KR20100128148A - Microarray and fabrication method thereof - Google Patents

Microarray and fabrication method thereof Download PDF

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Publication number
KR20100128148A
KR20100128148A KR1020090046618A KR20090046618A KR20100128148A KR 20100128148 A KR20100128148 A KR 20100128148A KR 1020090046618 A KR1020090046618 A KR 1020090046618A KR 20090046618 A KR20090046618 A KR 20090046618A KR 20100128148 A KR20100128148 A KR 20100128148A
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South Korea
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mold
microarray
carbon
present
plate
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KR1020090046618A
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Korean (ko)
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김광범
박상훈
김광헌
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연세대학교 산학협력단
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Publication of KR20100128148A publication Critical patent/KR20100128148A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

PURPOSE: A microarray and a manufacturing method thereof are provided to effectively diffuse outside materials including an electrolyte or gas, and to secure the excellent stability. CONSTITUTION: A microarray comprises more than two plate structure bodies containing a carbon system nanomaterial. The plate structure bodies are forming a lamellar structure by being separated with each other. A manufacturing method of the microarray comprises the following steps: inserting a precursor solution with the carbon system nanomaterial inside a mold; cooling the mold to make a template by the coagulation; and separating the template.

Description

Microarray and its manufacturing method

The present invention relates to a microarray including a carbon-based nanomaterial and a manufacturing method thereof.

Carbon-based nanomaterials, such as carbon nanotubes (CNTs) or fullerenes, have new properties and functions different from those developed until now, and various studies have been conducted until recently.

For example, carbon nanotubes are allotropes composed of carbon present in a large amount on the earth, and graphite sheets are rolled to a nano size diameter to form a tube, and have excellent mechanical and chemical stability. Depending on the angle at which the graphite sheet is curled, it exhibits various electrical properties such as conductors or semiconductors. In addition, carbon nanotubes are relatively long in length and have a hollow structure, and emitters, VFDs (Vacuum Fluorescent Displays), white light sources, field emission displays (FEDs), and energy storage materials. (ex. lithium ion secondary batteries, hydrogen storage fuel cells and electrodes of ultra high capacity capacitors), infinitely applicable to nanowires, AFM / STM tips, single-electron devices, gas sensors, medical and engineering micro parts and high-performance composites Has application potential

In order for such a carbon-based nanomaterial to be put into practical use, development of nanodevice technology is required. Accordingly, studies on the device formation along with a method of synthesizing carbon-based nanomaterials such as carbon nanotubes have been actively conducted. As an example of such research, a method of manufacturing a carbon nanotube structure by aligning and growing carbon nanotubes in a vertical direction on a substrate, or dispersing carbon nanotube powder in a predetermined solvent, using deep coating and solution casting Or a method of manufacturing a structure by filtering or the like is known (Chemical Communication, 2002, 962, Angewandte Chemie International Edition 2004, 43, 1146, Advanced Material 2007, 19, 2535, Advanced Material 2008, 20, 45). However, the above-described conventional methods have a limitation in that it is impossible to control the spacing between the structures (ex. Plates including carbon nanotubes) and the pore characteristics, and can be applied only to the formation of two-dimensional thin films.

An object of the present invention is to provide a microarray including a carbon-based nanomaterial and a method for manufacturing the same.

The present invention includes two or more plate-like structures containing carbon-based nanomaterials as a means for solving the above problems,

The plate-like structures are spaced apart from each other to provide a microarray having a layered structure.

As another means for solving the above problems, the present invention is a first step of charging a precursor solution containing a carbon-based nanomaterial in a mold having a different thermal conductivity of the wall surface and the bottom surface; A second step of cooling the mold in which the precursor solution is charged in the first step to form a mold through solidification of the solvent of the precursor solution; And

It provides a method of manufacturing a microarray comprising a third step of removing the mold formed in the second step.

The microarray of the present invention includes two or more plate-like structures in which carbon-based nanomaterials are stably agglomerated therein, and the structures are separated from each other at a predetermined interval to form a layered structure. The microarray of the present invention is an air gap formed between the plate-like structure, etc., the external inflow material (ex. Electrolyte or gas) can be efficiently diffused, has excellent stability, for example, various energy storage materials, filtration membrane It can be effectively applied in various fields such as chemical detectors or gas sensors. In addition, according to the method of the present invention, it is possible to freely control the pore characteristics and structure of the microarray as described above.

The present invention includes at least two plate-like structure containing a carbon-based nanomaterial,

The plate-like structure is disposed in a state spaced apart from each other, and relates to a microarray forming a layered structure.

Hereinafter, the micro array according to the present invention will be described in more detail.

The term "microarray" used in the present invention is two or more, preferably 20 or more, more preferably 50 or more, even more preferably 500 or more structures (ex. Plate-like structure) is regular at the micrometer level The structure is arranged as, which may also be referred to as a microstructure (Microstructrue). At this time, the upper limit of the number of structures constituting the microarray is not particularly limited. For example, the microarray of the present invention may include 10,000 or less, preferably 5,000 or less structures (ex. Plate-like structure). have. On the other hand, in the present invention, each structure (ex. Plate-like structure) constituting the microarray is preferably arranged in a state having regularity in three dimensions, more specifically, the microarray of the present invention, When the horizontal direction of the plate-like structure is the x-axis, the vertical direction is the y-axis, and the thickness direction is the z-axis, the x- and y-axis as well as the regular structure may be arranged in the z-axis direction. have. In addition, the term "micrometer level" used by this invention means the case where it has a size small enough so that the shape can be discriminated through the microscope of 100 times or more magnification, for example. Thus, for example, the microarray of the present invention has a three-dimensional structure, and its average length in the transverse direction is about 1,000 μm to 50,000 μm, preferably about 5,000 μm to 10,000 μm, The average length is about 1,000 μm to 50,000 μm, preferably about 5,000 μm to 10,000 μm, and the height may be about 1,000 μm to 50,000 μm, preferably about 5,000 μm to 10,000 μm.

The microarray of the present invention includes at least two plate-like structure (plate) that is included in the state in which the carbon-based nanomaterials are stably agglomerated therein, the structure is separated from each other at a predetermined interval to form a layered structure. Accordingly, the microarray of the present invention can efficiently diffuse external inflow substances (ex. Electrolyte or gas) into the voids formed between the structures, and has excellent stability of the plate-shaped structure itself. It can be effectively applied in various fields such as various energy storage materials (eg, secondary cells, fuel cells or super capacitors), filtration membranes, chemical detectors or gas sensors.

On the other hand, the term "layered structure" used in the present invention refers to the case where the plate-like structures constituting the microarray are not connected to each other and form a layered structure in a spaced apart state (hereinafter referred to as "lamellar structure"). And plate-like structures arranged in a spaced apart state are connected by other structures grown from opposing surfaces, and when viewed from the top, the structure exhibits a shape in which a large number of cells are collected (hereinafter, “ May be referred to as a "cellular structure".

That is, when the microarray of the present invention has a cellular structure, the microarray grows in the thickness direction of the plate-like structure, and at least two structures that connect the plate-like structures to each other (hereinafter, "second structure"). May be referred to as). In this case, the thickness direction of the plate-shaped structure may mean, for example, the z-axis direction mentioned above. Further, in the present invention, the direction in which the second structure is formed is not particularly limited, and may be variously formed in a direction perpendicular to the plane of the plate-shaped structure or in a range of 0 ° or more and less than 90 °. In addition, the composition constituting the second structure is not particularly limited, and may be, for example, the same as the plate-like structure constituting the layered structure.

In addition, in the microarray of the present invention, the plate-like structure or the second structure that connects the structure forming a layered structure may have an average thickness of about 0.2 μm or more, preferably 0.5 μm or more. If the average thickness of the plate-shaped structure is less than 0.2 µm, the overall structural stability of the microarray is lowered, and there is a fear of easily collapsing to external magnetic poles. On the other hand, the upper limit of the thickness of the plate-like structure or the second structure in the present invention is not particularly limited, for example, it can be controlled in the range of 10 ㎛ or less, preferably 5 ㎛ or less.

In the microarray of the present invention, the average spacing between the plate-like structures forming the layered structure may also be in the range of 0.5 µm to 50 µm, preferably 1 µm to 30 µm, more preferably 5 µm to 20 µm. If the average spacing between the plate-shaped structures is less than 0.5 µm, the pore characteristics of the microarray may be deteriorated. If the average spacing is greater than 50 µm, the pore size may be too large and structural stability may be deteriorated.

In addition, when the microarray of the present invention has a cellular structure, the average spacing between the second structures connecting the plate-shaped structures is 0.5 µm to 50 µm, preferably 1 µm to 30 µm, more preferably 5 µm to 20 µm. It can be in the range of. If the average spacing between the second structures is less than 0.5 µm, the pore characteristics of the microarray may be degraded. If the average thickness is greater than 50 µm, the pore size may be too large, resulting in a decrease in structural stability.

In the microarray of the present invention, a specific kind of carbon-based nanomaterial included in the plate-like structure or the second structure is not particularly limited. In the present invention, for example, as the carbon-based nanomaterial, carbon nanotubes (ex. Single-walled, double-walled or multi-walled carbon nanotubes; and metallic or semiconducting carbon nanotubes); One kind or two or more kinds of carbon fibers (eg, VGCF (Vapor Growth Carbon fiber, etc.), graphene, or fullerene) may be used.

In addition, the average size of the carbon-based nanomaterials in the present invention may be in the range of 1 nm to 1,000 nm, preferably 5 nm to 100 nm, more preferably 10 nm to 20 nm. The term "average size of carbon-based nanomaterials" used in the present invention means, when the nanomaterial has a tube or rod shape (ex. Carbon nanotubes or carbon fibers), at least one dimension of the length or cross-sectional diameter. In the case of having a spherical (ex. Fullerene), it may mean the particle diameter, and in the case of having a two-dimensional shape (ex. Graphene), it may mean one or more dimensions of the width, length, or thickness thereof. And, if it has an irregular shape, it may mean the average diameter or length. When the average size of the carbon-based nanomaterials in the present invention is less than 1 nm, there is a fear that the nanomaterials are aggregated in the structure and the physical properties are lowered. There exists a possibility that manufacturing efficiency may fall.

In the microarray of the present invention, the plate-like structure or the second structure connecting the same may further include a binder (eg, a polymer binder) together with the carbon-based nanomaterial described above. In the microarray of the present invention, the binder may serve to stably exist the carbon-based nanomaterials included in the structure.

The kind of the binder that can be used in the present invention is not particularly limited, and a general material known in the art may be used without limitation. In the present invention, for example, an aqueous polymer binder can be used as the binder, and specifically, an epoxy resin, an alginate-based resin, a polyurethane, a polyalkylene oxide (ex. Polyethylene oxide or polypropylene jade). Seed), acrylic resin (ex. Ethylene-co-acrylate), vinyl resin (ex. Polyvinyl alcohol or polyvinyl butyral, etc.), amide resin (ex. Polyamide), cellulose resin (ex. Methyl cellulose, ethyl Cellulose, hydroxyethyl cellulose, and the like) or chitin-based resins (ex. Chitosan), or a mixture or copolymers of two or more kinds thereof may be used. Preferably, chitin-based resins such as chitosan and / or polyvinyl alcohol, etc. Of polyvinyl resin may be used, but is not limited thereto.

In the plate-like structure or the second structure of the microarray of the present invention, the binder is 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 50 parts by weight, more preferably 100 parts by weight of the carbon-based nanomaterial. It may be included in an amount of 15 to 30 parts by weight. If the content of the binder is less than 5 parts by weight, the structural stability of the microarray may be lowered. If the content of the binder exceeds 100 parts by weight, the content of the carbon-based nanomaterials is relatively lowered, and thus the electrical, chemical and mechanical properties of the microarray may be reduced. It may become difficult to express.

In the present invention, the method for producing such a microarray is not particularly limited.

For example, the microarray of the present invention includes a first step of charging a precursor solution containing a carbon-based nanomaterial into a mold having different thermal conductivity from a wall surface and a bottom surface; A second step of cooling the mold in which the precursor solution is charged in the first step to form a mold through solidification of the precursor solution solvent; And

It can be produced by a method comprising a third step of removing the mold formed in the second step.

In the first step of the present invention, a precursor solution containing a carbon-based nanomaterial is charged into a mold.

At this time, the precursor solution, for example, (1) acid-treated carbon-based nanomaterials; And (2) mixing the acid-treated carbon-based nanomaterial and the binder in a solvent.

In the step (1) of the present invention is a process of performing an acid treatment on the carbon-based nanomaterials, through such a process, it is possible to improve the dispersibility by giving a hydrophilicity to the carbon-based nanomaterials that are usually hydrophobic. have. For example, carbon nanotubes, which are representative nanomaterials, usually exhibit hydrophobicity. Hydrophilic functional groups (ex. COOH, etc.) are added to the tube with the removal of the metal catalyst introduced during the growth process through the acid treatment. It can be provided to give hydrophilicity.

In the step (1) of the present invention, the method of acid treatment of the carbon-based nanomaterial is not particularly limited. It can be carried out by maintaining the process. At this time, the type of acidic solution that can be used is not particularly limited, and may be, for example, an aqueous solution containing one or more kinds of strong acids such as sulfuric acid, nitric acid or hydrochloric acid. In the present invention, the acidic solution is preferably a strong acid solution having a pH of 5.5 or less.

On the other hand, in the present invention, if the acid treatment temperature is less than 60 ℃, it is difficult to give chemical modification to the carbon-based nanomaterials, there is a fear that the efficiency of imparting hydrophilicity is lowered, if it exceeds 90 ℃, problems in process stability may occur . In addition, in the present invention, if the acid treatment time is less than 2 hours, the chemical modification of the carbon-based nanomaterial may be insufficient, and the hydrophilicity imparting effect may be lowered. If the acid treatment time is more than 8 hours, further effects cannot be expected and economical efficiency Falls.

In the present invention, after the acid treatment of step (1), the carbon-based nanomaterials are separated by an appropriate method (ex. Filtration, centrifugation), and then powdered by washing and / or drying. Applicable to 2).

Step (2) of the present invention is a step of preparing a precursor solution by mixing the acid-treated carbon-based nanomaterial and the binder in a solvent.

At this time, the mixing ratio of the carbon-based nanomaterial may be appropriately selected in consideration of the dispersibility of the material and the performance of the desired array, for example, the concentration in the precursor solution is about 0.2 wt% to 40 wt It may be mixed so as to be%. If the concentration is less than 0.2 wt%, the array formation efficiency may be lowered, or the amount of the material supporting the structure may be reduced, resulting in a decrease in structural stability. Moreover, when the said concentration exceeds 40 wt%, the dispersibility of a nanomaterial may fall, and there exists a possibility that the regularity of the space | interval between the plate-shaped structure or 2nd structure in a microarray may fall.

In addition, the mixing ratio of the binder in step (2) may also be appropriately selected in consideration of the desired array and the like, for example, may be mixed so that the concentration in the precursor solution is 0.1 wt% to 10 wt%. If the concentration of the binder is less than 0.1 wt%, the structural stability of the microarray may be lowered. If it exceeds 10 wt%, the viscosity of the precursor solution may be too high, and the dispersibility of the carbon-based nanomaterial may be reduced. There is a concern that it is difficult to synthesize an array of three-dimensional structures.

The solvent used in the precursor solution is not particularly limited, but is preferably an aqueous solvent which solidifies in the cooling process of the mold to be described later to form a mold, and representative examples thereof include water (ex. Distilled water). Can be mentioned. However, the above is only one aspect of the present invention, and the present invention can be used without limitation as long as it can effectively form a mold in the steps described later.

In step (2) of the present invention, in order to increase the effect of inducing subcooling to the solvent compositionally in the precursor solution, a suitable cooling auxiliary solvent may be further mixed. Through such mixing of the cooling auxiliary solvent, the supercooling degree of the precursor solution can be increased, and the formation efficiency of the mold can be improved. In addition, the cooling aid solvent may allow the mold to be formed more regularly, thereby further improving the regularity of the microarray.

The type of cooling co-solvent that can be used in the present invention is not particularly limited as long as it can perform the above-described action. In the present invention, for example, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, boric acid, carbonic acid, hydrofluoric acid or phosphoric acid; Alcohols such as methanol, ethanol, propanol or butanol and the like; Ketones such as acetone, butanone or propanone; Or a mixture of one or more kinds of ethers such as dimethyl ether or diethyl ether, and the like, and it is preferable to use an acid-based solvent, and more preferably to use acetic acid, but is not limited thereto.

In this invention, it can mix so that the density | concentration in the precursor solution of the said cooling auxiliary solvent may be 0.01 M-10 M, Preferably it is 0.05 M-2 M. If the concentration is less than 0.01 M, the effect of the addition of the cooling co-solvent may be insignificant. If the concentration exceeds 10 M, the solidification point of the precursor solution becomes too low, making it difficult to form a regular shaped mold (ex. Ice mold). There is concern.

In the present invention, after the precursor solution is prepared through the steps (1) and (2), a process of performing an appropriate sonication treatment on the solution may be further performed. Through such ultrasonic treatment, the dispersion efficiency of the carbon-based nanomaterial and the binder can be further improved. In this case, the sonication conditions are not particularly limited and may be appropriately selected so that the dispersion efficiency of each component in the precursor solution may be increased.

In the first step of the present invention, the precursor solution prepared as described above is charged into a mold. At this time, the mold needs to be appropriately controlled so that the mold (ex. Ice mold) formed by solidification of the solvent (ex. Distilled water) in the precursor solution can grow in one direction. Specifically, in the present invention, the material forming the wall surface and the bottom surface of the mold may be controlled to have different thermal conductivity so that the one-way mold is formed in the precursor solution. More specifically, in the present invention, the mold may have a relatively high thermal conductivity of the material forming the bottom surface, as compared with the thermal conductivity of the material forming the wall surface, wherein the thermal conductivity (H b ) of the bottom surface and the wall surface The difference H b -H w of the thermal conductivity H w may be in the range of 10 W / (m · K) to 500 W / (m · K). In the present invention, when the difference in thermal conductivity is less than 10 W / (m · K) or exceeds 500 W / (m · K), the one-way regularity of the mold formed in the precursor solution may be lowered.

In addition, in the present invention, the specific thermal conductivity of the material constituting the wall surface and the bottom surface of the mold is not particularly limited as long as it satisfies the above-described difference in thermal conductivity. In the present invention, for example, the wall surface may be formed of a material having a thermal conductivity of 0.01 W / (m · K) to 1 W / (m · K), and the bottom portion may have a thermal conductivity of 10 W /. It can comprise through the raw material which is (m * K)-500 W / (m * K).

Specifically, for example, in the present invention, the mold wall surface is a fluorine-based resin such as Teflon; Vinyl resins such as polyvinyl chloride; Olefin resins such as polyethylene; Amide resins; Or various synthetic resins or plastic materials having low thermal conductivity, including phenolic resins, and the like, and the bottom surface thereof includes one or more metal materials having high thermal conductivity, such as copper, gold, silver, iron, aluminum, or platinum, or The alloy etc. can be used.

In the present invention, by manufacturing the mold from the material as described above, it is possible to promote one-way solidification in the precursor solution by allowing a lot of heat to escape to the bottom surface of the relatively high thermal conductivity during cooling of the mold. . However, the configuration of such a mold is only one example for promoting unidirectional mold formation in the precursor solution. In the present invention, for example, one-way solidification can be promoted by adjusting the respective thicknesses while the wall and bottom surfaces of the mold are made of the same material.

In one aspect of the present invention, the mold wall surface preferably has a thickness of 0.1 mm to 10 mm and a height of 10 mm to 100 mm. In addition, in one aspect of the present invention, the bottom surface of the mold preferably has a thickness of 0.2 mm to 20 mm, and its area is preferably 4 mm 2 to 2,500 mm 2 .

In the present invention, the shape of the mold configured as described above is not particularly limited, and may be formed in various shapes including, for example, cylindrical, square pillars, and polygonal pillars. Further, in the present invention, for example, as shown in FIG. 1, the mold M into which the precursor solution P is charged may be mounted to the stage 20 connected to the position control device 10, Thereby, the sedimentation position and sedimentation speed of the mold in the 2nd step mentioned later can be controlled precisely.

Meanwhile, in the first step of the present invention, the amount of the precursor solution charged in the mold may be about 0.1 mL to 500 mL, preferably about 1 mL to 50 mL. However, if the amount of the precursor solution is only one aspect of the present invention, in the present invention, the amount of the precursor solution or the shape of the mold can be freely changed according to the microarray to be synthesized.

The second step of the present invention is the step of cooling the mold in which the precursor solution is charged in the first step, whereby the solvent in the solution solidifies, thereby forming a regular mold in one direction.

The method of cooling the mold in the second step of the present invention is not particularly limited, and for example, as shown in FIG. 1, using the stage 20 connected to the position control device 10, the cooling medium 30 is provided. It can be carried out by sedimenting the mold at a constant speed and direction in the flask 40 is stored. In the present invention, by controlling the settling rate of the mold in this process, it is possible to control the solidification rate of the solvent of the precursor solution and the growth behavior of the mold (ice).

The process of forming the mold by solidification of the solvent in the second step of the present invention will be described with reference to the drawings.

As shown in FIG. 2A, when the mold loaded with the precursor solution is settled in a predetermined cooling medium, solidification starts in one direction from the lower direction to the upper direction of the mold in preferential contact with the refrigerant. In this one-way solidification process, the solute in the precursor solution forms a compositional subcooled region in front of the solidification interface, whereby the interface of the mold (ex. Ice) has regularity, as shown in FIG. It grows into a three-dimensional columnar or lamellar shape.

In the growth of such a mold, the solidification rate of the solvent affects the compositional supercooling and the behavior of the carbon-based nanomaterial in the precursor solution, thereby determining the shape of the formed mold and the shape of the structure. For example, the faster the solidification rate of the solvent, the greater the compositional supercooling in front of the solidification interface of the mold, the mold grows forward than the sides to form a columnar mold, and the slower the solidification rate, It grows laterally along with the lamellar shape. In addition, when the solidification speed is sufficiently slow, the mold grows laterally than the front, and the lamellar mold has a larger area, and thus, microarrays having larger pores can be formed. That is, in the growth process of the mold as described above, as shown in Figure 2c, the carbon-based nanomaterials contained in the precursor solution is aggregated while moving to the side of the mold, the solidification of the mold in the process of removing the mold to be described later Depending on the speed, cellular or lamellar microarrays are formed.

In the present invention, the solidification rate of the mold as described above can be controlled by, for example, controlling the sedimentation rate of the mold into the cooling medium. In one aspect of the invention the settling velocity of the mold into the cooling medium is from 1 μm / s to 3,000 μm / s, preferably from 10 μm / s to 2,000 μm / s, more preferably from 100 μm / s to 1,500 μm. It can be controlled within the range of / s. In the present invention, when the settling speed of the mold is less than 1 µm / s or more than 3,000 µm / s, the mold solidification speed may be too fast or slow, and the formation efficiency of the mold may be lowered. In the present invention, in particular, the shape of the mold can be controlled by controlling the settling speed of the mold, and as a result, the structure of the final microarray can be controlled. For example, in order to produce a lamellar microarray in the present invention, for a cooling medium having a temperature of about -200 ° C, the sedimentation rate of the mold can be controlled in a range of less than about 500 µm / s, and the cellular In order to produce a microarray of structure, the sedimentation rate can be controlled in a range of about 500 μm / s or more for a cooling medium whose temperature is also about -200 ° C.

Meanwhile, in the present invention, the type of cooling medium in which the mold is settled is not particularly limited, and for example, a general cooling medium such as liquid nitrogen, carbon dioxide, propane, butane or ammonia may be used, and liquid nitrogen may be used. It is preferred to use, but is not limited thereto.

Further, in the present invention, the temperature of the cooling medium is also not particularly limited, and can be appropriately controlled in the range of -300 ° C to -100 ° C, for example. However, the temperature of the cooling medium is only one aspect of the present invention, and in the present invention, the temperature of the cooling medium can be freely controlled in consideration of the solidification rate of the desired solvent, the settling speed of the mold, and the like.

The third step of the present invention is a process of finally producing a microarray by removing the mold formed in the second step. The method for removing the mold in the present invention is not particularly limited, and can be removed by, for example, a freeze drying method. When the mold is removed in this manner, the solute containing the carbon-based nanomaterial is solidified in the process, thereby forming a microarray. In the present invention, the conditions under which the above freeze drying is performed are not particularly limited. For example, the freeze drying may be performed at a temperature of −30 ° C. or lower and a pressure of 0.1 mbar or lower for 20 hours or more.

In the freeze-drying process of the present invention, the lower limit or upper limit of the temperature, pressure and process time is not particularly limited. In the present invention, for example, the temperature of the freeze-drying can be appropriately controlled in the range of -60 ℃ or more, the pressure is 0.001 mbar or more, and the process time in the range of 48 hours or less.

< Example >

Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited to the examples given below.

Example  One

Carbon nanotube powder (cross section average diameter: 10 nm to 15 nm, average length 10 µm to 10 µm, product name: CM-95, manufacturer: Hanwha Nanotech) was added to an aqueous solution of nitric acid (concentration: 60 wt%), at 80 ° C. After acid treatment for 6 hours, it was dried under appropriate conditions and powdered again. Subsequently, to 100 mL of an aqueous acetic acid solution (acetic acid concentration: 0.05M) prepared by mixing acetic acid in distilled water, chitosan (product name: Chitosan, practical grade, manufacturer: Aldrich) was added at a concentration of 1 wt%, and for 12 hours. Stir and mix uniformly. Subsequently, an acid treated carbon nanotube powder was added to the aqueous solution in which chitosan was dissolved in an amount of 4 wt%, and ultrasonic waves were irradiated to prepare a uniform aqueous solution. Subsequently, 0.5 mL of the prepared aqueous solution was charged to the mold. At this time, the mold is fixed to the stage 20 connected to the position control device 10, as shown in the accompanying Figure 1, the wall surface is Teflon (thermal conductivity: 0.25 W / (mK), thickness: 3 mm, height: 30 mm), the bottom surface was made of copper (heat conductivity: 400 W / (mK), thickness 3 mm). The mold (M) loaded with the aqueous solution (P) was settled in the liquid nitrogen refrigerant stored in the dual flask 40 and kept at a temperature of -196 占 폚 at a sedimentation rate of 200 mu m / s. In the aqueous solution through the above treatment, after the mold formation due to the solidification of the solvent is completed, the mold was lyophilized for 24 hours at a temperature of -50 ℃ and pressure of 0.01 mbar to prepare a lamellar microarray.

Example  2

A microarray of cellular structure was prepared in the same manner as in Example 1 except that the settling speed of the mold loaded with the precursor solution was controlled to 1,000 μm / s.

Test Example  1. Scanning electron microscope SEM ) analysis

The structures of the microarrays prepared in Examples 1 and 2 were analyzed by scanning electron microscopy (SEM), and the results are shown in FIG. 3. (A) and (b) of FIG. 3 are enlarged photographs of the lamellar structure prepared in Example 1 at magnifications of 80 times and 180 times, respectively, and FIGS. 3 (c) and (d) (A) is an enlarged photograph of magnifications of 2,500 times and 12,000 times, respectively. As can be seen from (a) to (d) of FIG. 3, the microarray having a three-dimensional structure is stably formed over the entire region, and also has a regular three-dimensional structure having the same orientation in an area of several thousand micrometers. It was confirmed that was formed. In particular, as can be seen from (b) of FIG. 3, not only the x and y axes, but also the regular arrays were formed at the level of thousands of micrometers along the z-axis according to the growth direction of the template. As can be seen from (c) of 3, in the case of the microarray manufactured in Example 1, the wall thickness was about 1 µm, and the wall-wall spacing was about 10 µm, and from FIG. It was found that the individual carbon nanotubes maintained a stable structure in which they were well intertwined.

3 (e) and 3 (f) are photographs taken at a magnification of 200 times and 3,500 times the microarray of the cellular structure prepared in Example 2, respectively. As can be seen from (e) and (f) of FIG. 3, it was confirmed that a stable, regular three-dimensional array was formed over the entire area, and the wall thickness of the array was about 1 μm, and the wall and the wall The interval between them was confirmed to be about 15 μm.

From the above analysis results, in the case of the microarray according to the present invention, the plate-shaped structure (wall) has an empty porous structure, thereby providing a passage through which components (ex. Electrolyte or gas) flowing from the outside can be smoothly diffused. In addition, it can be confirmed that each carbon-based nanomaterial (carbon nanotube) has a stable structure in which each structure is well entangled.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically an example of the apparatus for manufacturing the microarray of this invention.

2 is a view schematically showing a process of manufacturing a microarray in the manufacturing method of the present invention.

3 shows scanning electron micrographs of the microarrays prepared in Examples 1 and 2. FIG.

&Lt; Description of reference numerals &

10: position control device 20: stage

30: refrigerant 40: flask

M: Mold W: Mold Wall

B: bottom P: precursor solution

Claims (30)

At least two plate-like structures containing a carbon-based nanomaterial, The plate-like structure is spaced apart from each other, forming a layered microarray. The microarray of claim 1, further comprising two or more second structures that grow in the thickness direction of the plate-like structure and connect the structures. The microarray according to claim 1, wherein the plate-like structure has an average thickness of 0.2 µm or more. The microarray according to claim 1, wherein the average spacing between the plate-like structures is 0.5 µm to 50 µm. 3. The microarray of claim 2 wherein the average spacing between the second structures is between 0.5 μm and 50 μm. The microarray of claim 1, wherein the carbon-based nanomaterial is at least one selected from the group consisting of carbon nanotubes, carbon fibers, graphene, and fullerenes. The microarray of claim 1, wherein the carbon-based nanomaterial has an average size of 1 nm to 1,000 nm. The microarray of claim 1, wherein the plate-like structure further comprises a binder. 9. The binder according to claim 8, wherein the binder is at least one selected from the group consisting of epoxy resins, alginate resins, polyurethanes, polyalkylene oxides, acrylic resins, vinyl resins, amide resins, cellulose resins and chitin resins. Microarray to do. The microarray of claim 8, wherein the plate-shaped structure comprises 5 parts by weight to 100 parts by weight of a binder based on 100 parts by weight of the carbon-based nanomaterial. A first step of charging a precursor solution containing a carbon-based nanomaterial into a mold having different thermal conductivity from a wall surface and a bottom surface; A second step of cooling the mold in which the precursor solution is charged in the first step to form a mold through solidification of the solvent of the precursor solution; And A method of manufacturing a microarray comprising a third step of removing the mold formed in the second step. The method of claim 11, wherein the precursor solution comprises the steps of: (1) acid treating the carbonaceous nanomaterial; And (2) mixing the acid-treated carbonaceous nanomaterial and a binder in a solvent. 13. The microarray according to claim 12, wherein the acid treatment of step (1) is performed by immersing the carbonaceous nanomaterial in an acidic solution and maintaining it at a temperature of 60 ° C to 90 ° C for 2 to 8 hours. Manufacturing method. The method of claim 13, wherein the acidic solution comprises at least one selected from the group consisting of sulfuric acid, nitric acid and hydrochloric acid. 13. The method of claim 12, wherein the mixing concentration of the carbonaceous nanomaterial in step (2) is 0.2 wt% to 40 wt%. 13. The method of claim 12, wherein the mixing concentration of the binder in step (2) is 0.1 wt% to 10 wt%. 13. The method of claim 12, wherein the solvent of step (2) is water. 13. The process of claim 12, wherein the cooling co-solvent is further mixed in step (2). 19. The method of claim 18, wherein the cooling co-solvent is at least one selected from the group consisting of acids, alcohols, ketones and ethers. 19. The method of claim 18, wherein the mixing concentration of the cooling co-solvent is controlled in the range of 0.01 M to 10 M. The method according to claim 11, wherein the difference H b -H w between the bottom surface thermal conductivity H b and the wall thermal conductivity H w of the mold of the first step is 10 W / (m · K) to 500 W / (m * K) The manufacturing method of the microarray characterized by the above-mentioned. The method of manufacturing a microarray according to claim 11, wherein the bottom surface thermal conductivity of the mold of the first step is 10 W / (m · K) to 500 W / (m · K). 12. The method of claim 11, wherein the mold wall surface of the first step has a thickness of 0.1 mm to 10 mm and the bottom surface has a thickness of 0.2 mm to 20 mm. 12. The method of claim 11, wherein the amount of precursor solution charged to the mold in the first step is controlled to between about 0.1 mL and 500 mL. 12. The method of claim 11, wherein the cooling of the mold in the second step is performed by settling the mold into a cooling medium. The method of manufacturing a microarray according to claim 25, wherein the settling velocity of the mold into the cooling medium is controlled within a range of 1 µm / s to 3,000 µm / s. 27. The method of claim 25, wherein the cooling medium is liquid nitrogen, carbon dioxide, propane, butane or ammonia. The method of claim 25, wherein the temperature of the cooling medium is from -300 deg. C to -100 deg. 12. The method of claim 11, wherein the removal of the mold in the third step is performed by freeze drying. 30. The method of claim 29, wherein the freeze drying is performed for at least 20 hours at a temperature of -30 [deg.] C. and a pressure of 0.1 mbar or lower.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104155353A (en) * 2014-07-31 2014-11-19 深圳市容大感光科技股份有限公司 Preparation method of three-dimensional carbon microarray and hydrotalcite composite material and application of three-dimensional carbon microarray and hydrotalcite composite material as non-enzymatic sensor
KR101632371B1 (en) * 2015-01-15 2016-06-21 한국과학기술원 Composite ceramic structure, method for producing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104155353A (en) * 2014-07-31 2014-11-19 深圳市容大感光科技股份有限公司 Preparation method of three-dimensional carbon microarray and hydrotalcite composite material and application of three-dimensional carbon microarray and hydrotalcite composite material as non-enzymatic sensor
CN104155353B (en) * 2014-07-31 2016-03-30 深圳市容大感光科技股份有限公司 The preparation method of a kind of three-dimensional carbon microarray and hydrotalcite composite material and as the application without enzyme sensor
KR101632371B1 (en) * 2015-01-15 2016-06-21 한국과학기술원 Composite ceramic structure, method for producing same

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