CN102127807A - Method for preparing ternary-component AlxGaI-xN nanocone - Google Patents
Method for preparing ternary-component AlxGaI-xN nanocone Download PDFInfo
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- 239000002110 nanocone Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims description 36
- 238000009834 vaporization Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- 229910002704 AlGaN Inorganic materials 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 19
- 239000002243 precursor Substances 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 6
- 229910005267 GaCl3 Inorganic materials 0.000 abstract 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 abstract 3
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 150000004767 nitrides Chemical class 0.000 description 12
- 239000002070 nanowire Substances 0.000 description 11
- 230000008016 vaporization Effects 0.000 description 8
- 230000005684 electric field Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
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- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000004098 selected area electron diffraction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000018199 S phase Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000003491 array Methods 0.000 description 2
- 238000005136 cathodoluminescence Methods 0.000 description 2
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Abstract
The invention relates to a method for preparing ternary-component AlxGaI-xN nanocone, realizing control in the full-ingredient range (x is larger than 0 and smaller than 1). The method for preparing the ternary-component AlxGaI-xN nanocone comprises the following steps of: making anhydrous GaCl3 as a gallium source and anhydrous AlCl3 as an aluminum source with a nitrogen source by adopting a chemical vapor deposition method under the condition that the evaporation temperatures of GaCl3 and AlCl3 are respectively 70-90 DEG C and 130-150 DEG C to generate single-phase AlxGaI-xN nanocone, wherein x is larger than 0 and smaller than 1, the preferred nitrogen source is NH3, and the deposition temperature is 650-800 DEG C. In the invention, the vapor partial pressure of reaction precursors GaCl3 and AlCl3 is finely controlled in a tube furnace of a three-segment temperature area to obtain a one-dimensional nano material with a single-crystal structure and uniformly distributed components, and the atom ratio of Al/Ga can be controlled in the full-ingredient range (x is larger than 0 and smaller than 1) by changing growth conditions.
Description
Technical field
The present invention relates to a kind of preparation ternary component Al
xGa
1-xThe method of N nanocone.
Background technology
With GaN is the physico-chemical property (as high-melting-point, high electronics saturated travelling speed, high breakdown electric field, high heat conductance, low thermal coefficient of expansion, high chemical stability, big piezo-electric modulus etc.) of the III group-III nitride (AlN, GaN, InN and multicomponent alloy thereof) of representative because of its broad-band gap and excellence, become third generation semiconductor material, in high temperature high power electron device and opto-electronic device (as field-effect transistor, photodiode, laser diode etc.), obtained successful Application (F. A. Ponce
Et al.,
Nature1997,
386, 351-359; S. N. Mohammad
Et al.,
Prog. Quantum Electron.1996,
20, 361-525; O. Ambacher,
J. Phys. D:Appl. Phys.1998,
31, 2653-2710; P. Kung
Et al.,
Opto-Electron. Rev.2000,
8, 201-239.).The band gap of AlN, GaN and InN is respectively 6.2,3.4 and 0.7 eV.They form multicomponent alloy Al easily
xGa
yIn
1-x-yN by the composition of modulation multicomponent alloy, can make its band gap continuous modulation between 6.2 ~ 0.7eV.The change of III group-III nitride band gap will cause the change of performances such as its electricity, optics, piezoelectricity, and for example by changing the composition of III group-III nitride, its luminous spectrum can be adjustable continuously to ultraviolet region near infrared.Along with the development of nanoscale science and technology, III group-III nitride one dimension Nano structure (especially certainly to array) has caused extensive studies interest.III group-III nitride one dimension Nano structure is the basis of the multiple novel quantum device of development, at nano luminescent diode (R. X. Yan
Et al.,
Nat. Photonics2009,
3, 569-576.), field-effect transistor (Y. Huang
Et al.,
Nano Lett.2002,
2, 101-104.) and nanometer generating (C. T. Huang
Et al.,
J. Am. Chem. Soc.2010,
132, 4766-4771.) etc. the aspect shows good prospects for application; Simultaneously, character such as the electricity that III group-III nitride one dimension Nano structure represented, optics and machinery are also being brought into play important effect (S. K. Lim aspect the understanding of relevant rudimentary theory and the explaination
Et al.,
Nano Lett.2009,
9, 3940-3944; S. Chattopadhyay
Et al.,
Crit. Rev. Solid State Mat. Sci.2009,
34, 224-279.), so preparation, performance and the application of III group-III nitride one dimension Nano structure are current advanced subject.
Up to now, people have been developed the one dimension Nano structure that several different methods prepares the III group-III nitride.The various one dimension Nano structures of binary composition nitride such as nanotube, nano belt, nano wire and nanocone etc. all successfully prepare and report, comprise AlN(Q. Wu
Et al.,
J. Am. Chem. Soc.2003,
125, 10176-10177; C. Liu
Et al.,
J. Am. Chem. Soc.2005,
127, 1318-1322; C. Y. He
Et al.,
J. Am. Chem. Soc.2010,
132, 4843-4847.), GaN(C. C. Chen
Et al.,
J. Am. Chem. Soc.2001,
123, 2791-2798; J. Goldberger
Et al.,
Nature2003,
422, 599-602; T. Kuykendall
Et al.,
Nat. Mater.2004,
3, 524-528.), InN(S. Vaddiraju
Et al.,
Nano Lett.2005,
5, 1625-1631.) etc.2007, people such as T. Kuykendall realized ternary component In
xGa
1-xThe preparation of N nano wire and in the composition regulation and control of full composition range, its band gap can be in 1.1～3.4 eV scopes modulation, present continuously adjustable luminous (T. Kuykendall from the near ultraviolet to the near infrared region after exciting
Et al.,
Nat. Mater.2007,
6, 951-956.).Yet, for the very important ternary component nitride of another kind Al
xGa
1-xN, although people have dropped into very big effort, the growth of its one dimension Nano structure and composition regulation and control remain one and are full of challenging problem.
Before the present invention, the correlative study of AlGaN system mostly concentrates on thin-film material.People have been developed metal organic vapor (MOVPE), molecular beam epitaxy (MBE) and metal organic chemical vapor deposition several different methods such as (MOCVD) and have been prepared the AlGaN film, and form the modulation that realizes glow peak by changing it.People also attempt to prepare the one dimension Nano structure of AlGaN, for example, H. people such as J. Choi attempts being equipped with the AlGaN nano wire by the CVD legal system, has finally made GaN@AlGaN nuclear sheath type nano wire, and spontaneous being separated (H. J. Choi has taken place in generative process nanowire product
Et al.,
J. Phys. Chem. B2003
, 107,8721-8725.); J. people such as Su attempts to prepare the AlGaN nano wire by mocvd method, has finally also made GaN@AlGaN coaxial nanowire heterojunction structure (J. Su
Et al.,
Appl. Phys. Lett.2005
, 87,183108.).L. people such as Hong and Y.S. Park has prepared single-phase AlGaN one dimension Nano structure by CVD and plasma body auxiliary MBE method respectively, but the scope very little (0 ~ 15%) of composition regulation and control in their report, and do not adopt reliable laboratory facilities to characterize composition and the structure and homogeneity (the L. Hong thereof of product
Et al.,
Appl. Phys. Lett.2006,
89, 193105; Y. S. Park
Et al.,
Nanotechnology2006,
17, 4640-4643.).In sum, the preparation of ternary component AlGaN one dimension Nano structure and full composition regulation and control thereof are still one and are full of challenging problem, reason is that the growth conditions of GaN and AlN is difficult to coupling, easily spontaneous being separated is taken place in the AlGaN product and can not obtain single-phase AlGaN nanostructure.
Summary of the invention
The invention provides a kind of preparation ternary component Al
xGa
1-xThe method of N nanocone can realize the regulation and control in the full composition range in 0＜x＜1.
Described preparation ternary component Al
xGa
1-xThe method of N nanocone is: adopt chemical Vapor deposition process, with anhydrous GaCl
3Be the gallium source, anhydrous AlCl
3For the aluminium source, at GaCl
3And AlCl
3Vaporization temperature be respectively under 70～90 ℃ and 130～150 ℃ of conditions, with the nitrogenous source reaction, generate single-phase Al
xGa
1-xN nanocone, wherein 0＜x＜1.
Preferred nitrogenous source is NH
3, depositing temperature is 650 ~ 800 ℃.The embodiment of the invention is partly selected 700 ℃ of depositing temperatures.
The length in reaction times influences the length of nano material, and the reaction times is long more, and the length of gained nano material is long more.The preferred reaction time is 2 ~ 4 hours.
As preferred version, described chemical Vapor deposition process carries out in three sections warm area tube furnaces, is sequentially with first cold zone, second cold zone, sedimentary province in described three sections warm area tube furnaces, and gallium source and aluminium source place first cold zone and second cold zone respectively.Concrete operation can be: gallium source and aluminium source steam are that the carrier gas Ar band of gas of 150 ~ 400 mL/min is to sedimentary province by flow, simultaneously, flow is that the nitrogen source gas of 5 ~ 30 mL/min is transported to sedimentary province and gallium source and aluminium source steam and reacts, and generates the AlGaN product.
The substrate material that adopts during deposition is a common practise, as Si substrate commonly used.
Before this, the applicant has been developed a kind of chemical Vapor deposition process and has been prepared the AlN nanocone certainly to array, passes through AlCl
3And NH
3Between chemical reaction, (~ 700 ℃) have made AlN nanocone (C. Liu at a lower temperature
Et al.,
J. Am. Chem. Soc.2005,
127, 1318-1322; Chinese invention patent ZL200310106239.9).Similar method is extended to the GaN system, passes through GaCl
3And NH
3Between chemical reaction, made the GaN nano column array (X. B. Wang,
Et al., Adv. Mater.2010,
22, 2155-2158).On this basis, the present invention designs and has improved experimental installation, finely regulating pre-reaction material (GaCl in the tube furnace of three sections warm areas
3And AlCl
3) partial vapor pressure, make its reaction conditions coupling, realized single-phase Al
xGa
1-xThe preparation of N one dimension Nano structure array, the monodimension nanometer material that obtains has single crystal structure, distributed components and can be by changing growth conditions its Al/Ga atomic ratio of (x=0 ~ 1) modulation in full composition range.This continuous component modulation is also embodied in the cathodoluminescence performance (CL) and the field of product and launches in the progressively differentiation of (FE) performance.Ternary component Al
xGa
1-xThe preparation of N nano-cone array and full composition thereof are regulated to development Performances of Novel Nano-Porous electron device and photoelectric device provides basic substance.
In order to obtain single-phase Al
xGa
1-xThe N nanocone, GaCl
3And AlCl
3Vaporization temperature must control within the specific limits, otherwise will be because of the partial vapor pressure product phenomenon of phase separation that do not match.Optimized reaction conditions of the present invention is: GaCl
3And AlCl
3Vaporization temperature must be controlled at respectively in 70～90 ℃ and 130～150 ℃ of scopes.Otherwise, work as GaCl
3The GaN-AlGaN two-phase occurs in the higher then product of vaporization temperature, work as AlCl
3AlN-AlGaN two-phase (accompanying drawing 5) appears in the higher then product of vaporization temperature.In the said temperature scope, change the precursor vaporization temperature, can realize Al
xGa
1-xThe composition of N monodimension nanometer material modulation of (0＜x＜1) in full composition range.
Adopt preparation method of the present invention, only using GaCl
3Can make during for raw material certainly to the GaN nano-wire array; Only using AlCl
3Can make the AlN nano-cone array during for raw material.According to AlCl
3The order that increases gradually of partial vapor pressure, the modulation GaCl of system
3And AlCl
3Partial vapor pressure, can obtain a series of different single-phase Al that form
xGa
1-xN sample, the pattern of sample are certainly to nano-cone array (accompanying drawing 2).Measure the different Al that form
xGa
1-xThe XRD spectrum of N sample between 30 ° to 40 °, can be observed three characteristic diffraction peaks (100), (002) and (101) is unimodal, and be offset to the high angle direction gradually, corresponding X ray energy dispersion spectrum (EDS) shows that the Ga content in the series of samples reduces gradually, Al content raise gradually (accompanying drawing 3).The lattice parameter that calculates from XRD has further shown Al along with the change curve of Al content is linear
xGa
1-xThe composition of N nanocone can regulation and control (accompanying drawing 4) in full composition range.High-resolution-ration transmission electric-lens (HRTEM) and corresponding selected area electron diffraction (SAED) show Al
xGa
1-xThe N nanocone has the single crystal structure of wurtzite phase, edge
cDirection of principal axis growth (accompanying drawing 6), the composition on the single nanocone be evenly distributed (accompanying drawing 7).
The present invention has prepared single-phase Al by simple CVD process
xGa
1-xThe N nano-cone array, and realized its full composition regulation and control.Successive composition modulation has also caused the performance modulation of AlGaN product, and for example the unlatching and the threshold field of an emission of the CL band edge of product and an emission show as progressively evolving trend.CL spectrum shows Al
xGa
1-xThe band gap of N nanocone increases with Al content and becomes big.Sample GaN, Al
0.16Ga
0.84N and Al
0.51Ga
0.49The band edge emission wavelength of N is respectively 366,348 and 308 nm(accompanying drawings 8), corresponding band gap is respectively 3.40,3.57 and 4.03 eV [because AlN is oxidized easily, only observing relevant with defective low-yield luminous in the luminous spectrum of AlN sample].The different field transmission test results that form sample show: the unlatching electric field (
E To, produce 10 μ A/cm
2The needed electric field of electric current) and threshold field (
E Thr, produce 1 mA/cm
2The needed electric field of electric current) increases (accompanying drawing 9), i.e. GaN＜Al along with the increase of Al content in the sample
0.34Ga
0.66N＜Al
0.61Ga
0.39N＜AlN(subordinate list 1).This is because along with Al content increases, the band gap of sample broadens gradually, causes the reduction of carrier concentration in the sample.The variation of cathodoluminescence and field emission performance has further proved Al
xGa
1-xThe composition modulation of N nanocone.Ternary component Al
xGa
1-xThe preparation of N nano-cone array and composition are tuned as its application in Performances of Novel Nano-Porous electron device and photoelectric device basic substance are provided.
Principal feature of the present invention and advantage are as follows:
1. the present invention is a pre-reaction material with the muriate, and vaporization temperature is low, by the vaporization temperature that three sections warm area tube furnaces are regulated precursor respectively, can make growth conditions coupling and makes monophasic Al
xGa
1-xN nanocone structure.
2. the present invention is by changing precursor GaCl
3And AlCl
3Vaporization temperature come modulation GaCl
3And AlCl
3Partial vapor pressure, can realize Al easily
xGa
1-xN nano-cone array modulation of (from x=0 to 1) in full composition range.
The present invention can be on the Si of 1cm * 1cm substrate depositing Al
xGa
1-xThe N nano-cone array has been realized Al
xGa
1-xThe large area deposition of N nano-structure array.Substrates such as also available quartz plate, copper sheet, titanium sheet, stainless steel substrates, sapphire sheet are as the substrate of material growth, and the material of substrate does not have obvious influence to the growth of nanocone.
4. the prepared Al of the present invention
xGa
1-xN nano-cone array size homogeneous, to several microns, tip diameter is approximately 10 nm to length from hundreds of nanometers, and base diameter is 50～90 nm.Because it has big length-to-diameter ratio and sharp keen tip, and potential using value is arranged in the emission on the scene.
5. method provided by the invention can be extended to other multicomponent mixture III group-III nitride.Select suitable pre-reaction material according to requirement of experiment, utilize similar CVD method synthetic other multicomponent mixture III group-III nitride monodimension nanometer material array on multiple substrate.
6. preparation technology provided by the present invention is simple to operate, is suitable for scale operation.
Description of drawings
Fig. 1. the preparation Al that the present invention is used
xGa
1-xThe experimental installation synoptic diagram of N nano-cone array.Tube furnace is made of three warm areas among the figure, and each warm area has independently heating unit.The part that water coolant and fan place two warm areas to be connected is in order to reduce to minimum to the phase mutual interference between each warm area.Anhydrous GaCl
3And AlCl
3Powder is placed on cold zone (I) and (II) respectively, and the Si substrate is placed on sedimentary province.By changing the vaporization temperature of precursor, can modulation GaCl
3And AlCl
3Partial vapor pressure.Ar gas feeds from low-temperature end, as protection gas and transmission GaCl
3And AlCl
3The carrier gas of steam.NH
3Gas is delivered directly to sedimentary province by the minor diameter silica tube.
Fig. 2. the Al of different composition the (from x=0 to 1)
xGa
1-xThe scanning electron microscope of N nanostructure (SEM) photo.The composition of the upper left corner for recording by SEM-EDS among the figure, the upper right corner is a sample number into spectrum.
Fig. 3. the different series A l that form
xGa
1-xThe XRD of N sample and EDS result, the content of Al increases gradually in the sample from top to bottom.(a) the meticulous spectrum of XRD.Test condition: sweep velocity and step-length be respectively 0.04925 (°/s) and 0.004186 (°).Three characteristic diffraction peaks (100), (002) and (101) that have shown sample in the spectrum.(002) diffraction peak the strongest in the spectrum is unimodal, does not divide, and has shown the single-phase feature of sample.(b) the SEM-EDS spectrum has marked contained element among the figure.
Fig. 4. the lattice parameter of sample
cWith
aRelation [numerical value of lattice parameter is calculated and got by XRD spectrum among Fig. 3 (a) among the figure, and Al content is recorded by corresponding SEM-EDS spectrum among Fig. 3 (b)] with Al content.The theoretical value that straight line calculates for the Vegard theorem (the lattice parameter value of GaN and AlN
c=5.176 and 4.991 and
a=3.181 and 3.113), put experimental point into different sample correspondences.
Fig. 5. the XRD of two samples that are separated spectrum (a, c) and the SEM photo (b, d).The vaporization temperature of the pre-reaction material of these two samples is as follows:
First sample (a, b): T (GaCl
3)=114 ℃; T (AlCl
3)=140 ℃.GaCl
3Vaporization temperature higher.
Second sample (c, d): T (GaCl
3)=80 ℃; T (AlCl
3)=162 ℃.AlCl
3Vaporization temperature higher.
The XRD of two samples spectrum has the existence of division peak between 34.63 ° [positions at GaN (002) peak] and 35.96 ° [position at AlN (002) peak], the splitting table at (002) peak is understood in the nanocone that makes under this condition and occurred being separated.
Fig. 6. the prepared difference of the present invention is formed Al
xGa
1-xThe high-resolution-ration transmission electric-lens of N nanocone (HRTEM) photo and corresponding selected area electron diffraction style (SAED).The composition of being demarcated in the HRTEM photo is measured by TEM-EDS.Horizontal dotted line in the electron-diffraction diagram is the reference line of a reference, compares the distance of point diffraction to the center spot for convenience.(00
l) (
l=1,2,3,4) gradually the increase along with the increase of Al content x of the distance of point diffraction between the spot of center illustrate accordingly (00
l) spacing shrinking.Show prepared Al
xGa
1-xThe N nanocone is a single crystal structure, but and has a composition of modulation.
Fig. 7. three typical nanocone are done the compositional analysis of 7 points by TEM-EDS along the direction of growth.The below is the TEM figure of three samples.The beam spot diameter, of electron beam is about 10 nm.For each sample, along the direction of growth of nanocone, the minor fluctuations of element Ga and Al content shows the composition uniform distribution of whole nanocone.
Fig. 8. the Al that the prepared difference of the present invention is formed
xGa
1-xN alloy nano awl (GaN, Al
0.16Ga
0.84N, Al
0.51Ga
0.49N and AlN) normalized CL spectrum under the room temperature.
Fig. 9. the prepared difference of the present invention form certainly to Al
xGa
1-xN nanocone (GaN, Al
0.34Ga
0.66N, Al
0.61Ga
0.39N and AlN) field emission-electric field curve (
J-
ECurve).Cathode and anode spacing during transmission test is 100 μ m.
Embodiment
Embodiment 1With anhydrous GaCl
3With anhydrous AlCl
3For the precursor deposition makes single-phase Al
xGa
1-xThe N nano-cone array.
With the anhydrous GaCl of 0.4 g
3With anhydrous AlCl
3Be positioned over the cold zone (I) of three sections warm area tube furnaces (as accompanying drawing 1) and (II) respectively, substrate is positioned over sedimentary province (III).System vacuumizes repeatedly with mechanical pump before heat temperature raising and fills Ar gas three times, to remove the oxygen G﹠W in the reactive system.Under the Ar gas shiled, sedimentary province is warming up to 700 ℃ (temperature rise rate be 10 ℃/min), cold zone (I) and (II) respectively fast (about 10 minutes) be warmed up to 80 ℃ of (GaCl
3Vaporization temperature) and 140 ℃ of (AlCl
3Vaporization temperature).When temperature rises to designated value, the Ar airshed is transferred greatly to 300 mL/min, and feed NH
320 mL/min, GaCl
3And AlCl
3Steam by the Ar band of gas to sedimentary province and NH
3Solid/liquid/gas reactions, deposition obtains the AlGaN product on substrate.Reaction times is 2～4 hours, and reaction finishes the back system and be cooled to room temperature under the Ar gas shiled.Show that from the result of SEM and XRD products therefrom is six side's phase Al
xGa
1-xN nano-cone array (accompanying drawing 2 and accompanying drawing 3:S6).
Embodiment 2Form adjustable single-phase Al
xGa
1-xThe preparation of N nano-cone array.
Similar to operation steps among the embodiment 1, this example is by changing precursor GaCl
3And AlCl
3Vaporization temperature come modulation GaCl
3And AlCl
3Partial vapor pressure, thereby realize single-phase Al
xGa
1-xThe preparation of N nano-cone array and composition modulation thereof.In order to obtain monophasic Al
xGa
1-xThe N nanocone, GaCl
3And AlCl
3The mutual coupling of partial vapor pressure.Institute of the present invention optimized reaction conditions is: GaCl
3And AlCl
3Vaporization temperature be respectively 70～90 ℃ and 130～150 ℃.In this temperature range, according to AlCl
3The order that increases gradually of partial vapor pressure, the modulation GaCl of system
3And AlCl
3Partial vapor pressure, can obtain series A l
xGa
1-xThe N sample.Characterization result shows that products therefrom is the different single-phase Al that form
xGa
1-xThe N nano-cone array (accompanying drawing 2 and accompanying drawing 3:S2 ~ S5, S7 ~ S10).
The vaporization temperature of the precursor of sample 2-10 correspondence and the depositing temperature of product are as shown in the table:
| Sample number into |
2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| GaCl 3Vaporization temperature (℃) | 90 | 87 | 84 | 82 | 80 | 78 | 75 | 72 | 70 |
| AlCl 3Vaporization temperature (℃) | 130 | 132 | 136 | 138 | 140 | 142 | 144 | 146 | 150 |
Embodiment 3With anhydrous GaCl
3For the precursor deposition makes the GaN nano-wire array.
With anhydrous GaCl
3Powder is positioned over the cold zone of three sections warm area tube furnaces (as accompanying drawing 1), and substrate is positioned over sedimentary province.System vacuumizes repeatedly with mechanical pump before heat temperature raising and fills Ar gas three times, to remove the oxygen G﹠W in the reactive system.Under the Ar gas shiled, sedimentary province is warming up to 700 ℃ (temperature rise rate be 10 ℃/min), simultaneously with cold zone fast (about 10 minutes) be warmed up to 80 ℃.When temperature rises to designated value, the Ar airshed is transferred greatly to 300 mL/min, and feed NH
320 mL/min, GaCl
3Steam by the Ar band of gas to sedimentary province and NH
3Solid/liquid/gas reactions, deposition obtains the GaN product on substrate.Reaction times is 2～4 hours, and reaction finishes the back system and be cooled to room temperature under the Ar gas shiled.Show that from the result of SEM and XRD products therefrom is six side's phase GaN nano-wire arrays (accompanying drawing 2 and accompanying drawing 3:S1).
Embodiment 4With anhydrous AlCl
3For the precursor deposition makes the AlN nano-cone array.
With anhydrous AlCl
3Powder is positioned over the cold zone of three sections warm area tube furnaces (as accompanying drawing 1), and substrate is positioned over sedimentary province.System vacuumizes repeatedly with mechanical pump before heat temperature raising and fills Ar gas three times, to remove the oxygen G﹠W in the reactive system.Under the Ar gas shiled, sedimentary province is warming up to 700 ℃ (temperature rise rate be 10 ℃/min), simultaneously with cold zone fast (about 10 minutes) be warmed up to 140 ℃.When temperature rises to designated value, the Ar airshed is transferred greatly to 300 mL/min, and feed NH
320 mL/min, GaCl
3Steam by the Ar band of gas to sedimentary province and NH
3Solid/liquid/gas reactions, deposition obtains the AlN product on substrate.Reaction times is 2～4 hours, and reaction finishes the back system and be cooled to room temperature under the Ar gas shiled.Show that from the result of SEM and XRD products therefrom is six side's phase AlN nano-wire arrays (accompanying drawing 2 and accompanying drawing 3:S11)
Embodiment 5The preparation of the AlGaN nano-cone array that is separated.
Departed from the temperature range of optimizing among the embodiment 2, the AlGaN nano-cone array that can obtain being separated.For example, pre-reaction material GaCl
3And AlCl
3Vaporization temperature when being respectively 114 ℃ and 140 ℃, GaCl
3Vaporization temperature higher, in this case gained nanocone product consist of GaN-AlGaN(accompanying drawing 5:a, b); For another example, pre-reaction material GaCl
3And AlCl
3Vaporization temperature when being respectively 80 ℃ and 162 ℃, AlCl
3Vaporization temperature higher, in this case gained nanocone product consist of AlN-AlGaN(accompanying drawing 5:c, d).
Provide sample (GaN, Al among Fig. 9
0.34Ga
0.66N, Al
0.61Ga
0.39N and AlN nanostructure) unlatching electric field (E
To) and threshold field (E
Thr) as shown in table 1.
Table 1.GaN, Al
0.34Ga
0.66N, Al
0.61Ga
0.39Unlatching electric field (the E of N and AlN nanostructure
To) and threshold field (E
Thr)
Claims (5)
1. one kind prepares ternary component Al
xGa
1-xThe method of N nanocone is characterized in that, adopts chemical Vapor deposition process, with anhydrous GaCl
3Be the gallium source, anhydrous AlCl
3For the aluminium source, at GaCl
3And AlCl
3Vaporization temperature be respectively under 70～90 ℃ and 130～150 ℃ of conditions, with the nitrogenous source reaction, generate single-phase Al
xGa
1-xN nanocone, wherein 0＜x＜1.
2. preparation ternary component Al as claimed in claim 1
xGa
1-xThe method of N nanocone is characterized in that, nitrogenous source is NH
3, depositing temperature is 650 ~ 800 ℃.
3. preparation ternary component Al as claimed in claim 1 or 2
xGa
1-xThe method of N nanocone is characterized in that the reaction times is 2 ~ 4 hours.
4. preparation ternary component Al as claimed in claim 3
xGa
1-xThe method of N nanocone, it is characterized in that gallium source and aluminium source steam are that the carrier gas Ar band of gas of 150 ~ 400 mL/min is to sedimentary province by flow, simultaneously, flow is that the nitrogen source gas of 5 ~ 30 mL/min is transported to sedimentary province and gallium source and aluminium source steam and reacts, and generates the AlGaN product.
5. preparation ternary component Al as claimed in claim 1 or 2
xGa
1-xThe method of N nanocone, it is characterized in that described chemical Vapor deposition process carries out in three sections warm area tube furnaces, be sequentially with first cold zone, second cold zone, sedimentary province in described three sections warm area tube furnaces, gallium source and aluminium source place first cold zone and second cold zone respectively.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194729A (en) * | 2013-03-27 | 2013-07-10 | 中国科学院物理研究所 | Method for preparing metal chalcogenide film |
| CN104528668A (en) * | 2014-12-19 | 2015-04-22 | 华南理工大学 | AlxGa1-xN nanowire array as well as preparation method and application thereof |
| CN107699951A (en) * | 2017-09-29 | 2018-02-16 | 沈阳理工大学 | Monocrystalline high Al contents AlxGa1‑xThe preparation method of N ternary alloy nano rods |
| CN107740189A (en) * | 2017-09-29 | 2018-02-27 | 沈阳理工大学 | High Al contents AlxGa1‑xN ternary alloy three-partalloy microcrystalline balls and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544315A (en) * | 2003-11-10 | 2004-11-10 | �Ϻ���ͨ��ѧ | Unidimensional aluminium nitride nanometer structure array and its preparation method |
| CN101077784A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院金属研究所 | Nano CaAl4O7 material and preparing method thereof |
| CN101580224A (en) * | 2009-06-01 | 2009-11-18 | 南京大学 | Patterning preparation method for nano array |
-
2011
- 2011-01-31 CN CN2011100336199A patent/CN102127807B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544315A (en) * | 2003-11-10 | 2004-11-10 | �Ϻ���ͨ��ѧ | Unidimensional aluminium nitride nanometer structure array and its preparation method |
| CN101077784A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院金属研究所 | Nano CaAl4O7 material and preparing method thereof |
| CN101580224A (en) * | 2009-06-01 | 2009-11-18 | 南京大学 | Patterning preparation method for nano array |
Non-Patent Citations (1)
| Title |
|---|
| 《Applied Physics Letters》 20061106 L.Hong et al Self-catalytic growth of single-phase AlGaN alloy nanowires by chemical vapor deposition 第193105-1页左栏第1段到第193105-3页右栏第3段 1-5 第89卷, 第19期 * |
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| CN103194729A (en) * | 2013-03-27 | 2013-07-10 | 中国科学院物理研究所 | Method for preparing metal chalcogenide film |
| CN104528668A (en) * | 2014-12-19 | 2015-04-22 | 华南理工大学 | AlxGa1-xN nanowire array as well as preparation method and application thereof |
| CN104528668B (en) * | 2014-12-19 | 2016-06-22 | 华南理工大学 | A kind of AlxGa1-xN nano-wire array and preparation method thereof and application |
| CN107699951A (en) * | 2017-09-29 | 2018-02-16 | 沈阳理工大学 | Monocrystalline high Al contents AlxGa1‑xThe preparation method of N ternary alloy nano rods |
| CN107740189A (en) * | 2017-09-29 | 2018-02-27 | 沈阳理工大学 | High Al contents AlxGa1‑xN ternary alloy three-partalloy microcrystalline balls and preparation method thereof |
| CN107740189B (en) * | 2017-09-29 | 2019-05-14 | 沈阳理工大学 | High Al contents AlxGa1-xN ternary alloy three-partalloy microcrystalline balls and preparation method thereof |
| CN107758727A (en) * | 2017-10-23 | 2018-03-06 | 沈阳理工大学 | AlxGa1‑xN ternary alloy three-partalloy tapers are nanocrystalline and preparation method thereof |
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