CN107758727B - AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline and preparation method thereof - Google Patents

AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline and preparation method thereof Download PDF

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CN107758727B
CN107758727B CN201710993675.4A CN201710993675A CN107758727B CN 107758727 B CN107758727 B CN 107758727B CN 201710993675 A CN201710993675 A CN 201710993675A CN 107758727 B CN107758727 B CN 107758727B
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沈龙海
齐东丽
吕伟
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Shenyang Ligong University
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Abstract

A kind of AlxGa1‑xN ternary alloy three-partalloy cone cell is nanocrystalline and preparation method thereof, belongs to the technical field of semiconducting alloy nano material preparation.The AlxGa1‑xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell includes using Aluminum Chloride Hexahydrate (AlCl3·6H2O), gallium and ammonia are reaction raw materials, assemble reaction unit, the logical Ar gas into device, under normal pressure, 900 DEG C -1000 DEG C of reaction temperature of setting, meanwhile, it is passed through the NH that flow is 20~30sccm3The Ar for being 20~30sccm with flow maintains 1~1.5h, cooling, and Al is prepared on quartz substrate using vapour deposition processxGa1‑xN ternary alloy three-partalloy cone cell is nanocrystalline, and Al component adjustable extent is 0 < x≤0.51.It with bottom is quadrangle, the pyramid structure that side is triangle.This method simple process, it is reproducible, without phase point, production cost it is low, without adding any catalyst and template, be easy to commercial introduction application.

Description

AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline and preparation method thereof
Technical field
The invention belongs to the technical fields of semiconducting alloy nano material preparation, and in particular to a kind of AlxGa1-xN ternary is closed Golden cone cell is nanocrystalline and preparation method thereof.
Background technique
Tri-nitride AlN and GaN are important wide bandgap semiconductor photoelectric material, direct band gap with higher 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 section It is greatly enthusiastic to grind worker.High Al contents AlGaN material is to prepare ultraviolet detector, deep-UV light-emitting diode, plate to show Show the mainstay material of equal photoelectric devices, deep ultraviolet LED prepared therefrom is since small in size, structure is simple, integration is good, and the longevity Life 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, has huge society And economic benefit.In addition, medical treatment, sterilization, printing, data storage and in terms of have major application valence Value.
Currently, can prepare the LED of ultraviolet band by changing Al component in AlGaN alloy, the increase of Al component makes it Issue shorter wavelengths of shine.But with the increase of Al component, preparation, doping and the luminescent device production of AlGaN alloy Difficulty is high, and luminous efficiency reduces.Restrict high Al contents AlGaN deep ultraviolet light source light-emitting efficiency essentially consists in shortage suitably Substrate causes high Al contents AlGaN extension ply stress big, is easy cracking, influences crystal quality.Cone-shaped nano structure extension is raw It is small with the lattice mismatch of substrate material in length, with substrate generate stress can largely be fallen by cone cell crystal on side face relaxation or It all eliminates, to reduce or eliminate dislocation.In addition, the factors such as the dimension of nano structural material, pattern, size and they Special performance is closely related, and constructs the basis of nano functional device.Therefore, the physics excellent based on AlGaN alloy material Performance and its there is potential application prospect in terms of making photoelectric device, the AlGaN alloy nanostructures of high Al contents have drawn Extensive concern has been played,.
The synthetic method of AlGaN ternary alloy nano structure mainly has at present: (1) chloride chemical vapour deposition process；(2) Metal-organic chemical vapor deposition equipment (MOCVD)；(3) molecular beam epitaxy (MBE).The first preparation method, reaction raw materials chlorine Compound is easy to deliquesce, and price is more expensive.The reactant that second of MOCVD preparation method uses is organic source, needs to carry out anti- Malicious measure.The characteristics of reaction source that the third MBE method uses is simple, but MBE method is due to itself, and its cost is high It is expensive, be not suitable for commercialized development.And all there is spontaneous phenomenon of phase separation in MOCVD and MBE method.
The present invention utilizes homemade gas-phase deposition system, uses Aluminum Chloride Hexahydrate (AlCl3·6H2O), gallium and ammonia For reaction raw materials, 900 DEG C -1000 DEG C of range of reaction temperature, prepared in quartz substrate using vapour deposition process under normal pressure AlxGa1-xN cone cell is nanocrystalline, and Al component adjustable extent is 0 x≤0.51 <.This method simple process, it is reproducible, without phase Point, production cost it is low, without adding any catalyst and template, be easy to commercial introduction application.There is presently no utilize the method The Al of realizationxGa1-xThe nanocrystalline report of N ternary alloy three-partalloy cone cell.
Summary of the invention
It is that the present invention solves it is a key issue that providing a kind of AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline and its preparation side Method, the AlxGa1-xNanocrystalline N ternary alloy three-partalloy cone cell is AlxGa1-xN ternary semiconductor alloy cone cell is nanocrystalline, the AlxGa1-xN The nanocrystalline preparation method of ternary alloy three-partalloy cone cell uses Aluminum Chloride Hexahydrate (AlCl3·6H2O), gallium and ammonia are that reaction is former Expect, 900 DEG C -1000 DEG C of range of reaction temperature, is prepared using vapour deposition process using quartz substrate as substrate under normal pressure AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline, and Al component adjustable extent is 0 < x≤0.51.This method simple process, repeatability It is good, without phase point, production cost it is low, without adding any catalyst and template, be easy to commercial introduction application.
A kind of Al of the inventionxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline, is different Al component wurtzite structure AlxGa1-xN Ternary semiconductor alloy cone cell is nanocrystalline, Al component adjustable extent be 0 < x≤0.51, the cone cell it is nanocrystalline have bottom be four Side shape, the pyramid structure that side is triangle, the side length of the quadrangle of bottom are 400~800nm, the height of side triangle For 200~350nm.
A kind of Al of the inventionxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, comprising the following steps:
Step 1, reaction unit is assembled
(1) prepare quartz substrate
Quartz plate is cleaned, ultrasound air-dries, obtains dry quartz substrate；
(2) placing response raw material
Dry quartz substrate is placed in the top of first ceramic boat one end, first ceramic boat of distance it is vertical away from From for 5~6mm, metal Ga is put into first ceramic boat other end, the horizontal distance of metal Ga and the nearest one end of quartz substrate For 3~5cm；
By AlCl3·6H2O is put into second ceramic boat one end and third ceramic boat one end, in second ceramic boat AlCl3·6H2AlCl in O and third ceramic boat3·6H2O mass is equal, in mass ratio, total AlCl3·6H2O: metal Ga =(1~2): 1；
(3) reaction unit is assembled
First ceramic boat and the second ceramic boat are put into the first quartz ampoule open at one end, the second ceramic boat is placed with AlCl3·6H2Close to first quartzy channel closure one end, one end that the first ceramic boat is placed with quartz substrate is located at for one end of O One quartz ampoule open at one end, and quartz substrate is outside the first quartzy tube opening；
Third ceramic boat is put into the second quartz ampoule open at one end, third ceramic boat is placed with AlCl3·6H2One end of O Close to the second quartz ampoule open at one end；
First quartz ampoule and the second quartz ampoule are placed horizontally at the different warm areas in horizontal quartz tube furnace, the first quartz Tube opening one end and the second quartz ampoule open at one end are contrary, assemble reaction unit and are tested；
The horizontal quartz tube furnace is provided with air inlet pipe and exhaust pipe；
Step 2, it ventilates
It will be slowly evacuated to 50Pa in horizontal quartz tube furnace, is passed through Ar gas and carries out gas washing, to entire horizontal quartz tube In formula furnace for behind Ar compression ring border, continue to be passed through Ar to horizontal quartz tube furnace be normal pressure, by the air-flow side of horizontal quartz tube furnace Terminad exhaust pipe is put into sink and carries out fluid-tight, guarantees that air pressure is normal pressure in the furnace of horizontal quartz tube furnace；
Step 3, heating reaction
With heating rate be 30 DEG C~50 DEG C/min, horizontal quartz tube furnace is heated up, meanwhile, be passed through flow be 20~ The NH of 30sccm3The Ar for being 20~30sccm with flow, wherein press flow-rate ratio, NH3: Ar=1:1；
After horizontal quartz tube furnace is warming up to reaction temperature, 1~1.5h is maintained, closes heating system, and stops being passed through NH3；
Described heats up horizontal quartz tube furnace specifically, the first quartz ampoule will be placed in horizontal quartz tube furnace The temperature of conversion zone is warming up to 900 DEG C~1000 DEG C；The reaction zone of the second quartz ampoule will be placed in horizontal quartz tube furnace The temperature in domain is warming up to 150 DEG C~200 DEG C；
Step 4, cooling
Ar flow is adjusted to 100sccm, the temperature of the conversion zone of the first quartz ampoule is placed with to horizontal quartz tube furnace Degree is down to 500 DEG C, and stopping is passed through Ar, and closes exhaust pipe, and cooled to room temperature obtains being deposited on quartz substrate surface Yellowish substance, as AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline.
Wherein,
In the step step 1 (1), the quartz plate cleaning, ultrasound, air-dried concrete operations are as follows: by quartz plate It cleaned with acetone, be placed in and contain in spirituous beaker, be put into supersonic wave cleaning machine and carry out 8~15min of cleaning, be placed in air Middle natural air drying；
In the step step 1 (2), the purity of the metal Ga is more than or equal to 99.999wt.%.
In the step step 1 (2), the AlCl3·6H2O is that purity is more than or equal to 97wt.%.
In the step step 1 (3), in the horizontal quartz tube furnace, the air inlet pipe of setting is located at the second quartz Tube opening side, the exhaust pipe of setting are set to the first quartzy tube opening side.
A kind of Al of the inventionxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell has compared with the prior art Beneficial effect is:
1. synthetic method of the invention is a kind of vapor transport deposition method, deposition substrate quartz substrate is placed on the first quartz At the nozzle of pipe, this is to grow Al under condition of normal pressurexGa1-xThe nanocrystalline key of N ternary alloy three-partalloy cone cell.Inside first quartz ampoule AlCl3·6H2O plays the role of transmitting the source Ga to quartz substrate and provides the source Al.
AlCl is housed in the second quartz ampoule3·6H2The warm area of O ceramic boat is 150 DEG C~200 DEG C, plays in reaction process and holds The effect in the continuous supplement source Al, to improve AlxGa1-xThe component of Al in N ternary alloy three-partalloy.
2. the quartz test tube open at one end that the present invention uses facilitates the vapour pressure concentration that the source Ga is concentrated, metal Ga drop With the difference of quartz substrate distance, different Al component Al are resulted inxGa1-xThe formation of N ternary alloy nano crystalline substance.
3. the present invention has reaction raw materials simple, preparation process is simple, range of deposition is larger, reproducible, no phase point, raw The features such as at low cost and easy to spread is produced, is applicable to largely industrialize the different Al component Al of growthxGa1-xN ternary alloy three-partalloy It is nanocrystalline
4. any catalyst is not used in the present invention, under normal pressure under the conditions of, different Al components are prepared on quartz substrate Wurtzite structure AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline.
Detailed description of the invention
Fig. 1 is growth Al of the inventionxGa1-xThe experiment schematic diagram of N ternary alloy nano crystalline substance；
Wherein, in figure, SiO2For quartz substrate；
Fig. 2 is the NH that flow-rate ratio is 20:20sccm3And Ar, the Al that temperature is prepared under the conditions of being 950 DEG C0.51Ga0.48N alloy XRD spectrum；
Fig. 3 is the Al of small multiplying power0.51Ga0.48The scanning electron microscopic picture of N ternary alloy nano crystalline substance；
Fig. 4 is the Al of enlargement ratio0.51Ga0.48The scanning electron microscopic picture of N ternary alloy nano crystalline substance.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Following embodiment, the raw material A lCl of use3·6H2O is to analyze pure AR, and traditional Chinese medicines reagent, purity is greater than 97%.Using Metal Ga purity be more than or equal to 99.999wt.%.
In following embodiment, the length of the first quartz test tube is 25cm, diameter 20mm, and the length of the second quartz test tube is 15cm。
Embodiment 1
A kind of AlxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, comprising the following steps:
Step 1, reaction unit is assembled
(1) prepare quartz substrate
Quartz plate is cleaned with acetone, is placed in and contains in spirituous beaker, is put into supersonic wave cleaning machine and is cleaned 10min is placed in natural air drying in air, obtains dry quartz substrate；
(2) placing response raw material
Dry quartz substrate is placed in the top of first ceramic boat one end, first ceramic boat of distance it is vertical away from From for 5mm, metal Ga is put into first ceramic boat other end, metal Ga and the horizontal distance of the nearest one end of quartz substrate are 3cm；
By AlCl3·6H2O is put into second ceramic boat one end and third ceramic boat one end, in second ceramic boat AlCl3·6H2AlCl in O and third ceramic boat3·6H2O mass is equal, in mass ratio, total AlCl3·6H2O: metal Ga =1:1；
(3) reaction unit is assembled
First ceramic boat and the second ceramic boat are put into the first quartz ampoule open at one end, the second ceramic boat is placed with AlCl3·6H2Close to first quartzy channel closure one end, one end that the first ceramic boat is placed with quartz substrate is located at for one end of O One quartz ampoule open at one end, and quartz substrate is outside the first quartzy tube opening；
Third ceramic boat is put into the second quartz ampoule open at one end, third ceramic boat is placed with AlCl3·6H2One end of O Close to the second quartz ampoule open at one end；
First quartz ampoule and the second quartz ampoule are placed horizontally at the different warm areas in horizontal quartz tube furnace, the first quartz Tube opening one end and the second quartz ampoule open at one end are contrary, assemble reaction unit and are tested, wherein experiment signal Figure is shown in Fig. 1.SiO in Fig. 12For quartz substrate.
The horizontal quartz tube furnace is provided with air inlet pipe and exhaust pipe, and the air inlet pipe of setting is located at the second quartz ampoule and opens Mouth side, the exhaust pipe of setting are set to the first quartzy tube opening side.
Step 2, it ventilates
It will be slowly evacuated to 50Pa in horizontal quartz tube furnace, is passed through Ar gas and carries out gas washing, to entire horizontal quartz tube In formula furnace for behind Ar compression ring border, continue to be passed through Ar to horizontal quartz tube furnace be normal pressure, by the air-flow side of horizontal quartz tube furnace Terminad exhaust pipe is put into sink and carries out fluid-tight, guarantees that air pressure is normal pressure in the furnace of horizontal quartz tube furnace；
Step 3, heating reaction
With heating rate for 30 DEG C/min, horizontal quartz tube furnace is heated up, meanwhile, it is passed through the NH that flow is 20sccm3 The Ar for being 20sccm with flow, wherein press flow-rate ratio, NH3: Ar=1:1；
After horizontal quartz tube furnace is warming up to reaction temperature, 1h is maintained, closes heating system, and stops being passed through NH3；
Described heats up horizontal quartz tube furnace specifically, the first quartz ampoule will be placed in horizontal quartz tube furnace The temperature of conversion zone is warming up to 900 DEG C；The temperature of the conversion zone of the second quartz ampoule will be placed in horizontal quartz tube furnace It is warming up to 150 DEG C；
Step 4, cooling
Ar flow is adjusted to 100sccm, the temperature of the conversion zone of the first quartz ampoule is placed with to horizontal quartz tube furnace Degree is down to 500 DEG C, and stopping is passed through Ar, and closes exhaust pipe, and cooled to room temperature obtains being deposited on quartz substrate surface Yellowish substance, as AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline.
Al manufactured in the present embodimentxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline, and XRD spectrum characteristic peak (100) is corresponding to spread out Firing angle is 32.89 °, as shown in Fig. 2, showing that product is with fine zinc between the angle of diffraction of wurtzite structure AlN and GaN Mine structure AlGaN crystal.By its corresponding lattice constant of the calculating of (100) diffraction maximum, and according to Vegard law, calculate Obtain AlxGa1-xThe x=0.51 of N ternary alloy three-partalloy semiconductor Al component.The stereoscan photograph of different enlargement ratios shows to prepare Obtained AlxGa1-xN ternary alloy three-partalloy is the pyramid structure that bottom is quadrangle, side is triangle, is similar to pyramid knot The side length of structure, the quadrangle of bottom is 400~800nm, and a height of 200~350nm of side triangle is specifically shown in Fig. 3 and figure Shown in 4.
Embodiment 2
A kind of AlxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, comprising the following steps:
Step 1, reaction unit is assembled
(1) prepare quartz substrate
Quartz plate is cleaned with acetone, is placed in and contains in spirituous beaker, is put into supersonic wave cleaning machine and is cleaned 8min is placed in natural air drying in air, obtains dry quartz substrate；
(2) placing response raw material
Dry quartz substrate is placed in the top of first ceramic boat one end, first ceramic boat of distance it is vertical away from From for 6mm, metal Ga is put into first ceramic boat other end, metal Ga and the horizontal distance of the nearest one end of quartz substrate are 5cm；
By AlCl3·6H2O is put into second ceramic boat one end and third ceramic boat one end, in second ceramic boat AlCl3·6H2AlCl in O and third ceramic boat3·6H2O mass is equal, in mass ratio, total AlCl3·6H2O: metal Ga =2:1；
(3) reaction unit is assembled
First ceramic boat and the second ceramic boat are put into the first quartz ampoule open at one end, the second ceramic boat is placed with AlCl3·6H2Close to first quartzy channel closure one end, one end that the first ceramic boat is placed with quartz substrate is located at for one end of O One quartz ampoule open at one end, and quartz substrate is outside the first quartzy tube opening；
Third ceramic boat is put into the second quartz ampoule open at one end, third ceramic boat is placed with AlCl3·6H2One end of O Close to the second quartz ampoule open at one end；
First quartz ampoule and the second quartz ampoule are placed horizontally at the different warm areas in horizontal quartz tube furnace, the first quartz Tube opening one end and the second quartz ampoule open at one end are contrary, assemble reaction unit and are tested, wherein experiment signal Figure is shown in Fig. 1.SiO in Fig. 12For quartz substrate.
The horizontal quartz tube furnace is provided with air inlet pipe and exhaust pipe, and the air inlet pipe of setting is located at the second quartz ampoule and opens Mouth side, the exhaust pipe of setting are set to the first quartzy tube opening side.
Step 2, it ventilates
It will be slowly evacuated to 50Pa in horizontal quartz tube furnace, is passed through Ar gas and carries out gas washing, to entire horizontal quartz tube In formula furnace for behind Ar compression ring border, continue to be passed through Ar to horizontal quartz tube furnace be normal pressure, by the air-flow side of horizontal quartz tube furnace Terminad exhaust pipe is put into sink and carries out fluid-tight, guarantees that air pressure is normal pressure in the furnace of horizontal quartz tube furnace；
Step 3, heating reaction
With heating rate for 50 DEG C/min, horizontal quartz tube furnace is heated up, meanwhile, it is passed through the NH that flow is 30sccm3 The Ar for being 30sccm with flow, wherein press flow-rate ratio, NH3: Ar=1:1；
After horizontal quartz tube furnace is warming up to reaction temperature, 1.5h is maintained, closes heating system, and stops being passed through NH3；
Described heats up horizontal quartz tube furnace specifically, the first quartz ampoule will be placed in horizontal quartz tube furnace The temperature of conversion zone is warming up to 1000 DEG C；The temperature of the conversion zone of the second quartz ampoule will be placed in horizontal quartz tube furnace Degree is warming up to 200 DEG C；
Step 4, cooling
Ar flow is adjusted to 100sccm, the temperature of the conversion zone of the first quartz ampoule is placed with to horizontal quartz tube furnace Degree is down to 500 DEG C, and stopping is passed through Ar, and closes exhaust pipe, and cooled to room temperature obtains being deposited on quartz substrate surface Yellowish substance, as AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline.
Embodiment 3
A kind of AlxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, comprising the following steps:
Step 1, reaction unit is assembled
(1) prepare quartz substrate
Quartz plate is cleaned with acetone, is placed in and contains in spirituous beaker, is put into supersonic wave cleaning machine and is cleaned 15min is placed in natural air drying in air, obtains dry quartz substrate；
(2) placing response raw material
Dry quartz substrate is placed in the top of first ceramic boat one end, first ceramic boat of distance it is vertical away from From for 6mm, metal Ga is put into first ceramic boat other end, metal Ga and the horizontal distance of the nearest one end of quartz substrate are 5cm；
By AlCl3·6H2O is put into second ceramic boat one end and third ceramic boat one end, in second ceramic boat AlCl3·6H2AlCl in O and third ceramic boat3·6H2O mass is equal, in mass ratio, total AlCl3·6H2O: metal Ga =1.5:1；
(3) reaction unit is assembled
First ceramic boat and the second ceramic boat are put into the first quartz ampoule open at one end, the second ceramic boat is placed with AlCl3·6H2Close to first quartzy channel closure one end, one end that the first ceramic boat is placed with quartz substrate is located at for one end of O One quartz ampoule open at one end, and quartz substrate is outside the first quartzy tube opening；
Third ceramic boat is put into the second quartz ampoule open at one end, third ceramic boat is placed with AlCl3·6H2One end of O Close to the second quartz ampoule open at one end；
First quartz ampoule and the second quartz ampoule are placed horizontally at the different warm areas in horizontal quartz tube furnace, the first quartz Tube opening one end and the second quartz ampoule open at one end are contrary, assemble reaction unit and are tested.
The horizontal quartz tube furnace is provided with air inlet pipe and exhaust pipe, and the air inlet pipe of setting is located at the second quartz ampoule and opens Mouth side, the exhaust pipe of setting are set to the first quartzy tube opening side.
Step 2, it ventilates
It will be slowly evacuated to 50Pa in horizontal quartz tube furnace, is passed through Ar gas and carries out gas washing, to entire horizontal quartz tube In formula furnace for behind Ar compression ring border, continue to be passed through Ar to horizontal quartz tube furnace be normal pressure, by the air-flow side of horizontal quartz tube furnace Terminad exhaust pipe is put into sink and carries out fluid-tight, guarantees that air pressure is normal pressure in the furnace of horizontal quartz tube furnace；
Step 3, heating reaction
With heating rate for 40 DEG C/min, horizontal quartz tube furnace is heated up, meanwhile, it is passed through the NH that flow is 20sccm3 The Ar for being 20sccm with flow, wherein press flow-rate ratio, NH3: Ar=1:1；
After horizontal quartz tube furnace is warming up to reaction temperature, 1.5h is maintained, closes heating system, and stops being passed through NH3；
Described heats up horizontal quartz tube furnace specifically, the first quartz ampoule will be placed in horizontal quartz tube furnace The temperature of conversion zone is warming up to 950 DEG C；The temperature of the conversion zone of the second quartz ampoule will be placed in horizontal quartz tube furnace It is warming up to 150 DEG C；
Step 4, cooling
Ar flow is adjusted to 100sccm, the temperature of the conversion zone of the first quartz ampoule is placed with to horizontal quartz tube furnace Degree is down to 500 DEG C, and stopping is passed through Ar, and closes exhaust pipe, and cooled to room temperature obtains being deposited on quartz substrate surface Yellowish substance, as AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline.

Claims (6)

1. a kind of AlxGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, which comprises the following steps:
Step 1, reaction unit is assembled
(1) prepare quartz substrate
Quartz plate is cleaned, ultrasound air-dries, obtains dry quartz substrate；
(2) placing response raw material
Dry quartz substrate is placed in the top of first ceramic boat one end, the vertical range of first ceramic boat of distance is Metal Ga is put into first ceramic boat other end by 5 ~ 6mm, and the horizontal distance of metal Ga and the nearest one end of quartz substrate is 3 ~ 5 cm；
By AlCl3·6H2O is put into second ceramic boat one end and third ceramic boat one end, in second ceramic boat AlCl3·6H2AlCl in O and third ceramic boat3·6H2O mass is equal, in mass ratio, total AlCl3·6H2O: metal Ga= (1 ~ 2): 1；
(3) reaction unit is assembled
First ceramic boat and the second ceramic boat are put into the first quartz ampoule open at one end, the second ceramic boat is placed with AlCl3· 6H2Close to first quartzy channel closure one end, one end that the first ceramic boat is placed with quartz substrate is located at the first quartz ampoule for one end of O Open at one end, and quartz substrate is outside the first quartzy tube opening；
Third ceramic boat is put into the second quartz ampoule open at one end, third ceramic boat is placed with AlCl3·6H2One end of O is being leaned on Nearly second quartz ampoule open at one end；
First quartz ampoule and the second quartz ampoule are lain in a horizontal plane in the different warm areas of horizontal quartz tube furnace, the first quartzy tube opening One end and the second quartz ampoule open at one end are contrary, assemble reaction unit and are tested；
The horizontal quartz tube furnace is provided with air inlet pipe and exhaust pipe；
Step 2, it ventilates
It will be slowly evacuated to 50Pa in horizontal quartz tube furnace, is passed through Ar gas and carries out gas washing, to entire horizontal quartz tube furnace In for behind Ar compression ring border, continue to be passed through Ar to horizontal quartz tube furnace be normal pressure, by the airflow direction end of horizontal quartz tube furnace End exhaust pipe is put into sink and carries out fluid-tight, guarantees that air pressure is normal pressure in the furnace of horizontal quartz tube furnace；
Step 3, heating reaction
With heating rate for 30 DEG C ~ 50 DEG C/min, horizontal quartz tube furnace is heated up, meanwhile, being passed through flow is 20 ~ 30sccm's NH3The Ar for being 20 ~ 30sccm with flow, wherein press flow-rate ratio, NH3: Ar=1:1；
After horizontal quartz tube furnace is warming up to reaction temperature, 1 ~ 1.5h is maintained, closes heating system, and stops being passed through NH3；
Described heats up horizontal quartz tube furnace specifically, the reaction that will be placed with the first quartz ampoule in horizontal quartz tube furnace The temperature in region is warming up to 900 DEG C ~ 1000 DEG C；The temperature of the conversion zone of the second quartz ampoule will be placed in horizontal quartz tube furnace Degree is warming up to 150 DEG C ~ 200 DEG C；
Step 4, cooling
Ar flow is adjusted to 100sccm, the temperature drop of the conversion zone of the first quartz ampoule is placed with to horizontal quartz tube furnace To 500 DEG C, stopping is passed through Ar, and closes exhaust pipe, and cooled to room temperature obtains being deposited on micro- Huang on quartz substrate surface Color substance, as AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline；
The Al of preparationxGa1-xNanocrystalline N ternary alloy three-partalloy cone cell is different Al component wurtzite structure AlxGa1-xN ternary semiconductor closes Golden cone cell is nanocrystalline, and Al component adjustable extent is 0 < x≤0.51；
The AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline to have the pyramid structure that bottom is quadrangle, side is triangle, The side length of the quadrangle of bottom is 400 ~ 800 nm, a height of 200 ~ 350nm of side triangle.
2. Al as described in claim 1xGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, which is characterized in that described In step 1 (1), the described quartz plate cleaning, ultrasound, air-dried concrete operations are as follows: quartz plate is cleaned with acetone, is placed in and fills It in the beaker of alcohol, is put into supersonic wave cleaning machine and carries out 8 ~ 15min of cleaning, be placed in natural air drying in air.
3. Al as described in claim 1xGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, which is characterized in that described In step 1 (2), the purity of the metal Ga is more than or equal to 99.999wt.%.
4. Al as described in claim 1xGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, which is characterized in that described In step 1 (2), the AlCl3·6H2O is that purity is more than or equal to 97wt.%.
5. Al as described in claim 1xGa1-xThe nanocrystalline preparation method of N ternary alloy three-partalloy cone cell, which is characterized in that described In step 1 (3), in the horizontal quartz tube furnace, the air inlet pipe of setting is located at the second quartzy tube opening side, the row of setting Tracheae is set to the first quartzy tube opening side.
6. a kind of AlxGa1-xN ternary alloy three-partalloy cone cell is nanocrystalline, which is characterized in that using described in claim 1 ~ 5 any one Preparation method is made.
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