CN113061860A - Magnesium nanowire film and preparation method and application thereof - Google Patents

Magnesium nanowire film and preparation method and application thereof Download PDF

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CN113061860A
CN113061860A CN202110308343.4A CN202110308343A CN113061860A CN 113061860 A CN113061860 A CN 113061860A CN 202110308343 A CN202110308343 A CN 202110308343A CN 113061860 A CN113061860 A CN 113061860A
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magnesium
nanowire
magnetron sputtering
substrate
film
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CN113061860B (en
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梁慧
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Xuzhou University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to the technical field of metal films, and provides a preparation method of a magnesium nanowire film. When the inclination angle of the magnetron sputtering substrate is 60 degrees < alpha <89 degrees, the magnetron sputtering substrate is obliquely incident, in the deposition process, the diffusion of magnesium atoms occurs in the projection direction of a magnetron sputtering beam on the surface of the film, and the diffusion in the direction parallel to the surface of the film is only determined by the incident angle, so that the magnesium nanowires can grow to be uniform in diameter and uniform in distribution; when the temperature of the substrate is 25-100 ℃, the well-separated magnesium nanowires can be obtained. Experimental results show that when the temperature of the substrate is 25 ℃ and the inclination angle of the substrate is 85 ℃, the magnesium nanowires in the magnesium nanowire film are well dispersed, the diameters of the nanowires are 25-50 nm, and the nanowires can be used as a hydrogen storage solid material.

Description

Magnesium nanowire film and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal thin films, in particular to a magnesium nanowire thin film and a preparation method and application thereof.
Background
With the global warming problem and the increase of fossil fuel consumption, renewable energy sources such as hydroelectric power, solar power, and wind power are increasingly replacing conventional fuels. Hydrogen has a higher chemical energy than fossil fuels, and the exhaust gas produced in fuel cells is water vapor, without any other greenhouse gases or harmful emissions. Thus, hydrogen has great potential for use over conventional fuels. However, prior to the use of hydrogen as an economically viable fuel, there is a need to address the problems of hydrogen production, distribution and storage, and particularly the problem of hydrogen storage. Since solid materials have higher bulk density and are safer than gases or liquids, the problem of storing hydrogen is often solved by storing hydrogen in solid materials.
Among solid materials for storing hydrogen, magnesium has characteristics of abundance, low cost, low density, low toxicity, and high hydrogen capacity and reversibility, so that magnesium is a commonly used solid material for storing hydrogen. However, the material has the defects of high desorption temperature, slow hydrogen absorption power and high possibility of oxidizing magnesium by oxygen, so that hydrogen is not easy to diffuse in the material. Over the years, various studies have been devoted to solving the above-mentioned problems. Such as Energy Rev.2017,72,523-534, research into reducing Mg/MgH by mechanical ball milling in the presence (or absence) of catalyst materials2(less than 1 μm) of the particles, thereby significantly improving the adsorption kinetics of the solid material. However, this method yields Mg/MgH2The particle size is still large and only improves the adsorption kinetics of the solid material, but not the thermodynamic parameters. Therefore, there is a need to further obtain Mg/MgH of smaller size2The particle size is used for simultaneously solving the problems that the magnesium hydrogen storage material has high desorption temperature, slow hydrogen absorption power and easy oxidation of magnesium by oxygen.
Disclosure of Invention
The invention aims to provide a magnesium nanowire film and a preparation method and application thereof, wherein the magnesium nanowire in the magnesium nanowire film prepared by the invention is small in size, and the diameter of the magnesium nanowire can reach 25-50 nm.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a magnesium nanowire film, which adopts magnetron sputtering to deposit the magnesium nanowire film on a substrate,
the target material of the magnetron sputtering is an Mg target;
the distance between the Mg target and the substrate is 60-80 mm;
the magnetron sputtering is carried out under the protection of argon;
the temperature of the substrate during magnetron sputtering is 25-100 ℃;
the inclination angle of the substrate during magnetron sputtering is 60 degrees < alpha <89 degrees.
Preferably, the substrate comprises a conductive silicon wafer, SiO2Flakes or Al2O3And (3) slicing.
Preferably, the purity of the Mg target is 99.99 wt% or more.
Preferably, the temperature of the substrate during magnetron sputtering is 25-80 ℃.
Preferably, the magnetron sputtering power is 20-100W.
Preferably, the working voltage during magnetron sputtering is 0.13-1.3 Pa.
Preferably, the magnetron sputtering time is 10-60 min.
The invention also provides the magnesium nanowire film prepared by the preparation method of the technical scheme, wherein the diameter of the magnesium nanowire in the magnesium nanowire film is 20-100 nm.
The invention also provides the application of the magnesium nanowire film in the technical scheme as a solid hydrogen storage material.
The invention provides a preparation method of a magnesium nanowire film, which is characterized in that the magnesium nanowire film is deposited on a substrate by adopting magnetron sputtering, and a target material of the magnetron sputtering is limited to be an Mg target; the distance between the Mg target and the substrate is 60-80 mm; magnetron sputtering is carried out under the protection of argon; the temperature of the substrate is 25-100 ℃ during magnetron sputtering; the inclination angle of the substrate during magnetron sputtering is 60 degrees < alpha <89 degrees. The invention controls the appearance of the nano Mg film by controlling the inclination angle and the temperature of the substrate during magnetron sputtering. When the inclination angle of the magnetron sputtering substrate is 60 degrees < alpha <89 degrees, the magnetron sputtering substrate is obliquely incident, in the deposition process, the diffusion of magnesium atoms occurs in the projection direction of a magnetron sputtering beam on the surface of the film, and the diffusion in the direction parallel to the surface of the film is only determined by the incident angle, so that the magnesium nanowires can grow to be uniform in diameter and uniform in distribution; when the temperature of the substrate is 25-100 ℃, the well-separated magnesium nanowires can be obtained. Experimental results show that when the temperature of the substrate is 25 ℃ and the inclination angle of the substrate is 85 ℃, the magnesium nanowires in the magnesium nanowire film are well dispersed, the diameters of the nanowires are 25nm, and the nanowires can be used as a solid hydrogen storage material.
Drawings
FIG. 1 is an SEM image of a thin film of magnesium nanowires prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a thin film of magnesium nanowires prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a thin film of magnesium nanowires prepared in example 3 of the present invention;
FIG. 4 is an SEM image of a thin film of magnesium nanowires prepared in example 4 of the present invention;
FIG. 5 is an SEM image of a thin film of magnesium nanowires prepared in example 5 of the present invention;
FIG. 6 is an SEM image of a magnesium nanowire thin film prepared in comparative example 1 of the present invention;
FIG. 7 is a simulation of the growth of a thin film of magnesium nanowires prepared in example 6 of the present invention;
FIG. 8 is an XPS spectrum of a magnesium nanowire film prepared in example 6 of the present invention;
FIG. 9 is an SEM image of the magnesium nanowire thin films prepared in examples 7 to 13 of the present invention;
FIG. 10 is a graph showing kMC simulation results of the effect of the deposition angle α of the magnesium nanowire thin film prepared in examples 7 to 13 of the present invention on the tilt angle β of the magnesium nanowire;
FIG. 11 is an SEM image of the magnesium nanowire thin films prepared in examples 14 to 17 of the present invention;
FIG. 12 is a Monte Carlo kinetic simulation diagram of the magnesium nanowire thin films prepared in examples 14-17 of the present invention.
Detailed Description
The invention provides a preparation method of a magnesium nanowire film, which adopts magnetron sputtering to deposit the magnesium nanowire film on a substrate and comprises the following steps:
the target material of the magnetron sputtering is an Mg target;
the distance between the Mg target and the substrate is 60-80 mm;
the magnetron sputtering is carried out under the protection of argon;
the temperature of the substrate during magnetron sputtering is 25-100 ℃;
the inclination angle of the substrate during magnetron sputtering is 60 degrees < alpha <89 degrees.
The invention adopts magnetron sputtering to deposit the magnesium nanowire film on the substrate. The magnetron sputtering apparatus of the present invention is not particularly limited, and a magnetron sputtering apparatus known to those skilled in the art may be used. In the present invention, the magnetron sputtering apparatus is preferably a cylindrical stainless steel reaction chamber.
In the invention, the target material of the magnetron sputtering is an Mg target. In the present invention, the purity of the Mg target is preferably 99.99 wt% or more, more preferably 99.999 wt% or more. In the present invention, when the purity of the Mg target is in the above range, it is more advantageous to obtain a magnesium nanowire thin film having high purity.
The size of the Mg target is not particularly limited, and the Mg target can be adjusted according to actual conditions. In the present invention, the Mg target is preferably 2 inches in diameter and 0.25 inches thick.
In the invention, the distance between the Mg target and the substrate is 60-80 mm, preferably 75-80 mm, and most preferably 80 mm. In the invention, the distance between the Mg target and the substrate affects the carrier concentration and the mobility, and when the distance between the Mg target and the substrate is in the range, the magnesium nanowire film with high quality can be obtained more favorably.
In the present invention, the substrate preferably comprises a conductive silicon wafer (100) single-polished, Al2O3Flakes or SiO2And (3) slicing. The source of the substrate is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The invention preferably cleans the substrate before magnetron sputtering. The operation mode of the cleaning is not particularly limited in the present invention, and a cleaning mode known to those skilled in the art may be adopted. In the present invention, the cleaning agent is preferably ultrapure water. In the present invention, the cleaning can remove impurities from the surface of the substrate.
The invention preferably adjusts the vacuum degree in the reaction chamber to be 1.6 multiplied by 10 before magnetron sputtering-4～1.6×10-6Pa, more preferably 1.6X 10-5～1.6×10-6Pa. In the present invention, when the degree of vacuum in the magnetron sputtering is in the above range, air in the reaction chamber can be removed.
The device for regulating the vacuum degree during magnetron sputtering is not particularly limited, and the device for regulating the vacuum degree, which is well known by the technical personnel in the field, can be adopted. In the present invention, the vacuum degree regulating device is preferably a turbo molecular pump.
In the invention, the magnetron sputtering is carried out under the protection of argon. The invention uses argon as working gas, which can prevent magnesium oxidation during magnetron sputtering. The flow of the argon is not specially limited, and the argon flow is adjusted according to the actual experimental process.
In the invention, the temperature of the substrate during magnetron sputtering is 25-100 ℃, and preferably 25-80 ℃. In the invention, the diameter of the magnesium nanowire in the magnesium nanowire film is determined by the temperature of the substrate during magnetron sputtering, and when the temperature of the substrate during magnetron sputtering is in the range, the diameter of the magnesium nanowire in the magnesium nanowire film can be ensured to be 25-100 nm.
In the present invention, the tilt angle of the substrate at the time of magnetron sputtering is 60 ° < α <89 °, preferably 65 ° < α <85 °. In the invention, in the sputtering process, a grazing angle deposition system is used for controlling the inclination of the substrate, and when the inclination angle of the substrate is in the range, the diameter of the magnesium nanowire in the magnesium nanowire film can be ensured to be 25-100 nm.
In the present invention, the operating voltage during magnetron sputtering is preferably 0.13 to 1.3Pa, and more preferably 0.2 to 0.26 Pa. In the invention, when the working voltage in the magnetron sputtering is in the range, the shape of the magnesium nanowire in the magnesium nanowire film can be further controlled.
In the invention, the magnetron sputtering power is preferably 20-100W, more preferably 30-50W, and most preferably 50W. In the invention, when the magnetron sputtering power is in the range, the shape of the magnesium nanowire in the magnesium nanowire film can be further controlled.
In the invention, the magnetron sputtering time is preferably 10-60 min, and more preferably 15-30 min. In the invention, when the magnetron sputtering time is in the range, the morphology of the magnesium nanowires in the magnesium nanowire film can be further controlled.
The invention adopts magnetron sputtering to deposit the nano-structure magnesium film on the substrate, controls the appearance of the nano-Mg film by controlling the inclination angle of the substrate and the temperature of the substrate during magnetron sputtering, has good dispersion of the magnesium nanowires in the magnesium nanowire film, and can obtain the size far lower than that of the magnesium nanowires in the prior art.
The invention also provides the magnesium nanowire film prepared by the preparation method of the technical scheme, wherein the diameter of the magnesium nanowire in the magnesium nanowire film is 25-100 nm.
The diameter of the magnesium nanowire in the magnesium nanowire film provided by the invention is 25-100 nm, and the magnesium nanowire in the magnesium nanowire film is well dispersed.
The invention also provides the application of the magnesium nanowire film in the technical scheme as a solid hydrogen storage material.
The application method of the magnesium nanowire film as the solid hydrogen storage material is not particularly limited, and the application method of the solid hydrogen storage material known by the technical personnel in the field can be adopted.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The experiment was carried out in a cylindrical stainless steel reaction chamber (height: 60cm, diameter: 42 cm). The reaction chamber was evacuated by a turbomolecular pump, and a magnetron cathode was mounted on the top of the reaction chamber, using a 2 inch diameter and 0.25 inch thick Mg target (99.99 wt% purity). A conductive silicon wafer (100) was used as a substrate, which was located at a distance of 80mm below a Mg target, the substrate tilt angle was controlled using a grazing angle deposition (GLAD) system, tilted at an angle α of 85 °, and cleaned with ultrapure water before deposition.
The magnesium target was sputtered in a direct current mode in an argon atmosphere. In the sputtering process, the power is 50W, the voltage is 0.26Pa, the time is 20min, and the vacuum degree is 1.6 multiplied by 10-5Pa, the temperature of the substrate is 25 ℃, and the magnesium nanowire film is prepared.
The SEM image of the magnesium nanowire thin film prepared in example 1 was scanned using a scanning electron microscope and is shown in fig. 1. As can be seen from FIG. 1, when the substrate temperature is 25 ℃ and alpha is 85 degrees, the inclination angle of the obtained nanowire is 22 degrees, the diameter of the magnesium nanowire in the magnesium nanowire film is 25-50 nm, and the separation of the magnesium nanowire is good.
Example 2
The difference from example 1 was that the temperature of the substrate was 40 deg.C, and the other steps were the same as example 1.
The SEM image of the magnesium nanowire thin film prepared in example 2 was scanned using a scanning electron microscope and is shown in fig. 2. As can be seen from FIG. 2, when the substrate temperature is 40 ℃ and alpha is 85 ℃, the inclination angle of the obtained nanowire is 22 degrees, the diameter of the magnesium nanowire in the magnesium nanowire film is 45-65 nm, the magnesium nanowire is well separated, and the inclination angle of the nanowire is reduced, which is caused by the fact that atomic diffusion is enhanced due to the increase of the substrate temperature.
Example 3
The difference from example 1 was that the temperature of the substrate was 60 deg.C, and the other steps were the same as example 1.
The SEM image of the magnesium nanowire thin film prepared in example 3 was scanned using a scanning electron microscope and is shown in fig. 3. As can be seen from FIG. 3, when the substrate temperature is 60 ℃ and alpha is 85 degrees, the inclination angle of the obtained nanowire is 21 degrees, the diameter of the magnesium nanowire in the magnesium nanowire film is 60-75 nm, and the separation of the magnesium nanowire is good. It can be seen that the nanowire width is slightly broadened, and the atomic diffusion effect continues to increase as the substrate temperature increases.
Example 4
The difference from example 1 was that the temperature of the substrate was 80 ℃ and the other steps were the same as in example 1.
The SEM image of the magnesium nanowire thin film prepared in example 4 was scanned using a scanning electron microscope and is shown in fig. 4. As can be seen from FIG. 4, when the substrate temperature is 80 ℃ and alpha is 85 degrees, the inclination angle of the obtained nanowire is 21 degrees, the diameter of the magnesium nanowire in the magnesium nanowire film is 65-100 nm, the separation of the magnesium nanowire is good, and the diameter of the nanowire is continuously increased.
Example 5
The difference from example 1 was that the temperature of the substrate was 100 deg.C, and the other steps were the same as example 1.
The SEM image of the magnesium nanowire thin film prepared in example 5 was scanned using a scanning electron microscope and is shown in fig. 5. As can be seen from fig. 5, when the substrate temperature is 100 ℃ and α is 85 °, the inclination angle of the obtained nanowire is 0 °, the magnesium nanowire is not clearly separated, and bulk magnesium appears at the top, because the shadow shielding effect is overcome by atomic diffusion, and the temperature influence is dominant.
Comparative example 1
The difference from example 1 was that the temperature of the substrate was 200 deg.C, and the other steps were the same as example 1.
The SEM image of the magnesium nanowire thin film prepared in comparative example 1 was obtained by scanning with a scanning electron microscope and is shown in fig. 6. As can be seen from FIG. 6, when the substrate temperature is 200 ℃ and alpha is 85 degrees, the inclination angle of the obtained nanowire is 0 degree, the nanowire structure completely disappears, and the SEM represents the cross-sectional morphology of the magnesium film and completely presents bulk magnesium.
The examples 1-5 and the comparative example 1 prove that the morphology of the magnesium film is completely controlled by the temperature, and when the temperature range is not between 25 and 100 ℃, the magnesium nanowire film cannot be obtained.
Example 6
A magnesium nanowire thin film was prepared by the method of example 1, which is different from example 1Is characterized by a sputtering power of 50W, alpha 0 DEG and PTot＝0.26Pa。
The growth of the magnesium thin film prepared in example 6 was simulated using monte carlo software as shown in fig. 7. As can be seen from fig. 7: as the energy of the magnesium atoms diffusing leftwards and rightwards is increased, the pores of the magnesium film are reduced, and the width of the magnesium nanowire is increased. However, as the energy of the upward movement of the magnesium atoms is increased, the pores of the magnesium film are unchanged, and the width of the magnesium nanowire is not changed. Therefore, the morphology of the magnesium film is mainly determined by the parallel diffusion of magnesium atoms.
The magnesium nanowire film prepared in example 6 was detected by an X-ray photoelectron spectrometer, and the XPS spectrum obtained is shown in fig. 8. As can be seen from fig. 8: the electron transitions of Mg, O and C of the film were 49.5eV (Mg2p), 285eV (C1s) and 530eV (O1s), respectively. Further quantitative analysis of these signals revealed that the film contained approximately 50% oxygen atoms and 10% carbon atoms, the presence of which could be related to surface contamination during transport of the sample from the reaction chamber to the XPS instrument.
Example 7
The difference from the example 1 is that the inclination angle of the substrate during the grazing angle deposition is 60 degrees, and other steps are the same as the example 1 to prepare the magnesium nanowire film.
Example 8
The difference from the example 1 is that the inclination angle of the substrate during the grazing angle deposition is 70 degrees, and other steps are the same as the example 1, and the magnesium nanowire film is prepared.
Example 9
The difference from the example 1 is that the inclination angle of the substrate during the grazing angle deposition is 80 degrees, and other steps are the same as the example 1 to prepare the magnesium nanowire film.
Example 10
The difference from the example 1 is that the inclination angle of the substrate during the grazing angle deposition is 82.5 degrees, and other steps are the same as the example 1, and the magnesium nanowire film is prepared.
Example 11
The difference from the example 1 is that the inclination angle of the substrate during the glancing angle deposition is 85 degrees, and other steps are the same as the example 1 to prepare the magnesium nanowire film.
Example 12
Except that the inclination angle of the substrate during the glancing angle deposition was 87 ° as in example 1, the other steps were the same as in example 1, and a magnesium nanowire thin film was prepared.
Example 13
The difference from the example 1 is that the inclination angle of the substrate during the glancing angle deposition is 89 degrees, and other steps are the same as the example 1 to prepare the magnesium nanowire film.
Scanning the magnesium nanowire films prepared in examples 7 to 13 by using a scanning electron microscope to obtain SEM images as shown in FIG. 9. As can be seen from fig. 9, the tilt angle β of the nanowires in the magnesium nanowire thin film strongly depends on α at an incident angle of 60 ° < α <89 °. At larger oblique angles of incidence (greater than 60 deg.), the shadowing mechanism is enhanced, forming pillars that are inclined towards the magnesium target. With the increase of alpha, beta is obviously increased, and when alpha is greater than 85 degrees, beta is kept stable. This is because when the incident direction of the sputtered atoms is perpendicular to the deposited film surface, the diffusion distance of the atoms is only about a few atomic distances in each direction, and a magnesium film with a nano-morphology cannot be prepared; however, when sputtering is at an angle to the substrate, incident obliquely, the diffusion of its atoms during deposition occurs in the direction of the projection of the sputter beam on the film surface, and the diffusion in the direction parallel to the film surface is determined only by the angle of incidence. Therefore, when the incident angle is 60 degrees < alpha <89 degrees, the magnesium nanowire thin film which is well separated and has the diameter of 20-50 nm can be obtained.
The kMC simulation results of the analysis of the magnesium nanowire films prepared in examples 7 to 13, which indicate the influence of the deposition angle α on the tilt angle β of the magnesium nanowire, are shown in fig. 10. As can be seen from fig. 10, the tilt angle β of the nanowires in the magnesium nanowire thin film strongly depends on α.
Example 14
The sputtering power and the inclination angle alpha are respectively fixed at 50W and 85 DEG, PTot0.13Pa, the rest of the procedure was the same as in example 1.
Example 15
The difference from example 14 is that PTot0.26Pa, the rest of the procedure was the same as in example 1.
Example 16
The difference from example 14 is that PTot0.65Pa, the rest of the procedure was the same as in example 1.
Example 17
The difference from example 14 is that PTotThe pressure was 1.3Pa, and the remaining steps were the same as in example 1.
Scanning electron microscopy was used to examine the magnesium nanowire films prepared in examples 14-17, and the SEM images are shown in FIG. 11. From FIG. 11, it can be seen that P isTotWhen the inclination angles of the magnesium nanowires in the obtained magnesium nanowire film are respectively 0.13Pa, 0.26Pa, 0.65Pa and 1.3Pa, the inclination angles of the magnesium nanowires in the obtained magnesium nanowire film are respectively 51 +/-1.0 degrees, 44 +/-1.0 degrees, 24 +/-1.0 degrees and 5 +/-0.5 degrees.
Monte Carlo kinetic simulations of the magnesium nanowire films prepared in examples 14-17 are shown in FIG. 12. As can be seen from FIG. 12, the tilt angle β of the magnesium nanowire is taken as PTotThe variables of the function, where 0.13Pa corresponds to the minimum required to sustain the magnetron discharge. FIG. 12 shows following PTotThe increase in β decreases rapidly, from β 51 ± 1.0 ° at 0.13Pa to β 5 ± 0.5 ° at 1.3 Pa. This indicates that the change in the tilt angle of the magnesium nanowires can be attributed to the change with PTotThis is likely due to the reduced flux of incident particles, resulting in an increased probability of collision.
The test results of the embodiment show that the magnesium nanowire film with the diameter of 25-100 nm and good separability can be prepared by the preparation method provided by the invention and can be used as a solid hydrogen storage material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a magnesium nanowire film adopts magnetron sputtering to deposit the magnesium nanowire film on a substrate:
the target material of the magnetron sputtering is an Mg target;
the distance between the Mg target and the substrate is 60-80 mm;
the magnetron sputtering is carried out under the protection of argon;
the temperature of the substrate during magnetron sputtering is 25-100 ℃;
the inclination angle of the substrate during magnetron sputtering is 60 degrees < alpha <89 degrees.
2. The method of claim 1, wherein the substrate comprises a conductive silicon wafer, SiO2Flakes or Al2O3And (3) slicing.
3. The production method according to claim 1, wherein the purity of the Mg target is 99.99 wt% or more.
4. The preparation method according to claim 1, wherein the temperature of the substrate during magnetron sputtering is 25-80 ℃.
5. The preparation method according to claim 1, wherein the magnetron sputtering power is 20-100W.
6. The preparation method according to claim 1, wherein the working voltage during magnetron sputtering is 0.13 to 1.3 Pa.
7. The preparation method according to claim 1, wherein the magnetron sputtering time is 10-60 min.
8. The magnesium nanowire film prepared by the preparation method of any one of claims 1 to 7, wherein the diameter of the magnesium nanowires in the magnesium nanowire film is 20 to 100 nm.
9. Use of the thin film of magnesium nanowires of claim 8 as a solid state material for hydrogen storage.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411028A (en) * 2022-01-21 2022-04-29 徐州工程学院 Trace nickel composite layered magnesium composite material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060251917A1 (en) * 2004-10-12 2006-11-09 Southwest Research Institute Method for magnetron sputter deposition
US20180204976A1 (en) * 2015-07-13 2018-07-19 Crayonano As Nanowires or nanopyramids grown on graphitic substrate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060251917A1 (en) * 2004-10-12 2006-11-09 Southwest Research Institute Method for magnetron sputter deposition
US20180204976A1 (en) * 2015-07-13 2018-07-19 Crayonano As Nanowires or nanopyramids grown on graphitic substrate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411028A (en) * 2022-01-21 2022-04-29 徐州工程学院 Trace nickel composite layered magnesium composite material and preparation method and application thereof

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