KR20070121125A - Process for patterning using self-assembly of terminal functional group - Google Patents

Abstract

A method for forming a pattern using self-alignment of a terminal functional group is provided to improve a contact angle of a pattern by using self-alignment caused by mutual repulsion of a hydrophobic functional group and a hydrophilic functional group. A first monolayer(110) made of a material having a functional group of a first polarity is formed on the upper surface of a substrate(100). A second monolayer(120) made of a material having a functional group of a second polarity opposite to the first polarity is formed between the first monolayers. A solution containing a device material distributed into a solvent having the functional group of the first or second polarity is coated on the upper surface of the substrate. A heat treatment is performed on the substrate coated with the device material to form a pattern on the substrate. The first polarity can be a phenyl group. The solvent can be a hydrophilic solvent.

Description

Process for Patterning Using Self-Assembly of Terminal Functional Group

1A to 1E illustrate a process of forming a pattern on a conventional substrate.

2A through 2F are steps illustrating a process of forming a fine pattern of metal wires on a substrate according to an exemplary embodiment of the present invention.

3A-3E schematically illustrate the manufacturing process of a stamp that can be used to form a monolayer film with hydrophobic functional groups on a substrate in accordance with a preferred embodiment of the present invention.

4A through 4F are steps showing a process of forming a fine pattern of metal wiring on a substrate according to another preferred embodiment of the present invention.

5A through 5F illustrate step by step of forming a fine pattern of an organic insulating layer on a substrate on which a metal electrode is formed, according to another exemplary embodiment of the present invention.

FIG. 6 is a SEM photograph of a substrate on which a first monolayer film is formed on a substrate in accordance with a preferred embodiment of the present invention. FIG.

<Description of the symbols for the main parts of the drawings>

100, 200, 300: substrate 110, 210, 310: the first monolayer film

120, 220, 320: second monolayer film 130, 230: dispersion solution

132, 232: Nanoparticle 150: Master

160: stamp 330: insulator composition

The present invention relates to a method of forming a pattern on a substrate, and more particularly, to a method of forming a pattern such as metal wiring on a substrate using self-array by interaction between end functional groups.

In flat panel display devices such as semiconductor devices and liquid crystal display devices, the pattern process is an important process that greatly affects the performance of the manufactured device. Accordingly, in recent years, research is being conducted to improve device performance. In particular, various attempts have been made to improve device performance by forming a fine metal pattern. The most commonly used pattern forming process up to now is a process using a photoresist (PR), which is a photosensitive material, and FIGS. 1A to 1E schematically illustrate a step for forming a pattern of a metal wiring using PR. The process chart shown.

First, as shown in FIG. 1A, the metal thin film layer 12 is deposited on the upper surface of the substrate 10 made of a semiconductor material such as silicon oxide or an insulating material such as glass, and then, for example, using a spin-coating method or the like. As shown in FIG. 1B, the photoresist layer 14, which is a photosensitive polymer, is formed on the upper surface of the metal thin film layer 12. Subsequently, as shown in FIG. 1C, the mask 16 is positioned on the upper surface of the photoresist layer 14 and irradiated with ultraviolet (UV) light. Generally, a photoresist may be classified into a positive type and a negative type. In this drawing, a negative type photoresist is used as an example.

When the UV light is irradiated, the photoresist of the UV irradiated region except for the region covered by the mask 16 changes its chemical structure. Accordingly, when the developer is irradiated, the photoresist layer 14 in the region not irradiated with ultraviolet rays is removed as shown in FIG. 1D, and a constant photoresist pattern 14a is formed only in the region irradiated with ultraviolet rays. When the etchant is applied in a state in which the metal thin film layer 12 is blocked by the photoresist pattern 14a formed only in the region irradiated with ultraviolet rays, the blocking by the photoresist pattern 14a as shown in FIG. 1E is performed. The remaining metal thin film layer 12 except for the region is removed. Thereafter, as shown in FIG. 1F, when the photoresist pattern 14a that serves as a barrier is peeled off by applying a stripper, only a predetermined metal pattern 12a remains on the substrate 10, thereby completing the metal wiring.

By the way, in the case where the metal wiring is to be formed using the existing process as described above, after the metal thin film is deposited, the process of forming the photoresist layer, the exposure process through UV irradiation, the developing process of removing the part subjected to UV irradiation, and the photosensitive light Since the process of etching the metal thin film with the polymer open and the process of peeling off the photoresist layer functioning as a barrier, the process is not only too complicated but also in the case of an electric element having a plurality of patterns, it is necessary to separately form each pattern. The manufacturing cost rises because the photoresist process must be performed, which is undesirable.

In order to solve the problem of the pattern process using a conventional photo-lithography technique, for example, Korean Patent Laid-Open Publication No. 2003-38401 discloses a method of forming a pattern on a display device having a large area through a printing method of transferring an ink layer. I'm proposing. However, as described in the specification of the above publication, there is a problem in that the ink pattern is easily peeled off because the adhesion between the ink and the layer to be processed is weak. To solve this problem, chemical treatment such as primer coating / plasma treatment / UV treatment and physical treatment are performed. There is a problem that a treatment process must be involved.

The present invention has been proposed to solve the above problems, and an object of the present invention is to provide a method for forming a complex fine pattern on a substrate through an economical and efficient method without a complicated process.

Another object of the present invention is to provide a method capable of forming extremely fine patterns on a substrate using nano-sized metal powders and self-aligning properties depending on the degree of affinity between terminal functional groups.

Other objects and advantages of the present invention will become more apparent from the accompanying drawings and the accompanying drawings.

The present invention is to solve the above problems, the present invention forms a molecular monolayer film having a hydrophobic functional group and a hydrophilic functional group at the end of the upper surface of the substrate, dispersed in a solvent that can be combined with the hydrophilic functional group on the upper surface By applying a solution containing the fine material, it is a method of forming a desired pattern only in the selected area on the substrate.

According to the present invention, there is provided a method of forming a pattern on a substrate, comprising: (a) forming a first monolayer film of a material having a functional group of a first polarity on an upper surface of the substrate; (b) forming a second monolayer film of material having functional groups of a second polarity opposite to the first polarity between the first monolayer films; (c) applying a solution containing device material dispersed with a solvent having a functional group of a first polarity or a functional group of a second polarity to the front of the substrate; and (d) heat treating the substrate to which the device material is applied to form a pattern on the substrate.

When the functional group of the first polarity is a hydrophobic functional group, the functional group of the second polarity is a hydrophilic functional group, and the functional group of the second polarity is a hydrophobic functional group when the functional group of the first polarity is a hydrophilic functional group. Preferred hydrophobic functional groups may be an alkyl group or an aromatic ring, and materials having such hydrophobic functional groups include silane-based materials substituted with alkyl groups or phenyl groups. Hydrophilic functional groups on the other hand include silane materials having such hydrophilic functional groups as alkoxy groups, preferably epoxy groups.

In addition, solvents that may be used in connection with the present invention include hydrophobic or hydrophilic solvents having a functional group capable of chemically reacting with a functional group formed in a region to be patterned, for example, an amine group or hydroxy at the terminal. Hydrophilic solvents having groups can be used. In this case, a surfactant may be used to minimize the repulsive force at the interface between the device material and the solvent. For example, when a hydrophilic solvent is used, a silane-based material substituted with an amine group may be used.

Device materials dispersed in a solution according to the present invention include nano-sized metal particles for forming metal lines or metal electrodes, organic molecules for forming an organic insulating film, or organic-inorganic hybrid molecules.

According to a preferred embodiment of the present invention, the solvent in which the device material is dispersed may be applied to the front surface of the substrate by using an inkjet printing nozzle, and after the solvent in which the device material is dispersed is self-arranged to a specific area of the substrate, If the heat treatment is performed in a temperature range of 100 ~ 150 ℃ can be obtained a variety of fine patterns.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the present invention.

2A to 2F are process diagrams showing step by step processes for forming a pattern on a substrate according to an exemplary embodiment of the present invention. First, as shown in FIG. 2A, a material having a first polarity capable of forming the first monolayer film 110 on the upper surface of the substrate 100 made of a hydrophilic material such as silicon oxide, glass, or plastic is formed in the protruding pattern. Apply the stamp 160 is attached.

The stamp 160 shown in FIG. 2A is preferably a 'soft mold' such as, for example, an elastic material such as poly dimethyl siloxane (PDMS), silicone rubber, polyurethane, polyurethane acrylate, polyimide, or the like. 3A to 3F illustrate a step-by-step process of manufacturing the stamp 160 and contacting the material having the hydrophobic functional group in the protruding pattern of the stamp 160.

First, as shown in FIG. 3A, a silicon nitride (SiN _x ) or silicon oxide (SiO ₂ ), which is an inorganic material, is deposited on a flat mold or base substrate 151, or a photoresist layer may be formed through phtolithography. By using the coating method to form a pattern 152 having a desired size and height in the form of metal or metal oxide is laminated to produce a master (master, 150). The base substrate 150 constituting the master 150 may be, for example, a material such as silicon or quartz. Subsequently, as shown in FIG. 3B, an elastic material layer 162 having an elastomer such as PDMS and polyurethane acrylate is preferably applied to the entire surface of the master 150 on which the pattern 152 is formed. The elastic layer 162 is placed at room temperature or at an appropriate temperature to allow curing. Next, when the cured elastic material layer 162 is removed from the master 150, the stamp 160 having the protruding pattern 164 corresponding to the pattern 152 formed on the master as shown in FIG. 3C. Is completed. Then, as shown in FIG. 3D, the stamp 160 having the protruding pattern 164 is replaced with a resin 170, for example, PDMS, in which a material 110 having a hydrophobic functional group such as an alkyl silane is impregnated at its end. When pressed with the resin 170 to be made, a material capable of forming the hydrophobic first monolayer film 110 is attached to the lower end of the protruding pattern 164 of the stamp 160 as shown in FIG. 3E.

Referring again to the pattern formation process according to the present invention, as described above, a stamp 160 having a material having a first polarity attached to the protruding pattern is applied to the substrate 100. Accordingly, as shown in FIG. 2B, the material of the first polarity is transferred to the selection area corresponding to the protruding pattern of the stamp 160 among the substrate areas, so that the material of the first polarity is a molecular self-aligned monolayer film (self). A first monolayer film 110, which constitutes an assembled monolayer (SAM), is formed. When the substrate 100 is made of silicon oxide, glass, or the like without any treatment, the substrate 100 has hydrophilicity, and thus, the material having the first polarity forming the first monolayer film 110 may have a polarity of the substrate. Use materials with polarity that differentiates them from Therefore, according to the present exemplary embodiment, the material having the first polarity capable of forming the first monolayer film 110 uses a material having hydrophobic terminal functional groups having no polarity. According to the present invention, the first monolayer film 110 formed of a specific region of the substrate 100 is preferably formed at a height of approximately 0.5 to 3 nm.

As described above, the terminal hydrophobic functional group capable of forming the first monolayer film 110 may be an alkyl group. As such, the material having the terminal functional group of the alkyl group is preferably a silane system having an alkyl group having 1 to 20 carbon atoms. It is a substance. As such a material capable of forming the first monolayer film 110 having a hydrophobic functional group, methyl dichlorosilane, methyl trichlorosilane, dimethyl chlorosilane, and dimethyl Dimethyl dichloro silane, chloromethyl methyl dichloro silane, propyl trichlorosilane, propyl methyl dichlorosilane, propyl methyl dichloro silane, trimethyl chloro silane, Trimetyhl fluoro silane, trimethyl bromo silane, tetramethyl silane, triethyl chloro silane, tetraethyl silane, propyltrichlorosilane propyl trichloro silane, tri-isoproyl chloro silane, octyl trichloro silane, dodecyl Substances, such as dodecyl trichloro silane and an octadecyl trichloro silane, are mentioned.

The SEM photograph of the substrate surface-treated by applying octadecyltrichlorosilane as a substance having a hydrophobic functional group to the substrate using a stamp according to the present embodiment is shown in FIG. 6. In the drawing, the light colored portion is the portion in which the self-aligned monolayer film of octadecyltrichlorosilane is formed, and the dark colored portion in the center is the upper surface of the substrate which is not surface treated. As shown, the self-aligned monolayer film was formed at a height of 2 nm, the line width of the substrate on which the metal electrode pattern was formed was about 8 nm, and the contact angle CA was excellently measured at 113 占 so that a fine pattern could be formed. Confirmed that it can.

Subsequently, the entire surface of the substrate 100 formed in the selected region of the first monolayer film 110 is immersed in a solution containing a material having terminal functional groups of a second polarity opposite to the first polarity. A material having a second polar functional group contained in the solution because there is no interaction between the first polar functional group formed at the end of the first monolayer film 110 and the second polar functional group of the material contained in the solution. Since the first monolayer film 110 is not formed, only the hydrophilic region of the substrate 100 having the hydroxyl group (-OH) formed on the surface thereof is self-aligned. Accordingly, as illustrated in FIG. 2B, a second monolayer film 120 having a molecular level in which a material having a terminal functional group having a second polarity is self-aligned is formed between regions in which the first monolayer film 110 is formed. Therefore, the substrate 100 is divided into a hydrophobic region in which the first monolayer film 110 is formed and a hydrophilic region in which the second monolayer film 120 is formed.

According to this embodiment, since the hydrophobic functional group is used as the terminal functional group of the first monolayer film 110, the terminal functional group of the second polarity uses a hydrophilic functional group. As a material for forming the second monolayer film having hydrophilic functional groups in the present embodiment, it is preferable to use a silane-based material in which two or more hydrophilic functional groups are formed in consideration of interaction with the substrate 100. Hydrophilic functional groups that can be used in connection with this embodiment are preferably alkoxy groups, more preferably epoxy groups with rings formed at the ends.

In connection with the present embodiment, a material having a hydrophilic functional group capable of forming the second monolayer film 120 includes trimethoxy silane, triethoxy silane, and chloromethyltrimethoxysilane. trimethoxy silane, methyl trimethoxy silane, chloromethyl triethoxy silane, methyl triethoxy silane, dichloromethyl triethoxy silane, Chloromethyl methyl dimethoxy silane, chloromethyl methyl diethoxy silane, dichoromethyl triethoxy silane, methyl tripropoxy silane, methyl Tributoxysilane (methyl tributoxy silane), methyl dimethoxy silane (methyl dimethoxy silane), methyl diethoxy silane (dimethyl diethoxy silane), dimethyl dimethoxy silane (dimehty) dimethoxy silane, dimethyl diethoxy silane, tetramethoxy silane, tetraethoxy silane, propyl trimethoxy silane, tetrapropoxy silane silane, tetraisopropoxy silane, propyl trimethoxysilane, chloropropyl trimethoxy silane, propyl triethoxy silane, chloropropyl tree Ethoxysilane (chloropropyl triethoxy silane), chloropropyl methyl dimethoxy silane, chloropropyl methyl diethoxy silane, butyl trimethoxy silane, butyl triethoxy Butyl triethoxy silane, tetrabutoxy silane, tetrakis (buxoxy ethoxy) silane, octyl tree Ethoxysilane (octyl triethoxy silane), octyl methyl diethoxy silane, dodecyl trimethoxy silane, dodecyl methyl dimethoxy silane, octadecyl trimeth Octadecyl trimethoxy silane, octadecyl methyl dimethoxy silane, octadecyl triethoxy silane, octadecyl methyl diethoxy silane, cyclohexyl trie Glycidoxypropyltriethoxysilane, such as cyclohexyl triethoxy silane, 3-glycidoxy propyl trimethoxysilane, and glycidoxypropyl triethoxy silane ), Glycidoxy propyl methyl diethoxy silane, glycidoxy propyl methyl diethoxy silane, and the like. All.

Subsequently, as shown in FIG. 2D, a device material dispersed by, for example, an organic solvent is contained on the entire surface of the substrate 100 on which a separate self-aligned monolayer film is formed so as to be divided into a hydrophilic region and a sour region. Apply the solution. As a method of applying the solution in which the element material is dispersed in the context of the present invention, a method of applying the solution to the entire surface of the substrate through a nozzle may be used, for example, by ink-jetting.

On the other hand, the device material contained in the solution applied to the upper surface of the substrate 100 on which the self-aligned monolayer film is formed in accordance with the present invention, such as nano metal particles, nano wires, organic insulating films, etc. Organic materials and inorganic materials which can be used as a raw material of an organic thin film and an organic-inorganic hybrid thin film are mentioned. In the present exemplary embodiment, nanoparticles capable of forming metal patterns of electrodes such as gate electrodes, source / drain electrodes, data lines, and pixel electrodes of TFTs may include hydrophilic functional groups such as amine groups (NH _2). The case where it is disperse | distributed to the organic solvent which has) is demonstrated as an example.

Nanoparticles dispersed by an organic solvent having an amine group have a specific shape depending on the interaction with the organic solvent, and in particular, as shown in the drawing, there is little affinity with the nanoparticles in the organic solvent surrounding the nanoparticles. The amine functional group has a micelle form that protrudes out of the nanoparticles so as not to contact the nanoparticles. In order to induce the dispersion of such nanoparticles, a dispersant may be included in the solution.

Metal element materials that can be formed into nanoparticles according to this embodiment include conventional metal materials such as gold, silver, aluminum, nickel, tungsten, molybdenum, aluminum-neodymium mixtures, ITO, and the like. On the other hand, as an organic solvent having a hydrophilic functional group at the terminal surrounding the nanoparticles, isopropyl alcohol, butyl alcohol, 2-methoxy ethanol, 2-butoxyethanol, 1-butanol having a hydroxyl group at the terminal , Alcohol solvents such as 1-pentanol, isobutanol, ethylhexanol, 1-octanol, cyclohexanol, octanol, decanol, dodecanol, or pyrimidine, pyrrolidine, alkyl having 1 to 20 carbon atoms Amine solvents such as amines, and acetate solvents such as ethyl acetate and butyl acetate.

On the other hand, in order to have a micelle form in which the hydrophilic functional groups, such as amine functional groups, at the end of the organic solvent surrounding the nanoparticles are directed to the outside, it is necessary to induce a form that reduces the surface tension between the nanoparticles and the amine groups. Surfactants may be included in the organic solvent. As the surfactant which can be used according to the present invention, an ionic surfactant or a nonionic surfactant may be used. For example, when using an organic solvent having a hydrophilic functional group such as an amine group or a hydroxy group, such a hydrophilic functional group may be used. Particular preference is given to using cationic surfactants which do not function.

Surfactants that can be used according to the present invention include nonionic surfactants such as alkoxy fatty acids, alkoxy alcohols, alkoxy polysiloxanes. On the other hand, as the ionic surfactant, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane (N- (6-aminohexyl) -3-aminopropyl trimethoxy silane) substituted with an alkylamine group, aminohexylamino Methyltriethoxysilane (aminohexyl aminomethyl triethoxy silane), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-aminoethyl) -3-aminopropyl trimethoxy silane), N- (2- Aminoethyl) -3-aminopropyltriethoxysilane (N- (2-aminoethyl) -3-aminopropyl triethoxy silane), N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (N-β- (aminoetyhl) -γ-aminopropyl methyl dimethoxy silane), N- [N '-(2-aminoethyl) aminoethyl] -3-aminopropyltrimethoxysilane (N- [N']-(2-aminoethyl) aminoethyl ] -3-aminopropyl trimethoxy silane), N- [N '-(2-aminoethyl) aminoethyl] -3-aminopropyltriethoxysilane (N- [N']-(2-aminoethyl) aminoethyl] -3 -aminopropyl triethoxy silane), N- [N '-(2-aminoethyl) aminoethyl]- 3-aminopropylmethyldimethoxysilane (N- [N ']-(2-aminoethyl) aminoethyl] -3-aminopropyl methyl dimethoxy silane), N- [N'-(2-aminoethyl) aminoethyl] -3- Aminopropyl methyl diethoxysilane (N- [N ']-(2-aminoethyl) aminoethyl] -3-aminopropyl methyl dimethoxy silane), 3- (N-cyclohexylamino) propyltrimethoxysilane (3- (N- silane-based materials such as cyclohexyl amino) propyl trimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, and the like. It may be used as a solvent itself or may also function as a dispersant.

As described above, when nanoparticles dispersed by an organic solvent having an amine group as a hydrophilic functional group are applied to the upper surface of the substrate, the amine group having the hydrophilic functional group is formed on the hydrophilic region of the substrate 100. Hydrophilic functional groups formed at the ends of the epoxy group is arranged friendly, as shown in Figure 2e reacts with the carbon of the epoxy group to form a chemical bond with the carbon while breaking the ring of the epoxy group. Accordingly, the nanoparticles 132 contained in the solvent 130 of the hydrophilic functional group are also concentrated to the upper end of the second monolayer film 120, which is a hydrophilic region, to form the dispersion pattern 131.

As such, when the substrate in which the dispersion pattern 131 is formed only in the hydrophilic region is subjected to a sintering process of heat treatment at a predetermined temperature, the substrate is deposited in the region where the nanoparticles formed in the dispersion pattern 131 are attached. The liquid organic solvent, the first monolayer film 110 and the second monolayer film 120 are almost removed. As a result, as shown in FIG. 2F, the metal pattern 134 is formed only at a portion where the second monolayer film 120, which has formed the hydrophilic region of the substrate 100, is formed, thereby completing the metal wiring. In this step, the heat treatment may be performed depending on the type of organic solvent and nanoparticles used, but the temperature of the heat treatment may vary. Preferably, the heat treatment is performed at a temperature in the range of 100 to 150 ° C.

According to the above-described embodiment, a first monolayer film 110 having hydrophobic functional groups is first formed as a selected region of the hydrophilic substrate, and then a hydrophilic functional group having a polarity opposite to that of the first monolayer film 110 is formed. The second monolayer film 120 is formed. However, for example, after coating or applying a hydrophobic material to the entire surface of the substrate, the first process is performed to convert the polarity of the substrate 100 to hydrophobicity, and then the first monolayer film 110 having a hydrophilic functional group is formed. It is also possible to form the second monolayer film 120 having a hydrophilic functional group.

As a result, according to the present exemplary embodiment, when the terminal functional group forming the first monolayer film 110 and the terminal functional group forming the second monolayer film 120 have polarities opposite to each other, terminal functional groups having a specific polarity in a desired region. After forming a self-aligned monolayer film (SAM) having a self-aligned monolayer film having a terminal functional group of the opposite polarity to the remaining region, and preferably by applying nanoparticles dispersed in a hydrophilic organic solvent to the metal electrode only in the hydrophilic region A pattern can be formed.

Moreover, according to the above-described embodiment, the organic solvent is arranged only in a monolayer film having hydrophilic functional groups by using an organic solvent in which the hydrophilic functional groups are formed. However, the nanoparticles are hydrophobic. When dispersed in an organic solvent, the organic solvent applied to the substrate may be configured to self-align on top of the monolayer film having hydrophobic functional groups and to form a metal pattern only in this portion. Hydrophobic organic solvents that can be used in such cases include aliphatic hydrocarbon solvents such as hexane; Aromatic solvents such as toluene, xylene, nitrobenzene; Ketone solvents such as methyl ethyl ketone and acetone; Ether solvents such as cyclohexanone, tetrahydrofuran, ethylene glycol monoethyl ether and diethylene glycol monobutyl ether; Or silicone solvents such as alkyl silanes.

Meanwhile, according to the above-described embodiment, a process of immersing a substrate on which a monolayer film having a first polarity is formed in a solution containing a material having a second polarity opposite to the first polarity to form a self-aligned monolayer film having different polarities A second polarized monolayer film was formed between the monolayer films of the first polarity through. However, after forming the monolayer monolayer of the first polarity, the monofunctional layer of the second polarity can be formed by chemically converting the terminal functional groups of the monolayer film in the selected region to change to have functional groups having different polarities. According to the present exemplary embodiment, the process of forming the metal pattern on the upper surface of the substrate is shown in stages, and detailed descriptions thereof will be omitted.

First, as shown in FIG. 4A, the first monolayer film 210 having an aromatic ring, which is a hydrophobic functional group, is formed on the front surface of the substrate 200. In the present exemplary embodiment, since the first monolayer film 210 is formed on the entire surface of the substrate 200, the substrate 200 is immersed in a solution containing the first polar material formed at the end of the hydrophobic functional group or the inkjet printing method. For example, a method of applying the first polar material to the entire surface of the substrate 200 by spraying the solution onto the upper surface of the substrate through a nozzle may be used.

As a first polar material constituting the first monolayer film 210 according to the present embodiment, as described below, a material having a functional group capable of converting terminal functional groups into polarity by UV may be, for example, a material having an aromatic ring. Include. A material capable of forming the first monolayer film 210 according to the present embodiment includes a phenyl-based silane material, preferably phenyl trichlorosilane, phenylaminomethyltrichlorosilane methyl trichloro silane) and tert-butyl diphenyl chlorosilane.

Subsequently, as shown in FIG. 4B, when the mask 250 having a predetermined pattern is formed on the upper surface of the substrate 200 on which the first monolayer film 210 is formed and irradiated with UV, the mask 250 is covered by the mask 250. While the terminal hydrophobic functional group of the first monolayer film 210 formed in the region does not change at all, the aromatic ring, which is the terminal hydrophobic functional group of the first monolayer film 210 formed in the UV-irradiated region, is chemically modified and thus is shown in FIG. 4C. As shown in FIG. 2, the second monolayer film 220 is formed by being substituted with a hydrophilic hydroxyl group. As a result, a hydrophilic region is formed in the region to which UV is irradiated by UV irradiation, and a hydrophobic region remains in the unirradiated region.

Subsequently, a hydrophilic amine group is formed at a terminal thereof so that the nanoparticle 232 serving as a raw material of the metal thin film can be dispersed in the substrate 200 which is divided into the first monolayer film 210 and the second monolayer film 220. When immersed in the organic solvent 230, the organic solvent 230 is initially applied to the entire surface of the substrate 220, as shown in Figure 4d. However, since hydrophilic amine groups arranged to protrude outward from the organic solvent 230 form a chemical affinity such as a hydrogen bond and a hydroxyl group which is a hydrophilic functional group of the second monolayer film 220, as shown in FIG. 4E. The organic solvent is concentrated only on the second monolayer film 220 to form the dispersion pattern 231.

Subsequently, when the heat treatment process is performed on the substrate 200 at a predetermined temperature, as shown in FIG. 4F, the metal pattern 234 may be formed only in the hydrophilic region where the second monolayer film was formed, thereby completing the metal electrode. have.

Meanwhile, in the above-described embodiment, an example in which an organic solvent in which nano-sized metal particles are dispersed is used to form a metal electrode is described as an example. However, an insulator composition including an organic polymer, an organic low molecule, or the like may be appropriately used instead of the nano particles. By dispersing in a solvent, an organic thin film such as an organic insulating film, an organic-inorganic hybrid thin film, an organic semiconductor layer, or the like may be formed. FIGS. 5A to 5E illustrate steps of forming an organic insulating film according to a preferred embodiment of the present invention. It is a process chart.

As shown in FIG. 5A, a stamp 160 to which a material having a hydrophobic functional group at its end is attached to the protruding pattern as a functional group having a first polarity is applied to the upper surface of the substrate 300 on which the metal electrode 302 is formed. As a result, as shown in FIG. 5B, a first monolayer film 310 having a hydrophobic functional group is formed on the upper surface of the metal electrode 302 in contact with the protruding pattern of the stamp 160. The remaining portion forms a hydrophilic region as the glass and silicon oxide portion.

Subsequently, when the entire surface of the substrate 300 on which the metal electrode 302 and the first monolayer film 310 is formed is immersed in a solution containing a material having a hydrophilic functional group at the end thereof, the first monolayer film 310 is terminated. There is a kind of repulsion between the hydrophobic functional groups formed and the hydrophilic functional groups contained in the solution. Accordingly, as shown in FIG. 5C, the second monolayer film 320 having the hydrophilic functional group at the end of the upper surface of the substrate, that is, the left and right sides of the metal electrode 302, according to the self-arrangement between the molecules is magnetic. It is formed by an array. According to the present exemplary embodiment, the negative functional group material constituting the first monolayer film 310 and the hydrophilic functional material constituting the second monolayer film 320 are as described above.

Next, an element material dispersed in an organic solvent on the entire surface of the substrate 300 divided into a hydrophobic region in which the metal electrode 302 and the first monolayer film 310 are formed, and a hydrophilic region in which the second monolayer film 320 is formed. When the insulator composition 330 is applied, initially, as shown in FIG. 5D, the insulator composition 330 in which the device material 332 is dispersed is disposed on the front surface of the substrate 300 including both the hydrophobic region and the hydrophilic region. Is applied. The insulator composition according to the present embodiment includes a general organic monomer and / or an organic polymer and an organic solvent for dissolving or dispersing them, and, when used as an organic-inorganic hybrid device, further includes a hybrid material such as an organic-inorganic metal hybrid material. Can be.

At this time, as the organic polymer that can be added to the organic insulator composition according to the present embodiment, polythiophene, polyaniline, polyacetylene, polypyrrole, polyphenylenevinylene, PEDOT, polycarbonate, polyvinyl alcohol, polymethyl methacrylate Polymer organic compounds such as, but not limited to, polymethacrylamide, PEDOT / PSS mixtures.

In addition, organic monomers included in the composition for organic insulation include methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, ethylene glycol dimethacrylate. (ethylene glycol dimethacrylate), ethylene glycol diacrylate, n-butyl methacrylate, n-butyl acrylate, n-butyl acrylate, stearyl methacrylate ), Stearyl acrylate, pentaerythritol triacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, vinyl acetate, etc. Of course, it includes organic active materials such as melocyanine, phthalocyanine, ferricene, pentacene, C60, thiophene oligomer.

On the other hand, the organic-inorganic metal hybrid material obtained by reacting copper phthalocyanine or a silane type compound with an organometallic compound as a hybrid material is included. Meanwhile, a dispersant may be included to induce dispersion of organic molecules and organic-inorganic hybrid materials.

In particular, a solvent having an appropriate functional group can be used to disperse the organic molecules or inorganic molecules used in forming the organic insulating film or the organic-inorganic hybrid thin film. Solvents that can be used in connection with this embodiment include substituted or unsubstituted hydrocarbons such as hexane, 1,2-dichloroethane, 1,2,3-trichloropropane; Aromatic solvents such as toluene, xylene, 3-nitro-trifluorobenzene, methylnaphthalene, methoxynaphthalene, dichlorobenzene, dichlorotoluene, chloronaphthalene, diphenylethane and quinoline; Ketone solvents such as methyl ethyl ketone and acetone; A polar solvent including an ether solvent such as cyclohexanone, tetrahydrofuran, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, isopropyl alcohol, butyl alcohol, 2-methoxyethanol, Alcohol solvents such as 2-butoxyethanol, 1-butanol, 1-pentanol, isobutanol, ethylhexanol, 1-octanol, cyclohexanol, octanol, decanol, and dodecanol; Or amine solvents such as N-menylpyrrolidone, pyrimidine, pyrrolidine, alkylamine having 1 to 20 carbon atoms, and acetate solvents such as ethyl acetate and butyl acetate; Hydrophilic solvents such as dimethyl formamide, dikenylsulfoxide may be included.

When the organic compound or hybrid compound constituting the insulator composition described above is used as the device material, the material is self-arranged to the hydrophobic monolayer film or is friendly to the hydrophilic monolayer film depending on the polarity of the organic solvent in which the device material is dispersed. Although self-aligned, in this embodiment, an organic-inorganic hybrid material 332 dispersed by, for example, a hydrophilic organic solvent will be described as an example.

When the insulator composition 330 is made of a hydrophilic organic solvent, the organic-inorganic hybrid material 332 forming the insulator composition is dispersed by the hydrophilic organic solvent. Therefore, as described above, the organic-inorganic hybrid material 332 and the hydrophilic organic solvent form a structure capable of reducing the surface tension. Preferably, when a suitable surfactant is mixed in the solvent, the hydrophilic organic solvent and the organic-inorganic hybrid material are used. In the vicinity of 332, the hydrophilic functional group of the organic solvent forms an micelle structure in which the hydrophilic functional groups protrude outward. Surfactants as described above may be used to induce micelle structures between the hydrophilic functional groups of such organic solvents and organic-inorganic hybrid materials.

On the other hand, when an organic-inorganic hybrid material is dispersed in an organic solvent having a hydrophobic functional group, it is preferable to use a nonionic surfactant. As well as the nonionic surfactant described above, an alkoxylated polysiloxane or an alkoxy group As the substituted silane-based material, a silane-based material having the terminal functional group of the alkyl group, alkoxy group or epoxy group described above can be used.

Accordingly, the hydrophilic functional group of the organic solvent acts in a friendly manner with the hydrophilic functional group formed at the end of the second monolayer film 320 in the hydrophilic region, so that the insulator composition is only arranged at the upper end of the hydrophilic region as shown in FIG. 4E. do. Accordingly, the hybrid material 332 contained in the insulator composition having the hydrophilic solvent is also formed only at the upper end of the second monolayer film 320 which is the hydrophilic region to form the dispersion pattern 331.

Subsequently, when the substrate on which the dispersion pattern 331 is formed is heat-treated at a predetermined temperature, an organic-inorganic hybrid material in the dispersion pattern 331 is deposited and a liquid organic solvent is removed. Accordingly, as shown in FIG. 5F, the organic insulating layer 334 is completed only on the hydrophilic region of the substrate 300, that is, the left and right sides of the metal electrode 302.

In the present embodiment, the first insulating film having a hydrophobic functional group and the second monolayer film having a hydrophilic functional group are successively formed, and then an organic insulating film is formed by applying a hybrid material dispersed in a hydrophilic organic solvent. However, in the case where the substrate is subjected to pretreatment and its polarity is changed, first, a first monolayer film having hydrophilic functional groups is formed on the upper part of the metal electrode, and then a second monolayer film having hydrophobic functional groups is formed in the left and right regions of the metal electrode. It may also be possible to apply a hybrid material dispersed in a hydrophobic organic solvent to form an organic insulating film before and after the metal electrode.

In the above, a preferred embodiment of the present invention has been described, but this is merely to illustrate the present invention, and the present invention is not limited thereto. Rather, it will be apparent to those skilled in the art that various modifications and variations can be easily made based on the embodiments described above. However, it will be apparent from the appended claims that such various modifications and changes fall within the scope of the present invention without departing from the spirit of the present invention.

In the present invention, a material having polarities opposite to each other at the end is laminated by a self-arrangement in a selected region of the substrate, and then the hydrophilic or hydrophobic end formed at the end of the organic solvent in which the nano metal particles, the organic polymer, and the hybrid material are dispersed. The pattern was formed through a method of dispersing an organic solvent in accordance with the affinity between the functional group and the self-aligned material in selected regions of the substrate.

Therefore, the process is greatly simplified as compared with the process or printing process using a conventional photo-lithography method was able to reduce the manufacturing cost and improve the efficiency of the process.

In addition, since the self-alignment by mutual repulsion of the hydrophilic functional group and the hydrophobic functional group is used, the contact angle of the formed pattern is improved, and various fine patterns can be precisely formed on the upper surface of the substrate.

Therefore, the technique according to the present invention is expected to be applicable to, for example, metal electrodes using nanoparticles, organic thin film formation, organic insulating film formation using organic and inorganic hybrid materials, and nanowires.

Claims (22)

As a method of forming a pattern on a substrate, (a) forming a first monolayer film of a material having a functional group of a first polarity on an upper surface of the substrate; (b) forming a second monolayer film of material having functional groups of a second polarity opposite to the first polarity between the first monolayer films; (c) applying a solution containing device material dispersed with a solvent having a functional group of a first polarity or a functional group of a second polarity to the front of the substrate; (d) heat treating the substrate to which the device material is applied to form a pattern on the substrate. The method of claim 1, Wherein the functional group of the first polarity is a hydrophobic functional group and the functional group of the second polarity is a hydrophilic functional group. The method of claim 1, Wherein the functional group of the first polarity is a hydrophilic functional group and the functional group of the second polarity is a hydrophobic functional group. The method according to claim 2 or 3, Wherein said hydrophobic functional group is an alkyl group. The method according to any one of claims 1 to 3, In the step (a), the first monolayer film is formed on the upper surface of the part of the substrate, and the step (b) is performed by immersing the substrate in a solution containing the material having the second polarity. How to form a pattern on. The method of claim 5, The first monolayer film is methyl dichloro silane (methyl dichloro silane), methyl trichloro silane (methyl trichloro silane), dimethyl chloro silane (dimethyl chloro silane), dimethyl dichloro silane (dimethyl dichloro silane), chloromethyl methyl dichlorosilane (chloromethyl methyl dichloro silane, propyl trichloro silane, propyl methyl dichloro silane, propyl methyl dichloro silane, trimethyl chloro silane, trimetyhl fluro silane, trimethyl bromosilane trimethyl bromo silane, tetramethyl silane, triethyl chloro silane, tetraethyl silane, propyl trichlorosilane, propyl trichlorosilane, tri-isoproyl chloro silane, octyl trichloro silane, dodecyl trichloro silane, octadecyl trichloro A method for forming a pattern on a substrate, characterized in that it is formed from a material selected from the group consisting of octadecyl trichloro silane. The method according to claim 2 or 3, And said hydrophilic functional group is an alkoxy group. The method of claim 7, wherein The second monolayer film is trimethoxy silane (trimethoxy silane), triethoxy silane (triethoxy silane), chloromethyl trimethoxy silane (chloromethyl trimethoxy silane), methyl trimethoxy silane (methyl trimethoxy silane), chloromethyl tri Chloromethyl triethoxy silane, methyl triethoxy silane, dichloromethyl triethoxy silane, chloromethyl methyl dimethoxy silane, chloromethylmethyldiethoxysilane (chloromethyl methyl diethoxy silane), dichloromethyl triethoxy silane (dichoromethyl triethoxy silane), methyl tripropoxy silane (methyl tripropoxy silane), methyl tributoxy silane, methyl dimethoxy silane , Methyl diethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, tetramethoxy Tetramethoxy silane, tetraethoxy silane, propyl trimethoxy silane, tetrapropoxy silane, tetraisopropoxy silane, tetraisopropoxy silane, propyltrimethoxysilane (propyl trimethoxy silane), chloropropyl trimethoxy silane, propyl triethoxy silane, chloropropyl triethoxy silane, chloropropylmethyldimethoxysilane dimethoxy silane, chloropropyl methyl diethoxy silane, butyl trimethoxy silane, butyl triethoxy silane, tetrabutoxy silane, tetrakis (Butoxyethoxy) silane (tetrkis (buxoxy ethoxy) silane), octyl triethoxy silane (octyl triethoxy silane), octyl methyl diethox y silane, dodecyl trimethoxy silane, dodecyl methyl dimethoxy silane, octadecyl trimethoxy silane, octadecyl methyl methoxy silane dimethoxy silane, octadecyl triethoxy silane, octadecyl methyl diethoxy silane, cyclohexyl triethoxy silane, 3-glycidoxypropyltrimethoxy Glycidoxy propyl triethoxysilane, such as 3-glycidoxy propyl trimethoxy silane, Glycidoxy propyl triethoxy silane, Glycidoxy propyl methyl diethoxy silane And a substrate formed from a material selected from the group consisting of glycidoxy propyl methyl diethoxy silane How to form a pattern on the top. The method of claim 1, In the step (a), the first monolayer film is formed on the upper surface of the substrate, and the step (b) is performed by replacing the functional groups of the first polarity with the functional groups of the second polarity by reacting with UV. How to form a pattern. The method according to any one of claims 1 to 9, Wherein said functional group of said first polarity is a phenyl group. The method of claim 10, The first monolayer film is selected from the group consisting of phenyl trichloro silane, phenyl amino methyl trichlorosilane, and tert-butyl diphenyl chloro silane. A pattern for forming a pattern on a substrate, wherein the pattern is formed from a material to be formed. The method of claim 1, And said solvent is a hydrophilic solvent. The method according to any one of claims 1 to 12, The solvent is a method of forming a pattern on a substrate, characterized in that the terminal has an amine group or a hydroxyl group. The method of claim 1, The method of forming a pattern on a substrate, characterized in that in the step (c) the surfactant is contained in the solution. The method of claim 14, The surfactant is N- (6-aminohexyl) -3-aminopropyltrimethoxysilane (N- (6-aminohexyl) -3-aminopropyl trimethoxy silane), aminohexyl aminomethyl triethoxy silane ), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-aminoethyl) -3-aminopropyl trimethoxy silane), N- (2-aminoethyl) -3-aminopropyltrie N- (2-aminoethyl) -3-aminopropyl triethoxy silane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane (N-β- (aminoetyhl) -γ-aminopropyl methyl dimethoxy silane ), N- [N '-(2-aminoethyl) aminoethyl] -3-aminopropyltrimethoxysilane (N- [N']-(2-aminoethyl) aminoethyl] -3-aminopropyl trimethoxy silane), N -[N '-(2-aminoethyl) aminoethyl] -3-aminopropyltriethoxysilane (N- [N']-(2-aminoethyl) aminoethyl] -3-aminopropyl triethoxy silane), N- [N '-(2-aminoethyl) aminoethyl] -3-aminopropylmethyldimethoxysilane (N- [N']-( 2-aminoethyl) aminoethyl] -3-aminopropyl methyl dimethoxy silane), N- [N '-(2-aminoethyl) aminoethyl] -3-aminopropyl methyl diethoxysilane (N- [N']-(2- aminoethyl) aminoethyl] -3-aminopropyl methyl dimethoxy silane), 3- (N-cyclohexyl amino) propyl trimethoxy silane, aminopropyl trimethoxysilane silane) and aminopropyl triethoxy silane. A method for forming a pattern on a substrate, wherein the material is selected from the group consisting of: silane; The method of claim 1, And the device material is a nano-sized metal particle, organic molecule, or organic-inorganic hybrid molecule. The method according to any one of claims 1 to 16, And the device material is a material selected from gold, silver, aluminum, nickel, tungsten, molybdenum, aluminum-neodymium mixture, ITO. The method of claim 1, Wherein the solution is an insulator composition. The method of claim 1, Step (d) is a method of forming a pattern on a substrate, characterized in that carried out at a temperature range of 100 ~ 150 ℃. The method of claim 1, The method of forming a pattern on a substrate, characterized in that step (a) is performed using a stamp. The method of claim 20, Wherein said stamp is made from PDMS, polyurethane acrylate. The method of claim 1, The method of forming a pattern on a substrate, characterized in that step (c) is performed using an inkjet printing method.

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