阅读说明：本技术 一种氧化镓纳米线及其制备方法和应用 (Gallium oxide nanowire and preparation method and application thereof ) 是由 马淑芳 刘松 黄鑫 许并社 黄彪 李磊 徐超明 欧阳辉灿 于 2021-08-17 设计创作，主要内容包括：本发明公开了一种以砷化镓为镓源用CVD法生成氧化镓纳米线及其制备方法和应用,涉及半导体材料技术领域。该制备方法,包括以下步骤：向硅衬底上制备金纳米颗粒；将砷化镓粉体及所述硅衬底相隔置于单开口的耐高温管体内,随后将所述管体置于管式炉中,并将所述管体的开口端朝向所述管式炉的出气口,在真空条件下,通入氢气和惰性气体的混合气体后,进行加热,即在所述硅衬底上制得所述氧化镓纳米线。本发明采用砷化镓为镓源,用单温区管式炉烧制氧化镓纳米线,只需通入一种氢氩混合气,且真空度只需维持在500Pa左右,制备出的氧化镓纳米线表面光滑,纳米线长径比均匀且操作简单,可重复性高。(The invention discloses a gallium oxide nanowire generated by a CVD method by taking gallium arsenide as a gallium source and a preparation method and application thereof, relating to the technical field of semiconductor materials. The preparation method comprises the following steps: preparing gold nanoparticles on a silicon substrate; and (2) placing gallium arsenide powder and the silicon substrate in a single-opening high-temperature-resistant tube body at intervals, then placing the tube body in a tube furnace, enabling the opening end of the tube body to face an air outlet of the tube furnace, introducing mixed gas of hydrogen and inert gas under a vacuum condition, and then heating to obtain the gallium oxide nanowires on the silicon substrate. According to the invention, gallium arsenide is used as a gallium source, the gallium oxide nanowire is fired by the single-temperature-zone tube furnace, only one hydrogen-argon mixed gas needs to be introduced, the vacuum degree only needs to be maintained at about 500Pa, the surface of the prepared gallium oxide nanowire is smooth, the length-diameter ratio of the nanowire is uniform, the operation is simple, and the repeatability is high.)

1. A preparation method of gallium oxide nanowires is characterized by comprising the following steps:

preparing gold nanoparticles on a silicon substrate;

the gallium arsenide powder and the silicon substrate are arranged in a single-opening high-temperature resistant tube body at intervals,

the silicon substrate is arranged on one side close to the opening of the tube body, and the side, which is covered with the gold nanoparticles, of the silicon substrate is obliquely arranged towards the gallium arsenide powder;

then placing the tube body in a tube furnace, leading the opening end of the tube body to face an air outlet of the tube furnace, heating after introducing mixed gas of hydrogen and inert gas under the vacuum condition,

when the temperature of the position, located in the tubular furnace, of the gallium arsenide powder is 800-900 ℃ and the temperature of the position, located in the silicon substrate, of the tubular furnace is 550-650 ℃, preserving the heat for 1-1.5 hours, and then preparing the gallium oxide nanowires on the silicon substrate; and adjusting the distance between the silicon substrate and the gallium arsenide powder in the tube body in advance according to the temperatures of different areas in the inner cavity of the tube furnace.

2. The method for preparing gallium oxide nanowires of claim 1, wherein the diameter of the gold nanoparticles is 20 to 100 nm.

3. The method according to claim 1, wherein the hydrogen gas is 5 to 10% by volume of the mixed gas.

4. The method for preparing gallium oxide nanowires of claim 3, wherein the flow rate of the mixed gas is 30 to 60 sccm.

5. The method for preparing gallium oxide nanowires of claim 1, wherein the tube furnace is a single temperature zone tube furnace; the pipe body is positioned at the position where the gallium arsenide powder is placed and is arranged at the middle heat source of the tube furnace.

6. The method for preparing gallium oxide nanowires of claim 5, wherein the distance between the silicon substrate and the gallium arsenide powder in the tube body is adjusted in advance according to the temperatures of different regions of the inner cavity of the tube furnace, and specifically the method comprises the following steps:

s1, empty burning the tube furnace, and measuring a temperature distribution curve from a middle heat source area of the tube furnace to a furnace mouth by using a metal thermometer when the temperature of the middle heat source of the tube furnace is 800-900 ℃;

s2, determining the distance from the intermediate heat source to the area with the temperature of 550-650 ℃ between the furnace mouth and the intermediate heat source through a temperature distribution curve;

and S3, adjusting the placement distance between the silicon substrate and the gallium arsenide powder in the tube body according to the distance determined in the step S2.

7. The method of preparing gallium oxide nanowires of claim 1, wherein the preparation of gold nanoparticles onto a silicon substrate is performed by the following steps:

plating a gold nano-film on a silicon chip by using a vacuum coating instrument, then annealing the silicon chip plated with the gold nano-film for 8-12 min at the temperature of 450-550 ℃ under the vacuum condition, and naturally cooling to room temperature to obtain the gold nano-particles prepared on the silicon substrate.

8. The method for preparing gallium oxide nanowires according to claim 1, wherein the silicon substrate is inclined from the side coated with the gold nanoparticles to the gallium arsenide powder by an angle of 10 to 20 °.

9. The gallium oxide nanowire prepared by the preparation method according to any one of claims 1 to 8, wherein the diameter of the cross section of the gallium oxide nanowire is 50 to 150 nm.

10. Use of the gallium oxide nanowires of claim 9 in the preparation of a semiconductor.

Technical Field

The invention relates to the technical field of semiconductor materials, in particular to a gallium oxide nanowire generated by a CVD method by taking gallium arsenide as a gallium source and a preparation method and application thereof.

Background

With the arrival of the big data age, the application range and the demand of semiconductor materials are increased year by year, wherein the wide-bandgap semiconductor materials play an important role in the aspects of high-power semiconductor devices, ultraviolet detection and ultraviolet communication. Gallium oxide is taken as a wide bandgap semiconductor material with the bandgap width perfectly matched with the photon energy of the deep ultraviolet band, and is a key object of research of people at present. The research on the gallium oxide nanowire is helpful for deeply researching the basic problems of the internal carrier concentration of the gallium oxide material, the carrier service life, the carrier migration mechanism, the gallium oxide doping and the like. The current preparation methods of gallium oxide nanowires mainly include metal chemical vapor deposition, liquid phase methods, chemical vapor deposition methods, and the like. The equipment for preparing the gallium oxide nanometer by the metal chemical vapor deposition method is expensive and is difficult to bear by common mechanisms. The gallium oxide nanowires prepared by the liquid phase method have poor morphology and can introduce impurities. The chemical vapor method for preparing gallium oxide mainly uses a radio frequency magnetron sputtering system, and the prepared nanowire is impure, and the process is complex and has poor repeatability. The gallium oxide nanowires prepared by the tube furnace mostly use metal gallium or gallium oxide as a gallium source, the preparation process is complex, oxygen needs to be introduced, and strict requirements are provided for the amount of the introduced oxygen and the vacuum degree in the firing process.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and provides gallium oxide (Ga)₂O₃) Nanowires and a preparation method and application thereof. According to the invention, gallium arsenide is used as a gallium source, the gallium oxide nanowire is fired by the single-temperature-zone tube furnace, only one hydrogen-argon mixed gas needs to be introduced, the vacuum degree only needs to be maintained at about 500Pa, the surface of the prepared gallium oxide nanowire is smooth, the length-diameter ratio of the nanowire is uniform, the operation is simple, and the repeatability is high.

The invention aims to provide a preparation method of a gallium oxide nanowire, which comprises the following steps:

preparing gold nanoparticles on a silicon substrate;

the gallium arsenide powder and the silicon substrate are arranged in a single-opening high-temperature resistant tube body at intervals,

the silicon substrate is arranged on one side close to the opening of the tube body, and the side, which is covered with the gold nanoparticles, of the silicon substrate is obliquely arranged towards the gallium arsenide powder;

then placing the tube body in a tube furnace, leading the opening end of the tube body to face an air outlet of the tube furnace, heating after introducing mixed gas of hydrogen and inert gas under the vacuum condition,

when the temperature of the position, located in the tubular furnace, of the gallium arsenide powder is 800-900 ℃ and the temperature of the position, located in the silicon substrate, of the tubular furnace is 550-650 ℃, preserving the heat for 1-1.5 hours, and then preparing the gallium oxide nanowires on the silicon substrate; and adjusting the distance between the silicon substrate and the gallium arsenide powder in the tube body in advance according to the temperatures of different areas in the inner cavity of the tube furnace.

Preferably, the diameter of the gold nanoparticle is 20-100 nm.

Preferably, the hydrogen gas accounts for 5-10% of the volume of the mixed gas.

More preferably, the flow rate of the mixed gas is 30 to 60 sccm.

Preferably, the tube furnace is a single-temperature-zone tube furnace; the pipe body is positioned at the position where the gallium arsenide powder is placed and is arranged at the middle heat source of the tube furnace.

More preferably, the distance between the silicon substrate and the gallium arsenide powder in the tube body is adjusted in advance according to the temperatures of different areas in the inner cavity of the tube furnace, specifically according to the following steps:

s1, empty burning the tube furnace, and measuring a temperature distribution curve from a middle heat source area of the tube furnace to a furnace mouth by using a metal thermometer when the temperature of the middle heat source of the tube furnace is 800-900 ℃;

s2, determining the distance from the intermediate heat source to the area with the temperature of 550-650 ℃ between the furnace mouth and the intermediate heat source through a temperature distribution curve;

and S3, adjusting the placement distance between the silicon substrate and the gallium arsenide powder in the tube body according to the distance determined in the step S2.

Preferably, the preparation of gold nanoparticles onto a silicon substrate is carried out according to the following steps:

plating a gold nano-film on a silicon chip by using a vacuum coating instrument, then annealing the silicon chip plated with the gold nano-film for 8-12 min at the temperature of 450-550 ℃ under the vacuum condition, and naturally cooling to room temperature to obtain the gold nano-particles prepared on the silicon substrate.

Preferably, the inclination angle of the side of the silicon substrate, which is covered with the gold nanoparticles, to the gallium arsenide powder is set to be 10-20 degrees.

The second purpose of the invention is to provide a gallium oxide nanowire, wherein the cross-sectional diameter of the gallium oxide nanowire is 50-150 nm.

The third purpose of the invention is to provide an application of the gallium oxide nanowire in preparing semiconductors.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, gallium arsenide is used as a gallium source, the gallium oxide nanowire is fired by the single-temperature-zone tube furnace, only one hydrogen-argon mixed gas needs to be introduced, the vacuum degree only needs to be maintained at about 500Pa, the surface of the prepared gallium oxide nanowire is smooth, the length-diameter ratio of the nanowire is uniform, the operation is simple, and the repeatability is high.

Drawings

FIG. 1 is a graph (A) showing the temperature distribution of the intermediate heat source zone from the furnace mouth in the tubular furnace according to the present invention, and a schematic view (B) showing the placement of the tubular body in the tubular furnace.

FIG. 2 is a diagram of an experimental apparatus for gallium oxide nanowire preparation provided in examples 1-3.

Fig. 3 is an SEM image of gallium oxide nanowires provided in example 1.

Fig. 4 is an XRD spectrum of the gallium oxide nanowire provided in example 1.

FIG. 5 is an SEM image of a prepared gold nanofilm provided in example 2

Fig. 6 is an SEM image of gallium oxide nanowires provided in example 2.

Fig. 7 is an SEM image of gallium oxide nanowires provided in example 3.

Fig. 8 is a diagram of an experimental apparatus for preparing gallium oxide nanowires provided in example 4.

Fig. 9 is an SEM image of gallium oxide nanowires provided in example 4.

FIG. 10 is a graph of the absorption curves of the nanowires provided in examples 1 to 4.

Detailed Description

In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.

It should be noted that the experimental methods in the following examples are all conventional methods unless otherwise specified; the reagents and materials used are commercially available, unless otherwise specified.

In the following embodiments, a single-temperature-zone tube furnace is selected, see fig. 2; the pipe body is positioned at the middle heat source of the pipe furnace where the gallium arsenide powder part is arranged.

When the tube body is placed in the tube furnace, the distance between the silicon substrate and the gallium arsenide powder in the tube body is adjusted in advance according to the temperatures of different areas in the inner cavity of the tube furnace, as shown in fig. 1, specifically according to the following steps:

s1, empty burning the tube furnace, and measuring a temperature distribution curve chart 1(A) from a middle heat source area of the tube furnace to a furnace mouth by using a metal thermometer when the temperature of the middle heat source of the tube furnace is 800-900 ℃;

s2, determining the distance from the intermediate heat source to the area with the temperature of 550-650 ℃ between the furnace mouth and the intermediate heat source through a temperature distribution curve;

and S3, adjusting the placement distance between the silicon substrate and the gallium arsenide powder in the tube body according to the distance determined in the step S2, as shown in the figure 1 (B).

The tube body selected in the following embodiments is a single-opening quartz glass tube.

Example 1

A preparation method for generating gallium oxide nano-wires by using gallium arsenide as a gallium source and a CVD method comprises the following steps:

1) cleaning a Si sheet: a single-side polished single crystal silicon wafer having a thickness of 1mm and a specification of 100mm was cut into a size of 10mm × 5mm with a glass cutter. Then ultrasonically cleaning the glass bottle by acetone, deionized water and ethanol for 10min respectively, and finally blowing the glass bottle by nitrogen for drying and putting the glass bottle into a clean glass bottle for later use;

2) the preparation process of the gold (Au) nanoparticles comprises the following steps: an Au particle film (hereinafter referred to as Au film) with a particle size of 20nm is plated on a cleaned silicon wafer by a small vacuum coating apparatus under a current of 70A for 4 min. Then placing the silicon chip plated with the Au film into a vacuum rapid annealing furnace, rapidly annealing for 10min at 500 ℃, naturally cooling to room temperature, and placing into a clean container for later use;

3)Ga₂O₃the preparation process of the nanowire comprises the following steps: taking a single-opening clean quartz glass tube with the length of 20cm, the inner diameter of 5mm and the thickness of 1mm, weighing about 0.3g of gallium arsenide powder, pouring the gallium arsenide powder into the glass tube, placing the gallium arsenide powder at the bottom of the tube, taking a silicon wafer in the sheet 2), raising the silicon wafer with graphite paper, placing the silicon wafer into the glass tube, enabling one side of the silicon wafer, which is coated with gold nanoparticles, to have an inclination angle of about 15 degrees towards gallium arsenide powder, and enabling the distance between the silicon wafer and the GaAs powder to be equal to the distance between a material growth temperature area in the tube furnace and a central heat preservation area, wherein the material growth temperature area is an area for placing the silicon wafer;

putting the glass tube into a tube furnace, and positioning the gallium arsenide powder at the bottom of the glass tube right below a heating resistance wire in the middle of the tube furnaceConnecting a gas circuit of the tube furnace, opening a mechanical pump to vacuumize the tube furnace, and introducing hydrogen-argon mixed gas (H) after the pressure is stable (about 150Pa)₂5%) of the gallium oxide nanowire on the silicon substrate, keeping the tubular furnace vacuumized during the firing process, introducing hydrogen-argon mixed gas, keeping the pressure in the tubular furnace at about 500Pa, opening the tubular furnace, setting the temperature to be 80min, heating the tubular furnace from room temperature to 800 ℃, then adding the mixture into the tubular furnace from 800 ℃ to 850 ℃ for 10min, keeping the temperature at 850 ℃ for 1h, keeping the temperature of the silicon wafer covered with the gold nano-film at 600 ℃, then cooling the silicon wafer from 850 ℃ to 500 ℃ for 30min, and finally naturally cooling the silicon wafer from 500 ℃ to room temperature to take out the sample, thus obtaining the gallium oxide nanowire on the silicon substrate.

Example 2

The same as example 1, except that:

the time for evaporating the Au thin film is 2min, and the thickness of the Au thin film is about 10 nm.

Example 3

The same as example 1, except that:

the time for evaporating the Au thin film is 3min, and the thickness of the Au thin film is 15 nm.

Example 4

The same as example 1, except that:

the time for evaporating the Au thin film is 2min, and the thickness of the Au thin film is about 10 nm;

Ga₂O₃the preparation process of the nanowire comprises the following steps: a clean alumina porcelain boat 15cm long, 10mm inside diameter, and 1.5mm thick was taken, and about 0.3g of GaAs powder was weighed into one end of the boat as shown in FIG. 8. Then taking a silicon chip in the step 2), heightening with graphite paper, putting the silicon chip into the other end of the porcelain boat, putting the silicon chip into a glass tube, enabling one side of the silicon chip, which is covered with the gold nano-film, to have an inclination angle of about 15 degrees towards the gallium arsenide powder, and enabling the distance between the silicon chip and the GaAs powder to be equal to the distance between a material growth temperature area in the tubular furnace and a central heat preservation area, wherein the material growth temperature area is an area for placing the silicon chip; covering a clean ceramic chip with the width of 20mm and the thickness of 1.5mm on the ceramic boat, wherein the ceramic chip is 10 cm;

placing the porcelain boat into a tube furnace to make the low gallium arsenide powder in the porcelain boat positioned in the tube furnaceConnecting a gas circuit of the tube furnace under the medium heating resistance wire, opening a mechanical pump to vacuumize the tube furnace, and introducing hydrogen-argon mixed gas (H) after the pressure is stable (about 150Pa)₂5%) of the gallium oxide nanowire, keeping the tube furnace vacuumized during the firing process, introducing hydrogen and argon mixed gas, enabling the pressure in the tube furnace to be stabilized at 500Pa, opening the tube furnace, setting the temperature to be 80min, heating the tube furnace from room temperature to 800 ℃, enabling the temperature of the silicon wafer covered with the gold nano film to be 600 ℃, then adding the silicon wafer covered with the gold nano film to 850 ℃ from 800 ℃ after 10min, keeping the temperature for 1h at 850 ℃, then cooling the silicon wafer from 850 ℃ to 500 ℃ after 30min, and finally naturally cooling the silicon wafer to room temperature to take out a sample, thus obtaining the gallium oxide nanowire on the silicon substrate.

In order to illustrate the correlation performance of the gallium oxide nanowires prepared by the preparation method of the gallium oxide nanowires provided by the invention, the gallium oxide nanowires provided in examples 1 to 4 are tested for correlation performance, as shown in fig. 3 to 7 and fig. 9.

Fig. 3 is an SEM image of gallium oxide nanowires provided in example 1.

As can be seen from FIG. 3, most of the prepared gallium oxide nanowires have smooth surfaces and uniform length-diameter ratio, and the diameter of the nanowires is about 100 nm.

Fig. 4 is an XRD spectrum of the gallium oxide nanowire provided in example 1.

As can be seen from FIG. 4, the XED characteristic of the material shows the peak position and β -Ga₂O₃The PDF card of (1) is in perfect correspondence, and the material can be judged to be beta-Ga₂O₃。

Fig. 5 is an SEM image of the prepared gold nanofilm provided in example 2.

As can be seen from FIG. 5, the gold nanofilm had agglomerated into gold nanoparticles, and the particle diameter was about 30 nm.

Fig. 6 is an SEM image of gallium oxide nanowires provided in example 2.

As can be seen from FIG. 6, most of the prepared gallium oxide nanowires have smooth surfaces and uniform length-diameter ratio, and the diameter of the nanowires is about 50 nm.

Fig. 7 is an SEM image of gallium oxide nanowires provided in example 3.

As can be seen from FIG. 7, most of the prepared gallium oxide nanowires have smooth surfaces and uniform length-diameter ratio, and the diameter of the nanowires is about 150 nm.

Fig. 9 is an SEM image of gallium oxide nanowires provided in example 4.

As can be seen from FIG. 9, most of the prepared gallium oxide nanowires have smooth surfaces and uniform length-diameter ratio, and the diameter of the nanowires is about 50 nm.

FIG. 10 is a graph of the absorption curves of the nanowires provided in examples 1 to 4.

As can be seen from FIG. 10, the nanowires have a significant absorption effect in the deep ultraviolet band around 270nm, and have the potential for deep ultraviolet detection.

In conclusion, gallium arsenide is used as a gallium source, the single-temperature-zone tube furnace is used for firing the gallium oxide nanowire, only one hydrogen-argon mixed gas needs to be introduced, the vacuum degree only needs to be maintained at about 500Pa, the surface of the prepared gallium oxide nanowire is smooth, the length-diameter ratio of the nanowire is uniform, the operation is simple, and the repeatability is high.

The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.