CN107699951A - Monocrystalline high Al contents AlxGa1‑xThe preparation method of N ternary alloy nano rods - Google Patents

Monocrystalline high Al contents AlxGa1‑xThe preparation method of N ternary alloy nano rods Download PDF

Info

Publication number
CN107699951A
CN107699951A CN201710906430.3A CN201710906430A CN107699951A CN 107699951 A CN107699951 A CN 107699951A CN 201710906430 A CN201710906430 A CN 201710906430A CN 107699951 A CN107699951 A CN 107699951A
Authority
CN
China
Prior art keywords
ternary alloy
preparation
aluminium powder
contents
alloy nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710906430.3A
Other languages
Chinese (zh)
Other versions
CN107699951B (en
Inventor
沈龙海
吕伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Ligong University
Original Assignee
Shenyang Ligong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang Ligong University filed Critical Shenyang Ligong University
Priority to CN201710906430.3A priority Critical patent/CN107699951B/en
Publication of CN107699951A publication Critical patent/CN107699951A/en
Application granted granted Critical
Publication of CN107699951B publication Critical patent/CN107699951B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

A kind of monocrystalline high Al contents AlxGa1‑xThe preparation method of N ternary alloy nano rods, the silicon chip that deposit thickness is 0.5~1.0mm stringer aluminium powders is prepared first.Metal Al powder is laid in reaction boat one end again, silicon chip is placed in top, and Ga drops are placed in into the reaction boat other end, reaction unit is put into one end open quartz test tube, closed, vacuumizes；As vacuum≤5Pa, argon gas is passed through, after whole atmosphere is argon gas, adjusts argon flow amount, when being heated to 900~1000 DEG C, regulation argon flow amount is 40~60sccm, meanwhile, it is passed through the ammonia with argon flow amount same traffic, 1~3h is kept, furnace cooling, obtains the monocrystalline Al of high Al contentsxGa1‑xN ternary alloy nano rods, Al components adjustable extent are 0.88≤x≤0.92.This method technique is simple, it is reproducible, without be separated, production cost is low, without any catalyst and template is added, be easy to commercial introduction application.

Description

Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods
Technical field
The invention belongs to the technical field of group iii nitride semiconductor alloy nanostructures growth, and in particular to a kind of monocrystalline High Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods.
Background technology
III-nitride AlN and GaN are important wide bandgap semiconductor photoelectric materials, have higher direct band gap and excellent Good photoelectric properties.With the fast development of GaN base blue-ray LED, the research of shorter wavelength ultraviolet LED light source has also evoked scientific research Worker's greatly enthusiasm.High Al contents AlGaN material is to prepare ultraviolet detector, deep-UV light-emitting diode, FPD Deng the mainstay material of photoelectric device, deep ultraviolet LED prepared therefrom is due to small volume, simple in construction, integration is good, and the life-span It is long, power consumption is low, environment-protecting and non-poisonous, has greater advantages than the traditional gas ultraviolet source such as mercury lamp and xenon lamp, have huge society and Economic benefit.In addition, there is major application value in medical treatment, sterilization, printing, data storage and secret communication etc..
At present, restrict essentially consisting in for high Al contents AlGaN deep ultraviolet light source light-emitting efficiencies and lack suitable substrate, cause High Al contents AlGaN extension ply stress is big, and easily cracking, influences crystal mass.Due in one-dimensional nano structure epitaxial growth with The lattice mismatch of backing material is small, and the geometry of one-dimensional nano structure enables misfit strain really to be disappeared by side wall, you can Will fall with stress major part relaxation caused by substrate or all eliminate, so as to reduce or eliminate dislocation, crystal mass is improved.This Outside, the factor such as the dimension of low-dimension nano material, pattern, size and their special performance are closely related, and construct a nanometer work( The basis of energy device.Therefore, based on the excellent physical property of AlGaN alloy materials and its in making utility model photoelectric device side There is potential application prospect in face, and the preparation of the AlGaN alloy nanostructures of high Al contents has caused extensive concern, but The growth of high Al contents AlGaN one-dimensional nano structures is still also faced with many difficult and challenge.
The synthetic method of AlGaN nanostructureds mainly has at present：(1) chloride chemical vapour deposition process；(2) metal is organic Thing chemical vapor deposition (MOCVD)；(3) molecular beam epitaxy (MBE).The first preparation method, its reaction raw materials chloride are easy Deliquescence, and it is expensive.The reactant that second of MOCVD preparation method uses is organic source, it is necessary to carry out gas precautions.The The characteristics of reaction source that three kinds of MBE methods use is simple, but MBE methods are due to itself, and it is costly, is not suitable for business Industryization develops.And all there is spontaneous phenomenon of phase separation in MOCVD and MBE methods.
The present invention utilizes homemade gas-phase deposition system, using gallium and business aluminium powder as reaction raw materials, at ambient pressure, temperature Area's (900 DEG C -1000 DEG C), by controlling reaction temperature and the distance between gallium source and growth substrates, realizes monocrystalline AlGaN The growth of ternary alloy nano rod.To prepare the Al of high Al contentsxGa1-xN ternary alloy three-partalloy semiconductors, deposit one on a silicon substrate Sheet metal Al powder, realize rich Al growing environment.There is presently no realize the adjustable Al of high Al contents using the methodxGa1- xThe report of N ternary alloy nano rods.
The content of the invention
It is that the present invention solves it is a key issue that providing a kind of monocrystalline high Al contents AlxGa1-xThe system of N ternary alloy nano rods Preparation Method, this method are reaction raw materials using metallic aluminium powder, gallium and ammonia, 900 DEG C -1000 DEG C of range of reaction temperature, gas Phase sedimentation grows, and prepares the monocrystalline Al of high Al contentsxGa1-xN ternary alloy nano rods, Al components adjustable extent are 0.88 ≤x≤0.92.This method technique is simple, it is reproducible, without be separated, production cost is low, without adding any catalyst and mould Plate, it is easy to commercial introduction application.
A kind of monocrystalline high Al contents Al of the present inventionxGa1-xThe preparation method of N ternary alloy nano rods, including following step Suddenly：
Step 1, pre-deposition thin layer aluminium powder
(1) silicon chip is ultrasonically treated, obtains the silicon chip after ultrasound；
Aluminium powder is added in reagent, ultrasonic vibration is carried out and is uniformly dispersed, obtain the aluminium powder mixed liquor after ultrasound；
(2) silicon chip after ultrasound is put into the aluminium powder mixed liquor after ultrasound, natural air drying, obtaining deposition has thin layer of aluminum The silicon chip of powder；Wherein, the deposit thickness of thin layer aluminium powder is 0.5~1.0mm.
Step 2, preparation is prepared
Metal Al powder is evenly laid out in reaction boat one end, the silicon chip that deposition has thin layer aluminium powder is being placed in metal Al powder just Upper vertical distance is at 5~6mm, deposition has the one side of thin layer aluminium powder upward；
Ga drops are placed in the reaction boat other end, Ga liquid has level of the silicon chip close to Ga liquid end of thin layer aluminium powder with deposition Distance is 2~5mm；Wherein, in mass ratio, metal Al powder：Ga=(1~2):1；
It is standby after whole reaction unit is arranged as stated above；
Step 3, vacuumize, lead to argon gas
(1) reaction unit after arranging is put into the quartz test tube of one end open, wherein, the reaction dress after arranging The axis and the diameter parallel of the quartz test tube of one end open put, and react boat and be put into one end of Ga liquid away from quartz test tube Opening；
(2) quartz test tube equipped with reaction unit is placed in the reaction zone of horizontal quartz tube stove, it is closed, start to take out very It is empty；
As vacuum≤5Pa of horizontal quartz tube stove, argon gas is passed through, the flow that is passed through of argon gas is 300~700sccm, After the atmosphere in whole device is argon gas, it is 80~150sccm that regulation argon gas, which is passed through flow, keeps the cavity pressure of reaction system Strong is normal pressure；
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 10~50 DEG C/min, works as reaction system Furnace temperature reach design temperature for 900~1000 DEG C when, regulation argon flow amount is 40~60sccm, meanwhile, ammonia is passed through, by stream Measure ratio, argon gas：Ammonia=1:1, after keeping 1~3h, stop heating；
(2) furnace cooling, when temperature is down to 650~750 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmospher Enclose, cool to room temperature with the furnace；
(3) completely after cooling, reaction unit is taken out, it is Al to be deposited on material on thin layer aluminium powder silicon substrate surfacexGa1-xN Ternary alloy nano rod.
It is described supersound process is carried out to silicon chip to concretely comprise the following steps in described step 1 (1)：With deionized water or second Alcohol is cleaned by ultrasonic to silicon chip, and its object is to be cleaned by ultrasonic the surface impurity of silicon chip.
In described step 1 (1), the purity of described aluminium powder is >=99.999%, and its average grain diameter is 5~10 μm.
In described step 1 (1), the reagent of described aluminium powder ultrasonic vibration is one in ethanol, methanol, acetone or hexane Kind or several mixing, the addition of reagent be to be defined so that aluminium powder is fully dispersed in reagent；
In described step 1 (1), the time of described ultrasonic vibration is 10~60min.
In described step 2, the purity of described metal Al powder is >=99.999%, and its average grain diameter is 5~10 μm.
In described step 2, the silicon chip for having thin layer aluminium powder will be deposited as growth substrates.
In described step 2, described reaction boat is aluminium oxide ceramics boat.
It is described when vacuum≤5Pa of horizontal quartz tube stove, the purpose for being passed through argon gas exist in described step 3 (2) In to reaction system progress gas washing, it is 10~60min to be passed through the time.
Al prepared by the present inventionxGa1-xN ternary alloy nanos rod is different Al components wurtzite structure AlxGa1-xN ternarys are closed Gold nanorods, Al components adjustable extent are 0.88≤x≤0.92.
The described adjustable mode of Al components be had according to temperature and Ga liquid synsedimentarys thin layer aluminium powder silicon chip away from It can be adjusted from difference.
The Al of preparationxGa1-xN ternary alloy nanos rod is canescence, a diameter of 600~700nm of nanometer rods, a length of 4~ 5 microns, the top of nanometer rods is in hexagon or hexagonal taper.
Above-mentioned, the flow control for being passed through gas uses mass flowmenter.
A kind of monocrystalline high Al contents Al of the present inventionxGa1-xThe preparation method of N ternary alloy nano rods, compared to existing skill Art, its advantage are：
1. the synthetic method of the present invention is a kind of vapor transport deposition method, one layer of thin aluminium of its pre-deposition on a silicon substrate Powder is AlxGa1-xN ternary alloy nanos rod can deposit one layer thin in the key of silicon chip substrate Epitaxial growth, silicon chip Aluminium powder is on the one hand can to make AlN self-catalysis nucleation on a silicon substrate, so as to realize AlxGa1-xThe extension life of N alloy nano rods It is long, overcome under condition of normal pressure, 900 DEG C of -1000 DEG C of warm area pure metal sources and NH3Can not be nucleated on silicon substrate in reaction system, The difficulty that nucleation rate is low and adhesion is poor；On the other hand rich Al growing environment can be provided, promote high Al contents AlxGa1-xN The growth of semiconducting alloy, and suppress the phenomenon being separated.
2. the quartz test tube for the one end open that the present invention uses contributes to concentrating metals Ga and Al vapour pressure concentration, metal Ga drops and the difference of silicon chip distance, result in different Al components AlxGa1-xThe formation of N alloys.
3. the present invention has, reaction raw materials are simple, and preparation technology is simple, range of deposition is larger, reproducible, no phase separation, The features such as production cost is low and easy to spread, it is applicable to substantial amounts of industrialization growth AlGaN nanostructured crystal.
4. any catalyst is not used in the present invention, using Al self-catalysis Direct-Nitridation methods, it is fine to realize different Al components Zinc ore structure AlxGa1-xN ternary alloy nano rods.
Brief description of the drawings
Fig. 1 is present invention growth AlxGa1-xThe experiment schematic diagram of N ternary alloy nano rods.
It is 2mm, the Al prepared under condition of different temperatures that Fig. 2, which is Ga sources away from silicon chip distance,xGa1-xThe XRD spectrum of N alloys： (a)900℃；(b)950℃；(c)1000℃.
Fig. 3 is 950 DEG C, Ga sources away from silicon chip apart from it is different when the Al for preparingxGa1-xThe XRD spectrum of N alloys.(a)2mm； (b)5mm。
Fig. 4 is Al0.88Ga0.12The scanning electron microscopic picture of N ternary alloy nano rods；Wherein, (a) multiplication factor 10000 ×, (b) multiplication factor 80000 ×.
Fig. 5 is Al0.88Ga0.12The EDS power spectrums of N ternary alloy nano rods.
Embodiment
With reference to embodiment, the present invention is described in further detail.
In following examples, the quartz test tube a diameter of 20mm, a length of 150mm of use.
In following examples, the quartz tube 80mm of horizontal quartz tube stove, constant temperature section length is 34.5cm, uses quality Flowmeter controls gas flow.
In following examples, Al is grownxGa1-xThe experiment schematic diagram of N ternary alloy nano rods is shown in Fig. 1.
Embodiment 1
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, comprises the following steps：
Step 1, pre-deposition thin layer aluminium powder
(1) silicon chip is ultrasonically treated with deionized water, after cleaning, obtains the silicon chip after ultrasound；
It is that the aluminium powder that 99.999 average grain diameters are 5 μm is added in ethanol by purity, carries out ultrasonic vibration 20min, work as aluminium powder After being uniformly dispersed, the aluminium powder mixed liquor after ultrasound is obtained；
(2) silicon chip after ultrasound is put into the aluminium powder mixed liquor after ultrasound, natural air drying, obtaining deposition has thin layer of aluminum The silicon chip of powder；The deposit thickness of thin layer aluminium powder is 0.5mm.
Step 2, preparation is prepared
10g purity is evenly laid out in aluminium oxide ceramics boat one end for 99.999% metal Al powder, deposition there is into thin layer The silicon chip of aluminium powder is as growth substrates, and it is at 5~6mm to be placed in vertical range directly over metal Al powder, and deposition has thin layer aluminium powder One side upward；
5g Ga drops are placed in the aluminium oxide ceramics boat other end, Ga liquid has the silicon chip of thin layer aluminium powder close to Ga with deposition The horizontal range at liquid end is 2mm；
It is standby after whole reaction unit is arranged as stated above；
Step 3, vacuumize, lead to argon gas
(1) reaction unit after arranging is put into the quartz test tube of one end open, wherein, the reaction dress after arranging The axis and the diameter parallel of the quartz test tube of one end open put, and aluminium oxide ceramics boat is put into one end of Ga liquid away from quartz The opening of test tube；
(2) quartz test tube equipped with reaction unit is placed in the reaction zone of horizontal quartz tube stove, it is closed, start to take out very It is empty；
As vacuum≤5Pa of horizontal quartz tube stove, it is passed through argon gas and gas washing is carried out to reaction system, argon gas is passed through stream Measure as 500sccm, after 20min, after the atmosphere in whole device is argon gas, it be 100sccm that regulation argon gas, which is passed through flow, holding The chamber pressure of reaction system is normal pressure；
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 30 DEG C/min, when the stove of reaction system Temperature reach design temperature for 900 DEG C when, regulation argon flow amount be 50sccm, meanwhile, be passed through flow for 50sccm ammonia, holding After 2h, stop heating；
(2) furnace cooling, when temperature is down to 700 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN ternary alloy nano rods.
The Al of preparationxGa1-xN ternary alloy nano rods, it is x=0.92 AlxGa1-xN semiconducting alloys, its XRD spectrum are special Levy peak (100), the angle of diffraction of (002) and (101) shows product for tool between the wurtzite structure AlN and GaN angle of diffraction There is wurtzite structure AlGaN crystal, see a in Fig. 2.
Embodiment 2
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, with embodiment 1, difference exists In, step 4, heating
(1) under argon gas protection, reaction system is heated, heating rate is 30 DEG C/min, when the stove of reaction system Temperature reach design temperature for 950 DEG C when, regulation argon flow amount be 50sccm, meanwhile, be passed through flow for 50sccm ammonia, holding After 2h, stop heating；
(2) furnace cooling, when temperature is down to 700 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN ternary alloy nano rods.
The Al of preparationxGa1-xN ternary alloy nano rods, it is x=0.9 AlxGa1-xN semiconducting alloys, its XRD spectrum are special Levy peak (100), the angle of diffraction of (002) and (101) shows product for tool between the wurtzite structure AlN and GaN angle of diffraction There is wurtzite structure AlGaN crystal, see in Fig. 2 a in b and Fig. 3.
Embodiment 3
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, with embodiment 1, difference exists In,
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 30 DEG C/min, when the stove of reaction system Temperature reach design temperature for 1000 DEG C when, regulation argon flow amount be 50sccm, meanwhile, be passed through flow for 50sccm ammonia, guarantor After holding 2h, stop heating；
(2) furnace cooling, when temperature is down to 700 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN ternary alloy nano rods.
The Al of preparationxGa1-xN ternary alloy nano rods, it is x=0.91 AlxGa1-xN semiconducting alloys, its XRD spectrum are special Levy peak (100), the angle of diffraction of (002) and (101) shows product for tool between the wurtzite structure AlN and GaN angle of diffraction There is wurtzite structure AlGaN crystal, see c in Fig. 2.
According to, XRD spectrum binding analysis in embodiment 1-3 figure, the AlxGa1-xThe characteristic peak of N ternary alloy nano rods Offset relative to wurtzite structure AlN to low-angle direction, offset is related to experiment condition.Pass through the meter of (100) diffraction maximum Its corresponding lattice constant is calculated, and according to Vegard laws, Al is calculatedxGa1-xN ternary alloy three-partalloy semiconductor Al components are adjustable Scope is 0.88≤x≤0.92.
Embodiment 4
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, with embodiment 1, difference exists In,
Difference one：
Step 2, preparation is prepared
It is 5mm that Ga liquid has horizontal range of the silicon chip of thin layer aluminium powder close to Ga liquid end with deposition；
Difference two：
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 30 DEG C/min, when the stove of reaction system Temperature reach design temperature for 950 DEG C when, regulation argon flow amount be 50sccm, meanwhile, be passed through flow for 50sccm ammonia, holding After 2h, stop heating；
(2) furnace cooling, when temperature is down to 700 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN (x=0.88) nanometer rods.
The Al of preparationxGa1-xN ternary alloy nano rods, it is x=0.88 AlxGa1-xN semiconducting alloys, its XRD spectrum are special Levy peak (100), the angle of diffraction of (002) and (101) shows product for tool between the wurtzite structure AlN and GaN angle of diffraction There is wurtzite structure AlGaN crystal, see b in Fig. 3.
To the Al of preparationxGa1-xN (x=0.88) nanometer rods are scanned analysis, and its scanning electron microscope (SEM) photograph is shown in Fig. 4, from figure It can draw, Al0.88Ga0.12The pattern of N ternary alloy nano rods, its a length of 4-5 micron, diameter 600-700nm, top is in Hexagon or hexagonal taper.
To the Al of preparationxGa1-xN (x=0.88) nanometer rods carry out energy spectrum analysis, Fig. 5 are seen, from figure in terms of corresponding energy spectrum diagram Go out AlxGa1-xN (x=0.88) nanometer rods contain Al, Ga and N element.
Embodiment 5
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, comprises the following steps：
Step 1, pre-deposition thin layer aluminium powder
(1) silicon chip is ultrasonically treated with ethanol, after cleaning, obtains the silicon chip after ultrasound；
It is that the aluminium powder that 99.999 average grain diameters are 10 μm is added in methanol by purity, carries out ultrasonic vibration 60min, work as aluminium powder After being uniformly dispersed, the aluminium powder mixed liquor after ultrasound is obtained；
(2) silicon chip after ultrasound is put into the aluminium powder mixed liquor after ultrasound, natural air drying, obtaining deposition has thin layer of aluminum The silicon chip of powder；The deposit thickness of thin layer aluminium powder is 1.0mm.
Step 2, preparation is prepared
It is that metal Al powder that 99.999% average grain diameter is 5 μm is evenly laid out in aluminium oxide ceramics boat one end by 5g purity, For the silicon chip for having thin layer aluminium powder using depositing as growth substrates, it is at 5~6mm to be placed in vertical range directly over metal Al powder, is sunk Product has the one side of thin layer aluminium powder upward；
5g Ga drops are placed in the aluminium oxide ceramics boat other end, Ga liquid has the silicon chip of thin layer aluminium powder close to Ga with deposition The horizontal range at liquid end is 2mm；
It is standby after whole reaction unit is arranged as stated above；
Step 3, vacuumize, lead to argon gas
(1) reaction unit after arranging is put into the quartz test tube of one end open, wherein, the reaction dress after arranging The axis and the diameter parallel of the quartz test tube of one end open put, and aluminium oxide ceramics boat is put into one end of Ga liquid away from quartz The opening of test tube；
(2) quartz test tube equipped with reaction unit is placed in the reaction zone of horizontal quartz tube stove, it is closed, start to take out very It is empty；
As vacuum≤5Pa of horizontal quartz tube stove, it is passed through argon gas and gas washing is carried out to reaction system, argon gas is passed through stream Measure as 700sccm, after 10min, after the atmosphere in whole device is argon gas, it be 150sccm that regulation argon gas, which is passed through flow, holding The chamber pressure of reaction system is normal pressure；
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 10 DEG C/min, when the stove of reaction system Temperature reach design temperature for 950 DEG C when, regulation argon flow amount be 60sccm, meanwhile, be passed through flow for 60sccm ammonia, holding After 1h, stop heating；
(2) furnace cooling, when temperature is down to 750 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN ternary alloy nano rods.
Embodiment 6
A kind of monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, comprises the following steps：
Step 1, pre-deposition thin layer aluminium powder
(1) silicon chip is ultrasonically treated with ethanol, after cleaning, obtains the silicon chip after ultrasound；
It is that the aluminium powder that 99.999 average grain diameters are 8 μm is added in methanol by purity, carries out ultrasonic vibration 10min, work as aluminium powder After being uniformly dispersed, the aluminium powder mixed liquor after ultrasound is obtained；
(2) silicon chip after ultrasound is put into the aluminium powder mixed liquor after ultrasound, natural air drying, obtaining deposition has thin layer of aluminum The silicon chip of powder；The deposit thickness of thin layer aluminium powder is 0.5mm.
Step 2, preparation is prepared
It is that the metal Al powder that 99.999% average grain diameter is 10 μm is evenly laid out in aluminium oxide ceramics boat one by 10g purity End, the silicon chip that has thin layer aluminium powder will be deposited and be used as growth substrates, be placed in directly over metal Al powder vertical range as at 5~6mm, Deposition has the one side of thin layer aluminium powder upward；
5g Ga drops are placed in the aluminium oxide ceramics boat other end, Ga liquid has the silicon chip of thin layer aluminium powder close to Ga with deposition The horizontal range at liquid end is 3mm；
It is standby after whole reaction unit is arranged as stated above；
Step 3, vacuumize, lead to argon gas
(1) reaction unit after arranging is put into the quartz test tube of one end open, wherein, the reaction dress after arranging The axis and the diameter parallel of the quartz test tube of one end open put, and aluminium oxide ceramics boat is put into one end of Ga liquid away from quartz The opening of test tube；
(2) quartz test tube equipped with reaction unit is placed in the reaction zone of horizontal quartz tube stove, it is closed, start to take out very It is empty；
As vacuum≤5Pa of horizontal quartz tube stove, it is passed through argon gas and gas washing is carried out to reaction system, argon gas is passed through stream Measure as 300sccm, after 60min, after the atmosphere in whole device is argon gas, it be 80sccm that regulation argon gas, which is passed through flow, holding The chamber pressure of reaction system is normal pressure；
Step 4, heat
(1) under argon gas protection, reaction system is heated, heating rate is 50 DEG C/min, when the stove of reaction system Temperature reach design temperature for 900 DEG C when, regulation argon flow amount be 40sccm, meanwhile, be passed through flow for 40sccm ammonia, holding After 2h, stop heating；
(2) furnace cooling, when temperature is down to 650 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, with Stove is cooled to room temperature；
(3) completely after cooling, reaction unit is taken out, the greyish white material being deposited on thin layer aluminium powder silicon substrate surface, is AlxGa1-xN ternary alloy nano rods.

Claims (10)

  1. A kind of 1. monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano rods, it is characterised in that the preparation method bag Include following steps：
    Step 1, pre-deposition thin layer aluminium powder
    (1) silicon chip is ultrasonically treated, obtains the silicon chip after ultrasound；
    Aluminium powder is added in reagent, ultrasonic vibration is carried out and is uniformly dispersed, obtain the aluminium powder mixed liquor after ultrasound；
    (2) silicon chip after ultrasound is put into the aluminium powder mixed liquor after ultrasound, natural air drying, obtaining deposition has thin layer aluminium powder Silicon chip；Wherein, the deposit thickness of thin layer aluminium powder is 0.5~1.0mm；
    Step 2, preparation is prepared
    Metal Al powder is evenly laid out in reaction boat one end, the silicon chip that deposition has thin layer aluminium powder is placed in directly over metal Al powder Vertical range is at 5~6mm, and deposition has the one side of thin layer aluminium powder upward；
    Ga drops are placed in the reaction boat other end, Ga liquid has horizontal range of the silicon chip close to Ga liquid end of thin layer aluminium powder with deposition For 2~5mm；Wherein, in mass ratio, metal Al powder：Ga=(1~2):1；
    It is standby after whole reaction unit is arranged as stated above；
    Step 3, vacuumize, lead to argon gas
    (1) reaction unit after arranging is put into the quartz test tube of one end open, wherein, reaction unit after arranging The diameter parallel of axis and the quartz test tube of one end open, and react one end opening away from quartz test tube that boat is put into Ga liquid Mouthful；
    (2) quartz test tube equipped with reaction unit is placed in the reaction zone of horizontal quartz tube stove, it is closed, start to vacuumize；
    As vacuum≤5Pa of horizontal quartz tube stove, argon gas is passed through, the flow that is passed through of argon gas is 300~700sccm, is treated whole Atmosphere in individual device is after argon gas, it is 80~150sccm that regulation argon gas, which is passed through flow, and the chamber pressure for keeping reaction system is Normal pressure；
    Step 4, heat
    (1) under argon gas protection, reaction system is heated, heating rate is 10~50 DEG C/min, when the stove of reaction system Temperature reach design temperature for 900~1000 DEG C when, regulation argon flow amount is 40~60sccm, meanwhile, ammonia is passed through, by flow Than argon gas：Ammonia=1:1, after keeping 1~3h, stop heating；
    (2) furnace cooling, when temperature is down to 650~750 DEG C, ammonia flow is closed, is continually fed into argon gas, ensures argon atmosphere, Cool to room temperature with the furnace；
    (3) completely after cooling, reaction unit is taken out, it is Al to be deposited on material on thin layer aluminium powder silicon substrate surfacexGa1-xN ternarys Alloy nano rod.
  2. 2. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In described to carry out supersound process to silicon chip and concretely comprise the following steps in described step 1 (1)：With deionized water or ethanol to silicon Substrate is cleaned by ultrasonic.
  3. 3. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In in described step 1 (1), the purity of described aluminium powder is >=99.999%, and its average grain diameter is 5~10 μm.
  4. 4. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In, in described step 1 (1), the reagent of described aluminium powder ultrasonic vibration be one kind in ethanol, methanol, acetone or hexane or Several mixing, the addition of reagent are to be defined so that aluminium powder is fully dispersed in reagent；In described step 1 (1), described ultrasound The time of concussion is 10~60min.
  5. 5. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In in described step 2, the purity of described metal Al powder is >=99.999%, and its average grain diameter is 5~10 μm.
  6. 6. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In in described step 2, described reaction boat is aluminium oxide ceramics boat.
  7. 7. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In, it is described as vacuum≤5Pa of horizontal quartz tube stove in described step 3 (2), argon gas is passed through, is passed through the time as 10 ~60min.
  8. 8. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In the Al of preparationxGa1-xN ternary alloy nanos rod is different Al components wurtzite structure AlxGa1-xN ternary alloy nano rods, Al Component adjustable extent is 0.88≤x≤0.92.
  9. 9. monocrystalline high Al contents Al as claimed in claim 1xGa1-xThe preparation method of N ternary alloy nano rods, its feature exist In the regulative mode of described Al component adjustable extents is to have the silicon chip of thin layer aluminium powder according to temperature and Ga liquid synsedimentarys It is adjusted apart from difference.
  10. 10. the monocrystalline high Al contents Al as described in any one in claim 1 or 8xGa1-xThe preparation of N ternary alloy nano rods Method, it is characterised in that the Al of preparationxGa1-xN ternary alloy nanos rod is canescence, nanometer rods a diameter of 600~ 700nm, a length of 4~5 microns, the top of nanometer rods is in hexagon or hexagonal taper.
CN201710906430.3A 2017-09-29 2017-09-29 Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano stick Active CN107699951B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710906430.3A CN107699951B (en) 2017-09-29 2017-09-29 Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano stick

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710906430.3A CN107699951B (en) 2017-09-29 2017-09-29 Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano stick

Publications (2)

Publication Number Publication Date
CN107699951A true CN107699951A (en) 2018-02-16
CN107699951B CN107699951B (en) 2019-04-30

Family

ID=61176235

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710906430.3A Active CN107699951B (en) 2017-09-29 2017-09-29 Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano stick

Country Status (1)

Country Link
CN (1) CN107699951B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101477950A (en) * 2009-01-20 2009-07-08 苏州纳米技术与纳米仿生研究所 Synthesizing process for InN, GaN and AIN low-dimensional nano structure material
CN102127807A (en) * 2011-01-31 2011-07-20 南京大学 Method for preparing ternary-component AlxGaI-xN nanocone
CN104313548A (en) * 2014-10-08 2015-01-28 上海理工大学 Preparation method of gallium nitride nanowires

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101477950A (en) * 2009-01-20 2009-07-08 苏州纳米技术与纳米仿生研究所 Synthesizing process for InN, GaN and AIN low-dimensional nano structure material
CN102127807A (en) * 2011-01-31 2011-07-20 南京大学 Method for preparing ternary-component AlxGaI-xN nanocone
CN104313548A (en) * 2014-10-08 2015-01-28 上海理工大学 Preparation method of gallium nitride nanowires

Also Published As

Publication number Publication date
CN107699951B (en) 2019-04-30

Similar Documents

Publication Publication Date Title
Solís-Pomar et al. Growth of vertically aligned ZnO nanorods using textured ZnO films
CN107785241B (en) A method of preparing beta-gallium oxide film on a silicon substrate
CN105463580A (en) Preparation method of cadmium selenide or cadmium sulfide two-dimensional monocrystal nanosheet
Wu et al. Effects of seed layer characteristics on the synthesis of ZnO nanowires
CN103160929B (en) The preparation method of a kind of monocrystal AIN nano cone and nanometer sheet
CN103305817B (en) A kind of Tube furnace epitaxial system
CN107119319B (en) Cuprous iodide two-dimensional material, preparation and application thereof
CN104762608B (en) A kind of preparation method of the controllable horizontal CdS nano-wire arrays of the direction of growth
CN107699951B (en) Monocrystalline high Al contents AlxGa1-xThe preparation method of N ternary alloy nano stick
CN104695020B (en) A kind of strip InAs nano belt and its preparation and application
CN104891456A (en) One-dimensional alpha-Si3N4 nano material and preparation method thereof
CN103539087B (en) A kind of method preparing aluminum nitride nanowire
CN108060458B (en) A kind of preparation facilities and method of nonpolarity indium nitride nano-crystal film
CN101289172B (en) Process for preparing InN nano-wire and nano-rods by vapor transport method
CN107699856B (en) Using evaporation coating-electric field induction controllable preparation orientation Bi-Te-Se nano column array method
CN111470485B (en) Gold phosphide nanosheet and controllable preparation method and application thereof
CN107740189A (en) High Al contents AlxGa1‑xN ternary alloy three-partalloy microcrystalline balls and preparation method thereof
CN103173738A (en) Preparation method for GaN nanostructure with adjustable Ga vacancy
CN109881255B (en) Tetragonal phase and/or hexagonal phase cobalt selenide two-dimensional material and preparation and application thereof
Tian et al. Effect of different O 2/N 2 flow rate on the size and yield of ZnO nanostructures
Shi et al. Morphology and growth mechanism of novel zinc oxide nanostructures synthesized by a carbon thermal evaporation process
CN106757358A (en) A kind of growing method of aluminum-nitride single crystal nano-tube array
CN203205451U (en) Nano nonpolar surface GaN cone array material
CN102162135A (en) Preparation method of ZnS/Si nuclear-shell nanowires or nanobelts and polycrystal Si tubes
Noothongkaew et al. Zinc oxide nano walls synthesized by chemical vapor deposition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant