KR20120010388A - Manufacturing method of zinc oxide nanorods with nano pore on surface and zinc oxide nanorods with nano pore on surface made by the same - Google Patents

Abstract

PURPOSE: A method for manufacturing a zinc oxide nano-rod with pores on the surface thereof and the zinc oxide nano-rod are provided to control the surface shape of the zinc oxide nano-rod and to increase the specific surface area of the zinc oxide nano-rod by thermally treating the zinc oxide nano-rod at a specific temperature. CONSTITUTION: A method for manufacturing a zinc oxide nano-rod with pores on the surface thereof includes the following: a zinc precursor is dissolved in a solvent to form a sol solution, and the sol solution is coated on a substrate; a zinc oxide seed layer is deposited to form a zinc oxide substrate; the zinc oxide substrate is immersed in the mixed aqueous solution of the zinc precursor and an amine-based compound; a hydrothermal treating process is implemented at a temperature between 90 and 220 degrees Celsius for 5 to 12 hours; zinc oxide nano-rods are deposited and grown; the zinc oxide substrate with the zinc oxide nano-rods is cooled to the room temperature; and the zinc oxide nano-rods are heated to a temperature between 300 and 1000 degrees Celsius under one condition of argon, nitrogen, and inert gas atmospheres.

Description

MANUFACTURING METHOD OF ZINC OXIDE NANORODS WITH NANO PORE ON SURFACE AND ZINC OXIDE NANORODS WITH NANO PORE ON SURFACE MADE BY THE SAME}

The present invention relates to a method for producing zinc oxide nanorods having nanopores on the surface and to zinc oxide nanorods having nanopores on the surface prepared thereby.

Zinc oxide (ZnO) is a broadband semiconductor material and has been widely used in various fields such as high voltage electric and electronic devices, piezoelectric devices, gas sensors, sunscreens, and transparent conductive films. The production method of zinc oxide can be generally classified into a dry method and a wet method. In the dry method, a zinc oxide powder is obtained by dissolving and vaporizing a metal zinc to obtain zinc oxide powder by oxidation with air in a vapor state, and zinc hydroxide or zinc carbonate with coal. There is a method obtained by reducing. In the former method, zinc oxide in the form of particles is generally obtained, and it may be difficult to produce a particle size of 100 nm or less, and the latter method may be difficult to obtain high purity powder due to the purity of the powder to be produced. have. In the wet method, a small size powder can be obtained by precipitation of basic zinc carbonate by reaction with a ZnSO ₄ or ZnCl ₂ solution and a Na ₂ CO ₃ solution, followed by filtration, washing with heat and decomposition at about 400 ° C. It may be difficult to control the shape due to irregular shape.

Recently, many studies on zinc oxide nanostructures have been conducted. In general, nanostructures range in size from several nanometers (nm) to hundreds of nanometers (nm) and exhibit a variety of physical and chemical properties not found in conventional bulk-type materials. Therefore, by using these nanomaterials and nanostructures, more advanced and miniaturized electronic, electrochemical and optical devices can be realized, and new features and structures that were not possible before can be realized [Y. Xia at al, Advanced Materials, Vol. 15, p. 353 (2003); G. Tseng, Science, Vol. 294, p. 1293 (2001). Zinc oxide nanostructures have unique properties derived from these nanostructures and can be used in many fields such as ultraviolet light emitting devices (LEDs), gas sensors, solar cells, and thin film transistors.

Examples of nanostructures known to date include quantum dots, nano powders, nanorods, nanowires, nanotubes, quantum wells, nano thin films, and nanocomposites. (nano composite) and so on. Among these, zinc oxide (ZnO) nanorods (nanorods) can improve photocatalyst efficiency as much as possible by increasing the exposed area when coated on a glass substrate.

Conventionally, in the method of manufacturing the zinc oxide nanorods, a method of forming the nanorods to form a long length or controlling the morphology is developed, but a method for increasing the exposed area by controlling the surface shape of the zinc oxide nanorods. The back was not developed.

An object of the present invention is to provide a method for producing zinc oxide nanorods having nanopores on the surface by controlling the surface shape of the zinc oxide nanorods and zinc oxide nanorods having nanopores on the surface produced thereby.

The present invention to achieve the above object

a) zinc oxide / substrate formation step of dissolving a zinc precursor in a solvent to form a sol solution, and then coating the sol solution on a substrate to deposit a zinc oxide seed layer;

b) a hydrothermal step of immersing the zinc oxide / substrate in a mixed aqueous solution of a zinc precursor and an amine compound, followed by hydrothermal treatment at 90 to 220 ° C. for 5 to 12 hours to deposit and grow zinc oxide nanorods;

c) cooling the zinc oxide / substrate on which the zinc oxide nanorods are deposited and grown to room temperature; And

d) a heat treatment step of heating the zinc oxide nanorods prepared in step c) to 300 to 1000 ° C. under any one of argon (Ar), nitrogen, an inert gas atmosphere, and a vacuum; Provided is a method for producing a zinc oxide nanorod having nanopores in it.

In the present invention, the step a) is

(1) A 1 to 3 molar ratio is used based on a zinc precursor containing 1 to 3 carbon atoms having a low boiling point as a solvent and mixing monoethanolamine as a stabilizer to the alcohol, wherein the monoethanolamine is added in the next step. Preparing a solvent mixture by mixing to prepare a solvent mixture;

(2) a sol preparation step of preparing a sol by dissolving 0.3 to 0.9 mol / L of a zinc precursor in the solvent mixture obtained in the solvent mixture preparation step;

(3) homogenization step of homogenizing the sol by stirring for 1 hour to 3 hours at a temperature of 50 to 70 ℃;

(4) a preheating step of coating a sol containing zinc obtained in the homogenizing step on a substrate and preheating in an electric furnace; And

(5) a post-heating step of oxidizing and crystallizing the substrate from which the solvent is removed through the pre-heating step in an electric furnace; provides a method of manufacturing zinc oxide nanorods having nano-pores on the surface.

In the present invention, the substrate of step a) is a silicon substrate, P-type silicon substrate, Al ₂ O ₃ substrate, MgAl ₂ O ₄ substrate, Al ₂ O ₃ substrate, GaN buffer layer formed, wafer substrate, ITO substrate, quartz glass It provides a method for producing zinc oxide nanorods having nanopores on the surface, characterized in that any one selected from the group consisting of a substrate, a plastic substrate.

In the present invention, the zinc precursor of step a) and b) is zinc chloride (ZnCl ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), zinc citrate (Zn ₃ [O ₂ CCH ₂ C (OH) (CO ₂ ) CH ₂ CO ₂ ] ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ ˜6H ₂ O) (zinc of nitrate hexahydrate), and zinc ahseteyiteuyi hydrate _{(Zn (OOCCH 3) 2?} 2H 2 O) (zinc acetate dehydrate) zinc nanorods oxide having nano-pores on the surface, characterized in that at least one member selected from the group consisting of compound It provides a manufacturing method.

In the present invention, the amine compound of step b) is hexamethyleneamine (hexamethyleneamine), hexamethylenetetraamine (hexamethylenetetramine (HMT), cyclohexylamine, monoethanolamine (monoethanolamine), diethanolamine (diethanolamine) And triethanolamine (triethanolamine) provides a method for producing zinc oxide nanorods having nanopores on the surface, characterized in that at least one selected from the group consisting of.

In the present invention, as the heat treatment temperature is increased in step d), the average pore diameter of the nanopores formed on the surface of the zinc oxide nanorods increases, and the pore density decreases. It provides a method for producing zinc oxide nanorods.

In the present invention, the alcohol having a low boiling point of 1 to 3 carbon atoms as the solvent of step 1) provides a method for producing zinc oxide nanorods having nano pores on the surface, characterized in that 2-methoxy alcohol.

In the present invention, the preheating step is repeated 2 to 7 times to provide a method for producing a zinc oxide nanorod having a nano-pores on the surface characterized in that it is carried out.

The present invention also provides a zinc oxide nanorod having nanopores on its surface by the production method of the present invention. The present invention also provides a semiconductor device comprising zinc oxide nanorods having nanopores on the surface produced by the production method of the present invention. In the present invention, the semiconductor element is any one of a light receiving element, a light emitting element, a solar cell, a memory element, a FET, a surface acoustic wave (SAW) application element, a communication filter element, an FED, a sensor element, a ferroelectric element, and a ferromagnetic element.

According to the method for producing zinc oxide nanorods having nanopores on the surface of the present invention, the surface shape of the zinc oxide nanorods is controlled, the specific surface area is increased, and the structural and optical properties are improved by forming nanopores by heat treatment. It can be applied to semiconductor devices such as light emitting devices, solar cells, memory devices, FETs, surface acoustic wave (SAW) application devices, and communication filter devices.

1 is a SEM image and a cross-sectional SEM image (inside) of a zinc oxide nanorod having nanopores on its surface according to one comparative example and one embodiment of the present invention.
Figure 2 is a SEM image of the surface of the zinc oxide nanorods having nanopores on the surface according to a comparative example and an embodiment of the present invention.
Figure 3 is a graph showing the pore density and the average pore diameter according to the heat treatment temperature of the zinc oxide nanorods according to the comparative example and one embodiment of the present invention.
4 is an XRD diffraction graph according to a heat treatment temperature of zinc oxide nanorods according to one comparative example and one embodiment of the present invention.
5 is a PL spectra according to a heat treatment temperature of a zinc oxide nanorod according to one comparative example and one embodiment of the present invention.
Figure 6 is a graph showing the PL strength ratio of the NBE and DLE according to the heat treatment temperature of the zinc oxide nanorods according to one comparative example and one embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily carry out the present invention.

First, a) a zinc precursor is dissolved in a solvent to form a sol solution, followed by a zinc oxide / substrate formation step of depositing a zinc oxide seed layer by coating the sol solution on a substrate.

The substrate may be any one of a silicon substrate, a P-type silicon substrate, an Al ₂ O ₃ substrate, an MgAl ₂ O ₄ substrate, an Al ₂ O ₃ substrate having a GaN buffer layer, a wafer substrate, an ITO substrate, a quartz glass substrate, and a plastic substrate. Preferred, but not necessarily limited to. In particular, silicon substrates are widely used in zinc oxide growth due to many advantages such as low cost and availability of large size substrates.

However, due to the large lattice constant difference between the silicon substrate and zinc oxide, defects may occur at the interface between them, which may adversely affect the structural and optical properties of the zinc oxide. In order to alleviate the lattice constant difference between the silicon substrate and zinc oxide, a buffer layer and seed material that reduces lattice mismatch is first deposited on the silicon substrate before zinc oxide deposition. As the buffer layer and the seed material, Zn, Ag, ZnO, GaN, or TiN may be used, but is not limited thereto.

In the present invention, a method of forming the buffer layer and the seed layer on the substrate may use a general deposition method used in the technical field to which the present invention belongs, and specifically, chemical vapor deposition and sputtering. , Evaporation or sol-gel.

The method for forming the buffer layer and the seed material according to the present invention on the substrate by a sol-gel method of dissolving a zinc precursor in a solvent to form a sol, then gelling it to produce a zinc oxide thin film, (1) carbon number as a solvent A solvent mixture is prepared by using a low boiling point alcohol of 1 to 3 and mixing monoethanolamine as a stabilizer to the alcohol, wherein the monoethanolamine is mixed in a 1: 1 molar ratio based on the zinc precursor added in the next step. Preparing a solvent mixture to prepare a; (2) a sol preparation step of preparing a sol by dissolving 0.3 to 0.9 mol / L of a zinc precursor in the solvent mixture obtained in the solvent mixture preparation step; (3) a preheating step of coating a sol containing zinc obtained in the sol preparation step on a substrate and preheating in an electric furnace; And (4) a post-heating step in which the substrate from which the solvent is removed through the pre-heating step is heated in an electric furnace to oxidize and crystallize.

The solvent mixture preparation step of (1) uses a low boiling point alcohol having 1 to 3 carbon atoms as a solvent, and mixed with monoethanolamine as a stabilizer to the alcohol, wherein the monoethanolamine is added to the zinc precursor. It is mixed so as to have a 1: 1 molar ratio on the basis of. Since the monoethanolamine functions to stabilize the zinc precursor constituting the sol, the monoethanolamine is preferably used in the same amount as the zinc precursor.

The zinc precursor is zinc chloride (ZnCl ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), zinc citrate (Zn ₃ [O ₂ CCH ₂ C (OH) (CO ₂ ) CH ₂ CO _{2] 2),} zinc nitrate _{(Zn (NO 3) 2)} , zinc nitrate hexahydrate _{(Zn (NO 3) 2?} 6H 2 O) and zinc ahseteyiteuyi hydrate _{(Zn (OOCCH 3) 2?} 2H 2 O It is preferably at least one compound selected from the group consisting of, but is not necessarily limited thereto. The zinc precursor is heated in subsequent post-heating steps to oxidize and crystallize to form a thin film of zinc oxide.

The sol preparation step of (2) is a step of making it suitable for coating on a substrate in order to obtain a thin film, in particular in the subsequent preheating step, and also functions as a main regulator of increasing the c-axis crystal orientation according to the present invention. In the solvent mixture obtained in the solvent mixture preparation step, the zinc precursor is dissolved in a molar ratio of 1: 1. When the mixing molar ratio of the zinc precursor is less than 1: 1 or more than 1: 1, there is a problem that the crystal orientation in the (002) plane c-axis direction is lowered, resulting in a structure of polycrystal.

In the homogenization step of (3), the prepared sol is homogenized by stirring for 1 hour to 3 hours at a temperature of 50 to 70 ℃. By performing this homogenization step, the sol is made more homogeneous so that foreign matters and the like are not formed in the resulting zinc oxide layer.

The preheating step (4) serves as a main regulator of increasing the c-axis crystal orientation in accordance with the present invention, coating the sol containing zinc obtained in the sol homogenization step on the substrate, and in the electric furnace Preheating, particularly preferably heating in a temperature range of 270 to 320 ° C. to blow off the residual solvent and organic material. If the preheating temperature is lower than 270 ° C or higher than 320 ° C, the crystal orientation of the (002) plane in the c-axis direction may be lowered as described above, resulting in a polycrystalline structure.

This preheating step (4) is preferably repeated after each coating, the coating number is preferably 2 to 7 times. It can be understood that it is necessary to make the zinc oxide to be obtained an appropriate thickness. That is, less than two times may be a problem that the obtained thin film of zinc oxide is too thin, if more than seven times too thick. However, it will be apparent to those skilled in the art that the number of coatings can be adjusted as needed.

The post-heating step (5) is a step of oxidizing and crystallizing the substrate from which the solvent is removed through the pre-heating step in an electric furnace, and can be understood to be the same as or similar to the conventional method.

When a zinc oxide / substrate having a zinc oxide seed layer deposited is prepared by the above method, zinc oxide nanorods are deposited and grown by hydrothermal synthesis. In hydrothermal synthesis, the type and concentration of the microstructure to be grown can be controlled by adjusting the type, concentration and reaction temperature of the reaction precursor. In the present invention, b) the zinc oxide / substrate is mixed with a zinc precursor and an amine compound. It is immersed in an aqueous solution and hydrothermally treated at 90 to 220 ° C. for 5 to 12 hours to carry out a hydrothermal step of depositing and growing zinc oxide nanorods.

The zinc precursor is zinc chloride (ZnCl ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), zinc citrate (Zn ₃ [O ₂ CCH ₂ C (OH) (CO ₂ ) CH ₂ CO _{2] 2),} zinc nitrate _{(Zn (NO 3) 2)} , zinc nitrate hexahydrate _{(Zn (NO 3) 2?} 6H 2 O) and zinc ahseteyiteuyi hydrate _{(Zn (OOCCH 3) 2?} 2H 2 O It is preferably at least one compound selected from the group consisting of, but is not necessarily limited thereto.

The amine compound is hexamethyleneamine (hexamethyleneamine), hexamethylenetetramine (hexamethylenetetramine (HMT), cyclohexylamine, monoethanolamine (monoethanolamine), diethanolamine (diethanolamine) and triethanolamine (triethanolamine) It is preferably one or more selected from, and more preferably hexamethylenetetramine (HMT), but is not necessarily limited thereto.

When the prepared zinc oxide / substrate is immersed in the mixed aqueous solution of the zinc precursor and the amine compound, the zinc oxide nanorods on the substrate start to deposit and grow in a constant direction. Such hydrothermal synthesis is preferably carried out for 5 to 12 hours at 90 to 220 ℃, which means that the nanorods do not grow sufficiently at a temperature or a shorter time than the above range, and the nanorod is no longer at a temperature or a longer time than the above range. Because it does not grow.

Thereafter, c) the zinc oxide / substrate on which the zinc oxide nanorods are deposited and grown is gradually cooled at room temperature. It is preferable to wash the cooled substrate with distilled water and to give nitrogen gas. As a result, a substrate in which nanorods are grown can be obtained.

Finally, d) the zinc oxide nanorods are heated by heating to 300 to 700 ° C. under any one of argon (Ar), nitrogen, an inert gas atmosphere, and vacuum. As a result, pores of several nanometers (nm) size are formed on the surface of the nanorods (FIG. 1). This is because volatile gases are released by thermal energy during heat treatment, and zinc nitrate and unreacted materials rise to the surface and evaporate to form pores on the nanorod surface.

In this step, as the heat treatment temperature increases, the average pore diameter of the nanopores formed on the surface of the zinc oxide nanorods increases, and the pore density decreases. This can be confirmed in Experimental Example 2 and FIG. 3 to be described later.

The heat treatment step not only affects the pore diameter and the pore density, but is also known to reduce defects caused by zinc and zinc pores in zinc oxide through heat treatment, thereby improving structural properties.

Zinc oxide nanorods having nanopores on the surface by the manufacturing method has an advantage that the surface area is increased, and the pore diameter and pore density of the nanopores can be adjusted according to temperature. In addition, the zinc oxide nanorods have an advantage that the optical properties are improved by reducing the defects and improving the crystallinity of the zinc oxide nanorods by the unique shape of the nano-pores and heat treatment.

Zinc oxide nanorods by the manufacturing method of the present invention having improved structural and optical properties are suitable for semiconductor devices. Such semiconductor devices include light receiving devices, light emitting devices, solar cells, memory devices, FETs, surface acoustic wave (SAW) application devices, communication filter devices, FEDs, sensor devices, ferroelectric devices, and ferromagnetic devices.

Hereinafter, the technology disclosed herein will be described in more detail with reference to Examples. However, the disclosed technology is not limited only to the following examples.

< Comparative example  1>

P-type silicon (100) substrate was immersed in piranha solution (H ₂ SO ₄ : H ₂ O ₂ = 8: 1) and washed for 15 minutes at 110 ℃ hydrofluoric acid (HF 50%: H ₂ O = 1: It was immersed in 9) for 1 minute.

0.6 M zinc acetate [Zn (CH ₃ COO) ₂ -H ₂ O] was dissolved in a solvent of 0.6M 2-methoxyethanol in a molar ratio of 1: 1, and monoethanolamine (MEA) was added thereto. To prepare a sol solution. The prepared sol solution was stirred at 60 ° C. for 2 hours until it became a clear homogeneous solution.

After leaving the sol solution for 1 day, it was centrifuged at 3000 rpm for 20 seconds to spin coat the P-type silicon substrate. The solvent was then preheated at 300 ° C. for 10 minutes to evaporate the solvent and remove the organic residue. This spin coating and preheating process were repeated three times. Then, a zinc oxide seed layer (seed layer) was post-heated (postheat) for 1 hour in an air atmosphere of 550 ℃ to prepare a zinc oxide / P-type silicon.

Teflon tube after stirring sufficiently with an aqueous solution of 0.3M hexahydrate zinc nitrate [Zn (NO ₃ ) _2- H ₂ O] and 0.3M hexamethylenetetraamine (HMT, [C ₆ H ₁₂ N ₄ ]) Transferred to a built-in stainless steel autoclave.

The zinc oxide / P-type silicon was immersed in the aqueous solution and left at 140 ° C. for 6 hours. Thereafter, the autoclave was slowly cooled to room temperature, and washed with distilled water while flowing 6N nitrogen gas onto the P-type silicon (100) substrate.

< Example  1>

After proceeding in the same manner as in Comparative Example 1, further heat treatment at 300 ℃ for 20 minutes under an argon (argon) atmosphere.

< Example  2>

All of the conditions are the same as in Example 1, but was heat-treated at 500 ° C. instead of 300 ° C. under an argon atmosphere.

< Example  3>

All of the conditions are the same as in Example 1, but the heat treatment at 700 ℃ instead of 300 ℃ in an argon (argon) atmosphere.

< Experimental Example  1> SEM  Picture

SEM and surface and cross-sectional shapes of the zinc oxide nanorods prepared in Comparative Example 1 and Examples 1 to 3 were measured. 1 and 2 show (a) Comparative Example 1 (before heat treatment), (b) Example 1 (300 ° C), (c) Example 2 (500 ° C), and (d) Example 3 (700 ° C). Surface SEM photographs and transverse SEM photographs (internal photographs) of zinc oxide nanorods with nanopores.

As can be seen in Figures 1 and 2, the prepared zinc oxide shows the shape of hexagonal (hexagonal shaped) nanorods regardless of the heat treatment, the nanorods are grown in a direction perpendicular to the substrate, the length of the nanorods is about It was confirmed that it is substantially constant to 6㎛. In addition, pores that were not identified before heat treatment began to appear after heat treatment, and as the heat treatment temperature was increased, the diameters of the nano pores on the surface of the nanorods were increased.

< Experimental Example  2> pore density and pore diameter  Measure

Pore density and pore diameter of the zinc oxide nanorods prepared in Comparative Example 1 and Examples 1 to 3 were measured. 3 is a graph showing pore density and pore diameter of zinc oxide nanorods according to heat treatment temperature.

As can be seen in Figure 3, as the heat treatment temperature was increased it was confirmed that the pore density decreases, the pore diameter increases. The pore densities at 300, 500 and 700 ° C. were 1.30 × 10 ⁷ , 1.03 × 10 ⁷ and 7.00 × 10 ⁶ cm ^-2 , and the pore diameters were 15, 22 and 25 nm at each temperature. As the temperature increases, the moving distance between the volatile gas and the unreacted material increases and is released to the surface. As a result, the volatile gas and the unreacted material aggregate, thereby increasing the pore diameter while decreasing the pore density.

< Experimental Example  3> XRD diffraction  analysis

Of the zinc oxide nanorods prepared in Comparative Example 1 and Examples 1 to 3 XRD diffraction analysis was performed. This is shown in FIG. 4.

As can be seen in FIG. 4, strong ZnO peaks (002) and weak ZnO peaks (004) were observed at all heat treatment temperatures. Strong ZnO peaks were greater in Examples 1-3 than in Comparative Example 1. A strong ZnO peak appeared at about 34.5 ^o , indicating that the grown zinc oxide nanorods were grown in the c-axis direction of the hexagonal crystal structure.

< Experimental Example  4> PL ( photoluminescence Spectra analysis

In order to investigate the optical properties of the zinc oxide nanorods prepared in Comparative Example 1 and Examples 1 to 3 was performed PL (photoluminescence) spectra analysis. This is shown in FIG. 5.

As can be seen in Figure 5, the photoluminescence (PL) spectra showed two emission peaks. One is the near band-edge emission (NBE) peak in the ultraviolet region due to free exciton emission, which is the excitation recombination of zinc oxide, which appeared at about 381 nm and was almost unaffected by the presence of nanopores. The other was a deep level emission (DLE) peak of the visible region due to defects, which appeared in the region of about 610 to 623 nm and moved in the long wavelength direction as the nanopores were formed and also as the heat treatment temperature increased.

FIG. 6 is a graph showing the ratio ( _{N NBE} / I _DLE ) of NBE (I _NBE ) peak size and DLE (I _DLE ) peak size of zinc oxide nanorods according to heat treatment temperature. FIG. As the temperature increased, I _NBE / I _DLE was found to increase from 0.28 to 1.14.

This is because the emission efficiency is increased and nano-structure defects are reduced by the unique shape of the nano-pores and the improvement of the crystallinity of the nanorods by heat treatment. A small number of defects increased the NBE luminous efficiency and decreased the DLE luminous efficiency, thereby increasing I _NBE / I _DLE .

Claims (11)

a) zinc oxide / substrate formation step of dissolving a zinc precursor in a solvent to form a sol solution, and then coating the sol solution on a substrate to deposit a zinc oxide seed layer;
b) a hydrothermal step of immersing the zinc oxide / substrate in a mixed aqueous solution of a zinc precursor and an amine compound, followed by hydrothermal treatment at 90 to 220 ° C. for 5 to 12 hours to deposit and grow zinc oxide nanorods;
c) cooling the zinc oxide / substrate on which the zinc oxide nanorods are deposited and grown to room temperature; And
d) a heat treatment step of heating the zinc oxide nanorods prepared in step c) to 300 to 1000 ° C. under any one of argon (Ar), nitrogen, an inert gas atmosphere, and a vacuum; A method for producing a zinc oxide nanorod having nanopores in it.
The method of claim 1,
Step a)
(1) A low boiling point alcohol having 1 to 3 carbon atoms is used as a solvent, and monoethanolamine is mixed with the alcohol as a stabilizer. Preparing a solvent mixture by mixing to prepare a solvent mixture;
(2) a sol preparation step of preparing a sol by dissolving 0.3 to 0.9 mol / L of a zinc precursor in the solvent mixture obtained in the solvent mixture preparation step;
(3) homogenization step of homogenizing the sol by stirring for 1 hour to 3 hours at a temperature of 50 to 70 ℃;
(4) a preheating step of coating a sol containing zinc obtained in the homogenizing step on a substrate and preheating in an electric furnace; And
(5) a post-heating step of oxidizing and crystallizing the substrate from which the solvent is removed through the pre-heating step in an electric furnace;
The method of claim 1,
The substrate of step a) may be a silicon substrate, a P-type silicon substrate, an Al ₂ O ₃ substrate, an MgAl ₂ O ₄ substrate, an Al ₂ O ₃ substrate having a GaN buffer layer, a wafer substrate, an ITO substrate, a quartz glass substrate, or a plastic substrate. Method for producing zinc oxide nanorods having nanopores on the surface, characterized in that any one selected from the group consisting of.
The method of claim 1,
The zinc precursor of step a) and b) is zinc chloride (ZnCl ₂ ), zinc sulfate (ZnSO ₄ ), zinc acetate (Zn (CH ₃ CO ₂ ) ₂ ), zinc citrate (Zn ₃ [O ₂ CCH _{2 C (OH) (CO 2)} CH 2 CO 2] 2), zinc nitrate _{(Zn (NO 3) 2)} , zinc nitrate hexahydrate _{(Zn (NO 3) 2?} 6H 2 O) and zinc ahseteyiteuyi hydrate (Zn ( OOCCH ₃ ) ₂ ? 2H ₂ O) A method for producing zinc oxide nanorods having nanopores on the surface, characterized in that at least one compound selected from the group consisting of.
The method of claim 1,
The amine compound of step b) is hexamethyleneamine (hexamethyleneamine), hexamethylenetetramine (hexamethylenetetramine (HMT), cyclohexylamine, monoethanolamine, diethanolamine (diethanolamine) and triethanolamine (triethanolamine) Method for producing zinc oxide nanorods having nanopores on the surface, characterized in that at least one selected from the group consisting of.
The method of claim 1,
In step d), as the heat treatment temperature increases, the average pore diameter of the nanopores formed on the surface of the zinc oxide nanorods increases, and the pore density decreases. Manufacturing method.
The method of claim 2,
Alcohol having a low boiling point of 1 to 3 carbon atoms as the solvent of step 1) is 2-methoxy alcohol production method of zinc oxide nanorod having nano pores on the surface.
The method of claim 2,
The preheating step is repeated 2 to 7 times, characterized in that the manufacturing method of zinc oxide nanorod having nano pores on the surface.
Zinc oxide nanorods having nanopores on the surface produced by the method of any one of claims 1 to 8.
A semiconductor device comprising zinc oxide nanorods having nanopores on a surface produced by any one of claims 1 to 8.
The method of claim 10,
The semiconductor device may be any one of a light receiving device, a light emitting device, a solar cell, a memory device, a FET, a surface acoustic wave (SAW) application device, a communication filter device, a FED, a sensor device, a ferroelectric device, and a ferromagnetic device. device.

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