TW201507975A - Method for manufacturing a nickel nanotube and structure thereof - Google Patents

Abstract

The present invention relates to a method for manufacturing a nickel nanotube and structure thereof, in which after transforming metal nickel on a quartz substrate into an island-shaped nano-nickel cluster by annealing, a manganese-doped zinc oxide layer is set up to cover the island-shaped nano-nickel cluster first, and then during the process of sintering the manganese-doped zinc oxide layer, the island-shaped nano-nickel cluster is extended upward to form a tube body structure. The nanotube made of metal nickel has the potential of being used in the field of gas detection or as catalysts.

Description

Preparation method and structure of nickel nano tube

The invention relates to a preparation method and a structure of a nickel nano tube, in particular to a processing step of annealing, sintering and the like, so that an island-shaped nano nickel group is formed into a nickel-nano tube in a manganese-doped zinc oxide film, as A novel and excellent nickel nanotube tube preparation method and structure thereof used in the fields of gas detection, catalyst and the like.

With the demand for miniaturization of various products, the human science and technology civilization will gradually enter the so-called nano era from the micron era. When the scale of the material is reduced to the nanometer level, due to the quantum confinement effect and the ratio of the surface area to the volume, the physical, mechanical and chemical properties of the nanomaterial after shrinking with the scale are the same as those of the bulk material. There are differences in characteristics, such as a decrease in the melting point of the metal material and an increase in the energy gap of the semiconductor material. Therefore, in addition to changing the chemical composition of materials to obtain the properties of different materials, humans can further control the basic characteristics of the same chemical composition such as melting point, color, and by controlling the size and shape of nanomaterials. Light, electricity, magnetic and other properties. With this feature, many high-performance products or technologies that were previously impossible to achieve in the micron era will have the opportunity to be realized in the field of nanotechnology.

For nanotechnology products, one-dimensional nanostructures such as nanotubes, nanowires, and nanorods are more challenging to handle and study because of their special structure. It is also a part of the most development space.

In the research and development of nanotubes, most of them are non-metallic carbon nanotubes, and nanocarbon tubes are first discovered by transmission electron microscopy. It has been confirmed by many theories and experiments that the various properties of the nanostructured tubular structure of the graphite structure may vary depending on the diameter of the pipe, the number of layers of the graphite layer, and the direction in which the graphite layer is crimped. The method for preparing the carbon nanotubes is mainly based on arc discharge and laser evaporation, and then the VLS (vapor-liquid-solid) method is used to make the carbon nanotubes by the addition of a metal catalyst in the process. Production tends to be stable and simple. Although the growth of carbon nanotubes is not difficult, how to effectively control the diameter of the carbon nanotubes, the number of graphite layers, and the direction of the graphite layer to obtain a large number of carbon nanotube products with uniform properties is still present. The bottleneck of the nano carbon control process.

In the field of nanowires, there are a variety of metal materials, and the preparation method may be the aforementioned VLS method, Template-assisted growth method, oxide-assisted growth method or nano-grain-assisted growth method, etc., but these The nanowire or the nanocolumn is still quite different in structure from the hollow tubular structure, and there are still few nanotubes prepared using metal materials.

Considering the characteristics of the application of the nanotube body, how to provide a preparation method of the metal tube as the nano tube body is a problem to be solved by the present invention.

The main object of the present invention is to provide a method for preparing a nickel nanotube, which is formed by forming a nanometer-sized nickel metal tube under the operation of a device which can be obtained by a general laboratory, and which does not need to be consumed. It will take a long time to complete.

Another object of the present invention is to provide a method for preparing a nickel nanotube, in particular to prepare a nano-scale tube composed of a metal material, which is different from a simple nano-column, and thus has a completely different technology from the prior art. The development benefits and uses exist.

A further object of the present invention is to provide a structure of a nickel nanotube which is located between a manganese-doped zinc oxide material and is a hollow thin tube structure having a size range as a gas detection or catalyst development study. A considerable advantage.

In order to achieve the above object, the present invention discloses a method for preparing a nickel nanotube and a structure thereof, which comprises the steps of: providing a nickel metal layer on a surface of a substrate; annealing the nickel metal layer to form a plurality of island-shaped nano-nickel clusters; a manganese-doped zinc oxide layer disposed on the substrate and covering the island-shaped nano-nickel clusters; and sintering the manganese-doped zinc oxide layer to form the island-shaped nano nickel The cluster extends upwardly and penetrates the manganese-doped zinc oxide layer to form a plurality of nickel nanotubes. Through this operation, a large number of nickel nanotubes can be formed at the place where the manganese-doped zinc oxide layer is located, and can be further utilized in the industry.

1‧‧‧Substrate
1A‧‧‧Quartz substrate
2‧‧‧ Nickel metal layer
21‧‧‧ island-shaped nano nickel group
22‧‧‧Ninet tube
22A‧‧‧Body Department
22B‧‧‧ Hollow
22C‧‧‧Open end
3‧‧‧Manganese doped zinc oxide layer
S1~S4‧‧‧ steps

First: it is a flow chart of the steps of the present invention;
Second A~E diagram: it is a schematic diagram of the structure changes in each step in the present invention;
The third figure is a schematic diagram of the structural change of step S4 in the present invention;
Figure 4 is a transmission electron micrograph of the nickel nanotubes prepared by the present invention; and a fifth figure: it is a partially amplified penetrating electron of the prepared nickel nanotubes of the present invention. Microscope photo.

For a better understanding and understanding of the features and advantages of the present invention, the preferred embodiments and the detailed description are described as follows:

First, please refer to the first figure, which discloses the operation process of the present invention, which includes the steps:
Step S1: disposing a nickel metal layer on the surface of a substrate;
Step S2: annealing the nickel metal layer to form a plurality of island-shaped nano nickel groups;
Step S3: disposing a manganese-doped zinc oxide layer on the substrate and covering the island-shaped nano-nickel clusters; and step S4: sintering the manganese-doped zinc oxide layer to extend the island-shaped nano-nickel clusters upward A plurality of nickel nanotubes are formed through the manganese-doped zinc oxide layer.

Then, in conjunction with the structural changes shown in the second A to E drawings, in order to form the structure of the nickel nanotubes, the present invention firstly provides the nickel metal layer 2 on the surface of the substrate 1 in step S1, which is used herein. The substrate 1 is a quartz substrate.

The method of disposing the nickel metal layer 2 on the substrate 1 can be carried out by sputtering. After placing the substrate 1 into the sputtering machine cavity, the mechanical pump is used to rough the cavity to about 5×10 ^-2 Torr, and then the Turbo Molecular Pump is used for fine pumping. After 3×10 ^-6 Torr or less; after turning on the substrate rotation motor, open the gas line and set the gas flow rate via the flow controller (MFC) and then argon gas. Then, after turning on the DC Power and fixing the working pressure at 5.5×10 ^-3 Torr, pre-plating for 5 minutes to remove the oxides and contaminants on the surface of the nickel target and stabilize the plasma for a while, then turn it on again. The shutter is coated; finally, after the coating is completed, the DC Power is turned off, and then the gas line is closed, and the vacuum is taken to take out the sample having the nickel metal layer 2 covering the surface of the substrate 1.

Next, in step S2, the nickel metal layer 2 on the substrate 1 is annealed. In the present invention, the substrate 1 covered with the nickel metal layer 2 is placed in a Rapid Thermal Annealing (RTA), and the temperature is maintained at 500 ° C for 15 minutes, and the heating rate is 25 ° C / sec, followed by By cooling the furnace body to room temperature, an island-shaped nano-nickel cluster 21 structure having a uniform distribution on the surface of the quartz substrate 1 can be obtained.

After converting the nickel metal layer 2 into the island-shaped nano-nickel group 21, the next step is to place a mixed material of manganese and zinc oxide on the substrate 1 and cover the island-shaped nano-nickel group 21, A manganese-doped zinc oxide layer 3 is formed. In this step, the method of setting the nickel metal layer 2 on the surface of the substrate 1 with reference to step S1 is also performed by magnetron sputtering.

Here, the sample having the island-shaped nano-nickel group 21 on the substrate 1 is first placed in a sputtering machine cavity, and the cavity is first roughened by a mechanical pump to 5×10 ⁻² Torr or less, and then the vortex molecule is used. The pump is pumped to 3×10 ^-6 Torr or less. After the substrate rotation motor is turned on, the gas line is opened and the flow rate of the argon gas is set via the flow controller. Then, DC (manganese target) and RF (zinc oxide target) Power were turned on and the required crucible was adjusted, and the working pressure was fixed at 1.1 × 10 ^-2 Torr. After pre-plating for 5 minutes to remove oxides and contaminants on the surface of the target and allowing the plasma to stabilize for a period of time, the baffle is opened for coating. Finally, turn off the DC and RF Power when the coating is completed, then close the gas line, and open the high vacuum valve to make the chamber vacuum return to below 3×10 ^-6 Torr, and then wait for cooling for at least 90 minutes to make the sample. After the temperature has dropped to room temperature, the cavity can be evacuated and the sputtered sample removed.

Next, in step S4, the final high-temperature sintering treatment is performed to extend the island-shaped nano-nickel group 2 upward to penetrate the manganese-doped zinc oxide layer 3, and the nickel metal is formed by adhering to the wall surface on the path. The plurality of nickel nanotube tubes 22 can be referred to the schematic diagram of the third figure. The finally formed nickel nanotube tube 22 is a hollow tube body which is composed of the tube body portion 22A and the hollow portion 22B at the center of the tube body portion. The hollow portion 22B forms one end of the tubular body portion 22A to form an open end 22C. The tubular body portion 22A is disposed on the quartz substrate 1A while the outer side of the tubular body portion 22A is surrounded by the manganese-doped zinc oxide layer 3. In this step, the sample completed in the above step was placed in a high temperature furnace and sintered at 1200 ° C for 2 hours, and the heating rate was 10 ° C / min.

Please refer to the electron micrograph of the fourth figure, which is an example of the observation of a plurality of nickel nanotubes 22 on the layer of the manganese-doped zinc oxide layer 3 after the above steps. In addition, the partial enlargement of the fifth figure can be referred to together, and the tube diameter of the nickel nanotubes 22 is about 15 to 25 nm.

In conjunction with the steps disclosed above, the present invention allows nanometer-sized nickel metal tubes to be formed under the operation of equipment available in general laboratories, and which can be completed without a long waiting time. These formed nanotubes are made of metallic nickel, so they have potential for industrial use such as gas detection and catalyst. With their size structure, it is expected that these nickel nanotubes will have excellent reaction efficiency. , in line with the needs of the industry. Therefore, under the advantages of the threshold of the manufacturing process, the cost of the manufacturing process or the expectation and application range of the finished product performance, the present invention undoubtedly provides a highly economical and practical value for the preparation of nickel nanotubes. Method and its structure.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the variations, modifications, and modifications of the shapes, structures, features, and spirits described in the claims of the present invention. All should be included in the scope of the patent application of the present invention.

S1~S4‧‧‧ steps

Claims (10)

A method for preparing a nickel nanotube, comprising the steps of:
Forming a nickel metal layer on a surface of a substrate;
Annealing the nickel metal layer to form a plurality of island-shaped nano nickel clusters;
Forming a manganese-doped zinc oxide layer on the substrate and covering the island-shaped nano-nickel clusters; and sintering the manganese-doped zinc oxide layer to extend the island-shaped nano-nickel clusters upward through the manganese-doped oxide A plurality of nickel nanotubes are formed by the zinc layer. The preparation method according to claim 1, wherein in the step of disposing the nickel metal layer on the surface of the substrate, the nickel metal layer is provided by sputtering. The preparation method according to claim 1, wherein the substrate is a quartz substrate. The preparation method according to claim 1, wherein in the step of annealing the nickel metal layer, the annealing temperature is 500 °C. The preparation method of claim 4, wherein in the step of annealing the nickel metal layer, the annealing time is 15 minutes. The preparation method according to claim 1, wherein in the step of disposing the manganese-doped zinc oxide layer on the substrate, the manganese-doped zinc oxide layer is provided by magnetron sputtering. The preparation method according to claim 1, wherein in the step of sintering the manganese-doped zinc oxide layer, the sintering temperature is 1200 °C. The preparation method according to claim 7, wherein in the step of sintering the manganese-doped zinc oxide layer, the sintering time is 120 minutes. The preparation method according to claim 1, wherein the nickel nanotubes have a diameter of 15 to 25 nm. A nickel nanotube structure comprising:
a tube body; and a hollow portion located at a center of the tube body portion and having the tube body portion having at least one open end;
Wherein, the tube body portion is disposed on a quartz substrate, the tube body portion is made of nickel metal, and the outer side of the tube body portion is covered by a manganese-doped zinc oxide layer, and the tube body tube The diameter system is between 15 and 25 nanometers.