KR20060084883A - Electrically conductive multi-layered electrode and electrochemical devices thereof - Google Patents

Abstract

The present invention relates to a conductive multilayer thin film, a method for manufacturing the same, and an electrochemical device including the same, and more particularly, to a multilayer thin film having an improved response speed by inserting a non-conductive layer between electrically conductive layers, and a method for manufacturing the same. It relates to an electrochemical device. The present invention is laminated using the ionic bonding properties of the ionic compound, the process of dipping and removing the substrate in each solution containing the selected conductive ionic compound to be laminated, and the non-conductive ionic compound solution in the middle By inserting a dipping process into the conductive film, a conductive thin film can be manufactured with easy electron transfer and a uniform thickness of the thin film.

Conductive polymer, anionic compound, cationic compound, self-assembly, electron transfer

Description

Method for manufacturing a conductive multilayer thin film electrode and an electrochemical device including the same {Electrically Conductive Multi-Layered Electrode and Electrochemical Devices Thereof}

1 is a schematic diagram showing a combination of various ionic compound layers according to the present invention,

2 is a schematic diagram showing the lamination of a conductive thin film according to Example 1 of the present invention;

3 is a schematic diagram showing a cross section of an all-solid flexible electrochemical device manufactured according to Example 19 of the present invention;

Figure 4 is a photograph of the device for electronic paper showing the electrochromic properties of the electrochemical device manufactured by Example 18 of the present invention.

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

1: ITO film

2: conductive thin film

3: solid polymer electrolyte

4: ITO film

The present invention relates to a conductive multilayer thin film, a method for manufacturing the same, and an electrochemical device including the same, and more particularly, to a multilayer substrate in which at least one non-conductive compound layer region is interposed between a conductive compound layer, and a conductive anion. Dipping into a solution of a cationic or conductive cationic compound to form a monomolecular film of a conductive anionic or a conductive cationic compound on the substrate, and a solution of a conductive or nonconductive compound having an ionicity of opposite charge to that of the monomolecular film formed on the substrate. Repeating dipping at least two times the lamination of the monomolecular film of the conductive or nonconductive ionic compound to the substrate, wherein the repetition step includes laminating the monomolecular film of the at least one nonconductive ionic compound. However, the final step of the repetition step is conductive conductivity Method of producing a conductive thin film including the step of laminating a monomolecular film of the compound and to an electrochemical device comprising the same.

An electrochemical device is an electrochromic device in which chemical properties of an electrode are changed by an oxidation-reduction reaction of an electrically occurring material. Electrochromic is the reversible control of the color of a material by electrochemical redox reactions. The color changes in accordance with the change of energy absorption by electron transfer accompanying oxidation or reduction. Electrochromic properties of conductive polymers have recently attracted a lot of attention as they can be applied to flexible displays, electrochromic glass windows called smart windows, devices for controlling light transmission, and next-generation low-voltage displays. Among them, polyaniline has been spotlighted as a conductive polymer such as having good conductivity and stability.

Polyaniline is classified into three states according to the oxidation state such as compounds (I), (II) and (III) shown in Scheme 1 below.

In Scheme 1, the reduced leucoemeraldine (I) is transparent yellow, and when it is oxidized, it becomes a dark green emeraldine salt (II), so that one benzene ring is a quinoid (quinoid form). Change. The further oxidation occurs, the blue furnigraniline (III) state, all the benzene ring is changed to the quinoid.

However, the conductive polymer, such as polyaniline, has low solubility in general solvents and is difficult to prepare into a thin film having a nanometer thickness, and in an oxidized and colored state, it changes to a quinoid structure and reacts with water or oxygen to rapidly change the number of electrochromic repetitions. There is a problem to reduce. In addition, the macromolecular properties of the conductive polymer thin film are determined by the microstructure of the molecule, and in order to optimize the electrochemical properties of the prepared thin film, the structure of the used molecular layer should be more precisely controlled, which is more uniform. And the development of a manufacturing method that can produce a thin film easy to control the thickness is required.

As a specific example for manufacturing such a thin film, Korean Patent No. 214254 discloses an electrochromic device in which a conductive polyaniline N-alkylsulfonate or a copolymer thereof having excellent solubility is dissolved at a concentration of 1 to 40 parts by weight in a polar solvent. The present invention discloses a method for preparing a polymer solution and an electrochromic polymer thin film and an electrochromic device manufactured by coating the same, but the above method has a problem in that a thin film of about several nanometers cannot be uniformly produced.

In Korean Patent Laid-Open Nos. 10-1999-0088611 and German Patent No. 1998-24126, an inorganic ion-storage compound wherein one layer contains conductive electrochromic polydioxythiophene and the further layer is based on a metal oxide or such A UV-stable electrochromic assembly having a layered structure in which a gel electrolyte containing a mixture of ion-storing compounds is contained in a mixture of ultraviolet absorbers is disclosed, but a conductive electrochromic polydioxythiophene layer can be formed. There is a problem that it is difficult to manufacture a thin film of about a meter, there is also a problem that the thickness control of the thin film is not made well.

In addition, Korean Patent No. 362939 discloses a method of treating an organic compound on a conductive transparent oxide surface and forming a self-assembled thin film on the treated transparent transparent oxide surface, but the disclosed self-assembled thin film does not have electrochromic properties. During the manufacture of a thin film by uniformly stacking layers with a thickness of more than a layer, there is a problem in that the thin films are not laminated to a uniform thickness and are difficult to be practically used.

In Korean Patent Publication No. 10-2003-0034887, an electrochromic thin film is prepared by a lamination method in which layers of charged molecules are alternately stacked by using electrostatic attraction between cations and anions or forces between other molecules, wherein the ion is In the selection of the ionic compound, an anionic conductive polymer substituted with a specific alkylsulfonate group and a specific cationic compound are used, and the substrate is immersed in each solution in which the selected ionic compound is dissolved and then removed. A method for producing a variety of thicknesses uniformly is disclosed. However, although the multilayer thin film can be manufactured by the above method, there is a problem in that electrochromic responsiveness is low because electron transfer characteristics are not controlled.

In order to solve the above problems, the present inventors use an electrostatic attraction between a cation and an anion or another layer of stacked layers of charged molecules by using forces between other molecules to facilitate electron transfer, but also electrochemical response characteristics. While continuing to study this improved conductive multilayer thin film, the inventors found that electron transfer is facilitated by controlling the stacking order of the electrically conductive ionic compound layer and the non-conductive ionic compound.

It is therefore an object of the present invention to provide a conductive thin film laminated with at least one nonconductive compound layer zone interposed between the conductive compound layers.

Another object of the present invention is to dip a substrate into a conductive anionic compound solution to form a monomolecular film of a conductive anionic compound on the substrate, and to dip the substrate into a conductive or nonconductive ionic compound solution of opposite charge to the monomolecular film formed on the substrate. Repeating at least two or more steps of depositing a monomolecular film of a conductive or nonconductive ionic compound on the substrate, the repeating step comprising laminating a monomolecular film of at least one nonconductive ionic compound, The final step of the repetition step is to provide a method for producing a conductive thin film which is a step of laminating a monomolecular film of a conductive ionic compound.

Still another object of the present invention is to dip a substrate into a conductive cationic compound solution to form a monomolecular film of a conductive cationic compound on the substrate, and to immerse a conductive or nonconductive ionic compound solution of opposite charge with the monomolecular film formed on the substrate. Repeating at least two or more steps of laminating a monomolecular film of a conductive or nonconductive ionic compound on the substrate, the repeating step including laminating a monomolecular film of at least one nonconductive ionic compound, The final step of the repeating step is to provide a method for producing a conductive thin film which is a step of laminating a monomolecular film of a conductive ionic compound.                         

Still another object of the present invention is to provide an electrochemical device including the conductive thin film according to the present invention.

In one aspect, the present invention provides a conductive thin film laminated with at least one conductive compound layer region interposed between the conductive compound layers.

In another aspect, the present invention provides a method for forming a monomolecular film of a conductive anionic or conductive cationic compound by dipping a substrate in a conductive anionic or conductive cationic compound solution; Repeating at least two or more steps of laminating a monolayer of conductive or nonconductive ionic compound on the substrate by dipping in a solution of a conductive or nonconductive compound having ionicity opposite to that of the monolayer formed on the substrate (II) Wherein the step II includes laminating a monomolecular film of at least one non-conductive ionic compound, but a final step provides a method of manufacturing a conductive thin film, which is laminating a monomolecular film of a conductive ionic compound.

In yet another aspect, the present invention provides an electrochemical device including the conductive thin film according to the present invention.

Here, the monomolecular film means that the molecular layer is formed as one, for example, the monomolecular film of the cationic compound means that the layer of the cationic compound only is formed on the substrate in the thickness direction.

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

The conductive thin film according to the invention consists of a region of at least one nonconductive compound layer interposed between the conductive compound layers. The conductive thin film according to the present invention comprises a plurality of conductive compound layers, wherein the conductive compound layer is composed of a conductive anionic compound or a cationic compound.

The conductive anionic compound may be one compound selected from the group consisting of compounds substituted with alkylsulfonate groups represented by the following Chemical Formula 1, but not limited thereto.

,

,

(1d) (1e)

,

,

(1f) (1g)

(1h)

(In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, a halogen element, a methyl group, a methoxy group or a nitro group, at least one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen. R ₅ , R ₆ and R ₇ are an alkylene group having 2 to 20 carbon atoms, polyethylene oxy group or an alkylene-polyethyleneoxy group, A is a bond or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; Is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms or -CH _2- (CH ₂ ) _L- [C (R) (R ')] m- (CH ₂ ) _L -CH _2- (where R is R 'is the same as or different from each other and is hydrogen or an alkyl group having 1 to 20 carbon atoms, l is an integer of 0 to 3, m is an integer of 0 or 1); X is hydrogen, an alkali metal ion, or a tetraalkylammonium ion A and b are integers of 1 or more.)

In the general formula (1), the halogen element is preferably fluorine, chlorine, bromine or iodine, the alkali metal ion is preferably sodium ion, potassium ion or lithium ion, the tetraalkylammonium ion is ammonium ion, tetramethylammonium ion, It is preferably tetraethylammonium ion or tetrabutylammonium ion, but is not limited thereto.

The cationic compound may be, but is not limited to, at least one compound selected from the group consisting of cationic compounds of Formula 2 below.

,

,

(Where, Y ^- is a halogen ion, ClO ₄ ^- or PF ₆ ^-, and, R ₈ is a halogen atom a substituted or unsubstituted alkylene group or a C 1 -C 20 - (CH ₂ CH ₂ O) _n - (where, n is an integer from 1 to 20), and x is an integer of 3 or more.)

In the formula (2), the halogen element is preferably fluorine, chlorine, bromine or iodine, but is not limited thereto.

Also in the conductive thin film according to the invention at least one non-conductive compound zone is inserted between the layers of the conductive compound. Electron transfer takes place between the molecules and between the molecular layers, whereby the non-conductive compound zone is located between the conductive compound layers to improve electron transfer properties.

In particular, in the case of electron transfer, electrons should be efficiently transferred from the main layer to the receiving layer. When the electrons are transferred to the upper layer of the conductive layer, if the electron conductivity of the upper layer is high, the transfer may occur efficiently, but the electrons are captured. As such, electronic hopping must be enabled accordingly.

Therefore, the non-conductive compound zone according to the present invention allows the ionic compound layer to be inserted at an interval where electron transfer hopping may occur, for example, 1 nm to 100 nm in thickness so that electron transfer can occur efficiently.

The nonconductive compound zone includes at least one nonconductive anionic compound layer or a nonconductive cationic compound layer. The nonconductive anionic compound may be at least one compound selected from the group consisting of dextran sulfate, poly-L-lysine (p-Lys), and poly-L-glutamic acid (p-Glu), but is not limited thereto. The non-conductive cationic compounds are also poly (ethylene imine) (PEI, 90%, MW 60 000), doped polyaniline, (triphenylphosphoranylidene) ammonium chloride (BTPPA ⁺ Cl ^­ ), Octyltrimethylammonium bromine (OTAB), decyltrimethylammonium bromine (DeTAB), dodecyltrimethylammonium bromine (DTAB) and at least one compound selected from the group consisting of cationic chitosan is preferred, but not limited thereto.

In the conductive thin film according to the present invention, a conductive or nonconductive anionic compound and a conductive or nonconductive cationic compound may be alternately arranged, in which case one compound layer exhibits opposite charge with a neighboring compound layer and thus has ionic bonding properties. It is firmly bonded by the layer so that the combined layer can function as a bilayer.

The number of layers of the nonconductive compound constituting the nonconductive compound layer zone is not limited, but the thickness of the entire nonconductive compound layer is preferably 1 nm to 100 nm. If the total thickness of the non-conductive compound layer is 100 nm or more, electron transfer may not be easy, and thus the electrochemical properties may not be good. It may not appear. In addition, there is no limitation on the number or positions of the non-conductive compound layer regions to be inserted, but the final layer of the conductive thin film is preferably a conductive layer.

The conductive thin film according to the present invention is prepared using the ionic bonding properties of the anionic compound and the cationic compound by a lamination method such as self-assembly.

Specifically, in one embodiment, the method for manufacturing a conductive thin film according to the present invention is to immerse a substrate in a conductive anionic compound solution to form a monomolecular film of a conductive anionic compound on the substrate, and to form a monomolecular film having a reverse charge and ionicity on the substrate. And dipping the monolayer of the conductive or nonconductive ionic compound on the substrate by dipping in a conductive or nonconductive compound solution having at least two or more times.

In another aspect, the method for manufacturing a conductive thin film according to the present invention is to dip a substrate into a solution of a conductive cationic compound to form a monomolecular film of a conductive cationic compound on the substrate, and has a conductivity having opposite ionicity to the monomolecular film formed on the substrate. Or dipping a non-conductive compound solution to deposit a monolayer of a conductive or nonconductive ionic compound on the substrate at least twice.

Here, the repeating step includes laminating a monomolecular film of at least one non-conductive ionic compound, but since the final layer of the conductive thin film is preferably a conductive layer, the final step of the repeating step is laminating a monomolecular film of the conductive ionic compound. It is preferable that it is a step.

The conductive anionic compound may be one compound selected from the group consisting of compounds substituted with an alkylsulfonate group of Formula 1, but not limited thereto. In the formula 1, the halogen element is preferably fluorine, chlorine, bromine or iodine, the alkali metal ion is preferably sodium ion, potassium ion or lithium ion, and the tetraalkylammonium ion is ammonium ion, tetramethylammonium ion, tetraethyl It is preferably an ammonium ion or tetrabutylammonium ion, but is not limited thereto.

The cationic compound may be, but is not limited to, at least one compound selected from the group consisting of the cationic compound of Formula 2. In Chemical Formula 2, the halogen element is preferably fluorine, chlorine, bromine or iodine, but is not limited thereto.

In addition, the nonconductive anionic compound may be at least one compound selected from the group consisting of dextran sulfate, poly-L-lysine (p-Lys), and poly-L-glutamic acid (p-Glu), but is not limited thereto. , The nonconductive cationic compound is poly (ethylene imine) (PEI, 90%, MW 60 000), doped polyaniline, (triphenylphosphoranylidene) ammonium chloride (BTPPA ⁺ Cl ^­ ), Octyltrimethylammonium bromine (OTAB), decyltrimethylammonium bromine (DeTAB), dodecyltrimethylammonium bromine (DTAB), and at least one compound selected from the group consisting of cationic chitosan, but are not limited thereto.

A solution containing an ionic compound (hereinafter referred to as an 'ionic compound solution') used to prepare a conductive thin film according to the present invention may be prepared by the methods disclosed in Korean Patent Nos. 00168658 and 0214254, etc. In the present invention, particularly in the case of a conductive or nonconductive anionic compound solution, 0.001 to 30% by weight of the conductive or nonconductive anionic compound is prepared by dissolving in 70 to 99.999% by weight of a polar solvent, and a conductive or nonconductive cationic compound solution. Silver can be prepared by dissolving 0.001-30% by weight of a conductive or nonconductive cationic compound in 70-99.999% by weight of a polar solvent. When the content of the ionic compound in the composition ratio is less than 0.001% by weight, the thin film is not uniformly formed. If the content exceeds 30% by weight, it is difficult to control the thickness of the thin film.

The substrate according to the present invention may be a surface-treated indium tin oxide (ITO) transparent substrate, a silicon wafer, a platinum electrode, a conductive electrode such as a gold electrode, or a conductive particle coated glass, quartz, a plastic film, or a mica. , Silicon wafers, aluminum plates, glass carbon, organic substrates, other transparent substrates, reflecting films or substrates surface-treated by a known method may be used, but is not limited thereto.

In addition, the time for dipping the substrate in the ionic compound solution is preferably in the range of 0.01 to 1 hour, but is not limited thereto.

Referring to a more specific manufacturing method of the conductive thin film according to the present invention.

In order to prepare the conductive thin film, the process of dipping and removing the substrate in the solution containing the anionic compound and the solution containing the cationic compound is alternately repeated, so that the non-conductive compound layer is inserted between the conductive compound layers. Dipping into a nonconductive ionic compound is included in the middle. For example, when the substrate is dipped in the conductive anionic compound solution for 0.01 to 1 hour and washed to make the first layer of the thin film into the conductive anionic compound layer, a monomolecular film of the conductive anionic compound is formed on the substrate.

Then, when the substrate on which the thin film of the first layer is formed is dipped into the conductive cationic compound solution in the same manner as above, the conductive anionic compound of the first layer and the conductive cationic compound of the solution are self-assembled by the ionic bonding properties. Removal from the solution and washing forms a second layer of conductive cationic compound layer, wherein the first and second layers form a bilayer.

In this case, the second layer and the third layer may be combined to form a double layer, in which case a pair of the conductive cationic compound layer and the conductive anionic compound layer may be referred to as a bilayer.

Then, the substrate is dipped in and removed from the nonconductive anionic compound solution for 0.01 to 1 hour in order to allow the non-conductive anionic compound layer to be laminated on the third layer again, and the nonconductive anionic compound layer is laminated to the fourth layer. When the cationic compound layer is laminated, a thin film in which a nonconductive ionic compound layer is inserted is formed between the conductive ionic compound layers.

If the non-conductive ionic compound layer is to be more than two layers, the fourth layer may be laminated with a non-conductive cationic compound layer, and then the non-conductive compound may be laminated as many as the desired number of layers, and then the conductive compound may be laminated. In the same manner, the order of the ionic compound layers may be variously changed by appropriately adjusting the order (see FIGS. 1 and 2).

According to the method of manufacturing a conductive thin film according to the present invention, a conductive multilayer thin film having various arrangements and number of layers may be manufactured according to the number of dipping times and the type and order of dipping ionic compound solutions. In addition, it is possible to easily adjust the overall thickness within the range of 0.5 to 2000nm by adjusting the dipping time, the kind of the ionic compound and the like.

An electrochemical device comprising a conductive thin film according to the present invention comprises an electrode, an electrolyte layer and a counter electrode (relative electrode) including the conductive thin film according to the present invention.

The electrode includes a substrate on which a thin film according to the present invention is laminated, and the substrate includes a conductive electrode such as a surface-treated ITO transparent substrate, a silicon wafer, a platinum electrode, and a gold electrode, or glass, quartz, or plastic coated with conductive particles. A film, a mica, a silicon wafer, an aluminum plate, a glass carbon, an organic substrate, another transparent substrate, a reflective film, or a substrate surface-treated by a known method may be used, but is not limited thereto.

As the electrolyte layer, an ion conductive electrolyte solution or an ion conductive membrane can be used. As the ion conductive electrolyte solution, a solution in which a known electrolyte salt is dissolved may be used, and the ion conductive electrolyte solution may be used in the manufacture of an electrochromic device by injection or vacuum entry, but is not limited thereto. The ion conductive membrane may be prepared by using a membrane coated with a known electrolyte salt in a polymer, or applying a polymer solution in which an electrolyte salt is dissolved to the conductive thin film by spin coating, vacuum injection, or dip coating to remove a solvent. It may be prepared by a process, but may be prepared by applying a composition composed of an electrolyte salt, a polymerizable monomer, an initiator and the like to the electrode including the conductive thin film and then curing by heat or light, but is not limited thereto.

The counter electrode may include, but is not limited to, a conductive electrode such as an ITO transparent substrate, a silicon wafer, a platinum electrode, or a gold electrode, glass coated with conductive particles, quartz, a plastic film, a mica, an aluminum plate, a glass carbon, or an organic Substrates, other transparent substrates, reflective films, transparent electrodes coated with inorganic oxides such as WO ₃ (tungsten oxide) or biologinous electrochromic compounds, and the like. In particular, when used for a display or tag, it is preferable to use a transparent substrate for at least one of the counter electrode and the conductive multilayer film substrate.

The electrochemical device according to the present invention is not limited thereto, but the counter electrode is adhered to the ion conductive film by compression or lamination, or when the ion conductive solution is used as an electrolyte layer, the spacer is bonded to the ion conductive material after the adhesion. The solution can be prepared by injection and sealing by injection, vacuum injection or the like. In addition, when manufacturing an ion conductive film by light or thermal curing, a composition composed of an electrolyte salt, a polymerizable monomer, an initiator, and the like is applied to an electrode including the conductive thin film, and then covered with a top electrode, and cured by applying light or heat. An element can be manufactured by the method of making it.

In the manufacture of the electrochemical device, a spacer may be used for thickness control as needed, and wires, sensors, color filters, and light sources for introducing power may be additionally attached.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention specifically, and the scope of the present invention is not limited by these examples.

 <Example 1>

1. Synthesis of Chemical Formula 1d-1 Compound (Chemical Polymerization)

First, 0.8 g of 4-anilino-1-butylsulfonate sodium salt [Aldrich, USA] and 0.2 g of aniline [Aldrich, USA] were dissolved in a 10% aqueous hydrochloric acid solution and then immersed in an ice bath to keep the temperature at 0 ° C. The solution was stirred for 1 hour while adding an aqueous solution of 1 g of sodium persulfate [Aldrich, USA]. Stirring at 0 ° C. for 8 hours to obtain a dark green polymer solution, using a dialysis membrane [microfilter, USA] to filter out low molecular weight impurities of 3500 or less molecular weight from the green polymer solution and then Removed using. The process of purifying with the dialysis membrane was repeated 3 to 5 times, the solvent was removed, and then dried under vacuum to synthesize polymer 1d-1 in the form of black green powder.

2. Synthesis of Compound of Formula 1d-2 (Electrochemical Polymerization)

To 100 ml of acetonitrile solution [Aldrich, USA] of 0.1M 4-anilino-1-butylsulfonate sodium salt [Aldrich, USA] was added a small amount of 5% aqueous solution of perchloric acid [Aldrich, USA] and added to the reaction vessel. Put in. A small amount of 5% aqueous perchloric acid solution [Aldrich, USA] was then added to 10 ml of acetonitrile solution of 0.1 M aniline [Aldrich, USA] and placed in the reaction vessel. Ag / AgCl as the reference electrode, platinum wire as the counter electrode, and ITO glass plate [Short Korea, Korea] as the working electrode, circulating the blue-green polymer 1d-2 membrane at 50 mV / sec between the potentials of 0 to 1.0V. It was grown on a glass plate. It was placed in an acetonitrile solution of monomeric 0.1M lithium perchlorate salt [Aldrich, USA] for 12 hours, then washed with acetonitrile solution [Aldrich, USA] and dried under nitrogen atmosphere.

3. Synthesis of Compound of Formula 1c-1 (R7 =-(CH ₃ ) CHCH ₂ CH _2- )

Isobutyleneoxypyrrolebutanesulfonate monomers were synthesized using known methods (J. Org. Chem., 66 (21), 6873-6882, 2001), followed by 4-anilino-1-butylsulfonate sodium Polymer Formula 1c-1 was synthesized using the same method as used in the synthesis of Formula 1d-1, except that the synthesized monomer was used instead of the salt.

4. Synthesis of Compound of Formula 1h-1

0.1 M polyisobutyleneoxypyrrolebutanesulfonate (PIBOPBUS) acetonitrile solution prepared using a known method (J. Org. Chem., 66 (21), 6873 -6882, 2001) [Aldrich, USA] A small amount of 5% aqueous perchloric acid solution was added to 100 ml and placed in a reaction vessel. A small amount of 5% aqueous perchloric acid solution was then added to 150 ml of acetonitrile solution [0.1] of 0.1 M 4-anilino-1-butylsulfonate sodium salt and placed in the reaction vessel. A green-green polymer film was grown on the ITO glass plate by circulating at 50 mV / sec between potentials of 0 to 1.0 V with Ag / AgCl as the reference electrode, platinum wire as the counter electrode, and ITO glass plate as the working electrode. It was placed in an acetonitrile solution of 0.1 M lithium perchlorate salt without monomer, soaked for 12 hours, washed with acetonitrile solution and dried under nitrogen atmosphere.

<Example 2>

Fabrication of conductive polymer multilayers by self-assembly

Electropolymerization as a polymer wherein R ₅ is-(CH ₂ ) _3- , R ₁ , R ₂ , R ₃ , and R ₄ are all hydrogen and X is tetrabutylammonium in the compound of formula 1a prepared by a known method. 0.02 g of the polymer 1d-2 prepared by the above was dissolved in 10 ml of distilled water ( I ). In addition, 0.02 g of vinylbenzyldimethyloctadecylammonium chloride (VOAC-1) having R ₈ of-(CH ₂ ) ₇ -in Chemical Formula 2a was dissolved in 10 ml of distilled water ( II ). In addition, polyaniline was added to dimethylacetamide at a concentration of 20 mg / ml using a known method (JH Cheung, WB Stockton, and MF Rubner, Macromolecules 1997, 30, 2712-2716) and stirred for one day. Then, the mixture was ultrasonically stirred for 9 hours, the remaining mass was removed, mixed with water of pH 3.2 at a ratio of 9: 1, and then the pH was adjusted to 2.5 to 2.6 with HCl to prepare an aqueous solution PAN-1. ( III ).

ITO glass plates [Short Korea, South Korea] were treated with N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane to show hydrophilicity. Thereafter, it was immersed in the negatively charged aqueous solution 1d-2 ( I ) for 10 minutes, taken out, washed the surface with distilled water, and the remaining distilled water was removed with nitrogen gas. Subsequently, the ITO glass plate was immersed in a positively charged conductive solution PAN-1 ( III ) for 10 minutes, taken out, washed with distilled water, and the remaining distilled water was removed with nitrogen gas to form a 1d-2 / PAN-1 double layer. It was.

Subsequently, the double layered substrate was immersed in a negatively charged aqueous solution 1d-2 ( I ) and a positively charged nonconductive aqueous solution VOAC-1 ( II ) for 10 minutes, washed with distilled water, and then the remaining distilled water was purged with nitrogen. Removal with gas gave a 1d-2 / VOAC-1 bilayer.

Then, the method of forming the 1d-2 / PAN-1 bilayer and the 1d-2 / VOAC-1 bilayer is repeated six times in sequence, and the 1d-2 / PAN-1 bilayer is further formed so that the final bilayer is conductive. A total of 15 bilayers were fabricated with a self-assembled electrochromic multilayer thin film.

The prepared multilayer thin film was examined for absorbance change by applying ultraviolet spectroscopy. As a result, the absorbance measured at 320 nm, 360 nm, and 440 nm increased with each increase in the number of bilayers, thereby confirming that PANBUS / cationic layers (where cations are VOAC-1 or PAN-1) were well formed. . In addition, as a result of measuring the change in thickness according to the number of layers, it was confirmed that the thickness also increased uniformly as the number of double layers increased.

<Examples 3 to 13>

In Example 2, the conductive anionic compound solution, the conductive cationic compound solution, the non-conductive cationic compound solution, and the self-assembly conditions were changed as shown in Table 1 below to prepare a conductive thin film, the structure of the multilayer of the conductive thin film, The absorbance, the thickness of the multilayer film, the number of layers of the double layer, etc. were measured and the results are shown in Table 1.

1) Expressed as ionic compound (g) / solvent (g).

2) electrode / indicated by [(cation layer / anionic layer) _{can be double-layer} / (cation layer / anionic layer) _can ..... _{double layer] can section.}

3) Examine the absorbance at 430 nm.

4) Unit: nm

5) Indicates the number of bilayers.

In Table 1, ITO-g is glass coated with ITO (conductivity 10 S / cm, Schott),

ITO-f is a plastic film coated with ITO (conductivity 150 S / cm, Schott)

Au-q is a quartz coated with gold,

SW is silicon wafer,

Au-PolC is a polycarbonate plate coated with gold (manufacturer of the invention),

1a-1 is represented by Chemical Formula 1a, provided that R ₁ to R ₄ is H, R ₅ is (CH ₂ ) ₄ and X is Na),

1b-1 is a compound of Formula 1b, wherein A is CH ₂ , R ₆ is (CH ₂ ) ₅ , X is K, and O. Stephan, P. Schottland, P.-Y. Le Gall, C. Chevrot, C Mariet, MJ Carrier, Electroanal. Chem. 1998, 443, 217).

1c-1 is represented by Chemical Formula 1c, wherein B is CH ₂ C (CH ₃ ) H-CH ₂ , R ₇ is (CH ₂ ) ₄ and X is K,

1e-1 is a compound of Formula 1e (wherein R ₅ is-(CH ₂ ) _5- , B is CH ₂ CH ₂ -CH ₂ , R ₇ is-(CH ₂ ) ₅ and X is Na),

1f-1 is represented by Chemical Formula 1f, wherein A is CH ₂ CH _2, B is CH ₂ C (CH ₃ ) H-CH _2, R ₆ is-(CH ₂ ) ₄ , and R ₇ is-(CH ₂ ) ₆ X is Na),

1 g-1 is a chemical formula 1 g (wherein R ₁ is F, R ₃ is Br, R ₂ and R ₄ is H, R ₅ is (CH ₂ ) ₄ , A is CH ₂ , and R ₆ is-(CH ₂ ) ₅ And X is Na),

1h-1 is a chemical formula 1h (wherein R ₁ is F, R ₃ is Br, R ₂ and R ₄ is H, R ₅ is (CH ₂ ) ₄ , B is CH ₂ C (CH ₃ ) H-CH ₂ R ₇ is-(CH ₂ ) ₉ ),

1b-2 is a compound of Formula 1b, wherein A is CH ₂ , R ₆ is (CH ₂ ) ₁₁ , X is Na, and O. Stephan, P. Schottland, P.-Y. Le Gall, C. Chevrot, C Mariet, MJ Carrier, Electroanal. Chem. 1998, 443, 217).

DXS is dextran sulfate,

VOAC-2 is of the formula 2a, wherein R ₈ is-(CH ₂ ) ₁₁ -and Y is Br;

VOAC-3 is of the formula 2a wherein R ₈ is-(CH ₂ ) ₁₇ -and Y is Cl;

PAN-1 is represented by Chemical Formula 2b (wherein Y is ClO ₄ ),

PAN-2 is represented by Chemical Formula 2b (where Y is dodecylbenzenesulfonate),

PAN-3 is represented by Chemical Formula 2b (where Y is CF ₃ SO ₃ ),

PEI is synthesized using the method disclosed in Fischer P., Laschewsky A., Layer-by-layer adsorption of identically charged polyelectrolytes, Macromolecules, 33 (3), (2000) 11001102),

PAHs are poly (allylamin hydrochloride) (Lvov YM, Decher G., M ㆆ hwald H., Assembly, layer deposited ultrathin films of poly (vinyl sulfate) and poly (allylamine), Langmuir, 9 (2), (1993) 481486) using the method disclosed in

PDDA is poly (diallyldimethylammonium chloride) (Lesser C., Gao M., Kirstein S., Highly luminescent thin films from alternating deposition of CdTe nanoparticles and polycations, Mater. Sci. Eng., C8­C9 (1999) 591 Synthesized using the method disclosed in

PLLs were prepared using the method described in poly-L-lysine (Cooper ™, Campbell AL, Crane RL, Formation of polypeptide-dye multilayers by an electrostatic self-assembly technique, Langmuir, 11 (7), (1995) 27132718). Synthesized),

PVTH is poly (vinylphenyl-trimethylammonium hydroxide) (Yoo D., Lee J.-K., Rubner MF, Investigations of new self-assembled multilayer thin films based on alternately adsorbed layers of polyelectrolytes and functional dye molecules, Mater. Res. Soc. Symp. Proc., 413 (1996) 395400 (Electrical, Optical, and Magnetic Properties of Organic Solid State Materials III).

CC is cationic chitosan (Lvov Y., Onda M., Ariga K., Kunitake T., Ultrathin films of charged polysaccharides assembled alternately with linear polyions, J. Biomater. Sci., Polym. Ed., 9 (4) , (1998) 345355).

<Example 14>

Preparation of Photocurable Polymer Electrolyte Composition

Methoxypolyethylene glycol monomethacrylate 2.5 g (molecular weight 1000) [Polyscience, USA], triallyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H)- 0.3 g Trione [Aldrich, USA], 2.5 g polyethylene glycol dimethyl ether (molecular weight 330) [Aldrich, USA] and 0.25 g Tarocure 1173 [Ciba Specialty Chemicals, Switzerland], 0.25 g as photoinitiator Lithium trifluoromethanesulfonate [Merck, USA] was mixed. Then titanium dioxide [Degussa, Germany] having a mass ratio of 10% of the mixture was added and stirred for 2 hours to prepare a photocurable polymer electrolyte composition.

<Example 15>

Preparation of Photocurable Polymer Electrolyte Composition

Methoxypolyethylene glycol monomethacrylate 2.5 g (molecular weight 750) [Polyscience, USA], triallyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione [Aldrich, USA] 0.3 g, polyethylene glycol dimethyl ether (molecular weight 330) [Aldrich, USA] 2.5 g and 0.25 g of Tarocure 1173 [Ciba Specialty Chemicals, Switzerland] as photoinitiator, 0.25 g of lithium trifluoromethane Sulfonate [Merck, USA], 0.1 g of 0.1 M HClO ₄ aqueous solution was mixed. Then titanium dioxide [Degussa, Germany] having a mass ratio of 5% of the mixture was added and stirred for 2 hours to prepare a photocurable polymer electrolyte composition.

<Example 16>

Preparation of Liquid Electrochromic Device

A spacer having a thickness of 20 μm was inserted between the ITO glass coated with the conductive thin film prepared in Example 3 and the platinum plate as the counter electrode. A small amount of 10% perchloric acid was added thereto, acetonitrile solution in which 0.1 M lithium perchlorate was dissolved, and then sealed to prepare a liquid electrochromic device. When the voltage of 1V was applied to the manufactured electrochromic device, the color changed to dark blue within 0.1 second.

The change in color is obtained by oxidizing the conductive polymer of the conductive electrode to give a color, thereby confirming that the electrochromic device is coated with the conductive polymer film.

<Example 17>

Preparation of Liquid Electrochromic Device

A spacer having a thickness of 30 μm was inserted between the ITO glass coated with the conductive thin film prepared in Example 13 and the counter electrode ITO. A small amount of 15% acetic acid was added thereto, acetonitrile solution in which 0.1 M sodium perchlorate was dissolved, and then sealed to prepare a liquid electrochromic device. When the voltage of 1.1V was applied to the manufactured electrochromic device, the color changed to dark purple within 0.5 seconds.

<Example 18>

Fabrication of Solid Electrochromic Device

After applying the photocurable electrolyte solution prepared in Example 14 on the ITO glass plate coated with the conductive thin film prepared in Example 4 and covering the ITO glass plate with a counter electrode, the solid-state electrochromic device was irradiated with ultraviolet light of 365nm wavelength Prepared. A schematic diagram of the prepared solid electrochromic device is shown in FIG. 3.

<Example 19>

Fabrication of Solid Electrochromic Device

The same method as in Example 18 was used except that the conductive thin film prepared in Example 12 was used as the conductive thin film, and a plastic film coated with ITO was used. As a result, a solid electrochromic device having a color change from dark brown to pale yellow according to voltage was produced.

<Example 20>

Electrochromic Experiment of Electrochromic Device

The change in color with respect to the voltage was observed by changing the applied voltage to -3.0V and 3.0V in the electrochromic device manufactured in Example 18. The response time and color contrast were measured at 570nm while the applied voltage was changed from -3.0V to 3.0V every 30 seconds. The coloration / discoloration time was measured for the measurement of the response time and the coloring time and the discoloration time were defined as the time taken for 90% of the total absorbance to change.

The solid electrochromic device prepared in Example 18 was analyzed by a large time charge method (chronocoulometry) and the results are shown in FIG. 4. In FIG. 4, after the voltage of 3 V was applied to the electrochemical device for 1 second, 2 seconds, and 5 seconds, the electrochromic property was maintained even after the power was removed. Coloring / coloring responsiveness was shown for 3.0 V (duration: 30 seconds). The coloring / coloring property is maintained in the colored state or reduced state even when the power supply is interrupted, showing excellent memory characteristics. The coloring / bleaching repeatability was more than 1000 times, and the color contrast when the voltage was changed at 1 second intervals. Was 0.1.

The solid electrochromic device prepared in Example 18 was electrochemically analyzed by cyclic voltammetry using a BAS100B electrochemical analyzer. The result was a cyclic voltammogram (reference electrode: Ag / AgCl, counter electrode: platinum plate, electrode area: 11 cm ² , circulation rate: 50 mV / sec), oxidation peak at 650 mV, reduction peak at 490 mV. Each appeared. When comparing this with the liquid electrochromic device prepared in Example 16, the solid electrochromic device manufactured according to Example 18 showed a broader curve than the liquid electrochromic device prepared according to Example 13, and the magnitude of the current peak was Was smaller.

<Examples 21 to 27>

In Examples 18 and 19, the electrochemical device was manufactured by changing the conductive film, the electrolyte, the charge, that is, the device manufacturing conditions as shown in Table 2 below, and the response time, color, and color contrast were measured, and the results are shown in Table 2. Indicated.

Electrochemical Properties of Electrochemical Devices According to Examples 21-27 Example Conductive film Electrolyte / Layer Thickness (㎛) Counter electrode Response time (colored / discolored) (seconds) Color (oxidation / reduction) Color contrast 21 Example 6 Example 14/20 ITO-g 10/15 Green / colorless 0.142 22 Example 3 Example 14/50 ITO-g coated with WO ₃ 6/12 Bluish green / colorless 0.093 23 Example 4 Example 15/10 ITO-g 5/6 Green / colorless 0.130 24 Example 5 Example 15/20 ITO-f 6/7 Green / colorless 0.142 25 Example 7 Example 14/20 Platinum plate 11/14 Bluish green / colorless 0.19 26 Example 8 Example 15/20 ITO coated with WO ₃ 5/5 Bluish green / colorless 0.11 27 Example 11 Example 15/1 ITO-f 4/3 Red / yellow 0.12

As described above, the conductive thin film manufactured according to the present invention has excellent electrochemistry such as easy electron transfer, uniform thickness of ㎚ size, very fast coloring / coloring response, and excellent memory properties and repeatability. Has characteristics.

The conductive thin film facilitates the transfer of electrons in the conductive thin film in the electrochemical device accompanied with the oxidation-reduction reaction, and the electrochemical device manufactured according to the present invention facilitates the redox reaction so that the response speed is fast and the display, e-book It can be applied to various fields such as electronic paper, ID, tag, electronic label, portable computer, sunglasses, car rearview mirror, solar control window, decorative products, chemical sensor, biosensor, photoelectric sensor and information memory processing device.

Claims (17)

A conductive thin film laminated with at least one non-conductive compound layer region interposed between the electrically conductive compound layers. The method of claim 1, And the conductive compound layer is a conductive anionic compound layer or a conductive cationic compound layer. The method of claim 2, The conductive anionic compound is at least one compound selected from the group consisting of a compound substituted with an alkylsulfonate group of Formula 1 and the conductive cationic compound is at least one compound selected from the group consisting of a cationic compound of Formula 2 Conductive thin film. [Formula 1]

(1d) (1e)

(1f) (1g)

(1h) (In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, a halogen element, a methyl group, a methoxy group or a nitro group, at least one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen. R ₅ , R ₆ and R ₇ are an alkylene group having 2 to 20 carbon atoms, polyethylene oxy group or an alkylene-polyethyleneoxy group, A is a bond or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms; Is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, or -CH _2- (CH ₂ ) _L- [C (R) (R ')] m- (CH ₂ ) _L -CH _2- (where R is And R 'are the same or different from each other and are hydrogen or an alkyl group having 1 to 20 carbon atoms, l is an integer of 0 to 3, m is an integer of 0 or 1); X is hydrogen, an alkali metal ion, or a tetraalkylammonium ion A and b are integers of 1 or more.) [Formula 2]

,

(Where, Y ^- is a halogen ion, ClO ₄ ^- and PF ₆ ^-, and, R ₈ is an alkylene group, or unsubstituted or substituted by a halogen atom having 1 to 20 - (CH ₂ CH ₂ O) _n - (where , n is an integer of 1 to 20), and x is an integer of 3 or more, respectively.) The method of claim 3, wherein The halogen elements of Formula 1 and Formula 2 are fluorine, chlorine, bromine or iodine, the alkali metal ions of Formula 1 are sodium ions, potassium ions or lithium ions, and the tetraalkylammonium ions of Formula 1 are ammonium ions, tetra A conductive thin film which is methylammonium ion, tetraethylammonium ion, or tetrabutylammonium ion. The method of claim 1, Wherein the nonconductive compound layer zone comprises a nonconductive anionic compound layer and / or a nonconductive cationic compound layer. The method of claim 5, The nonconductive anionic compound is at least one compound selected from the group consisting of dextran sulfate, poly-L-lysine (p-Lys) and poly-L-glutamic acid (p-Glu), wherein the nonconductive cationic compound is Poly (ethylene imine) (PEI, 90%, MW 60 000), doped polyaniline, (triphenylphosphoranylidene) ammonium chloride (BTPPA ⁺ Cl ^­ ), Octyltrimethylammonium bromine (OTAB), decyltrimethylammonium bromine (DeTAB), dodecyltrimethylammonium bromine (DTAB), and a conductive thin film which is at least one compound selected from the group consisting of cationic chitosan. The method according to any one of claims 2 to 6, A conductive thin film in which the conductive or nonconductive anionic compound layer and the conductive or nonconductive cationic compound layer are alternately arranged. The method according to claim 1 or 5, A conductive thin film having a thickness of one nonconductive compound layer region interposed between the conductive compound layers is 1 nm to 100 nm. Dipping the substrate into a solution of a conductive anionic or conductive cationic compound to form a monomolecular film of a conductive anionic or conductive cationic compound on the substrate; And Repeating the step (II) of stacking the monomolecular film of the conductive or nonconductive ionic compound on the substrate by dipping in a solution of the conductive or nonconductive compound having ionicity opposite to that of the monomolecular film formed on the substrate. Wherein the step II includes laminating a monomolecular film of at least one non-conductive ionic compound, but the final step is laminating a monomolecular film of a conductive ionic compound. The method of claim 9, The conductive or nonconductive anionic compound solution contains 0.001 to 30% by weight of the conductive or nonconductive anionic compound and 70 to 99.999% by weight of a polar solvent, and the conductive or nonconductive cationic compound solution is 0.001 to 30% by weight. A method for producing a conductive thin film comprising% of a conductive or nonconductive cationic compound and 70 to 99.999% by weight of a polar solvent. The method according to claim 9 or 10, The conductive anionic compound is at least one compound selected from the group consisting of a compound substituted with an alkylsulfonate group of Formula 1 and the conductive cationic compound is at least one compound selected from the group consisting of a cationic compound of Formula 2 Method for producing a conductive thin film. The method of claim 11, The halogen element of Formula 1 and Formula 2 is fluorine, chlorine, bromine or iodine, the alkali metal ion of Formula 1 is sodium ion, potassium ion or lithium ion, the tetraalkylammonium ion of Formula 1 is ammonium ion, A method for producing a conductive thin film which is tetramethylammonium ion, tetraethylammonium ion or tetrabutylammonium ion. The method according to claim 9 or 10, The nonconductive anionic compound is at least one compound selected from the group consisting of dextran sulfate, poly-L-lysine (p-Lys) and poly-L-glutamic acid (p-Glu), wherein the nonconductive cationic compound is Poly (ethylene imine) (PEI, 90%, MW 60 000), doped polyaniline, (triphenylphosphoranylidene) ammonium chloride (BTPPA ⁺ Cl ^­ ), Octyltrimethylammonium bromide (OTAB), decyltrimethylammonium bromide (DeTAB), dodecyltrimethylammonium bromide (DTAB) and a method for producing a conductive thin film which is at least one compound selected from the group consisting of cationic chitosan. The method of claim 9, Method for producing a conductive thin film made dipping in the compound solution for 0.01 to 1 hour. The method of claim 9, The substrate is a conductive ITO transparent substrate, silicon wafer, platinum electrode, gold electrode or conductive particles coated glass, quartz, plastic film, mica, silicon wafer, aluminum plate, glass carbon, organic substrate or reflective film Method for producing a thin film. Electrochemical device comprising a conductive thin film according to claim 1. The method of claim 16, The electrochemical device comprises an electrode, an electrolyte layer and a counter electrode comprising the conductive thin film.

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