm.
Embodiment 48 has 800 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 800 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 800 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 150-300nm.
Embodiment 49 has 850 ℃ of temperature of reaction, NH on the Fe catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Fe catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 0.5-1 μ m.
Embodiment 50 has 850 ℃ of temperature of reaction, NH on the Co catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Co catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 0.5-1 μ m.
Embodiment 51 has 850 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 240min obtains the AlN nano column array on substrate, and its diameter is 0.5-1 μ m.
Implement 52 and 850 ℃-670 ℃ of temperature of reaction, NH on the Ni catalyzer silicon substrate are arranged at evaporation
3/ N
2Mixed gas flow 150ml/min, 140 ℃ of preparations of gasification temperature AlN nanometer flower.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 140 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 670 ℃ in the 180min internal linear and obtains AlN nanometer flower subsequently, what form the nanometer flower is nano-pillar or nanocone, wherein the diameter of nano-pillar is 150-200nm, and the mean diameter of nano-pillar is 150nm, and the top is 15nm.
Embodiment 53 has 850 ℃-700 ℃ of temperature of reaction, NH on the Ni catalyzer quartz substrate at evaporation
3/ N
2Mixed gas flow 150ml/min, 120 ℃ of preparations of gasification temperature AlN nano column array.
There is the silicon substrate of the thick Ni catalyzer of 10nm to insert in the tube furnace evaporation, under argon gas atmosphere, rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min with the temperature rise rate of 15 ℃/min
3/ N
2Gas mixture (contains NH
34%), simultaneously fast with anhydrous AlCl
3Be heated to 120 ℃ of gasifications, steam is gone into reaction zone by the Ar band of gas.Under 850 ℃ of conditions, growth 60min, temperature of reaction drops to 700 ℃ in the 30min internal linear subsequently, continues reaction 150min down at 700 ℃, obtains the AlN nano column array of semi-directional, and wherein the diameter of nano-pillar is 40-200nm.
Claims (7)
1, a kind of preparation method of AlN one dimension Nano structure array is characterized in that the AlCl with gasification
3For the Al source, with NH
3/ N
2Gas mixture is the N source, there are silicon chip, quartz plate or the porous alumina formwork substrate of the Fe-series catalyst of iron, cobalt or nickel to insert in the stove load, under argon gas atmosphere, be warming up to 700～1000 ℃ of required temperature of growth earlier, then argon gas is switched to the NH that flow is 50～200ml/min
3/ N
2Gas mixture is with anhydrous AlCl
3Rapid heating gasifies and is brought into by the Ar carrier gas, grows NH then under 700～1000 ℃ of temperature condition
3With N
2Volume ratio be 1: 10～24, utilize gas-solid phase reaction to have in load that deposition obtains AlN one dimension Nano structure array on the substrate of catalyzer, comprise nanocone, nano-pillar or rod, nanometer flower or the nanometer coral bunch of AlN.
2,, it is characterized in that Fe-series catalyst being loaded on the substrate by pickling process, sputtering method or vapour deposition method by the preparation method of the described aluminium nitride one dimension Nano structure of claim 1 array.
3, by the preparation method of described aluminium nitride one dimension Nano structure of claim 1 and array thereof, it is characterized in that anhydrous AlCl
3130～190 ℃ of the temperature of rapid heating gasification.
4 preparation methods by the described aluminium nitride one dimension Nano structure of claim 1 array is characterized in that temperature of reaction 800-900 ℃, anhydrous AlCl on silicon chip, quartz plate or porous alumina formwork
3Gasification temperature 170-180 ℃ of preparation AlN one-dimensional nano-array.
5, by the preparation method of the described aluminium nitride one dimension Nano structure of claim 1 array, it is characterized in that temperature of reaction 700-800 ℃, gasification temperature 130-190 ℃ preparation AlN nano-cone array on silicon chip: have the silicon substrate of Fe-series catalyst to insert in the tube furnace load, under argon gas atmosphere, temperature rise rate with 15 ℃/min rises to 750 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture wherein contains NH
34%, simultaneously fast with anhydrous AlCl
3Be heated to 140-145 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas; Under 750 ℃ of conditions, growth 240min obtains the AlN nano-cone array, and its vertical yardstick is 20-50nm.
6, by the preparation method of the described aluminium nitride one dimension Nano structure of claim 1 array, it is characterized in that temperature of reaction 800-900 ℃, gasification temperature 150-190 ℃ preparation AlN nano-pillar on quartz plate, there is the quartz plate of Fe-series catalyst to insert in the tube furnace load, under argon gas atmosphere, temperature rise rate with 15 ℃/min rises to 850 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture contains NH
34%, simultaneously fast with anhydrous AlCl
3Be heated to 170-180 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas; Under 850 ℃ of conditions, growth 90-120min obtains the AlN nano-pillar, and its yardstick is 1-2 μ m.
7, by the preparation method of the described aluminium nitride one dimension Nano structure of claim 1 array, it is characterized in that temperature of reaction 900-1000 ℃, gasification temperature 130-190 ℃ preparation AlN nanometer flower array on quartz plate, to there be the quartz plate of Fe-series catalyst to insert in the tube furnace with load, under argon gas atmosphere, temperature rise rate with 15 ℃/min rises to 950 ℃ from room temperature, then argon gas is switched to the NH that flow is 150ml/min
3/ N
2Gas mixture contains NH
34%, simultaneously fast with anhydrous AlCl
3Be heated to 170-180 ℃ of gasification, steam is gone into reaction zone by the Ar band of gas; Under 950 ℃ of conditions, growth 90-120min obtains AlN nanometer flower array, and the six prismatical yardsticks of forming the nanometer flower are 1-2 μ m.
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| CN100413780C (en) * | 2005-04-30 | 2008-08-27 | 中国科学院金属研究所 | Nano stick array material |
| CN1318293C (en) * | 2005-07-22 | 2007-05-30 | 西安交通大学 | Method for solid-phase double decomposition to synthesize nanometer aluminium nitride |
| US20110127544A1 (en) * | 2008-05-06 | 2011-06-02 | Kyma Technologies | Group iii nitride templates and related heterostructures, devices, and methods for making them |
| CN101580224B (en) * | 2009-06-01 | 2012-09-05 | 南京大学 | Patterning preparation method for nano array |
| CN102219180B (en) * | 2010-04-14 | 2013-05-01 | 中国科学院理化技术研究所 | Method for synthesizing one-dimensional inorganic nano cone structure material by pressure control in VLS process |
| CN101887793A (en) * | 2010-06-29 | 2010-11-17 | 华南理工大学 | Method for preparing copper-doped aluminum nitride base diluted magnetic semiconductor nano rods |
| CN101993050B (en) * | 2010-12-01 | 2012-07-04 | 沈阳工业大学 | Method for preparing AlN nanowire macro ordered array by using secondary template method |
| US8409895B2 (en) * | 2010-12-16 | 2013-04-02 | Applied Materials, Inc. | Gallium nitride-based LED fabrication with PVD-formed aluminum nitride buffer layer |
| CN102127807B (en) * | 2011-01-31 | 2012-08-22 | 南京大学 | Method for preparing ternary-component AlxGaI-xN nanocone |
| CN103160929B (en) * | 2013-03-21 | 2015-08-12 | 沈阳理工大学 | The preparation method of a kind of monocrystal AIN nano cone and nanometer sheet |
| CN104016315A (en) * | 2014-06-12 | 2014-09-03 | 兰州大学 | Method for preparing aluminum nitride nanotube array |
| CN106206212A (en) * | 2016-07-25 | 2016-12-07 | 六盘水师范学院 | A kind of method growing controlled AlN ordered nano array |
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