CN109132996B

CN109132996B - Rapid deposition method of magnetic nanowire array with ordered period

Info

Publication number: CN109132996B
Application number: CN201811187585.7A
Authority: CN
Inventors: 王杰; 俞正民
Original assignee: Liaocheng University
Current assignee: Liaocheng University
Priority date: 2018-10-12
Filing date: 2018-10-12
Publication date: 2020-11-13
Anticipated expiration: 2038-10-12
Also published as: CN109132996A

Abstract

The invention relates to a rapid deposition method of a periodically ordered magnetic nanowire array, which adopts a Halbach array magnet to induce and rapidly deposit the ordered magnetic nanowire array on the surface of a substrate. The preparation method comprises the steps of dispersing the magnetic nanowires in a solvent, enabling the surface of the substrate to be tightly attached to the magnetic surface of the Halbach array magnet, enabling a certain amount of magnetic nanowire solution to be in contact with the other surface of the substrate, rapidly depositing and directionally arranging the magnetic nanowire arrays on the surface of the substrate, recovering the solvent, preparing the substrate with the periodic magnetic nanowire arrays on the surface, and the like. The invention utilizes the strong magnetic field attraction of the Halbach array to separate and directionally arrange the magnetic nanowires and the solvent, thereby realizing the rapid assembly of the magnetic nanowire array and the recycling of the solvent, reducing the environmental pollution and promoting the development of optoelectronic devices and information engineering.

Description

Rapid deposition method of magnetic nanowire array with ordered period

Technical Field

The invention relates to a rapid deposition method of a magnetic nanowire array with ordered period, belonging to the field of photoelectronic devices or information engineering.

Background

The nanowire ordered array has potential application value in the fields of magnetics, sensing, transparent electrodes and the like due to the optimized structure of the nanowire ordered array. The traditional ordered nanowire array is mainly obtained by the technologies of nano-imprinting, self-assembly and the like and the traditional magnetic field induction between two magnetic poles.

Nanoimprinting mainly uses a complicated lithography technology for preparing a nano-array template through a lithography mask, and the size is limited. The self-assembly method mainly generates ordered arrangement through the action of a solvent, and the multi-azimuth array arrangement is difficult to regulate and control. The traditional magnetic field induction method is to generate a uniform magnetic field between two magnetic poles through an expensive electromagnetic field or a permanent magnet, and can control the ordered arrangement of the magnetic nanowires, but the equipment is expensive, the solvent volatilization process period needs a long time, and the solvent volatilization in a large amount is easy to cause environmental pollution and resource waste. The adoption of Halbach array magnet to quickly assemble the periodically ordered magnetic nanowire array has not been reported.

Disclosure of Invention

The invention aims to solve the problems that the traditional assembled magnetic nanowire array has long period, the solvent cannot be recycled and the like, and provides an environment-friendly, orientation-controllable and rapid method for depositing the magnetic nanowire ordered array.

The invention provides a method for inducing magnetic nanowires to deposit on the surface of a substrate by using a Halbach array magnet, and the magnetic nanowires and a solvent are quickly separated by using magnetic attraction, so that a periodically ordered magnetic nanowire array is obtained on the surface of the substrate.

The technical scheme of the invention is as follows:

the dispersion liquid containing the magnetic nanowires is prepared to have the concentration of 0.01-10 mg/ml. Mixing for 2min with oscillator, stirrer or ultrasonic instrument to form stable and uniform dispersion;

clinging the substrate material to the surface of the magnetic surface of the Halbach array magnet;

and (2) contacting the exposed surface of the substrate with a dispersion containing the magnetic nanowires, rapidly depositing the magnetic nanowire array on the surface of the substrate under the attraction action of a magnetic field, separating the substrate with the ordered magnetic nanowire array on the surface from the solvent, drying the substrate under an infrared drying lamp or in flowing air, and separating the substrate with the ordered magnetic nanowire array on the surface from the Halbach array magnet to obtain the substrate with the periodic magnetic nanowire ordered array on the surface.

The magnetic nanowire mainly comprises a nickel-based nanowire, a cobalt-based nanowire and an iron-based nanowire. The nickel-based nanowire mainly comprises a nickel nanowire, a nickel/metal or oxide composite nanowire, wherein the metal comprises one of cobalt, iron, copper, silver and gold, and the oxide comprises one or more of titanium dioxide, indium tin oxide, tin oxide and zinc oxide. The cobalt-based nanowire mainly comprises a cobalt nanowire, a cobalt/metal or oxide composite nanowire, wherein the metal comprises one of nickel, iron, copper, silver and gold, and the oxide comprises one or more of titanium dioxide, indium tin oxide, tin oxide and zinc oxide. The iron-based nanowire mainly comprises an iron nanowire and an iron/metal or oxide composite nanowire, wherein the metal comprises one of nickel, cobalt, copper, silver and gold, and the oxide comprises one or more of titanium dioxide, indium tin oxide, tin oxide and zinc oxide.

The substrate is a non-magnetic substrate and mainly comprises a substrate such as hard glass, quartz, a silicon wafer and the like and a flexible organic plastic substrate such as PET, polyimide and the like.

The Halbach array magnet periodic structure arrangement mode has a plurality of modes, mainly comprises a linear array, a circular ring array and the like, and preferably selects the linear array.

The exposed surface of the substrate is contacted with a dispersion containing magnetic nanowires, comprising placing the dispersion over the substrate and placing the substrate over the dispersion.

The method for separating the substrate with the ordered magnetic nanowire array on the surface from the solvent mainly comprises the steps of pouring or extracting the solvent above the substrate for recovery, and extracting the solvent or pulling the substrate below the substrate for recovery of the solvent.

Compared with the traditional method, the method has the characteristics of controllable linear density of the nanowires in unit area, high deposition speed, environmental friendliness and the like. The method can be applied to the preparation of magnetic memory devices, sensing devices, transparent conductive films and the like.

Drawings

FIG. 1 is a schematic diagram of depositing a periodic array of magnetic nanowires on the surface of a linear array Halbach magnet in accordance with example 4 of the present invention;

FIG. 2 is a photomicrograph of an array of single-oriented nickel nanowires prepared according to example 4 of the present invention at 100 magnifications, wherein (a) the coverage is 10%, and (b) the coverage is 30%;

fig. 3 is a photomicrograph of ordered grids of vertically stacked nickel nanowires prepared in example 5 of the present invention at 100 magnifications, where (a) the coverage is 10% of the vertical stacking of the single-orientation magnetic nickel nanowires, and (b) the coverage is 30% of the vertical stacking of the single-orientation magnetic nickel nanowires.

Detailed Description

The technical solution of the present design will be described in detail with reference to examples and experimental examples, but the scope of protection is not limited thereto.

Example 1

Dissolving 1.2g of sodium hydroxide in 35ml of ethylene glycol, and stirring for 2 hours to obtain a uniform solution; adding 10ml of hydrazine hydrate solution (the mass content is 80 percent) into the solution, stirring and mixing the solution evenly, placing the solution above a 0.2T neodymium iron boron permanent magnet, and heating the solution in water bath at 60 ℃. 5ml of 0.1M nickel chloride glycol solution is dropwise added by an injector, and is taken out after 10min of reaction, so that the floating gray nickel nanowire is obtained above the solution. Separating the nanowires from the solution, washing with isopropanol for 3 times to obtain nickel nanowire dispersion liquid dispersed in the isopropanol, and using the nickel nanowire dispersion liquid to prepare the surface-deposited nickel nanowire array.

Example 2

The nickel nanowires in example 1 were dispersed in a certain amount of isopropyl alcohol to prepare dispersions of nickel nanowires with different contents, and the dispersions were mixed for 2min using an oscillator to obtain a uniformly dispersed nickel nanowire dispersion. Attaching the PET substrate to Halbach magnet (magnetic pole spacing 0.5mm, suction 65 g/cm)²) The magnetic surface of the PET substrate is fixed with a liquid groove with a certain area. Pouring the nickel nanowire dispersion liquid into a liquid tank, standing for 1min, extracting and recovering the solvent by using a needle tube, and volatilizing a small amount of the solvent on the surface of the substrate by adopting a natural air drying method. And after drying, separating the substrate from the Halbach magnet and the liquid bath to obtain the substrate with the surface provided with the unidirectional periodic magnetic nanowire array.

And preparing the magnetic nano array substrate with different coverage rates on the surface by regulating and controlling the content of nickel in the nickel nanowire dispersion liquid. The relationship between the coverage rate of the magnetic nanowires on the surface of the substrate and the amount of the nickel nanowires is shown in table 1.

TABLE 1 relationship between coverage of magnetic nanowires on substrate surface and nickel nanowire usage

As can be seen from table 1, the coverage area of the magnetic nanowire array on the surface of the substrate increases with the increase of the usage amount of the nickel nanowires, and the coverage area is in a linear relationship, so that the usage amount of the nickel nanowire dispersion can effectively control the coverage rate of the nanowire array, and data can be provided for the application of the nanowire arrays with different coverage rates.

Example 3

The substrate with the surface nickel nanowire coverage rate of 10% in the embodiment 2 is dried at 80 ℃ for 24 h. And rotating the PET substrate with the surface having the single orientation by 90 degrees, tightly attaching the PET substrate to the surface of the Halshell magnet again, and repeating the steps of deposition, solvent recovery and drying in the embodiment 2 to obtain the nickel nanowire ordered grid substrate with the surface having the vertical orientation.

Example 4

And (3) soaking the PET substrate with the nickel nanowire ordered grid on the surface in the embodiment 3 in 0.1M dilute hydrochloric acid solution for 1min, taking out, soaking in deionized water for washing, and drying at 80 ℃ to obtain the conductive transparent electrode.

Claims

1. A rapid deposition method of a periodically ordered magnetic nanowire array is characterized in that the rapid deposition method is to rapidly assemble the periodic magnetic nanowire array on the surface of a substrate by using a Halbach array magnet to realize rapid separation of nanowires and a solvent; the Halbach array form mainly comprises a linear array and a circular array; the magnetic nanowires are mainly nickel-based nanowires, cobalt-based nanowires or iron-based nanowires; dispersing magnetic nanowires in an organic solvent, and stirring and mixing to form stable and uniform dispersion liquid; and then placing the substrate on the surface of the Halbach magnet, then contacting the substrate with a proper amount of dispersion liquid, and finally separating the substrate with the ordered magnetic nanowire array on the surface from the solvent.

2. The method of claim 1, wherein the halbach array is in the form of a linear array.

3. The method of claim 1, wherein the magnetic nanowires are nickel-based nanowires.

4. The method of claim 3, wherein the nickel-based nanowires comprise primarily nickel nanowires, nickel/metal, or oxide composite nanowires, wherein the metal comprises one of cobalt, iron, copper, silver, gold, wherein the oxide comprises one or more of titanium dioxide, indium tin oxide, zinc oxide; the cobalt-based nanowire mainly comprises a cobalt nanowire, a cobalt/metal or oxide composite nanowire, wherein the metal comprises one of nickel, iron, copper, silver and gold, and the oxide comprises one or more of titanium dioxide, indium tin oxide, tin oxide and zinc oxide; the iron-based nanowire mainly comprises an iron nanowire and an iron/metal or oxide composite nanowire, wherein the metal comprises one of nickel, cobalt, copper, silver and gold, and the oxide comprises one or more of titanium dioxide, indium tin oxide, tin oxide and zinc oxide.

5. The method of claim 1, wherein contacting the substrate with the appropriate amount of dispersion comprises pouring the nanowire dispersion onto a surface of the substrate, spraying the dispersion onto a surface of the substrate, and immersing the substrate in the dispersion comprising the nanowires.

6. The method of claim 5, wherein the substrate having the ordered magnetic nanowire array on the surface is separated from the solvent by: the solvent above the substrate is recovered by pouring or drawing, and the solvent below the substrate is recovered by drawing or pulling the substrate.