KR20110011167A - Method of fabricating a zinc oxide based 2 dimensional nanostructure and zinc oxide based 2 dimensional nanostructure manufatured thereof - Google Patents

Abstract

PURPOSE: A method for fabricating a zinc oxide-based 2 dimensional nanostructure is provided to form a 2 dimensional nanostructure which is vertically grown on a substrate with high inconsistency of a lattice constant through a phase separation process. CONSTITUTION: A method for fabricating a zinc oxide-based 2 dimensional nanostructure comprises the steps: supplying a zinc-containing precursor, metal-containing precursor and gas-containing oxygen to a substrate(100) with an oxide film to form an amorphous metal oxide layer(104); forming amorphous layers(106) employing the metal as a main component on an amorphous metal-oxide layer, and single-crystal seed layers(108) employing zinc as a main component between the amorphous layers; and selectively forming a 2 dimensional nanostructure(112) on the single crystal seed layers.

Description

Method of fabricating a zinc oxide based two-dimensional nanostructure comprising a nanowall and a zinc oxide based two-dimensional nanostructure prepared using the same {Method of fabricating a zinc oxide based 2 dimensional nanostructure and zinc oxide based 2 dimensional nanostructure manufatured

The present invention relates to a method for producing a zinc oxide-based two-dimensional nanostructure comprising a nanowall, and to a zinc oxide-based two-dimensional nanostructure prepared by using the same, more specifically, a large mismatch between the lattice constant with zinc oxide The present invention also relates to a method for manufacturing a zinc oxide based two-dimensional nanostructure and a method for manufacturing a zinc oxide based two-dimensional nanostructure manufactured by using the same and growing vertically on a substrate.

Nanostructures using metal oxide semiconductors are manufactured in various forms such as nanodots, nanowires, nanowalls and nanotubes. As the metal oxide semiconductor used in such nanostructures, group III-V and group II-VI compound semiconductors are mainly used, and recently, zinc oxide is mainly used in group II-VI compound semiconductors.

Zinc oxide is a wurzite crystal structure with a hexagonal system. It is a direct transition oxide semiconductor material with a wide bandgap of 3.37 eV and a large exciton bonding energy at room temperature. . Zinc oxide has high transmittance, refractive index and large piezoelectric constant in the visible light region. Due to these characteristics, zinc oxide can be used in photonic crystals, optical modulator waveguides, varistors, solar cells, transparent electrodes, surfaceacoustic wave filters, and laser diodes. It is variously used as a light-emitting device such as a light emitting device, a flat panel display or a field emission display (FED), photodetectors, a gas sensor, an ultraviolet blocking film, and the like.

Zinc oxide, which is used as an electronic device, has been generally used in the form of a thin film, but has recently been used as a zinc oxide-based nanostructure. For example, zinc oxide nanowires can achieve maximum efficiency by increasing the critical emission current density. In addition, the zinc oxide nanowires may have a quantum confinement effect due to a size effect due to a small diameter, thereby obtaining maximum luminous efficiency. In addition, the zinc oxide nanowall has a higher mechanical strength in terms of a Young's module than the nanowire, and has a large surface area, so that the zinc oxide nanowall may have a high luminous efficiency when used as a light emitting device. In addition, the nanowall may have high sensitivity when used as a gas sensor.

As a method of manufacturing the zinc oxide-based nanostructures including the nanowalls described above, synthesis in solution, thermal chemical vapor deposition, organometallic chemical vapor deposition (MOCVD), and molecular beam epitaxy There are several methods, such as a molecular beam epitaxy.

For example, the zinc oxide nanowires may be epitaxially grown using a metal catalyst. The epitaxy can be advanced by a Vapor-Liquid-Solid (VLS) mechanism by growing using a chemical vapor deposition (CVD) process employing a metal catalyst such as Au. According to the method described above, as the nanowires grow, the gold forming the seed is moved to the tip portion of the nanowires, and zinc tends to move to the lower end. Metal catalysts cause problems such as deterioration in optical properties due to non-luminescent recombination, difficulty in controlling the conductivity of the nanowires, and deterioration in the orientation of the nanowires.

Various methods have been attempted to solve this problem, and one of them is epitaxy using a metalorganic chemical vapor deposition (MOCVD) process in which a vapor-solid (VS) mechanism is applied. Even if the use of the ZnO can proceed to the growth of zinc oxide nanowires. However, depending on the temperature at which the organometallic chemical vapor deposition process is performed, it may affect the growth direction of the nanowires and the formation of spontaneous interfacial layers. Furthermore, when the process is performed at a high temperature of 500 ° C. or higher, nanowires do not grow on a substrate formed of a large mismatch between zinc oxide and lattice constant, such as silicon or silicon oxide. This is because the zinc oxide precursor cannot be adsorbed onto the substrate in the high temperature process, or even if the zinc oxide precursor is easily adsorbed even if adsorbed.

Zinc oxide-based nanowalls also grow randomly, rather than vertically, on a substrate having a large mismatch between zinc oxide and lattice constant, such as a silicon substrate. Accordingly, studies have been made to form nanowalls on a substrate having a small mismatch between zinc oxide and a lattice constant, for example, a gallium nitride substrate or a sapphire substrate. However, gallium nitride substrates and sapphire substrates are expensive substrates and thus are not suitable for practical application.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a method for manufacturing a zinc oxide-based two-dimensional nanostructure, which is vertically grown on a substrate having a large mismatch in lattice constant due to introduction into an amorphous metal oxide layer and contributes to forming a fine thickness. .

Another object of the present invention is to provide a zinc oxide-based two-dimensional nanostructure, which grows vertically on a substrate having a large inconsistency in lattice constant due to introduction into an amorphous metal oxide layer and contributes to forming a fine thickness.

According to an aspect of the present invention for achieving the above technical problem, there is provided a method for producing a zinc oxide-based two-dimensional nanostructure. In the method of manufacturing the zinc oxide-based two-dimensional nanostructure, a process of supplying a zinc-containing precursor, a metal-containing precursor, and an oxygen-containing gas on a substrate having an oxide film is performed to form an amorphous metal oxide layer containing the metal on the oxide film. It is provided. A single crystal seed which maintains the process and adopts zinc and zinc among the metals as a main component between the amorphous layers and the amorphous layers which adopt the zinc and the metal of the metal as a main component on the amorphous metal oxide layer Form the layers. The process is maintained to selectively form two-dimensional nanostructures on the single crystal seed layers. The metal is in an amorphous phase above the single crystal formation temperature of the zinc.

In some embodiments of the present disclosure, the two-dimensional nanostructure may be formed to have nanowires formed between the nanowires and the nanowires on the single crystal seed layers. The nanowalls may be formed at the monolayer level.

In other embodiments, before forming the amorphous metal oxide layer, the process may be maintained to form an oxide film in which the metal is diffused in the oxide film.

In still other embodiments, the oxide layer may be formed of a natural oxide layer.

In still other embodiments, the amorphous metal oxide layer may be formed to a thickness of 10 to 20 nm.

In yet other embodiments, the single crystal seed layers, the amorphous layers, and the two-dimensional nanostructure are formed of Mg _x Zn _1-x O (0 <x <1) ternary alloy film, wherein the single crystal seed layer They may be formed to have a value of 0.1 ≦ x ≦ 0.4, the amorphous layers may be formed to have a value of 0.8 ≦ x ≦ 0.9, and the nanostructures may be formed to have a value of 0.01 ≦ x ≦ 0.2.

In still other embodiments, the supply of the precursors and the gas may proceed at a pressure of 1 torr or less at a temperature of 500 to 1000 ° C. for at least 10 minutes.

In still other embodiments, the metal may comprise magnesium. The magnesium containing precursor may be supplied at 0.5 to 2.5 μmol / minute. The magnesium-containing precursor may be any one selected from the group consisting of bis-cyclopentadiyl magnesium (Cp ₂ Mg), methyl magnesium iodide (MeMgI) and dimethyl magnesium (Et ₂ Mg).

In still other embodiments, the zinc containing gas may be dimethylzinc [Zn (CH ₃ ) ₂ ], diethylzinc [Zn (C ₂ H ₅ ) ₂ ], zinc acetate [Zn (OOCCH ₃ ) ₂ OH H ₂ O ], Zinc acetate anhydride [Zn (OOCCH ₃ ) ₂ ] and zinc acetylacetonate [Zn (C ₅ H ₇ O ₂ ) ₂ ] and any one selected from the group consisting of oxygen, gas containing oxygen, ozone, It may include any one selected from the group consisting of nitrogen dioxide, water vapor and carbon dioxide.

In still other embodiments, the chemical vapor deposition methods may be performed using thermal CVD, organometallic chemical vapor deposition (MOCVD), or plasma chemical vapor deposition (PECVD).

In still other embodiments, the substrate may include any one selected from the group consisting of silicon, sapphire, gallium nitride, silicon oxide, silicon nitride, zinc oxide, and ITO.

According to another aspect of the present invention for achieving the above technical problem, a zinc oxide-based two-dimensional nanostructure is provided. The zinc oxide based two-dimensional nanostructure has an amorphous phase above a single crystal formation temperature of zinc on a substrate. An amorphous metal oxide layer containing a metal having; On the amorphous metal oxide layer are amorphous layers which adopt the zinc and the metal of the metal as a main component. Between the amorphous layers are single crystal seed layers which adopt the zinc as the main component of the zinc and the metal. Two-dimensional nanostructures are selectively formed on the single crystal seed layers.

According to the present invention, an amorphous metal oxide layer is formed on a substrate through a chemical vapor deposition process using a zinc-containing precursor, an oxygen-containing gas, and a precursor containing a metal having an amorphous phase above the single crystal formation temperature of zinc. The phase separation process is performed to separate the amorphous layer and the single crystal seed layer on the amorphous metal oxide layer to form a two-dimensional nanostructure such as a nanowall that grows vertically and densely on a substrate having a high mismatch between zinc oxide and lattice constant. have. The nanowall formed by the process may have a very thin thickness and may have high sensitivity when applied to a gas sensor.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described below. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments disclosed herein are being provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. In the drawings, the thicknesses of the layers and regions are exaggerated for clarity. Like numbers refer to like elements throughout. Also, an element or layer is referred to as "on" or "on" of another element or layer by interposing another layer or other element in the middle as well as directly above the other element or layer. Include all cases. In addition, what is referred to as a "below" also encompasses both the case directly below another element or layer as well as intervening another layer or the like in the middle.

Hereinafter, a method of manufacturing a zinc oxide-based two-dimensional nanostructure according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 to 7. 1 to 7 are cross-sectional views illustrating a method of manufacturing a zinc oxide-based two-dimensional nanostructure according to an embodiment of the present invention.

Referring to FIG. 1, a substrate 100 is provided. The substrate 100 may be formed to include any one selected from the group consisting of silicon, sapphire, gallium nitride, silicon oxide, silicon nitride, zinc oxide, sapphire, and ITO, for example. Subsequently, ultrasonic cleaning is performed on the substrate 100, and ultrasonic cleaning may be performed by, for example, chemical cleaning with acetone and methanol, followed by cleaning with pure water. Subsequently, the substrate 100 can be dried in an oven at a predetermined temperature.

Next, after loading the cleaned substrate 100 into a chamber (not shown) maintained at a predetermined temperature, a zinc-containing precursor to the substrate 100 through an injection member such as a shower head (not shown) in the chamber, The process of supplying a metal containing precursor and an oxygen containing gas can proceed. In this case, the metal is formed in an amorphous phase above the single crystal formation temperature of zinc, for example, may be magnesium, and in this embodiment, magnesium will be described as an example. In addition, the process carried out in the present embodiment may be, for example, thermal chemical vapor deposition (thermal CVD), organometallic chemical vapor deposition (MOCVD) or plasma chemical vapor deposition (PECVD).

In addition, the zinc-containing precursor is, for example, dimethylzinc [Zn (CH ₃ ) ₂ ], diethylzinc [Zn (C ₂ H ₅ ) ₂ ], zinc acetate [Zn (OOCCH ₃ ) ₂ OH ₂ O], zinc acetate Anhydride [Zn (OOCCH ₃ ) ₂ ] and zinc acetylacetonate [Zn (C ₅ H ₇ O ₂ ) ₂ ]. The magnesium-containing precursor may be any one selected from the group consisting of bis-cyclopentadinymagnesium (Cp ₂ Mg), methylmagnesium iodide (MeMgI) and dimethylmagnesium (Et ₂ Mg). In this case, the magnesium containing precursor may be supplied at 0.5 to 2.5 mol / min. The oxygen containing gas may be any one selected from the group consisting of oxygen, ozone, nitrogen dioxide, water vapor and carbon dioxide. The precursors and the gas may be supplied at the same time, but may be sequentially performed depending on the process conditions. In addition, argon gas can be supplied into the chamber as a carrier gas.

Meanwhile, the precursors and the gas may be supplied at a pressure of 1 torr or less at a temperature of 500 to 1000 ° C., which is a temperature at which a single crystal of zinc is generated. Temperature control in the chamber can be controlled using an induction coil, which is indirect heating.

An oxide layer 102 may be formed in the process of supplying the precursors and the gas. The oxide film 102 may be formed of a native oxide formed by oxygen supplied at the beginning of the process.

Referring to FIG. 2, magnesium is diffused into the oxide film 102 to maintain the process in which the precursors and the gas are supplied to form a metal diffusion oxide film 102a. Accordingly, the metal diffusion oxide film 102a may be formed on the whole or part of the oxide film 102.

Referring to FIG. 3, an amorphous metal oxide layer 104 may be formed inside or on the metal diffusion oxide film (not shown) by maintaining the process, and specifically, a magnesium oxide layer having an amorphous phase may be formed. In this case, the amorphous metal oxide layer 104 may be further grown on the metal diffusion oxide film and formed to a thickness of 10 to 20 nm.

Referring to FIG. 4, a single crystal adopting zinc as a main component between the amorphous layers 106 and the amorphous layers 106 adopting magnesium as the main component on the amorphous metal oxide layer 104 is maintained by the process. Seed layers 108 are formed. In this case, when defining the meaning of the main component as a relatively high content of components other than oxygen, the single crystal seed layers 108 contain relatively more zinc than magnesium, and the amorphous layers 106 contains relatively more magnesium than zinc. That is, the amorphous layers 106 and the single crystal seed layer 108 are formed according to the relative content between magnesium and zinc, and thus, a phase separation process may be performed on the amorphous metal oxide layer 104. Specifically, the single crystal seed layers 108 and the amorphous layers 106 may be formed of Mg _x Zn _1-x O (0 <x <1) ternary alloy films, respectively, and the single crystal seed layers 108 Is formed to have a value of 0.1 ≦ x ≦ 0.4, and the amorphous layers 106 may be formed to have a value of 0.8 ≦ x ≦ 0.9.

According to the present embodiment, the amorphous layers 106 and the single crystal seed layers 108 are 500 due to the amorphous metal oxide layer 104 on the substrate having a large mismatch between zinc oxide and lattice constant, such as a silicon substrate or a silicon oxide substrate. It can be easily adsorbed even in a high temperature process of more than ℃. This is due to the metal oxide layer 104 having a lattice structure similar to that contained in the single crystal seed layers 108 and the amorphous layers 106. In addition, the amorphous layers 106 may occupy a larger area than the single crystal seed layers 108 depending on the process conditions such as the flow rate, the pressure and the temperature in the chamber during the supply of the precursors and the gas. Can be formed. This is because magnesium has a higher adsorption energy than zinc. Accordingly, the amorphous layers 106 may occupy more area than the single crystal seed layers 108, and the width of the single crystal seed layers 108 may be suppressed from increasing.

5, the single crystal seed layers 108 may be formed to extend horizontally on the amorphous metal oxide layer 104 exposed between the amorphous layers 106 by continuing the process.

Referring to FIG. 6, the nanowires 110 may be selectively formed on the single crystal seed layers 108 by maintaining the process. At the same time, the networks 111 may be grown laterally or on the horizontally extending single crystal seed layers 110. The nanowires 110 and the networks 111 may be grown. It may be formed after about 10 minutes have elapsed since the process is started, and the networks 111 may be formed to have a shape of a nanowall according to the process conditions.

Referring to FIG. 7, the process is continued so that the nanowires 110 are further grown vertically, and the networks 111 are connected to each other between the nanowires 110 to form two-dimensional nanostructures. Field 112 may be formed. Specifically, the nanowalls 112 may grow when the process is performed for a total of 20 minutes or more. The nanowall may be formed at the monolayer level and may have a thickness of 10 nm or less. On the other hand, the nanowall may also be formed of Mg _x Zn _1-x O (0 <x <1) ternary alloy film, in this case may be formed to have a value of 0.01≤x≤0.2.

According to the present exemplary embodiment, the single crystal seed layers 108 having a small size are formed due to the amorphous layers 106 so that the small diameter nanowires 110 may grow vertically on the single crystal seed layers 108. In addition, the thickness of the nanowalls 112 grown between the nanowires 110 may also be thinly formed.

Hereinafter, the zinc oxide-based zinc oxide-based two-dimensional nanostructure according to the embodiment of the present invention will be described with reference to FIG. 7 again.

An amorphous metal oxide layer 104 is positioned on the substrate 100, and the amorphous metal oxide layer 104 forms an amorphous phase above a single crystal formation temperature of zinc. It may be an oxide film of a metal having. In this case, the metal may be magnesium, and in this embodiment, the case of magnesium will be described as an example. On the amorphous metal oxide layer 104, single crystal seed layers 108 employing zinc as the main component are disposed between the amorphous layers 106 employing magnesium as the main component and the amorphous layers 106. The meanings of the main components mentioned herein are omitted since they have been described above. Optionally nanostructures are formed on the single crystal seed layers 108. The nanostructures may include nanowires 112 formed between the nanowires 110 and the nanowires 110 on the single crystal seed layers 108. The nanowall may be formed at the monolayer level, for example, may be formed to a thickness of less than 10nm. Since each member is substantially the same as those mentioned in the above-mentioned manufacturing method, description thereof will be omitted.

According to the present embodiment, not only the small diameter nanowires 110 grow vertically on the single crystal seed layers 108, but also the thickness of the nanowalls 112 grown between the nanowires 110. It is also thin. The thin nanowalls 112 may be used as channels of transistors used in chemical sensors and biosensors and gas sensors. In the case where the nanowalls 112 have a monolayer-level thin thickness, atoms in the channel can participate most of the reaction with the gases around the transistor, so that the sensitivity of the gas sensor can be improved.

Experimental Examples

Hereinafter, the present invention will be described in more detail with reference to experimental and comparative examples. However, the following experimental examples are for illustrating the present invention, it should be understood that the present invention is not limited by the following experimental examples.

8 is a scanning electron microscope (SEM) photograph of a zinc oxide based two-dimensional nanostructure and comparative examples according to an embodiment of the present invention.

In the experimental examples, the zinc oxide-based two-dimensional nanostructure of the present embodiment was prepared as follows. The nanostructures fabricated in these experimental examples were formed using an organometallic chemical vapor deposition process. Specifically, ultrasonic cleaning was performed for 5 minutes in the order of acetone, methanol, and pure water for an n-type doped silicon substrate, followed by a drying process in an oven at a temperature of about 80 ° C. The substrate was then placed in a chamber. The temperature of the chamber was maintained at 500 ° C. and the pressure in the chamber was maintained at 0.001 torr using an induction coil, which is an indirect heating method. Next, zinc-containing gas, dimethylzinc [Zn (CH ₃ ) ₂ ], was added to the chamber. The initial 30 seconds were supplied, followed by a bis-cyclopentadinymagnesium (Cp ₂ Mg), magnesium containing precursor, at a flow rate of 0.5 to _2.5 μmol / min, continuously with 50 seconds of oxygen gas into the chamber. At the same time, 6N argon gas was used as the carrier gas in the chamber, ie, organometallic chemical vapor deposition for 10 minutes at a temperature of 500 ° C. Proceeding to grow the zinc oxide-based two-dimensional nanostructures on the silicon substrate.

Comparative examples according to the conventional method compared with the present embodiment was produced as follows. Instead of a silicon substrate, a sapphire (Al ₂ O ₃ ) substrate and a p-type doped gallium arsenide (GaAs) substrate are used, except that an amorphous metal oxide layer is formed. The deposition process was performed.

As can be seen in FIG. 8, zinc oxide-based nanowires and zinc oxide-based nanowalls grown on a silicon substrate are vertically aligned to a thickness that is substantially the same as or rather thinner than other substrates having a small mismatch between zinc oxide and lattice constant. Confirmed.

9 is a SEM photograph showing the progress of the process over time when the conventional method is applied. The formation of the nanowall on the n-type doped silicon substrate is substantially the same as the formation of the nanowall on the p-type doped gallium arsenide substrate. However, in the case of the p-type doped gallium arsenide substrate, the growth stage can be easily distinguished.

As shown in FIG. 9, when the minute elapsed, the growth of the structure was not achieved, but the thin layer covering the pores was formed after the elapse of 5 minutes. After 10 minutes, some nanowires and nanosheets were observed, and after 20 minutes, the nanowall structure connected to the network structure was formed. Based on this, it can be seen that the nanowall is not formed at the beginning of growth but is growing step by step.

10 are transmission electron microscope (TEM) photographs and X-ray diffraction (XRD) photographs of the zinc oxide-based two-dimensional nanostructures fabricated by the method according to the present embodiment. 10A and 10B are images and diffraction patterns of a zone axis measured with [2-1-10] _ZnO . The coordinate system shown here is a miller index used to indicate coordinates with respect to a wurtzite structure such as zinc oxide. Here, the coordinate (hkil) represents a hexagonal structure lattice plane, of which h, k and l are equal to the Miller index of the cubic structure, and i is represented by -hk.

 For example, the lattice plane shown in FIG. 1C is represented by the {01-11} lattice plane (where it is a representative lattice plane including the (0111) plane) with coordinates of h = 0, k = 1 and l = 1. .

As shown in FIG. 10, it can be seen that it is well grown vertically on the silicon substrate, and it can be seen that the nanowalls having a predetermined width are combined to form a network structure. 10C and 10D are images and diffraction patterns measured by the region axis of _ZnO , and diffraction patterns of the {-2112} _ZnO plane are clearly seen. This result shows that the nano-month {-2112} _ZnO surface and the {01-10} mainly growing _ZnO surface.

11 are high resolution TEM photographs and EDX (Energy Dispersive Analysis) photographs of zinc oxide based two-dimensional nanostructures fabricated by the method according to the present embodiment.

11A is an enlarged image of a nanowire. The atomic weight ratios of magnesium in the single crystal seed layer 108, the bottom 110a and the top 110b of the nanowire are 36at%, 13at% and 9.6at%, respectively. It can be seen that the zinc component increases toward the top of the nanowires so that the nanowires have urethane structures. 11B shows that the amorphous metal oxide layer 104 and the amorphous layer 106 are 97at% and 78at%, respectively. 11C is an enlarged image of the nanowall and the nanowire. The bottom 112a and top 112b of the nanowall show 4.8 at% and 16 at%, respectively. It can be seen that the zinc component increases toward the top of the nanowall, so the nanowall also has a urtzite structure. Meanwhile, in FIG. 11C, as can be seen from the image of the interface portion with the substrate 100 on which the nanowall is grown, it can be seen that the individual single crystal seed layer 108 widens and meets horizontally on the metal oxide layer 104. While the single crystal seed layer 108 is a single crystal, it was confirmed that the amorphous layer was covered around the single crystal seed layer 108. It is thought that the adsorption of the zinc oxide-based reactant no longer occurs on the amorphous layer 106, and thus the single crystal seed layer 108 has not grown any longer. This shows that the phase transition occurs as a single crystal or amorphous depending on the extent of magnesium in the zinc oxide.

12 is a graph illustrating measurement of PL (PhotoLuminescence) according to wavelengths of nanowires and nanowalls manufactured by the method according to the present embodiment. It can be seen that the optical properties of nanowalls are superior to nanowires due to the solid solution of magnesium and the excellent crystallographic properties of nanowires.

Although the present invention has been described in detail through the representative embodiments, those skilled in the art to which the present invention pertains can make various modifications without departing from the scope of the present invention. Will understand. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims below and equivalents thereof.

1 to 7 are cross-sectional views illustrating a method of manufacturing a zinc oxide-based two-dimensional nanostructure according to an embodiment of the present invention.

8 is a scanning electron microscope (SEM) photograph of a zinc oxide based two-dimensional nanostructure and comparative examples according to an embodiment of the present invention.

9 is a SEM picture showing the progress of the process over time when the conventional method is applied.

10 are transmission electron microscope (TEM) photographs and X-ray diffraction (XRD) photographs of the zinc oxide-based two-dimensional nanostructures fabricated by the method according to the present embodiment.

11 are high resolution TEM photographs and EDX (Energy Dispersive Analysis) photographs of zinc oxide based two-dimensional nanostructures fabricated by the method according to the present embodiment.

12 is a graph illustrating measurement of PL (PhotoLuminescence) according to wavelengths of nanowires and nanowalls manufactured by the method according to the present embodiment.

Claims (21)

Supplying a zinc-containing precursor, a metal-containing precursor, and an oxygen-containing gas on a substrate having an oxide film to form an amorphous metal oxide layer containing the metal in the oxide film, A single crystal seed which maintains the process and adopts zinc and zinc among the metals as a main component between the amorphous layers and the amorphous layers which adopt the zinc and the metal of the metal as a main component on the amorphous metal oxide layer To form layers, Maintaining the process to selectively form two-dimensional nanostructures on the single crystal seed layers, The metal is a method of producing a zinc oxide-based two-dimensional nanostructures of the amorphous phase above the single crystal formation temperature of the zinc. The method of claim 1, The two-dimensional nanostructure is a method of manufacturing a zinc oxide based two-dimensional nanostructures are formed to have nanowires and nanowalls formed between the nanocrystals on the single crystal seed layers. The method of claim 2, The nanowall is a method of manufacturing a zinc oxide-based two-dimensional nanostructure is formed at the monolayer (monolayer) level. The method of claim 1, Before forming the amorphous metal oxide layer, maintaining the process to form the oxide film in which the metal is diffused in the oxide film. The method of claim 1, The oxide film is a method of manufacturing a zinc oxide-based two-dimensional nanostructure formed of a natural oxide film. The method of claim 1,  The amorphous metal oxide layer is a method of manufacturing a zinc oxide-based two-dimensional nanostructure is formed to a thickness of 10 to 20 nm. The method of claim 1, The single crystal seed layers, the amorphous layers, and the two-dimensional nanostructure are formed of an Mg _x Zn _1-x O (0 <x <1) ternary alloy film, wherein the single crystal seed layers are 0.1 ≦ x ≦ 0.4. It is formed to have a value, the amorphous layers are formed to have a value of 0.8≤x≤0.9, the two-dimensional nanostructures are formed to have a value of 0.01≤x≤0.2 method of manufacturing a zinc oxide-based two-dimensional nanostructure . The method of claim 1, The precursor and the supply of the gas proceeds at a pressure of 1 torr or less at a temperature of 500 to 1000 ℃ for at least 10 minutes. The method of claim 1, The metal is a method of manufacturing a zinc oxide-based two-dimensional nanostructure containing magnesium. The method of claim 9, The magnesium-containing precursor is a method for producing a zinc oxide-based two-dimensional nanostructure is supplied at 0.5 to 2.5 mol / min. The method of claim 9, The magnesium-containing precursor is a zinc oxide-based two-dimensional nanostructure comprising any one selected from the group consisting of bis-cyclopentadinymagnesium (Cp ₂ Mg), methyl magnesium iodide (MeMgI) and dimethyl magnesium (Et ₂ Mg). Method of preparation. The method of claim 1, The zinc-containing gas may be dimethyl zinc [Zn (CH ₃ ) ₂ ], diethyl zinc [Zn (C ₂ H ₅ ) ₂ ], zinc acetate [Zn (OOCCH ₃ ) ₂ OH ₂ O], zinc acetate anhydride [Zn (OOCCH ₃ ) ₂ ] and zinc acetylacetonate [Zn (C ₅ H ₇ O ₂ ) ₂ ], wherein the oxygen-containing gas comprises oxygen, ozone, nitrogen dioxide, water vapor and carbon dioxide Method for producing a zinc oxide-based zinc oxide-based two-dimensional nanostructure comprising any one selected from the group. The method of claim 1, The chemical vapor deposition method is a method of producing a zinc oxide-based two-dimensional nanostructures are carried out using thermal CVD, organometallic chemical vapor deposition (MOCVD) or plasma chemical vapor deposition (PECVD). The method of claim 1, And the substrate is formed to include any one selected from the group consisting of silicon, sapphire, gallium nitride, silicon oxide, silicon nitride, zinc oxide, and ITO. Amorphous phase above the single crystal formation temperature of zinc on the substrate An amorphous metal oxide layer containing a metal having; Amorphous layers positioned on the amorphous metal oxide layer and adopting the metal as the main component of the zinc and the metal; Single crystal seed layers positioned between the amorphous layers and adopting zinc of the zinc and the metal as main components; And Zinc oxide nanowires comprising a two-dimensional nanostructure selectively formed on the single crystal seed layers. The method of claim 15, The two-dimensional nanostructures are zinc oxide-based two-dimensional nanostructures comprising nanowires formed between the nanowires on the single crystal seed layers. The method of claim 15, The nanowall is zinc oxide-based two-dimensional nanostructure is formed at the monolayer level (monolayer) level. The method of claim 15,  The amorphous metal oxide layer is a zinc oxide based two-dimensional nanostructure having a thickness of 10 to 20 nm. The method of claim 15, The single crystal seed layers, the amorphous layers, and the two-dimensional nanostructure include Mg _x Zn _1-x O (0 <x <1) ternary alloy film, wherein the single crystal seed layers have a value of 0.1 ≦ x ≦ 0.4. And wherein the amorphous layers have a value of 0.8 ≦ x ≦ 0.9 and the nanostructures have a value of 0.01 ≦ x ≦ 0.2. The method of claim 15, The metal oxide zinc-based two-dimensional nanostructures containing magnesium. The method of claim 15, The substrate is formed of a zinc oxide based zinc oxide based two-dimensional nanostructures formed of any one selected from the group consisting of silicon, sapphire, gallium nitride, silicon oxide, silicon nitride, zinc oxide, and ITO.

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