CN111204719A - Gallium nitride nanotube and preparation method thereof - Google Patents
Gallium nitride nanotube and preparation method thereof Download PDFInfo
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 75
- 239000002071 nanotube Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 239000011787 zinc oxide Substances 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002073 nanorod Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 238000004544 sputter deposition Methods 0.000 claims abstract description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 28
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 28
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000004140 cleaning Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 14
- 239000011258 core-shell material Substances 0.000 claims description 13
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0632—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with gallium, indium or thallium
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention discloses a gallium nitride nanotube and a preparation method thereof, belonging to the field of preparation of morphology control materials. The method comprises the following steps: (1) performing surface pretreatment on the substrate, and sputtering a zinc oxide buffer layer on the surface of the substrate by adopting a direct-current magnetron sputtering method; (2) and (3) placing the substrate in a reaction kettle filled with a reaction solution, and carrying out hydrothermal reaction to generate the zinc oxide nanorod. (3) And placing the substrate with the zinc oxide nanorods in an atomic beam deposition cavity to deposit a gallium nitride shell layer. (4) And (3) measuring a proper amount of prepared sulfuric acid solution by using a liquid transfer gun and dropping the sulfuric acid solution on the substrate with the zinc oxide/gallium nitride nuclear shell layer, so that the sulfuric acid solution fully corrodes the zinc oxide nano rod, and finally, the gallium nitride nano tube is left on the substrate. The invention realizes the controllable preparation of the gallium nitride nanotube, and the preparation method is simple, good in repeatability and reliable in quality.
Description
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.
Claims (10)
1. A preparation method of a gallium nitride nanotube is characterized by comprising the following steps:
(1) cleaning and drying the substrate, and sputtering a layer of zinc oxide on the substrate by a direct current magnetron sputtering method to obtain the substrate with the buffer layer;
(2) soaking the substrate with the buffer layer in the step (1) in a mixed solution of zinc nitrate and hexamethylenetetramine, then heating to perform hydrothermal reaction, washing and drying to obtain a substrate with zinc oxide nanorods;
(3) putting the substrate with the zinc oxide nanorods grown in the step (2) in an atomic beam deposition cavity to deposit a gallium nitride shell layer to obtain a substrate with a zinc oxide/gallium nitride core shell;
(4) and dropwise adding a dilute sulfuric acid solution on the substrate with the zinc oxide/gallium nitride core shell, soaking the surface of the zinc oxide/gallium nitride core shell substrate with the dilute sulfuric acid solution, standing for reaction, heating and drying, repeating for 2-3 times, washing and drying to obtain the gallium nitride nanotube.
2. The method for preparing gallium nitride nanotubes according to claim 1, wherein the substrate of step (1) is one of a silicon substrate, a silicon dioxide substrate, and an aluminum oxide substrate.
3. The method for preparing gallium nitride nanotubes according to claim 1, wherein the thickness of the zinc oxide in step (1) is 80-120 nm.
4. The method of claim 1, wherein in the mixed solution of zinc nitrate and hexamethylenetetramine in step (2), the concentration of zinc nitrate is 0.02-0.03M, and the concentration of hexamethylenetetramine is 0.02-0.03M.
5. The method of claim 4, wherein the molar ratio of zinc nitrate to hexamethylenetetramine in the mixed solution of zinc nitrate and hexamethylenetetramine in step (2) is 1: 1.
6. The method for preparing gallium nitride nanotubes according to claim 1, wherein the temperature of the hydrothermal reaction in step (2) is 90-95 ℃, the time of the hydrothermal reaction is 5-8h, the temperature of drying is 60-80 ℃, and the time of drying is 5-10 min.
7. The method for preparing GaN nanotubes according to claim 1, wherein in step (3), the reaction temperature for depositing the GaN shell is 200-300 ℃, and the atmosphere for depositing the GaN shell is a mixed atmosphere of hydrogen and nitrogen; the volume ratio of the hydrogen to the nitrogen is 1: 4.
8. the method for preparing gallium nitride nanotubes according to claim 1, wherein in 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.
9. The method for preparing gallium nitride nanotubes according to claim 1, wherein the dilute sulfuric acid solution of step (4) has a pH of 1.5 to 4; the standing reaction time is 5-10 min; the temperature for heating and drying is 50-70 ℃.
10. A gallium nitride nanotube produced by the production method according to any one of claims 1 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040175844A1 (en) * | 2002-12-09 | 2004-09-09 | The Regents Of The University Of California | Sacrificial template method of fabricating a nanotube |
| KR20040092583A (en) * | 2003-04-24 | 2004-11-04 | 학교법인 포항공과대학교 | Core-removed nano structure and preparation thereof |
| TW200832853A (en) * | 2007-01-19 | 2008-08-01 | Univ Nat Changhua Education | Method for manufacturing cleaved facets of nitride semiconductor devices |
| CN101247022A (en) * | 2007-02-14 | 2008-08-20 | 陈伟立 | Method for producing split crack mirror face of gallium nitride semiconductor component |
| CN102616730A (en) * | 2011-02-01 | 2012-08-01 | 成功大学 | Manufacturing method of hollow nanotube structure |
| CN103219434A (en) * | 2012-01-18 | 2013-07-24 | 陈敏璋 | Composite substrate, manufacturing method thereof and light emitting component |
| TW201443255A (en) * | 2013-05-13 | 2014-11-16 | Univ Nat Taiwan | Method for producing gallium nitride |
| CN104419982A (en) * | 2013-09-05 | 2015-03-18 | 国家纳米科学中心 | Inner-diameter-controllable porous mono-crystalline gallium nitride micro/nano-tube array and preparation method thereof |
| WO2018115419A1 (en) * | 2016-12-23 | 2018-06-28 | Solvay Sa | Hollow composite, method of preparing the same, and electrocatalyst including the same |
| CN108701710A (en) * | 2016-02-29 | 2018-10-23 | 三星显示有限公司 | The nanometer rods for manufacturing the method for nanometer rods and being manufactured by this method |
-
2020
- 2020-02-29 CN CN202010133005.7A patent/CN111204719A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040175844A1 (en) * | 2002-12-09 | 2004-09-09 | The Regents Of The University Of California | Sacrificial template method of fabricating a nanotube |
| KR20040092583A (en) * | 2003-04-24 | 2004-11-04 | 학교법인 포항공과대학교 | Core-removed nano structure and preparation thereof |
| TW200832853A (en) * | 2007-01-19 | 2008-08-01 | Univ Nat Changhua Education | Method for manufacturing cleaved facets of nitride semiconductor devices |
| CN101247022A (en) * | 2007-02-14 | 2008-08-20 | 陈伟立 | Method for producing split crack mirror face of gallium nitride semiconductor component |
| CN102616730A (en) * | 2011-02-01 | 2012-08-01 | 成功大学 | Manufacturing method of hollow nanotube structure |
| CN103219434A (en) * | 2012-01-18 | 2013-07-24 | 陈敏璋 | Composite substrate, manufacturing method thereof and light emitting component |
| TW201443255A (en) * | 2013-05-13 | 2014-11-16 | Univ Nat Taiwan | Method for producing gallium nitride |
| CN104419982A (en) * | 2013-09-05 | 2015-03-18 | 国家纳米科学中心 | Inner-diameter-controllable porous mono-crystalline gallium nitride micro/nano-tube array and preparation method thereof |
| CN108701710A (en) * | 2016-02-29 | 2018-10-23 | 三星显示有限公司 | The nanometer rods for manufacturing the method for nanometer rods and being manufactured by this method |
| WO2018115419A1 (en) * | 2016-12-23 | 2018-06-28 | Solvay Sa | Hollow composite, method of preparing the same, and electrocatalyst including the same |
Non-Patent Citations (1)
| Title |
|---|
| 蔡珣等: "《现代薄膜材料与技术》", 30 September 2007 * |
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