CN1319852C - High purity gallium nitride nanometer line preparation method - Google Patents
High purity gallium nitride nanometer line preparation method Download PDFInfo
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- CN1319852C CN1319852C CNB2005100481977A CN200510048197A CN1319852C CN 1319852 C CN1319852 C CN 1319852C CN B2005100481977 A CNB2005100481977 A CN B2005100481977A CN 200510048197 A CN200510048197 A CN 200510048197A CN 1319852 C CN1319852 C CN 1319852C
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Abstract
The present invention relates to a generation method for preparing a gallium nitride nanometer line of high purity. The present invention uses gallium oxide Ga2O3 as raw material, ammonia gas NH3 is used as reaction gas, and the argon gas Ar of inert gas is used as shield gas; a silicon plate is used as product growing carrier substrate, anhydrous alcohol, acetone and deionized water are used as cleaning agents of the silicon plate, and the deionized water is used as a cleaning agent of a quartz raw material boat; a catalyst is not used, and a gallium nitride nanometer line is directly grown on the silicon plate by ammonification reaction under the high temperature of 950 DEGC; the present invention simplifies the preparation technological flow, effectively prevents the generation of accessory substances, and improves the yield, the purity and the precision of the product by grinding and sieving the raw material, washing the silicon plate and the quartz raw material boat, pumping air by the program control of a tube type high temperature furnace controller, inputting the argon gas and the ammonia gas, warming up, and cooling, and finally, the solid gallium nitride nanometer line of light yellow and in a line shape is obtained; the product has the characteristics of flat and even shape, order arrangement, uniform and linear appearance, stable optical, chemical and physical properties, short preparation flow, high growth speed of the product, high yield, high purity and high linear precision; the yield can reach 95%, the purity can reach 98.6%, the diameter reaches 5 to 20 nm, and the average length of the single line is from 30 to 50 mum. The present invention is an ideal method for preparing the solid gallium nitride nanometer line of high purity and light yellow and in a line shape.
Description
Technical Field
The invention relates to a preparation method of high-purity gallium nitride nanowires, belonging to the technical field of preparation and generation methods of inorganic compound semiconductor materials.
Background
The nano wire and carbon nano tube of semiconductor material are raw materials for manufacturing nano-scale electronic and optical devices, the gallium nitride nano wire of one-dimensional III-V group compound has unique optical and electrical properties, has wide application prospect in visible light, ultraviolet light and other photoelectronic devices, is a wide straight band gap semiconductor, has high electronic saturation drift velocity, and is one of the most superior materials for manufacturing blue light diodes and high-power photoelectronic devices.
In recent years, important scientific research schedules have been mentioned in the preparation research of inorganic compound gallium nitride nanowires, and the common preparation methods include: the method mainly uses a catalyst or a template for limitation, so impurities are inevitably introduced, the purity and the yield of the product are greatly influenced, the raw material proportion of the preparation method is not strict, the process flow is not reasonable enough, the preparation method is complicated, the preparation period is prolonged, byproducts are easily generated, the optical, physical and chemical properties of the product are unstable, the application of the product and the performance of a photoelectric device of the product are influenced, the shape of the product nanowire is changed, the diameter of the product is unstable, the surface is not smooth enough, and the linear length is not balanced enough.
Disclosure of Invention
Object of the Invention
The invention aims to overcome the defects of the background technology, adopts a novel preparation method, does not use a catalyst, adopts direct reaction in a high-temperature furnace to generate gallium nitride nanowires, uses gallium oxide fine powder as a raw material, ammonia gas as a reaction gas, argon gas as a protective gas, a silicon plate as a product growth carrier, and directly performs ammoniation reaction in the high-temperature furnace under the protection of inert gas argon gas to generate high-purity pale yellow, solid and linear gallium nitride nanowires, thereby simplifying the preparation process flow and improving the purity, precision and yield of the product.
Technical scheme
The chemical substances used in the invention are: gallium oxide, ammonia gas, hydrogen gas, acetone, absolute ethyl alcohol and deionized water
In grams, milliliters and centimeters3As a unit of measure
Gallium oxide: ga2O31 g +/-0.1 g
Ammonia gas: NH (NH)32600 cm3Plus or minus 10 cm3
Argon gas: ar 9000 cm3Plus or minus 10 cm3
Acetone: CH (CH)3COCH320 ml +/-1 ml
Anhydrous ethanol CH3CH2OH 20 ml. + -. 1 ml
Deionized water: h2O140 ml +/-2 ml
The preparation of the growth carrier substrate used in the invention is as follows: silicon plate Si
The specification is as follows: in mm as a unit of size
Silicon plate: length x width x thickness x 10 x 2mm
The preparation and growth method of the invention comprises the following steps:
(1) selecting chemicals
The chemical raw materials required by the mixture ratio are carefully selected,and the purity is controlled as follows:
gallium oxide: 99.999 percent
Ammonia gas: 99.999 percent
Argon gas: 99.999 percent
Acetone: 99.5 percent
Anhydrous ethanol: 99.7 percent
Deionized water: 98.8 percent
(2) Selecting and preparing a growth carrier substrate: silicon plate
Controlling the surface roughness of the carrier substrate required by preparation, wherein the surface is straight, smooth and mirror-like;
(3) grinding and sieving raw materials
Grinding the chemical substance raw material gallium oxide required by the proportion by using an agate mortar and a grinding rod, then sieving the ground chemical substance raw material gallium oxide with a 300-mesh screen, and repeatedly grinding and sieving the ground chemical substance raw material gallium oxide to obtain fine powder with the average particle size of 45 mu m;
(4) ultrasonic cleaning of the substrate: silicon plate
The silicon plate with the raw materials placed in the opposite direction is mechanically cleaned by an ultrasonic cleaner:
step 1: washing the mixture in an ultrasonic cleaner for 15 minutes +/-1 minute by using 20 milliliters +/-1 milliliter of acetone, and then taking out and airing the mixture;
step 2: washing the mixture in an ultrasonic cleaner for 15 minutes +/-1 minute by using 20 milliliters +/-1 milliliter of absolute ethyl alcohol, and then taking out and airing the mixture;
and 3, step 3: washing the mixture with 40 ml plus or minus 1 ml of deionized water in an ultrasonic cleaner for 20minutes plus or minus 1 minute, and taking out the mixture;
(5) wash quartz raw materials boat
Washing with 100 ml plus or minus 1 ml of deionized water in an ultrasonic cleaner for 20 minutes plus or minus 1 minute, and taking out;
(6) vacuum drying treatment
Placing the silicon plate and the quartz raw material boat which are washed for three times in a vacuum drying oven, and drying at the drying temperature of 50 +/-3 ℃ for 15 +/-1 min;
(7) placing the raw material gallium oxide fine powder
Placing 1 g +/-0.1 g of fine gallium oxide powder serving as a raw material in a quartz raw material boat, and uniformly paving;
(8) ammoniation reaction product growth
Placing a quartz raw material boat and a silicon plate: opening the tubular high-temperature furnace, placing the quartz raw material boat containing the gallium oxide fine powder in a high-temperature region in the tubular high-temperature furnace, and placing a silicon plate 2cm below the quartz raw material boat along the ammonia gas input direction, namely a low-temperature region in the furnace;
connecting an argon input pipe, an ammonia input pipe and a vacuum pump exhaust pipe into the tubular high-temperature furnace, installing a controller at the upper part of the tubular high-temperature furnace, connecting the controller with an argon electromagnetic valve, an ammonia electromagnetic valve and a vacuum pump electromagnetic valve, and arranging an air outlet in the middle of the right end of the tubular high-temperature furnace;
and (3) extracting air from the tubular high-temperature furnace: closing the air outlet, starting the vacuum pump and the tubular high-temperature furnace controller, pumping out air in the tubular high-temperature furnace to enable the tubular high-temperature furnace to be in an approximate vacuum state, keeping the vacuum degree at 0.1MPa, and controlling by the controller;
heating a tubular high-temperature furnace: starting the tubular high-temperature furnace to heat the furnace, controlling the heating speed by the controller, heating the furnace from the normal temperature of 20 +/-3 ℃ to 950 +/-2 ℃, wherein the heating speed is 7 ℃/min, the heating time is 133 +/-1 min, and the constant-temperature heat preservation time is 70 +/-1 min;
argon Ar as protective gas is input for the first time:
turning off the vacuum pump, turning on the argon gas input tube, argon gas bottle and gas flowmeter, and inputting 4500 cm of inert protective gas argon gas into the furnace3Input speed of 200 cm3A/minute, input time 20 minutes ± 1 minute;when the gas pressure in the furnace reaches 1 x 105When the pressure is Pa (standard atmospheric pressure), the air outlet is opened to naturally adjust the pressure in the furnace and keep the pressure stable;
inputting reaction gas ammonia NH3：
Opening an ammonia gas input pipe, an ammonia gas bottle and a gas flowmeter, and inputting reaction gas ammonia gas 2600 cm into the furnace3Input speed of 70 cm3The input time is 30 minutes +/-1 minute, ammoniation reaction is carried out, the product grows, ammonia gas and gallium oxide fully react, and the reaction formula is as follows:
in the formula: h2-hydrogen
Ga-Ga
N-nitrogen
NH-hydrogenated Nitrogen
And (3) inputting argon Ar as protective gas for the second time:
after the ammoniation reaction, 4500 cm of inert protective gas argon is input again3Input speed of 200 cm3A/minute input time of 20 minutes ± 1 minute;
under the state of 950 +/-2 ℃, gallium nitride grains are generated on a silicon plate in the reaction process of gallium oxide and ammonia gas, the gallium nitride grains continue to grow according to a gas-solid mechanism (VS), and after the gallium nitride fine powder is decomposed, light yellow linear gallium nitride, namely light yellow, solid and linear gallium nitride nanowires are deposited and grown on the silicon plate;
(9) cooling down
Closing the tubular high-temperature furnace, the controller, the vacuum pump, the argon bottle, the ammonia bottle and the gas outlet, cooling the product on the silicon plate to the normal temperature of 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 190 +/-5 min;
(10) collecting the product
After cooling, taking the silicon plate out of the tubular high-temperature furnace, collecting the product on the silicon plate in a colorless transparent glass container, and hermetically storing;
(11) detection, analysis, comparison
Detecting, analyzing and comparing the appearance, structure, components, purity, linear length, diameter, optics, chemistry and physical properties of the prepared light yellow, solid and linear gallium nitride nanowires, carrying out phase analysis on the gallium nitride by using an X-ray diffractometer, carrying out appearance analysis on the gallium nitride nanowires by using a field emission scanning electron microscope, carrying out yield analysis by using a chemical analyzer, and carrying out purity analysis by using an electron dispersion energy spectrum;
(12) packaging and storing
Placing the prepared light yellow, solid and linear gallium nitride nanowire product into a colorless transparent glass container, and hermetically storing the product in a clean and dry environment at the storage temperature of 20 +/-3 ℃ to strictly prevent water, moisture, sun and acid-base corrosion.
The preparation and growth of the high-purity gallium nitride nanowire are carried out in a tubular high-temperature furnace, the growth temperature of the high-temperature ammoniation reaction is 950 +/-2 ℃, the temperature is raised from the normal temperature of 20 +/-3 ℃, the temperature raising speed is 7 ℃/min, the temperature raising time is 133 +/-1 min, the growth time of the constant-temperature heat preservation reaction is 70 +/-1 min, the first time of inputting protective gas argon is 20 +/-1 min, the input argon amount is 4500 cm3Input speed of 200 cm3Per minute; the argon gas as the protective gas is input for the second time20 minutes plus or minus 1 minute, and the input argon amount is 4500 cm3Input speed of 200 cm3Per minute; the amount of ammonia gas input into the reaction gas is 2600 cm3Input speed of 70 cm3A/minute input time of 30 minutes ± 1 minute; cooling to 20 +/-3 deg.C at 5 deg.C/min for 190 +/-5 min.
The ammonification reaction and the product growth are carried out in a tubular high-temperature furnace, the middle of the tubular high-temperature furnace 1 is a high-temperature tube 2, the left end of the high-temperature tube 2 is provided with a cooling first circulating water jacket 21, the right end of the high-temperature tube 2 is provided with a cooling second circulating water jacket 22, the upper part of the first circulating water jacket 21 is a water inlet, the lower part of the first circulating water jacket is a water outlet, and the upper part of the second circulating water jacket 22 is a water inlet and the lower part of; the upper left part of the high-temperature tube 2 is connected with an argon tube 7, the argon tube 7 is connected with an argon bottle 6, the argon bottle 6 is connected with a first electromagnetic valve switch 8, and the first electromagnetic valve switch 8 is connected with a controller 12 through a lead; the left lower part of the high-temperature pipe 2 is connected with an ammonia pipe 10, the ammonia pipe 10 is connected with an ammonia bottle 9, the ammonia bottle 9 is connected with a second electromagnetic valve switch 11, and the second electromagnetic valve switch 11 is connected with a controller 12 through a lead; the right upper part of the high-temperature pipe 2 is connected with an exhaust pipe 4, the exhaust pipe 4 is connected with a vacuum pump 3 at the upper part, the vacuum pump 3 is connected with a third electromagnetic valve switch 5, and the third electromagnetic valve switch 5 is connected with a controller 12 through a lead; the middle part in the high-temperature tube 2 is a high-temperature area 23, a quartz raw material boat 16 is placed, the middle right part in the high-temperature tube 2 is a low-temperature area 19, a silicon plate seat 29 and a silicon plate 17 are placed, raw material gallium oxide fine powder 18 is placed in the quartz raw material boat 16, the distance between the quartz raw material boat 16 and the silicon plate 17 is 2cm, the placing height of the silicon plate 17 is equal to the height of the quartz raw material boat 16, and a gallium nitride product 28 is arranged on the upper part of the silicon plate 17; the middle part of the right end of the tubular high-temperature furnace 1 is provided with an air outlet 20.
Effect
Compared with the prior art, the invention has obvious advancement and is prepared by using gallium oxide Ga2O3Using ammonia NH as raw material3Using inert gas Ar as protective gas, silicon plate as substrate of growth carrier, and anhydrous alcohol CH as reaction gas3CH2OH, acetone CH3COCH3Deionized water H2O is a silicon plate cleaning agent, anddeionized water H2O is quartz raw material boat cleaning agent, no catalyst is used, gallium nitride nano-wires are directly generated on a silicon plate at the high temperature of 950 ℃, ammonia gas and argon gas are always covered in the tubular high-temperature furnace in the ammoniation reaction process, the invasion of harmful gas and substances is effectively prevented, and Ga in the quartz raw material boat after the decomposition of gallium oxide fine powder2The O gas replenishes Ga atoms and Ga to the silicon plate in the input direction of the ammonia gas2O molecule, Ga and Ga are increased2The content of O, argon input, ammonia input, vacuum pump air pumping and temperature rise and heat preservation of the tubular high-temperature furnace are all controlled by a controller, the preparation process flow of the gallium nitride nanowire is simplified, the generation of byproducts is prevented, the purity, the precision and the yield of the product are improved, the light yellow, solid and linear gallium nitride nanowire is finally obtained, the product is neat in appearance, ordered and uniform in arrangement, linear, stable in optical, chemical and physical properties, short in preparation flow, fast in product growth, high in yield which can reach 95%, good in purity which can reach 98.6%, high in linear precision, 5-20nm in diameter and 30-50 mu m in average length of a single wire, and the method is an ideal method for preparing the high-purity light yellow, solid and linear gallium nitride nanowire.
Drawings
FIG. 1 is a flow chart of a process for preparing gallium nitride nanowires
FIG. 2 is a coordinate diagram of the temperature rise, constant temperature and temperature preservation, gas input and cooling of the tubular high-temperature furnace
FIG. 3 is a view showing the overall structure and state of preparation of the tube-type high-temperature furnace
FIG. 4 is a graph of X-ray diffraction intensity coordinates of the product
FIG. 5 is an energy dispersion spectrum of a product gallium nitride nanowire
FIG. 6 is an image of the product nanowire obtained by scanning electron microscopy at 14000 times magnification
FIG. 7 is an 84000 times magnification image of the product nanowire by transmission electron microscope
FIG. 8 is a stripe state diagram of adjacent crystal planes of the product
FIG. 9 is a photoluminescence spectrum of product nanowires
As shown in the figures, the list of reference numbers is as follows:
1. the device comprises a tubular high-temperature furnace, 2 parts of a high-temperature tube, 3 parts of a vacuum pump, 4 parts of an exhaust tube, 5 parts of a third electromagnetic valve switch, 6 parts of an argon bottle, 7 parts of an argon tube, 8 parts of a first electromagnetic valve switch, 9 parts of an ammonia bottle, 10 parts of an ammonia tube, 11 parts of a second electromagnetic valveswitch, 12 parts of a controller, 16 parts of a quartz raw material boat, 17 parts of a silicon plate, 18 parts of gallium oxide fine powder, 19 parts of a low-temperature zone, 20 parts of an air outlet, 21 parts of a first circulating water jacket, 22 parts of a second circulating water jacket, 23 parts of a high-temperature zone, 28 parts of a gallium nitride product and 29 parts of a silicon plate seat.
Detailed description of the preferred embodiments
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows a flow chart of a process for preparing high-purity gallium nitride nanowires, wherein each preparation parameter is strictly controlled and sequentially operated.
The chemical materials of gallium oxide, ammonia gas, argon gas, acetone, absolute ethyl alcohol, deionized water and a silicon plate which are required by preparation are strictly selected, and the purity and the precision are controlled, so that impurities are not involved, and byproducts are prevented from being generated.
The required chemical substances are weighed strictly according to the proportion, the storage and conveying speed of the gas is controlled well, and the quantity value does not exceed the maximum and minimum range so as not to influence the output.
The silicon plate is a growth carrier of a product nanowire and is very important, the surface of the silicon plate is favorable for the reaction of raw material gas on the silicon plate, the silicon plate is strictly cleaned in an ultrasonic cleaner by firstly using acetone, then using absolute ethyl alcohol and finally using deionized water, and the silicon plate is dried in a vacuum drying oven after being cleaned, so that the silicon plate is keptclean and is not polluted.
The quartz raw material boat is a carrier for containing fine gallium oxide raw material powder, is also very important, and is strictly cleaned by deionized water in an ultrasonic cleaner and dried in a vacuum drying oven after cleaning, so that the quartz raw material boat is kept clean and cannot be polluted.
The tubular high-temperature furnace is a furnace body for preparing, ammoniating and growing products, and needs to be strictly sealed, air leakage is avoided, the opening and closing of an air outlet are strictly controlled, otherwise, the growth and reaction processes of the products are directly influenced.
The inert protective gas argon is conveyed for the second time, the ammonia reaction is carried out before and after, the protective atmosphere is provided, the effect of removing other harmful gases is achieved, and the sufficient conveying amount and conveying speed are required.
The reaction gas ammonia is the main chemical substance for ammonification reaction and generation of gallium nitride product, is the main raw material for gas-solid conversion, and must be kept in sufficient total amount, and the ammonia amount will be lost in a trace amount in the reaction process and in the state of opening the vacuum pump and exhausting gas from the gas outlet, so the supplement and storage of the ammonia amount must be sufficient, and the ammonia amount must not be intermittent, and the ammonia amount must be continuously input, so as to ensure the normal operation of ammonification reaction.
Ga at temperatures above 800 ℃2O3Begin to decompose into Ga2O and Ga, NH at above 850 DEG C3The molecule can be gradually decomposed into NH2NH and N, so that the ammoniation reaction is more complete.
Forthe equipment required for preparation: agate mortar, grinding rods, screens, vacuum drying boxes, ultrasonic cleaners, silicon plates, tubular high-temperature furnaces, quartz raw material boats, product bottles, vacuum pumps, argon bottles, ammonia bottles, controllers, detection instruments and the like, and the like are required to be kept clean and free of pollution.
In the process of preparing and generating the high-purity gallium nitride nanowire, the shape of the prepared high-purity gallium nitride nanowire can be slightly changed due to grinding of raw materials, sieving, cleaning of a silicon plate, drying treatment, high-temperature ammoniation reaction, growth of a product, input of protective gas, input of reaction gas, air pumping of a vacuum pump, detection and analysis, but the chemical, optical and physical properties of the gallium nitride nanowire are not influenced, and the application of the gallium nitride nanowire in the field of luminescence is not influenced.
The chemical material proportion for preparing the gallium nitride nano-wire is determined in a preset numerical range and is measured in grams, milliliters and centimeters3As a metering unit, in terms of kilograms, liters and meters during industrial preparation3In measured units, the products are all asNanometer and micrometer are used as measuring units.
FIG. 2 is a diagram showing the relationship between the temperature rise, the constant temperature, the gas input and the cooling of the tubular high-temperature furnace, when the temperature of the tubular high-temperature furnace is raised from 20 +/-3 ℃ to 950 +/-2 ℃, intersecting at the point A, the temperature rise speed is 7 ℃/min, 133 min +/-1 min is needed, the first protective gas argon input time is 20 min +/-1 min, namely an A-B section, the time for inputting reaction gas ammonia is 30 minutes plus or minus 1 minute, namely a B-C section, the time for inputting protective gas argon for the second time is 20 minutes plus or minus 1 minute, namely the C-D section, the time of the high temperature of 950 +/-2 ℃ is the A-D section, the time is 70 minutes, after the preparation is finished, and (3) closing the high-temperature furnace, the vacuum pump, the air outlet, the argon bottle, the ammonia bottle and the controller, and cooling the product along with the furnace at the cooling speed of 5 ℃/min for 190 min +/-5 min.
Fig. 3 shows the overall structure and the preparation state diagram of the tubular high-temperature furnace, the operation of the high-temperature furnace is strictly performed, the operation is performed according to the process sequence, the controller 12 can control the high-temperature furnace 1, the vacuum pump 3, the argon bottle 6, the ammonia bottle 9, the electromagnetic valve switches 5, 8 and 11, the preparation process is controlled by the controller in order, the high-temperature furnace and all connecting parts are firm, the condensation circulating water jackets 21 and 22 are cooling devices of the high-temperature tube 2, a water inlet and a water outlet form flowing water circulation cooling, the silicon plate and the quartz raw material boat are placed stably, the direction is correct, the position is proper, the distance between the silicon plate and the quartz raw material boat is 2cm, and the argon gas and the ammonia gas in the furnace are.
Fig. 4 is a diagram showing X-ray diffraction coordinates of the product, in which the ordinate is a relative intensity index and the abscissa is a 2-fold diffraction angle, and diffraction peaks (100), (002), (101), (102), (110), (103), (112) and (201) in the diagram correspond to diffraction angles of 32.4 °, 34.5 °, 36.8 °, 48.0 °, 57.8 °, 63.6 °, 69.1 ° and 70.6 °, respectively, indicating that the obtained product is a single hexagonal wurtzite GaN crystal.
FIG. 5 is a graph showing an energy dispersion spectrum of a GaN nanowire, in which the nanowire contains only Ga and N, and no other impurity element, and the abscissa of the graph shows an energy value unit keV of 103Electron volts, and the ordinate is the relative intensity index.
FIG. 6 is an image of the product nanowires obtained by scanning electron microscopy at 14000 times magnification, wherein the gallium nitride nanowires are in an interwoven state, and the average length of a single wire is 30-50 μm.
FIG. 7 shows a linear morphology diagram of product nanowire amplified 84000 times by transmission electron microscopy, which shows that the grown nanowire is straight and smooth, and the diameter of the nanowire is 5-20 nm.
Fig. 8 shows an arrangement diagram of adjacent interplanar spacing of the product, wherein the adjacent interplanar spacing is 0.276nm, the adjacent interplanar spacing corresponds to the (100) crystal plane of the nanowire, the arrow in the diagram points to the growth direction, the growth direction is parallel to the (100) crystal plane, and the obtained gallium nitride nanowire product has a hexagonal wurtzite structure.
Fig. 9 shows a photoluminescence spectrum of the product nanowire, where two photoluminescence peaks are visible, the dominant wavelength of the high-intensity one is 365nm, and the dominant wavelength of the low-intensity one is 556nm, and the luminescence peak corresponds to yellow light emission of wurtzite GaN, and there are no other impurity peaks, and the GaN nanowire has high purity and good optical quality.
Example 1
Each preparation device is in a quasi-working state;
accurately weighing 1 g of gallium nitride and 2600 cm of ammonia according to the proportion39000 cm of argon320 ml of acetone, 20 ml of absolute ethyl alcohol and 140 ml of deionized water;
grinding and sieving: repeatedly grinding and sieving gallium oxide to obtain fine powder with a 300-mesh sieve;
ultrasonic cleaning of a silicon plate: 20 ml of acetone, 20 ml of absolute ethyl alcohol and 40 ml of deionized water;
ultrasonically cleaning a quartz raw material boat: 100 ml of deionized water;
and (3) drying treatment: drying the silicon plate and the quartz raw material boat in a drying box at the temperature of 50 +/-3 ℃;
placing raw materials, a silicon plate and a quartz raw material boat: placing the gallium oxide fine powder in a quartz raw material boat, placing the quartz raw material boat in a high-temperature area of a tubular high-temperature furnace, and placing a silicon plate in a low-temperature area;
ammoniation reaction, product growth:
and (3) extracting air from the tubular high-temperature furnace: closing the air outlet, starting the vacuum pump and the controller, pumping out air in the furnace, and keeping the vacuum degree at 0.1 MPa;
heating a tubular high-temperature furnace: heating from the normal temperature of 20 +/-3 ℃ to 950 +/-2 ℃, wherein the heating speed is 7 ℃/min, and the heating time is 133 +/-1 min;
argon gas was fed for the first time: turning off the vacuum pump, opening the gas outlet, turning on the controller, argon bottle, inputting 4500 cm of argon3Input speed of 200 cm3One minute, the input time is 20 minutes plus or minus 1 minute, and the pressure in the furnace is 1X 105Pa, closing the argon bottle after inputting;
inputting reaction gas ammonia: opening an ammonia gas input pipe, an ammonia gas bottle and a controller, and inputting 2600 cm of ammonia gas3Input speed 70 cm3The input time is 30 minutes +/-1 minute per minute, the ammoniation reaction is carried out, and the product grows on a silicon plate;
argon gas is input for the second time: after the ammoniation reaction, 4500 cm of argon is input again3Input speed of 200 cm3A/minute input time of 20 minutes ± 1 minute;
gallium nitride crystal grains are generated on the silicon plate, the gallium nitride crystal grains continue to grow according to a gas-solid (VS) mechanism, and light yellow, solid and linear gallium nitride nanowires are generated through decomposition and deposition;
and (3) cooling: closing the tubular high-temperature furnace, the controller, the vacuum pump, the argon bottle, the ammonia bottle and the gas outlet, cooling the product on the silicon plate to the normal temperature of 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 190 +/-5 min;
collecting a product: and (4) after cooling, collecting the product on the silicon plate in a colorless and transparent glass container, and hermetically storing the product, thereby completing the whole preparation and growth process.
Claims (2)
1. A preparation method of high-purity gallium nitride nanowires is characterized by comprising the following steps: the following chemistry was used: gallium oxide, ammonia gas, hydrogen, acetone, absolute ethyl alcohol and deionized water;
the preparation steps are as follows;
(1) selecting chemicals
The chemical substances are selected and the purity is controlled as follows:
gallium oxide: 99.999 percent
Ammonia gas: 99.999 percent
Argon gas: 99.999 percent
Acetone: 99.5 percent
Anhydrous ethanol: 99.7 percent
Deionized water: 98.8 percent
(2) Selecting and preparing a growth carrier substrate:
taking a silicon plate with the thickness of 10 multiplied by 2mm as a substrate of a growth carrier;
controlling the surface roughness of the glass substrate to ensure that the surface of the glass substrate is flat, smooth and bright and is a mirror surface;
(3) grinding and sieving raw materials
Grinding gallium oxide with agate mortar and grinding rod, sieving with 300 mesh sieve, and repeatedly grinding and sieving to obtain fine powder with average particle size of 45 μm;
(4) ultrasonic cleaning silicon plate
Mechanically cleaning the silicon plate with the raw materials by using an ultrasonic cleaner;
step 1: washing the mixture in an ultrasonic cleaner for 15 minutes +/-1 minute by using 20 milliliters +/-1 milliliter of acetone, and then taking out and airing the mixture;
step 2: washing the mixture in an ultrasonic cleaner for 15 minutes +/-1 minute by using 20 milliliters +/-1 milliliter of absolute ethyl alcohol, and then taking out and airing the mixture;
and 3, step 3: washing the mixture with 40 ml plus or minus 1 ml of deionized water in an ultrasonic cleaner for 20 minutes plus or minus 1 minute, and taking out the mixture;
(5) wash quartz raw materials boat
Washing with 100 ml plus or minus 1 ml of deionized water in an ultrasonic cleaner for 20 minutes plus or minus 1 minute, and taking out;
(6) vacuum drying treatment
Placing the silicon plate and the quartz raw material boat which are washed for three times in a vacuum drying oven, and drying at the drying temperature of 50 +/-3 ℃ for 15 +/-1 min;
(7) placing the raw material gallium oxide fine powder
Putting 1 g +/-0.1 g of gallium oxide fine powder into a quartz raw material boat, and uniformly paving;
(8) ammoniation reaction product growth
Placing a quartz raw material boat and a silicon plate: opening the tubular high-temperature furnace, placing the quartz raw material boat containing the gallium oxide fine powder in a high-temperature region in the tubular high-temperature furnace, and placing a silicon plate 2cm below the quartz raw material boat along the ammonia gas input direction, namely a low-temperature region in the furnace;
connecting an argon input pipe, an ammonia input pipe and a vacuum pump exhaust pipe into the tubular high-temperature furnace, installing a controller at the upper part of the tubular high-temperature furnace, connecting the controller with an argon electromagnetic valve, an ammonia electromagnetic valve and a vacuum pump electromagnetic valve, and arranging an air outlet in the middle of the right end of the tubular high-temperature furnace;
and (3) extracting air from the tubular high-temperature furnace: closing the air outlet, starting the vacuum pump and the tubular high-temperature furnace controller, pumping out air in the tubular high-temperature furnace to enable the tubular high-temperature furnace to be in an approximate vacuum state, keeping the vacuum degree at 0.1MPa, and controlling by the controller;
heating a tubular high-temperature furnace: starting the tubular high-temperature furnace to heat the furnace, and controlling the heating speed by the controller, wherein the temperature is increased from 20 +/-3 ℃ to 950 +/-2 ℃, the heating speed is 7 ℃/min, the heating time is 133 +/-1 min, and the constant-temperature heat preservation time is 70 +/-1 min;
argon as a protective gas is input for the first time:
turning off the vacuum pump, turning on the argon gas input tube, argon gas bottle and gas flowmeter, and inputting 4500 cm of inert protective gas argon gas into the furnace3Input speed of 200 cm3A/minute, input time 20 minutes ± 1 minute; when the gas pressure in the furnace reaches 1 x 105When Pa is needed, the air outlet is opened to naturally adjust the air pressure in the furnace and keep the air pressure stable;
inputting reaction gas ammonia:
opening the ammonia gas input pipe, the ammonia gas bottle and the gas flowmeter, and delivering the ammonia gas into the furnaceReaction gas ammonia gas 2600 cm3Input speed of 70 cm3Performing ammoniation reaction for 30 minutes +/-1 minute per minute, and allowing the product to grow to fully react ammonia gas and gallium oxide;
argon as a protective gas is input for the second time:
after the ammoniation reaction, 4500 cm of inert protective gas argon is input again3Input speed of 200 cm3A/minute input time of 20 minutes ± 1 minute;
(9) cooling down
Closing the tubular high-temperature furnace, the controller, the vacuum pump and the gas outlet, cooling the product on the silicon plate to 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 190 +/-5 min;
(10) collecting the product
After cooling, taking the silicon plate out of the tubular high-temperature furnace, collecting the product on the silicon plate in a colorless transparent glass container, and hermetically storing;
(11) packaging and storing
Placing the prepared light yellow, solid and linear gallium nitride nanowire product into a colorless transparent glass container, and hermetically storing the product in a clean and dry environment at the storage temperature of 20 +/-3 ℃ to strictly prevent water, moisture, sun and acid-base corrosion.
2. The method of preparing high purity gallium nitride nanowires according to claim 1, wherein: the ammonification reaction and the product growth are carried out in a tubular high-temperature furnace, a high-temperature tube (2) is arranged in the middle of the tubular high-temperature furnace (1), a first cooling circulating water jacket (21) is arranged at the left end of the high-temperature tube (2), a second cooling circulating water jacket (22) is arranged at the right end of the high-temperature tube, the upper part of the first circulating water jacket (21) is a water inlet, the lower part of the first circulating water jacket is a water outlet, and the upper part of the second circulating water jacket (22) is a water inlet and the lower; the upper left part of the high-temperature tube (2) is connected with an argon tube (7), the argon tube (7) is connected with an argon bottle (6), the argon bottle (6) is connected with a first electromagnetic valve switch (8), and the first electromagnetic valve switch (8) is connected with a controller (12) through a lead; the left lower part of the high-temperature pipe (2) is connected with an ammonia pipe (10), the ammonia pipe (10) is connected with an ammonia bottle (9), the ammonia bottle (9) is connected with a second electromagnetic valve switch (11), and the second electromagnetic valve switch (11) is connected with a controller (12) through a lead; the right upper part of the high-temperature pipe (2) is connected with an air exhaust pipe (4), the air exhaust pipe (4) is connected with a vacuum pump (3) at the upper part, the vacuum pump (3) is connected with a third electromagnetic valve switch (5), and the third electromagnetic valve switch (5) is connected with a controller (12) through a lead; the middle part in the high-temperature tube (2) is a high-temperature area (23) for placing a quartz raw material boat (16), the middle right part in the high-temperature tube (2) is a low-temperature area (19) for placing a silicon plate seat (29) and a silicon plate (17), raw material gallium oxide fine powder (18) is placed in the quartz raw material boat (16), the distance between the quartz raw material boat (16) and the silicon plate (17) is 2cm, the placing height of the silicon plate (17) is equal to the height of the quartz raw material boat (16), and the upper part of the silicon plate (17) is a gallium nitride product (28); the middle part of the right end of the tubular high-temperature furnace (1) is provided with an air outlet (20).
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| CN102936006A (en) * | 2012-10-24 | 2013-02-20 | 北京工业大学 | Low-cost low-pollution gallium nitride nano-wire preparation generation method |
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| CN102011192B (en) * | 2010-09-21 | 2013-01-02 | 南京航空航天大学 | GaN nanowire array carrying functional groups and making method and application thereof |
| CN103387213B (en) * | 2012-05-09 | 2016-01-06 | 国家纳米科学中心 | A kind of gallium nitride nano-wire and preparation method thereof |
| CN103173738A (en) * | 2013-03-22 | 2013-06-26 | 新疆大学 | Preparation method for GaN nanostructure with adjustable Ga vacancy |
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