KR101483512B1 - Method for Manufacturing Thin Film and Nanorod of Zinc Oxide(ＺｎＯ) - Google Patents

Abstract

The present invention relates to a method for producing zinc oxide (ZnO) nanorods and thin films, and a method for mass-producing zinc oxide nanorods and thin films at room temperature and atmospheric pressure.

The present invention relates to a method for producing zinc oxide nanorods and thin films,

Preparing an aqueous NaCl solution containing 35 to 75 g of NaCl dissolved in 1 L of DI (Deionized) Water on a zinc-plated substrate; Maintaining the NaCl aqueous solution constant at a temperature ranging from 25 to 40 캜; The zinc substrate was charged into the NaCl aqueous solution maintained at a constant temperature for 2 hours to 30 minutes to 5 hours to grow the zinc oxide nanorods or maintained for 3 hours to 24 hours to remove some or all of the grown nanorods Zinc oxide thin film; And forming a zinc oxide nanorod and a zinc oxide thin film as described above, and then removing the zinc-plated substrate in an aqueous solution. The present invention also provides a method for manufacturing a zinc oxide nanorod and a thin film.

According to the present invention, it is possible to obtain uniform and transparent zinc oxide thin films and zinc oxide nanorods arranged in one direction in a more inexpensive and easy manner.

Zinc oxide, nanorod, thin film, normal temperature, normal pressure, galvanized steel sheet

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a zinc oxide nanorod and a thin film,

The present invention relates to a method for preparing zinc oxide (ZnO) nanorods and thin films, and more particularly, to a method for manufacturing zinc oxide (ZnO) nanorods and thin films by growing a one-dimensional zinc oxide nanorods and a zinc oxide thin film on a zinc Zinc oxide nanorods, and thin films.

In general, zinc oxide is a direct transition type semiconductor material having a band gap of 3.32 eV at room temperature. It is a transparent material for a semiconductor, a piezoelectric, a ferroelectric, a ferromagnetic material, a conductor, And the like.

Further, since zinc oxide can be grown on various substrates, it has a possibility to be made into various devices by taking advantage of such properties.

For example, in the case of growing on Si or GaAs, it can be implemented by a sensor together with other ICs on the substrate.

In addition, when grown on glass or sapphire, it can be implemented as an optical sensor or other optical device. Furthermore, when grown on a piezoelectric substrate such as quartz or lithium niobate, SAW Surface Acoustic Wave) properties.

In addition, the zinc oxide layer may be appropriately doped with a semiconductor such as Si, a metal layer such as Pt or Au, a transparent conductive layer such as ITO, or the like to be used for forming various devices.

On the other hand, zinc oxide is a polar semiconductor structure, and its surface energy is different for each (0002) plane as the surface finishes with one of zinc or oxygen with respect to the (0002) plane. Due to such crystallographic properties, the growth rate of c- It is.

When grown on the R-plane of the sapphire substrate, it is reported that the film grows in a two-dimensional layered form. However, in other cases, the probability of growing in the c-axis perpendicular to the substrate is high and rod- It seems to happen.

Therefore, many rod-shaped and thin-film zinc oxide growths have been reported to date using these properties, and the reported growth patterns are mostly nanorods or nanorods of very small diameters.

For example, Huang et al. (Huang et al., Science 292, 1897, 2001) reported the first successful growth of zinc oxide nanorods, and when ZnO nanorods were grown without using a catalyst Park et al., Appl. Phys. Lett., 88, 251903, 2006), and the growth of nano-belt-type oxidized dendrites (Zheng Wei Pen et al., Science 291, 1947, 2001).

However, the reported zinc oxide thin films and nanorods have a limitation to be formed on sapphire or silicon, and zinc oxide thin films should be grown at a growth temperature of about 300 ° C or higher and nanorods at 450 ° C or higher.

This process is required to lower the process temperature when using as a transparent electrode or an electrode on a polymer device. Therefore, a room temperature normal pressure zinc oxide thin film and a nanorod growth process are indispensably required.

The present invention solves the problems of the prior art in which a zinc oxide thin film and a nanorod are synthesized in a small amount at a high temperature and a vacuum, and is intended to provide a method for mass-producing a zinc oxide nanorod and a thin film at normal temperature and atmospheric pressure, There is a purpose.

Hereinafter, the present invention will be described.

The present invention relates to a method for producing zinc oxide nanorods,

Preparing an aqueous NaCl solution containing 35 to 75 g of NaCl dissolved in 1 L of DI (Deionized) Water on a zinc-plated substrate;

Maintaining the NaCl aqueous solution constant at a temperature ranging from 25 to 40 캜;

Charging a zinc-coated substrate in the NaCl aqueous solution maintained at a constant temperature for 2 hours and 30 minutes to 5 hours to grow zinc oxide nanorods; And

And a step of growing the zinc oxide nanorods as described above, and then removing the zinc-coated substrate in an aqueous solution. The present invention also relates to a method of manufacturing the zinc oxide nanorods and the thin film.
The present invention also provides a method for producing a zinc oxide thin film,
Preparing an aqueous NaCl solution containing 35 to 75 g of NaCl dissolved in 1 L of DI (Deionized) Water on a zinc-plated substrate;
Maintaining the NaCl aqueous solution constant at a temperature ranging from 25 to 40 캜;
Holding a zinc-coated substrate in the NaCl aqueous solution maintained at a constant temperature for 3 hours to 24 hours to grow zinc oxide nanorods and changing at least a portion of the grown nanorods to a zinc oxide thin film; And
Growing the zinc oxide nanorods as described above, changing at least a portion of the grown nanorods to a zinc oxide thin film, and then removing the zinc-coated substrate in an aqueous solution. And a manufacturing method thereof.

According to the present invention, it is possible to obtain uniform and transparent zinc oxide thin films and zinc oxide nanorods arranged in one direction in a more inexpensive and easy manner than the conventional ones, and the zinc oxide thin films and nanorods can be used in many applications It can be used to make shapes.

Hereinafter, the present invention will be described in detail.

As described above, in the case of using a chemical vapor deposition method or a physical vapor deposition method at the time of growing nanorods, a process cost is high in a conventional technology in which a process temperature is 300 ° C or more and a vacuum process There is a problem that a substrate or a lower element which is weak in heat is damaged due to a high process temperature.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a method for easily and mass-producing zinc oxide nanorods and thin films at normal temperature in an aqueous solution of NaCl at normal pressure.

In order to prepare zinc oxide thin films and nanorods according to the present invention, it is necessary to prepare a zinc-plated substrate and an NaCl aqueous solution.

The zinc-plated substrate is not particularly limited, but one of a galvanized steel sheet, a zinc-plated metal sheet, a zinc-coated polymer and a zinc-coated glass sheet may be used by a conventional dipping method or a sputtering method .

Although the dipping method is not particularly limited, there are a hot dip galvanizing method and an electro-galvanizing method, and a hot dip galvanizing method is preferable.

Examples of the material to be galvanized include stainless steel, general steel, tool steel, polymer, glass, and silicon.

The NaCl aqueous solution is preferably an aqueous solution in which 35 to 75 g of NaCl is dissolved in 1 L of DI (Deionized) Water.

When the amount of NaCl dissolved in the NaCl aqueous solution is less than 35 g, the density of the generated nanorods is low and the thickness of the thin film becomes thin. When the amount of NaCl is more than 75 g, the nanorods are agglomerated to decrease the surface area, The amount of NaCl dissolved in the NaCl aqueous solution is preferably limited to 35 to 75 g of NaCl in 1 L of DI (Deionized) Water.

The NaCl aqueous solution is kept constant in a thermostat or the like at a temperature range of 25 to 40 캜.

When the temperature of the NaCl aqueous solution is too low or too high, it becomes difficult to produce nanorods or thin films.

The zinc-plated substrate was charged into a NaCl aqueous solution maintained at a constant temperature for 2 hours and 30 minutes to 5 hours to grow zinc oxide nanorods or maintained for 3 hours to 24 hours, A part or all of the rod is changed to a zinc oxide thin film, and then the zinc-plated substrate is removed in an aqueous solution.

When the zinc-plated substrate is charged into the NaCl aqueous solution, it is preferable that the zinc-plated substrate does not touch the bottom of the bath containing the NaCl aqueous solution. For example, it is preferable to keep the zinc plating substrate floating over 1 cm.

When the time for holding the zinc-plated substrate in the NaCl aqueous solution is less than 2 hours 30 minutes, the zinc oxide nanorods are not sufficiently formed, and when the time exceeds 24 hours, the increase in the amount of the thin film is no longer achieved.

In the present invention, in order to obtain only zinc oxide nanorods, the zinc-plated substrate is maintained in an aqueous solution of NaCl for 2 hours and 30 minutes to 5 hours, and zinc oxide nanorods formed to obtain zinc oxide nanorods and thin films together The zinc-plated substrate may be removed in an aqueous solution of NaCl before the thin film is converted into a thin film. If only the zinc oxide thin film is formed, the zinc-plated substrate may be removed in the aqueous NaCl solution.

Hereinafter, the present invention will be described with reference to Fig.

FIG. 1 shows a flow chart of a process for manufacturing a zinc oxide nanorod and a thin film according to a preferred embodiment of the present invention.

As shown in Fig. 1, the surface of the zinc-plated substrate is cleaned (S1) in order to remove foreign substances on the surface of the zinc-plated substrate used for growing zinc oxide, if necessary.

The cleaning process is not particularly limited, but it is preferable to remove foreign matters on the surface through, for example, immersing in acetone and alcohol.

The substrate to be used for growing the zinc oxide nanorods and thin films according to the present invention is not particularly limited. For example, a substrate such as a stainless steel, a general steel, a tool steel, a polymer, glass, or silicon may be immersed or sputtered It is preferable to use a substrate on which a zinc coating layer is formed by a conventional process.

Next, an NaCl aqueous solution having a constant composition is prepared (S2).

The NaCl aqueous solution is prepared by dissolving 35 to 75 g of NaCl in 1 L of DI (Deionized) Water.

The NaCl aqueous solution prepared as described above is placed in a bath or the like in which a bath can be maintained and maintained at a temperature.

The NaCl aqueous solution is maintained at a constant temperature in a temperature range of 25 to 40 DEG C in a thermostat tank before immersing the specimen (S3).

The zinc-plated substrate is charged into the NaCl aqueous solution maintained at a constant temperature as described above (S4).

The present invention can be implemented, for example, through an aqueous solution chemistry. In the case of a chemical reaction in an aqueous solution, the substrate is charged in such a manner that the substrate floats in an aqueous solution tank whose temperature is controlled.

After charging the substrate into the NaCl aqueous solution as described above, the zinc oxide nanorods were grown for 2 hours to 30 minutes to 5 hours, or the zinc oxide nanorods were grown for 3 hours to 24 hours to partially or completely remove the zinc oxide nanorods Zinc oxide thin film (S5).

Next, the zinc-plated substrate is removed in an aqueous NaCl solution (S6).

Hereinafter, the present invention will be described more specifically by way of examples.

(Example)

2 is an electron micrograph and compositional analysis of the surface of the zinc-plated substrate.

As can be seen in FIG. 2, the substrate surface is a Zn-coated specimen and is a flat surface.

3 is a photograph of the shape of the zinc oxide nanorods formed according to the present invention by an electron microscope.

3, the NaCl aqueous solution prepared by dissolving 50 g of NaCl in 1 L of DI (Deionize) Water was placed in a bath and kept constant at 25 ° C. Then, the zinc-plated substrate of FIG. 2 was charged into the NaCl aqueous solution for 4 hours To grow zinc oxide nanorods.

As shown in FIG. 3, the zinc oxide nanorods have a length of about 10 μm and are grown in a densified form on the upper side of the substrate, and the upper end of each bar has a sharp end of the needle-like shape.

FIG. 4 is an electron micrograph and compositional analysis chart of the zinc oxide nanorods after changing the zinc oxide nanorods to a zinc oxide thin film by holding the specimen of FIG. 3 for 12 hours (from when the zinc oxide nanoparticles are introduced into the aqueous NaCl solution).

As shown in FIG. 4, the composition ratio of oxygen is higher than that of the zinc coating of FIG. 2, indicating that a zinc oxide thin film is formed.

The devices using the structural features of the present invention can be various application devices.

For example, when using the upper transparent electrode in a display device, since the process temperature and pressure are at room temperature and normal pressure, there is an advantage that a transparent upper electrode can be formed without affecting the display device. In addition, .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process flow chart showing an example of a process for producing a zinc oxide nanorod and a thin film according to the present invention; FIG.

FIG. 2 is a scanning electron micrograph of a zinc-coated substrate coated with zinc on stainless steel. FIG.

3 is a scanning electron micrograph of zinc oxide nanorods grown in aqueous NaCl solution at room temperature using the substrate of FIG.

FIG. 4 is an electron micrograph of a zinc oxide thin film grown in a normal-temperature NaCl aqueous solution using the substrate of FIG.

Claims (4)

A method of producing a zinc oxide nanorod, Preparing an aqueous NaCl solution containing 35 to 75 g of NaCl dissolved in 1 L of DI (Deionized) Water on a zinc-plated substrate; Maintaining the NaCl aqueous solution constant at a temperature ranging from 25 to 40 캜; Charging a zinc-coated substrate in the NaCl aqueous solution maintained at a constant temperature for 2 hours and 30 minutes to 5 hours to grow zinc oxide nanorods; And And growing the zinc oxide nanorods as described above, and then removing the zinc-coated substrate in an aqueous solution. The method of manufacturing a zinc oxide nanorods according to claim 1, wherein the zinc-plated substrate is zinc-plated by a hot-dip galvanization method. A method of producing a zinc oxide thin film, Preparing an aqueous NaCl solution containing 35 to 75 g of NaCl dissolved in 1 L of DI (Deionized) Water on a zinc-plated substrate; Maintaining the NaCl aqueous solution constant at a temperature ranging from 25 to 40 캜; Holding a zinc-coated substrate in the NaCl aqueous solution maintained at a constant temperature for 3 hours to 24 hours to grow zinc oxide nanorods and changing at least a portion of the grown nanorods to a zinc oxide thin film; And Growing the zinc oxide nanorods as described above, changing at least a portion of the grown nanorods to a zinc oxide thin film, and then removing the zinc-coated substrate in an aqueous solution. Gt; The zinc oxide thin film manufacturing method according to claim 3, wherein the zinc-plated substrate is zinc-plated by a hot-dip galvanizing method.

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