WO2013051892A2

WO2013051892A2 - Membrane comprising metal nanotubes, and method for manufacturing same

Info

Publication number: WO2013051892A2
Application number: PCT/KR2012/008090
Authority: WO
Inventors: 박호범; 백운규; 송태섭; 신혜진
Original assignee: 한양대학교 산학협력단
Priority date: 2011-10-06
Filing date: 2012-10-05
Publication date: 2013-04-11
Also published as: KR20130037425A; WO2013051892A3; KR101367561B1

Abstract

Provided are a membrane comprising metal nanotubes and a method for manufacturing same. The membrane comprises: a substrate having a plurality of holes; and a plurality of metal nanotubes which are aligned in the direction extending upward from the surface of the substrate, which are spaced apart from each other, and each of which has an open end. According to the present invention, the membrane comprising metal nanotubes as an inorganic material which have cylindrical air pores is used to achieve quick permeation even with a low pressure, and strong resistance of the membrane against chemical and physical stimulations can be obtained. Therefore, the replacement cycle of the membrane can be lengthened in order to enable efficient operation.

Description

Separation membrane comprising metal nanotube and manufacturing method thereof

The present invention relates to a separator having a cylinder-shaped pores and a method of manufacturing the same, and more particularly, to a separator comprising a metal nanotube and a method of manufacturing the same.

A membrane is a material that can separate a specific component by selectively passing or excluding a desired material from a bicomponent or multicomponent mixture. With the development of the industry, various membrane materials and processes are being developed, which are largely classified into reverse osmosis membranes, ultrafiltration membranes, and microfiltration membranes, depending on the level of separation.

The ideal separator should have a high permeability and a high permeability to selectively permeate the desired material. In order to minimize the resistance of the fluid inside the membrane during material permeation and to have a fast permeability, a cylinder shape with less bend of pores is suitable. In addition, in order to increase the separation efficiency by the size of the material, a membrane having uniform pores is required.

Generally, membranes are manufactured in the form of flat membranes or hollow fiber membranes using polymer materials such as cellulose acetate (CA) and poly sulfone (PSf) .The membrane separator using polymers has uneven pores and sponge-like pores. The resistance to the inside of the membrane during water permeation is large, and the separation range by size is not constant. In addition, in order to increase the separation efficiency of the hollow fiber membrane, it is necessary to maximize the actual separation area by reducing the inner diameter and increasing the density of the hollow fiber membrane per unit area, but the inner diameter that can be manufactured is limited to several tens of micrometers.

An example of making cylinder-shaped pores by using a polymer is a method of making vertical pores by etching ion weakened portions by irradiating ion beams on the surface of strong polycarbonate (PC) or polyethylene (PE) polymer membranes (track etching ) Is commercialized only. However, the separation membrane has a non-uniform structure such that the porosity is very low, less than 5%, and two or three adjacent pores overlap each other to form pores two times larger than the original pores.

Because of this limitation of polymers, inorganic separators are also partly commercialized. When aluminum oxide is used, a cylindrical membrane having a porosity of about 50% can be realized. However, due to high porosity and mechanical properties of the inorganic material, brittleness is strong, so that it is easily broken and difficult to be used in actual processes.

Although research is being conducted to form separators by forming pores in inorganic materials (eg, silicon, silicon nitride, etc.) having a thickness of tens to hundreds of nanometers by heat treatment, lithography, or heavy ion etching, but the thickness is thin to withstand pressure of 1 bar or more. It is difficult and easy to break the situation is not applied to the actual situation.

In addition, the conventional polymer membrane is low in resistance to external stimuli such as temperature, pH, oxidant, physical stimulation or organic fouling has the disadvantage that the membrane must be frequently replaced when used in the actual process.

Therefore, the resistance inside the membrane is minimized to have high permeability and at the same time high selectivity, and organic matter fouling the surface of the separator has little effect of lowering the separation efficiency, and strong resistance to organic solvents, strong acids or strong bases, and oxidation conditions. There is a need for the development of a new separator having. In particular, the development of a membrane having pores in the form of a cylinder using a strong inorganic material is expected to be able to produce a membrane having high permeability and selectivity and resistant to physical stimuli.

The technical problem to be solved by the present invention is to provide a separator comprising a metal nanotube having excellent permeability and durability.

Another technical problem to be solved by the present invention is to provide a method for producing a separator comprising a metal nanotube.

In order to solve the above technical problem, an aspect of the present invention provides a separator. The separator includes a substrate having a plurality of holes; And a plurality of metal nanotubes oriented in an upward direction from the substrate surface, arranged to be spaced apart from each other, and having an open end.

In order to solve the above technical problem, another aspect of the present invention provides a method of manufacturing a separator. The manufacturing method includes forming a plurality of nanorods oriented upwardly from the surface of the substrate and arranged spaced apart from each other on the substrate; Coating a metal on the nanorods to form a tubular metal layer surrounding the nanorods; Etching the upper ends of the nanorods and the tubular metal film to form metal nanotubes having open ends; And forming a plurality of holes in the substrate.

According to the present invention, since a separator including metal nanotubes is used as an inorganic material having cylinder-type pores, resistance to compression pressure may be increased, and rapid permeability may be achieved even at low pressure. In addition, since the pressurization pressure can be lowered during water treatment, energy cost required for operation can be reduced, and the required size of the facility can be reduced compared to a conventional separator based on the same amount of water treatment. In addition, since it is resistant to chemical and physical stimuli, it is possible to increase the replacement cycle of the membrane, and thus there is an advantage in that efficient operation is possible.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 to 5 are cross-sectional views illustrating a method of manufacturing a separator according to an embodiment of the present invention.

6 is a schematic perspective view of a separator including a metal nanotube array according to an embodiment of the present invention.

FIG. 7 is an SEM image of a ZnO nanorod array prepared in Preparation Example 1. FIG.

FIG. 8 is an SEM image of a core-shell structured ZnO nanorod-silicon coating film prepared in Preparation Example 1. FIG.

9 are SEM images of the silicon nanotube array manufactured in Preparation Example 1. FIG.

FIG. 10 is an SEM image of an epoxy resin-coated silicon nanotube array prepared in Preparation Example 2. FIG.

FIG. 11 is an SEM image of ZnO nanorods prepared in Preparation Example 3. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms and should be understood to include all equivalents and substitutes included in the spirit and scope of the present invention. In the drawings, the thicknesses of layers and regions may be exaggerated or omitted for ease of explanation and clarity. Like numbers refer to like elements throughout. In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Referring to FIG. 1, a plurality of nanorods 110 oriented upward from the surface of the substrate 100 and spaced apart from each other are formed on the substrate 100.

The substrate 100 is not particularly limited as long as it can form the nanorod 110 thereon, and may be an inorganic substrate, an organic substrate, or a substrate having a structure in which two or more of them are stacked in the same or different types. In addition, the substrate 100 may be appropriately selected in consideration of the type of separator to which it is applied, the function in the separator, and the ease of hole formation corresponding to the channel of the fluid. As an example, if the purpose of removing ions in the water by electrical potential by applying a voltage to the separator, the substrate 100 may be prepared as a conductive substrate.

The nanorod 110 arranged on the substrate 100 may be, for example, a nanorod made of a metal oxide such as zinc oxide, aluminum oxide, or magnesium oxide. However, the material of the nanorod 110 is not particularly limited as long as it is a material that can be selectively removed after the metal coating film is formed as in the process described below with reference to FIG. 3. For example, the nanorod 110 may have a diameter of 10 nm to 200 nm, and a length of 300 nm to 20 μm.

The nanorod 110 may be formed by various methods known in the art, such as a top-down method or a bottom-up method.

For example, the nanorod 110 may be formed by disposing a bulk material serving as a base material on the substrate 100 and then performing an etching process using patterning and lithography.

As another example, the nanorod 110 may be formed by a hydrothermal synthesis method in which a metal oxide seed layer is formed on a substrate 100, and the substrate on which the seed layer is formed is immersed in a nanorod growth solution containing metal ions. It may be. In this case, the seed layer may be a metal oxide nanoparticles coated layer or a metal oxide thin film layer, and serves as a base layer for growing the metal oxide nanorods in the [001] direction.

On the other hand, the nanorod 110 may be formed in a cone (top) shape of the upper. Here, the cone shape means that the nanorod 110 has a shape that becomes thinner toward the upper portion, that is, the portion of the nanorod 110 farther from the substrate 100. The shape of the nanorod 110 can be controlled by a variety of methods, for example, when forming the nanorod 110 with zinc oxide nanorods, diaminoprop in the nanorod growth solution in which zinc ions are dissolved. By adding a shape control agent such as pane, a nanorod having a cone shape can be formed.

Referring to FIG. 2, a metal coating 122 is formed on the nanorod 110 to form a tubular metal layer 122 surrounding the nanorod 110. Throughout this specification, the metal is defined to include materials classified as metalloids as well as materials classified as metals. For example, the metal may include any one selected from silicon, germanium, tin, aluminum, zinc, silver, gold, and platinum or an alloy thereof.

The tubular metal film 122 is a structure corresponding to a precursor of a metal nanotube to be described later, and the thickness thereof may be appropriately set in consideration of the thickness of the metal nanotube finally formed. For example, the tubular metal film 122 may be formed to a thickness of 10nm to 150nm.

The tubular metal film 122 may be formed by a vapor deposition method in which a metal precursor gas is brought into contact with the nanorod 122. However, the present invention is not limited thereto, and other conventional deposition methods or coating methods known in the art may be used.

For example, SiH ₄ , SiCl ₄ , GeH ₄ may be used as the metal precursor gas, but the present invention is not limited thereto, and any metal compound gas may be used as long as it can be used in the art. Do.

In addition, the metal precursor gas may further include a dopant precursor gas. It is possible to increase the conductivity of the metal film 122 coated on the nanorod 100 by the addition of the dopant, or to modify the surface of the metal film 122 to be hydrophilic or hydrophobic according to a desired purpose. . The dopant may include, for example, boron, aluminum, gallium, thallium, indium, phosphorus, arsenic, antimony, bismuth, and the like, and the dopant precursor gas may be BH ₃ or PH ₅ , but is not limited thereto. .

The tubular metal film 122 is formed by using the nanorod 110 as a template, thereby forming a core-shell nanostructure consisting of the nanorod 110 core and the metal film 122 shell. . Therefore, when the upper shape of the nanorod 110 has a cone shape, the upper shape of the tubular metal film 122 may also have a cone shape.

In addition, the metal coated in the process of forming the tubular metal film 122 by coating the metal on the nano-rod 110 may be coated along the surface of the substrate 100 as well as the nano-rod (110). Accordingly, the tubular metal films 122 may have a structure in which their lower ends are connected to each other by the metal film 124 coated along the substrate surface.

3 and 4, in the core-shell nanostructure shown in FIG. 2, all of the nanorods 110 of the core portion are etched and the upper end of the tubular metal layer 122 of the shell portion is etched. The opened metal nanotubes 120 are formed. Hereinafter, a structure referred to herein as a metal nanotube means a metal nanotube having an open end unless otherwise specified.

Etching the nanorods 110 and the tubular metal film 122 to form the metal nanotubes 120 may be performed by various known dry etching methods, wet etching methods, or a combination thereof. .

Specifically, as shown in FIGS. 3 and 4, the forming of the metal nanotubes 120 may be performed by first removing the nanorods 110 corresponding to the core parts, and then forming the tubular metal films corresponding to the shell parts. 122) may be used to etch the top.

For example, after selectively thermally decomposing only the nanorod 110 except for the tubular metal film 122 by heat treatment under a reducing atmosphere (FIG. 3), the tubular metal film remaining by dry etching using plasma ( 122 may be etched (FIG. 4). In this case, the heat treatment may be performed under a hydrogen atmosphere, and the nanorods 110 may be thermally decomposed or thermally decomposed through a reduction reaction. The gas used for the dry etching is not particularly limited as long as it can be used in the art, and for example, any one or more gases selected from the group consisting of Ar, Cl ₂ , SF ₆ , and CF ₄ may be used. have.

In addition, as described above, the forming of the metal nanotubes 120 may include etching the upper end of the tubular metal film 122 corresponding to the shell part, and then removing the nanorod 110 corresponding to the core part. Can be used (not shown).

As an example, the upper end of the tubular metal film 122 is etched by dry etching using plasma to expose at least an upper surface of the nanorod 110, and then subjected to heat treatment in a reducing atmosphere or to wet etching using an etchant. Only the nanorod 110 can be selectively removed.

In this case, in particular, when the tubular metal film 122 has a cone shape, the length of the upper end of the tubular metal film 122 may be adjusted by etching the upper end diameter (specifically, the inner diameter of the upper end). The metal nanotubes 120 may be formed. That is, if the tubular metal film 122 has a cone shape, as the length of the etched length increases, the inner diameter of the upper end of the finally manufactured metal nanotube 120 will increase. Therefore, the inner diameter of the upper end of the metal nanotubes 120 by a simple process (specifically, the etching time is controlled) of adjusting the length of etching the metal film 122 according to the size of particles to be separated from the fluid. There is an advantage that can be easily controlled.

In addition, if necessary, the metal nanotubes 120 may be heat treated under an oxidizing atmosphere. In this case, an oxide film may be formed on the surface of the metal nanotubes 120 that are finally formed, and through this, surface characteristics of the metal nanotubes 120 may be modified.

As described above, the metal nanotube array 130 including the plurality of metal nanotubes 120 having open ends may be formed on the substrate 100. In the present application, the metal nanotube array 130 refers to an aggregate of a plurality of metal nanotubes 120.

On the other hand, the method of manufacturing a separator according to the present embodiment, before etching the upper end of the tubular metal film 122 corresponding to the shell portion, by coating a polymer resin on the substrate 100 to the plurality of metal nanotubes ( The method may further include forming a polymer resin layer (not shown) that fills at least some of the spaces of the space 120.

For example, in the forming of the polymer resin layer, after removing the nanorod 110 corresponding to the core portion, and before etching the tubular metal layer 122 corresponding to the shell portion, the substrate 100 is formed. It may be carried out by coating a solution in which the polymer resin is dispersed in the phase, followed by drying and curing. The polymer resin may be a curable resin such as an epoxy resin, but is not limited thereto.

According to this, the metal nanotube array 130 can secure more improved mechanical strength and structural stability by forming the polymer resin layer.

Referring to FIG. 5, a plurality of holes h are formed in the substrate 100 on which the metal nanotubes 120 having open ends are formed. The hole h is a channel into which the fluid to be separated is injected, and may be formed in a desired size and shape using various known etching processes.

In this case, a part of the metal nanotube array 130 is exposed at its lower end through the hole h formed in the substrate 100. Meanwhile, as described with reference to FIG. 2, the metal coated in the tubular metal film 122 formation process may be coated along the surface of the substrate 100 as well as the nanorod 110. Accordingly, the tubular metal films 122 may have a structure in which lower ends thereof are connected to each other by the metal film 124 coated along the surface of the substrate 100. Therefore, even when the hole h is formed in the substrate 100, the metal nanotubes positioned in the hole h region do not collapse and maintain their structural stability.

Meanwhile, in the present exemplary embodiment, a plurality of holes h are formed in the substrate 100 after the metal nanotubes 120 are formed. However, the present invention is not limited thereto, and after the nanorods 110 are formed. In any step, the step of forming the hole h in the substrate 100 may be performed.

According to another embodiment of the present invention, a separator including an array of metal nanotubes is provided.

6 is a schematic perspective view of a separator including a metal nanotube array according to the present embodiment.

As shown in FIG. 6, the separator according to the present exemplary embodiment includes a substrate 100 having a plurality of holes and a metal nanotube array 130 positioned on the substrate 100. Specifically, the metal nanotube array 130 includes a plurality of metal nanotubes 120 oriented upward from the surface of the substrate 100, spaced apart from each other, and having an open end.

Meanwhile, the separator according to the present embodiment may be a separator manufactured by the above-described manufacturing method with reference to FIGS. 1 to 5.

Accordingly, the metal nanotubes may include any one or two or more alloys selected from silicon, germanium, tin, aluminum, zinc, silver, gold, and platinum, and may have conductivity or surface by addition of a suitable dopant. It may have hydrophilicity or hydrophobicity.

In addition, the length of the metal nanotube 120 may be 300nm to 20㎛, the inner diameter may be 10nm to 200nm, the thickness may be 10nm to 150nm.

In addition, the upper shape of the metal nanotube 120 may be a cone (not shown).

In addition, the metal nanotube array 130 may further include a polymer resin layer (not shown) to fill at least a part of the space of the separation space.

Hereinafter, preferred experimental examples are presented to help understand the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

1) A 200 nm thick SiNx layer was deposited on both surfaces of a Si wafer having a thickness of 500 to 700 μm having a [001] direction using low pressure chemical vapor deposition (LPCVD). Subsequently, a square pattern (700 um × 700 um to 500 um × 500 um) was formed on one surface of the substrate through patterning using a PR process and a lithography process. After the SiNx layer exposed through the patterning process was removed using a reactive ion etcher (SF ₆ gas 5 sccm, 5 mTorr, 180 seconds under RF power 100 W), the substrate was removed by 40wt% KOH solution. Wet etching was carried out at 80 ℃ for 15 hours using.

2) After the above process, a ZnO thin film having a thickness of 200 nm is formed on the surface of the substrate on which the pattern is not formed by using RF-sputter equipment, and 0.025M zinc nitrate (Zinc) is formed on the substrate on which the ZnO thin film is formed. nitrate) and 0.025M methamine (metheneamine) was immersed in an aqueous solution, and then left for 24 hours at 90 ℃, ZnO nanorods were grown on the substrate in the vertical direction. ZnO nanorod growth was repeated 3 to 15 times in the same aqueous solution to grow the ZnO nanorods to the desired length. The thickness of the layer which consists only of the obtained ZnO nanorods was 6 micrometers, and the diameter of the ZnO nanorods was 80-120 nm.

3) of the ZnO nanorods the state diluted with (10% (by volume in H ₂ gas), H ₂ gas and SiH ₄ onto the array substrate), a gas in the chamber in which the hydrogen atmosphere and a temperature of 545 ℃ maintain H ₂ In the case of 10 ~ 40 sccm, SiH _{4 For} 12 minutes at a flow rate (flow rate) of 50 ~ 80 sccm to form a silicon coating film.

4) Subsequently, the silicon coated nanorods were arranged in a hydrogen atmosphere at a temperature of 550 to 750 ° C. while flowing H ₂ at a flow rate of 100 to 400 sccm and Ar at a flow rate of 100 to 400 sccm. By heat-treating for at least time to selectively remove only ZnO, silicon nanotubes with closed vertically arranged ends on the substrate were obtained.

5) After injecting the silicon nanotubes into the reactive ion etcher, and etched with chlorine gas (80 sccm, 80 mTorr, 35 ~ 70 seconds under RF power 150 W conditions) to the end of the opening silicon nanotubes Got it. The opening size was controlled to 10-40 nm according to the etching time. The thickness of the layer consisting only of the silicon nanotubes with the terminal openings was 6 μm.

6) The silicon nanotube formed substrate was placed in a reactive ion etcher, and the SiNx layer remaining on the back side of the substrate was removed by SF ₆ gas (600 sec under 5 sccm, 5 mTorr, RF power 100 W). A plurality of holes were formed in the substrate.

On the other hand, in the present example, after removing ZnO, the process of opening the end of the silicon nanotube was performed, but if necessary, after etching the end of the silicon nanotube first, the process of removing ZnO was performed to open the silicon Nanotubes can be formed.

Referring to FIG. 7, it can be seen that a plurality of ZnO nanorods oriented in a direction upward from the substrate surface and arranged to be spaced apart from each other according to the present example.

Referring to FIG. 8, it can be seen that the ZnO nanorods are positioned in the core portion, and the coating layer is formed in the form of the silicon surrounding the ZnO nanorods in the shell portion.

9, as the etching time is increased to 35 seconds (a), 40 seconds (b), 55 seconds (c) and 70 seconds (d), the diameters of the openings are about 15 nm, 20 to 25 nm, respectively. It can be seen that the increase to 30 ~ 40nm and 35 ~ 40nm.

Except for coating the epoxy resin on the substrate before the process of step 6) in Preparation Example 1, the same method as in Preparation Example 1 was carried out.

Referring to Figure 10, it can be seen that the epoxy resin is coated while filling the separation space of the silicon nanotubes.

In order to control the shape of the top portion of the ZnO nanorod, in step 2), 190 mM of 1,3-diaminopropane (1,3-DAP) was added with 0.025M zinc nitrate and 0.025M. The same procedure as in Preparation Example 1 was performed except that methamine was added to the aqueous solution in which metheneamine was dissolved.

FIG. 11 is an SEM image of ZnO nanorods prepared in Preparation Example 3. FIG.

Referring to FIG. 11, it can be seen that the ZnO nanorods prepared according to the present Preparation Example have a cone shape in which the ends thereof become thinner.

Gas permeation experiment was performed to investigate the stability and permeation characteristics of the separator prepared in Preparation Example 1.

Gases used in the gas permeation experiment were H ₂ , He, N ₂ , O ₂ , CH ₄ , CO ₂ , SF ₆ , and permeability and selectivity of each gas were measured under normal temperature and pressure of 0.5 bar. The gas permeability of a 60 nm diameter cylinder was compared with the gas permeability predicted in the Knudsen flow, which is ideal for following the Knudsen flow.

In the case of silicon nanotubes with pores of 60 nm, the transmittance of He was 2.1 × 10 ⁸ barrer, which is 100 times faster than the theoretical value, compared to 2.8 × 10 ⁶ barrer, which is expected by Knudsen flow.

In order to compare the characteristics, the same experiment was carried out with a trench-etched polycarbonate separator having pore sizes of 50 nm and 100 nm, and an aluminum oxide separator having pore sizes of 100 nm, respectively.

The 50nm polycarbonate separator showed 4.5x10 ⁵ barrer of theoretical value and 1.7 × 10 ⁶ barrer of experimental value, which showed 4 times faster transmission than theoretical value. On the other hand, 100nm polycarbonate membrane showed almost similar permeability with theoretical value 2.5 × 10 ⁶ barrer and experimental value 2.0 × 10 ⁶ barrer, and 100nm aluminum oxide membrane showed theoretical value 4.2 × 10 ⁷ barrer and experimental value 6.7 × 10 ⁷ barrer. .

Using the separator prepared in Preparation Example 1, the permeation characteristics of ultrapure water were examined before being applied to a water treatment process in which organic materials were mixed.

The water in the tank was pressurized with a pressure of 1 bar using N ₂ , and this was applied to a dead-end system equipped with a separator to measure the permeability of water coming through the separator. In order to compare the effects of the physicochemical properties of the membrane surface, the permeability of water through the pores was predicted using the Hagen-poisuille model and compared with the experimental data.

In the case of the membrane of the silicon nanotube having a pore diameter of 60nm, the experimental value was 6,600LMH, which was about 13 times faster than the theoretical value of 476LMH.

In the same manner as in Example 1, a polycarbonate separator and an aluminum oxide separator were used to compare properties.

In the polycarbonate membrane having a pore diameter of 50 nm, the theoretical value was 74 LMH and the experimental value was 505 LMH, which showed 6 times faster permeability than the theoretical value. Seemed.

Meanwhile, the aluminum oxide separator having a pore diameter of 100 nm showed 1.5 times faster transmittance with a theoretical value of 1,650 LMH and an experimental value of 2,682 LMH.

The cylinder-shaped pores of the nanotubes from the analytical examples 1 and 2 can improve the permeability by smoothly flowing the fluid, and unlike the conventional polymer membrane, when using the silicon separator, the surface characteristics of the silicon nanotubes It can be confirmed that the permeability can be further improved by affecting the flow of the fluid.

Therefore, according to the separator of the present invention can be expected to improve the permeation efficiency at a lower pressure than the conventional process. In addition, since the pressurized pressure can be lowered during water treatment, energy cost required for operation can be reduced, and the size of the facility can be reduced compared to a conventional separator based on the same amount of water treatment. In addition, since inorganic materials such as silicon are resistant to chemical and physical stimuli, it is possible to increase the replacement cycle of the separator and thus have an advantage of enabling efficient operation.

As mentioned above, although the present invention has been described in detail with reference to preferred embodiments, the present invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art within the spirit and scope of the present invention. You can change it.

[Description of the code]

100: substrate 110: nanorod

120: metal nanotube 122: tubular metal film

130: metal nanotube array

Claims

A substrate having a plurality of holes; And

And a plurality of metal nanotubes oriented in an upward direction from the surface of the substrate and arranged to be spaced apart from each other and having open ends.
The method of claim 1,

The metal nanotube is a separator comprising any one or two or more alloys selected from silicon, germanium, tin, aluminum, zinc, silver, gold and platinum.
The method of claim 1,

Separation membrane having a surface of the metal nanotube having a hydrophilic or hydrophobic.
The method of claim 1,

Separation membrane of the metal nanotube length of 300nm to 20㎛.
The method of claim 1,

Separation membrane of the metal nanotube thickness is 10nm to 150nm.
The method of claim 1,

Separation membrane of the inner diameter of the metal nanotubes from 10nm to 200nm.
The method of claim 1,

The upper shape of the metal nanotube is a cone (cone) separation membrane.
The method of claim 1,

Separation membrane further comprising a polymer resin layer to fill at least a portion of the spaced space of the plurality of metal nanotubes.
Forming a plurality of nanorods oriented upwardly from the substrate surface and arranged spaced apart from each other on a substrate;

Coating a metal on the nanorods to form a tubular metal layer surrounding the nanorods;

Etching the upper ends of the nanorods and the tubular metal film to form metal nanotubes having open ends; And

Separator manufacturing method comprising the step of forming a plurality of holes in the substrate.
The method of claim 9,

The nanorod is a separation membrane manufacturing method consisting of a metal oxide.
The method of claim 10,

The metal oxide nanorods are formed by a hydrothermal synthesis method.
The method of claim 9,

The coating of the metal is a separation membrane manufacturing method performed by vapor deposition using a metal precursor gas.
The method of claim 12,

The metal precursor gas further comprises a dopant precursor gas.
The method of claim 9,

The nanorod is a separation membrane manufacturing method that is etched by a dry etching method or a wet etching method.
The method of claim 9,

The top of the tubular metal film is a separator manufacturing method which is etched by a dry etching method.
The method of claim 9,

Before etching the upper end of the tubular metal film, the method of manufacturing a separator further comprising coating a polymer resin on the substrate.