JP2003231738A - Conductive organic thin film and its production process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive organic thin film containing at least one conjugated bond group selected from a polypyrrolyl group and a polythienylene group, and its production process. <P>SOLUTION: The conductive organic thin film comprises a conductive polymer (34) containing, as the repeating molecular units of the polymer, a terminal bonding group covalently bonded to the surface of a base material (1, 2) containing active hydrogen atoms on its surface, at least one conjugated bond group selected from a polypyrrolyl group and a polythienylene group, and an organic group with no active hydrogen atom, present between the terminal bonding group and the conjugated bond group, wherein the conjugated bond groups are polymerized with the conjugated bond groups of other molecules to form the conductive polymer. The polymerization of the conjugated bond groups is effected by electrolytic oxidation polymerization, catalytic polymerization or actinic radiation polymerization. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive organic thin film and a method for manufacturing the same. More specifically, it relates to a conductive polymer film composed of a monomolecular film or a monomolecular cumulative film formed on the surface of a substrate.

[0002]

2. Description of the Related Art There have been various proposals for organic conductive films. The applicant has already proposed a conductive film containing a conductive conjugated group such as polyacetylene, polydiacetylene, polyacene, polyphenylene, polyphenylene, polypyrrole, and polyaniline (Japanese Patent Laid-Open No. 2 (1
990) -27766, USP 5,008,127, EP-A-0385656, EP-A
-0339677, EP-A-0552637, USP5,270,417, JP-A-5 (199
3) -87559, JP-A-6-1994-242352).

The conventional organic conductive film has a problem that its conductivity is lower than that of metal.

[0004]

In order to solve the above-mentioned conventional problems, the present invention is a conductive organic thin film having higher conductivity than conventional organic conductive films, preferably higher than metal. And a method for producing the same and a 3-pyrrolyl compound used therein.

[0005]

In order to achieve the above-mentioned object, the conductive organic thin film of the present invention is selected from a terminal bonding group covalently bonded to the surface of a base material containing active hydrogen, a polypyrrolyl group and a polyphenylene group. At least one conjugated bond group, and an organic group containing no active hydrogen between the terminal bond group and the conjugated bond group is included in the repeating molecular unit of the polymer, and the conjugated bond group is a conjugated bond group of another molecule. It is characterized in that it is polymerized with to form a conductive polymer.

Next, the method for producing a conductive organic thin film of the present invention comprises a terminal functional group capable of covalently bonding to the surface of a base material containing active hydrogen, and at least one conjugated bond group selected from polypyrrolyl group and polychenylene group. And a compound containing an organic group containing no active hydrogen in the molecule between the terminal bonding group and the conjugated bonding group is brought into contact with the surface of the base material containing active hydrogen on the surface, and a covalent bond is formed by an elimination reaction. An organic thin film is formed by the above, and the conductive polymer is formed by carrying out a conjugated bond between the conjugate bondable groups by at least one polymerization method selected from electrolytic oxidation polymerization, catalytic polymerization and energy beam irradiation polymerization. To do.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the reason why the organic thin film has conductivity is that the molecules constituting the aggregated group of organic molecules are conjugated and polymerized. Here, the conductive organic thin film (hereinafter also referred to as “conductive polymer”) is an assembly of organic molecules bound by a conjugated bond involved in electrical conduction, and is formed of a polymer having a conjugated bond chain (conjugated system). Has been done. The conductive polymer is formed in the direction between the electrodes. The conjugated bond chain polymer is not strictly continuous in one direction, and polymer chains in various directions may be formed.

In the present invention, the conductivity (ρ) of the conductive organic thin film is 1 S / cm or more, preferably 1 × 10 ³ S.
/ Cm or more, more preferably 5.5 × 10 ⁵ S / cm
As described above, the most preferable value is 1 × 10 ⁷ S / cm or more. All the above values are for room temperature (25 ° C.), 60% relative humidity and no dopant.

The portion of the conductive polymer is poly (3-pyrrole) containing no active hydrogen in the N group, and poly (3-pyrrole) containing no active hydrogen in the N group and poly (1-pyrrole). It is preferably a polymer and at least one polymer selected from poly (3-chenylene) or a copolymer thereof. In the case of a copolymer, the monomer residue of the present invention is preferably 50 mol% or more.

In the conductive polymer of the present invention, a thin film obtained by polymerization by electrolytic oxidation polymerization has a particularly high electric conductivity.

The terminal bonding group is siloxane (--SiO 2).
-) And at least one bond selected from SiN-bonds.

The terminal bonding group is formed by at least one elimination reaction selected from dehydrochlorination reaction, dealcoholization reaction and deisocyanation reaction. For example, when the functional group at the terminal of the molecule is -SiCl ₃ , -Si (OR) ₃ (where R is an alkyl group having 1-3 carbon atoms), or -Si (NCO) ₃ , the surface of the substrate or the surface of the substrate is -OH group, -CHO group, -on the surface of the formed underlayer
When active hydrogen contained in COOH group, -NH ₂ group,> NH group, etc. is present, dehydrochlorination reaction, dealcoholation reaction or deisocyanate reaction occurs, and chemisorption molecules are formed on the surface of the substrate or on the substrate. Covalently bond to the surface of the underlayer.

The molecular film formed by this method is referred to in the art as a "chemisorption film" or "self assembling film", but in the present invention, it is referred to as "chemisorption film". Call. Moreover, the forming method is called "chemisorption method".

In the present invention, the conductive molecules are preferably oriented. Alignment of molecules is performed by rubbing
It is formed by at least one selected from the gradient liquid removal treatment from the reaction solution after covalently bonding the molecule to the substrate surface by the elimination reaction, the irradiation treatment of the polarized light, and the orientation due to the fluctuation of the molecule in the polymerization step. Is preferred.

The conductive organic thin film is transparent to light having a wavelength in the visible region. This is because the film thickness is on the nanometer level (usually 10 nm or less, 50 nm even with molecular modification).
Below), and the wavelength region of visible light (300 nm to 80 nm).
It is much thinner than 0 nm).

The molecular unit forming the conductive organic thin film is preferably represented by the following formula (A1-5).

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

(In the formulas A1-A3, Z is an ester group (-COO-) or an oxycarbonyl group (-OCO).
-), Carbonyl group (-CO-) and carbonate (-)
OCOO-) group, at least one functional group selected from an azo (-N = N-) group or a chemical bond (-), R is an alkyl group having 1 to 3 carbon atoms, R1, R2, R3 and R4 are hydrogen, An organic group containing an alkyl group having 1 to 10 carbon atoms or an unsaturated group, m and n are integers, and m + n is 2 or more and 25 or less,
Y is oxygen (O) or nitrogen (N), E is hydrogen or an alkyl group having 1-3 carbon atoms, p is an integer of 1, 2, or 3, u is an integer of 1-6, preferably an integer of 1-3. Is. The chemical adsorbent molecule for forming the conductive organic thin film is represented by, for example, the following formula (B1-5).

[0023]

[Chemical 16]

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Chemical 20]

(In the formulas B1-B5, Z is an ester group (-COO-) or an oxycarbonyl group (-OCO).
-), Carbonyl group (-CO-) and carbonate (-)
OCOO-) group, at least one functional group selected from an azo (-N = N-) group or a chemical bond (-), R is an alkyl group having 1 to 3 carbon atoms, R1, R2, R3 and R4 are hydrogen, An organic group containing an alkyl group having 1 to 10 carbon atoms or an unsaturated group, m and n are integers, and m + n is 2 or more and 25 or less,
D is a halogen atom, an isocyanate group and 1-3 carbon atoms
At least one reactive group selected from the alkoxyl groups, E is hydrogen or an alkyl group having 1 to 3 carbon atoms, p is an integer of 1, 2 or 3, and u is an integer of 1-6, preferably 1
-3 is an integer. The compound of the formulas B1-B5 contains a plurality of pyrrole rings or cenyl rings in one molecule, so that a conductive polymer can be formed without making the adsorbed molecules densely present on the surface of the substrate.

In the compounds of the above formulas B1-B5, the case where the terminal is a trichlorosilyl group (-SiCl ₃ ) is preferable because the reactivity with the base material is high.

The monomolecular layer may be laminated to form a monomolecular cumulative film by repeating the monomolecular layer forming step a plurality of times. Particularly, when an unsaturated group such as a vinyl bond is introduced into R1, R2, R3 or R4 of the compound of the formula B1-B5, for example, an energy ray such as an electron beam or an X-ray in an atmosphere containing water. A hydroxyl group (—OH) can be introduced by irradiating with. Also, -COOH can be introduced by immersing in an aqueous solution of potassium permanganate. Other methods include oxygen plasma treatment, UV /
Ozone treatment, corona treatment, or immersion in a mixed solution of concentrated sulfuric acid and potassium dichromate (chromium mixed acid solution treatment)
And so on. By doing so, active hydrogen can be introduced, and thus the monomolecular film can be further cumulatively bonded.

Further, after alternately repeating the monomolecular layer forming step and the tilting (orienting) step, in the conductive polymer forming step, the conductive polymer is formed in each monomolecular layer of the monomolecular cumulative film. Alternatively, the conductive monomolecular cumulative film may be formed by collectively forming.

Further, a conductive monomolecular cumulative film may be formed by repeating a series of steps consisting of the monomolecular layer forming step, the gradient treatment step and the conductive polymer forming step.

As the polymerization method, there is at least one polymerization method selected from electrolytic oxidative polymerization, catalytic polymerization and energy ray irradiation polymerization. Before forming the conductive polymer by the electrolytic oxidation, at least one prepolymerization selected from catalytic polymerization and energy ray irradiation polymerization may be performed.

The energy rays are ultraviolet rays, far ultraviolet rays,
It is preferably at least one selected from X-rays and electron beams.

The energy rays are at least one selected from polarized ultraviolet rays, polarized deep ultraviolet rays, and polarized X-rays, and the inclined alignment treatment and the formation of the conductive polymer may be performed at the same time.

Since the organic molecule contains a polar functional group, the sensitivity to an applied electric field is high and the response speed is high. Therefore, the conductivity of the organic thin film can be changed at high speed. When an electric field is applied, a change in conductivity of the organic thin film is caused by the polar functional group responding to the electric field.
It is considered that this was caused because the influence of the response spread to the structure of the conductive polymer.

It is also possible to further improve the conductivity by incorporating a charge transferable dopant substance into the conductive polymer by doping. As the dopant substance, any dopant substance such as iodine, BF ⁻ ions, alkali metals such as Na and K, and alkaline earth metals such as Ca can be used. Further, it may contain a minor component contained in the solution in the organic film forming step or a dopant substance due to contamination which is inevitably mixed from a glass container or the like.

Since the organic molecules constituting the conductive monomolecular layer are in a fairly well oriented state, the conjugated bond chain of the conductive polymer exists in a specific plane. Therefore, the conductive polymer formed in the monolayer is linearly connected in a predetermined direction. Due to the linearity of the conductive polymer, it has high conductivity anisotropy. Further, the linearity of the conductive polymer means that the respective conjugated bond chains (conjugated system) forming the conductive polymer are arranged substantially in parallel on the same plane in the monomolecular layer. Therefore, the conductive monolayer has a high conductivity,
Moreover, it has uniform conductivity. Further, due to the linearity of the conductive polymer, it has a conjugated bond chain with a high degree of polymerization in a monomolecular layer.

According to another example, it is possible to provide a conductive monomolecular film and a conductive monomolecular accumulated film having extremely good conductivity even when the film thickness is thin.

In the case of a conductive monomolecular cumulative film, since the conductive polymer is formed in each conductive monomolecular layer, the conductivity of the conductive polymer of the monomolecular cumulative film is determined by the layer of the laminated monomolecular film. Depends on the number. Therefore, a conductive organic thin film having a desired conductivity can be provided by changing the number of stacked conductive monomolecular layers. For example, in the case of a conductive cumulative film in which the same conductive monomolecular layer is laminated, the conductivity of the conductive polymer contained therein is almost proportional.

In the conductive monomolecular cumulative film, the tilt angle of the orientation of the organic molecules may be different for each monomolecular layer as long as the directions of the conductive polymers formed in all monomolecular layers are the same. . Further, not all monomolecular layers need to be composed of the same organic molecule. Further, it may be a conductive monomolecular cumulative film composed of different kinds of organic molecules for each conductive monomolecular layer.

Further, in the case of the conductive monomolecular cumulative film, the conductive monomolecular layer closest to the base material is bonded to the base material by a chemical bond, so that the durability is excellent in peeling resistance and the like.

The inclination direction of the organic molecule in the inclination treatment step means the direction of a line segment in which the long axis of the organic molecule is projected on the surface of the base material. Therefore, the angles of inclination with respect to the substrate do not have to be the same.

An aggregate group of organic molecules constituting a monolayer is
In the tilting process, it is possible to accurately tilt in a predetermined direction. Generally, the molecules that make up the monolayer can be oriented. Since it can be oriented with high accuracy, a conductive polymer having directionality can be easily formed in the conductive polymer forming step.

When the oriented organic molecules in the monomolecular layer are conjugated with each other, a conductive polymer having a high degree of polymerization and linearly connected can be formed. In addition, the linearity of the conductive polymer can form a uniform conductive monolayer.

In another example, polarized light having a wavelength in the visible light region is used as the polarized light. According to this example, it is possible to prevent or suppress the peeling of the organic molecules forming the organic thin film and the destruction of the organic thin film due to the destruction of the organic molecules themselves.

According to another example, when an organic thin film is formed on the surface of a substrate that has been subjected to a rubbing treatment, the organic molecules forming the organic thin film are inclined in a predetermined direction. Generally, the rubbing direction in the rubbing process is the same as the tilt direction of the formed organic molecules.

As the rubbing cloth used in the rubbing treatment, a cloth made of nylon or rayon can be used. Using a rubbing cloth made of nylon or rayon as described above is appropriate for the purpose of improving the alignment accuracy.

In the step of forming the conductive polymer, one or more polymerization methods are applied, and the molecules forming the organic thin film are conjugated with each other by polymerization or by polymerization and crosslinking after the polymerization to form a conductive polymer. May be. According to this example, it is possible to form a conductive polymer that enables electrical conduction by connecting the polymerizable groups of the organic molecule with a conjugated bond. As the type of polymerization, at least one polymerization method selected from electrolytic oxidative polymerization, catalytic polymerization, and energy beam irradiation polymerization can be used. In particular, when the conductive polymer is completed by electrolytic oxidation polymerization in the final step, high conductivity can be obtained.

When the molecule forming the organic thin film has a plurality of polymerizable groups bonded by a conjugated bond, the polymer formed by the polymerization of one of the polymerizable groups is further subjected to a crosslinking reaction and the other. By forming a conjugated bond with the polymerizable group,
A conductive polymer having a structure different from the structure after polymerization can be formed. At this time, the other polymerizable group on the side chain of the polymer formed by polymerization is crosslinked.

A polymerization method selected from the group consisting of a catalytic polymerization method, an electrolytic polymerization method and an energy beam polymerization method may be applied in the step of carrying out the polymerization. In order to efficiently form a conductive polymer, first, a catalytic polymerization method and / or energy beam polymerization is performed, and in the final step, the reaction is completed by electrolytic oxidation polymerization.

When a plurality of cross-linking steps are adopted, a combination of cross-linking steps having different actions may be used, but a combination of steps having the same action but different reaction conditions is also included. For example,
The conductive polymer may be formed by performing a crosslinking step by irradiation with the first type of energy beam after the crosslinking step by catalytic action and further performing a crosslinking step by irradiation with the second type of energy beam.

It is also possible to use polarized ultraviolet rays, polarized deep ultraviolet rays, or polarized X-rays as the energy beam, and to perform the tilting step and the conductive polymer forming step at the same time. According to this example, the organic molecules forming the organic thin film can be tilted (orientated) in a predetermined direction, and the organic molecules can be conjugated to each other. Therefore, the process can be simplified.

As the base material used in the present invention, a base material having active hydrogen on its surface or having active hydrogen added thereto is used. Glass,
The type of base material such as metal, ceramics, plastic, or paper does not matter. If the surface has a small amount of active hydrogen, Si
Cl ₄ , HSiCl ₃ ,, SiCl ₃ O- (SiCl ₂ -O) _n -SiCl ₃ (where n is 0 or more
6 or less), Si (OCH ₃ ) ₄ , HSi (OCH ₃ ) ₃ , Si (OCH ₃ ) ₃ O- (Si
(OCH ₃ ) ₂ -O) _n -Si (OCH ₃ ) ₃ (where n is an integer of 0 or more and 6 or less). The compound can also be formed by a chemical adsorption method, and it is preferable to form a thin film having a film thickness of about 1 to 10 nm because transparency is not impaired. Further, a silica film or an Al ₂ O ₃ film may be formed by using a vapor deposition method. Also,
Active hydrogen can be provided by activating the surface of the base material by corona discharge or plasma irradiation.

The organic conductive film of the present invention has high conductivity and high transparency. Applications that take advantage of this property are electric wires,
Motor, generator, condenser (capacitor), transparent electrode (replacement of ITO), semiconductor device wiring / CPU wiring (does not generate heat due to electric resistance), electromagnetic wave shield, conductive glass, transparent antenna wire, surface heating film, CRT glass surface filter ( It can be used for various applications such as static electricity prevention), vehicle glass, and window glass for buildings.

(Embodiment 1) In Embodiment 1, a method of manufacturing the organic thin film and a structure thereof will be described when the organic thin film is a monomolecular film.

First, the manufacturing method will be described. Conducting a monomolecular layer forming step (chemical adsorption film forming step) of forming a monomolecular film on the base material by bringing an organic molecule having a conjugated polymerizable functional group into contact with the base material, and then forming the monomolecular film By performing the conductive region forming step of forming a conductive region having a conductive polymer in which the molecules are linked by a conjugated bond in a predetermined direction on at least a part of the monomolecular film, the monomolecular film having the conductive region can be formed. In the above, it is preferable to orient (tilt) the organic molecules formed in the chemical adsorption film forming step in a predetermined direction. By doing so, a conductive region having a high degree of polymerization and high conductivity can be formed.

Here, in the monomolecular film and the monomolecular layer, inclining in a predetermined direction is the same as orienting the organic molecules constituting the monomolecular film.
Also referred to as orientation for a monomolecular film or a monomolecular layer.

As a method for forming such an oriented monomolecular film, the substrate surface is rubbed before the monolayer forming step (pretreatment step), and the monomolecular film is rubbed on the rubbed substrate surface. A method of forming a film, a method of forming an oriented monomolecular film by subjecting the monomolecular film to orientation treatment after the monomolecular layer forming step (gradient treatment step), and the like can be applied. In addition, a manufacturing method including a pretreatment step and a gradient treatment step can form a conductive polymer having extremely excellent linearity.

With the manufacturing method including the washing step subsequent to the above-mentioned monomolecular layer forming step, it is possible to form a monomolecular film without stains on the surface. In addition, with the manufacturing method including the doping step of doping the charge-moving dopant, the conductivity of the conductive region can be easily improved. In addition, after the conductive region forming step, if it is a manufacturing method including a step of forming an insulating protective film on the monomolecular film,
A monomolecular film with a protective film having excellent durability such as peeling resistance can be produced. Each step will be described below.

In the monomolecular layer forming step, the base material may be formed by immersing the base material in an organic solution containing film material molecules, or by applying the organic solution onto the base material. May be formed. Alternatively, the monomolecular film may be formed by exposing the base material to a gas containing film material molecules.

When an organic molecule having a functional group capable of being chemically adsorbed to the substrate at the end, such as a silane-based surfactant, is used as a film material molecule, durability such as peeling resistance fixed on the substrate is obtained. An excellent monomolecular film can be formed. When forming the laminated film of the second and subsequent layers, the chemisorption method or the Langmuir-Blodgett method can be applied.

The monomolecular layer forming step may be a step of forming a monomolecular film on the entire surface or a part of the surface of the base material, or the monomolecular film is formed on the base material in a predetermined pattern. It may be a process. For example, after forming a coating film (resist pattern) on a site other than the pattern for forming a monomolecular film on the surface of the base material, and contacting the base material on which the coating film is formed with the film material molecule to form a monomolecular film By removing the coating, a monomolecular film can be formed in a predetermined pattern.

Next, in the washing step, after the monomolecular layer forming step, the substrate on which the monomolecular film is formed can be immersed in an organic solvent for washing to wash and remove unadsorbed organic molecules. It is preferable to use a non-aqueous organic solvent as the cleaning organic solvent.

Next, the orientation treatment step may be a step of rubbing the surface of the substrate in one arbitrary direction,
A rubbing process may be performed so that the rubbing direction is different for each predetermined portion. The rubbing treatment method will be described in the following inclination treatment process. The rubbing device used in the alignment treatment process and the rubbing device used in the tilt treatment process are the same device, and the difference is whether or not a monomolecular film is formed on the substrate (FIG. 5A).

An example of the pretreatment process when the rubbing direction is made different for each predetermined part will be described below. A coating is formed on the surface of the base material in a predetermined first pattern (resist pattern), the surface of the base material on which the coating is not formed is rubbed in the predetermined first rubbing direction, and the coating is removed after the rubbing treatment. After that, a coating film (resist pattern) is formed on the surface of the base material in a second pattern different from the first pattern, and the surface of the base material on which the coating is not formed is rubbed in a predetermined second rubbing direction to perform a rubbing treatment. The coating is removed later. This makes it possible to form a portion that has been rubbed in the first rubbing direction and a portion that has been rubbed in the second rubbing direction. Further, a complicated rubbing pattern can be formed by repeating this with different rubbing directions.

Next, in the alignment treatment step (gradient treatment step), a rubbing alignment method, a photo-alignment method, a liquid draining alignment method or the like is applied to align the organic molecules constituting the monomolecular film in a predetermined direction. You can 5A to 5C are schematic perspective views for explaining an alignment method for inclining (aligning) molecules that form an organic thin film. FIG. 5A is a rubbing alignment method, FIG. 5B is an optical alignment method, and FIG. 5C is a liquid. This is a cut orientation method.

In the rubbing orientation method, as shown in FIG. 5A, the substrate 1 having the monomolecular film 4 formed thereon is brought into contact with the monomolecular film 4 while being conveyed in a predetermined direction (substrate conveying direction) C. The rubbing roll 42 wound around the rubbing cloth 41 is rotated in the rotation direction A, and the surface of the monomolecular film 4 is rubbed with the rubbing cloth 41, so that the organic molecules forming the monomolecular film 4 are oriented in the rubbing direction B. Is the way. As a result, the monomolecular film 4 oriented in the rubbing direction B is formed on the base material 1.
Can be formed.

In the photo-alignment method, as shown in FIG. 5B, ultraviolet rays or visible rays 4 are applied to the polarizing plate 43 having the transmission axis direction D.
5 to irradiate the organic molecule forming the monomolecular film 4 with the polarized light 46 in the polarization direction E. Linearly polarized light is preferred as the polarized light. Thereby, the monomolecular film 4 oriented in the polarization direction can be formed on the base material 1.

As shown in FIG. 5C, the liquid-slip alignment method pulls up the base material 1 in the pulling direction F while keeping a predetermined inclination angle with respect to the liquid surface of the organic solvent 44 for washing, and the monomolecular This is a method of orienting the organic molecules forming the film 4 in the liquid draining direction G. Thereby, the oriented monomolecular film 4 can be formed on the substrate 1.

Although not shown in the drawing, the orientation can also be achieved by the fluctuation of molecules in the solution during the catalytic polymerization or electrolytic oxidation polymerization.

It may be a step of applying any one of the liquid draining alignment method, the rubbing alignment method, the photo alignment method, and the alignment due to the fluctuation of the molecule in the solution at the time of polymerization, or a combination of a plurality of alignment methods. May be applied sequentially. When different oriented methods are combined to form an oriented monomolecular film in an accurately oriented state, it is preferable that the rubbing direction, the polarization direction, and the liquid draining direction are the same direction.

Further, it may be a step of orienting the monomolecular film in one direction wholly or partly, or may be a step of orienting by changing the orientation direction for each predetermined portion. When the alignment direction is different for each predetermined part, it is preferable to apply a rubbing alignment method or a photo-alignment method. It is also possible to apply a rubbing orientation method to make the orientation direction different for each predetermined portion.

Further, when the photo-alignment method is applied and the alignment direction is made different for each predetermined portion, for example,
After irradiating the first polarized light through the first photomask on which the predetermined pattern is formed, the first photomask is formed on the second photomask on which the predetermined pattern different from the pattern of the first photomask is formed. The second polarized light having a polarization direction different from the polarization direction of the polarized light may be irradiated. Furthermore, a complicated alignment pattern can be formed by using a plurality of photomasks having different patterns and a plurality of types of polarized light having different polarization directions.

By scanning and irradiating the monomolecular film with polarized light while changing the polarization direction, it is possible to form not only a linearly continuous conductive polymer but also a curved continuous conductive polymer.

Next, in the conductive region forming step, the molecules forming the monomolecular film can be polymerized or crosslinked to form a conjugated system. A catalyst polymerization method, an electrolytic polymerization method, an energy beam irradiation polymerization method, or the like can be applied as a polymerization method for performing polymerization or crosslinking.

The conductive polymer may be formed by repeating the polymerization or crosslinking step a plurality of times. For example, when an organic molecule having a plurality of conjugated polymerizable functional groups (polymerizable functional groups that polymerize by a conjugated bond) is used as the film material molecule,
A conjugated system (conjugated bond chain) can be formed in each of a plurality of parallel planes included in the monolayer.

Further, when the polymerization or crosslinking is carried out a plurality of times, the polymerization method or the polymerization conditions may be different for each time.
Here, the polymerization conditions mean reaction conditions when the same polymerization method is used. For example, when the type of catalyst and reaction temperature are different in catalytic polymerization, when the applied voltage is different in electrolytic polymerization, and the type of beam, the energy of the beam and the irradiation intensity of the beam are different in the energy beam irradiation polymerization. This is the case.

Further, it may be a step of forming a conductive region in all or a part of the monomolecular film, or a step of forming a plurality of conductive regions electrically insulated from each other in the monomolecular film. Good. The case where the conjugated polymerizable functional group contained in the film material molecule is a catalytic polymerizable functional group, an electrolytic polymerizable functional group, or an energy beam irradiation polymerizable functional group will be described below.

First, the case where the organic molecule forming the monomolecular film has a catalytically polymerizable functional group will be described. The conductive polymer can be formed by bringing the monomolecular film and the catalyst into contact with each other. Therefore, the monolayer may be dipped in a solution containing the catalyst, the solution containing the catalyst may be applied to the monolayer, or the monolayer may be exposed to a gas atmosphere containing the catalyst. The catalyst-containing gas may be blown onto the monomolecular film.

In addition, the alignment treatment step (tilt treatment step)
If not performed, the monolayer is oriented by flowing a solution containing the catalyst in a certain direction to the surface of the monolayer, or by blowing a gas containing the catalyst in a certain direction to the surface of the monolayer. It is possible to form a conductive polymer as well as to form a conductive polymer. Therefore, the alignment treatment step can be omitted, and a conductive region containing a conductive polymer that extends in a predetermined direction can be formed.

When forming a plurality of electrically conductive regions that are electrically insulated from each other, a coating film (resist pattern) having a predetermined pattern is formed on the monomolecular film and then contacted with a catalyst to form the coating film. A conductive region can be formed in a portion that has not been formed. If unnecessary, the film may be removed.

Secondly, the case where the organic molecule constituting the monomolecular film has an electropolymerizable functional group will be described. By contacting a pair of electrodes with a potential difference to the monolayer,
It is possible to form a conductive polymer that extends in a predetermined direction. Therefore, a pair of electrodes for electrolytic polymerization which are in contact with the surface or the side surface of the monomolecular film and are separated from each other may be formed and a voltage may be applied between the formed pair of electrodes. Alternatively, a pair of external electrodes may be brought into contact with the side surfaces so that the electrodes are separated from each other, and a voltage may be applied between the pair of external electrodes.

In the case of forming a plurality of electrically conductive regions electrically insulated from each other, a plurality of pairs of electrodes are formed in a predetermined pattern, and a predetermined potential is applied to the electrodes so that the electrodes having different potentials are electrically conductive. Regions can be formed. At this time, a potential may be applied to only two electrodes to form one conductive region at a time, or a potential may be applied to three or more electrodes to form a plurality of conductive regions at the same time.

In the above, by forming an electrode and carrying out electrolytic polymerization, a monomolecular film having a conductive region with a terminal can be manufactured. If unnecessary, these electrodes are removed.

Thirdly, the case where the organic molecule forming the monomolecular film has an energy beam irradiation polymerizable functional group will be described. A conductive polymer can be formed by irradiating the monomolecular film with an energy beam. Light, X-rays, electron beams or the like can be used as the energy beam. Preferably, polarized light or polarized X-rays are used as the energy beam.

Further, the alignment treatment step (tilt treatment step)
Even when the step is not performed, it is possible to align the monomolecular film and form a conductive polymer by irradiating polarized light. Therefore, the alignment treatment step can be omitted, and a conductive region containing a conductive polymer that extends in a predetermined direction can be formed.

In the case of forming a plurality of conductive regions electrically insulated from each other, the first pattern having a predetermined pattern is formed.
After irradiating the energy beam through the photo mask of No. 2, the energy beam is radiated through the second photo mask on which a predetermined pattern different from the pattern of the first photo mask is formed.

At this time, the energy beam irradiated through the first photomask and the energy beam irradiated through the second photomask do not have to be the same energy beam. Furthermore, when polarized light or polarized X-rays are used as the energy beam, their polarization directions need not be the same. For example, by using a plurality of photomasks having different patterns and a plurality of types of polarized light having different polarization directions, conductive regions having different directions of the conductive polymer can be easily formed.

By scanning and irradiating the monomolecular film with the energy beam, a plurality of electrically conductive regions electrically insulated from each other can be formed more easily. At this time, if polarized light or polarized X-rays are used as the energy beam, it is possible to easily form conductive regions in which the directions of the conductive polymers are different from each other. Further, if scanning irradiation is performed while keeping the polarization direction and the scanning direction (energy beam traveling direction) parallel to each other, it is possible to form a conductive polymer that is curvilinearly continuous in a predetermined direction.

In order to efficiently form the above-mentioned conductive polymer, there is a means of carrying out catalytic polymerization and / or polymerization by irradiation with a light energy beam first, and finally completing the network by electrolytic oxidation polymerization. Catalytic polymerization and /
Polymerization by light energy beam irradiation has a high polymerization rate, and electrolytic oxidative polymerization is not so fast, but since polymerization is carried out while passing a current, a large current flows at the moment the network is completed, so it is easy to determine whether or not it is completed. Can be detected.

Next, in the doping step, the conductivity can be easily improved by doping the dopant having a charge transfer property. The dopant may be an acceptor dopant (electron acceptor) such as iodine (I ₂ ) or BF 4 ⁻ ion, or a donor dopant (electron donor) such as Li.

Next, in the base material insulating film forming step, an insulating film such as a silica film or an aluminum oxide film can be formed on the base material. In order to use it for a transparent electrode or the like, it is necessary to form a transparent film. In addition, if a film that forms film-forming molecules is easily chemisorbed as an insulating film,
A monomolecular film can be formed regardless of the material of the base material.

Finally, in the protective film forming step, an insulating protective film is formed on the surface of the monomolecular film. By performing the protective film forming step, a monomolecular film having excellent durability such as peeling resistance can be formed. Further, a monomolecular film containing a dopant can reduce evaporation of the dopant due to dedoping. In addition, a transparent protective film is formed for use as a transparent electrode or the like.

An example of the structure of a monomolecular film having a conductive region formed by the above manufacturing method is shown in FIGS. Figure 1A
-C is a cross-sectional view schematically showing a monomolecular film having a conductive region, which is formed on the glass substrate 1, for example. Figure 1A
Is a state in which the monomolecular film 4 is fixed to the surface of the substrate 1 by covalent bond, the conjugated polymerizable functional group 9 is polymerized to form the conductive region 6 in the entire region, and the conductive polymer 5 is formed. Indicates. FIG. 1B shows a plurality of partial regions (conductive regions 6,
6) shows a monomolecular film on which the conductive polymer 5 is formed.
FIG. 1C shows a monomolecular film made of an organic molecule having a conjugated polymerizable functional group inside and having a conductive polymer formed in a plurality of partial regions (conductive region 6).

FIG. 2 shows the conductive polymer 5 in the monomolecular film 4.
FIG. 3 is a schematic plan view for explaining the direction of FIG. In drawings other than FIG. 2, the meandering conductive polymer is represented as a straight line without a meander or a curve without a meander.

3A to 3D show examples of patterns of the conductive region in the monomolecular film having the conductive region. 3A to 3D are plan views schematically showing configuration examples of the conductive region 6 of the monomolecular layer containing the conductive polymer formed on the base material. FIG. 3A is a monolayer 4 in which a conductive polymer 5 continuous in one direction is formed in the entire region, and FIG. 3B is a parallel conductive region in which a conductive polymer 5 continuous in one direction is formed in each conductive region 6. 3 shows a monolayer 4 having 6 and FIG.
FIG. 3D shows the direction of the conductive polymer formed in each conductive region, which shows the monolayer 4 having the conductive regions 6 arranged in a matrix in which the conductive polymer 6 is formed in each conductive region. Shows a monomolecular layer 4 having conductive regions 6 arranged in an arbitrary pattern, which are not the same and the shape of each conductive region is not the same.

The structure of a monomolecular film having a conductive region formed on a base material is shown in FIGS. 4A-B. 4A-B
It is sectional drawing which shows typically the structural example of the monomolecular film formed on the base material. FIG. 4A shows the monomolecular film formed on the base material 1 with the base material insulating film 2, and FIG. 4B shows the monomolecular film 4 formed on the base material 1 and having the protective film 3 formed on the surface. . Although not shown, a structure in which an insulating film, a monomolecular film, and a protective film are sequentially laminated on the base material may be formed on the base material.

FIGS. 6A and 6B are perspective views schematically showing a constitutional example in which a conductive region is formed at a selective portion on the base material. FIG. 6A shows a structure in which a plurality of conductive regions 6 are formed in a monomolecular film 4 formed on all parts of a substrate 1, and FIG. 6B is a monomolecular film in which conductive regions 6 are formed in all regions. 4
The structure formed in multiple numbers on the base material 1 is shown.

(Embodiment 2) In Embodiment 2, an example of a monomolecular cumulative film having a conductive region will be described.

When forming a monomolecular cumulative film, the first layer is formed by a chemisorption method. The chemical adsorption method or the Langmuir-Blodgett method may be applied to the second and subsequent layers. However, it is simple and preferable that all the layers are a monomolecular laminated film formed by the chemical adsorption method. Further, although the alignment treatment step (gradient treatment step) has been described in the first embodiment, its importance is greater in the case of a monomolecular film, than in the case of a monomolecular film. Hereinafter, a manufacturing method including an alignment treatment step will be described.

In the method for producing a monomolecular cumulative film having a conductive region according to the present invention, various combinations and sequences of a monomolecular layer forming process, a conductive region forming process, and an alignment treatment process are possible. Below, preferred manufacturing methods are Manufacturing Method 1 to
5 will be described.

In the manufacturing method 1, the monomolecular layer forming step is performed plural times in succession to form the monomolecular cumulative film, and then the conductive area forming step is performed to form the monomolecular cumulative film having the conductive area. It is a manufacturing method.

In the manufacturing method 2, the monomolecular layer forming step and the orientation treatment step (gradient treatment step) are alternately performed a plurality of times,
This is a manufacturing method of forming a monomolecular cumulative film having a conductive region by stacking oriented monomolecular layers and then performing a conductive region forming step.

In the manufacturing method 3, a series of steps of sequentially carrying out the monomolecular layer forming step, the orientation processing step (gradient processing step) and the conductive area forming step are carried out a plurality of times to form a monomolecular cumulative film having a conductive area. It is a manufacturing method.

In the manufacturing method 4, after the monomolecular layer forming step, the orientation processing step (gradient processing step) and the conductive area forming step are sequentially performed to form a monomolecular film having a conductive area, a plurality of monomolecular layer forming steps are performed. This is a manufacturing method in which a monomolecular cumulative film having a conductive region is formed by performing the conductive region forming step successively.

In the manufacturing method 5, after performing the pretreatment step, the monomolecular layer forming step is continuously performed a plurality of times, and then the conductive area forming step is performed to form the monomolecular cumulative film having the conductive area. It is a manufacturing method. Further, it is also preferable that the manufacturing method is any one of the manufacturing methods 1 to 5 after the pretreatment step.

Even when the above-mentioned manufacturing methods 1 to 5 are used, what kind of conductive area pattern is formed in the monomolecular cumulative film having the conductive area, and what kind of orientation is used in the alignment treatment step. The superiority varies depending on the manufacturing method depending on the method applied, what kind of polymerization method is applied in the conductive region forming step, and the like. Therefore, it is important to select an optimum manufacturing method for forming a monomolecular cumulative film having a desired conductive region.

The manufacturing methods 1 to 5 may be a manufacturing method further including any one or more of a base insulating film forming step, a cleaning step, a doping step, and a protective film forming step. For details of each of the monomolecular layer forming step, the conductive region forming step, the pretreatment step, the orientation step, the base insulating film forming step, the cleaning step, the doping step and the protective film forming step, refer to Embodiment 1 above. However, in the following, differences between the respective steps caused depending on whether the organic thin film is a monomolecular film or a monomolecular cumulative film will be described.

In each monomolecular layer forming step, the same film material molecule may be used to form a monomolecular cumulative film composed of one type of organic molecule, or different film material molecules may be used to form a monomolecular layer. A monomolecular cumulative film having different constituent molecules may be formed for each.

Next, the applicability of the rubbing alignment method and the photo-alignment method in the alignment treatment step will be described. In the monomolecular film forming step, the substrate is pulled up from the solution containing the film-constituting molecules at a predetermined angle, usually perpendicular to the solution surface,
This means that the liquid crystal orientation is performed in the single molecule forming step.

The rubbing orientation method is a method of orienting the organic molecules constituting the film by rubbing the surface of the film, and therefore when applied to a monomolecular cumulative film having a large number of laminated layers, The monolayer cannot be sufficiently oriented. Therefore, the rubbing orientation is suitable when applying the manufacturing methods 2 to 4. Manufacturing method 1
In the case of applying the above to form a monomolecular cumulative film having a small number of laminated layers, the rubbing orientation method can be used.

On the other hand, since the photo-alignment method can be applied to a monomolecular cumulative film having a large number of laminated layers, it is suitable for any of the manufacturing methods 1 to 5. However, when the number of layers is excessively increased and the light transmittance is deteriorated, it becomes impossible to sufficiently orient the monomolecular layer as the lower layer on the substrate side.

Next, in the case where the catalytic polymerization method, the electrolytic polymerization method, and the energy beam irradiation polymerization method are applied in the conductive region forming step, preferable manufacturing methods will be described for each polymerization method.

Since the catalytic polymerization method is a method of inducing a polymerization reaction by bringing the surface of the monomolecular cumulative film into contact with the catalyst, a sufficiently polymerized conductive polymer is formed in the monomolecular layer on the lower side of the substrate. Will be difficult to do. Therefore, when the catalytic polymerization method is applied, the manufacturing method 4 is suitable. When forming a monomolecular cumulative film having an extremely small number of layers, the above-mentioned manufacturing method 1 or manufacturing method 2 may be used.

When the electrolytic polymerization method is applied, when a voltage is applied to the pair of electrodes in contact with the surface of the monomolecular accumulated film, a sufficiently polymerized conductive polymer is formed in the monomolecular layer on the lower side of the substrate. Therefore, it is preferable to apply a voltage to the electrode in contact with the side surface of the monomolecular film. In this way, if voltage is applied to the electrodes that are in contact with the side surface,
The conductive polymer can be formed in each monomolecular layer of the monomolecular cumulative film by applying any of the above-mentioned manufacturing methods 1 to 5. Furthermore, the electrolytic polymerization method is suitable for forming a conductive region on the entire surface of the monomolecular cumulative film or for forming a conductive region penetrating the monomolecular cumulative film.

Since the energy beam irradiation polymerization method can be applied to a monomolecular cumulative film having a large number of laminated layers, it is suitable for any of the manufacturing methods 1 to 5. However, in the case where the number of layers is excessively increased and the transmittance of the energy beam is deteriorated, it becomes impossible to sufficiently orient the lower molecular layer on the substrate side.

Next, the cleaning step is preferably performed after each single layer is formed.

Next, it is preferable that the doping step is individually performed on the monomolecular layer on which the conductive polymer is formed. Therefore, when performing the doping step, it is preferable to apply the manufacturing method 3, and preferably after each conductive region forming step of the manufacturing method 3.

7A-C show a structural example of the conductive region of the monomolecular cumulative film formed by the above manufacturing method. Figure 7A
Shows an X-type monomolecular cumulative film in which the orientation directions of the monolayers 4 are the same, and FIG. 7B is an X-type monomolecular cumulative film in which the orientation direction is strengthened for each monolayer 4. 7C is an X-type monomolecular cumulative film oriented in either of two orientation directions for each monomolecular layer 4.

(Embodiment 3) An electric cable according to this embodiment will be described with reference to FIGS. 8A to 8C. 8A-C
[Fig. 3] is a diagram schematically showing a structural example of an electric cable using a conductive region on which a monomolecular film is formed as a core wire. Figure 8A
Is a cross-sectional view of an electric cable that is formed on the outer surface of a core wire 11 made of glass or metal, and is provided with a conductive monomolecular film 6 having a conductive region in all areas, the surface of which is covered with an electrically insulating film 13. is there. FIG. 8B shows a rectangular column-shaped insulating substrate 1.
1 is formed on the surface and the outer surface is covered with an insulating protective film 13
FIG. 3 is a perspective view of an electric cable of a collective electric wire type including a monomolecular film 4 having four conductive regions coated with a. Figure 8C
[FIG. 3] is a perspective view of a collective electrode type flat cable formed on a base material and provided with a monomolecular film 4 having an entire conductive region 6 and four pairs of contacts 7. The flat cable of FIG. 8C is a flat cable including four core wires because the conductive region of the organic thin film has high conductivity anisotropy.

In addition, the insulating substrate 1 shown in FIGS. 6A-B.
By further forming an insulative protective film on the organic thin film 4 having the conductive region 6 on it, a flat cable of the collecting electrode type can be provided.

(Embodiment 4) The organic thin film of the present invention can provide various devices used as conducting wires, collective wiring, electrodes, and transparent electrodes. For example, electronic devices such as semiconductor elements, capacitors, and semiconductor devices, and optical devices such as liquid crystal display devices, electroluminescent elements, and solar cells can be provided.

For example, FIGS. 9A-B are cross-sectional views schematically showing a structural example of a capacitor in which the conductive region formed on the monomolecular film is used as an electrode, and FIG. 9A shows the monomolecular film having the conductive region 6. 9 is a structure in which each of the monomolecular films 4 is placed inside and the dielectric 8 is sandwiched between the two base materials 1 on which the dielectric films 8 are formed. FIG. It is a structure in which a monomolecular film 4 having a region 6 is formed. In FIGS. 9A and 9B, when the metal contact 7 (wiring, lead wire) penetrating the conductive region 6 is formed in the direction orthogonal to the direction of the conductive polymer, a uniform voltage can be applied to the entire surface of the organic thin film electrode. ,preferable.

The pyrrole compound of the present invention comprises, for example, a step of reacting 3-alkylpyrrole or 4-alkylpyrrole with terminal bromo 1-alkyl to synthesize (alkylpyrrolyl) alkyl, and the above-mentioned (alkylpyrrolyl) ) By reacting alkyl with trichlorosilane, (alkylpyrrolyl) alkyltrichlorosilane can be synthesized. In the case of alkyl (alkylpyrrolyl) alkyltrichlorosilane, for example, a step of reacting alkyl (alkylpyrrole) with terminal bromo1-alkyl to synthesize alkyl (alkylpyrrolyl) alkyl, and the above-mentioned synthesized alkyl (alkylpyrrolyl) It can be synthesized by reacting alkyl) with trichlorosilane.

[0126]

EXAMPLES The present invention will be specifically described below based on examples. In the following examples, simply indicating “%” means “% by mass”.

Synthesis Example 1 [1] Synthesis Step 1. 11-bi (1-pyrrolyl) -1-
Synthesis of Undecene In accordance with the reaction formula shown in the following chemical formula (C1), 83.9 g (0.
567 mol), dehydrated tetrahydrofuran (THF) 20
0 ml was charged and cooled to 5 ° C or lower.

To this, 354 ml (0.567 mol) of a 1.6 M n-butyllithium hexane solution was added dropwise at 10 ° C. or lower. After stirring at the same temperature for 1 hour, 600 ml of dimethyl sulfoxide was added and THF was distilled off by heating to replace the solvent. Next, 11-bromo-1-undecene 14
5.2 g (0.623 mol) was added dropwise at room temperature. After the dropping, the mixture was stirred at the same temperature for 2 hours.

Next, 600 mol of water was added to the reaction mixture, hexane extraction was performed, and the organic layer was washed with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off.

Further, the residue was mixed with hexane / ethyl acetate =
Purified with silica gel column at 50/1, 141.8 g
11-bi (1-pyrrolyl) -1-undecene was obtained.

[0131]

[Chemical 21]

The yield was 91.2%.

[0133] Here, (a) of the following formula 22 containing an alkyl group at a site other than the covalently bondable group next to the pyrrolyl group or an unsaturated group such as a vinyl group or an ethynyl group at the terminal
Using the starting material substituted with the group represented by-(g), the molecularly modified 11-bi (1-pyrrolyl) -1-undecene was obtained.

[0134]

[Chemical formula 22]

[2] Synthesis Step 2. Synthesis of 11-bi (1-pyrrolyl) -undecenyltrichlorosilane The following reactions were carried out according to reaction formula 2 shown in the following chemical formula (C2).

[0136]

[Chemical formula 23]

In a pressure resistant test tube with a 50 ml cap, 11
2.5 g (-9.1-pyrrolyl) -1-undecene (9.1 x
10 ^-3 mol), trichlorosilane 2.0 g (1.48 ×)
_{^{10 - 2 mol), H 2}} PtCl 6 · 6H 2 O in 5% isopropyl alcohol - was reacted for 9 hours Le solution 0.01g at charged 50 ° C.. When the reaction was checked by NMR, it was found that the reaction had proceeded about 50%.

Here, a compound in which an alkyl group at a site other than a covalent bondable group next to a pyrrolyl group or an organic group containing an unsaturated group such as a vinyl group or an ethynyl group at the end is substituted is used as a raw material, and a chemical formula Also in the case of the reaction of (3), similarly, molecularly modified trichlorosilane was obtained.

(Synthesis Example 2) Trichlorosilyl which undergoes dehydrochlorination reaction with a bipyrrolyl group, an oxycarbonyl group (-OCO-) which is a polarizable functional group, and active hydrogen (for example, a hydroxyl group (-OH)) on the substrate surface. substance group (-SiCl ₃₎ and the following formula with (D1) (PEN: 6- bi (1-pyrro
lyl) hexyl-12,12,12-trichloro-12-siladodecanoate)
Was synthesized according to the following steps.

[0140]

[Chemical formula 24]

(D1) Step 1 Synthesis of 6-Bromo-1- (tetrahydropyranyloxy) hexane 197.8 g (1.0%) of 6-bromo-1-hexanol was added to a 500 ml reaction vessel.
(9 mol) was charged and cooled to 5 ° C or lower. Dihydropyran (102.1 g, 1.21 mol) was added dropwise thereto at a temperature of 10 ° C or lower. After the dropping was completed, the temperature was returned to room temperature and the mixture was stirred for 1 hour. The residue obtained by the reaction was purified by silica gel column with hexane / IPE (diisopropyl ether) = 5/1 and 263.4 g of 6-
Bromo-1- (tetrahydropyranyloxy) hexane was obtained. The yield was 90.9%. The reaction formula of Step 1 is shown in the following formula (D2).

[0142]

[Chemical 25]

Step 2 Synthesis of N- [6- (tetrahydropyranyloxy) hexyl] bipyrrole 83.6 g (0.567 mol) of pyrrole and 200 ml of dehydrated tetrahydrofuran (THF) were charged in a 2 liter reaction vessel under an argon stream, and 5 ° C. Cooled to: To this was added 354 ml (0.567 mol) of a 1.6 M n-butyllithium hexane solution at 10 ° C. or lower. After stirring at the same temperature for 1 hour, 600 ml of dimethyl sulfoxide was added and THF was distilled off by heating to replace the solvent. Next, 165.2 g of 6-bromo-1- (tetrahydropyranyloxy) hexane
(0.623 mol) was added dropwise at room temperature. After the dropping, the mixture was stirred at the same temperature for 2 hours.

600 mol of water was added to the reaction mixture, and the mixture was extracted with hexane, and the organic layer was washed with water. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The residue is hexane / ethyl acetate = 4
Silica gel column purification at 1/1 gave N- [6- (tetrahydropyranyloxy) hexyl] bipyrrole.
The yield was 75.2%. The reaction formula of step 2 is the following formula (D
3).

[0145]

[Chemical formula 26]

Step 3 Synthesis of N- (6-hydroxyhexyl) -bipyrrole 0.418 m of N- [6- (tetrahydropyranyloxy) hexyl] bipyrrole obtained above in a 1 liter reaction vessel.
ol, methanol 450 ml, water 225 ml, concentrated hydrochloric acid 3
7.5 ml was charged and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into 750 ml of saturated saline and extracted with IPE. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained residue was purified by silica gel column with n-hexane / ethyl acetate = 3/1 to obtain N- (6-hydroxyhexyl) -bipyrrole.
The yield was 90.3%. The reaction formula of step 3 is represented by the following formula (D
4).

[0147]

[Chemical 27]

(D4) Step 4 Synthesis of N- [6- (10-undecenoyloxy) hexyl] -bipyrrole N- (6-hydroxyhexyl) -in a 2 liter reaction vessel.
0.371 mol of bipyrrole and 33.2 g of dry pyridine
(0.420 mol) and dry toluene 1850 ml were charged, and 10-undecenoyl chloride 75.7 g at 20 ° C or lower.
A solution of (0.373 mol) in dry toluene (300 ml) was added dropwise. The dropping time was 30 minutes. Then, the mixture was stirred at the same temperature for 1 hour. The reaction mixture was poured into 1.5 liters of ice water and acidified with 1N hydrochloric acid. The mixture was extracted with ethyl acetate, the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was removed to obtain 128.2 g of a crude product. This was purified with a silica gel column with n-hexane / acetone = 20/1 to obtain N- [6- (10-undecenoyloxy) hexyl] -bipyrrole. Yield 8
It was 0.1%. The reaction formula of Step 4 is shown in the following formula (D5).

[0149]

[Chemical 28]

Step 5 Synthesis of PEN N- [6- (10-
Undecenoyloxy) hexyl] -bipyrrole (6.
0 × 10 ^-3 mo1), trichlorosilane 0.98 g (7.2
(3 × 10 ⁻³ mol) and 0.01 g of a 5% isopropyl alcohol solution of H ₂ PtC1 ₆ · 6H ₂ 0 were charged and reacted at 100 ° C. for 12 hours. After treating this reaction solution with activated carbon, 2.66
The low boiling point component was distilled off under reduced pressure of × 10 ³ Pa (20 Torr). PEN was obtained with a yield of 81.7%. The reaction formula of Step 5 is shown in the following formula (D6).

[0151]

[Chemical 29]

(D6) In order to replace the terminal trichlorosilyl group with a trimethoxysilyl group, the above chemical formula 1 is used.
PEN with 3 moles of methyl alcohol and room temperature (25
Stir at (° C.) to carry out dehydrochlorination reaction. If necessary, the hydrogen chloride is separated as sodium chloride by adding sodium hydroxide.

(Example 1) In the same manner as in Synthesis Example 1, 11- [bi (3-N-methylpyrrolyl) represented by the following formula (E1):
-Undecenyltrichlorosilane was synthesized.

[0154]

[Chemical 30]

However, as the starting material, the following formula (E
The bi (3-N-methylpyrrolyl) bromine shown in 2) was used.

[0156]

[Chemical 31]

11- [bi (3-N) represented by the following formula (E1):
Chemical adsorption liquid E was prepared by diluting methylpyrrolyl) -undecenyltrichlorosilane to 1% with a dehydrated dimethyl silicone solvent.

Further, as shown in FIG. 10A, the thickness of 0.
The electrically insulating silica film 2 having a thickness of 0.5 μm was formed on the surface of the electrically insulating polyimide base material 21 having a thickness of 2 mm.

Next, the polyimide base material 21 was dipped in the chemical adsorption solution E to chemically adsorb the chemically adsorbed molecules on the surface of the silica film 2 (monomolecular layer forming step). After the monomolecular layer forming step, the polyimide base material 21 was immersed in a chloroform solution to wash and remove unreacted film material molecules remaining on the polyimide base material 21. As a result, the monomolecular film 14 having no stain on the surface was formed (FIG. 10A).

At this time, since a large number of hydroxyl groups containing active hydrogen are present on the surface of the silica film 2 on the polyimide base material 21, a covalent bond is formed by a dechlorination reaction between these hydroxyl groups and the -SiCl bonding group of the chemisorption molecule. A monomolecular film 14 composed of chemisorbed molecules represented by the chemical formula (E3) by chemically bonding with
Are formed. However, in the chemical formula (E3),
All the -SiCl bonding groups in the chemisorption molecule are silica films 2
In the case of reaction with the surface, at least one -S
It suffices that the iCl bonding group reacts with the surface of the silica film 2.

[0161]

[Chemical 32]

Next, the surface of the formed monomolecular film 14 is rubbed by using a rubbing apparatus (FIG. 5A) used for producing a liquid crystal alignment film to remove chemisorbed molecules constituting the monomolecular film 14. Oriented (tilt process step) (FIG. 10)
B). Rubbing cloth 4 made of rayon in the rubbing process
Using a rubbing roll 42 having a diameter of 7.0 cm and 1 wound, a pressing depth of 0.3 mm and a nip width of 11.7 m
The rubbing was performed under the conditions of m, rotation speed 1200 rotations / s, and table speed (base material traveling speed) 40 mm / s. At this time, the monomolecular film 24 was oriented (tilted) substantially parallel to the rubbing direction.

Next, a vacuum deposition method, a photolithography method and an etching method are applied to the surface of the monomolecular film 24,
After a pair of platinum electrodes 17 having a length of 50 mm are vapor-deposited at a distance of 5 mm, they are immersed in ultrapure water at room temperature, and a voltage of 8 V is applied between the pair of platinum electrodes 17 for 6 hours to perform electrolytic oxidation. Polymerization was performed (conductive region forming step). Thereby, a conductive region 16 having a conductive polymer containing a conductive polypyrrole-type conjugated system, which has the following chemical formula (C5) as a polymerized unit and is continuous in a predetermined direction (rubbing direction), can be formed between a pair of platinum electrodes 17. (Conductive region forming step) (FIG. 10)
D).

[0164]

[Chemical 33]

The film thickness of the obtained organic conductive film was about 2.0 n.
m, and the thickness of the polypyrrole portion was about 0.2 nm.

A current of 1 mA was able to flow by applying a voltage of 8 V between the pair of platinum electrodes 17 through the organic conductive film. Therefore, the conductivity of the conductive polymer is about 10 ³ S without doping impurities such as donors and acceptors.
A monomolecular film 34 having a conductive area of / cm was obtained.

Since the conductivity of the conductive region formed as described above is about 1/10 to 1/100 of that of metal, if the monomolecular film 34 is laminated, it can be used for wiring of functional devices such as semiconductor elements and capacitors. It was a level that could be used for electrodes.
In addition, since the monomolecular film 34 according to this example does not absorb light having a wavelength in the visible region, it can be used as a transparent electrode for liquid crystal display devices, electrolytic light emitting devices, solar cells, etc. when laminated.

Although the polyimide base material 21 provided with the insulating silica film 2 on the surface is used in the above-mentioned embodiment, the same applies to the polyimide base material 21 provided with the insulating aluminum oxide film on the surface. As a result, a monomolecular film having a conductive region was obtained. Further, even if a conductive aluminum base material is used instead of the polyimide base material, by providing a silica film on the base material surface or by subjecting the base material surface to an oxidation treatment, a single molecule having a similar conductive region is formed. A film was obtained.

Although the rubbing orientation method was applied in the tilting process of the above-mentioned embodiment, the rubbing treatment was applied to the surface of the polyimide base material provided with the silica film before the monomolecular layer forming process, and then the same procedure was performed. If the monomolecular film is formed by the method described above, a monomolecular film oriented in the rubbing direction can be formed, and if a conductive region is formed by the same method thereafter, the monomolecular film having a conductive region with similar conductive characteristics is formed. was gotten.

Although the rubbing alignment method was applied in the tilting process of the above-mentioned embodiment, the chemistry for forming the monomolecular film 14 even when ultraviolet rays are irradiated through the polarizing plate 43 as shown in FIG. 5B. It is possible to form a monomolecular film 24 in which the adsorbed molecules 22 are oriented substantially parallel to the polarization direction (photo-alignment method). Then, if a conductive region is formed by the same method as described above, a conductive region with higher conductivity is formed. A monomolecular film 34 having the above was obtained.
The light used in the photo-alignment method is not limited to the above-mentioned polarized ultraviolet light, and any light having a wavelength absorbed by the monomolecular film 34 can be used.

In the above-mentioned cleaning process of this embodiment, the polyimide base material 1 is removed from the cleaning chloroform solution.
5C, when the surface of the polyimide base material 1 is set to the liquid surface of the chloroform solution 44 for cleaning and the liquid is drained by pulling it up almost vertically, the chemical adsorption that forms the monomolecular film It was possible to form the monomolecular film 24 in which the molecules 22 were oriented substantially parallel to the liquid draining direction (liquid draining orientation method). Thereby, the cleaning process and the tilting process can be performed at the same time. Further, the liquid crystal alignment-treated monomolecular film is subjected to photo-alignment treatment, and then a conductive region is formed by the same method as described above to obtain a monomolecular film 34 having a conductive region with a conductivity of 10 ⁴ S / cm. Was given.

Example 2 5-hexyl- (3-methylpyrrolyl) octadecenyltrichlorosilane represented by the following chemical formula (D1) synthesized by the same method as in Synthesis Example 1 was used and dehydrated with an organic solvent of dimethyl silicone. A chemical adsorption liquid was prepared by diluting it to 1%.

[0173]

[Chemical 34]

Next, an insulating thin film having a thickness of 0.5 μm, such as a silica protective film or Al ₂ O, is formed on the surface of an insulating polyimide base material 101 (which may be glass or a conductive metal base material) having a thickness of 0.2 mm. The protective film 102 of ₃ was formed (FIG. 11A).

Next, the surface of the silica film is chemically adsorbed by immersing it in the adsorbent, and the unreacted substance remaining on the surface is washed away with chloroform to form a monomolecular film 103 of the substance. It was selectively formed (FIG. 11B).

At this time, the surface of the substrate (silica film or Al
₂ O ₃ film) has a large number of hydroxyl groups containing active hydrogen. Therefore, a molecule represented by the following chemical formula (F2) in which the -SiCl group of the substance undergoes a dehydrochlorination reaction with the hydroxyl group to covalently bond to the surface of the substrate A monomolecular film 103 composed of was formed.

[0177]

[Chemical 35]

Thereafter, as shown in FIG. 11C, using a rubbing apparatus 104 used for producing a liquid crystal alignment film, a rayon cloth 105 (Yoshikawa Kako Co., Ltd .: YA-20-R) was used.
When the rubbing treatment is performed in the direction substantially perpendicular to the electrode gap under the conditions of indentation depth of 0.3 mm, nip width of 11.7 mm, rotation speed of 1200 rotations, and table speed of 40 mm / sec, the molecules forming the monomolecular film are almost parallel to the rubbing direction. A monomolecular film 103 ′ oriented in the vertical direction was obtained (FIG. 11D).

Next, a pair of platinum electrodes (source and drain electrodes) 106 and 106 'having a length of 50 mm were vapor-deposited on the surface of the monomolecular film at intervals of 5 mm, and were placed in ultrapure water at room temperature (25 ° C.) for 6 times. A direct current electric field of 8 V was applied between the electrodes for a time to carry out electrolytic oxidative polymerization of the pyrrolyl group 107. As a result, as shown in FIG. 11E and the following chemical formula (D3), the electrodes were connected by a conductive polypyrrolyl group 107 ′ (conjugated bond group), and the conductivity at room temperature (25 ° C.) was 4 × 10 ^3. A conductive monomolecular film 108 of S / cm (in the case of this monomolecular film, a current of 4 mA could be passed by applying an electric field of 8 V) was obtained (FIG. 1).
1F).

[0180]

[Chemical 36]

This conductivity is 1/10 to 1/10 that of metal.
It was about 0, which was a level that could be used for wiring and electrodes of functional devices such as semiconductor devices and capacitors if laminated. In addition, since this coating is a monomolecular film and has a very thin film thickness at the nanometer level, it hardly absorbs light having a wavelength of visible light and transmits it. For this reason, it is at a level that can be used for transparent electrodes of liquid crystal display devices, electroluminescent devices, solar cells and the like.

Here, when the molecules constituting the monomolecular film are oriented, when the ultraviolet rays 122 are irradiated through the polarizing plate 121 (FIG. 12A), the molecules 123 constituting the monomolecular film are almost in the polarization direction. A monomolecular film oriented in parallel was obtained, and then a conductive monomolecular film having more excellent conductivity was obtained by polymerizing in the same manner as described above.

As the light used for the photo-alignment, if the light has a wavelength absorbed by the monomolecular film, it was possible to perform the photo-alignment by using the polarized light in the ultraviolet light or the visible light region.

Further, after forming the same monomolecular film, it is immersed again in the cleaning liquid 124, which is chloroform, and the same cleaning is carried out. Further, when the base material is raised and the liquid is drained off, the molecules constituting the monomolecular film are formed. There almost parallel monomolecular film 123 'is obtained which is oriented in the draining direction, then, when the electrolytic oxidation polymerization in the same manner as described, 10 ⁴ S at room temperature (25 ° C.)
A cm conductive film was obtained (Fig. 12B).

Further, if the step of pulling the substrate upright and draining it is performed before the photo-alignment, the orientation can be further improved.

Note that such a coating is used for the electroluminescent device (E
L) or an indium tin oxide alloy (ITO) transparent electrode used in a solar cell.

When a plurality of electroconductive conjugated bond groups in the layer are oriented in a specific direction, a monomolecular film or a monomolecular cumulative film having a conductivity of 10 ³ S / cm or more is prepared. ,
It could also be used as an electrode of a capacitor, wiring of a semiconductor IC chip, or an electromagnetic shield film.

Example 3 As shown in FIG. 13, instead of the polyimide substrate 101 in Example 1, a Si substrate 131 was used.
(Used as gate electrode), a silicon dioxide film (SiO ₂ ) 132 is formed in place of the protective film 102, and a similar conductive monomolecular film 133 is formed, and then a pair of platinum electrodes (source 134, respectively). Use as drain 135 electrode) 5 μm
Except for forming at intervals, the same process is performed and the above S
A thin film transistor (TF) having an iO ₂ film as a gate insulating film
A T) type organic electronic device (three-terminal element) 136 could be produced (FIG. 13).

In this device, the channel of the TFT is
Since each end is composed of a polypyrrolyl group which is a conjugated bond group bonded to the source and drain electrodes,
An organic TFT having a field effect mobility of about 1000 cm ² / V · S several hundreds or more was easily obtained.

(Embodiment 4) As shown in FIG. 14, first,
Since a large number of organic electronic devices are used as liquid crystal operation switches, a three-terminal organic electronic device 142 is formed on the surface of an acrylic base material (0.5 mm thick) 141 in the same process as in Example 1.
A plurality of groups are arranged and formed in a matrix, and further,
The respective source side and gate side electrodes were connected by a source wiring and a gate wiring, respectively. A transparent electrode 143 was formed on the drain side electrode using an indium-tin oxide alloy (ITO).

Next, a polyimide coating film was formed on the surface of the array substrate by a usual method, and rubbing was performed to form an alignment film 144, thereby preparing an array substrate 145.

On the other hand, in parallel, a matrix of RGB color elements 147 are arranged in a matrix on the surface of the acrylic substrate 146 to form a color filter, and further a conductive transparent electrode 148 is formed on the front surface to form a color filter substrate. Material 149 was produced.

Next, a polyimide film was formed on the surface of the color filter and rubbed to prepare an alignment film 144 '.

Next, the array substrate on which the alignment film is formed
145 and the color filter substrate 149 are laminated so that the alignment films face each other, and the spacer 150 is sandwiched between the epoxy adhesive 151 and the epoxy adhesive 151 except for the sealing portion, and the peripheral portion is sealed and adhered at a predetermined interval. A cell was prepared.

Finally, TN type liquid crystal 152 is injected and sealed, and an IC chip incorporating peripheral circuits is mounted,
The TN type liquid crystal display device 155 could be manufactured by installing the polarizing plates 153 and 153 ′ in front and rear and incorporating the backlight 154 (FIG. 1).
4).

According to this method, it is not necessary to heat the base material in the manufacture of the array. Therefore, even if a base material having a low glass transition point (Tg) such as an acrylic base material is used, a sufficiently high image quality liquid crystal display device can be obtained. I was able to create it.

At this time, the gate electrode of the organic electronic device
As an insulating monomolecular film or an insulating monomolecular cumulative film in contact with
A hydrocarbon-containing surfactant (eg CH₃-(CH₂)₉-S
i-Cl ₃) And CH by the chemisorption method₃-(CH₂)₉-Si (-O-)₃
Was formed into a monolayer. In this case, the withstand voltage characteristic is 0.
5 x 10^TenV / cm-1 x 10^TenGreatly up to V / cm
I made it. Its peel strength is 1 ton / cm²To a degree
As a result, a highly reliable liquid crystal display device could be manufactured.

In the fourth embodiment, an example of producing a bottom gate type liquid crystal display device is shown, but it can be applied to a top gate type liquid crystal display device.

(Embodiment 5) As shown in FIG. 15, first,
Since a large number of organic electronic devices are used as the operation switches of the electroluminescent device, the three-terminal organic electronic device 162 group is formed in a matrix shape on the surface of the polyether sulfone base material (thickness 0.2 mm) 161 by the same process as in Example 1. A plurality of them were arranged and formed, and further, the respective source side and gate side electrodes were connected by a source wiring and a gate wiring, respectively.
In addition, a transparent electrode 163 is formed on the drain side electrode using an indium-tin oxide alloy (ITO) to form the array substrate 1.
64 was produced.

Next, a hole transport layer 165 is deposited on the transparent electrode 163 connected to the drain of the three-terminal organic electronic device, and the red light emitting layer 166 (2,3,7,8,12,13,17) is further deposited. , 18-octaethyl-21H23H-porphine platinum (I
I)), a green light emitting layer 66 '(tris (8-quinolinolato) aluminum) and a blue light emitting layer 166 "(4,4'-bis (2,2-diphenylvinyl) biphenyl) are mask-deposited, respectively, and then electron The transport layer 167 is vapor-deposited on the entire surface to form a cathode 168 (for example, an alloy of Mg and Ag, an alloy of Al and Li, or a stack of LiF and Al on the electron transport layer 167), and finally, a peripheral circuit. An EL type display device 169 was manufactured by mounting an IC chip incorporating the above (FIG. 15).

According to this method, since it is not necessary to heat the base material in manufacturing the array, an EL type display device having a sufficiently high image quality can be produced even if the polyether sulfone base material is used.

At this time, the gate electrode of the organic electronic device
And the surfactant containing the hydrocarbon group used in Example 4 above.
When an insulating film is formed, the withstand voltage characteristic is 0.5 × 10.^TenV /
cm ~ 1 x 10^TenV / cm could be greatly improved. That
Peel resistance is 1 ton / cm ²Good and reliable
Liquid crystal display device was manufactured.

Further, in the step of connecting and forming the electroluminescent films individually connected to the drain of the three-terminal organic electronic device, three types of electroluminescent films which respectively emit red, blue and green light are formed to form an electroluminescent film. A luminescence type color display device could be manufactured.

(Example 6) Bi (3- obtained in Synthesis Example 2)
(Methylpyrrolyl) group, a polarizable functional group oxycarbonyl group (-OCO-), and a trichlorosilyl group that undergoes dehydrochlorination reaction with active hydrogen (eg, hydroxyl group (-OH)) on the substrate surface.
(-SiCl ₃ ) and a substance of the following chemical formula (G1) (6- (bi
pyrrolyl) hexyl-12,12,12-trichloro-12-siladodecanoa
te) was synthesized.

[0205]

[Chemical 37]

[0206] To replace the terminal trichlorosilyl group with a trimethoxysilyl group, PEN of the above chemical formula 1 is used.
Is stirred with 3 molar times of methyl alcohol at room temperature (25 ° C.) to cause dehydrochlorination reaction. If necessary, the hydrogen chloride is separated as sodium chloride by adding sodium hydroxide. The obtained trimethoxysilane compound can also be used as a raw material for a chemisorption film by a dealcoholization reaction. II. Method for forming molecular film A chemical adsorption liquid G was prepared by diluting the compound of the above chemical formula (G1) to 1 wt% with a dehydrated dimethyl silicone solvent.

Next, a silica base layer having a thickness of 2 nm was formed on the surface of a glass substrate having a thickness of 5 mm. This silica underlayer was prepared by diluting tetrachlorosilane (SiCl ₄ ) to 1% with dehydrated dimethyl silicone organic solvent to prepare a chemisorption underlayer solution, and coating this chemisorption underlayer solution on one side of a glass substrate. , Tetrachlorosilane (SiCl ₄ ) and a hydroxyl group (-OH) on the surface of the glass substrate are caused to undergo dehydrochlorination reaction, and then washed with chloroform to remove unreacted substances, and trichlorosilanol (Cl ₃ Si). A monolayer of -O-) was formed. Next, it was reacted with water to substitute for the (OH) ₃ Si—O— film, and a hydroxyl group was introduced to form a silica underlayer.

Next, the surface of the silica underlayer is coated with the chemical adsorbent G to carry out a chemical adsorption reaction, and the unreacted substance remaining on the surface is removed by washing with chloroform. Was formed.

At this time, since a large number of hydroxyl groups containing active hydrogen are present in the silica underlayer, --S of the substance (G1) is obtained.
A monomolecular film composed of a molecule represented by the following chemical formula (G2) in which the iCl group caused a dehydrochlorination reaction with the hydroxyl group and was covalently bonded to the substrate surface was formed.

[0210]

[Chemical 38]

III. Alignment Method of Molecular Film Next, the glass substrate on which the monomolecular film was formed was washed with a non-aqueous chloroform solution, dried, and then subjected to a rubbing alignment treatment shown in FIG. 5A to form an aligned monomolecular film. IV. Method for forming electrode Next, a nickel thin film was formed by vapor deposition on predetermined portions on both ends of the monomolecular film. Gap distance is 10cm, length is 30c
m first and second electrodes were formed. V. Polymerization method First, light energy beam polymerization was performed. As shown in FIG. 5B, polarized visible light having a polarization direction from the first electrode to the second electrode was irradiated at about 500 mJ / cm ² to preliminarily polymerize while aligning.

Then, in a pure aqueous solution, 5 V / c was applied between the electrodes.
m electrolysis was applied to carry out electrolytic oxidative polymerization. The conditions of the electrolytic oxidative polymerization were a reaction temperature of 25 ° C. and a reaction time of 8 hours. Thereby, electropolymerization was performed to form a conductive organic thin film. At this time, a conjugated bond is formed in a self-organizing manner along the direction of the electric field, and when the polymerization is completed, the first electrode and the second electrode are electrically connected by the conductive polymer. . The obtained organic conductive film had a thickness of about 2.0 nm, the polypyrrole portion had a thickness of about 0.2 nm, and the organic conductive film had a length of 10 cm and a width of 30 cm.

One unit of the obtained organic conductive film polymer is represented by the following chemical formula (E3).

[0214]

[Chemical Formula 39]

VI. Measurement The obtained conductive organic thin film was measured with a commercially available atomic force microscope (A
FM) (manufactured by Seiko Instruments Inc., SAP 38
00N) in AFM-CITS mode, voltage: 1
The conductivity ρ under the conditions of mV and current: 160 nA is ρ> 1 × 10 ⁷ S / without doping at room temperature (25 ° C.).
It was cm. This is the ammeter 1 × 10 ⁷ S / cm
This is because it was only possible to measure up to, and the needle was over and shook out. Gold, which is a metal with good conductivity, has a density of 5.2 × 10 ⁵ S / cm at room temperature (25 ° C.),
Since the silver content is 5.4 × 10 ⁵ S / cm, the conductivity ρ of the organic conductive film of this example is surprisingly high. Therefore, the organic conductive film of the present invention is a "supermetal conductive film".
Can be said.

In the present invention, it is possible to easily reduce the conductivity ρ of the organic conductive film by making the conductive network incomplete or by reducing the degree of molecular orientation.

The resulting conductive organic thin film was useful as a transparent electrode or electric wire.

As in Example 2, the chemical formula (E
CH ₂ ═CH—CH ₂ — is introduced at the 5-position of the molecule of 1), the conductive organic thin film represented by the chemical formula (E8) is formed, and then the double bond is oxidized to form a hydroxyl group ( -OH) was introduced, and then the pyrrolyl compound represented by the chemical formula (E1) was reacted to form a cumulative film.

Example 7 The chemical adsorption solution was prepared by diluting the compound obtained in Example 6 to 1% with dehydrated dimethyl silicone solvent. A glass fiber having a diameter of 1 mm was immersed in this chemical adsorbent at room temperature (25 ° C.) for 1 hour to cause a desalting reaction on the surface of the glass fiber to form a thin film. Then, the unreacted compound was washed away with chloroform in a non-aqueous solution. Thereby, the hydroxyl group on the surface of the glass fiber and the chlorosilyl group (-SiC) of the compound are
A hydrogen chloride reaction was caused with l) to form a monomolecular film.

Next, the glass fiber on which the monomolecular film was formed was immersed in a chloroform solution for cleaning, and when the glass fiber was pulled out from the chloroform solution, the monomolecular film was oriented by draining in the lengthwise direction.

Next, a nickel thin film was formed by vapor deposition on a part of the end of the glass fiber.

Then, in a pure aqueous solution, 5 V / c was applied between the electrodes.
m electrolysis was applied to carry out electrolytic oxidative polymerization. The conditions of the electrolytic oxidative polymerization were a reaction temperature of 25 ° C. and a reaction time of 8 hours. As a result, electropolymerization was performed to form a conductive polymer, and both electrodes were electrically connected. At this time, since a conjugate bond is formed in a self-organizing manner along the direction of the electric field, when the polymerization is completed, the electrodes are electrically connected by the conductive polymer. In this manner, a polypyrrole conjugated polymer film was formed on the glass fiber in a length of 10 mm along the axial direction of the glass fiber. The organic thin film had a thickness of about 2.0 nm, and the polypyrrole portion had a thickness of about 0.2 nm. Further, the obtained organic conductive film was transparent under visible light.

An electric cable was produced by forming an insulating film so as to cover the surface of the organic thin film thus obtained. A cross-sectional view of the obtained electric wire is shown in FIG. 8A. Figure 8
In A, 11 is a glass core wire, 6 is a polypyrrole electrolytic oxidation polymerization film, and 13 is a coating insulating film made of room temperature curable silicone rubber.

A commercially available atomic force microscope (AFM) (manufactured by Seiko Instruments Inc.,
SAP 3800N), in the AFM-CITS mode, under the conditions of voltage: 1 mV, current: 160 nA, the conductivity ρ is ρ> 1 at room temperature (25 ° C.) without doping.
It was × 10 ⁷ S / cm. This is the ammeter 1 × 1
This is because it was possible to measure only up to 0 ⁷ S / cm and the needle was over and shook off.

An electric cable was produced by forming an insulating film so as to cover the surface of the organic thin film thus obtained. A room temperature curable silicone rubber was used for the coating insulating film.

In this embodiment, the electric cable may form a collective electric wire including a plurality of core wires electrically insulated from each other.

Further, as the core wire for producing the electric wire, metal other than glass can be used. In the case of metal, a monomolecular film can be easily formed by forming an oxide on the surface.

(Embodiment 8) In Embodiments 1 to 7, whether or not the conductive molecules are oriented is determined by forming a liquid crystal cell 170 as shown in FIG. It can be confirmed by irradiating light and observing from a position of 180. In the liquid crystal cell 170, the conductive molecular films of the glass plates 171 and 173 on which the conductive molecular films 172 and 174 are formed are placed inside, and the distance between the gaps is kept at 5 to 6 μm, and the periphery is bonded with an adhesive.
The liquid crystal composition 176 (nematic liquid crystal,
For example, it was created by injecting "LC, MT-5087LA" manufactured by Chisso Corporation. (1) When the polarizing plates 177 and 178 are crossed, the orientation directions of the conductive molecular films 172 and 174 are aligned, and one of the polarizing plates is parallel and the other polarizing plate is orthogonal to this direction. If it is perfectly aligned, the liquid crystal is aligned and becomes a uniform black color. If the uniform black is not obtained, the orientation is poor. (2) When the polarizing plates 177 and 178 are parallel, the conductive molecular film 1
The alignment directions of 72 and 174 are aligned, and both polarization plates are parallel to this direction. If it is perfectly aligned, the liquid crystal is aligned and becomes a uniform white color. If the white color is not uniform, the orientation is poor.

When the base material on the back side is not transparent, one polarizing plate is provided on the upper side, and light is radiated from the surface for observation with reflected light.

By this method, it was confirmed that the conductive molecular films obtained in Examples 1 to 13 were oriented.

[0231]

INDUSTRIAL APPLICABILITY The present invention can provide an organic thin film made of a conductive polymer which can be used as a conductive wire, a wiring, an electrode or a transparent electrode. Further, a semiconductor device, a capacitor, a liquid crystal display element, an electroluminescent element, which uses the organic thin film made of the conductive polymer as a conductor, a wiring, an electrode and a transparent electrode,
A high-performance device such as a solar cell can be provided. Furthermore, an electric wire or the like using an organic thin film made of a conductive polymer can be provided.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing a monomolecular film containing a conductive polymer formed on a base material according to Embodiment 1 of the present invention, where A is a monomolecular film in which a conductive polymer is formed in the entire region. Membrane, B is a monomolecular film in which a conductive polymer is formed in a plurality of partial regions, C is a monomolecular film in which a conductive polymer is formed in a plurality of partial regions It is a film.

FIG. 2 is a schematic plan view for explaining the direction of a conductive polymer according to the first embodiment of the present invention.

FIG. 3 is a plan view schematically showing a configuration example of a conductive region of a monomolecular layer containing a conductive polymer formed on a base material according to the first embodiment of the present invention, in which A is a continuous conductive layer in one direction. The polymer is formed in the whole region in a monomolecular layer, B is a monolayer in which conductive regions are connected in one direction to each conductive region, and the parallel conductive region is formed in which a conductive polymer is formed. C is a conductive line in which conductive regions are connected in one direction. A monolayer having conductive regions arranged in a matrix in which polymers are formed, D is an arbitrary pattern in which the directions of the conductive polymers formed in the respective conductive regions are the same and the shapes of the respective conductive regions are not the same. It is a monomolecular layer having conductive regions arranged in a line.

FIG. 4 is a cross-sectional view schematically showing a structural example of a monomolecular film formed on a base material according to Embodiment 1 of the present invention, where A is a monomolecular film formed on a base material with an electrically insulating film. , B are monomolecular films formed on a base material and having a protective film formed on the surface thereof.

5A and 5B are schematic perspective views for explaining an alignment method for inclining (aligning) the molecules that form the organic thin film according to the first embodiment of the present invention, where A is a rubbing alignment method, B is an optical alignment method, and C is a C alignment method. Is a drainage orientation method.

FIG. 6 is a perspective view schematically showing a configuration example in which a conductive region is formed in a selective portion on a base material according to the first embodiment of the present invention, and A is a single portion formed on the entire base material portion. A structure in which a plurality of conductive regions are formed in the molecular film is shown, and B represents a structure in which a plurality of monomolecular films in which conductive regions are formed in the entire region are formed on a base material.

FIG. 7 is a cross-sectional view schematically showing an example of a laminated structure of a monomolecular cumulative film formed on a base material according to Embodiment 2 of the present invention, in which A indicates that the orientation directions of the monomolecular layers are the same. X-type monomolecular cumulative film, B is an X-type monomolecular cumulative film in which the inclination of the orientation direction becomes strong for each monomolecular layer, and C is 2 for each monomolecular layer.
It is an X-type monomolecular cumulative film oriented in any one of the two orientation directions.

FIG. 8A shows an electric cable having an electrically conductive monomolecular film formed on the outer surface of the core wire in the twelfth embodiment of the present invention and having the entire area as an electrically conductive area, the surface of which is covered with an electrically insulating film. Sectional view B is a collective wire type electric cable formed on the surface of a quadrangular prism-shaped insulator according to Embodiment 3 of the present invention and having an outer surface provided with a monomolecular film having four conductive regions coated with an insulating film. FIG. 3C is a perspective view of a flat cable of a collective electric wire type including a monomolecular film having a conductive region in all regions formed on a base material and three pairs of connecting portions in Embodiment 3 of the present invention. is there.

FIG. 9 is a cross-sectional view schematically showing a structural example of a capacitor in which a conductive region formed in a monomolecular film according to Embodiment 4 of the present invention is used as an electrode, wherein A is a monomolecular film having a conductive region. In addition, a structure in which a dielectric is sandwiched between two monolayers with each monolayer inside, and B indicates a structure in which a monolayer having a conductive region is formed on each of two parallel surfaces of the dielectric.

FIG. 10 is a cross-sectional view for explaining a process of manufacturing a monomolecular film having a conductive region in Embodiment 1 and Example 6 of the present invention, in which A is formed on a substrate after the monomolecular layer forming process. B monolayer film, B is tilted (orientated)
Oriented monomolecular film after the process, C is a monomolecular film immediately after starting the conductive region forming process of applying a voltage to a pair of electrodes formed on the surface in the polymerizing electrode forming process, and D is after the conductive region forming process. It is a monomolecular film on which a conductive polymer is formed.

11A to 11F are conceptual diagrams of a process for manufacturing an organic conductive film in Example 2 of the present invention.

12A and 12B are conceptual cross-sectional views for explaining a process of orienting molecules in a molecular layer in Example 2 of the present invention.

FIG. 13 is a conceptual sectional view for explaining an organic electronic device in Example 3 of the present invention.

FIG. 14 is a conceptual sectional view for explaining a liquid crystal display device in embodiment 4 of the present invention.

FIG. 15 is a conceptual sectional view for explaining an electroluminescence (EL) display device according to a fifth embodiment of the present invention.

FIG. 16 is an explanatory diagram showing a method for evaluating the orientation of conductive molecules in Example 8 of the present invention.

[Explanation of symbols]

1 Base material (base material) 2 Base insulating film 3 protective film 4 Monolayer (monolayer) 5 Conjugated system (conjugated bond chain) 6 Conductive area 7 Metal contacts (wiring) 8 Dielectric 9 Conjugated polymerizable functional groups 11 Insulating base material 13 Insulation protection film 14 Monomolecular film composed of organic molecules having a pyrrole group 16 Conductive region having polypyrrole type conductive polymer 17 Platinum electrode for electrolytic polymerization 21 Resin base material 24 Monomolecular film in which organic molecules having a pyrrole group are oriented 34 Monomolecular film having polypyrrole-type conductive polymer 41 Rubbing roll 42 rubbing cloth 43 Polarizer 44 Organic solutions for cleaning

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norio Mino             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 4J032 BA13 BA14 BB01 BB03 BC01                       BC02 BC03 BC07 BC12 BC21                       BC32

Claims (21)

[Claims] 1. A terminal bonding group covalently bonded to the surface of a base material containing active hydrogen on the surface, a conjugated bonding group group selected from a plurality of pyrrolyl groups and a plurality of cylene groups, and the terminal bonding group and the conjugate. An organic group containing no active hydrogen between the bonding groups is included in the repeating molecular unit of the polymer, and the plurality of conjugated bond groups are polymerized with a conjugated bond group or a conjugated bond group of another molecule to form a conductive polymer. A conductive organic thin film characterized by being formed. 2. The conductive organic thin film according to claim 1, wherein the polymerization is at least one selected from electrolytic oxidative polymerization, catalytic polymerization and energy beam irradiation polymerization. 3. The conductivity (ρ) of the conductive organic thin film is
The conductive organic thin film according to claim 1, which has a dopant of 1 S / cm or more at room temperature (25 ° C.). 4. The conductivity (ρ) of the conductive organic thin film is
1 × 10 ³ S without dopant at room temperature (25 ° C.)
The conductive organic thin film according to claim 3, wherein the conductive organic thin film has a thickness of not less than / cm. 5. The conductivity (ρ) of the conductive organic thin film is
5.5 × 10 without dopant at room temperature (25 ° C.)
The conductive organic thin film according to claim 4, which is ⁵ S / cm or more. 6. The polymer is poly (3-pyrrole) containing no active hydrogen in the N group, or a copolymer of poly (3-pyrrole) containing no active hydrogen in the N group and poly (1-pyrrole). , And poly (3-chenylene), poly (4-pyrrole) containing no active hydrogen in the N group, and copolymer of poly (4-pyrrole) containing no active hydrogen in the N group and poly (1-pyrrole) 2. The conductive organic thin film according to claim 1, which is at least one polymer selected from the group consisting of, and poly (4-chenylene), or a copolymer thereof. 7. The siloxane (—Si) is used as the terminal bonding group.
The conductive organic thin film according to claim 1, wherein the conductive organic thin film is at least one bond selected from O-) and SiN- bond (however, Si and N may have other bonding groups corresponding to the valence). . 8. The conductive organic thin film according to claim 1, wherein molecules constituting the conductive organic thin film are oriented. 9. The conductive organic thin film according to claim 1, wherein the conductive organic thin film is transparent to light having a wavelength in the visible region. 10. The polymer molecular unit forming the conductive organic thin film has the following chemical formulas (A1)-(A5).
The conductive organic thin film according to claim 1, which is represented by any one selected from the group consisting of: [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] (However, in the formula A1-A5, Z is an ester group (-C
OO-), oxycarbonyl group (-OCO-), carbonyl group (-CO-) and carbonate (-OCOO-)
Group, at least one functional group selected from an azo (-N = N-) group or a chemical bond (-), R is an alkyl group having 1 to 3 carbon atoms, R1, R2, R3 and R4 are hydrogen and 1 carbon atom. −
Organic group containing 10 alkyl groups or unsaturated groups, m, n
Is an integer, m + n is 2 or more and 25 or less, and Y is oxygen (O)
Alternatively, nitrogen (N) and E are hydrogen or an alkyl group having 1 to 3 carbon atoms, p is an integer of 1, 2, or 3, and u is an integer of 1-6. ) 11. The conductive organic thin film according to claim 1, wherein the conductive organic thin film further contains a dopant substance. 12. The conductive organic thin film according to claim 1, wherein the conductive organic thin film is a monomolecular film or a monomolecular cumulative film. 13. A terminal functional group capable of covalently bonding to a surface of a base material containing active hydrogen, at least one conjugated bond group selected from a polypyrrolyl group and a polyphenylene group, the terminal bond group and the conjugated bond group. During the period, a compound containing an organic group containing no active hydrogen in the molecule is brought into contact with the surface of the base material containing active hydrogen on the surface, and an organic thin film is formed by covalent bonding by an elimination reaction, and the conjugate bond is formed. A method for producing a conductive organic thin film, which comprises forming a conductive polymer by conjugate-bonding possible groups to each other by at least one polymerization method selected from electrolytic oxidation polymerization, catalytic polymerization and energy beam irradiation polymerization. 14. The terminal functional group is a halogenated silyl group, an alkoxysilane group or an isocyanate group,
The covalent bond is formed by active hydrogen on the surface of the substrate and at least one elimination reaction selected from a dehydrochlorination reaction, a dealcoholization reaction and a deisocyanation reaction.
A method for producing a conductive organic thin film as described in 1. 15. The polymer is poly (3-pyrrole) containing no active hydrogen in the N group, or a copolymer of poly (3-pyrrole) containing no active hydrogen in the N group and poly (1-pyrrole). , And poly (3-chenylene) with active hydrogen N
Poly (4-pyrrole) not containing a group, poly (4-pyrrole) not containing active hydrogen in an N group and poly (1-pyrrole)
14. The method for producing a conductive organic thin film according to claim 13, wherein the copolymer is a copolymer with a polymer, and at least one polymer selected from poly (4-chenylene) or a copolymer thereof. 16. An organic thin film after being covalently bound by the elimination reaction is subjected to an alignment treatment by rubbing, a gradient drainage treatment from a reaction solution after molecules are covalently bound to a substrate surface by the elimination reaction, and a polarized light. 15. The method for producing a conductive glass according to claim 13, wherein the irradiation treatment is performed, and at least one orientation treatment selected from orientations due to fluctuations of molecules during polymerization is performed. 17. A compound molecule containing at least one conjugated bond group selected from the polypyrrolyl group and the polyphenylene group, and an organic group containing no active hydrogen between the terminal bond group and the conjugated bond group in the molecule. The following chemical formula (B
The method for producing a conductive organic thin film according to claim 13, which is represented by any one of 1) to (B5). [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] (However, in the formula B1-B5, Z is an ester group (-C
OO-), oxycarbonyl group (-OCO-), carbonyl group (-CO-) and carbonate (-OCOO-)
Group, at least one functional group selected from an azo (-N = N-) group or a chemical bond (-), R is an alkyl group having 1 to 3 carbon atoms, R1, R2, R3 and R4 are hydrogen and 1 carbon atom. −
Organic group containing 10 alkyl groups or unsaturated groups, m, n
Is an integer, m + n is 2 or more and 25 or less, D is at least one reactive group selected from a halogen atom, an isocyanate group and an alkoxyl group having 1 to 3 carbon atoms, E is hydrogen or an alkyl group having 1 to 3 carbon atoms, p Is an integer of 1, 2 or 3, and u is an integer of 1-6. ) 18. The method for producing a conductive organic thin film according to claim 13, wherein the conductive organic thin film is formed into a monomolecular layer. 19. The method for producing a conductive organic thin film according to claim 13, wherein the energy beam is at least one selected from ultraviolet rays, deep ultraviolet rays, X-rays, and electron beams. 20. The energy beam is at least one selected from polarized ultraviolet rays, polarized deep ultraviolet rays, and polarized X-rays, and the alignment treatment and the formation of the conductive organic thin film are performed at the same time. Manufacturing method of conductive organic thin film. 21. The method for producing a conductive organic thin film according to claim 13, wherein a dopant is further added during or after the formation of the conductive organic thin film.