Gallium nitride nanotube and preparation method thereof
Technical Field
The invention belongs to the field of preparation of morphology control materials, and particularly relates to a gallium nitride nanotube and a preparation method thereof.
Background
Due to the size and the shape of the one-dimensional nano structure and excellent electric, optical and magnetic properties, the one-dimensional nano structure is widely applied to the fields of optics, electromagnetism, catalysis, biological detection, drug transportation and the like. The direct band gap wide band gap semiconductor gallium nitride (the band gap width is 3.4eV) is a typical representative of the third generation wide band gap semiconductor. Gallium nitride has many excellent characteristics such as large electron mobility, good electric and thermal conductivity, high breakdown field strength, high temperature resistance, corrosion resistance, good radiation resistance and the like. In addition, the material has a great application prospect in ultraviolet and blue light LED devices and ultraviolet detection devices, and is one of the most excellent materials for manufacturing high-power photoelectric devices.
At present, the preparation methods of the gallium nitride nano material are infinite, including chemical vapor deposition, metal organic chemical vapor deposition and pulsed laser deposition, and the preparation methods have the defect that the preparation methods all need higher temperature; the prepared gallium nitride nanometer material has the appearance including a nanometer rod, a nanometer tower, a nanometer wire and the like, but few literature reports about the preparation method of the gallium nitride nanometer tube exist, Jiangshuai and the like in a patent (application publication No. CN 104419982A) mention that the gallium nitride nanometer tube is prepared by a zinc oxide template through a chemical vapor deposition method at high temperature, but the preparation temperature is too high (850-. Therefore, it is very important to find a method for preparing the gallium nitride nanotube at low temperature.
The gallium nitride nanotube not only has the unique photoelectric and physicochemical characteristics of the gallium nitride nanomaterial, but also can be uniquely applied to the fields of photoelectric devices, catalysis, biological detection and the like due to the unique tubular structure. How to find a simple and controllable method for preparing the gallium nitride nanotube is the premise for realizing the application of the gallium nitride nanotube.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a gallium nitride nanotube and a preparation method thereof.
The invention aims to provide a preparation method of a gallium nitride nanotube, which is characterized in that a zinc oxide nanorod is used as a template, then an atomic beam is used for depositing a gallium nitride nanosheet layer, and the template is removed through acid corrosion to prepare the gallium nitride nanotube. The inner diameter, the outer diameter and the length of the gallium nitride nanotube can be controllably prepared by controlling the diameter and the length of the zinc oxide nanorod and the number of turns of gallium nitride deposited by an atomic beam; the method has good repeatability and reliable quality in the process of preparing the gallium nitride nanotube and is easy for large-scale production.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a gallium nitride nanotube, which comprises the following steps:
(1) ultrasonically cleaning the substrate for 10-15min by alcohol and deionized water respectively, drying the substrate by blowing nitrogen, and sputtering a zinc oxide buffer layer with the thickness of 80-120nm on the silicon substrate by adopting a direct-current magnetron sputtering method (the sputtering condition is that the power is 80W, the time is 150-200s, the argon gas is 12sccm, and the pressure is 0.3 Pa);
(2) placing the substrate sputtered with the buffer layer in a reaction kettle filled with reaction solution (70 ml; 0.02-0.03M zinc nitrate, 0.02-0.03M hexamethylenetetramine, and the molar ratio is 1: 1), carrying out hydrothermal reaction at 90-95 ℃ for 5-8h, taking out, washing with deionized water, and drying at 60-80 ℃ for 5-10 min;
(3) and placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer. The precursor is triethyl gallium (99.99 percent) and hydrogen-nitrogen mixed gas (the volume ratio is 1/4), the reaction temperature is 200-300 ℃, the plasma power is 200w, and the cycle times are 300-400. The method comprises the following specific steps: the pulse time of the triethyl gallium is 0.03-0.04s, the reaction time is 10-15s, the cleaning time is 40-60s, the plasma time of the nitrogen-hydrogen mixed gas is 10-20s, the cleaning is carried out for 40-60s again, and the steps are repeated for 400 times.
(4) Dropping a proper amount of prepared dilute sulfuric acid solution (100ml of water +1-3 drops of concentrated sulfuric acid) on the substrate with the zinc oxide/gallium nitride core shell growing thereon by using a liquid transfer gun, reacting for 5-10min, heating the substrate to 50-70 ℃, drying the dilute sulfuric acid solution, repeating for 2-3 times, dropping deionized water to wash impurity ions remained on the surface, and drying at 60-80 ℃.
Further, the substrate in the step (1) is one of a silicon substrate, a silicon dioxide substrate and an aluminum oxide substrate.
Further, the thickness of the zinc oxide in the step (1) is 80-120 nm.
Further, in the mixed solution of zinc nitrate and hexamethylenetetramine in the step (2), the concentration of zinc nitrate is 0.02-0.03M, and the concentration of hexamethylenetetramine is 0.02-0.03M.
Further, in the mixed solution of zinc nitrate and hexamethylenetetramine in the step (2), the molar ratio of zinc nitrate to hexamethylenetetramine is 1: 1.
Further, the temperature of the hydrothermal reaction in the step (2) is 90-95 ℃, the time of the hydrothermal reaction is 5-8h, the drying temperature is 60-80 ℃, and the drying time is 5-10 min.
Further, in the step (3), the reaction temperature for depositing the gallium nitride shell is 200-300 ℃, and the atmosphere for depositing the gallium nitride shell is the mixed atmosphere of hydrogen and nitrogen; the volume ratio of the hydrogen to the nitrogen is 1: 4.
further, in the step (3), the step of depositing the gallium nitride shell layer comprises: the triethyl gallium is pulsed for 0.03-0.04s, the reaction time is 10-15s, the cleaning time is 40-60s, the plasma time of the mixed atmosphere of nitrogen and hydrogen is 10-20s, cleaning is carried out again for 40-60s, and the steps are repeated for 400 times.
Further, the pH value of the dilute sulfuric acid solution in the step (4) is 1.5-4; the standing reaction time is 5-10 min; the temperature for heating and drying is 50-70 ℃.
The invention provides a gallium nitride nanotube prepared by the preparation method.
The preparation method of the gallium nitride nanotube provided by the invention is characterized in that the diameter and the length of the zinc oxide template are regulated and controlled by a hydrothermal method, and the number of atomic beam deposition turns is changed, so that the controllable preparation of the length, the inner diameter and the outer diameter of the gallium nitride nanotube is realized, the repeatability is good, the quality is reliable, and the large-scale preparation of the gallium nitride nanotube material can be realized.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method of the gallium nitride nanotube, the length and the diameter of the nanorod are controlled by a hydrothermal method, so that the controllable preparation of the length and the inner diameter of the gallium nitride nanotube can be realized;
(2) according to the preparation method of the gallium nitride nanotube, the controllable preparation of the wall thickness of the gallium nitride nanotube can be realized through the number of atomic beam deposition layers;
(3) the preparation method of the gallium nitride nanotube provided by the invention can be used for preparing the gallium nitride nanotube at low temperature.
Drawings
FIG. 1 is a schematic diagram of a process for preparing GaN nanotubes according to an embodiment of the invention;
the structure comprises a silicon layer 1, a zinc oxide buffer layer 2, a zinc oxide nanorod 3, a zinc oxide/gallium nitride core shell 4 and a gallium nitride nanotube 5, wherein the zinc oxide/gallium nitride core shell is formed by a silicon nitride layer and a zinc oxide/gallium nitride core shell;
FIG. 2 is a scanning electron micrograph of the zinc oxide nanorods prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of gallium nitride nanotubes prepared in example 1;
FIG. 4 is a scanning electron micrograph of the GaN nanotubes prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
In the embodiment, a specific process schematic diagram for preparing a gallium nitride nanotube can be shown in fig. 1, wherein a silicon layer 1, a zinc oxide buffer layer 2, a zinc oxide nanorod 3, a zinc oxide/gallium nitride core shell 4, and a gallium nitride nanotube 5 are provided.
The atomic beam deposition equipment model is as follows: jiaxing Kemin PEALD-100R.
Example 1
(1) Magnetron sputtering: ultrasonically cleaning a silicon substrate (a silicon layer 1) for 15min by alcohol and deionized water respectively, drying the silicon substrate by using nitrogen, and carrying out magnetron sputtering on the silicon substrate by using a direct-current magnetron sputtering method (the sputtering conditions are that the power is 80W, the time is 150s, the argon flow is 12sccm, and the pressure is 0.3Pa) to form a zinc oxide buffer layer 2 with the thickness of 80 nm;
(2) hydrothermal method: the substrate sputtered with the buffer layer is placed in a reaction kettle filled with reaction solution (70 ml; 0.02M zinc nitrate, 0.02M hexamethylenetetramine), hydrothermal reaction is carried out for 5h at 95 ℃, then the substrate is taken out, washed by deionized water and dried for 5min at 80 ℃ to obtain the zinc oxide nano rod 3, as shown in figure 2, the diameter of the nano rod is relatively uniform and is about 200 nm.
(3) Atomic beam deposition: and (3) placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer to obtain the zinc oxide/gallium nitride core shell 4. The precursor is triethyl gallium (99.99 percent) and hydrogen-nitrogen mixed gas (the volume ratio is 1/4), the reaction temperature is 200 ℃, the plasma power is 200w, and the cycle number is 400 times. The method comprises the following specific steps: the pulse time of the triethyl gallium is 0.03s, the reaction time is 10s, the cleaning time is 40s, the plasma time of the nitrogen-hydrogen mixed gas is 10s, the cleaning is carried out for 40s again, and the steps are repeated for 400 times.
(4) Acid corrosion: and (2) dropping 300 mu l of prepared dilute sulfuric acid solution (100ml of water +3 drops of concentrated sulfuric acid, the pH value is 1.5) on the substrate with the zinc oxide/gallium nitride core shell, reacting for 5min, heating the substrate to 60 ℃, drying the dilute sulfuric acid solution, repeating for 3 times, dropping deionized water to wash residual impurity ions on the surface, and drying at 80 ℃ to obtain the gallium nitride nanotube 5.
FIG. 3 is an x-ray diffraction pattern of the prepared nanotubes, wherein the diffraction peaks can be assigned to the (100), (101), (110) and (112) peaks of gallium nitride (PDF #88-2631), respectively. FIG. 4 shows that the prepared GaN nano material has a tubular structure by scanning electron microscopy, and the inner diameter of the GaN nano material is the diameter of the zinc oxide nano rod and is about 200 nm. In conclusion, the gallium nitride nanotube is successfully and controllably prepared by the method.
Example 2
(1) Ultrasonically cleaning a silicon dioxide substrate for 15min by alcohol and deionized water respectively, drying the silicon dioxide substrate by blowing nitrogen, and sputtering a zinc oxide buffer layer with the thickness of 80nm on the silicon substrate by adopting a direct-current magnetron sputtering method (the sputtering condition is that the power is 80W, the time is 150s, the argon flow is 12sccm, and the pressure is 0.3 Pa);
(2) the substrate sputtered with the buffer layer is placed in a reaction kettle filled with reaction solution (70 ml; 0.02M zinc nitrate, 0.02M hexamethylenetetramine), hydrothermal reaction is carried out for 5h at 95 ℃, then the substrate is taken out, washing is carried out by deionized water, and drying is carried out for 5min at 80 ℃ to obtain the zinc oxide nano-rod, wherein the diameter of the nano-rod is relatively uniform and is about 200 nm.
(3) And placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer. The precursor is triethyl gallium (99.99 percent) and hydrogen-nitrogen mixed gas (the volume ratio is 1/4), the reaction temperature is 200 ℃, the plasma power is 200w, and the cycle number is 400 times. The method comprises the following specific steps: the pulse time of the triethyl gallium is 0.04s, the reaction time is 10s, the cleaning time is 40s, the plasma time of the nitrogen-hydrogen mixed gas is 10s, the cleaning is carried out for 40s again, and the steps are repeated for 400 times.
(4) And (2) dropping 300 mu l of prepared dilute sulfuric acid solution (100ml of water +3 drops of concentrated sulfuric acid, ph-1.5) on the substrate with the zinc oxide/gallium nitride core shell, reacting for 5min, heating the substrate to 60 ℃, drying the dilute sulfuric acid solution, repeating for 3 times, dropping deionized water to wash impurity ions remained on the surface, and drying at 80 ℃ to obtain the gallium nitride nanotube.
Example 3
(1) Ultrasonically cleaning a silicon substrate for 15min by alcohol and deionized water respectively, drying the silicon substrate in a nitrogen atmosphere, and sputtering a zinc oxide buffer layer with the thickness of 80nm on the silicon substrate by a direct-current magnetron sputtering method (the sputtering condition is 80W in power, 150s in time, 12sccm of argon flow and 0.3 Pa);
(2) the substrate sputtered with the buffer layer is placed in a reaction kettle filled with reaction solution (70 ml; 0.02M zinc nitrate, 0.02M hexamethylenetetramine), hydrothermal reaction is carried out for 5h at 95 ℃, then the substrate is taken out, washed by deionized water and dried for 5min at 80 ℃ to obtain the zinc oxide nano rod, as shown in figure 2, the diameter of the nano rod is relatively uniform and is about 200 nm.
(3) And placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer. The precursor is triethyl gallium (99.99 percent) and hydrogen-nitrogen mixed gas (the volume ratio is 1/4), the reaction temperature is 200 ℃, the plasma power is 200w, and the cycle number is 400 times. The method comprises the following specific steps: the pulse time of the triethyl gallium is 0.03s, the reaction time is 10s, the cleaning time is 40s, the plasma time of the nitrogen-hydrogen mixed gas is 10s, the cleaning is carried out for 40s again, and the steps are repeated for 400 times.
(4) And (2) dripping 500 mu l of prepared dilute sulfuric acid solution (100ml of water +3 drops of concentrated sulfuric acid, ph-1.5) on a substrate with a zinc oxide/gallium nitride core shell, reacting for 5min, heating the substrate to 60 ℃, drying the dilute sulfuric acid solution, repeating for 2 times, dripping deionized water to wash residual impurity ions on the surface, and drying at 80 ℃ to obtain the gallium nitride nanotube.
Example 4
(1) Ultrasonically cleaning the silicon substrate by alcohol and deionized water for 15min respectively, drying by nitrogen, and sputtering a zinc oxide buffer layer with the thickness of 80nm on the silicon substrate by a direct-current magnetron sputtering method (the sputtering condition is 80W, the time is 150s, the argon flow is 12sccm, and the pressure is 0.3 Pa);
(2) the substrate sputtered with the buffer layer is placed in a reaction kettle filled with reaction solution (70 ml; 0.02M zinc nitrate, 0.02M hexamethylenetetramine), hydrothermal reaction is carried out for 8h at 95 ℃, then the substrate is taken out, washing is carried out by deionized water, and drying is carried out for 5min at 80 ℃ to obtain the zinc oxide nano-rod, wherein the diameter of the nano-rod is uniform and is about 250 nm.
(3) And placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer. The precursor is triethyl gallium (99.99 percent) and hydrogen-nitrogen mixed gas (the volume ratio is 1/4), the reaction temperature is 200 ℃, the plasma power is 200w, and the cycle number is 400 times. The method comprises the following specific steps: the pulse time of the triethyl gallium is 0.04s, the reaction time is 10s, the cleaning time is 40s, the plasma time of the nitrogen-hydrogen mixed gas is 10s, the cleaning is carried out for 40s again, and the steps are repeated for 400 times.
(4) And (2) dropping 300 mu l of prepared dilute sulfuric acid solution (100ml of water +3 drops of concentrated sulfuric acid, ph-1.5) on the substrate with the zinc oxide/gallium nitride core shell, reacting for 5min, heating the substrate to 60 ℃, drying the dilute sulfuric acid solution, repeating for 3 times, dropping deionized water to wash impurity ions remained on the surface, and drying at 80 ℃ to obtain the gallium nitride nanotube.
The invention is not limited to the atomic beam deposition method in the process of preparing the gallium nitride shell layer, and can also use the methods of metal organic chemical vapor deposition, pulsed laser deposition, magnetron sputtering, chemical vapor deposition and the like.
The invention provides a method for preparing a gallium nitride nanotube. The controllable preparation of the length, the inner diameter and the outer diameter of the gallium nitride nanotube can be realized. Is expected to be applied in the fields of LED, ultraviolet detector, biosensing, catalysis and the like.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.