CN1803627A - Method for preparing inorganic compound gallium nitride nanowire - Google Patents
Method for preparing inorganic compound gallium nitride nanowire Download PDFInfo
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- CN1803627A CN1803627A CN 200510048111 CN200510048111A CN1803627A CN 1803627 A CN1803627 A CN 1803627A CN 200510048111 CN200510048111 CN 200510048111 CN 200510048111 A CN200510048111 A CN 200510048111A CN 1803627 A CN1803627 A CN 1803627A
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Abstract
The disclosed preparation method for gallium nitride nano line comprises: using gallium oxide as material, indium oxide as catalyst, ammonia gas as reaction gas, argon gas as protective atmosphere, anhydrous alcohol as mixture, and all of acetone, anhydrous alcohol and deionized water as abluent for single-crystal silicon substrate; refining the material, controlling proportion and purity; optimizing the usage for catalyst, reaction gas, protective gas and other auxiliary agents; grinding and screening the material, supersonic cleaning the substrate; forming suspension to coat on the substrate; drying, vacuumizing, forcing ammonia gas, ammonifying at high temperature, growing the nano line; cooling, detecting, analyzing, and obtaining the objective product with diameter of 50nm-70nm and average length 90mum and well performance. This invention has short process, high yield of 95%, well purity of 98%, and belongs to ideal method for gallium nitride nano line.
Description
Technical Field
The invention relates to a method for preparing an inorganic compound gallium nitride nanowire, belonging to the technical field of methods for preparing and growing inorganic compounds.
Background
Gallium nitride is a III-V group inorganic compound semiconductor material, the forbidden band width is 3.4eV at room temperature, the exciton confinement energy is 20meV, and the material has the characteristics of excellent mechanical property, high luminous efficiency, high thermal conductivity, high temperature resistance, acid and alkali resistance and the like, is known as a third-generation semiconductor material, is an ideal material for manufacturing blue and green light-emitting diodes, laser diodes, ultraviolet detectors and photoelectric devices, and has wide application prospect in the fields of high-electron-mobility nano electronic devices, full-color panel display and the like.
The preparation and growth methods of the gallium nitride nanowire are divided into two forms, namely a physical method and a chemical method, wherein the physical method comprises a sublimation method, a laser ablation method, a laser deposition method, an evaporation condensation method and an arc discharge method, and the chemical method comprises a direct reaction method, a chemical vapor deposition method, a hot wire chemical vapor deposition method, a solution reaction method, an electrochemical method, a polymerization method, a template method and the like; although the preparation methods can prepare and generate the gallium nitride nanowires, the preparation methods have many defects, and some preparation methods have long preparation period, large energy waste and serious pollution; some products have low yield and low product purity; some depend on the limiting function of the template, the dependence of the growth process on the equipment is strong, and the growth process is difficult to realize; some prepared products have unstable chemical, physical and optical properties, which is not beneficial to the wide application of the products; the process flow of some preparation and growth methods is not strict enough, and the proportion is unreasonable, so that the appearance of the product is not ideal enough.
Disclosure of Invention
Object of the Invention
The invention aims to overcome the defects of the background technology, adopts a brand-new chemical vapor deposition method and preparation parameters, takes gallium oxide as a raw material, indium oxide as a catalyst, ammonia gas as a reaction gas, argon gas as a protective gas, absolute ethyl alcohol as a mixing agent, a monocrystalline silicon piece as a growth carrier, namely a substrate, takes acetone, absolute ethyl alcohol and deionized water as a monocrystalline silicon piece cleaning agent, and adopts grinding, sieving, ultrasonic dispersion of mixed raw material fine powder, ultrasonic cleaning of the substrate, spin coating of a spin coater with mixed turbid liquid, argon protection in a vacuum state, high-temperature ammoniation and growth to prepare uniformly-shaped, white, solid and linear gallium nitride nanowires, so as to simplify the preparation process and improve the yield and purity of products.
Technical scheme
The chemical substances used in the invention are: gallium oxide, indium oxide, acetone, absolute ethyl alcohol, ammonia gas, argon gas and deionized water
The combination ratio is as follows: in grams, milliliters and centimeters3As a unit of measure
Gallium oxide: ga2O30.5 g. + -. 0.0005 g
Indium oxide: in2O30.2 g. + -. 0.0005 g
Acetone: CH (CH)3 COCH 35 ml +/-0.5 ml
Anhydrous ethanol: CH (CH)3CH2OH 15 ml. + -. 0.5 ml
Ammonia gas: NH (NH)32400 cm3Plus or minus 10 cm3
Argon gas: ar 1000 cm3Plus or minus 5 cm3
Deionized water: h2O10 ml +/-1 ml
The preparation and growth method of the invention comprises the following steps:
1) selecting chemicals
The chemical substances required by the mixture ratio are carefully selected, and the purity is controlled as follows:
gallium oxide: 99.99 percent
Indium oxide: 99 percent
Acetone: 99.5 percent
Anhydrous ethanol: 99.7 percent
Ammonia gas: 99.999 percent
Argon gas: 99.999 percent
Deionized water: 99 percent
2) Grinding and sieving
Grinding the chemical substance raw materials gallium oxide and the catalyst indium oxide required by the proportion by using an agate mortar and a grinding rod respectively, then sieving the materials, wherein the mesh number of a screen is 400 meshes, and repeatedly grinding and sieving the materials to form micro powder, and the average particle size of the powder particles is 0.0185 mm;
3) ultrasonic cleaning substrate base plate monocrystalline silicon piece (10mm X1 mm)
Cleaning a monocrystalline silicon wafer containing gallium oxide and indium oxide by using an ultrasonic cleaner, cleaning the monocrystalline silicon wafer in the cleaner for 30 minutes +/-1 minute by using 5 ml +/-0.5 ml of acetone, then taking out the monocrystalline silicon wafer, cleaning the monocrystalline silicon wafer for 30 minutes +/-1 minute by using 5 ml +/-0.5 ml of absolute ethyl alcohol for a second time, and finally cleaning the monocrystalline silicon wafer for 30 minutes +/-1 minute by using 10 ml +/-1 ml of deionized water for three times;
4) vacuum drying treatment
Placing the cleaned monocrystalline silicon wafer in a vacuum drying box for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and thedrying time is 60 +/-2 minutes;
5) ultrasonic dispersive mixing
Weighing 0.2 g +/-0.0005 g of gallium oxide, placing the gallium oxide in a beaker, adding 5 ml +/-0.5 ml of absolute ethyl alcohol into the beaker, placing the beaker in a numerical control ultrasonic cleaner, and ultrasonically dispersing and mixing for 30 minutes +/-1 minute to obtain a uniform gallium oxide absolute ethyl alcohol suspension;
weighing 0.2 g +/-0.0005 g of indium oxide, placing the indium oxide in a beaker, adding 5 ml +/-0.5 ml of absolute ethyl alcohol into the beaker, placing the beaker in a numerical control ultrasonic cleaner, and ultrasonically dispersing and mixing for 30 minutes +/-1 minute to obtain a uniform indium oxide absolute ethyl alcohol suspension;
6) coating gallium oxide anhydrous ethanol suspension
Uniformly spin-coating a gallium oxide anhydrous ethanol suspension on a clean monocrystalline silicon piece by using a spin coater, and spin-coating while rotating the spin coater to uniformly coat the gallium oxide anhydrous ethanol suspension so as to form a layer of white film on the monocrystalline silicon piece by using the suspension;
7) drying treatment
Putting the white film on the monocrystalline silicon piece together with the monocrystalline silicon piece into a vacuum drying oven for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 20 +/-2 minutes;
8) coating indium oxide anhydrous ethanol suspension
Uniformly spin-coating the indium oxide anhydrous ethanol suspension on the white film formed on the monocrystalline silicon wafer by using a spin coater, and then forming a layer of faint yellow film;
9) drying treatment
And (3) putting the faint yellow film on the monocrystalline silicon piece together with the monocrystalline silicon piece into a vacuum drying box for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 20 +/-2 minutes.
10) High temperature ammoniation reaction
Placing the dried monocrystalline silicon wafer and the white film and the light yellow film on the monocrystalline silicon wafer into a quartz product boat, and placing 0.3 g +/-0.0005 g of gallium oxide micro powder in the product boat at a distance of 5mm +/-0.5 mm from the monocrystalline silicon wafer along the ammonia gas input direction;
then, opening the tubular high-temperature furnace, placing the quartz product boat and the reactant in a high-temperature area in the tubular high-temperature furnace, and then connecting an argon input pipe, an ammonia input pipe, an exhaust pipe and a vacuum pump into the tubular high-temperature furnace, wherein strict sealing is required to prevent air leakage;
vacuumizing the tubular high-temperature furnace: starting a vacuum pump, pumping out air in the tubular high-temperature furnace to ensure that the tubular high-temperature furnace is in a vacuum state, keeping the vacuum degree at 0.08Mpa, and continuously pumping vacuum;
starting the tubular high-temperature furnace, heating the tubular high-temperature furnace from the normal temperature of 20 +/-3 ℃ to the temperature of 1000 +/-5 ℃, wherein the heating speed is 8 ℃/min, the heating time is 122 min +/-2 min, and the constant-temperature heat preservation time is 45 min +/-2 min;
inputting protective gas argon Ar: opening the switch of the argon bottle, the gas flow display instrument and the argon input pipe, and inputting inert protective gas argon into the tubularhigh-temperature furnace by 1000 cm3Plus or minus 5 cm3Input speed of 200 cm3A/minute input time of 5 minutes ± 0.5 minutes;
inputting reaction gas ammonia NH3Carrying out ammoniation reaction and product growth: closing an argon input switch, opening an ammonia input switch, controlling flow, and inputting 2400 cm ammonia into the tubular high-temperature furnace3Plus or minus 10 cm3Input speed of 60 cm3And/min, input time is 40 min +/-2 min, gallium oxide and ammonia gas are fully reacted, and the reaction formula is as follows:
in the formula:
H2-Hydrogen gas
Ammonia NH at 1000 +/-5 deg.C during ammoniation reaction3Gradually decompose to obtain hydrogen H2Exist inIn the ammonification reaction system, In is oxidized In as a catalyst2O3By the action of (3), hydrogen H2Adding gallium oxide Ga2O3Reduction to gallium protoxide Ga2O gas, gaseous phase of gallium protoxide Ga2O and ammonia NH3Reacting to generate gallium nitride GaN molecules, depositing the gallium nitride GaN molecules on the surface of the monocrystalline silicon wafer substrate to form gallium nitride GaN crystal nuclei, and continuously growing the gallium nitride crystal nuclei according to a gaseous state-solid state mechanism to finally grow straight and smooth gallium nitride GaN nanowires;
at the temperature of 1000 +/-5 ℃, in the reaction process of gallium oxide and reaction gas ammonia gas, a light yellow film on a monocrystalline silicon piece is changed into a white film, namely white, solid and linear gallium nitride nanowires are generated by reaction;
11) cooling down
Closing the vacuum pump and the tubular high-temperature furnace at the same time, cooling the quartz product boat and the products to the normal temperature of 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 196 min +/-5 min;
12) collecting the product
After cooling, taking the quartz product boat and the product out of the tubular high-temperature furnace, collecting the product on the monocrystalline silicon wafer in a colorless transparent glass bottle, and hermetically storing;
13) detection, analysis, comparison
Detecting, analyzing and comparing the appearance, structure, composition, purity, linear length, diameter, chemical, physical and optical properties of the prepared and grown white, solid and linear gallium nitride nanowires, analyzing the gallium nitride structure by using an X-ray diffractometer, analyzing the appearance of the gallium nitride nanowires by using a field emission scanning electron microscope, analyzing the yield by using a chemical analyzer, and analyzing the purity by using an electron dispersion energy spectrum;
14) storage of
The prepared and grown white, solid and linear gallium nitride nanometer line product is sealed and stored in a colorless and transparent glass container in a dry and clean environment at the storage temperature of 20 +/-3 ℃, and is strictly waterproof, moistureproof, sunscreen and acid-base corrosion resistant.
SaidThe preparation of gallium nitride nano-wire is gallium oxide Ga2O3Indium oxide In as raw material2O3Ascatalyst, ammonia NH3As reaction gas, inert gas Ar is used as protective gas, monocrystalline silicon piece is used as substrate, and absolute ethyl alcohol CH is used3CH2OH as a mixing agent and acetone CH3COCH3Anhydrous ethanol CH3CH2OH, deionized water H2And O is a substrate monocrystalline silicon wafer cleaning agent.
The preparation and growth of the gallium nitride nanowire are carried out in a tubular high-temperature furnace, the high-temperature ammoniation reaction and the growth temperature are 1000 +/-5 ℃, the temperature is raised from the normal temperature of 20 +/-3 ℃, the temperature raising speed is 8 ℃/min, the temperature raising time is 122 +/-2 min, and the constant-temperature heat preservation time is 45 +/-2 min; the time for inputting protective gas argon is 5 minutes plus or minus 0.5 minute, and the quantity of the protective gas argon is 1000 cm3Plus or minus 5 cm3Input speed of 200 cm3Per minute; the reaction gas ammonia gas is input for 40 minutes +/-2 minutes, and the input ammonia gas amount is 2400 cm3Plus or minus 10 cm3Input speed of 60 cm3Per minute; the vacuum degree in the tubular high-temperature furnace is kept at 0.08 MPa.
Effect
Compared with the prior art, the invention has obvious advancement and is prepared by using gallium oxide Ga2O3Indium oxide In as raw material2O3As catalyst, ammonia NH3As reaction gas, inert gas Ar is used as protective gasThe body is prepared from monocrystalline silicon wafer as substrate and absolute ethyl alcohol CH3CH2OH as a mixing agent and acetone CH3COCH3Anhydrous ethanol CH3CH2OH, deionized water H2O is a substrate monocrystalline silicon wafer cleaning agent, reasonable chemical substance proportion is adopted, the selection is carried out, the purity control is carried out, the catalyst, the reaction gas, the protective gas, the mixing agent and the cleaning agent are optimized for use, and the absolute ethyl alcohol turbid liquid is spin-coated by grinding, sieving, ultrasonic cleaning of the substrate, ultrasonic dispersion and mixing of the raw materials, the catalyst and the spin coater, drying treatment, vacuumizing and argon gasProtection, ammonia gas input, high-temperature ammoniation reaction, cooling, detection, analysis and comparison, and finally obtaining the high-purity white, solid and linear gallium nitride nanowires, wherein the product is uniform in shape and arrangement, is linear, has the diameter of 50nm-70nm, has the average length of a single linear shape of 90 mu m, and has stable chemical, optical and physical properties, the preparation and growth method has the advantages of less used equipment, short process flow, high yield of 95 percent, good purity of 98 percent, and is an ideal method for preparing the white, solid and linear gallium nitride nanowires.
Drawings
FIG. 1 is a flow chart of a process for preparing gallium nitride nanowires
FIG. 2 is a coordinate diagram of ammoniation temperature, constant temperature, heat preservation and cooling time
FIG. 3 is a diagram showing the growth state of evacuation, gas protection, reaction gas, and ammonification reaction
FIG. 4 is a graph of X-ray diffraction intensity coordinates of the product
FIG. 5 is an image of the product film obtained by Field Emission Scanning Electron Microscope (FESEM) at 850 times magnification
FIG. 6 is an image of the product film by field emission scanning electron microscope at 5000 times magnification
FIG. 7 is a product topography diagram magnified by 10 ten thousand times by a product field emission scanning electron microscope
FIG. 8 is a graph of spacing between linear adjacent facets of the product
The part numbers shown in the figures are listed below:
1. a tubular high-temperature furnace, 2, a high-temperature zone, 3, a quartz product boat, 4, a monocrystalline silicon substrate, 5, a furnace base, 6, a vacuum pump, 7, a gallium oxide absolute ethyl alcohol film layer, 8, an indium oxide absolute ethyl alcohol film layer, 9, an argon gas input pipe, 10, an ammonia gas input pipe, 11 and gallium oxide powder
Detailed description of the preferred embodiments
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of gallium nitride nanowire process, wherein the preparation of the gallium nitride nanowire is strictly performed according to the flow chart, and each preparation parameter is strictly controlled and sequentially operated.
The chemical materials of gallium oxide, indium oxide, ammonia gas, argon gas, acetone, absolute ethyl alcohol and deionized water required by preparation are strictly selected, and purity control is carried out, so that impurities cannot intervene, and byproducts are prevented from being generated.
The required chemical substances are strictly weighed and controlled according to the proportion, and the gas is well controlled to be stored, conveyed and measured, so that the maximum and minimum ranges are notexceeded, and the output is not influenced.
Cleaning a monocrystalline silicon substrate by using acetone, absolute ethyl alcohol and deionized water, cleaning by using an ultrasonic cleaner, and drying in a vacuum drying oven after cleaning.
The raw materials of gallium oxide and catalyst indium oxide are respectively and repeatedly ground and sieved by an agate mortar and an agate grinding rod, the gallium oxide, the indium oxide and absolute ethyl alcohol are mixed by an ultrasonic cleaner to be respectively in a suspension state, then the suspension is respectively spin-coated on a monocrystalline silicon substrate by a spin coater, when the suspension is spin-coated, the suspension of gallium oxide absolute ethyl alcohol is firstly spin-coated, after vacuum drying, the suspension of indium oxide absolute ethyl alcohol is spin-coated, and the suspension is dried by a vacuum drying oven.
The monocrystalline silicon substrate is a square plate with the thickness of 10mm multiplied by 1mm, is a substrate attaching carrier of a product film, is required to be kept clean, is arranged in a quartz product boat before ammoniation reaction, 0.3 g of gallium oxide is arranged in the position 5mm away from the monocrystalline silicon substrate in the quartz product boat to provide a more sufficient gallium source, and then the product boat, the monocrystalline silicon substrate and 0.3 g of gallium oxide are arranged in a high-temperature area of a tubular high-temperature furnace.
The size of the catalyst indium oxide particles plays an important role in the growth and diameter of the nanowires, so the catalyst indium oxide particles must be strictly ground and sieved, the average particle size of the catalyst indium oxide particles is controlled to be 0.0185mm, and the smaller the particle size, the better the catalyst indium oxide particles.
The protective gas argon can make the tubular high-temperature furnace in the protective atmosphere of inert gas in the conveying process, and has the function of removing other harmful gases.
The ammoniation reaction gas ammonia keeps certain input speed, excessively low can cause the yield to descend, even make the product can not grow, so must strictly control the input speed of ammonia and the sufficiency of ammonia volume, under ammoniation reaction and vacuum pump open state, the ammonia volume has the trace loss, nevertheless can not influence going on of ammoniation reaction, can improve the factor of safety of ammoniation reaction simultaneously.
The tubular high-temperature furnace is a furnace body for ammoniation reaction and growth, and needs to be strictly sealed, so that air leakage is avoided, and the product growth and the whole reaction process are directly influenced.
For the equipment required for preparation: agate mortar, agate grinding rod, cleaning container, mixing container, vacuum drying oven, ultrasonic cleaner, spin coater, monocrystalline silicon wafer, tubular high temperature furnace, product boat, product bottle, vacuum pump, argon pipe, ammonia pipe, detecting instrument, etc. should be kept clean and not polluted.
In the process of preparing and growing the gallium nitride nanowire, due to grinding, sieving, dispersing, mixing and suspending of raw materials and a catalyst, ultrasonic cleaning, spin coating of a spin coater, drying treatment, high-temperature ammoniation, product growth, argon input of protective gas, ammonia input of reaction gas, vacuumizing, ammoniation chemical combination reaction and detection and analysis, the shape of the prepared gallium nitride nanowire can be slightly changed, but the chemical, physical and optical properties of the gallium nitride nanowire are not influenced, and the use of the galliumnitride nanowire in the application field 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 preparation3Is a unit of measurement.
FIG. 2 is a graph showing the relationship between the temperature rise, the constant temperature heat preservation and the cooling of a tubular high temperature furnace, when the temperature of the tubular high temperature furnace is raised from 20 +/-3 ℃ to 1000 +/-5 ℃, the temperature rise is 8 ℃/min, the temperature rise time is 122 +/-2 minutes, the temperature is kept at constant temperature, argon is input as a protective gas for 5 +/-0.5 minutes, namely an A-B section, ammonia as a reaction gas and the product growth time is 40 +/-2 minutes, namely a B-C section, after the temperature is kept at constant temperature, the tubular high temperature furnace is closed, the product in a product boat and the product in the boat are cooled along with the furnace, the cooling speed is 5 ℃/min, and the cooling time is 196 +/-2 minutes.
Fig. 3 is a diagram showing high-temperature ammonification, growth, gas protection and gas reaction states, wherein a tubular high-temperature furnace 1 is arranged on the upper portion of a furnace base 5, a high-temperature area 2 is arranged in the middle of the inside of the tubular high-temperature furnace 1, a quartz product boat 3 is arranged in the high-temperature area 2, a monocrystalline silicon substrate 4 is arranged in the quartz product boat 3, a white gallium oxide film 7 is coated on the upper layer of the monocrystalline silicon substrate 4 in a spinning mode, a light yellow indium oxide film 8 is coated on the gallium oxide film 7 in a spinning mode, gallium oxide powder 11 is arranged onthe left side of the quartz product boat, a vacuum pump 6 is arranged on the right side of the high-temperature furnace 1, an argon gas conveying pipe 9 and an ammonia gas conveying pipe 10 are arranged on the left side of the high-temperature furnace, and during operation, the.
Fig. 4 is a diagram showing the X-ray diffraction intensity coordinates of the product, in which the ordinate is a relative intensity index and the abscissa is a diffraction angle of 2 times, and in the diagram, diffraction peaks at 32.38 °, 34.54 °, 36.83 °, 48.07 °, 57.76 °, 63.40 °, 69.07 °, and 70.49 ° correspond to diffraction peaks at (100), (002), (101), (102), (110), (103), (112), and (201) crystal planes of the gallium nitride crystal, respectively.
FIGS. 5 and 6 are images of a product thin film grown on a silicon single crystal substrate by field emission Scanning Electron Microscope (SEM) magnification of 850 times and 5000 times, respectively, and it can be seen that the white thin film grown on the silicon single crystal substrate is formed by interlacing a plurality of threads and covers the silicon single crystal wafer, and the length unit of FIG. 5 is 10 μm and the length unit of FIG. 6 is 1 μm.
FIG. 7 shows a graph of a product field emission scanning electron microscope with a linear shape and a smooth linear shape, wherein the product field emission scanning electron microscope is magnified by 10 ten thousand times, and it can be seen that the generated gallium nitride nanowire is straight and smooth, the diameter of the nanowire is 50nm-70nm, the average length of a single linear shape is 90 μm, and the length unit in the graph is 100 nm.
Fig. 8 is a diagram showing an arrangement of adjacent lattice spacings of the product, where the adjacent lattice spacing is 0.275nm, and the growth direction of the nanowire and the (100) lattice form an angle of25 ° with respect to the (100) lattice plane of the gallium nitride nanowire, which further proves that the white product generated on the single-crystal silicon substrate is the gallium nitride nanowire with the hexagonal wurtzite structure, and the length unit in the diagram is 5 nm.
Example 1
Each preparation device is in a quasi-working state;
selecting according to the proportion, weighing and measuring 0.5 g of gallium oxide, 0.2 g of indium oxide, 5 ml of acetone, 15 ml of absolute ethyl alcohol and 2400 cm of ammonia gas3Argon gas 1000 cm 310 ml of deionized water;
grinding and sieving: repeatedly grinding gallium oxide and indium oxide, respectively, and sieving into fine powder with a 400-mesh sieve;
ultrasonic cleaning of a monocrystalline silicon substrate: 5 ml of acetone, 5 ml of absolute ethyl alcohol and 10 ml of deionized water are used as cleaning agents, and an ultrasonic cleaner is used for ultrasonic cleaning for 30 minutes respectively;
drying: drying in a vacuum drying oven for 60 minutes +/-2 minutes at the drying temperature of 60 +/-2 ℃;
ultrasonic dispersion and mixing: respectively dispersing and mixing 0.2 g of gallium oxide and 0.2 g of indium oxide in 5 ml of absolute ethyl alcohol, and dispersing for 30 minutes by ultrasonic to obtain gallium oxide absolute ethyl alcohol suspension and indium oxide absolute ethyl alcohol suspension;
spin coating gallium oxide anhydrous ethanol suspension: uniformly spin-coating the gallium oxide anhydrous ethanol suspension on a clean monocrystalline silicon piece by using a spin coater, and spin-coating while rotating the spin coater to uniformly coat the gallium oxide anhydrous ethanol suspension so as to form a layer of white film on the monocrystalline silicon piece;
and (3) drying treatment: putting the white film on the monocrystalline silicon piece together with the monocrystalline silicon piece into a vacuum drying oven for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 20 +/-2 minutes;
spin coating an indium oxide anhydrous ethanol suspension: coating the indium oxide anhydrous ethanol suspension on the white film formed on the monocrystalline silicon wafer by using a spin coater in a spinning mode, and then forming a layer of faint yellow film;
and (3) drying treatment: after spin coating and film forming, putting the monocrystalline silicon substrate and the film on the substrate into a vacuum drying oven, and drying at 60 +/-2 ℃ for 20 +/-2 minutes;
and (3) high-temperature ammonification reaction growth:
placing the product boat, the monocrystalline silicon substrate and the film on the substrate in a tubular high-temperature furnace, starting a vacuum pump to pump vacuum, heating the high-temperature furnace from the normal temperature of 20 +/-3 ℃ to the temperature of 1000 +/-5 ℃, and inputting protective gas argon for 5 minutes+/-0.5 min, input speed of 200 cm3A/min input of 1000 cm3Plus or minus 5 cm3；
Closing the argon switch, inputting reaction gas ammonia gas for 40 minutes +/-2 minutes at the input speed of 60 cm3Keeping the temperature for 40 minutes +/-2 minutes at constant temperature/minute, and inputting ammonia gas of 2400 cm3Plus or minus 10 cm3Growing the product, and carrying out ammoniation chemical combination reaction to generate white gallium nitride nanowires;
and (3) cooling: closing the vacuum pump and the tubular high-temperature furnace, cooling the product boat and the products thereof to the normal temperature of 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 196 min;
collecting a product: collecting the white, solid and linear gallium nitride nanometer line in a colorless transparent glass container, thereby completing the whole preparation process.
Claims (3)
1. A method for preparing inorganic compound gallium nitride nano-wires is characterized in that: the chemical substances used in the invention are: gallium oxide, indium oxide, acetone, absolute ethyl alcohol, ammonia gas, argon gas and deionized water
The combination ratio is as follows: in grams, milliliters and centimeters3As a unit of measure
Gallium oxide: ga2O30.5 g. + -. 0.0005 g
Indium oxide: in2O30.2 g. + -. 0.0005 g
Acetone: CH (CH)3COCH35 ml +/-0.5 ml
Anhydrous ethanol: CH (CH)3CH2OH 15 ml. + -. 0.5 ml
Ammonia gas: NH (NH)32400 cm3Plus or minus 10 cm3
Argon gas: ar 1000 cm3Plus or minus 5 cm3
Deionized water: h2O10 ml +/-1 ml
The preparation and growth method of the invention comprises the following steps:
1) selecting chemicals
The chemical substances required by the mixture ratio are carefully selected, and the purity is controlled as follows:
gallium oxide: 99.99 percent
Indium oxide: 99 percent
Acetone: 99.5 percent
Anhydrous ethanol: 99.7 percent
Ammonia gas: 99.999 percent
Argon gas: 99.999 percent
Deionized water: 99 percent
2) Grinding and sieving
Grinding the chemical substance raw materials gallium oxide and the catalyst indium oxide required by the proportion by using an agate mortar and a grinding rod respectively, then sieving the materials, wherein the mesh number of a screen is 400 meshes, and repeatedly grinding and sieving the materials to form micro powder, and the average particle size of the powder particles is 0.0185 mm;
3) ultrasonic cleaning substrate base plate monocrystalline silicon piece (10mm X1 mm)
Cleaning a monocrystalline silicon wafer containing gallium oxide and indium oxide by using an ultrasonic cleaner, cleaning the monocrystalline silicon wafer in the cleaner for 30 minutes +/-1 minute by using 5 ml +/-0.5 ml of acetone, then taking out the monocrystalline silicon wafer, cleaning the monocrystalline silicon wafer for 30 minutes +/-1 minute by using 5 ml +/-0.5 ml of absolute ethyl alcohol for a second time, and finally cleaning the monocrystalline silicon wafer for 30 minutes +/-1 minute by using 10 ml +/-1 ml of deionized water for three times;
4) vacuum drying treatment
Placing the cleaned monocrystalline silicon wafer in a vacuum drying box for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 60 +/-2 minutes;
5) ultrasonic dispersive mixing
Weighing 0.2 g +/-0.0005 g of gallium oxide, placing the gallium oxide in a beaker, adding 5 ml +/-0.5 ml of absolute ethylalcohol into the beaker, placing the beaker in a numerical control ultrasonic cleaner, and ultrasonically dispersing and mixing for 30 minutes +/-1 minute to obtain a uniform gallium oxide absolute ethyl alcohol suspension;
weighing 0.2 g +/-0.0005 g of indium oxide, placing the indium oxide in a beaker, adding 5 ml +/-0.5 ml of absolute ethyl alcohol into the beaker, placing the beaker in a numerical control ultrasonic cleaner, and ultrasonically dispersing and mixing for 30 minutes +/-1 minute to obtain a uniform indium oxide absolute ethyl alcohol suspension;
6) coating gallium oxide anhydrous ethanol suspension
Uniformly spin-coating a gallium oxide anhydrous ethanol suspension on a clean monocrystalline silicon piece by using a spin coater, and spin-coating while rotating the spin coater to uniformly coat the gallium oxide anhydrous ethanol suspension so as to form a layer of white film on the monocrystalline silicon piece by using the suspension;
7) drying treatment
Putting the white film on the monocrystalline silicon piece together with the monocrystalline silicon piece into a vacuum drying oven for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 20 +/-2 minutes;
8) coating indium oxide anhydrous ethanol suspension
Uniformly spin-coating the indium oxide anhydrous ethanol suspension on the white film formed on the monocrystalline silicon wafer by using a spin coater, and then forming a layer of faint yellow film;
9) drying treatment
And (3) putting the faint yellow film on the monocrystalline silicon piece together with the monocrystalline silicon piece into a vacuum drying box for drying treatment, wherein the drying temperature is 60 +/-2 ℃, and the drying time is 20 +/-2 minutes.
10) High temperature ammoniation reaction
Placing the dried monocrystalline silicon wafer and the white film and the light yellow film on the monocrystalline silicon wafer into a quartz product boat, and placing 0.3 g +/-0.0005 g of gallium oxide micro powder in the product boat at a distance of 5mm +/-0.5 mm from the monocrystalline silicon wafer along the ammonia gas input direction;
then, opening the tubular high-temperature furnace, placing the quartz product boat and the reactant in a high-temperature area in the tubular high-temperature furnace, and then connecting an argon input pipe, an ammonia input pipe, an exhaust pipe and a vacuum pump into the tubular high-temperature furnace, wherein strict sealing is required to prevent air leakage;
vacuumizing the tubular high-temperature furnace: starting a vacuum pump, pumping out air in the tubular high-temperature furnace to ensure that the tubular high-temperature furnace is in a vacuum state, keeping the vacuum degree at 0.08Mpa, and continuously pumping vacuum;
starting the tubular high-temperature furnace, heating the tubular high-temperature furnace from the normal temperature of 20 +/-3 ℃ to the temperature of 1000 +/-5 ℃, wherein the heating speed is 8 ℃/min, the heating time is 122 min +/-2 min, and the constant-temperature heat preservation time is 45 min +/-2 min;
inputting protective gas argon Ar: opening the switch of the argon bottle, the gas flow display instrument and the argon input pipe, and inputting inert protective gas argon into the tubular high-temperature furnace by 1000 cm3Plus or minus 5 cm3Input speed of 200 cm3A/minute input time of 5 minutes ± 0.5 minutes;
inputting reaction gas ammonia NH3Carrying out ammoniation reactionand product growth: closing an argon input switch, opening an ammonia input switch, controlling flow, and inputting 2400 cm ammonia into the tubular high-temperature furnace3Plus or minus 10 cm3Input speed of 60 cm3And/min, input time is 40 min +/-2 min, gallium oxide and ammonia gas are fully reacted, and the reaction formula is as follows:
in the formula:
H2- -hydrogen gas
Ammonia NH at 1000 +/-5 deg.C during ammoniation reaction3Gradually decompose to obtain hydrogen H2In the presence of a catalyst In an ammoniation reaction system2O3By the action of (3), hydrogen H2Adding gallium oxide Ga2O3Reduction to gallium protoxide Ga2O gas, gaseous phase of gallium protoxide Ga2O and ammonia NH3Reacting to generate GaN molecules of gallium nitride, depositing on the single crystalForming gallium nitride GaN crystal nucleuses on the surface of the crystal silicon wafer substrate, and continuously growing the gallium nitride crystal nucleuses according to a gas-solid mechanism to finally grow straight and smooth gallium nitride GaN nanowires;
at the temperature of 1000 +/-5 ℃, in the reaction process of gallium oxide and reaction gas ammonia gas, a light yellow film on a monocrystalline silicon piece is changed into a white film, namely white, solid and linear gallium nitride nanowires are generated by reaction;
11) cooling down
Closing the vacuum pump and the tubular high-temperature furnace at the same time, cooling the quartz product boat and the products to the normal temperature of 20 +/-3 ℃ along with the furnace, wherein the cooling speed is 5 ℃/min, and the cooling time is 196 min +/-5 min;
12) collecting the product
After cooling, taking the quartz product boat and the product out of the tubular high-temperature furnace, collecting the product on the monocrystalline silicon wafer in a colorless transparent glass bottle, and hermetically storing;
13) detection, analysis, comparison
Detecting, analyzing and comparing the appearance, structure, composition, purity, linear length, diameter, chemical, physical and optical properties of the prepared and grown white, solid and linear gallium nitride nanowires, analyzing the gallium nitride structure by using an X-ray diffractometer, analyzing the appearance of the gallium nitride nanowires by using a field emission scanning electron microscope, analyzing the yield by using a chemical analyzer, and analyzing the purity by using an electron dispersion energy spectrum;
14) storage of
The prepared and grown white, solid and linear gallium nitride nanometer line product is sealed and stored in a colorless and transparent glass container in a dry and clean environment at the storage temperature of 20 +/-3 ℃, and is strictly waterproof, moistureproof, sunscreen and acid-base corrosion resistant.
2. The method for preparing nanowires of inorganic compound gallium nitride as claimed in claim 1, wherein: the preparation of the gallium nitride nano-wire is gallium oxide Ga2O3Indium oxide In as raw material2O3As catalyst, ammonia NH3As reaction gas, inert gas Ar is used as protective gas, monocrystalline silicon piece is used as substrate, and absolute ethyl alcohol CH is used3CH2OH as a mixing agent and acetone CH3COCH3Anhydrous ethanol CH3CH2OH, deionized water H2And O is a substrate monocrystalline silicon wafer cleaning agent.
3. The method for preparing nanowires of inorganic compound gallium nitride as claimed in claim 1, wherein: the preparation and growth of the gallium nitride nanowire are carried out in a tubular high-temperature furnace, the high-temperature ammoniation reaction and the growth temperature are 1000 +/-5 ℃, the temperature is raised from the normal temperature of 20 +/-3 ℃, the temperature raising speed is 8 ℃/min, the temperature raising time is 122 +/-2 min, and the constant-temperature heat preservation time is 45 +/-2 min; the time for inputting protective gas argon is 5 minutes plus or minus 0.5 minute, and the quantity of the protective gas argon is 1000 cm3Plus or minus 5 cm3Input speed of 200 cm3Per minute; the reaction gas ammonia gas is input for 40 minutes +/-2 minutes, and the input ammonia gas amount is 2400 cm3Plus or minus 10 cm3Input speed of 60 cm3Per minute; the vacuum degree in the tubular high-temperature furnace is kept at 0.08 MPa.
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