KR20040107000A - Method for fabricating a carbon nanotube array using the nanopattern of supramolecules - Google Patents

Abstract

PURPOSE: A method for preparing a carbon nanotube (CNT) array, a method for preparing a CNT bio-nanoarray, and a method for detecting the reaction of a biomaterial and a bio-receptor by using the CNT bio-nanoarray are provided, to allow a nano-sized pattern to be formed by simple several steps of process and to allow the orientation of microstructure to be controlled easily. CONSTITUTION: A carbon nanotube array is prepared by forming a thin film of a self-assembling organic supramolecule on a substrate; annealing it to form a cylindrical regular structure by the self-assembly of the organic supramolecule; irradiating a UV ray to the structure to decompose the center part where a carbon chain is concentrated to form a nano-pattern of an organic supramolecule; etching it by using the nano-pattern as a mask to form a nano-pattern on a substrate; and arraying a carbon nanotube on the nano-pattern. Preferably the organic supramolecule is a disk-type or dendrimer fan-shaped organic supramolecule. Preferably the organic supramolecule is represented by the formula 6 or 7. A CNT bio-nanoarray is prepared by adhering a biomaterial or a bio-receptor to the CNT array obtained by the method.

Description

Method for fabricating a carbon nanotube array using the nanopattern of supramolecules}

An object of the present invention is to form an organic supramolecular pattern of several nanometers or less using self-assembly of organic supramolecules and UV etching, and to arrange the CNTs therein, and the CNTs obtained by the above method. The present invention relates to a method for producing a CNT-bio nanoarray, which comprises attaching a bioreceptor to a biomaterial or a biomaterial that binds to the biomaterial.

Until now, surface pattern formation has been mainly performed by photolithography using a polymer thin film as a photoresist. However, in order to realize a nanometer-sized high-precision pattern, the wavelength of light available and As a result, it is difficult to secure devices and technologies and to limit the resolution of the polymer itself.

Since 1990, there have been attempts to increase the resolution of patterns using shorter wavelengths of light, along with attempts to use them as new photoresist in existing photoelectric methods. In addition, a whole new concept of patterning technology has emerged, namely nano-patterning technology using soft lithography. This method has the advantage of being able to form patterns quickly and inexpensively and chain work, but in fact, the resolution limit is 100 nm, so it is difficult to expect an increase in resolution for further integration.

On the other hand, nano-pattern forming method (KR 10 / 263671B1) of a semiconductor device using organic molecules as a material for forming a pattern has a thickness of the fine pattern remaining in the groove by using one more buffer layer to secure an excessive etching margin. The technique of applying spacers to the buffer layer in order to secure the size of the grooves and to reduce the size of the grooves, but the number of process steps and the size of the pattern is several tens of nanometers.

Recently published self-assembly structure (KR 02 / 89528A) relates to a small-size structure to form a device widely used in the microelectronics industry, the self-assembly method proposed in the present invention is an array (array) While providing the ability to form, self-assembly itself does not determine the location of device formation within boundaries along the surface. Thus, the formation of devices within boundaries along the surface requires individual positioning techniques, where suitable positioning techniques are used in conjunction with self-assembly to form structures that can generally function as discrete components in integrated electronic circuits. do. The positioning method can delimit the structure using lithography, direct forming, or other positioning techniques such that a patterned substrate is formed, and the device is assembled by self-assembly on the substrate.

Self-assembled structures can be incorporated with structures formed by conventional chemical vapor deposition and physical vapor deposition techniques and integrated electronics can include integrated optical components. The self-assembled structure may be formed using a dispersion of nanoparticles by adjusting to obtain a desired structure formation according to the conditions of the material surface and the temperature and concentration conditions. On one surface of the substrate, a linker is used to chemically bond the other end to the nanoparticles, and selective bonding with the linker may be used to move to the self-assembly process.

Another alternative is to use natural interactions, such as electrostatic and chemical interactions, to direct the self-assembly process, where the nanoparticles are placed in small pores to position the nanoparticles within the boundaries defined by the porous region. It is stacked. Small holes may be found in certain materials such as inorganic oxides or two-dimensional organic crystals, and suitable holes may be formed, for example, by ion milling or chemical etching. However, the process is complicated and the pattern spacing remains at the level of several tens to one hundred nanometers.

In addition, a method of forming a nanometer high precision pattern using a self-assembled monolayer (KR 03 / 23191A) is known, and the present invention forms an aromatic imine molecular layer having a substituted end ring on a substrate, and the aromatic imine molecular layer Selectively bonding-cutting the substituents, and hydrolyzing the aromatic imine molecular layer in which the substituents are selectively bonded-cut, thereby providing a method of forming a pattern in a short time, but still staying at several tens of nanometers.

On the other hand, the surface of the tip of an atomic force microscope is buried with a surface-active molecule having a chemical affinity for a solid substrate, and a nano-level pattern is formed on the substrate with the tip of the tip, as if writing letters on paper. The deep-pen nanolithography method (Science, 283: 661, 1999) has the advantage of obtaining high resolution nanopatterns down to the 5nm level by using highly precise tips, but the patterns must be drawn one after the other. Since there is a problem in that it takes a long time to obtain a desired pattern (serial processing), there is a limit to practical application through mass production.

As described above, various methods such as photolithography, ultraviolet light, and X-ray etching method have been introduced, but the pattern formation below 100 nm has reached its limit. Instead of top-down methods, methods for bottom-up methods have been widely studied.

Upward structure-forming methods are based on the formation of microstructures of molecules by self-assembly. This basic technique is used to analyze microstructures of organic molecules by scanning electron microscopy (Hudson, SD et al., Science, 278). : 449, 1997) and papers confirming that the orientation of organic molecules depends on the substrate surface properties (Jung, HT et al., Macromolecules, 35: 3717, 2002). Only the orientation of organic molecules is described.

In addition, as in the method of forming a regular pattern using a block copolymer and a method of forming a dot pattern through chemisorption of metal (Park M. et al., Science, 276: 1401, 1997) Research into making a pattern of less than 100nm using is in progress, but due to the molecular chain of the polymer is a situation that stays on the pattern formation of more than a few tens of nanometers. In addition, when the block copolymer is used, the aspect ratio of the pattern to be formed is not large, the structure of the thin film is complicated, and there is a problem in that it is not easy to give the structural direction of the thin film.

On the other hand, microarray protein chips (microarray) is currently occupying a large proportion of research on diagnostic protomics (diagnostic protomics). Early array techniques (USP 5,143,854A), which used photolithographics to array polypeptides on the surface of substrates, have recently been tried in various ways. In particular, the development of microarray-type formats is becoming increasingly important in a variety of immunoassays, including antigen-antibody pairs and enzyme-liked immunosorbent assays. have.

However, protein arrays are not as easy to integrate or array in a practical format that is smaller or more sensitive than DNA arrays. In other words, the lattice pattern of DNA oligonucleotide can be generated on the surface of the substrate by photoetching technique, but for a protein composed of hundreds of amino acids, the antibody should generally have about 1400 amino acids. In order to achieve a higher density of grid patterns are required, but it is not easy to succeed.

Another problem is that proteins can easily lose their tertiary structure when handled under denaturing conditions ( Anal. Chem . 14A-15A, 2001; Anal. Chem., 73 , 8-12, 2001). There are many limitations in the operation.

The solution to these problems depends on how high the protein is arranged without losing the tertiary structure of the protein. To date, inkjet printing, drop-on-demand Technology, microcontact printing, and IBM's soft lithography. However, these methods also have spacing sizes ranging from tens of micrometers to several millimeters, and the development of highly integrated diagnostic protein nanoarrays with high density of real-life samples without losing the tertiary structure of the protein. Has never been tried.

Carbon nanotube (CNT) is a structure in which a graphite surface is rolled round, and a diameter of 1 to 20 nm is typical. Graphite has a strong and flat hexagonal lamellar structure due to its unique bonding arrangement. The top and bottom of the membrane is filled with free electrons, and the electrons move in parallel with the membrane in discrete states. Since the graphite layer is wound into a spiral and becomes CNTs, the edges are bonded at the point of phase. Changing the spiral or chirality of the tube changes the way the free electrons move. Thus, the motion of the free electrons is completely free and the nanotubes react like metals, or they must overcome barriers like semiconductors. The size of the barrier is determined by the diameter of the tube, and 1 eV is possible for the smallest diameter of the tube.

CNTs have excellent mechanical and chemical stability, can exhibit the properties of both semiconductors and conductors, and are small in diameter, long in length, and hollow, so they are excellent materials for flat panel display devices, transistors, and energy storage materials. Visible, its applicability as nano-sized various electronic devices is very large.

As a method of arranging CNTs on a substrate, a method of arranging the ends of CNTs by sulfur on gold has been reported (Langmuir, 16, p. 3569, 2000). In addition, by using lithography, a trimethylsilyl self assembly monolayer is formed on a silicon substrate, followed by patterning using an electron beam (E-beam), and adsorbing an amine group to the pattern. Then again here is an example of CNT adsorption (Chemical Physics Letters 303, 125, 1999). However, this conventional technology has a disadvantage that it is vulnerable to changes in the surrounding environment.

Example of using carbon-based nanotubes for the fabrication of nanometer-sized microscopy probes (USP 6159742), stable iodine-doped carbon nanotubes by doping CNTs with iodine ) Or examples of fabricating metallic nanoscale fibers (USP 6139919), and examples of fabricating electrochemiluminescent ruthenium complexes using functional biomolecule-modified nanotubes (USP 5866434). They did not apply CNT to the fabrication and development of bio-chips.

Accordingly, the present inventors have made efforts to develop an ultra-high density pattern forming method having a simpler process and a pattern size of several nanometers. As a result, pattern formation of several nanometers or less is possible using self-assembly and UV etching of organic supramolecules. The present invention was completed by binding or arranging CNTs to these nanopatterns.

An object of the present invention is to provide a method for producing a CNT array characterized in that the organic supramolecular pattern of several nanometers or less is formed by using self-assembly of organic supramolecules and UV etching, and CNTs are arranged thereon.

Another object of the present invention is to form a nano-pattern on the substrate or interlayer thin film, characterized in that it comprises the step of etching the substrate or the interlayer thin film on the substrate using the nanopattern of the organic supramolecules as a mask, to arrange the CNT It is to provide a method of manufacturing a CNT array characterized in that.

Still another object of the present invention is to provide a method for producing a CNT-bio nanoarray, which comprises attaching a biomaterial or a bioreceptor that binds to the biomaterial to the CNT array obtained by the above method.

1 is a diagram of a model of organic supramolecular self-assembly. FIG. 1A shows a three-dimensional structure in which a disk- or disk-shaped dendrimer 1 and a fan-shaped organic supramolecular 2 form a cylindrical shape 3 through self-assembly, and these cylinders are arranged in a hexagon (4). ) Is shown. FIG. 1B shows that rod-chain or cone-shaped molecules 5 form spheres 6 through self-assembly, which spheres are gathered and arranged in a constant structure 7 in three-dimensional space.

FIG. 2 is a schematic view showing that CNTs having a carboxyl group on an exposed substrate of an amine group are arranged on the substrate by amide bonds, and CNTs are stacked using a chemical having two amine groups as a linker.

3 is a schematic view showing a process of forming a nanopattern using self-assembly and UV etching of the organic supramolecular in accordance with the present invention.

4 is a TEM photograph showing that organic supramolecules form a regular structure.

In order to achieve the above object, in the present invention, (a) forming a thin film of organic supramolecules causing self-assembly on the substrate; (b) self-assembling the organic supramolecules by annealing to form a cylindrical regular structure; (c) irradiating UV to a cylindrical structure formed by self-assembly of the organic supermolecules to decompose the central part where the carbon chains are collected to form a nanopattern of the organic supermolecules; And (d) arranging the CNTs in the nanopatterns of the organic supramolecular molecules.

In a preferred embodiment of the present invention, before the step (a) it may be characterized in that the interlayer thin film of a metal, non-metal or organic material is formed on the substrate.

The present invention also includes the steps of (a) forming a thin film of organic supramolecules that causes self-assembly on a substrate; (b) self-assembling the organic supramolecules by annealing to form a cylindrical regular structure; (c) irradiating UV to a cylindrical structure formed by self-assembly of the organic supermolecules to decompose the central part where the carbon chains are collected to form a nanopattern of the organic supermolecules; (d) etching the substrate using the nanopattern of the organic supermolecule as a mask to form a nanopattern on the substrate; And (e) arranging the CNTs in the nanopatterns of the substrate.

According to an embodiment of the present invention, before the step (a) may further comprise the step of modifying the substrate surface to adjust the orientation of the pattern structure, the modification of the substrate surface on the surface It may be characterized by forming an interlayer thin film such as a metal or nonmetal thin film, a self-assembled monolayer (SAM), and other thin films corresponding to the end purpose.

In the present invention, although the organic molecule used the compound of the following [Formula 6] or [Formula 7], any organic molecule forming a columnar shape by self-assembly may be used without limitation.

[Formula 6] [Formula 7]

Organic molecules that self-assemble include disc or disc dendrimers 1, fan-shaped organic molecules 2, rod-chain or conical molecules 5 and the like. Examples of the wedge-shaped organic molecules are the compounds of the above [Formula 6] or [Chemical Formula 7], examples of the discotic organic molecules are the compounds of the following [Formula 8], and examples of the conical organic molecules are the compounds of the following [Formula 9] Can be mentioned.

[Formula 8]

[Formula 9]

Unlike organic polymers in which monomers are covalently linked, these organic molecules form a uniform structure by physical secondary bonds such as van der Waals attraction. These organic molecules are self-assembled by an appropriate temperature or concentration, an external magnetic field, or an electric field to form specific microstructures. The wedge-shaped molecules form a plate-like structure (1) through self-assembly, these plate-like structures form a column (3), and again form a three-dimensional structure (4) in which the cylinders are arranged in a hexagon (Fig. 1A). ). In addition, in the case of cone-shaped organic molecules 5, the cones are self-assembled to form a sphere 6, and the spheres are gathered and arranged in a constant structure 7 in a three-dimensional space (Fig. 1B).

In the present invention, the substrate (substrate) may be used a variety of materials such as silicon, glass, molten silica, polymer.

According to an embodiment of the present invention, the thin film of step (a) is preferably formed by spin-coating, rubbing, or solution spreading by forming a thin film on the surface of the water. Do.

According to one embodiment of the present invention, step (b) is preferably cooled slowly after raising above the liquid crystal phase transition temperature of the organic molecules using the temperature.

According to an embodiment of the present invention, the etching of the substrate or the metal thin film may preferably use reactive ion etching and / or ion milling.

Arranging the CNTs in the pillar-shaped organic molecule nanopattern may be characterized by arranging CNTs after depositing a metal catalyst on the substrate of the pattern, wherein the catalyst is iron, cobalt or nickel. You can do

In addition, the method of arranging CNTs on the nanopattern of the substrate may be prepared using a method of manufacturing CNTs known in the art, but preferably, the CNTs on the substrate are perpendicular to each other by chemical vapor deposition, electrophoresis or mechanical methods. Can be grown (KR 10-2002-1260A). After exposing the amine group to the pattern of the substrate, CNTs having a carboxyl group may be arranged on the substrate with amide bonds, and CNTs may be laminated using chemicals having two amine groups as linkers (FIG. 2).

The present invention also provides a method for producing a CNT-bio nanoarray, comprising attaching a biomaterial or a bioreceptor to a CNT array obtained by the above method, and nucleic acids, proteins, peptides, amino acids, enzyme substrates, ligands, amino acids on the CNT array. It provides a CNT-bio nanoarray, characterized in that the biomaterial or bioreceptor selected from the group consisting of, cofactors, carbohydrates, lipids, oligonucleotides and RNA is attached.

The term 'bio nanoarray' used in the present invention is a concept encompassing a bioreceptor that reacts with or binds to a biomaterial or a biomaterial to a nanopattern, and is defined as including a biochip and a biosensor.

Attaching biomaterials or bioreceptors to CNTs can be coupled to CNTs by applying a charge of opposite polarity to the net charge of the biomaterials or bioreceptors (KR 2003-0014997A), or using a binding aid. It can also be attached. Preferred binding aids may be characterized as chemicals with aldehydes, amines or imine groups attached to the carbon group ends.

The biomaterial or the bioreceptor binding to the biomaterial may be any one selected from the group consisting of nucleic acids, proteins, peptides, amino acids, enzyme substrates, ligands, amino acids, cofactors, carbohydrates, lipids, oligonucleotides, and RNA.

Biomaterials or bioreceptors, such as proteins, peptides and amino acids, have their own isoelectric points, and are net charges charged with neutrals, cations, and anions, depending on the strength of the ions in solution or pH conditions. Has In addition, by controlling the state of the solution, by randomly controlling the interaction of these biomaterials or bioreceptors with a constant charge, such as the electrostatic and hydrophobic interaction of the CNT, Different or different types of biomaterials or bioreceptors can be moved or arrayed.

The present invention also provides a method for detecting a reaction between a biomaterial and a bioreceptor, wherein the CNT-bio nanoarray is used.

According to the present invention, a protein-specific receptor which selectively binds to a target protein involved in a disease can be selectively attached by applying an electric field to a nanoarrayed CNT on one chip. It is also possible to selectively attach biomaterials or bioreceptors that can interact with different types of target proteins involved in various diseases by applying different polarity of electric fields to each CNT. Therefore, it is possible to accurately diagnose various types of diseases at once and in large quantities on a single chip.

Hereinafter, the present invention will be described in more detail.

According to a preferred embodiment of the present invention, first, the organic molecule of [Chemical Formula 6] or [Chemical Formula 7] is made of 1wt% solution using tetrahydrofuran (THF) as a solvent to form a thin film on the substrate. In forming a thin film, spin-coating, rubbing, or solution spreading is mainly used to form a thin film on the surface of the water. In the embodiment, a silicon wafer was used as a substrate, and surface modification was not performed (FIG. 3 (a)).

Since the organic molecules are self-assembled to raise the temperature slightly above the liquid crystal transformation temperature of the organic molecules. In the case of the organic molecules used in the present invention, since the liquid crystal phase transition temperature is about 30 ° C, the temperature was raised to 70 ° C for a sufficient transition and then cooled slowly (FIG.

UV is irradiated to the formed cylindrical organic supramolecular microstructure to decompose the cylindrical central part to form a hole-shaped pattern (FIG. 3 (c)).

After depositing and fixing a metal catalyst such as iron, cobalt, or nickel on the organic supramolecular pattern, CNTs were synthesized on the catalyst metal array. The synthesized CNTs form a CNT array by a regular arrangement of metal catalysts immobilized on a substrate (FIG. 3 (d)).

According to a preferred embodiment of the present invention, the organic molecules are self-assembled by heat treatment as follows.

The nature of the organic molecules can be modified by heat treatment, suitable starting materials for heat treatment include organic molecules produced by laser pyrolysis. In addition, organic molecules used as starting materials may undergo one or more pre-heating steps under different conditions. In the heat treatment of organic molecules formed by laser pyrolysis, further treatment improves crystallinity and contaminants such as elemental carbon. The stoichiometry can be changed, possibly by incorporating additional oxygen, or elements from other gaseous or non-gas compounds, for example. The organic molecules are generally preferably heated in an oven or the like to provide uniform heating. Treatment conditions are generally mild, so that a significant amount of particle sintering does not occur. Therefore, the heating temperature is preferably lower than the melting point of both the starting material and the product material. If the heat treatment involves a composition change, the size and shape of the molecules may change even at mild heating temperatures.

Self-assembled structures are generated on and / or within the surface of the material / substrate. The self-assembled structure can be positioned within the boundary so that each structure can form an element as part of a plurality of elements of circuits or appliances in such a way that the structure forms a positioned island. In particular, each structure may be a component of an integrated electronic circuit, which component may include, for example, an electrical component, an optical element and a photonic crystal.

In order to form the structure within a predetermined boundary, the formation of the self-assembled structure of interest generally requires a process of defining a limit of the structure and a self-assembly separate from the process. The demarcation process generally uses external forces to limit the structure. The self-assembly process itself generally does not delimit the structure. Self-assembly is based on the natural sensing function of the composition / material which, when combined, causes natural ordering in the resulting structure. In general, the positioning step may be performed before or after the self-assembly process, but the nature of the processing step may indicate a particular order. The net effect results in a self-assembled structure having a correspondingly covered range of nanoparticles within the boundaries, and a region outside the boundaries without these covering ranges. A separate demarcation process is connected to the self-assembly process by activating the self-assembly process within the boundary or making the area outside the boundary inactive. In general, an external force must be applied to perform the activation process or the deactivation process.

Formation of a uniform structure on the bulk of organic molecules can be confirmed by transmission electron microscopy. As a result of fabricating the sample through the process under the same conditions as used in this experiment, the results as shown in FIG. 4 were obtained, and it was found that the organic molecules formed a regular structure in the form of a hexagonal column.

Hereinafter, the present invention will be described with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

Example 1 Synthesis of Organic Molecules

The organic molecules of [Formula 6] and [Formula 7] used in the present invention were synthesized through a 6 step process as in <Scheme 1>. In the first step, potassium carbonate serving as a base was dissolved in diformamide at 65 ° C, and methyl 3,5-dihydroxy benzoate and perfluorododecyl bromide were added and refluxed for 8 hours. The compound of [Formula 1] is obtained by this.

The compound of [Formula 1] thus obtained was subjected to a reduction reaction from purified tetrahydrofuran to lithium aluminum hydride at room temperature for 2 hours to obtain a compound of [Formula 2], and then dissolved in a mixed solvent of dichloromethane and tetrahydrofuran. After the addition of about the amount of diformamide as a catalyst, the reaction of about 20 minutes at room temperature with thionyl chloride to give a compound of [Formula 3].

The next reaction, the esterification reaction, proceeded in the same manner as the first step. That is, the compound of [Formula 3] prepared in the previous step with methyl 3,5-dihydroxy benzoate in a solution of diformamide and potassium carbonate, and the reflux reaction at 65 ℃ for 18 hours to The compound was obtained.

The compound of [Formula 5] was synthesized by the hydrolysis of methyl ester by 10N potassium hydroxide in a mixed solvent of ethyl alcohol and tetrahydrofuran, the final step of the esterification reaction [Formula 6] and [Formula 7] The compounds of were synthesized in the same way as each other. That is, after dissolving the compound of [Formula 5], octanol or pentanol, and 4-dimethylaminopyridinium paratoluenesulfonate (DPTS) in a mixed solvent of dichloromethane and Freon 113, 1,3-dicyclohexyl Carbodiimide (DCC) was added to the reaction for 24 hours to obtain the compounds of [Formula 6] and [Formula 7].

Scanning electron microscopy confirmed that these organic molecules form a regular cylindrical structure of less than nanometers.

<Scheme 1>

Example 2: Modification of the Substrate Surface

In the present invention, a silicon wafer was used that did not change the properties of the substrate. If necessary, metals, nonmetals and other thin films can be formed on the substrate.

Example 3: Formation of Organic Molecular Thin Film

The organic supramolecular sample of [Formula 6] or [Formula 7] is dissolved in an organic solvent such as toluene, chloroform, benzene, tetrahydrofuran and ethyl acetate at about 1 wt%, and then the solution is 2000 to 4000 rpm on a silicon wafer. Spin coating at a rate of 10 to 40 seconds to form an organic molecular thin film (Fig. 3a). Since this process may be affected by the equipment or experimental conditions, the optimal conditions should be determined by trial and error.

Example 4: Annealing

The organic supramolecule of [Formula 6] or [Formula 7] forms self-assembly at about 30 ° C., but after raising the temperature to 70 ° C. at 2 ° C./min for sufficient movement, it is slowly cooled to 2 ° C./min and then regularly Microstructures were formed (FIG. 3B). By such heat treatment, the organic supramolecule of [Formula 6] or [Formula 7] forms a regular microstructure by self-assembly around 30 ° C.

In the case of the organic supramolecule used in the present invention, self-assembly occurs at 30 ° C., which may vary depending on the organic supramolecules used.

Example 5: UV Etching

UV was irradiated to the organic supermolecular microstructure obtained in Example 4 for about 10 to 30 minutes using a UV lamp having a wavelength of 254 nm. The portion of the carbon chain gathered by the UV wavelength used, that is, the center portion of the cylinder was decomposed to form a hole-shaped nanopattern (FIG. 3C). Residues decomposed by UV were removed using tertiary distilled water.

Example 6 Method of Forming Nanopattern on Substrate

The substrate was etched using the nanopattern of the organic supramolecular obtained in Example 6 as a mask to form a groove-shaped nanopattern on the substrate. In the present embodiment, an intermediate layer was not used on the substrate. However, when an intermediate thin film layer such as a metal, a nonmetal or a polymer is formed between the substrate and the organic supramolecular thin film, a groove-shaped nanopattern in the intermediate layer is formed using the formed organic supramolecular nanopattern as a mask. Can be formed.

Example 7 Nanopattern Fabrication of Magnetic Metals for High Density Recording Materials

First, a thin film of a magnetic metal to be used as a final recording material such as cobalt, nickel, and platinum alloy (Co ₆₈ Cr ₁₈ Pt ₁₄ ) was formed on a substrate, and then the procedures of Examples 1 to 5 were performed.

By using the nanopatterns of the organic supramolecules obtained as a mask, ion milling may be performed to prepare nanopatterns of magnetic metal thin films.

Example 8: Preparation of CNT Array

Iron, cobalt, or nickel metal catalysts were fixed on the substrate on which the nanopatterns of organic molecules obtained through Examples 1 to 6 were formed by thermal evaporation, sputtering, or the like. Removed by pyrolysis. In the same manner, metal catalysts such as iron, cobalt, or nickel were fixed in the grooves of the substrate obtained through Example 7.

After depositing and fixing the metal catalyst, while supplying the reaction gas such as C ₂ H ₂ , CH ₄ , C ₂ H ₄ , C ₂ H ₆ , CO into the chamber, a high frequency power is applied to the positive electrode to generate a glow discharge, thereby providing the fine catalyst. CNTs were synthesized on a metal array. The synthesized CNTs form a CNT array by a regular arrangement of immobilized metal catalysts (FIG. 3 (d)).

As another method, CNT arrays were prepared by vertically growing CNTs on the nanopatterned substrates obtained through Examples 1 to 7 using the method shown in Korean Patent Publication No. 2000-0001260.

In addition to this method, as shown in FIG. 2, after exposing the amine group to the groove of the substrate, CNTs having a carboxyl group may be arranged on the substrate by amide bonds, and CNTs may be laminated by using a chemical having two amine groups as a linker. .

Example 9: Preparation of Bio Nanoarrays

In order to bind the biomaterial or the bioreceptor to the groove-shaped nanopattern obtained in Example 6, the aldehyde is bonded to the substrate and the amine group is attached to the end of the biomaterial or the bioreceptor. The receptor was attached.

Example 10 Preparation of CNT-Bio Nanoarrays

Attaching the biomaterial or the bioreceptor to the CNT array fabricated in Example 8 is performed by applying a charge of a polarity opposite to the net charge of the biomaterial or the bioreceptor to the CNT or binding (KR 2003-0014997A) Alternatively, it may be attached using a bonding aid. Preferred binding auxiliaries may be used chemicals with aldehydes, amines or imine groups attached to the carbon group ends.

As described above, according to the present invention, the micropattern of several nanometers and below can be easily manufactured through a few simple steps, and the orientation of the microstructure can be easily controlled to easily manufacture the structure of the thin film.

In addition, the nanopatterns formed on the substrates can form high density recording materials, templates for the production of CNTs and metal nanowires, biodevices such as protein chips, DNA chips, and biosensors, and the formation of new nanopatterns. It can be used as a porous electrode for a mask and a battery, and can be usefully used for developing a separation membrane material and an anti-reflection coating material.

Claims (24)

Method of manufacturing a carbon nanotube (CNT) array, characterized in that it comprises the following steps: (a) forming a thin film of organic supramolecular on the substrate to cause self-assembly; (b) self-assembling the organic supramolecules by annealing to form a cylindrical regular structure; (c) irradiating UV to a cylindrical structure formed by self-assembly of the organic supermolecules to decompose the central part where the carbon chains are collected to form a nanopattern of the organic supermolecules; And (d) arranging CNTs in the nanopattern of the organic supramolecular. The method of claim 1, wherein an interlayer thin film of metal, nonmetal or organic material is formed on the substrate before step (a). Method of manufacturing a CNT array comprising the following steps: (a) forming a thin film of organic supramolecular on the substrate to cause self-assembly; (b) self-assembling the organic supramolecules by annealing to form a cylindrical regular structure; (c) irradiating UV to a cylindrical structure formed by self-assembly of the organic supermolecules to decompose the central part where the carbon chains are collected to form a nanopattern of the organic supermolecules; (d) etching the substrate using the nanopattern of the organic supermolecule as a mask to form a nanopattern on the substrate; And (e) arranging CNTs in the nanopattern of the substrate. 4. The method of claim 3, wherein an interlayer thin film of metal, nonmetal or organic material is formed on the substrate prior to step (a). The method according to claim 1 or 3, wherein the organic supramolecules are disc-shaped or dendrimer wedge-shaped organic supramolecules. The method according to claim 5, wherein the organic supramolecular is a compound of [Formula 6] or [Formula 7]. [Formula 6] [Formula 7] The method of claim 1 or 3, wherein step (b) is slow cooling after raising to above the liquid crystal phase transition temperature. The method of claim 1, wherein step (d) comprises depositing a metal catalyst on the substrate of the nanopattern and then arranging the CNTs. The method of claim 8, wherein the catalyst is iron, cobalt or nickel. The method of claim 3, wherein step (e) comprises CNTs having a carboxyl group on the substrate exposed with the amine group on the substrate with an amide bond, and laminating the CNTs using a chemical having two amine groups as a linker. Way. A biomaterial or bioreceptor selected from the group consisting of nucleic acids, proteins, peptides, amino acids, enzyme substrates, ligands, amino acids, cofactors, carbohydrates, lipids, oligonucleotides and RNAs in the CNT array obtained by the method of claim 1 or 2. Method for producing a CNT-bio nanoarray characterized in that to attach. 12. The method of claim 11, wherein an electric field is applied to the CNTs to attach the biomaterial or bioreceptor. 13. The method of claim 12, wherein a charge of polarity opposite to the net charge of the biomaterial or bioreceptor is applied to the CNT. 12. The method of claim 11, wherein the binding aid is used to attach the CNT and the biomaterial or bioreceptor. 15. The method of claim 14, wherein the binding aid is a chemical having an aldehyde, amine or imine group attached to the carbon group end. A biomaterial or bioreceptor selected from the group consisting of nucleic acids, proteins, peptides, amino acids, enzyme substrates, ligands, amino acids, cofactors, carbohydrates, lipids, oligonucleotides and RNA in the CNT array obtained by the method of claim 3 or 4. Method for producing a CNT-bio nanoarray characterized in that to attach. 17. The method of claim 16, wherein an electric field is applied to the CNTs to bind the biomaterial or bioreceptor. 18. The method of claim 17, wherein a charge of a polarity opposite to the net charge of the biomaterial or bioreceptor is applied to the CNT. The method of claim 16, wherein the binding aid is used to bind the CNT and the biomaterial or bioreceptor. 20. The method of claim 19, wherein the binding aid is a chemical having an aldehyde, amine or imine group attached to the carbon group end. In the group consisting of nucleic acids, proteins, peptides, amino acids, enzyme substrates, ligands, amino acids, cofactors, carbohydrates, lipids, oligonucleotides and RNA obtained by the method of claim 11, arranged in a CNT array arranged in nanopatterns of organic supramolecules. CNT-bio nanoarray, characterized in that the selected biomaterial or bioreceptor is attached. A nucleic acid, protein, peptide, amino acid, enzyme substrate, ligand, amino acid, cofactor, carbohydrate, lipid, oligonucleotide and CNT-bio nanoarray, characterized in that attached to the biomaterial or bioreceptor selected from the group consisting of RNA. 22. A method for detecting a reaction between a biomaterial and a bioreceptor using the CNT-bio nanoarray of claim 21. A method for detecting a reaction between a biomaterial and a bioreceptor according to claim 22, wherein the CNT-bio nanoarray is used.