KR20060011709A - The conductive and transparent substrate with thin layers of the high molecular compound polymers by self-assembly and the preparing method of it - Google Patents

Abstract

The present invention relates to a conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer and a method of manufacturing the same. More specifically, the surface of the conductive transparent substrate is formed by self-assembly of a polymer polymer polymerized with a monomer having an acidic or basic functional group. By forming a thin film on the substrate and forming an organic polymer thin film having electromagnetic or photochemically important and acidic or basic functional groups on the thin film, the surface can be effectively modified in a short time to suit the purpose of using the conductive transparent substrate. Based on the improved bonding between the conductive transparent substrate and the polymer thin film, the thin film is prevented from peeling off even under strong acidic and basic conditions, so that the thin film transistor liquid crystal display (TFT LCD), plasma display panel (PDP), EL and biochip ( including biochip) The present invention relates to a conductive transparent substrate having a thin film formed by self-assembly of a polymer, and a method of manufacturing the same, which can be used in various fields.

Polymers, conductive transparent substrates, self-assembled thin films, acid-base reactions

Description

The conductive and transparent substrate with thin layers of the high molecular compound polymers by self-assembly and the preparing method of it}             

1 is a graph quantifying the amount of imine groups per unit surface area with time deposited in a 2% PEI aqueous solution,

2 is a graph showing the quantitative amount of phosphomolybdic acid present on the surface of ITO, ITO / PEI and ITO / PEI / PAA / PEI by cyclic voltammetry;

3 is a graph quantifying the amount of phosphomolybdic acid per unit surface area according to the concentration of PEI solution,

4 is a scanning electron microscope (SEM) photograph of a cross section of an ITO / PEI / (PAA / PEI) ₁₀ self-assembled thin film, and it can be seen that the thickness of one polymer layer is 3.8 nm.

5 shows PEI / PEDOT (SA), PEI / PAA / PEI / PEDOT (SA), PEI / (PAA / PEI) ₂ / PEDOT (SA), PEI / (PAA / PEI) ₃ / PEDOT formed on the surface of ITO. (SA) and PEI / (PAA / PEI) ₄ / PEDOT (SA) is a graph showing the electric field luminous efficiency,

FIG. 6 shows the formation of a multilayer structure of PEI and PAA on the surface of ITO, followed by spin coating of PEDOT, a conductive polymer, spin coating a polyalkylfluorene emitting layer thereon, and a BaF ₂ / Ca / Al metal layer as an electrode. It is a graph showing the electric field luminescence after vacuum deposition,

7 is a graph showing diode characteristics of an ITO surface multilayer structure, where a is ITO, b is ITO / PEI / PAA, c is ITO / (PEI / PAA) ₂ , and d is ITO / (PEI / PAA) ₃ . Mean,

8 and 9 show SEM photographs and XRD spectra of Cd (OH) ₂ nanostructures formed on ITO surfaces;

FIG. 10 is a SEM photograph of PEI and PAA deposited at about 600 nm in ITO.

11 is a view showing the surface of the conductive transparent electrode by AFM, the rough surface of the ITO is remarkably flattened after the polymer layer is laminated,

FIG. 12 is a diagram illustrating the appearance of DNA spots with a dedicated laser scanner after coating the same DNA on the surface modified by the existing patent and the surface modified by the present invention, and then applying a dye to bind the DNA.

The present invention relates to a conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer and a method of manufacturing the same. More specifically, the surface of the conductive transparent substrate is formed by self-assembly of a polymer polymer polymerized with a monomer having an acidic or basic functional group. By forming a thin film on the substrate and forming an organic polymer thin film having electromagnetic or photochemically important and acidic or basic functional groups on the thin film, the surface can be effectively modified in a short time to suit the purpose of using the conductive transparent substrate. Based on the improved bonding between the conductive transparent substrate and the polymer thin film, the thin film is prevented from peeling off even under strong acidic and basic conditions, so that the thin film transistor liquid crystal display (TFT LCD), plasma display panel (PDP), EL and biochip ( including biochip) The present invention relates to a conductive transparent substrate having a thin film formed by self-assembly of a polymer, and a method of manufacturing the same, which can be used in various fields.

The conductive transparent substrate is manufactured by using a material having a property of transmitting electricity well while allowing light such as indium tin oxide (ITO) to pass through well. The conductive transparent substrate is used as a material of the transparent electrode widely used in the next generation display. Transparent electrodes can be used in display devices that adjust the display state by applying voltage across two glass plates containing liquid crystal. Thin-film transistor liquid crystal display (TFT LCD), plasma display panel (PDP), EL (Electroluminescence), FED ( Field Emission Display). Transparent electrodes are also used in optoelectronics, which use a flow of light and electrons simultaneously.

In order to use the conductive transparent substrate as a flat panel display device or a photochemical reaction electrode, a task of changing physical properties of the electrode surface must be preceded. The movement of electrons on the surface of the transparent electrode is greatly influenced by the type, thickness and interfacial phenomenon between the materials applied to the surface. In addition, the physical and chemical properties of the substrate surface can be changed by treating the photochemical material or active material on the conductive oxide surface.

2. Description of the Related Art A research on a conductive transparent substrate having a thin film used in various fields, including a transparent electrode, and a method of modifying a substrate surface have been made.

The method of modifying the substrate surface was initially very limited. Most of the modification methods were at the level of simple surface cleaning and were limited to thick film formation by methods such as spin coating, sputtering, rather than forming molecular layers. The method of coating the film on the surface was not suitable for use as a transparent electrode because the density of the fine pores rapidly increased when the thickness of the film became 0.1 μm or less.

In addition, a Langmuir-Blodgett (LB) technique for forming a thin film of molecular units has also been proposed, which transfers an organic material to the substrate by moving the substrate in a direction perpendicular to the water while compressing the organic material on the water surface to maintain a constant surface pressure. to be. This method overcomes the disadvantages of the conventional spin coating by making a thin film having a small pore density even in the case of a thin film. However, it is possible to control the thickness of the film on a molecular layer basis, but the formation of the film depends on physical adsorption. The adhesion, physical and chemical properties of the film were not satisfactory, and the film formation process was complicated.

In order to overcome this problem, a method of modifying a surface by forming a self-assembled thin film has been proposed. A self-assembled thin film was formed on the surface of gold to change the physical and chemical properties of the surface [US Patent 5,598, 193]. Self-assembly of molecules with functional groups of sulfur compounds can form very dense self-assembled thin films on the gold surface, but they are chemically unstable and have poor practical applicability. In addition, unlike the gold surface, the chemically stable organic thin film could be produced on the oxide surface, but it was not easy to form a thin film by self-assembly. There have been several reports in this regard, but there is a problem in that the uniform adsorption of organic compounds occurs without forming a uniform thin film by self-assembly. Since it is difficult to form a self-assembled thin film on the oxide surface, David E. King et al. Attempted to apply a silver thin film on the titanium dioxide surface and to form a self-assembled thin film of sulfur alkyl compound thereon [US Patent No. 5,591,690]. There were also material and technical limitations.

When a thin film of an organic compound is formed on an oxide surface, it proceeds by reacting a silicon compound on the surface [J. H. Moon, J. W. Shin, S. Y. Kim, J. W. Park, Langmuir 12, 4621 (1996), US Pat. No. 6,387,631. However, mainly used silicon alkoxide compounds react very sensitively to water and react with each other to form a three-dimensional network structure [J. P. Lee, H. K. Kim, C. R. Park, G. Y. Park, H. T. Kwak, S. M. Koo, M. M. Sung, J. Phys. Chem. B. 107, 8997 (2003). Therefore, it is very difficult to modify the oxide surface as a silicon alkoxide compound and there is a fatal problem in reproducibility.

On the other hand, the inventors recently received a patent registration in the Republic of Korea as a result of the study on the method for forming a self-assembled thin film on the surface of the conductive transparent electrode [Korea Patent Registration 10-0362939]. In this patent, a thin film was formed by self-assembling an organic compound having a basic structure of X-Cn-Y on a surface of a conductive transparent oxide. This was a breakthrough, but the functional group X, which is bound to the transparent oxide surface, was located only at one end of the entire molecule, and the force of van der Waals, a weak attraction that acts only at very short distances between molecules that are electrically neutral in self-assembly. Because of the strong acidic or basic conditions, the self-assembled thin film does not exist stably and is easily peeled off. In addition, since the time required for surface modification is very long, it is inconvenient for the manufacture of the device using the conductive transparent oxide and the subsequent inspection and use.

Attempts have been made to form a polymer layer in order to solve the problem of forming a monolayer on an oxide surface. Using the Langmuir-Blodgett (LB) technology, a single layer can be formed on the surface of the semiconductor wafer, which is not uniform on the surface, only mechanically planar, and uses physical adsorption, which imposes many constraints on the use due to the lack of bonding force on the surface. Paras, N. Prasad & WMKPW Wijekoon, Lanmuir-Blodgett Films, Organic Polymers for Photonics Aplications, pp. 3552-3554, Joseph C. Salamone, Polymeric Materials Encyclopedia, 1996]. B. Lanuitton, in US Patent Publication 2003/0003272, reported a method of forming a multilayer film of a polyelectrolyte by adsorption on conventional glass. However, due to the problem of forming a film through adsorption of the charged polymer electrolyte by a hydroxyl group present on the glass surface, there is a problem in the stability of the formed film, and furthermore a problem in the physical stability of the multilayer film stacked thereon. U.S. Patent Application Publication 2002/0177135 proposes a structure and a design method of a biochip, and mentions general matters of the surface treatment, which forms a thin film of sulfur compound on a gold surface and a nitrogen compound thin film on a carbon surface. And forming a thin film using a silicon alkoxide compound on the oxide surface and forming a multilayer structure based on these thin films. However, these gold and carbon applications have been limited, and the reaction of silicon alkoxide compounds at the oxide surface was a limiting method as mentioned above.

Accordingly, the present inventors have conducted research to solve such a problem. As a result, the present inventors have conducted conductive transparent polymers polymerizing monomers having acidic or basic functional groups instead of conventional monomolecular compounds in which acidic or basic functional groups existed at both ends of the organic compound. Self-assembly on the surface of the substrate to form a thin film based on it to form a multi-layered molecular structure of organic compounds, organometallic compounds, biopolymers and inorganic compounds having electromagnetic or photochemically important properties and having acidic or basic functional groups The present invention has been completed by knowing that it is possible to prepare a conductive transparent substrate having a thin film by self-assembly of a polymer polymer, which has a uniform and high bonding force on the surface of the conductive transparent substrate and is stable under strong acidic or basic conditions within a short time. It was.

Accordingly, the present invention relates to a conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer in which a polymer in which a basic functional group is introduced into a side chain is deposited on a conductive transparent substrate by an acid-base reaction, and a manufacturing method thereof. The purpose is to provide.

In addition, the present invention is a polymer thin film polymerized by polymerizing a monomer having a basic functional group introduced into a side chain, and another polymer polymer thin film polymerizing a monomer having an acidic functional group introduced into a side chain thereof. A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer having a multilayered structure, which is alternately deposited by acid-base reaction, hydrogen bond, covalent bond, or van der Waals interaction of the polymer polymer, and its manufacture Another purpose is to provide a method.

The present invention provides a conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer in which a basic polymer (X ₁ ) represented by the following Chemical Formula 1 is introduced into a side chain on a conductive transparent substrate, and is laminated by an acid-base reaction. It features.

In the above formula, X ₁ is selected from the group consisting of = NR, -NR ₂ , -NR ₃ (wherein R is hydrogen or an alkyl group having ₁ to ₂₀ carbon atoms) and a nitrogen-containing aromatic group, and Y is absent or carbon, oxygen, nitrogen , Phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more.

In addition, the present invention is a polymer polymer in which the basic functional group (X ₁ ) represented by Formula 1 on the side chain is laminated by an acid-base reaction on the conductive transparent substrate, and the acid functional group (X) represented by the following Formula 2 thereon ₂ ) a conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer in which the polymer polymer introduced into the side chain is laminated.

In the above formula, X ₂ is selected from the group consisting of hydroxyl group, sulfuric acid group, carboxyl group, phosphoric acid group and nitric acid group, Y is absent or selected from carbon, oxygen, nitrogen, phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more.

The present invention will be described in more detail as follows.

The present invention forms an organic thin film on the surface of a conductive transparent substrate by self-assembly of a polymer polymerized by polymerizing a monomer having an acidic or basic functional group, and is an electromagnetic or photochemically important organic polymer thin film having an acidic or basic functional group. By forming a film, not only can the surface be effectively modified in a short time to suit the purpose of using the conductive transparent substrate, but also the film is not peeled off under strong acidic and basic conditions based on the improved bonding force between the conductive transparent substrate and the polymer thin film. Conductive transparent substrates with thin films formed by self-assembly of polymer polymers that can be used in more applications, including thin film transistor liquid crystal displays (TFT LCDs), plasma display panels (PDPs), ELs and biochips. And preparation method thereof It relates.

The present invention uses a self-assembly of a polymer polymer polymerized monomer having an acidic or basic functional group to form a polymer multilayer film. This is a novel approach for modifying the surface of a conductive transparent substrate, which is a method that can modify the surface of a transparent substrate very uniformly and stably in a short time. As in the present invention, existing techniques for forming a polymer multilayer film such as using a naturally occurring charge on a glass surface without using a strong bond between an acid and a base use a physical adsorption method. Has a limit. On the contrary, when the polymer multilayer film is formed using the principle of forming an acid-base complex between a solid acid and a functional group of the polymer, the bonding force is increased to be stable at a wide range of pH and stable under strong acidic and basic conditions, and according to the purpose. The film of structure can be formed in a short time.

The polymer layer formed on the surface of the conductive transparent substrate may vary depending on the purpose for which the oxide is used, and may include a polymer, a biopolymer, an organic compound, an organometallic compound, an inorganic compound, and a polymer layer including the polymer having acidic or basic functional groups. This can be stacked. In general, a conductive transparent substrate is used as a transparent electrode for electromagnetic or photochemical purposes. The transparent electrode can be used for various purposes by stacking a monomolecular compound or a polymer compound having various functionalities on a polymer layer. For example, when a compound having a width of HOMO and LOMO corresponding to a visible, infrared or ultraviolet region is used on a conductive transparent substrate, the light energy can be easily converted into the flow of electrons. It can be used for photosensitive devices and the like. When a solar cell is manufactured by stacking a representative photosensitive material, Ru (2,2'-bipyridine-4,4'-dicarboxylic acid) ₂ (NCS) ₂ on a conductive transparent substrate self-assembled with an amine polymer, In addition to providing high efficiency and flexibility, this will provide the foundation for building flexible solar cells. In addition, when stacking compounds such as Fe (CN) ₆ ^-3 and Ru (NH ₃ ) ₆ ⁺³ having electrical properties, molecular electronics such as diodes and logic gates are used. It is possible to implement device characteristics for. In addition, materials such as DNA, RNA or protein are also laminated on a polymer uniformly coated on the surface of the conductive transparent electrode, so that they can be easily studied and observed in response to electrical properties or optical properties. Conventional methods of detecting biochemicals using biochips have been largely dependent on the measurement of fluorescence by light. However, in the case of constructing such biochips on a conductive transparent substrate according to the present invention, changes in electrical properties in addition to detection by light are applied. The substance can be detected by this.

The polymer used in the present invention is a compound having an acidic or basic functional group in the side chain of the monomer or a compound containing an anion or cation capable of such a function.

Examples of the compound having an acidic functional group include compounds containing sulfonic acids such as polystyrenesulfonic acid and polyvinylsulfonic acid, polyacrylic acid, polymethacrylic acid and maleic acid / vinylalkyl ethers. Compounds containing carboxylic acids such as maleic acid / vinylalkyl ether copolymer polyglutamic acid, compounds containing phosphites such as polyphosphoric acid, nitrates or nitrites Compounds consisting of a compound, a compound containing a hydroxy group, and copolymers thereof may be used. A compound containing an anion capable of functioning as a compound having an acidic functional group is a polymer that can be dissolved in a solvent, and any polymer polymer containing an anion with an acidic functional group can be used. In addition, anionic inorganic compound polymers and organometallic polymer compounds may be used together.

Examples of the compound having a basic functional group include an amine compound having a functional group of NH ₂ , NRH, NR ₂ , and NR ₃ and an aromatic compound including an amine group, wherein R is preferably C ₁ to C ₂₀ . The cation-containing polymer that can play such a role is preferably a compound having a quaternay ammonnium or an aromatic compound such as pyridinium salts and piperidinium salts. Can be used. Polyallylamine, sulfonated polyaniline, polyviologen, polyvinyl, polyethyleneimine and the like have stable basic groups. In addition, an inorganic cation and an organometallic cation may be used as necessary.

The polymer having an acidic and basic functional group can be selected a polymer of the appropriate strength, if necessary, any polymer that can be dissolved in a solvent can be used. In addition, the polymer may be an organic compound as well as an organometallic compound or an inorganic compound, if necessary.

The polymer deposited on the conductive transparent substrate is deposited according to the acidic or basic functional groups on the oxide surface. Organic, inorganic, and organometallic compounds having acidic or basic properties on the surface may be laminated in a single molecule layer or a multi-molecular layer to impart photochemical or electromagnetic properties. In this case, the compound to be used may be used without limitation as long as it has acidic or basic properties, or an amine group or a carboxyl group can be coordinated.

According to the present invention, in addition to modifying the surface of the conductive transparent substrate to have acidic or basic properties as described above, aldehyde may be modified. Although the necessity of the aldehyde-modified transparent electrode on the surface is being raised in reality, it is not easy to prepare the aldehyde-modified surface using the polymer electrolyte. However, in the case of the present invention, the amine on the surface of the substrate can be converted to aldehyde using a ninhydrin reaction, and the amount of aldehyde on the surface can be quantified through the reaction of forming the converted aldehyde with amine again. . Ninhydrin is a compound based on 1,2,3-triketohyrindene hydrate or 1,2,3-indentrione monohydrate, and may have a substituent on the benzene ring. it means.

Tin-doped indium oxide (ITO) is a typical conductive conductive substrate. Indium oxide is present on the surface of the compound, and the indium oxide is an acidic compound, which is acidic like alumina. Thus, the acidity of the surface can form the amine polymer layer by acid-base reaction upon encountering a suitable amine polymer compound. Once the polymer layer with the amine group is formed, the amine group adsorbs to the surface of the ITO and at the same time changes the surface to amine. The surface modified with amines can adsorb a polymer having an acidic functional group or an anion-containing polymer by an attraction force between an acid-base reaction or a charge. Since the modified transparent transparent substrate is modified with a polymer having an acidic or anionic surface, another layer is formed by self-assembly when immersed in a solution containing a basic functional group or a polymer having a cation. By repeating this process, a conductive transparent electrode of desired thickness modified with polymer can be made. The amount of tin doped into indium oxide as the conductive transparent substrate is preferably included to such an extent that it does not damage the conductivity, more preferably 5 to 30% of the total content.

In addition to the above ITO, oxides and sulfides having acid-base characteristics may be widely used as the conductive transparent substrate. Preferably, F-doped SnO ₂ , ZnO, CdO, and hydrates thereof may be used.

Once the polymer polymer has formed a thin film on the surface of the oxide by acid-base properties, the acid-base properties, attraction between cations and anions, hydrogen bonds, covalent bonds and van der Waals interaction By this, a multilayer polymer layer can be laminated.

The polymer for modifying the conductive transparent substrate may introduce functional functional groups into the main chain and the side chain as necessary, and C ?? C, C = C, C ?? CC ?? C, C ?? CC = C, Unsaturated carbon, such as C = CC = C, N = N, and a benzene ring, can be contained. In addition, in order to enhance the orientation of the aligned molecular axis, -NH-CO- amide group or the like can be contained in the molecular axis to increase the bonding between the molecular axes by hydrogen bonding. In addition, covalent bonds between molecular axes can be induced by polymerization reaction using unsaturated hydrocarbons in the molecular axis.

The polymer laminated on the conductive transparent substrate has various surface properties depending on the salt concentration in the solution. The surface roughness or thickness varies with the concentration of the salt. As the salt is added to the solution, it acts to mask the charge of the polymer. In this case, as the salt used, metal salts including NaCl, CaCl ₂ , MgCl ₂ , and organic salts including ammonium salts may be used.

Organic polymers, conductive polymers, inorganic compounds, organometallic compounds, metal ions, and the like may be stacked by polymers stacked on the surface of the conductive transparent electrode by acid-base characteristics and charge characteristics of the surfaces thereof. At this time, the photochemical or electromagnetic properties are imparted to the surface of the ITO by forming a multilayer structure of a material having photochemical or electromagnetic properties.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.

Example 1 Preparation of Multilayer Film Self-Assembled in Indium Tin Oxide (ITO)

A thin film of polyethyleneimine (PEI) was first formed by self-assembly on indium tin oxide (ITO), which is widely used as a conductive transparent substrate, and then a polyacrylic acid (PAA) thin film was formed thereon.

PEI having a molecular weight of 750,000 was dissolved in water to prepare a 2% aqueous solution of PEI, and the washed ITO was prepared in an appropriate size and immersed in an aqueous PEI solution. The amount of imine present on the surface was measured according to the time in which ITO was contained (FIG. 1). ITO was taken out and wiped several times with water to remove excess polymer particles physically adsorbed on the surface. Thereafter, ITO was soaked in an aqueous 1 mM phosphomolybdic acid solution for 10 minutes, then taken out, and the excess phosphoric acid was wiped off with water (H ₂ O). After drying, the amount of phosphomolybdic acid present on the surface of ITO was quantified by cyclic voltammetry (FIG. 2).

Example 2 Determination of the Polymer Self-Assembled According to the Concentration of the Polymer Polymer Solution

In the same manner as in Example 1, polyethyleneimine (PEI) thin films were self-assembled in ITO and thin film coverage for various concentrations of polyethyleneimine was quantified by cyclic voltammetry. The result is shown in FIG. 3.

Example 3 SEM photograph of the cut surface of the self-assembled thin film

Polyacrylic acid (PAA) was laminated by self-assembly on ITO on which polyethyleneimine (PEI) was laminated, and polyethyleneimine (PEI) was laminated by self-assembly thereon. The method of laminating PEI was the same as in Example 1, and lamination of PAA was made by dissolving 1% PAA in deionized water in an aqueous solution and soaking PTO-laminated ITO for 20 minutes. After repeating the self-assembly process 10 times PEI thin film and PAA thin film was observed by scanning electron microscopy (scanning electron microscopy). 4 shows that a layer of a polymer layer having a thickness of one layer of 3.8 nm is laminated.

Example 4 Surface Roughness According to the Number of Polymer Laminates

In the same manner as in Example 3, a multilayer structure of PEI and PAA was laminated on the surface of the ITO. Root mean square values vary depending on the number of layers of the stacked polymers, as shown in Table 1 below.

(Unit: Å)                 Scan Size Sample 5 μm 1 μm 0.5 μm ITO 30.48 26.12 23.13 ITO / PEI 31.97 21.98 17.73 ITO / PEI / (PAA / PEI) 31.53 27.80 18.94 ITO / PEI / (PAA / PEI) / (PAA / PEI) 24.67 19.15 8.99

Example 5 Quantification of Polyallylamine Self-Assembled on ITO Surface

A monolayer film of self-assembled polyallylamine (molecular weight 150,000) was formed on the surface of ITO. A 1% polyallylamine aqueous solution was prepared using water as a solvent. Cleanly washed ITO was prepared in an appropriate size and immersed in an aqueous polyallylamine solution. The amount of amine groups present on the surface of ITO was measured according to the time contained in the polymer aqueous solution. ITO was rescued and wiped several times with water to ensure that no excess polymer was physically deposited on the surface. ITO was soaked in 1 mM phosphomolybdic acid solution for 10 minutes, and then taken out to quantify the amount of amine by cyclic voltammetry. The amount of amines on the surface is 2.3 ㅧ 10 ^-10 mole / cm ² .

Example 6: ITO / (polyallylamine / polystyrenesulfonic acid) ₁₀ Thickness measurement

Polyallylamine self-assembled polystyrene sulfonic acid on the surface of the self-assembled polystyrene sulfonic acid was laminated by self-assembly. ITO, in which polyallylamine was laminated, was dipped in water deionized with 1% polystyrenesulfonic acid for 20 minutes. The sample was taken out, washed well with water and then self-assembled with the second polyallylamine layer in the manner according to Example 4. This procedure was repeated 10 times and the cut surface was observed by scanning electron microscopy. The laminated polymer layer had a thickness of 4.2 nm.

Example 7 Preparation of Aldehyde Modified ITO and Quantification of Aldehyde

The surface of ITO was aldehyde-modified using the polyethyleneimine (PEI, molecular weight 750,000) monolayer film of Example 1. The amine-modified ITO was immersed in a 10 mM solution of Ninhydrin for 15 minutes and then washed with methanol. The washed aldehyde surface was reacted with nitroaniline and an ethanol solution, and then hydrated with water to quantify the released nitroaniline to quantify the amount of aldehyde on the surface. The amount of aldehyde was 1.5 ㅧ 10 ^-10 mole / cm ² .

Example 8 Preparation of Multi-layer Film Self-Assembled in Fluorine Doped Tinoxide (FTO)

A thin film of polyethyleneimine (PEI) was first formed by self-assembly on FTO, and then a thin film of phosphomolybdic acid was formed thereon. The overall formation method is the same as in Example 1 and the amount of amine present on the surface was quantified by measuring the current electrochemically, which was 1.0 ㅧ 10 ^-10 mole / cm ² .

Example 9 Preparation of Multilayer Film Self-assembled in ZnO

ZnO was used as the conductive transparent substrate, a polyethylenimine thin film was formed, a heteropoly acid was adsorbed, and the amount of amine present on the surface was quantified by using an electrochemical method. The amount of amine was 1.3 dl 10 ^-10 mole / cm ² .

Example 10 Measurement of Electric Field Luminous Efficiency

After forming a multilayer structure of PEI and PAA on the surface of the ITO as in Example 4, self-assembling (SA) in a poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT) as a conductive polymer in an aqueous solution ) Thereafter, a polyalkylfluorene was spin coated with a light emitting layer, and then a BaF ₂ / Ca / Al metal layer was vacuum deposited onto the electrode. The formed EL (Electroluminescence) efficiency is the same as that of FIG. 5 and PEDOT (SA) in FIG. 5 means self-assembled in water.

Example 11 Measurement of Electric Field Luminance

PEDOT was thickly deposited on the PEDOT self-assembled layer of Example 10 by spin coating (SC). Thereafter, the light emitting layer and the electrode were attached as in Example 10, and then device characteristics were measured. This is shown in FIG. 6 and PEDOTsc means PEDOT spin coating.

Example 12 Diode Characteristics of an ITO Surface Multilayer Structure

The PEI and PAA multilayer structures were self-assembled on the surface of the ITO by the method of Example 3. The polymers self-assembled ITO was immersed in an aqueous solution of Fe (CN) ₆ ^-3 and Ru (NH ₃ ) ₆ ⁺³ dissolved for 1 hour. When a conter electrode is provided in this ITO sample and a current is passed, diode characteristics are shown (FIG. 7).

Example 13 Cd (OH) on ITO Surface ₂  Nano structure formation

A Cd (OH) ₂ nanofiber thin film was constructed on the surface of the ITO / PEI produced through the process of Example 3. ITO / PEI samples were soaked in a 0.1 C aqueous solution of CdCl ₂ and then 75 ° C. Soaked in water. This process was repeated 20 times to form Cd (OH) ₂ nanostructures on the surface of the ITO, and the SEM photographs and XRD spectra are shown in FIGS. 8 and 9.

Example 14 CuSe Formation on ITO Surface

While performing the same experiment as in Example 13, 0.1 M of CuCl ₂ was used as the metal solution, and then ITO samples were alternately immersed in 0.1 M solution of Na ₂ SeSO ₃ . This procedure was repeated 20 times to confirm CuSe formation by XRD spectrum.

Example 15 ZnO Formation on ITO Surface

For Example 14 ZnCl ₂ 0.1 M was used as the metal solution. Subsequently ITO / PEI was soaked alternately using a 75 ° C. aqueous solution. After 20 iterations, it was confirmed by XRD spectra of the resulting ZnO thin film.

Example 16 Conductive Transparent Substrate / Polymer Electrolyte / Fullerene

To form the organic molecular layer by the addition reaction on the surface of the ITO / polymer electrolyte, the specimen of the ITO / polymer electrolyte was immersed in a benzene solution containing 5 mM of fullerene (C ₆₀ ) and maintained at a temperature of about 50 ° C. for about 24 hours. Stored. Then remove the specimen, rinse thoroughly with benzene and dry well. Through this method, a double layer of a conductive transparent substrate / polymer electrolyte / fullerene structure can be formed.

Example 17 Introduction of a Functional Group Having a Double Bond in the Polymer Electrolyte on the ITO Surface

Pentacosadiynoic acid (C≡CC≡C (CH ₂ ) ₈ COOH) is contained in the main or side chain of the polymer electrolyte and laminated on the surface of the ITO. Investigate. This introduces a functional group having a double bond into the polymer electrolyte on the surface of the ITO. The measurement result of contact angle with respect to water of the obtained specimen was 65 degrees.

Example 18 Comparison of the Invention with the Prior Art

(1) Comparison of surface modification time

In the case of the prior art [Korea Patent Registration No. 10-0362939], it takes a minimum of several days or more under specific conditions to form a monolayer film in order for self-assembly to occur on the conductive transparent electrode. However, in the case of the present invention, the surface is modified in a short time of several minutes to several tens of minutes when the self-assembled polymer having a positive electrode on the conductive transparent electrode. Thus, the use of this patent allows surface modification in a short time, which facilitates later manufacture, inspection and use of the surface.

(2) Comparison of bonding force

Surfaces modified according to the invention exhibit strong properties for acidic and basic solutions. Even after soaking for several minutes in a strong base solution of pH 9-10, the surface of the conductive transparent substrate was not significantly affected. Since the substrate surface according to the present invention is less damaged even under the harsh conditions of a strong acid or a strong base, the use of the modified surface in the future may be various. On the contrary, in the case of the prior art, it shows a certain degree of durability under acidic conditions, but was immediately damaged under strong basic conditions. Table 2 shows ITO / DD (DD is 1,12 ?? diaminododecane), which is a surface modified using a conventional patent, and ITO / 6.5 bilayer (PEI and PAA lamination is 1 bilayer). This is the result of the change before and after reaction when the surface of) is put in strong acid and strong base conditions for 30 minutes.

Unit: × 10 ^-10 mole / cm ² division Untreated pH 2 pH 7 pH 9 ITO / DD 1.3 1.1 1.0 0.3 ITO / 6.5 bilayer 5.4 5.1 5.3 4.9

In order to observe the surface change, the amount of change in the amine functional groups present on the surface before and after acid and base treatment was measured. In the case of the prior art, it can be seen that the surface after the treatment is significantly damaged when the amount of the amine functional group after treatment is significantly reduced compared to before the treatment, but in the case of the present invention, the amount of the amine functional group is not changed. have. In the measurement method, phophomolybdic acid was attached to the surface to confirm the amount thereof.

(3) Formation experiment of multilayer film in a short time

Unlike the prior art, the present invention can effectively adjust the thickness of the modified surface in a short time. 10 is a SEM confirm that the PTO and PAA were stacked at about 600 nm in ITO, and the total experiment time was 40 minutes.

(4) Comparison of changes in surface roughness

ITO, which is a representative conductive transparent electrode, has various characteristics, but when the surface is observed by AFM or the like, the roughness is very rough with tens to hundreds of micro ohms. This feature did not change easily when the surface was modified using conventional patents. However, when the continuous polymer layer is laminated on the electrode by the method described above using the present invention, the roughness of the conductive transparent electrode can be lowered to several kW. FIG. 11 shows the surface confirmed by AFM, and the rough surface ITO is markedly flattened after the polymer layer is laminated.

(5) Applicability to Biochips

The great feature of the present invention is that the modified surface can fix DNA, protein, and the like. That is, unlike the prior art, it can be applied as a biochip. FIG. 12 shows the same DNA on the surface modified by the existing patent and the surface modified by the present invention, and then attaches a die to bind the DNA. This is a picture confirming the appearance of DNA dots. The more DNA fixed on the surface, the whiter the DNA spots become. In order to be used as a biochip, DNA must be rounded on the modified surface and the amount must be large. In this way, the surface of the existing patent is insufficient to be used as a biochip, whereas the existing patent can be used sufficiently as a biochip.

A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer according to the present invention and a method of manufacturing the same are formed by forming a thin film on the surface of the conductive transparent substrate by self-assembly of a polymer polymer polymerized with a monomer having an acidic or basic functional group. By forming a thin film of an organic, organometallic compound, biopolymer or inorganic compound having electromagnetic or photochemically important and acidic or basic functional groups on the thin film, the physical properties of the conductive transparent substrate can be effectively modified to suit the purpose of use. In addition, the thin film transistor liquid crystal display (TFT LCD), the plasma display panel (PDP), the EL or the biochip may be improved based on the improved bonding force between the conductive transparent substrate and the thin film to prevent the thin film from peeling off even under strong acidic and basic conditions. biochip) It can be used in various fields. In addition, various characteristics required for solar cells, photovoltaics, sensors, and molecular electronics can be applied to the surface of the conductive transparent electrode, and thus it is expected to be widely used in a wider range of fields.

In particular, it is innovative that the surface of the transparent electrode can be used as a base material of a biochip such as a DNA chip or a protein chip by modifying the surface with an amine or an aldehyde compound.

Claims (12)

A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer, wherein the polymer polymer in which the basic functional group (X ₁ ) represented by the following Chemical Formula 1 is introduced into the side chain is laminated on the conductive transparent substrate by an acid-base reaction. . [Formula 1]

In the above formula, X ₁ is selected from the group consisting of = NR, -NR ₂ , -NR ₃ (wherein R is hydrogen or an alkyl group having ₁ to ₂₀ carbon atoms) and a nitrogen-containing aromatic group, and Y is absent or carbon, oxygen, nitrogen , Phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more. The polymer polymer in which the basic functional group (X ₁ ) represented by the following Chemical Formula 1 is introduced into the side chain on the conductive transparent substrate is laminated by an acid-base reaction, and the acidic functional group (X ₂ ) represented by the following Chemical Formula 2 is deposited on the side chain thereon. A conductive transparent substrate with a thin film formed by self-assembly of a polymer polymer, characterized in that the introduced polymer polymer is laminated. [Formula 1]

In the above formula, X ₁ is selected from the group consisting of = NR, -NR ₂ , -NR ₃ (wherein R is hydrogen or an alkyl group having ₁ to ₂₀ carbon atoms) and a nitrogen-containing aromatic group, and Y is absent or carbon, oxygen, nitrogen , Phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more. [Formula 2]

In the above formula, X ₂ is selected from the group consisting of hydroxyl group, sulfuric acid group, carboxyl group, phosphoric acid group and nitric acid group, Y is absent or selected from carbon, oxygen, nitrogen, phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more. The layer of the polymer polymer in which the basic functional group (X ₁ ) represented by Formula 1 is introduced into the side chain and the polymer polymer in which the acidic functional group (X ₂ ) represented by Formula 2 is introduced into the side chain are alternating. A conductive transparent substrate with a thin film formed by self-assembly of a polymer polymer, characterized in that repeated to form a multi-layer structure. The conductive transparent substrate according to claim 1 or 2, wherein the conductive transparent substrate is selected from ITO, FTO, ZnO, CdO, CdSe, and CdS. The polymer polymer according to claim 1 or 2, wherein the polymer polymer in which the basic functional group (X ₁ ) represented by Formula 1 is introduced into the side chain or the acid polymer (X ₂ ) represented by Formula 2 is introduced into the side chain. A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer, wherein the main chain is a saturated or unsaturated hydrocarbon. The polymer chain according to claim 5, wherein the basic polymer (X ₁ ) represented by the formula ( ₁ ) is introduced into the side chain, or the acidic functional group (X ₂ ) represented by the formula ( ₂ ) is added to the main chain of the polymer polymer in which N = A conductive transparent substrate having a thin film formed by self-assembly of a polymer comprising N, benzene ring or -NH-CO-. The polymer according to claim 1 or 2, wherein the polymer having the basic functional group (X ₁ ) represented by Formula 1 in the side chain is a compound having a quaternary ammonium group, a pyridinium salt, a piperidinium salt, a polyallylamine, A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer, characterized in that sulfonated polyaniline, polybiologen or polyethyleneimine. 3. The polymer according to claim 2, wherein the polymer polymer in which the acidic functional group (X ₂ ) represented by Chemical Formula 2 is introduced into the side chain is polystyrenesulfonic acid, polyvinylsulfonic acid, polyacrylic acid, polymethacrylic acid, maleic acid / vinylalkyl ether copolymer polyglutamic acid. And a polyphosphoric acid, a nitrate-containing compound, a nitrite-containing compound, a hydroxy group-containing compound, or a copolymer thereof. A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer. The polymer according to claim 2, wherein the polymer polymer in which the basic functional group (X ₁ ) represented by Formula 1 is introduced into the side chain or the polymer polymer in which the acid functional group (X ₂ ) represented by Formula 2 is introduced into the side chain is represented by an acidic or basic functional group. A conductive transparent substrate formed with a thin film by self-assembly of a polymer polymer, characterized in that the biopolymer having a. A transparent electrode manufactured using the conductive transparent substrate according to claim 1. A conductive transparent substrate having a thin film formed by self-assembly of a polymer polymer, comprising depositing a polymer polymer having a basic functional group (X ₁ ) represented by Formula 1 on a side chain by an acid-base reaction on a conductive transparent substrate Manufacturing method. [Formula 1]

In the above formula, X ₁ is selected from the group consisting of = NR, -NR ₂ , -NR ₃ (wherein R is hydrogen or an alkyl group having ₁ to ₂₀ carbon atoms) and a nitrogen-containing aromatic group, and Y is absent or carbon, oxygen, nitrogen , Phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more. A first step of depositing, by an acid-base reaction, a polymer polymer having a basic functional group (X ₁ ) represented by Formula 1 on a side chain on a conductive transparent substrate; The second step of depositing the polymer polymer introduced into the side chain is an acidic functional group (X ₂ ) Method for producing a conductive transparent substrate with a thin film formed by self-assembly of a polymer comprising a. [Formula 1]

In the above formula, X ₁ is selected from the group consisting of = NR, -NR ₂ , -NR ₃ (wherein R is hydrogen or an alkyl group having ₁ to ₂₀ carbon atoms) and a nitrogen-containing aromatic group, and Y is absent or carbon, oxygen, nitrogen , Phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more. [Formula 2]

In the above formula, X ₂ is selected from the group consisting of hydroxyl group, sulfuric acid group, carboxyl group, phosphoric acid group and nitric acid group, Y is absent or selected from carbon, oxygen, nitrogen, phosphorus, sulfur, silicon and germanium elements, n is an integer of 1 or more, m is an integer of 0 or more.

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