JP2002115079A - Method of manufacturing functional organic thin film and method of manufacturing organic electronic device using the same as well as method of manufacturing display device using the same - Google Patents

Abstract

(57) [Problem] To provide a method for producing a functional organic thin film with high accuracy even in a small area. A method for producing a functional organic thin film fixed to a predetermined portion of a substrate surface by a covalent bond, comprising exposing active hydrogen to a predetermined portion (or a portion excluding the predetermined portion) of the substrate surface. A pretreatment step of subjecting a predetermined portion to a region having a higher exposed active hydrogen density than a portion excluding the predetermined portion by performing a treatment (or an active hydrogen removing process); A film having a functional group capable of reacting with a compound having a functional functional group and contacting the compound with active hydrogen in the region to form a functional organic thin film on a predetermined portion of the substrate surface And a forming step.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a functional organic thin film fixed to a substrate by covalent bonds. The present invention also relates to a method for manufacturing a two-terminal and three-terminal electronic device (organic electronic device) using an organic material for a channel portion. Further, the present invention relates to a method for manufacturing a liquid crystal display device and an electroluminescence display device (hereinafter, referred to as “EL display device”) using the organic electronic device.

[0002]

2. Description of the Related Art Conventionally, inorganic semiconductor materials such as silicon crystals have been used for electronic devices. However, with the progress of miniaturization, silicon defects have a problem that crystal defects become a problem, and device performance is affected by the crystals. In addition, there was a disadvantage that flexibility was poor.

Accordingly, the present inventors have invented an organic electronic device capable of solving the above-mentioned drawbacks and capable of responding at high speed, and have already filed an application (Japanese Patent Application No. 2000-243056).
issue). The present invention is characterized in that an organic thin film having a conductive network in which organic molecules having a photoresponsive functional group or a polar functional group are mutually conjugated is provided between electrodes.

In order to form an organic thin film in the form of a monomolecular film or a monomolecular cumulative film fixed at a desired position on a substrate surface by a covalent bond, the following method is generally employed. That is, first, a substrate having active hydrogen exposed is prepared, a resist pattern is formed on the substrate surface, and then immersed in a chemical adsorption solution in which a compound having a functional group reactive with active hydrogen is dissolved, and the substrate surface is exposed. A method is employed in which the active hydrogen exposed to the above is reacted with the above compound, and then the resist is removed.

[0005]

However, according to the above-described method, particularly when an organic thin film having a small area is formed,
Slight dissolution, expansion, shrinkage, etc. (mask defects) at the edge of the resist opening may directly affect the accuracy of the organic thin film. For this reason, development of a new method capable of forming an organic thin film with high accuracy has been desired.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for manufacturing a highly-functional organic thin film with a small area.

Another object of the present invention is to provide a method of manufacturing an organic electronic device which can cope with recent high integration. It is another object of the present invention to provide a method of manufacturing a display device using the organic electronic device.

[0008]

Means for Solving the Problems The present inventor has made intensive studies in order to develop a new method for forming a functional organic thin film with high precision. In the process, paying attention to the fact that the functional organic thin film is a film fixed by a covalent bond, prior to the formation of the film, the region where the film is to be formed on the surface of the base material is set to a region where the exposed active hydrogen density is high, and the film is formed. It was conceived that the region where no exposed active hydrogen density was formed should be divided into regions where no active hydrogen was formed. In other words, when forming a film fixed by a covalent bond to the substrate, if a clear boundary is provided on the substrate itself,
He recalled that a functional organic thin film could be formed more accurately than simply applying a mask such as a resist. Therefore, the present inventor
Prior to the film forming step, a predetermined portion of the substrate surface is subjected to an active hydrogen exposure treatment, or a portion excluding a predetermined portion of the substrate surface is subjected to an active hydrogen removal treatment, so that a predetermined portion (film formation scheduled) The present inventors have found that if a pretreatment step is performed in which the (area) is a region having a high exposed active hydrogen density, a highly accurate functional organic thin film can be formed even with a small area, and the present invention has been achieved.
And if this film formation technique is applied to the manufacture of organic electronic devices, it will be found that it is possible to provide organic electronic devices that can respond to recent high integration, and it will be possible to provide even higher-performance display devices. Was.

The present invention has the following features.

(Method for Producing Functional Organic Thin Film) The first method for producing a functional organic thin film of the present invention is a method for producing a functional organic thin film which is fixed to a predetermined portion of the surface of a substrate by a covalent bond. A pretreatment step of subjecting a predetermined portion of the base material surface to an active hydrogen exposure treatment to make the predetermined portion a region having a higher exposed active hydrogen density than a portion excluding the predetermined portion; In a high-density region, a compound having a functional group capable of reacting with active hydrogen and a functional functional group is brought into contact, and the compound is reacted with active hydrogen in the region, and a predetermined portion of the base material surface is formed. A film forming step of forming a functional organic thin film fixed by a covalent bond.

As described above, prior to the formation of the film,
If the substrate surface is divided into two regions using the exposed active hydrogen density as an index, a functional organic thin film fixed by covalent bonds by the reaction of active hydrogen and a functional group capable of reacting with active hydrogen can be obtained. Is formed in accordance with the divided state. Therefore, a functional organic thin film with high dimensional accuracy can be formed even with a small area. Further, the functional organic thin film formed in this manner is excellent in peeling resistance and the like, so that it is a film that can exhibit a predetermined function for a long period of time.

Here, in the present invention, the “predetermined portion on the surface of the substrate” is a portion arbitrarily selected from the surface of the substrate and refers to a portion of the surface of the substrate on which the functional organic thin film is formed. The “exposed active hydrogen density” refers to the number of active hydrogen exposed from the surface of the base material per unit area. further,
The “functional organic thin film” refers to a film composed of organic molecules having a specific function. Specific functions include a function of changing conductivity, magnetism, dielectric property, and conductivity, a function of regulating alignment of liquid crystal molecules, and antifouling properties such as water repellency and oil repellency. The “functional functional group” refers to a functional group involved in the function of the film, for example, a photoresponsive functional group such as a photoisomerizable functional group, and an electric field responsive property such as a polar functional group. Examples include a functional group and a polymerizable group capable of bonding with a conjugate bond.

In the above-mentioned production method, it is preferable to use a substrate to which active hydrogen is not exposed as the substrate. If such a base material is used, a portion excluding a predetermined portion is a region where active hydrogen is not exposed, so that a highly accurate functional organic thin film can be reliably formed. In addition,
"Substrate with no active hydrogen exposed" refers to a substrate to which active hydrogen is not exposed at all, as well as a substrate to which active hydrogen is substantially not present such that the membrane does not have exposed active hydrogen to sufficiently bond and fix it. Includes substrates that are not physically exposed.

It is preferable that one area of the predetermined portion on the surface of the base material is 1000 μm ² or less. When a film having such a small area is formed, if a film is formed only with a mask as in the past, a mask defect may adversely affect the accuracy of the film, but if pretreatment is performed as in the present invention, Since it is not affected by the mask defect, the improvement effect of the present invention is high.

[0015] The functional functional group is at least one functional group selected from the group consisting of a photoresponsive functional group, an electric field responsive functional group, and a polymerizable group capable of bonding via a conjugate bond. Is preferred. Further, it is preferable that the functional organic thin film is a monomolecular film in which molecules of the compound are arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are stacked. With such a film, the molecules are oriented to a certain extent, so that a functional organic thin film exhibiting a uniform function is obtained.

It is preferable to use a water-repellent single-layer substrate or a laminated substrate having a water-repellent coating formed on the surface as the substrate having no active hydrogen exposed on the surface. Furthermore, it is preferable to use a water-repellent synthetic resin substrate as the water-repellent single-layer substrate. Further, it is preferable to use an acrylic resin substrate, a polycarbonate resin substrate, or a polyether sulfone resin substrate as the synthetic resin substrate. Further, it is preferable to use an acrylic resin film, a polycarbonate film, or a polyethersulfone resin film as the water-repellent film constituting the laminated base material.

In the pretreatment step, it is preferable to use a method of oxidizing a predetermined portion of the substrate surface to give active hydrogen as the active hydrogen exposure treatment. Further, as a method of the oxidation, a predetermined portion of the surface of the substrate is exposed to excimer U in the presence of oxygen and hydrogen atom supply substances.
From the viewpoint of productivity and the like, it is preferable to apply at least one method selected from the group consisting of a V light irradiation method, an ultraviolet irradiation method, a plasma treatment method, and a corona treatment method. Further, in the pretreatment step, as the active hydrogen exposure treatment, a laminated substrate having a water-repellent organic film formed on the surface of the substrate where active hydrogen is exposed is prepared. It is preferable to use a method of oxidizing a part to remove the organic film and expose active hydrogen. Further, as the oxidation method, under an atmosphere containing oxygen, a predetermined portion of the surface of the laminated substrate, excimer UV light irradiation method,
It is preferable to use at least one of the ultraviolet irradiation method, the plasma treatment method, and the corona treatment method from the viewpoint of productivity and the like.

In the pre-treatment step, prior to the active hydrogen exposure treatment, a mask is provided on a portion of the substrate surface other than a predetermined portion, and the masked substrate is exposed to active hydrogen. It is preferable to carry out the conversion treatment because it is simple. The film forming step may be performed after removing the mask, or may be performed before removing the mask.

In the film forming step, the compound having a functional group capable of reacting with active hydrogen and a functional functional group is at least one selected from the group consisting of a halosilyl group, an isocyanate group and an alkoxysilyl group.
Using a compound having a kind of functional group and a functional functional group, when the compound is brought into contact with the region where the exposed active hydrogen density is high, a chemical adsorption liquid obtained by mixing the compound and a non-aqueous organic solvent is used. Use is preferred from the viewpoint of production efficiency and the like. Further, it is preferable to perform a cleaning step of cleaning the surface of the base material using a non-aqueous organic solvent after passing through the pretreatment step and the film forming step, since a clean film can be obtained.

A second method for producing a functional organic thin film according to the present invention is a method for producing a functional organic thin film which is fixed to a predetermined portion of the surface of a base material by covalent bonding. A pretreatment step of performing an active hydrogen removal treatment on the portion excluding the portion to make the predetermined portion a region where the exposed active hydrogen density is higher than that of the portion excluding the predetermined portion; A compound having a functional group capable of reacting with hydrogen and a functional functional group is brought into contact with each other to cause the compound to react with active hydrogen in the region, and is fixed to a predetermined portion of the substrate surface by a covalent bond. And a film forming step of forming a functional organic thin film.

As described above, even when the active hydrogen removal treatment is performed on a portion excluding a predetermined portion, the predetermined portion can be made a region having a high exposed active hydrogen density, and as a result, a function having high dimensional accuracy can be obtained. Organic thin film can be formed.

In the above-mentioned production method, it is preferable to use a substrate having active hydrogen exposed as the substrate.
Even with such a substrate, according to the above manufacturing method,
A highly accurate functional organic thin film can be formed by utilizing exposed active hydrogen that originally existed. The “substrate with active hydrogen exposed” refers to a substrate with active hydrogen exposed so that the film can be sufficiently bonded and fixed.

It is preferable that one area of the predetermined portion of the base material surface is not more than 1000 μm ² . Further, the functional functional group is preferably at least one type of functional group selected from the group consisting of a photoresponsive functional group, an electric field responsive functional group, and a polymerizable group capable of bonding by a conjugate bond. . Further, it is preferable that the functional organic thin film is a monomolecular film in which molecules of the compound are arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are stacked.

As the substrate having active hydrogen exposed on the surface, it is preferable to use a hydrophilic single-layer substrate or a laminated substrate having a hydrophilic film formed on the surface. Furthermore, it is preferable to use a metal substrate, a silicon substrate, a silicon nitride substrate, a silica substrate, or a glass substrate having an oxidized surface as the single-layer substrate. Further, it is preferable to use a metal film, a silicon film, a silicon nitride film, a silica film, or a glass film whose surface is oxidized as the hydrophilic film constituting the laminated base material.

In the pretreatment step, it is preferable to use a method of performing a chemical treatment on a portion other than a predetermined portion of the substrate surface to eliminate active hydrogen as the active hydrogen removal treatment. Further, as the chemical treatment, a compound having a functional group capable of reacting with active hydrogen is brought into contact with a portion other than a predetermined portion of the substrate surface, and the compound and the active hydrogen in a portion excluding the predetermined portion of the substrate surface are removed. It is preferable to use a method of reacting with the above because the treated portion is hardly peeled off and the subsequent treatment is easily performed. Further, in the pretreatment step, it is preferable to use a method of performing a physical treatment on a portion other than a predetermined portion of the substrate surface to remove active hydrogen as the active hydrogen removal treatment. Further, as the physical treatment, it is preferable to use a method of irradiating a portion except a predetermined portion on the surface of the base material with light in a vacuum to cut a covalent bond that has bound active hydrogen to the base material.

Prior to the active hydrogen removal treatment,
It is preferable to prepare a substrate with a mask applied to a predetermined portion of the substrate surface, perform an active hydrogen removal treatment on the masked substrate, and remove the mask prior to the film forming step. Further, in the film forming step, as the compound having a functional group capable of reacting with active hydrogen and a functional functional group, at least one selected from the group consisting of a halosilyl group, an isocyanate group and an alkoxysilyl group.
Using a compound having a kind of functional group and a functional functional group, when the compound is brought into contact with the region where the exposed active hydrogen density is high, a chemical adsorption liquid obtained by mixing the compound and a non-aqueous organic solvent is used. Preferably, it is used. After the pretreatment step and the film forming step, it is preferable to perform a washing step of washing the surface of the base material using a non-aqueous organic solvent.

(Manufacturing Method of Organic Electronic Device) According to the first method of manufacturing a two-terminal organic electronic device of the present invention, a first electrode formed on a substrate and a second electrode separated from the first electrode are formed. And a conductivity changing film that electrically connects the first electrode and the second electrode, wherein the conductivity changing film is part of an organic molecule group having a photoisomerizable functional group. Or has a conductive network all connected by conjugated bonds, and the conductivity of the conductive network,
A method for manufacturing a two-terminal organic electronic device that changes according to light irradiated on the conductivity changing film, wherein a predetermined portion of the substrate surface is subjected to an active hydrogen exposure treatment, and the predetermined portion is subjected to a predetermined process. A pretreatment step in which the exposed active hydrogen density is higher than that of the portion excluding the portion, and bonding to the active hydrogen density higher region by a conjugate bond with a functional group capable of reacting with active hydrogen and a photoisomerizable functional group. Contacting a compound having a polymerizable group with the compound, and reacting the compound with active hydrogen in the region to form a film that covalently fixes an organic molecule group composed of the compound to a predetermined portion of the substrate surface. A step, a polymerization step of forming a conductive network by forming a conductive network by conjugate bonding of some or all of the organic molecule groups by a polymerization reaction, and a counter electrode forming step of forming a first electrode and a second electrode on the substrate Be prepared Characterized in that was.

The above-described manufacturing method corresponds to the first method of manufacturing a functional organic thin film, and divides the surface of the substrate into two regions using the exposed active hydrogen density as an index before forming the film. As a result, it is possible to accurately form a conductivity changing film fixed and bound by a reaction with active hydrogen. The two-terminal organic electronic device thus obtained has a high sensitivity to light and a high response speed by including a photoisomerizable functional group in the conductivity changing film. Changes faster. Therefore, a technique for forming a two-terminal organic electronic device capable of high-speed response with high integration can be provided.

The change in conductivity upon irradiation with light is considered to be caused by the influence of the response of the photoisomerizable functional group to the structure of the conductive network.

The two-terminal organic electronic device obtained as described above is mainly intended for use as a switching element, but is not limited to this. The device has a memory function because the conductivity of the conductive network is changed by light having different wavelengths, and after the light is shielded, the conductivity is maintained without change. Therefore, it can be used as a memory element, a variable resistor, an optical sensor, and the like.

According to the first method of manufacturing a three-terminal organic electronic device of the present invention, a first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode A conductivity changing film for electrically connecting the second electrode and the second electrode; and a third electrode sandwiched between the substrate and the conductivity changing film and insulated from each other. , An electrode for controlling an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film has a polar functional group. It has a conductive network in which some or all of the organic molecule groups are connected by conjugate bonds, and the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. A method for manufacturing a three-terminal organic electronic device, comprising: An electrode forming step of forming a third electrode on the surface of the substrate, and exposing a predetermined portion of the substrate surface on which the third electrode is formed to active hydrogen exposure, so that the predetermined portion is removed from a portion excluding the predetermined portion. A pretreatment step to also make the exposed active hydrogen density high, and the exposed active hydrogen density is high, the active hydrogen-reactive functional group and the polar functional group and the polymerizable group capable of bonding with a conjugate bond. Contacting a compound having the formula: and reacting the compound with active hydrogen in the region to fix a group of organic molecules comprising the compound to a predetermined portion of the substrate surface by a covalent bond. A polymerization step of forming a conductive network by conjugate bonding of a part or all of the group by a polymerization reaction, and a counter electrode formation step of forming a first electrode and a second electrode on the substrate. Features.

The manufacturing method having the above-described structure corresponds to the first method for manufacturing a functional organic thin film, and can form a highly accurate conductivity changing film even if electrodes are formed on the substrate surface. The three-terminal organic electronic device thus obtained has a high sensitivity to an electric field and a high response speed by including a polar functional group in the conductivity changing film. Change is faster. Therefore, a technique for forming a three-terminal organic electronic device capable of high-speed response with high integration can be provided.

It is considered that the change in the conductivity when an electric field is applied is caused by the influence of the response of the polar functional group to the structure of the conductive network. The three-terminal organic electronic device obtained as described above is mainly intended for use as a switch element, but is not limited to this use.

According to a second method of manufacturing a two-terminal organic electronic device of the present invention, a first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode And a conductivity changing film that electrically connects the second electrode and the second electrode, wherein the conductivity changing film is configured such that some or all of the organic molecules having a photoisomerizable functional group are connected by a conjugate bond. A method for manufacturing a two-terminal organic electronic device, wherein the two-terminal organic electronic device has a conductive network, and the conductivity of the conductive network changes according to light irradiated on the conductivity changing film. A pretreatment step of performing an active hydrogen removal treatment on a portion of the surface excluding a predetermined portion to make the predetermined portion a region where the exposed active hydrogen density is higher than the portion excluding the predetermined portion; and a region where the exposed active hydrogen density is high. In addition, a functional that can react to active hydrogen And a compound having a functional group capable of photoisomerization and a polymerizable group capable of bonding via a conjugate bond, and reacting the compound with active hydrogen in the above-described region. A film forming step of fixing a group of organic molecules by a covalent bond, a polymerization step of forming a conductive network by conjugate bonding of some or all of the group of organic molecules by a polymerization reaction, and a first step of forming a conductive network on the substrate.
And a counter electrode forming step of forming an electrode and a second electrode.

The manufacturing method having the above structure corresponds to the above-described method for manufacturing the second functional organic thin film. Prior to the formation of the film, the substrate surface is exposed to the exposed active hydrogen density as an index.
Since it is partitioned into different kinds of regions, the conductivity changing film fixed and bound by the reaction with active hydrogen can be formed with high accuracy.
Therefore, a technique for forming a two-terminal organic electronic device capable of high-speed response with high integration can be provided.

The two-terminal organic electronic device obtained as described above is also assumed to be mainly used as a switch element, but can be used for a memory element, a variable resistor, an optical sensor, and the like.

According to a second method of manufacturing a three-terminal organic electronic device of the present invention, a first electrode formed on a substrate, a second electrode separated from the first electrode, and a first electrode formed on the substrate. A conductivity changing film for electrically connecting the second electrode and the second electrode; and a third electrode sandwiched between the substrate and the conductivity changing film and insulated from each other. , An electrode for controlling an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film has a polar functional group. It has a conductive network in which some or all of the organic molecule groups are connected by conjugate bonds, and the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. A method for manufacturing a three-terminal organic electronic device, comprising: An electrode forming step of forming a third electrode on the surface of the substrate, and performing an active hydrogen removing process on a portion of the substrate surface on which the third electrode is formed, except for a predetermined portion, excluding the predetermined portion. A pretreatment step of making the exposed active hydrogen density higher than that of the portion; and a polymerizable compound capable of binding to the active hydrogen density higher region by a conjugate bond with a functional group reactive with active hydrogen and a polar functional group. Contacting a compound having a group and reacting the compound with active hydrogen in the region to form a film forming step of covalently fixing an organic molecule group composed of the compound to a predetermined portion of the substrate surface;
A polymerization step of forming a conductive network by forming a part or all of the organic molecules in a conjugate bond by a polymerization reaction; and a counter electrode forming step of forming a first electrode and a second electrode on the substrate. It is characterized by having.

The manufacturing method having the above structure corresponds to the above-described method for manufacturing the second functional organic thin film, and can form a highly-accurate conductivity changing film even if electrodes are formed on the substrate surface. Therefore, a technique for forming a three-terminal organic electronic device capable of high-speed response with high integration can be provided.

The three-terminal organic electronic device obtained as described above is mainly intended for use as a switch element, but is not limited to this use.

In the method for manufacturing an organic electronic device corresponding to the first method for manufacturing a functional organic thin film, it is preferable to use a surface insulating substrate on which active hydrogen is not exposed as the substrate. Further, in the method of manufacturing an organic electronic device corresponding to the second method of manufacturing a functional organic thin film, it is preferable to use a surface insulating substrate having active hydrogen exposed as the substrate.

In the method for manufacturing an organic electronic device, it is preferable that the conductivity change film is a monomolecular film arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are stacked. In such a film, the molecules are in a state of being orientated to some extent, and the polymerizable groups in the molecules are neatly arranged at a substantially constant position from the substrate surface. A conjugate bond is formed substantially in parallel, and as a result, a conductive network having high conductivity can be formed.

It is preferable to apply a chemical adsorption method or a Langmuir-Blodgett method in the film forming step. According to these methods, a monomolecular film or a monomolecular cumulative film having an arbitrary thickness can be easily produced.

It is preferable to use a silane-based chemisorbing substance in the film forming step to which the chemisorption method is applied, because the device can be efficiently manufactured in a short time.

In the method for producing a two-terminal organic electronic device, it is preferable to use an azo group as the photoisomerizable functional group. An azo group is isomerized into the first trans isomer by irradiation with visible light and the second cis isomer by irradiation with ultraviolet light, so that a film whose conductivity is easily changed is formed. it can.

In the method for producing a three-terminal organic electronic device, it is preferable to use a carbonyl group and / or an oxycarbonyl group as the polar functional group. With these groups, the polarization is increased by the application of an electric field, and the sensitivity to the applied electric field is extremely high, so that a switch element having an extremely high response speed can be obtained.

The polymerizable group capable of bonding by a conjugate bond is at least one selected from the group consisting of a catalyst polymerizable functional group, an electrolytic polymerizable functional group, and a functional group polymerized by irradiation with an energy beam. It is preferable to use a functional group. If these functional groups are used, a catalyst polymerization method, an electrolytic polymerization method, or a polymerization method using energy beam irradiation can be applied during polymerization, and a conductivity changing film can be easily formed. It is preferable to use at least one functional group selected from the group consisting of a pyrrole group, a chenylene group, an acetylene group, and a diacetylene group as the catalytically polymerizable functional group. It is preferable to use a pyrrole group and / or a chenylene group as the electropolymerizable functional group. As the functional group polymerized by the energy beam irradiation, it is preferable to use an acetylene group and / or a diacetylene group.

In the case where the polymerizable group that can be bonded by the conjugate bond is an electrolytic polymerizable functional group, the counter electrode forming step is performed prior to the polymerization step, and in the polymerization step, It is preferable that a conductive network be formed by applying a voltage between the first electrode and the second electrode to cause an electrolytic polymerization reaction between the electropolymerizable functional groups. With such a configuration, the first electrode and the second electrode can be used for forming a conductive network, and the conductive network can be formed in a self-growing manner by applying a voltage between the two electrodes to perform polymerization. .

In the method for producing a two-terminal organic electronic device, in the case where the polymerizable group capable of binding by a conjugate bond is a pyrrole group and / or a phenylene group, which are electrolytically polymerizable functional groups, After forming a monolayer-like conductivity changing film via a film forming step, a polymerization step and a counter electrode forming step, the substrate on which the conductivity changing film is formed is attached to a pyrrole group and / or a chenylene group. And immersed in an organic solvent in which a compound having a photoisomerizable functional group is dissolved, and is in contact with the first electrode and the second electrode and between the first electrode or the second electrode and the organic solvent. Then, a voltage is applied between each of the external electrodes disposed above the conductivity change film, and a part or all of the molecule groups of the compound is formed on the surface of the monomolecular conductivity change film. Conjugated Conductive network can be a step of forming a film comprising formed. By doing so, the conductive network is formed in multiple stages,
A two-terminal organic electronic device capable of flowing a larger current can be provided.

Further, in the method for producing a two-terminal organic electronic device, when the polymerizable group capable of binding by a conjugate bond is a pyrrole group and / or a chenylene group which are an electropolymerizable functional group, After forming a monomolecular film before polymerization through a processing step, a film forming step, and a counter electrode forming step, the substrate on which the monomolecular film is formed is separated from a pyrrole group and / or a chenylene group by photoisomerization. Immersed in an organic solvent in which a compound having a functional group to be converted is dissolved, and is brought into contact with the organic solvent between the first electrode and the second electrode and between the first electrode or the second electrode and the organic solvent. A voltage is applied between each of the external electrodes disposed above the molecular film, and a conductive network is formed by forming a conjugate bond between the electropolymerizable functional groups in the monomolecular film by a polymerization reaction. To the to the surface of the monomolecular film, may be a step of part or all of the molecular groups of said compound forms a coating film formed by forming a conjugated bond to a conductive network. According to this method, in the case where the conductivity changing film is a monomolecular accumulation film, a single polymerization reaction is required for forming the conductive network, so that a two-terminal organic electronic device capable of flowing a larger current is used. Can be manufactured in a shorter time.

Similarly to the above, in the method for producing a three-terminal organic electronic device, the polymerizable group capable of bonding by the conjugate bond is a pyrrole group or / and / or an electropolymerizable functional group.
And when it is a chenylene group, the electrode forming step,
Through a pretreatment step, a film formation step, a polymerization step and a counter electrode formation step, after forming a monomolecular conductivity change film,
The substrate on which the conductivity changing film is formed is immersed in an organic solvent in which a compound having a pyrrole group and / or a chenylene group and a polar functional group is dissolved, and the first electrode and the second electrode are And between the first electrode or the second electrode and an external electrode that is in contact with the organic solvent and is disposed above the conductivity change film, to apply a voltage to the monomolecular state. A step of forming a conductive film on the surface of the conductivity changing film, in which a part or all of the molecules of the compound are conjugated to form a conductive network, can also be performed. Further, in the method for producing a three-terminal organic electronic device, in the case where the polymerizable group capable of bonding by a conjugate bond is a pyrrole group and / or a chenylene group, which are an electropolymerizable functional group, the electrode forming step After forming a monomolecular film before polymerization through a pretreatment step, a film forming step and a counter electrode forming step, the substrate on which the monomolecular film is formed is treated with a pyrrole group or / and a chenylene group. Immersed in an organic solvent in which a compound having a polar functional group is dissolved, and between the first electrode and the second electrode, and in contact with the first or second electrode and the organic solvent; A voltage is applied between each of the external electrodes disposed above the conductivity change film and a conductive network is formed by conjugate bonding of the electropolymerizable functional groups in the monomolecular film by a polymerization reaction. Together with the the surface of the monomolecular film, may be a step of part or all of the molecular groups of said compound forms a coating film formed by forming a conjugated bond to a conductive network.

(Manufacturing Method of Display Device) The first manufacturing method of the liquid crystal display device according to the present invention comprises a first electrode formed on a substrate, and a second electrode separated from the first electrode. A conductivity changing film for electrically connecting the first electrode and the second electrode, and a third electrode sandwiched between the substrate and the conductivity changing film and insulated from each other. The third electrode is an electrode that controls an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film includes: It has a conductive network in which some or all of the organic molecules having polar functional groups are connected by a conjugate bond, and the conductivity of the conductive network is applied to the conductivity changing film. Switch a three-terminal organic electronic device that changes according to the applied electric field. A method for manufacturing a liquid crystal display device used as a switch element, wherein a plurality of the switch elements are arranged in a matrix on a first substrate and a first alignment film is formed on the surface thereof. A step of forming a substrate, a step of forming a color filter substrate having a plurality of color elements arranged and arranged in a matrix on a second substrate, and a second alignment film formed on a surface thereof; Facing the array substrate and the color filter substrate at a predetermined interval with the first alignment film and the second alignment film inside, and filling and sealing liquid crystal between the two substrates, The step of fabricating the array substrate includes an electrode forming step of forming third electrodes in a matrix on the surface of the first substrate, and an active hydrogen exposure treatment on a predetermined portion of the substrate surface on which the third electrodes are formed. Give it A pretreatment step of setting the predetermined portion to a region where the exposed active hydrogen density is higher than that of the portion excluding the predetermined portion; and, in the region where the exposed active hydrogen density is high, a functional group reactive with active hydrogen and a polar functional group. A compound having a polymerizable group capable of bonding by a conjugate bond is brought into contact with the compound, and the compound is reacted with active hydrogen in the above-mentioned region, and an organic molecule group composed of the compound is covalently bonded to a predetermined portion of the substrate surface. A film forming step of fixing, a polymerization step of forming a conductive network by conjugate bonding of some or all of the organic molecule groups by a polymerization reaction, and forming a first electrode and a second electrode on the first substrate. Forming a counter electrode, and forming an alignment film on a substrate on which the first electrode, the second electrode, the third electrode, and the conductivity change film are formed. Process.

According to the above configuration, a liquid crystal display device using an organic TFT instead of an inorganic thin film transistor (TFT) can be manufactured. In the case of an organic TFT, since there is no step of processing at a high temperature, a plastic substrate having lower heat resistance than a glass substrate can be used. As a result, the range of substrate selection is expanded, and it is possible to provide a more versatile liquid crystal display device such as a device having excellent flexibility. Further, since a minute TFT can be manufactured, a high-performance liquid crystal display device can be provided.

In the above manufacturing method, it is preferable to use, as the first substrate, a surface insulating substrate having no active hydrogen exposed on the surface.

According to a second method of manufacturing a liquid crystal display device of the present invention, a first electrode formed on a substrate, a second electrode separated from the first electrode, A conductivity change film electrically connecting the two electrodes, and a third electrode sandwiched between the substrate and the conductivity change film and insulated from each other, wherein the third electrode is , An electrode for controlling an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film has a polar functional group. It has a conductive network in which some or all of the organic molecule groups are connected by conjugate bonds, and the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. Using a three-terminal organic electronic device as a switch element A method of manufacturing a display device,
A step of manufacturing an array substrate having a plurality of switch elements arranged in a matrix on a first substrate and having a first alignment film formed on a surface thereof; The elements are arranged in a matrix and
Manufacturing a color filter substrate having a second alignment film formed on the surface thereof; and setting the array substrate and the color filter substrate to a predetermined position with the first alignment film and the second alignment film inside. Facing each other at an interval, and filling and sealing liquid crystal between the two substrates. The step of manufacturing the array substrate includes forming an electrode on the surface of the first substrate by forming a third electrode in a matrix. A step of performing an active hydrogen removal process on a portion of the substrate surface excluding a predetermined portion on which the third electrode is formed, so that the predetermined portion becomes a region having a higher exposed active hydrogen density than the portion excluding the predetermined portion. In the treatment step, the exposed active hydrogen density region is brought into contact with a compound having a functional group capable of reacting with active hydrogen and a polymerizable group capable of bonding with a polar functional group and a conjugate bond, and contacting the compound with the compound. Activity in the above area A film forming step of covalently fixing an organic molecule group composed of the compound to a predetermined portion of the substrate surface, and a part or all of the organic molecule group is conjugated by a polymerization reaction. A polymerization step for forming a conductive network; a counter electrode formation step for forming a first electrode and a second electrode on the first substrate;
A step of forming an alignment film for forming a first alignment film on the substrate on which the electrode, the second electrode, the third electrode, and the conductivity change film are formed.

According to the above configuration, a liquid crystal display device using an organic TFT instead of an inorganic TFT can be manufactured.

In the above manufacturing method, it is preferable to use a surface insulating substrate having active hydrogen exposed on the surface as the first substrate.

According to a first method of manufacturing an EL display device of the present invention, a first electrode, a second electrode separated from the first electrode, and a first electrode formed on a substrate are provided. The third electrode, comprising: a conductivity change film electrically connecting the second electrode; and third electrodes sandwiched between the substrate and the conductivity change film and insulated from each other. Is an electrode for controlling an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film has a polar functional group. It has a conductive network in which some or all of the organic molecule groups have a conjugated bond, and the conductivity of the conductive network depends on the electric field applied to the conductivity changing film. A changing three-terminal organic electronic device was used as a switching element A method for manufacturing an L-type display device, comprising: a step of manufacturing an array substrate in which a plurality of the switch elements are arranged in a matrix on a substrate; and a step of forming a fluorescent material that emits light by applying a voltage on the array substrate. Forming a light-emitting layer; and forming a common electrode film on the light-emitting layer, wherein the step of manufacturing the array substrate includes the step of forming a third electrode in a matrix on the surface of the substrate; A pretreatment step of subjecting a predetermined portion of the substrate surface on which the third electrode is formed to an active hydrogen exposure treatment to make the predetermined portion a region having a higher exposed active hydrogen density than a portion excluding the predetermined portion; In the region where the exposed active hydrogen density is high, a compound having a functional group capable of reacting with active hydrogen and a polymerizable group capable of bonding with a polar functional group and a conjugate bond is brought into contact with the compound, and this compound and the above-mentioned region are used. Reacting with active hydrogen, forming a film to covalently fix a group of organic molecules composed of the compound to a predetermined portion of the substrate surface, and forming a conjugate bond of a part or all of the group of organic molecules by a polymerization reaction. A polymerization step to form a conductive network by
And a counter electrode forming step of forming a first electrode and a second electrode on the substrate.

According to the above configuration, an EL display device using an organic TFT instead of an inorganic TFT can be manufactured.

In the above manufacturing method, it is preferable to use a surface insulating substrate having no active hydrogen exposed on the surface as the substrate.

According to a second method of manufacturing an EL display device of the present invention, a first electrode, a second electrode separated from the first electrode, and a first electrode formed on a substrate are provided. The third electrode, comprising: a conductivity change film electrically connecting the second electrode; and third electrodes sandwiched between the substrate and the conductivity change film and insulated from each other. Is an electrode for controlling an electric field applied to the conductivity changing film by applying a voltage between the first electrode and the second electrode, and the conductivity changing film has a polar functional group. It has a conductive network in which some or all of the organic molecule groups have a conjugated bond, and the conductivity of the conductive network depends on the electric field applied to the conductivity changing film. A changing three-terminal organic electronic device was used as a switching element A method of manufacturing an L-type display device, comprising: a step of manufacturing an array substrate in which a plurality of the switch elements are arranged in a matrix on a substrate; and a step of forming a fluorescent material that emits light by applying a voltage on the array substrate. Forming a light emitting layer; and forming a common electrode film on the light emitting layer, wherein the step of manufacturing the array substrate includes an electrode forming step of forming third electrodes in a matrix on the substrate surface. Performing a process for removing active hydrogen on a portion of the substrate surface excluding a predetermined portion on which the third electrode is formed,
A pretreatment step of setting the predetermined portion to a region where the exposed active hydrogen density is higher than that of the portion excluding the predetermined portion; and, in the region where the exposed active hydrogen density is high, a functional group reactive with active hydrogen and a polar functional group. And a compound having a polymerizable group capable of bonding with a conjugate bond, and reacting the compound with active hydrogen in the region, and covalently bonding an organic molecule group composed of the compound to a predetermined portion of the substrate surface. Forming a first electrode and a second electrode on the substrate; forming a conductive network by forming a conductive network by conjugating a part or all of the organic molecule groups by a polymerization reaction. And a counter electrode forming step.

According to the above structure, an EL display device using an organic TFT instead of an inorganic TFT can be manufactured.

In the above manufacturing method, it is preferable to use a surface insulating substrate having active hydrogen exposed on the surface as the substrate.

In the above-described method for manufacturing an EL display device, in the step of forming the light emitting layer, three kinds of light emitting substances which emit red, blue or green light are formed at predetermined positions, and color display is performed. Then, an EL type color display device can be manufactured.

[0064]

Next, an embodiment of the present invention will be described.

(Embodiment 1) In the first method for producing a functional organic thin film of the present invention, a predetermined portion of a substrate surface is subjected to an active hydrogen exposure treatment to form a region having a high exposed active hydrogen density. Thereafter (pretreatment step), the region is contacted with a compound having a functional group capable of reacting with active hydrogen and a functional functional group, and the compound is covalently fixed to a predetermined portion of the substrate surface. This is a method of forming an organic thin film (film forming step).

As the substrate, a substrate to which active hydrogen is not exposed is used. For example, a water-repellent single-layer substrate or the surface of this single-layer substrate or a substrate to which active hydrogen described later is exposed is used. In addition, a laminated substrate having a water-repellent film formed thereon may be used. Examples of the water-repellent single-layer substrate include a water-repellent synthetic resin substrate such as an acrylic resin substrate, a polycarbonate resin substrate, and a polyether sulfone resin substrate.
Examples of the water-repellent film include a metal film such as aluminum, a synthetic resin film such as an acrylic resin, a polycarbonate resin, and a polyether sulfone resin, and a water-repellent organic film. The exposed active hydrogen density of these synthetic resin substrates and synthetic resin films is substantially zero. The shape of the substrate is not particularly limited, but is usually a plate-like substrate (single-layer substrate,
Laminated substrate) is used.

The pretreatment step is a step of performing an active hydrogen exposure treatment on a predetermined portion (a film formation planned area) of the substrate surface. The active hydrogen exposure treatment refers to a treatment for making active hydrogen exposed from the surface of the base material, specifically,
(1) A method of oxidizing a predetermined portion of the base material surface to provide active hydrogen, or (2) preparing a laminated base material having a water-repellent organic film formed on the surface of the base material where active hydrogen is exposed. A method of removing the organic film at a predetermined portion of the substrate surface to expose the active hydrogen is mentioned.

(1) A method of oxidizing a predetermined portion of the substrate surface to give active hydrogen. This method, in the presence of oxygen and hydrogen atom donors,
An oxidation method such as an excimer UV light irradiation method, an ultraviolet irradiation method, a plasma treatment method, and a corona treatment method can be applied to a predetermined portion of the substrate surface. The excimer UV light irradiation method will be specifically described as an example. In this method, first, oxygen is decomposed by irradiation with excimer UV light, and ozone is generated. Then, the ozone reacts with the hydrogen atom supply substance to generate active species having active hydrogen. On the other hand, at a predetermined portion on the surface of the base material, a covalent bond between atoms is broken by irradiation with excimer UV light to be cleaved, and the active species acts on the cleaved portion. In this manner, active hydrogen is applied to a predetermined portion of the substrate surface, and a region having a high exposed active hydrogen density is formed.

The predetermined portion is, as described above, a base material table.
Arbitrarily selected from the surface, this part is singular
There may be more than one. If there are multiple predetermined parts,
Even if those parts are the same shape, they are different shapes.
You may. In addition, the specified part (if there is more than one,
One) has a small area (specifically, 1000 μm)^TwoBelow)
If there is, higher than the case where the pretreatment step is not performed
There is a high tendency to form an accurate functional organic thin film. In addition,
The lower limit is 0.01 μm in consideration of the processing limit and the like. ^TwoIn
You.

Excimer U is applied only to a predetermined portion of the substrate surface.
As a method of irradiating the V light, a method of irradiating excimer UV light after exposing only a predetermined portion after covering a portion other than a predetermined portion with a mask material such as a resist, or irradiating only a predetermined portion with excimer UV light Method and the like.
In the method using the mask material, the mask material may be removed before forming a film after forming a region having a high exposed active hydrogen density, or the mask material may be removed by a film forming step. And may be removed after film formation. If the mask material is removed before the film formation, the functional organic thin film does not adhere to the stain derived from the mask material, so that a cleaner film can be obtained.If the mask material is removed after the film formation, the film is not formed. Part of the substrate surface becomes clean. Therefore, the timing of removing the mask material can be arbitrarily selected according to the subsequent use of the base material after film formation.

Examples of the hydrogen atom supply substance include water, ammonia and the like. When water is used as the substance, active hydrogen exists as -OH. On the other hand, when ammonia is used, active hydrogen exists as -NH.

(2) A method in which an organic film is removed from a predetermined portion of the surface of the laminated base material to expose active hydrogen. In this method, an excimer UV light irradiation method, an ultraviolet irradiation method, and the like are applied to a predetermined portion of a surface of a laminated substrate having a water-repellent organic film formed on a surface of a substrate where active hydrogen is exposed under an atmosphere containing oxygen. , A plasma treatment method, a corona treatment method, or the like. A specific description will be given using an ultraviolet irradiation method as an example. In this method, first, by irradiation of ultraviolet rays,
Oxygen is decomposed to produce ozone. When the ozone is further irradiated with ultraviolet rays, the ozone is decomposed to generate active oxygen. Since the active oxygen is an oxygen atom having a strong oxidizing property, the organic film reacts with the active oxygen and volatilizes and is removed as an organic oxide, carbon monoxide, water or the like. As a result, the active hydrogen is exposed only in a predetermined portion of the surface of the laminated base material. Here, the organic film includes an oil attached to the surface of the base material and an organic compound such as human sebum.

As a method of irradiating only predetermined portions with ultraviolet rays, a method of irradiating ultraviolet rays after exposing only predetermined portions by covering portions other than the predetermined portions with a mask material such as a resist, A method of spot irradiation and the like can be given. In the method using the mask material, the mask material may be removed before forming a film after forming a region having a high exposed active hydrogen density, or the mask material may be removed by a film forming step. And may be removed after film formation.

In the film forming step, a compound having a functional group reactive with active hydrogen and a functional functional group is brought into contact with the region having a high exposed active hydrogen density formed as described above. This is a step of covalently fixing to a predetermined portion of the substrate surface. For example, the method can be carried out by preparing a chemisorption solution comprising the above compound and a non-aqueous organic solvent which does not damage the base material, and then bringing the chemisorption solution into contact therewith. Examples of the method of contacting the chemical adsorption liquid include a method of dipping the substrate or the substrate with the mask material in the chemical adsorption liquid, a method of applying the chemical adsorption liquid to the surface of the substrate or the substrate with the mask material, and the like. can give.

The functional groups capable of reacting with active hydrogen in the above compounds include, for example, halogen, alkoxyl groups, isocyanate groups and the like. Examples of the functional functional group in the compound include, for example, a photoisomerizable functional group such as an azo group, a polar functional group such as a carbonyl group and an oxycarbonyl group, an acetylene group, a diacetylene group, a chenylene group, Examples thereof include a polymerizable group such as a pyrrole group that can be bonded by a conjugate bond.

In this step, as described above, for example, after preparing a chemical adsorption solution containing the compound, the substrate is immersed in the adsorption solution, or the adsorption solution is coated on the substrate. The above compound is brought into contact with the substrate surface. Due to this contact, a elimination reaction occurs between the functional group capable of reacting with active hydrogen in the compound and the active hydrogen exposed on the substrate surface, and the molecule group of the compound is fixed to the substrate surface by covalent bond. Is done.

In the present invention, a washing step for removing substances that are not bonded to the substrate can be performed. Specifically, a method of washing away unbound substances with a nonaqueous solvent for washing may be used. In this case, following the washing step, a drying step for removing the non-aqueous solvent is performed.

The functional organic thin film thus formed is formed after a predetermined portion is made into a region where the exposed active hydrogen density is high by the pretreatment step, so that the film has high dimensional accuracy. I have. In addition, since the organic molecules constituting the functional organic thin film are fixed to a predetermined portion of the surface of the base material by a covalent bond, a film having excellent peel resistance and adhesion can be obtained.

(Embodiment 2) In the second method for producing a functional organic thin film according to the present invention, in the pretreatment step, a portion other than a predetermined portion of the base material surface is activated in comparison with Embodiment 1 described above. The difference is that a hydrogen removal treatment is performed.

As the base material, a base material having active hydrogen exposed is used. For example, a hydrophilic single-layer base material or the surface of the single-layer base material or the above-mentioned base material having no active hydrogen exposed is used. And a laminated substrate having a hydrophilic film formed thereon. Examples of the hydrophilic single-layer substrate include a metal substrate having an oxidized surface, a silicon substrate, a silicon nitride substrate, a silica substrate, and a glass substrate. Examples of the hydrophilic film include a metal film having a oxidized surface, a silicon film, a silicon nitride film, a silica film, and a glass film. These have an exposed active hydrogen density of 5 / nm ² or more, which means that the exposed active hydrogen density is high. The shape of the substrate is not particularly limited, but usually, a plate-like substrate (single-layer substrate, laminated substrate) is used.

The pretreatment step is a step of performing an active hydrogen removal treatment on a portion of the substrate surface other than a predetermined portion (a region other than a region where a film is to be formed). The active hydrogen removal treatment is a treatment for changing the state in which active hydrogen is exposed to a state in which active hydrogen is not exposed. Specifically, (1) a chemical treatment is performed on a portion of the base material surface except a predetermined portion. To remove active hydrogen, and (2) a method of removing active hydrogen by performing physical treatment on a portion of the substrate surface other than a predetermined portion.

(1) A method in which a chemical treatment is applied to a portion other than a predetermined portion of the substrate surface. In this method, a compound having a functional group capable of reacting with active hydrogen is brought into contact with a portion other than a predetermined portion of the substrate surface,
In this method, active hydrogen is removed by reacting the functional group with active hydrogen in a portion other than the predetermined portion. According to this method, since the active hydrogen is removed by the elimination reaction between the functional group capable of reacting with the active hydrogen and the active hydrogen in the portion, the active hydrogen in the portion excluding a predetermined portion of the substrate surface is removed. be able to. Therefore, a predetermined portion of the substrate surface is a region where the exposed active hydrogen density is high.

As a method of bringing the compound into contact with a portion other than the predetermined portion, for example, a method of covering the predetermined portion with a mask material such as a resist, exposing only the portion other than the predetermined portion, and then contacting the compound. can give.

Examples of the compound having a functional group capable of reacting with active hydrogen include a compound represented by the following chemical formula (1).

[0085]

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X in the above formula (1) is halogen,
Examples include an alkoxyl group and an isocyanate group. Examples of Y in the above formula (1) include an alkyl group such as a methyl group and an ethyl group. Z in the above formula (1) represents an alkyl group such as a methyl group or an ethyl group;
Examples thereof include a fluorinated alkyl group in which part or all of the hydrogen atoms that constitute the alkyl group are substituted with fluorine atoms.
Note that Z is a functional group that stands in a direction away from the substrate.

Among the above compounds, compounds represented by the following chemical formulas (2) to (7) are preferred because they do not impair the functionality of the functional organic thin film and have good peel resistance. It is.

[0088]

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(2) A method in which a physical treatment is applied to a portion other than a predetermined portion of the substrate surface. In this method, active hydrogen exposed on the substrate surface is removed by breaking a covalent bond. Specifically,
First, a predetermined portion of the substrate surface is covered with a mask material such as a resist, and the exposed substrate surface is irradiated with ultraviolet light or the like in a vacuum. As a result, the covalent bond that has bound the active hydrogen to the substrate is broken, and the active hydrogen is removed. Then, by removing the mask material, a predetermined portion of the substrate surface becomes a region where the exposed active hydrogen density is high.

The method for manufacturing a functional organic thin film described in the first and second embodiments is applicable to a film that is fixed to a base material by a covalent bond, as a contamination prevention film, a liquid crystal alignment film, and a conductive film. It can be applied to various uses such as an insulating film and a conductivity changing film.

[0091]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an organic electronic device having a conductivity changing film will be specifically described with reference to the drawings.

(Embodiment 1) A description will be given based on FIGS. FIG. 1 to FIG. 6 are schematic explanatory views for explaining each step of a method for manufacturing a two-terminal organic electronic device using a substrate having no active hydrogen exposed on the surface. FIG.
FIG. 2 is a schematic cross-sectional view for explaining a state in which this device is switching with light.

First, as shown in FIGS. 1A and 1B,
An acrylic resin transparent substrate (exposed active hydrogen density is approximately 0) 1 which is a surface insulating substrate having no exposed active hydrogen on its surface is prepared, and a photoresist is applied to the surface of the substrate 1 and exposed and developed to form an opening. 2 (opening area: 600 μm per piece
² ) A resist pattern 3 was formed in a state where the resist pattern 3 was arranged so as to be spaced apart in the vertical and horizontal directions.

Then, as shown in FIG. 2, the substrate 1 on which the pattern 3 has been formed is irradiated with excimer UV light (KrF excimer laser) 4 under the condition of a humidity of 50%, thereby obtaining oxygen in the air. Was ozonized and the surface of the substrate exposed from the opening 2 was oxidized extremely thinly. At this time, it reacts with the moisture in the air, and a large number of hydroxyl groups (-OH) are formed on the surface.
Was formed in an exposed region 5. After that, the resist pattern 3 was removed.

On the other hand, an acetylene group (—C≡C—), which forms a conductive network through a conjugate bond by polymerization, an azo group (—N = N—), which is a photoisomerizable functional group, A compound having a chlorosilyl group (—SiCl), which is a functional group capable of reacting with hydrogen, represented by the following chemical formula (8) is diluted to 1% by mass with a dehydrated dimethylsilicone-based organic solvent, and then chemically adsorbed. Was prepared.

[0096]

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Next, the substrate 1 on which the region 5 has been formed is immersed in the chemical adsorption solution prepared as described above, and subjected to a dehydrochlorination reaction with the hydroxyl group (active hydrogen) in the region 5 and then washed with ethanol. Then, a monomolecular film 6 fixed by a covalent bond was formed on the surface of the substrate 1 (see FIG. 3). The monomolecular film 6 was fixed to the surface of the substrate 1 by a covalent bond as shown in FIG.

Subsequently, the acetylene groups in the monomolecular film 6 were polymerized in a Freon solvent using a Ziegler-Natta catalyst to form a polyacetylene-type conductive network 7 as shown in FIG.

Thereafter, as shown in FIG. 6, a nickel thin film is formed on the entire surface of the substrate 1 by vapor deposition, and the first film having a gap distance of 10 μm, a length of 30 μm and a thickness t ₁ of 0.1 μm is formed by photolithography. The electrode 8 and the second electrode 9 were formed by etching. Thus, a two-terminal organic electronic device including the first electrode 8, the second electrode 9, and the small-area conductivity changing film 10 for electrically connecting both electrodes was manufactured.

The device thus obtained is shown in FIG.
As shown in (2), when a voltage of several volts is applied between the first electrode 8 and the second electrode 9 and actually evaluated, since the two electrodes are connected by the polyacetylene-type conductive network 7,
A current of several nanoamperes (about 2 nA at 1 V) flowed. However, since the conductivity changing film 10 was irradiated with visible light before the evaluation, the azo group was of a trans type. Next, when the conductivity changing film 10 was continuously irradiated with the ultraviolet rays 11, the azo group in the film 10 was changed from the trans type to the cis type, and the current value became approximately 0 amperes. After that, when visible light 12 was applied, the azo group was changed from cis type to trans type, and the original conductivity was reproduced.

The reason why the above behavior is adopted is considered as follows. That is, the decrease in conductivity is due to the photoisomerization (transformation from trans-form to cis-form) of the azo group distorting the molecular orientation in the conductivity change film and decreasing the degree of conjugation of the polyacetylene-type conjugate bond. it is conceivable that. It is considered that the conductivity was restored because the azo group returned to the trans-form, the strain of the molecular orientation in the conductivity changing film was restored, and the degree of conjugation was restored.

As described above, the two-terminal organic electronic device of the first embodiment emits two types of light having different wavelengths,
The current between the electrodes could be switched by controlling the degree of conjugation of the conjugate bond in the film.

[Other Matters Related to Example 1] In Example 1, the compound represented by the chemical formula (8) was used, but the device of Example 1 is not limited to this. . With the configuration of the present device, a compound represented by the following general formula (9) is suitably used from the viewpoint of the conductivity of the conductive network and the like.

[0104]

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As A in the above formula (9), an acetylene group, a diacetylene group, a chenylene group, a pyrrole group and the like are preferable from the viewpoint of the conductivity of the conductive network.

As B in the above formula (9), a cis-trans type photoisomerizable functional group such as an azo group is preferable.

As D in the above formula (9), a halosilyl group, an isocyanate group, an alkoxysilyl group and the like are preferable from the viewpoint of reactivity. Further, as E in the above formula (9), an alkyl group such as a methyl group and an ethyl group, a hydrogen atom, a methoxy group, an ethoxy group and the like are used. M and n in the above formula (9) are such that m + n is 10 or more and 20 or more.
It is particularly preferable if it is within the following range.

Among the compounds represented by the above formula (9), the compounds represented by the following formulas (10) to (13) are preferable.

[0109]

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Further, in Example 1, the catalytic polymerization method was employed for forming the conductive network. However, the present device is not limited to this method. It has been confirmed that a conductive network can be formed even by employing a polymerization method of irradiating an energy beam such as a line.

Further, it has been confirmed that a conjugated system such as a polydiacetylene type, a polyacene type, a polypyrrole type, and a polychenylene type can be used as the conductive network in addition to the polyacetylene type conjugated system. In the case of the catalytic polymerization method, it has been confirmed that a pyrrole group, a chenylene group, and a diacetylene group were suitable as the polymerizable group in addition to the acetylene group. In the case of the electrolytic polymerization method, it has been confirmed that a pyrrole group and a chenylene group were suitable. Also, in the case of a polymerization method using energy beam irradiation, it has been confirmed that acetylene groups and diacetylene groups were suitable.

In Example 1, a polyacetylene-type conjugated system is used for the conductive network. However, if the degree of polymerization of the acetylene group is low, the electric resistance tends to increase.
In order to increase the on-state current, a dopant substance having a charge-transferring functional group (for example, a halogen gas or Lewis acid as an acceptor molecule and an alkali metal or ammonium salt as a donor molecule) may be used.
Incidentally, it was confirmed that when iodine was doped into the above-mentioned conductivity changing film, a current of 0.2 mA flowed when a voltage of 1 V was applied.

In the device configuration of the first embodiment,
When a larger on-current is required, it is preferable to reduce the distance between the electrodes or increase the electrode width. When a larger on-current is required, it is preferable to accumulate the monomolecular film to form a monomolecular accumulated film-like conductivity change film.

It has been confirmed that a Langmuir-Blodgett method other than the chemisorption method could be used for producing a monomolecular film or a monomolecular cumulative film.

When the first electrode and the second electrode are formed before the formation of the conductive network, both electrodes may be used for the electrolytic polymerization method when forming the conductive network. By the way, when a compound having an electropolymerizable functional group such as a pyrrole group or a chenylene group is used as a compound used for forming the conductivity changing film, a monomolecular film or a monomolecular cumulative film made of this compound is formed. It has been confirmed that when a voltage is applied between both electrodes after forming the first electrode and the second electrode, the electropolymerizable functional group is polymerized to form a conductive network.

Further, a conductivity changing film in the form of a monomolecular cumulative film may be formed by using the first electrode, the second electrode, and the external electrode. Incidentally, after forming a monomolecular film having a pyrrole group or a chenylene group, a first electrode, and a second electrode on a substrate, a compound having a functional group that photoisomerizes with a pyrrole group or a chenylene group is dissolved. Immersed in an organic solvent, and applying a first voltage between the first electrode and the second electrode, further contacting the first or second electrode with the organic solvent, and contacting the monomolecular film. By applying a second voltage between the first electrode and the external electrode disposed above the
It was confirmed that a film was formed on the monomolecular film, and that a conductive network was formed on each of the monomolecular film and the film. In this case, the device has a multi-stage conductive network.

Further, a monomolecular film composed of an organic molecule group having a pyrrole group or a chenylene group, a first electrode and a second electrode are formed on a substrate, and the pyrrole group or the chenylene group in the monomolecular film is polymerized. After forming a monolayer-shaped conductivity changing film having a conductive network formed by the reaction, immersed in an organic solvent in which a compound having a pyrrole group or a chenylene group and a functional group that photoisomerizes is dissolved, and A first voltage is applied between the first electrode and the second electrode, and the first electrode or the second electrode is in contact with the organic solvent and is disposed above the monolayer-shaped conductivity changing film. It was confirmed that a second voltage was applied between the film and the external electrode to form a film on the above-described monomolecular layer-shaped conductivity change film, and that a conductive network was formed on the film. In this case, the device has a multi-stage conductive network.

(Embodiment 2) A description will be given with reference to FIGS. FIGS. 8 to 11 are schematic diagrams for explaining each step of a method for manufacturing a three-terminal organic electronic device using a substrate on which active hydrogen is not exposed on the surface. Also,
FIG. 12 is a schematic explanatory diagram for explaining a situation in which this device is switching with an electric field.

First, as shown in FIG. 8, a transparent acrylic resin substrate (exposed active hydrogen density is approximately 0) 15 which is a surface insulating substrate having no active hydrogen exposed on the surface is prepared, and aluminum surface is formed on the substrate surface. (Al) was deposited, and the Al third electrode 16 having a length of 15 μm, a width of 40 μm, and a thickness of 0.05 μm was formed by etching using a photolithography method.

Next, as shown in FIG. 9, after forming a resist pattern 17 in the same manner as in the first embodiment, an excimer UV light irradiation (KrF excimer laser) 18 is applied to the substrate 15 on which the pattern 17 has been formed. By doing
Oxygen in the air was ozonized to form an oxide film 19 on the substrate surface exposed from the opening of the pattern 17 and an alumina film 20 on the third electrode surface. At this time, the oxide film 19 and the alumina film 20 were also regions in which a large number of hydroxyl groups were exposed on the surface by reacting with moisture in the air. After that, the resist pattern 17 was removed.

On the other hand, a pyrrole group (C ₄ H ₄ N—), which forms a conductive network through a conjugate bond by polymerization, and an oxycarbonyl group (—OCO—), which is a polar functional group,
And a chlorosilyl group (-SiCl), which is a functional group capable of reacting with active hydrogen on the surface of the substrate, and a compound represented by the following chemical formula (14) in a dimethyl silicone-based organic solvent dehydrated by 1% by mass. To prepare a chemisorption solution.

[0122]

Embedded image

Next, the substrate 15 on which the oxide film 19 and the alumina film 20 have been formed is immersed in the above-prepared adsorbent, and subjected to a dehydrochlorination reaction with the hydroxyl groups (active hydrogen) in the films 19 and 20. By washing with
A monomolecular film 21 fixed by a covalent bond was formed on the substrate surface (see FIG. 10).

Subsequently, as shown in FIG.
A nickel thin film is vapor-deposited on the entire surface, and the distance between the gaps is 10 μm and the length is 30 μm using photolithography.
Then, the first electrode 22 and the second electrode 23 having a thickness t ₂ of 0.1 μm were formed by etching. Then, an electric field of about 5 V / cm is applied between the first electrode and the second electrode in acetonitrile, and a conductive network is electrically connected between the first electrode and the second electrode by electrolytic polymerization. Formed. At this time, a conjugate bond is formed in a self-organizing manner along the direction of the electric field.
The electrode and the second electrode are electrically connected by the conductive network.

[0125] Then, BF to the surface of the change in conductance film ^- after doping ions were removed third electrode from the substrate side.
Thus, a three-terminal organic electronic device including the first electrode, the second electrode, a small-area conductivity change film electrically connecting the two electrodes, and the third electrode was manufactured.

The device thus obtained is shown in FIG.
As shown in FIG. 2, when a voltage of 1 V is applied between the first electrode 22 and the second electrode 23 and actually evaluated, the two electrodes are connected by a polypyrrole-type conductive network 24, and BF ^- ions are Since it was doped, a current of about 0.5 mA flowed. Next, when a voltage of 5 V was continuously applied between the first electrode 22 and the third electrode 16, the current between the first electrode 22 and the second electrode 23 became substantially 0 amperes. After that, when the applied voltage of 5 V was returned to 0 V, the original conductivity was reproduced.

The above behavior is considered to be as follows. That is, the decrease in the conductivity between the electrodes is due to the fact that when a voltage is applied between the third electrode and the first electrode, the oxycarbonyl group (-
It is considered that the polarization of OCO-) was advanced and the molecular orientation in the conductivity change film was distorted, and the degree of conjugation of the polypyrrole-type conjugate bond was reduced. It is considered that the conductivity was recovered because the polarization returned to the normal state, the strain of the molecular orientation in the conductivity changing film recovered, and the conjugation degree returned to the original state.

As described above, in the three-terminal organic electronic device of the second embodiment, by applying a voltage between the third electrode and the first electrode, the conjugate degree of the conjugate bond in the film is controlled, and The current between the electrode and the second electrode could be switched.

[Other Matters Related to Example 2] In Example 2, the compound represented by the chemical formula (14) was used, but the device of Example 2 is not limited to this. With the configuration of the present device, a compound represented by the following general formula (15) is suitably used from the viewpoint of the conductivity of the conductive network and the like.

[0130]

Embedded image

As B 'in the above formula (15), a polarizable functional group such as an oxycarbonyl group and a carbonyl group which is polarized by application of an electric field is preferable. It has been confirmed that switching can be performed at an extremely high speed with an oxycarbonyl group. In addition, it has been confirmed that switching can be performed even with a carbonyl group. Note that the above equation (15)
A, D, E, m, and n therein are the same as in the above-described formula (9).

Among the compounds represented by the above formula (15), the compounds represented by the following formulas (16) to (19) are preferable.

[0133]

Embedded image

In Example 2, the electroconductive polymerization method was used to form the conductive network. However, the present device is not limited to this method, but may be a catalytic polymerization method or a method using light, electron beam, X-ray, or the like. It has been confirmed that a conductive network can be formed even by employing a polymerization method in which an energy beam is irradiated.

Further, in addition to the polypyrrole type conjugated system, conjugated systems such as polyacetylene type, polydiacetylene type, polyacene type and polychenylene type can be used as the conductive network, and it was confirmed that the conductivity was high if these conjugated systems were used. are doing. In the case of the electrolytic polymerization method, in addition to the pyrrole group, a phenylene group is preferable as the polymerizable group.In the case of the catalytic polymerization method, in addition to the pyrrole group and the chenylene group, an acetylene group and a diacetylene group are preferable. In the case of the polymerization method using energy beam irradiation, it has been confirmed that acetylene groups and diacetylene groups were suitable.

In the second embodiment, BF 3 ^- ions are used as a substance to be doped. However, the present invention is not limited to this, and another dopant substance may be used. In addition, when the on-state current may be small, the doping with the dopant substance may be omitted. By the way, it was confirmed that a current of about 50 nA flowed by applying a voltage of 1 V when BF 3 ^- ions were not doped in the conductivity changing film.

In the device configuration of the second embodiment,
When a larger ON current is required, the distance between the electrodes can be reduced, the electrode width can be increased,
It is preferable that the monomolecular film is accumulated to form a monomolecular accumulated film-like conductivity change film.

It has been confirmed that a Langmuir-Blodgett method other than the chemisorption method could be used for producing a monomolecular film or a monomolecular cumulative film.

Further, a conductivity changing film in the form of a monomolecular cumulative film may be formed by using the first electrode, the second electrode, and the external electrode. Incidentally, after forming a third electrode, a monomolecular film having a pyrrole group or a chenylene group, a first electrode, and a second electrode on the substrate, a pyrrole group or a chenylene group and a polar functional group are formed. Immersed in an organic solvent having a compound dissolved therein, and applying a first voltage between the first electrode and the second electrode, and further contacting the first electrode or the second electrode with the organic solvent. By applying a second voltage between the monomolecular film and an external electrode disposed above the monomolecular film, a film is formed on the monomolecular film,
It has been confirmed that a conductive network could be formed on the monomolecular film and the coating, respectively. In this case, the device has a multi-stage conductive network.

On the substrate, a third electrode, a monomolecular film comprising a group of organic molecules having a pyrrole group or a chenylene group, a first electrode, and a second electrode are formed. After a pyrrole group or a phenylene group undergoes a polymerization reaction to form a monolayer-shaped conductivity changing film having a conductive network, the film is immersed in an organic solvent in which a compound having a pyrrole group or a phenylene group and a polar functional group is dissolved. And applying a first voltage between the first electrode and the second electrode, further contacting the first electrode or the second electrode with the organic solvent to form the monomolecular conductivity change film. By applying a second voltage between the upper electrode and the external electrode, a film is formed on the monomolecular conductivity change film, and a conductive network can be formed on the film. Checking . In this case, the device has a multi-stage conductive network.

[Other Matters Related to Embodiments 1 and 2]
In Examples 1 and 2, an acrylic resin transparent substrate was used as a surface insulating substrate having no active hydrogen exposed on the surface, but the present invention is not limited to this. For example, a single-layer substrate made of a synthetic resin such as a polycarbonate resin and a polyethersulfone resin, a laminated substrate in which a synthetic resin film is formed on the surface of a metal substrate, and the like can also be used. When using a laminated substrate with an insulating film on which the active hydrogen is not exposed on the surface of a conductive substrate such as a metal substrate, the substrate itself is not charged, and it has been confirmed that the operation stability of the device is improved. I have.

In Examples 1 and 2, the excimer UV light irradiation method was used as the active hydrogen exposure treatment. However, the present invention is not limited to this. For example, an ultraviolet irradiation method, a plasma treatment method, or a corona treatment method may be used. Make sure you can.
That is, it was confirmed that the active hydrogen exposure treatment could be performed by using a conventionally known excimer UV light irradiation device, UV ozone treatment device, plasma oxidation treatment device, and corona treatment device.

Further, in both Examples 1 and 2, the monomolecular film was formed after the resist pattern was removed, but it was confirmed that the film could be formed even before the resist pattern was removed.

It has been confirmed that, in the film forming step, the use of a chemically adsorbed solution in which a silane-based chemically adsorbed substance is dissolved in a non-aqueous organic solvent enables efficient and clean film formation. In addition, it has been confirmed that a cleaner film can be formed by washing with a non-aqueous organic solvent that does not damage the acrylic resin transparent substrate.

(Embodiment 3) A description will be given with reference to FIGS. FIG. 13 to FIG. 16 are schematic explanatory views for explaining each step of a method for manufacturing a two-terminal organic electronic device using a substrate having active hydrogen exposed on the surface.

First, as shown in FIG. 13A, a transparent glass substrate 30, which is a surface insulating substrate having active hydrogen exposed on the surface, is prepared, and a photoresist is applied to the surface of the substrate 30 and exposed and developed. , A resist pattern 31 in which resist portions are arranged in a state of being spaced apart in the vertical and horizontal directions
Was formed.

Next, as shown in FIG.
The substrate 30 on which the pattern 31 has been formed is used for removing active hydrogen.
Methyltrichlorosilane (CH_ThreeSi
Cl _Three) To dehydrated dimethyl silicone organic solvent
By immersing in the dissolved chemisorption solution, the substrate
The active hydrogen exposed on the surface is removed, and the surface is further etched with ethanol.
After washing with methyl chloride,
A molecular film 32 was formed. Then, the resist pattern
By removing 31, a predetermined portion of the substrate surface becomes
A substrate having a number 33 of exposed hydroxyl groups was prepared.
Was. The exposed active hydrogen density on the surface of the monomolecular film 32 is substantially
Is always 0.

Next, a monomolecular film made of the compound represented by the chemical formula (8) was formed in the same manner as in Example 1 using the substrate prepared as described above (see FIG. 14). After forming the first electrode 35 and the second electrode 36 (see FIG. 15), a polymerizable group in the monomolecular film 34 is polymerized so as to electrically connect the two electrodes, thereby providing a conductive network. A conductivity changing film was formed. Thus, a two-terminal organic electronic device was manufactured.

When the thus obtained device was actually evaluated by applying a voltage of several volts between the first electrode and the second electrode in the same manner as in Example 1, a polyacetylene type Since they were connected by a conductive network, a current of several nanoamperes (about 2 nA at 1 V) flowed (see FIG. 6). However, since the visible light was irradiated to the conductivity changing film before the evaluation, the azo group was of a trans type. Next, when the conductivity changing film is continuously irradiated with ultraviolet rays 11,
The azo group in the film changed from the trans type to the cis type, and the current value became approximately 0 amperes. After that, visible light 1
Upon irradiation with 2, the azo group was transferred from the cis type to the trans type, and the original conductivity was reproduced.

As described above, the two-terminal organic electronic device of the third embodiment emits two types of light having different wavelengths,
The current between the electrodes could be switched by controlling the degree of conjugation of the conjugate bond in the film.

Embodiment 4 Embodiment 4 is described with reference to FIGS.
This will be described with reference to FIG. FIG. 16 to FIG. 19 are schematic explanatory diagrams for explaining each step of a method for manufacturing a three-terminal organic electronic device using a substrate having active hydrogen exposed on the surface.

First, as shown in FIG. 16, a transparent glass substrate 41 which is a surface insulating substrate having active hydrogen exposed on the surface is provided.
Is prepared, aluminum (Al) is vapor-deposited on the surface of the substrate, and a third electrode 42 made of Al having a length of 15 μm, a width of 40 μm and a thickness of 0.05 μm is formed by photolithography.
Was formed by etching. After that, the surface of the third electrode 42 was spontaneously oxidized by being left in the air for a while.

Next, as shown in FIG.
A resist was applied to the surface of the substrate 41 so as to cover the electrode 42, and was exposed and developed to form a resist pattern 43 in which the resist portions were arranged so as to be separated in the vertical and horizontal directions.

Next, as shown in FIG.
The substrate 41 on which the pattern 43 has been formed is used for removing active hydrogen.
Methyltrichlorosilane (CH_ThreeSi
Cl _Three) To dehydrated dimethyl silicone organic solvent
By immersing in the dissolved chemisorption solution, the substrate
The active hydrogen exposed on the surface is removed, and the surface is further etched with ethanol.
After washing with methyl chloride,
After forming the molecular film 44, the resist pattern 43 is
By removing, a predetermined part of the substrate surface is
A substrate was formed in a region 45 where the acid groups were exposed. What
Note that a natural oxide film is formed on the surface of the third electrode 42.
And active hydrogen was exposed. Also, simply
The exposed active hydrogen density on the surface of the molecular film 44 is substantially 0.
You.

Then, using the above substrate, a monomolecular film 46 made of the compound represented by the chemical formula (14) was formed in the same manner as in Example 2 (see FIG. 18). After forming the two electrodes 48 (see FIG. 19),
The polymerizable groups in the monomolecular film 46 were polymerized so as to electrically connect the two electrodes to form a conductivity changing film having a conductive network, and the surface thereof was doped with BF 3 ^- ions. Thus, a three-terminal organic electronic device was manufactured.

When the thus obtained device was actually evaluated by applying a voltage of 1 V between the first electrode and the second electrode in the same manner as in Example 2, a polypyrrole-type conductive material was found between the two electrodes. Since they were connected by a network and were doped with BF ^- ions, a current of about 0.5 mA flowed (see Fig. 12). Next, when a voltage of 5 V was continuously applied between the first electrode and the third electrode, the current between the first electrode and the second electrode became approximately 0 amperes. And then,
When the applied voltage of 5 V was returned to 0 V, the original conductivity was reproduced.

As described above, in the three-terminal organic electronic device according to the fourth embodiment, by applying a voltage to the third electrode, the degree of conjugation of the conjugate bond in the film is controlled, and the first electrode and the second electrode are connected to each other. Could switch the current between them.

[Other Items Related to Embodiments 3 and 4]
In Examples 3 and 4, a transparent glass substrate was used as a surface insulating substrate having active hydrogen exposed on the surface.
It is not limited to this. A single-layer substrate having an oxidized surface and exhibiting insulating properties, a laminated substrate having an oxidized insulating film formed on the surface of various substrates, or the like can also be used. When a laminated substrate in which an insulating film in which active hydrogen is exposed is formed on the surface of a conductive substrate such as a metal substrate, the substrate itself is not charged, so that the operation stability of the device is improved.

In Examples 3 and 4, the method using methyltrichlorosilane was employed as the active hydrogen removal treatment. However, other chemical adsorbed substances [for example, the above-mentioned formulas (2) to (4)] were used.
Active hydrogen can be removed also by using a compound represented by (7).

The devices of Examples 3 and 4 are substantially the same as those of Examples 1 and 2 except that the substrates are different. The same can be said about the same. Therefore,
The description is omitted.

The organic electronic devices described in Embodiments 1 to 4 can be used as devices for various electronic apparatuses. Hereinafter, a case where the organic electronic device is used as a switch element in a display device will be described based on examples.

(Example 5) First, in the same manner as in Example 2, a plurality of organic electronic devices were arranged and arranged on the surface of an acrylic substrate as operation switches for liquid crystal, and an alignment film was formed on the surface. A TFT array substrate was manufactured. On the other hand, a plurality of color elements were arranged and arranged in a matrix on the substrate surface by a conventionally known method, and an alignment film was formed on the surface. Next, a pattern is formed on the alignment film surface of the TFT array substrate using a screen printing method except for a portion serving as a liquid crystal injection port, and then precured so that the alignment film surfaces of the color filter substrate face each other. Then, the adhesive was pressure-bonded to cure the patterned adhesive, thereby producing an empty cell. Then, a predetermined liquid crystal was vacuum-injected from the liquid crystal injection port and sealed to produce a liquid crystal cell, thereby manufacturing a liquid crystal display device.

The liquid crystal display device obtained as described above does not require substrate heating in the manufacture of a TFT array substrate, and therefore has a glass transition point (Tg) such as an acrylic substrate.
However, the TFT type liquid crystal display device has a sufficiently high image quality even when a substrate having a low point is used.

[0164] It should be noted that 3
Using the terminal organic electronic device, a liquid crystal display device similar to that of Example 5 could be manufactured.

(Example 6) In the same manner as in Example 2, a plurality of three-terminal organic electronic devices were arranged and arranged as operation switches on the surface of an acrylic substrate to produce a TFT array substrate. Thereafter, a pixel electrode connected to the three-terminal organic electronic device is formed using a conventionally known method, and TF is formed.
A light-emitting layer made of a fluorescent substance that emits light when an electric field was applied was formed on the T-array substrate, and a transparent common electrode facing the TFT array substrate was formed on the light-emitting layer, whereby an EL display device could be manufactured.

Further, when forming a light emitting layer, an EL type color display device could be manufactured by forming three types of elements which emit red, blue and green light at predetermined positions, respectively.

[0167] Note that 3 was produced in the same manner as in Example 4.
Even when the terminal organic electronic device was used, an EL display device similar to that of Example 6 could be manufactured.

[0168]

As described above, according to the structure of the present invention, the object of the present invention can be sufficiently achieved.
That is, according to the method for producing a functional organic thin film of the present invention, since a film is formed after a predetermined portion of the substrate surface is exposed to a region having a high active hydrogen density, the functional organic thin film can be accurately formed. it can. Further, by applying this manufacturing method, it is possible to provide an organic electronic device capable of coping with recent high integration, and it is possible to provide a display device using this organic electronic device. In the case of the organic electronic device, a step of processing at a high temperature as in the case of an inorganic electronic device is not required, so that a display device using a resin substrate or the like having excellent flexibility can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view for explaining a method for manufacturing a two-terminal organic electronic device (a pretreatment step) according to Example 1, and FIG. 1A is a perspective view showing a state in which a resist pattern is formed. (B) is a partially enlarged sectional view of (a).

FIG. 2 is a schematic cross-sectional view for explaining a manufacturing method (pre-processing step) of the two-terminal organic electronic device according to the first embodiment, and shows a state of active hydrogen exposure processing.

FIG. 3 is a schematic cross-sectional view for explaining a method for manufacturing a two-terminal organic electronic device (film forming step) according to Example 1.

FIG. 4 is a schematic cross-sectional view in which part A of FIG. 3 is enlarged to a molecular level.

FIG. 5 is a cross-sectional view schematically showing a state in which a conductive network is formed.

FIG. 6 is a schematic cross-sectional view for explaining the method for manufacturing a two-terminal organic electronic device (counter electrode forming step) according to Example 1.

FIG. 7 is a schematic cross-sectional view for explaining a situation where a device manufactured by the method for manufacturing a two-terminal organic electronic device according to Example 1 is switched by light.

FIG. 8 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (electrode forming step) according to Example 2.

FIG. 9 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (pretreatment step) according to Example 2.

FIG. 10 is a schematic cross-sectional view for explaining a method (film forming step) of manufacturing a three-terminal organic electronic device according to Example 2.

FIG. 11 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (counter electrode forming step) according to Example 2.

FIG. 12 is a schematic cross-sectional view for explaining a situation where a device manufactured by the method for manufacturing a three-terminal organic electronic device according to Example 2 is switched by an electric field.

FIG. 13 is a schematic cross-sectional view for explaining a method for manufacturing a two-terminal organic electronic device (pretreatment step) according to Example 3, where (a) is a view showing a state in which a resist pattern is formed. FIG. 4B is a view showing a state in which the resist pattern is removed after the active hydrogen removal treatment.

FIG. 14 is a schematic cross-sectional view for explaining a method (film forming step) of manufacturing a two-terminal organic electronic device according to Example 3.

FIG. 15 is a schematic cross-sectional view for explaining the method for manufacturing a two-terminal organic electronic device (counter electrode forming step) according to Example 3.

FIG. 16 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (electrode forming step) according to Example 4.

FIG. 17 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (pretreatment step) according to Example 4, in which (a) is a view showing a state where a resist pattern is formed; FIG. 4B is a view showing a state in which the resist pattern is removed after the active hydrogen removal treatment.

FIG. 18 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (film forming step) according to Example 4.

FIG. 19 is a schematic cross-sectional view for explaining the method for manufacturing a three-terminal organic electronic device (counter electrode forming step) according to Example 4.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Acrylic resin transparent substrate 2 Opening 3 Resist pattern 4 Excimer UV light irradiation 5 The area | region where many hydroxyl groups were exposed 6 Monomolecular film before it became a conductivity change film 7 Polyacetylene type conductive network 8 1st electrode 9 2nd electrode DESCRIPTION OF SYMBOLS 10 Conductivity change film 11 Ultraviolet light condensed for switching 12 Visible light condensed for switching 15 Acrylic resin transparent substrate 16 Third electrode 17 Resist pattern 18 Excimer UV light irradiation 19 Oxide film 20 Alumina film 21 Conduction Monomolecular film before becoming rate change film 22 First electrode 23 Second electrode 24 Polypyrrole-type conductive network 30 Transparent glass substrate 31 Resist pattern 32 Monomolecular film for removing active hydrogen 33 Region where many hydroxyl groups are exposed 34 Conductivity Monomolecular film before becoming rate changing film 35 First electrode 36 Second electrode 41 Transparent glass substrate 42 Third electrode 43 Resist pattern 44 Monomolecular film for removing active hydrogen 45 Region where many hydroxyl groups are exposed 46 Monomolecular film before becoming conductivity changing film 47 First electrode 48 Second electrode

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) H01L 29/786 H05B 33/12 B H05B 33/10 H01L 29/28 33/12 29/78 618B F term ( Reference) 2H092 JA24 KA09 MA02 MA08 MA22 MA30 PA04 PA08 3K007 AB04 AB18 BA06 CA01 DA01 FA01 4K044 AA01 AA12 AA13 AA16 BA21 CA04 CA53 5C094 AA05 AA43 BA03 BA12 BA27 BA43 CA19 CA24 DA13 DB04 EB02 ED03 FA01 DD01 DD01 DD01 DD14 EE03 FF01 GG05 GG32 GG42 GG57 HK02

Claims (62)

[Claims] 1. A method for producing a functional organic thin film fixed to a predetermined portion of a substrate surface by a covalent bond, comprising subjecting a predetermined portion of the substrate surface to an active hydrogen exposure treatment, A pretreatment step of setting the portion to a region where the exposed active hydrogen density is higher than that of the portion excluding the predetermined portion; and having a region capable of reacting with active hydrogen and a functional functional group in the region where the exposed active hydrogen density is high. Contacting the compound to react the compound with active hydrogen in the region,
A film forming step of forming a functional organic thin film which is fixed to a predetermined portion of the substrate surface by covalent bonding. 2. The method for producing a functional organic thin film according to claim 1, wherein a substrate having no active hydrogen exposed on the surface is used as the substrate. 3. The method according to claim 1, wherein the predetermined portion of the surface of the base material is one of
Area is 1000μm ^Two2. The function of claim 1, wherein:
Production method of conductive organic thin film. 4. The functional functional group is at least one functional group selected from the group consisting of a photoresponsive functional group, an electric field responsive functional group, and a polymerizable group capable of bonding via a conjugate bond. The method for producing a functional organic thin film according to claim 1. 5. The functional organic thin film according to claim 1, wherein the functional organic thin film is a monomolecular film in which molecules of the compound are arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are stacked. Manufacturing method. 6. The water-repellent single-layer substrate or the laminated substrate having a water-repellent coating formed on the surface is used as the substrate on which active hydrogen is not exposed on the surface. A method for producing a functional organic thin film. 7. The method for producing a functional organic thin film according to claim 6, wherein a water-repellent synthetic resin substrate is used as the water-repellent single-layer substrate. 8. The method for producing a functional organic thin film according to claim 7, wherein an acrylic resin substrate, a polycarbonate resin substrate, or a polyether sulfone resin substrate is used as the synthetic resin substrate. 9. The method for producing a functional organic thin film according to claim 6, wherein an acrylic resin film, a polycarbonate resin film, or a polyether sulfone resin film is used as the water-repellent film constituting the laminated base material. 10. The method for producing a functional organic thin film according to claim 1, wherein in the pretreatment step, a method of oxidizing a predetermined portion of a substrate surface to impart active hydrogen is used as the active hydrogen exposure treatment. . 11. The method of oxidation includes excimer UV light irradiation, ultraviolet irradiation, plasma treatment, and corona treatment on a predetermined portion of the substrate surface in the presence of oxygen and hydrogen atom supply substances. The method for producing a functional organic thin film according to claim 10, wherein at least one method selected from the group is applied. 12. In the pretreatment step, as the active hydrogen exposure treatment, a laminated base material having a water-repellent organic film formed on the surface of the base material where active hydrogen is exposed is prepared. The method for producing a functional organic thin film according to claim 1, wherein a method of oxidizing a predetermined portion of the surface to remove the organic film and expose active hydrogen is used. 13. The method of oxidization is selected from a group consisting of an excimer UV light irradiation method, an ultraviolet irradiation method, a plasma treatment method, and a corona treatment method on a predetermined portion of the surface of the laminated base material under an atmosphere containing oxygen. The method for producing a functional organic thin film according to claim 12, wherein at least one method is used. 14. Prior to the active hydrogen exposure treatment, a mask is provided on a portion of the substrate surface except for a predetermined portion, and the masked substrate is subjected to an active hydrogen exposure treatment. A method for producing a functional organic thin film according to claim 1. 15. The method for producing a functional organic thin film according to claim 14, wherein the film forming step is performed after removing the mask. 16. The method for producing a functional organic thin film according to claim 14, wherein the film forming step is performed before removing the mask. 17. In the film forming step, the compound having a functional group capable of reacting with active hydrogen and a functional functional group is at least one selected from the group consisting of a halosilyl group, an isocyanate group and an alkoxysilyl group. When a compound having a functional group and a functional functional group is used, and the above compound is brought into contact with the region where the exposed active hydrogen density is high, a chemical adsorption liquid obtained by mixing the compound and a non-aqueous organic solvent is used. The method for producing a functional organic thin film according to claim 1. 18. The method for producing a functional organic thin film according to claim 1, wherein a cleaning step of cleaning the surface of the base material using a non-aqueous organic solvent is performed after passing through the pretreatment step and the film forming step. 19. A method for producing a functional organic thin film which is fixed to a predetermined portion of a substrate surface by a covalent bond, wherein a portion excluding the predetermined portion of the substrate surface is subjected to an active hydrogen removal treatment, A pretreatment step of setting the predetermined portion to a region where the exposed active hydrogen density is higher than that of the portion excluding the predetermined portion; and, in the region where the exposed active hydrogen density is high, a functional group capable of reacting with active hydrogen and a functional functional group. And contacting the compound with the active hydrogen in the region,
A film forming step of forming a functional organic thin film which is fixed to a predetermined portion of the substrate surface by covalent bonding. 20. The method for producing a functional organic thin film according to claim 19, wherein a substrate having active hydrogen exposed on the surface is used as the substrate. 21. The method for producing a functional organic thin film according to claim 19, wherein the predetermined portion of the base material surface has one area of 1000 μm ² or less. 22. The functional group is at least one functional group selected from the group consisting of a photoresponsive functional group, an electric field responsive functional group, and a polymerizable group capable of bonding via a conjugate bond. 20. The method for producing a functional organic thin film according to claim 19. 23. The functional organic thin film according to claim 19, wherein the functional organic thin film is a monomolecular film in which molecules of the compound are arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are stacked. Manufacturing method. 24. The functional material according to claim 20, wherein the substrate having active hydrogen exposed on the surface is a hydrophilic single-layer substrate or a laminated substrate having a hydrophilic film formed on the surface. A method for producing an organic thin film. 25. The functional organic thin film according to claim 24, wherein a metal substrate, a silicon substrate, a silicon nitride substrate, a silica substrate, or a glass substrate having an oxidized surface is used as the single-layer substrate. Production method. 26. The functional organic material according to claim 24, wherein a metal film, a silicon film, a silicon nitride film, a silica film, or a glass film whose surface is oxidized is used as the hydrophilic film constituting the laminated base material. Manufacturing method of thin film. 27. The functional organic material according to claim 19, wherein in the pretreatment step, a method for removing active hydrogen by performing a chemical treatment on a portion excluding a predetermined portion of the substrate surface is used as the active hydrogen removal treatment. Manufacturing method of thin film. 28. As the chemical treatment, a portion having a functional group reactive with active hydrogen is brought into contact with a portion other than a predetermined portion of the substrate surface, and the compound and a portion excluding the predetermined portion of the substrate surface are contacted. 28. The method for producing a functional organic thin film according to claim 27, wherein a method of reacting the active hydrogen with the active hydrogen is used. 29. In the pretreatment step, as the active hydrogen removing treatment, a method of performing a physical treatment on a portion excluding a predetermined portion of a substrate surface to remove active hydrogen is used.
A method for producing a functional organic thin film according to claim 19. 30. A method of irradiating a portion except a predetermined portion of the substrate surface with light in a vacuum to cut off a covalent bond that has bound active hydrogen to the substrate, as the physical treatment. Item 30. The method for producing a functional organic thin film according to Item 29. 31. Prior to the active hydrogen removal treatment,
20. A method in which a mask is applied to a predetermined portion of the base material surface, an active hydrogen removing process is performed on the masked base material, and the mask is removed prior to the film forming step. Method for producing a functional organic thin film. 32. In the film forming step, the compound having a functional group capable of reacting with active hydrogen and a functional functional group is at least one selected from the group consisting of a halosilyl group, an isocyanate group and an alkoxysilyl group. When a compound having a functional group and a functional functional group is used, and the compound is brought into contact with the region where the exposed active hydrogen density is high, a chemical adsorption liquid obtained by mixing the compound and a non-aqueous organic solvent is used. 20. The method for producing a functional organic thin film according to claim 19. 33. The method for producing a functional organic thin film according to claim 19, wherein after the pretreatment step and the film forming step, a cleaning step of cleaning the surface of the base material using a non-aqueous organic solvent is performed. 34. A first electrode formed on a substrate, a second electrode separated from the first electrode, and a first electrode formed on the first electrode.
A conductivity changing film for electrically connecting the electrode and the second electrode, wherein the conductivity changing film is configured such that a part or all of the organic molecule group having a functional group capable of photoisomerization is connected by a conjugate bond. A method of manufacturing a two-terminal organic electronic device, wherein the two-terminal organic electronic device has a conductive network, wherein the conductivity of the conductive network changes according to light irradiated on the conductivity changing film. A pretreatment step of subjecting a predetermined portion of the substrate surface to an active hydrogen exposure treatment to make the predetermined portion a region where the exposed active hydrogen density is higher than a portion excluding the predetermined portion; and Contacting a compound having a functional group capable of reacting with active hydrogen and a functional group capable of photoisomerization with a polymerizable group capable of binding via a conjugate bond, and reacting the compound with active hydrogen in the region, Predetermined part of substrate surface A film forming step of covalently fixing an organic molecule group composed of the compound to the substrate; a polymerization step of forming a conductive network by conjugate bonding of a part or all of the organic molecule group by a polymerization reaction; A method for manufacturing a two-terminal organic electronic device, comprising: a counter electrode forming step of forming a first electrode and a second electrode thereon. 35. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; An electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of an organic molecule group having a polar functional group is connected by a conjugate bond. A method of manufacturing a three-terminal organic electronic device, wherein the three-terminal organic electronic device has a conductive network, wherein the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. An electrode forming step of forming a third electrode on the surface; and performing an active hydrogen exposure process on a predetermined portion of the substrate surface on which the third electrode is formed, so that the predetermined portion is exposed more actively than the portion excluding the predetermined portion. High hydrogen density region Pre-treatment step, the exposed active hydrogen density in a high region, a functional group capable of reacting with active hydrogen and a polar functional group and a compound having a polymerizable group capable of bonding with a conjugate bond, and contacted, Reacting a compound with active hydrogen in the region to form a film forming step of covalently fixing a group of organic molecules made of the compound to a predetermined portion of the substrate surface; A three-terminal organic electronic device, comprising: a polymerization step of forming a conductive network by conjugate bonding by a polymerization reaction; and a counter electrode forming step of forming a first electrode and a second electrode on the substrate. Manufacturing method. 36. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity changing film for electrically connecting the electrode and the second electrode, wherein the conductivity changing film is configured such that a part or all of the organic molecule group having a functional group capable of photoisomerization is connected by a conjugate bond. A method of manufacturing a two-terminal organic electronic device, wherein the two-terminal organic electronic device has a conductive network, wherein the conductivity of the conductive network changes according to light irradiated on the conductivity changing film. A pretreatment step of subjecting a portion of the substrate other than a predetermined portion to an active hydrogen removal treatment to make the predetermined portion a region where the exposed active hydrogen density is higher than the portion excluding the predetermined portion; and a region where the exposed active hydrogen density is high. In contact with a compound having a functional group capable of reacting with active hydrogen and a functional group capable of photoisomerization and a polymerizable group capable of bonding via a conjugate bond, and reacting the compound with active hydrogen in the region, On the substrate surface A film forming step of fixing a group of organic molecules composed of the compound to a fixed portion by a covalent bond; and a polymerization step of forming a conductive network by forming a part or all of the group of organic molecules into a conjugate bond by a polymerization reaction. A method for manufacturing a two-terminal organic electronic device, comprising: a counter electrode forming step of forming a first electrode and a second electrode on a substrate. 37. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; An electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of an organic molecule group having a polar functional group is connected by a conjugate bond. A method of manufacturing a three-terminal organic electronic device, wherein the three-terminal organic electronic device has a conductive network, wherein the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. An electrode forming step of forming a third electrode on the surface; and performing an active hydrogen removal process on a portion of the substrate surface on which the third electrode is formed, except for a predetermined portion, so that the predetermined portion is formed more than the portion excluding the predetermined portion. Exposed active hydrogen density A pre-treatment step to make the active region, the exposed active hydrogen density high region, contact with a compound having a functional group capable of reacting with active hydrogen, a polar functional group and a polymerizable group capable of bonding with a conjugate bond. Reacting the compound with active hydrogen in the region to fix a group of organic molecules comprising the compound to a predetermined portion of the surface of the substrate by covalent bonding. A three-terminal comprising: a polymerization step of forming a conductive network by forming a conductive network by conjugate bonding by polymerization reaction; and a counter electrode forming step of forming a first electrode and a second electrode on the substrate. A method for manufacturing an organic electronic device. 38. The method of manufacturing an organic electronic device according to claim 34, wherein a surface insulating substrate having active hydrogen not exposed on the surface is used as the substrate. Production method. 39. The method for manufacturing an organic electronic device according to claim 36, wherein a surface insulating substrate having active hydrogen exposed on the surface is used as the substrate. . 40. The method for manufacturing an organic electronic device according to claim 34, wherein the conductivity change film is formed by stacking a plurality of monomolecular films arranged in a monomolecular layer. A method for producing an organic electronic device, wherein the method is a monomolecular accumulation film. 41. The method for manufacturing an organic electronic device according to claim 34, wherein a chemical adsorption method or a Langmuir-Blodgett method is applied in the film forming step. Manufacturing method of electronic device. 42. The method of manufacturing an organic electronic device according to claim 41, wherein a silane-based chemisorbing substance is used in the film forming step to which the chemisorption method is applied. Method. 43. The method for producing a two-terminal organic electronic device according to claim 34, wherein an azo group is used as the photoisomerizable functional group. . 44. The method for producing a three-terminal organic electronic device according to claim 35, wherein a carbonyl group and / or an oxycarbonyl group is used as the polar functional group. Manufacturing method of electronic device. 45. The method for producing an organic electronic device according to claim 34, wherein the polymerizable group capable of bonding by a conjugate bond is a catalytic polymerizable functional group or an electrolytic polymerizable functional group. A method for producing an organic electronic device, comprising using at least one kind of functional group selected from the group consisting of a group and a functional group polymerized by energy beam irradiation. 46. The method for producing an organic electronic device according to claim 45, wherein the functional group capable of being polymerized by the catalyst is at least one selected from the group consisting of a pyrrole group, a chenylene group, an acetylene group, and a diacetylene group. A method for producing an organic electronic device, comprising using a functional group. 47. The method for manufacturing an organic electronic device according to claim 45, wherein a pyrrole group and / or a chenylene group are used as the electrolytically polymerizable functional group. 48. The method of manufacturing an organic electronic device according to claim 45, wherein an acetylene group and / or a diacetylene group is used as the functional group polymerized by the energy beam irradiation. Method. 49. The method for manufacturing an organic electronic device according to claim 34, wherein the polymerizable group capable of bonding by a conjugate bond is an electropolymerizable functional group. Prior to the step, the counter electrode forming step is performed, and in the polymerization step, a voltage is applied between the first electrode and the second electrode, whereby the electropolymerizable functional groups are subjected to an electrolytic polymerization reaction. Forming a conductive network. 50. The method for producing a two-terminal organic electronic device according to claim 34, wherein the polymerizable group capable of bonding via a conjugated bond is a pyrrole group and / or a phenylene group, which is an electropolymerizable functional group. In some cases, after the pretreatment step, the film formation step, the polymerization step, and the counter electrode formation step, after forming a monomolecular layer-shaped conductivity change film, a substrate on which the conductivity change film is formed is formed. Immersed in an organic solvent in which a compound having a pyrrole group and / or a chenylene group and a photoisomerizable functional group is dissolved, and between the first electrode and the second electrode, and between the first electrode and the second electrode. A voltage is applied between each of the two electrodes and an external electrode that is in contact with the organic solvent and is disposed above the conductivity change film, and a voltage is applied to the surface of the monomolecular conductivity change film,
A method for producing a two-terminal organic electronic device, comprising: performing a step of forming a coating film in which a conductive network is formed by conjugate bonding of some or all of the molecular groups of the compound. 51. The method for producing a two-terminal organic electronic device according to claim 34, wherein the polymerizable group capable of bonding through a conjugated bond is a pyrrole group and / or a phenylene group, which are an electropolymerizable functional group. In some cases, after forming a monomolecular film before polymerization through the pretreatment step, the film forming step and the counter electrode forming step, the substrate on which the monomolecular film is formed is treated with a pyrrole group or / And immersed in an organic solvent in which a compound having a phenylene group and a photoisomerizable functional group is dissolved, and between the first electrode and the second electrode, and between the first electrode or the second electrode and the organic A voltage is applied between each of the external electrodes placed in contact with the solvent and above the monomolecular film, and the electropolymerizable functional groups in the monomolecular film are conjugated to each other by a polymerization reaction to conduct the electric conduction. Net Forming a film formed by forming a conductive network on the surface of the monomolecular film, in which some or all of the molecular groups of the compound are conjugated and bonded to the surface of the monomolecular film. A method for manufacturing a two-terminal organic electronic device. 52. The method for producing a three-terminal organic electronic device according to claim 35, wherein the polymerizable group capable of bonding through a conjugated bond is a pyrrole group and / or a phenylene group, which is an electropolymerizable functional group. In some cases, through the electrode forming step, the pretreatment step, the film forming step, the polymerization step, and the counter electrode forming step, after forming a monolayer-shaped conductivity changing film, the conductivity changing film is formed. Is immersed in an organic solvent in which a compound having a pyrrole group and / or a chenylene group and a polar functional group is dissolved, and between the first electrode and the second electrode, and between the first electrode and the first electrode. Between an electrode or a second electrode and an external electrode that is in contact with the organic solvent and is disposed above the conductivity changing film,
Applying a voltage, respectively, performing a step of forming a conductive film formed on the surface of the monomolecular conductivity change film by forming a conductive network in which some or all of the molecule groups of the compound are conjugated. A method for producing a three-terminal organic electronic device, comprising: 53. The method for producing a three-terminal organic electronic device according to claim 35 or 37, wherein the polymerizable group capable of bonding through a conjugate bond is a pyrrole group or / and a phenylene group, which is an electropolymerizable functional group. In some cases, through the electrode forming step, a pretreatment step, a film forming step and a counter electrode forming step, after forming a monomolecular film before polymerization, a substrate on which the monomolecular film is formed, Immersed in an organic solvent in which a compound having a pyrrole group and / or a chenylene group and a polar functional group is dissolved, and between the first electrode and the second electrode, and between the first electrode and the second electrode And a voltage between the external electrodes that are in contact with the organic solvent and are disposed above the conductivity changing film, and conjugate the electropolymerizable functional groups in the monomolecular film by a polymerization reaction. Joined Forming a conductive network on the surface of the monomolecular film by forming a conductive network in which a part or all of the molecular groups of the compound are conjugated to form a conductive network. A method for manufacturing a three-terminal organic electronic device. 54. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; And an electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of the organic molecules having a polar functional group are connected by a conjugate bond. A liquid crystal display device using a three-terminal organic electronic device as a switch element, wherein the three-terminal organic electronic device has a conductive network formed in accordance with an electric field applied to the conductivity changing film. A method of manufacturing an array substrate in which a plurality of the switch elements are arranged in a matrix on a first substrate, and a first alignment film is formed on a surface thereof; 2 substrate Forming a color filter substrate in which a plurality of color elements are arranged in a matrix and a second alignment film is formed on the surface of the plurality of color elements; and the first alignment film and the second alignment film. Facing the array substrate and the color filter substrate at a predetermined interval on the inside, filling a liquid crystal between both substrates and sealing the two substrates, and the step of manufacturing the array substrate comprises: An electrode forming step of forming third electrodes in a matrix on the surface of the substrate, and performing an active hydrogen exposure treatment on a predetermined portion of the substrate surface on which the third electrode is formed, and converting the predetermined portion to a predetermined portion A pre-treatment step of making the exposed active hydrogen density higher than that of the portion excluding the above; With polymerizable group A film forming step of causing the compound to react with the active hydrogen in the region by contacting the compound with the active hydrogen in the region to fix a group of organic molecules comprising the compound to a predetermined portion of the substrate surface by covalent bonding; A polymerization step of forming a conductive network by conjugate bonding of a part or all of them by a polymerization reaction; a counter electrode formation step of forming a first electrode and a second electrode on the first substrate; A liquid crystal display comprising: an alignment film forming step of forming a first alignment film on a substrate on which a first electrode, a second electrode, a third electrode, and a conductivity changing film are formed. Device manufacturing method. 55. The method for manufacturing a liquid crystal display device according to claim 54, wherein a surface insulating substrate whose surface does not have active hydrogen exposed is used as the first substrate. Manufacturing method. 56. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; And an electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of the organic molecules having a polar functional group are connected by a conjugate bond. A liquid crystal display device using a three-terminal organic electronic device as a switch element, wherein the three-terminal organic electronic device has a conductive network formed in accordance with an electric field applied to the conductivity changing film. A method of manufacturing an array substrate having a plurality of switch elements arranged in a matrix on a first substrate and having a first alignment film formed on a surface thereof; On the board Producing a color filter substrate in which a number of color elements are arranged in a matrix and a second alignment film is formed on the surface thereof, and the first alignment film and the second alignment film are arranged inside. Facing the array substrate and the color filter substrate at a predetermined interval, and filling and sealing a liquid crystal between the two substrates, and the step of manufacturing the array substrate comprises: An electrode forming step of forming a third electrode in a matrix on the surface of the substrate; and performing an active hydrogen removal treatment on a portion except for a predetermined portion of the substrate surface on which the third electrode is formed, thereby forming a predetermined portion into the predetermined portion. A pre-treatment step of making the exposed active hydrogen density higher than that of the portion excluding the above, and a functional group capable of reacting with active hydrogen and a polar functional group can be bonded to the area having a higher exposed active hydrogen density by a conjugate bond. With a polymerizable group A film forming step of causing the compound to react with the active hydrogen in the region by contacting the compound to form a group of organic molecules comprising the compound by a covalent bond on a predetermined portion of the substrate surface; A polymerization step of forming a conductive network by conjugate bonding of a part or all of them by a polymerization reaction; a counter electrode formation step of forming a first electrode and a second electrode on the first substrate; A step of forming an alignment film for forming a first alignment film on a substrate on which the first electrode, the second electrode, the third electrode, and the conductivity change film are formed, A method for manufacturing a display device. 57. The method of manufacturing a liquid crystal display device according to claim 56, wherein a surface insulating substrate having active hydrogen exposed on the surface is used as the first substrate. Method. 58. A first electrode formed on a substrate, a second electrode separated from the first electrode, and the first electrode.
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; And an electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of the organic molecules having a polar functional group are connected by a conjugate bond. An electroluminescence type using a three-terminal organic electronic device as a switching element, wherein the electroconductive network has a conductive network formed as a switching element, and the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. A method for manufacturing a display device, comprising: a step of producing an array substrate in which a plurality of the switch elements are arranged in a matrix on a substrate; and a step of applying a voltage to the array substrate to emit light. Forming a common electrode film on the light emitting layer; and forming a third electrode on the surface of the substrate in the form of a matrix. Forming an active hydrogen on a predetermined portion of the substrate surface on which the third electrode is formed, and exposing the predetermined portion to a region having a higher exposed active hydrogen density than a portion excluding the predetermined portion. A pretreatment step to make the exposed active hydrogen density high region contact a compound having a functional group capable of reacting with active hydrogen and a polymerizable group capable of bonding with a polar functional group and a conjugate bond, Reacting the compound with active hydrogen in the region to fix a group of organic molecules comprising the compound to a predetermined portion of the substrate surface by covalent bonding; and a part or all of the group of organic molecules The polymerization reaction An electroluminescence type display, comprising: a polymerization step of forming a conductive network by conjugate bonding with each other, and a counter electrode forming step of forming a first electrode and a second electrode on the substrate. Device manufacturing method. 59. The method of manufacturing an electroluminescent display device according to claim 58, wherein a surface insulating substrate having no active hydrogen exposed on the surface is used as the substrate. Device manufacturing method. 60. A first electrode formed on a substrate, a second electrode separated from the first electrode, and
A conductivity change film that electrically connects the electrode and the second electrode;
A third electrode sandwiched between the substrate and the conductivity change film and insulated from the third electrode, wherein the third electrode applies a voltage between the first electrode and the second electrode; And an electrode for controlling an electric field applied to the conductivity changing film, and the conductivity changing film is configured such that a part or all of the organic molecules having a polar functional group are connected by a conjugate bond. An electroluminescence type using a three-terminal organic electronic device as a switching element, wherein the electroconductive network has a conductive network formed as a switching element, and the conductivity of the conductive network changes according to an electric field applied to the conductivity changing film. A method for manufacturing a display device, comprising: a step of manufacturing an array substrate in which a plurality of the switch elements are arranged in a matrix on a substrate; and a step of applying a voltage to the array substrate to emit light. Forming a common electrode film on the light emitting layer; and forming a third electrode on the surface of the substrate in a matrix. Forming an active hydrogen removal process on a portion of the substrate surface excluding a predetermined portion on which the third electrode is formed, so that the predetermined portion has an exposed active hydrogen density higher than that of the portion excluding the predetermined portion. A pretreatment step to make the region a high region, and contacting the region having a high active hydrogen density with a compound having a functional group capable of reacting with active hydrogen and a polymerizable group capable of bonding with a polar functional group and a conjugate bond. Reacting the compound with active hydrogen in the region to fix a group of organic molecules comprising the compound to a predetermined portion of the surface of the substrate by covalent bonding. Or all Electroluminescence, comprising: a polymerization step of forming a conductive network by conjugate bonding by a polymerization reaction; and a counter electrode formation step of forming a first electrode and a second electrode on the substrate. Method for manufacturing a type display device. 61. The method of manufacturing an electroluminescence display device according to claim 60, wherein a surface insulating substrate having active hydrogen exposed on the surface is used as the substrate. Production method. 62. The method of manufacturing an electroluminescent display device according to claim 58, wherein in the step of forming the light emitting layer, three kinds of light emitting substances that emit red, blue, or green light are specified. A method for manufacturing an electroluminescent color display device, wherein the color display is formed at a position indicated by (1).