JP2003234021A - Method for producing conductive organic thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a conductive organic thin film capable of easily forming, with precision, an organic thin film comprising a conductive region of a desired pattern. <P>SOLUTION: A coat of organic molecules containing an end bondable group which can form cobalent bonding with surface of a base material 1 and a conjugated bondable group which can polymerize with other molecules is formed on the surface of the base material 1. In a part which becomes a conductive region 3a, the conjugated bonding capable group is polymerized with the conjugated bondable group of other organic molecule to form a conjugated bonding chain. In a part which becomes an insulating region 3b, the conjugated bondable group is made to remain as non-polymerized state. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a conductive organic thin film including a conductive region formed in a pattern.

[0002]

2. Description of the Related Art Conventionally, inorganic materials represented by silicon crystals have been used for electronic devices. However, in such an inorganic material, as the miniaturization progresses, crystal defects become a problem, and there is a problem that device performance is greatly influenced by crystals.

On the other hand, the conductive organic thin film is attracting attention as a material that can cope with the progress of device miniaturization because its characteristics are hardly deteriorated even if it is subjected to fine processing. The applicant has already proposed, as a conductive organic thin film, an organic thin film containing a conjugated bond chain such as polyacetylene, polydiacetylene, polyacene, polyphenylene, polythiophene, polypyrrole, and polyaniline (for example, JP-A-2 (1990). -27766, USP 5,008,127, EP-
A-0385656, EP-A-0339677, EP-A-0552637, USP5,270,41
7, JP-A-5 (1993) -87559 JP, JP 6 (1994) -242352
Issue).

[0004]

Therefore, in view of the progress of miniaturization of various electronic devices, the present invention can easily and highly accurately form a conductive organic thin film having a desired patterned conductive region. An object of the present invention is to provide a method for producing a conductive organic thin film that can be used.

[0005]

In order to achieve the above object, a method for producing a conductive organic thin film according to the present invention comprises a conductive region selectively formed in a predetermined region of a base material surface, and the base material surface. A method for producing a conductive organic thin film including an insulating region formed in a region excluding the predetermined region, wherein the surface of the base material having active hydrogen or provided with active hydrogen has one of a molecule A terminal bondable group capable of forming a covalent bond with the surface of the substrate at the end of, and an organic molecule containing a conjugated bondable group capable of polymerizing with another molecule at any part of the molecule, By forming a covalent bond by a reaction between an end-bondable group of an organic molecule and active hydrogen on the surface of the base material, a coating film is formed on the surface of the base material, and in the portion that becomes the conductive region of the coating film, Groups that can be conjugated to other organic moieties Conjugated bondable group and polymerized for forming a conjugated bond chain, in the insulating region to become part of the coating, characterized in that to leave the conjugated bondable groups in the form of unpolymerized.

According to such a manufacturing method, a conductive region having a desired pattern can be easily and highly accurately formed on the conductive organic thin film. The "predetermined region" means a region where a conductive region on the surface of the base material is to be formed.

The conductive region formed by the present invention exhibits conductivity by forming a conjugated bond chain by polymerization of organic molecules and forming a conductive network by this conjugated bond chain. On the other hand, the insulating region is a region where the insulating property is maintained because the organic molecules are not polymerized and the conjugated bond chain as described above is not formed. Here, the "conductive network" means an aggregate of conjugated bond chains involved in electrical conduction.

In the above production method, it is preferable that the polymerization is carried out by at least one polymerization method selected from electrolytic polymerization, catalytic polymerization and energy beam irradiation polymerization. A method of polymerizing a portion to be a conductive region and leaving a portion to be an insulating region unpolymerized by using these polymerization methods will be described in detail later.

Further, in the above-mentioned manufacturing method, it is preferable that the organic molecules forming the coating film are oriented in at least a portion of the coating film which becomes the conductive region. By orienting the organic molecules, the covalently bondable groups can be arranged in a certain direction, and the covalently bondable groups can be arranged in close proximity to each other. As a result, the polymerization of organic molecules can be facilitated, and a conductive region having high conductivity can be formed.

Further, by orienting the organic molecules constituting the film, it becomes possible to arrange the conjugated bond chains constituting the conductive network substantially parallel to each other within a specific plane in the conductive organic thin film. Therefore, a directional conductive network can be formed, and conductive anisotropy can be imparted to the conductive region.

The term "orientate" means to incline each organic molecule forming the film in a predetermined direction. Further, in the present invention, the orientation direction of the organic molecule means the direction of a line segment in which the long axis of the organic molecule is projected on the surface of the substrate.

Examples of the orientation treatment method include a rubbing treatment, a treatment for draining the liquid in a predetermined direction from the surface of the substrate having the coating film, and a polarized light irradiation treatment. In addition, the organic molecules that form the film can be oriented also by the fluctuations of the molecules during the polymerization.

In the above manufacturing method, it is preferable that the coating film is a monomolecular film or a monomolecular cumulative film. According to this preferred example, a conductive monolayer or a conductive monolayer stack can be manufactured. Such a conductive organic thin film has an advantage that it exhibits extremely good conductivity even when the film thickness is small.

Further, in the case of a conductive monomolecular cumulative film, a desired conductivity can be obtained by changing the number of monomolecular layers. The conductivity of the monomolecular cumulative film depends, for example, on the number of laminated monomolecular layers. For example, when the same monomolecular film is accumulated, the conductivity is almost proportional to the cumulative number of monomolecular films. .

In the above manufacturing method, the organic molecule is
It includes an end-bondable group and a conjugate-bondable group.

The conjugated bondable group contains at least one group selected from a pyrrolyl group, a cenyl group, an ethynylene group (-C≡C-) and a diacetylene group (-C≡C-C≡C-). It is preferably a group.

When the conjugated bondable group contains a pyrrolyl group, a polypyrrole type conjugated bond chain can be formed, and when it contains a cenyl group, a polythiophene type conjugated bond chain can be formed. Further, when the conjugated bondable group contains an ethynylene group, it can form a polyacetylene-type conjugated bond chain, and when it contains a diacetylene group, it can form a polydiacetylene-type or polyacene-type conjugated bond chain. it can.

The end-bondable group is preferably a halogenated silyl group, an alkoxysilyl group or an isocyanate silyl group. The silyl halide group is particularly preferably a chlorosilyl group. Further, the alkoxysilyl group is particularly preferably an alkoxysilyl group having 1 to 3 carbon atoms.

When the terminal bonding group is a silyl halide group, a covalent bond can be formed by a dehydrohalogenation reaction with active hydrogen on the surface of the substrate. When the terminal bonding group is an alkoxysilyl group, a covalent bond can be formed by dealcoholation reaction with active hydrogen on the surface of the base material. When the terminal bonding group is an isocyanate silyl group, a covalent bond can be formed by a deisocyanation reaction with active hydrogen on the surface of the base material.

Further, in the above-mentioned production method, the covalent bond formed by the reaction between the terminal bondable group and the active hydrogen on the surface of the substrate is selected from a siloxane bond (-SiO-) and a -SiN- bond. It is preferably at least one bond. In this case, other bonding groups corresponding to the valence may be bonded to Si and N. Examples of the form in which the other bonding group is bonded include a form in which the organic molecule is polymerized by bonding the terminal bonding groups of the organic molecule.

Further, the organic molecule preferably contains a polar functional group containing no active hydrogen between the terminal bondable group and the conjugated bondable group. According to this preferable example, the molecules are liable to freely rotate in the polar functional group portion, so that the organic molecules constituting the coating are easily oriented.

Further, when such an organic molecule containing a polar functional group is used, the formed conductive region can be a region whose conductivity changes according to an applied electric field. Such a conductive region is useful as a constituent member of an organic device. It is considered that the change in the conductivity of the conductive region due to the application of the electric field occurs because the polar functional group responds to the electric field and the influence of the response propagates to the structure of the conductive network.

The polar functional group is an ester group (--CO
O-), oxycarbonyl group (-OCO-), carbonyl group (-CO-) and carbonate (-OCOO-)
It is preferably at least one group selected from the groups. As described above, a functional group whose polarization is increased by application of an electric field has extremely high sensitivity to an applied electric field and has extremely high response speed.

The organic molecule may contain a photoresponsive functional group between the terminal bondable group and the conjugate bondable group. When such an organic molecule containing a photoresponsive functional group is used, the conductive region to be formed can be a region whose conductivity changes according to the irradiation light. Such a conductive region is useful as a constituent member of an organic device. Examples of the photoresponsive functional group include an azo group (-N = N-).

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION An example of the manufacturing method of the present invention will be described below.

First, a coating film which is a precursor of a conductive organic thin film is formed on the surface of a base material. As the method of forming the coating film, for example, a chemical adsorption method or the like can be adopted.
According to these methods, a monomolecular film or a monomolecular cumulative film can be formed.

The case where the chemical adsorption method is adopted will be described below as an example of the film forming method. The chemisorption method is
In this method, the organic molecules to be the coating material are brought into contact with the surface of the base material to chemically adsorb the organic molecules on the surface of the base material.

As described above, the organic molecule serving as the coating material contains a terminal bondable group at one end of the molecule,
Those containing a covalently bondable group on any part of the molecule are used.

The conjugate bondable group is a functional group capable of forming a conjugate bond by polymerization with another molecule. Specific examples of the group capable of conjugate bonding are as described above.

The end-bondable group is a functional group capable of forming a chemical bond, preferably a covalent bond, by reacting with the surface of the substrate. Specific examples of the terminal bondable group are as described above.

Further, the organic molecule serving as the coating material preferably has a polar functional group or a photoresponsive functional group containing no active hydrogen between the group capable of conjugate bonding and the group capable of terminal bonding. Specific examples of the polar functional group and the photoresponsive functional group are as described above.

Preferred organic molecules include compounds represented by the following chemical formula (1) or (2).

[0033]

[Chemical 2]

In the above chemical formula, X is hydrogen, an organic group containing an ester group or an organic group containing an unsaturated group. Examples of the organic group containing an ester group include CH ₃ COO
_{-, C 2 H 5 COO-,} C 3 H 7 COO- , and the like. Further, as the organic group containing an unsaturated group, for example, H
₂ C = CH-, CH ₃ CH = CH- and the like.

In the above chemical formula, q is 0-10.
, Z is an ester group (—COO—), an oxycarbonyl group (—OCO—), a carbonyl group (—CO—) or a carbonate group (—OCOO—), and D is a halogen, an isocyanate group or a carbon number of 1 to 3. An alkoxyl group of
E is hydrogen or an alkyl group having 1 to 3 carbon atoms, m and n
Is 2 ≦ (m + n) ≦ 25, preferably 10 ≦ (m + n)
An integer satisfying ≦ 20 and p is an integer of 1 to 3.

Another example of the organic molecule is a compound represented by the following chemical formula (3) or (4). In the formula below, X, D, E, m, n, p
And q are the same as in the above formulas (1) and (2).

[0037]

[Chemical 3]

Further, another example of the organic molecule is a compound represented by the following chemical formula (5) or (6). In the formulas below, X, D, E, p and q are the same as in the formulas (1) and (2). Further, r is an integer of 2 to 25, preferably 10 to 20.

[0039]

[Chemical 4]

Further, as still another example of the preferable organic molecule, compounds represented by the following chemical formulas (7) to (10) can be mentioned. In the formulas below, X, D, E, p and q are the same as in the formulas (1) and (2). In addition, s and t are integers of 1 to 20, respectively.

[0041]

[Chemical 5]

As the base material, a base material having active hydrogen on the surface can be used. Active hydrogen on the surface of the base material is, for example, —OH group, —COOH group, —NH ₂ group, or —OH group.
It exists as an NH group. As the base material having active hydrogen, for example, a glass base material, a quartz base material, a silicon base material, a silicon nitride base material, or the like can be used.

Further, a treatment for applying active hydrogen was applied.
It is also possible to use a substrate. In this case, the base material body
Is not particularly limited and has active hydrogen.
Can be used as a base material or a base material that lacks active hydrogen.
Yes. Examples of the treatment for providing active hydrogen include SiC
l_Four, HSiCl₃, SiCl₃O- (SiCl₂-O) _n
-SiCl₃(However, n is an integer of 0 or more and 6 or less), Si
(OH)_Four, HSi (OH)₃, Si (OH)₃O- (S
i (OH)₂-O)_n-Si (OH)₃(However, n is 0 or less
Hydrophilicity by contacting the base material surface with an integer of 6 or less)
The method of forming the chemically adsorbed film can be adopted.
Further, on the surface of the base material, for example, SiO₂, Al₂O₃, Ti₂
O₃Also active by forming inorganic oxides such as
Hydrogen can be applied. Also, other processing methods
For example, corona treatment and plasma treatment, etc.
The method of activating the surface of the base material can be mentioned.

When the organic molecule is brought into contact with the surface of the substrate, the end-bondable group of the organic molecule reacts with the surface of the substrate,
Chemical bonds are formed, preferably covalent bonds. As a result, the organic molecules are fixed on the surface of the base material and a film is formed.

For example, when the terminal bondable group is a halogenated silyl group, an alkoxysilyl group or an isocyanate silyl group, these groups react with the active hydrogen on the surface of the substrate to dehydrohalogenate, dealcoholize or A covalent bond is formed by causing an elimination reaction such as a deisocyanation reaction. At this time, when the active hydrogen on the surface of the base material exists as an —OH group, a siloxane (—SiO—) bond is formed as the covalent bond, and the active hydrogen becomes —OH.
When present as an NH group, -S is used as the covalent bond.
An iN-bond is formed.

In the chemical adsorption method, as a method of bringing the organic molecules into contact with the surface of the base material, generally, organic molecules to be a coating material are added to a solvent to prepare a chemical adsorption liquid, and this is brought into contact with the surface of the base material. The method of letting is adopted. As the organic solvent, for example, a non-aqueous organic solvent such as xylene, toluene or dimethylsiloxane can be used. The concentration of the organic molecule in the chemical adsorption liquid is not particularly limited, but is, for example, 0.01 to 1 mol / L,
It is preferably 0.05 to 0.1 mol / L.

The time for contacting the base material with the chemical adsorbent is not particularly limited, but is, for example, 1 to 10 hours, preferably 1 to 3 hours. The temperature of the chemical adsorption liquid at this time is, for example, 10 to 80 ° C., preferably 2
It is 0 to 30 ° C.

As a method of bringing the surface of the base material into contact with the chemical adsorption liquid, for example, a method of immersing the base material in the chemical adsorption liquid, a method of applying the chemical adsorption liquid to the surface of the base material, or the like can be adopted.

In the case of forming a monomolecular cumulative film, after forming the monomolecular film of the first layer, the surface of the monomolecular film is further hydrophilized, and then the monomolecular film is formed by the same chemical adsorption method as described above. A molecular film may be formed. By repeating such hydrophilic treatment and chemisorption, a desired number of laminated films can be formed.

The method of hydrophilizing treatment is not particularly limited, but for example, when an unsaturated group such as a vinyl group is present on the surface of the monomolecular film, it is treated in an atmosphere containing water. A method of irradiating the surface of the molecular layer with an energy beam such as an electron beam or an X-ray can be adopted. According to this method, -OH groups can be introduced on the surface of the monomolecular film. Another method is to immerse the surface of the monomolecular film in an aqueous potassium permanganate solution. In this case, -COOH groups can be introduced on the surface of the monolayer.

When forming a monomolecular cumulative film, the second and subsequent monomolecular films can be formed by the Langmuir-Blodgett (LB) method or the like.
In this case, the hydrophilic treatment of the surface of the lower monolayer is not always necessary. However, it is preferable to perform the hydrophilic treatment because the lower monolayer and the upper monolayer can be chemically bonded to each other and a cumulative film having excellent durability can be formed.

When forming a monomolecular cumulative film, all layers may be made of the same organic molecule, or each layer may be made of different kinds of organic molecules. Further, the structure of the monomolecular cumulative film is not particularly limited and may be any of X-type, Y-type and Z-type structures.

After the coating is formed, it is preferable to wash the surface of the base material. By carrying out this washing step, unadsorbed organic molecules can be removed from the surface of the base material, and a surface-free coating film can be obtained. As the organic solvent for cleaning the base material, for example, chloroform, acetone, methanol, ethanol or the like can be used.

In the production method of the present invention, preferably, the organic molecules constituting the coating film are oriented in at least the portion which becomes the conductive region. By orienting the organic molecules, the conductivity of the formed conductive region can be further improved. As the orientation method, for example, the following method can be adopted.

(I) Rubbing treatment In the rubbing treatment, the surface of the coating is rubbed with a rubbing cloth in a certain direction. According to this rubbing treatment, the organic molecules forming the film can be oriented in the rubbing direction. As the rubbing cloth, a cloth made of nylon or rayon can be used.

Further, by rubbing the surface of the base material prior to forming the coating film and forming the coating film on the surface of the base material after the rubbing treatment, the organic molecules constituting the coating film are inclined in a predetermined direction. Can be oriented.
In this case, the orientation direction of the organic molecules is generally the same as the rubbing direction in the rubbing treatment.

(Ii) Polarized light irradiation treatment By irradiating the film with polarized light, the organic molecules constituting the film can be oriented. In this case, the orientation direction of the organic molecule is generally the same as the polarization direction. According to such an alignment method using polarized light irradiation treatment, it is possible to prevent or suppress breakage of the coating film due to desorption of organic molecules constituting the coating film from the surface of the base material or destruction of the organic molecules themselves. As the polarized light, it is preferable to use linearly polarized light having a wavelength in the visible light region.

(Iii) Liquid draining treatment The liquid draining treatment is carried out by wetting the surface of the base material on which the coating has been formed with a liquid and draining the liquid in a predetermined direction from the surface of the base material. In this case, the orientation direction of the organic molecules is generally the same as the liquid draining direction. This treatment can be carried out by immersing the base material having the coating film in a liquid and then pulling the base material out of the liquid while maintaining a predetermined inclination angle with respect to the liquid surface.

When the substrate is washed after forming the film,
The liquid draining treatment can be performed by setting the liquid draining direction of the solvent used for cleaning to a constant direction. In addition, the same orientation effect can be obtained by making the draining direction of the chemical adsorbent liquid constant when forming the film.

The liquid draining method is not limited to the method of pulling up the base material from the liquid, and a gas such as dry air is blown onto the substrate surface from a certain direction to scatter and remove the non-aqueous solvent in the same direction. It is also possible to adopt the method. In this case, the direction in which the non-aqueous solvent is scattered is the draining direction, and the organic molecules forming the coating can be oriented in this direction.

(Iv) Orientation by Fluctuation of Molecules in Polymerization Step in Solution In addition to the above three orientation methods, it is also possible to use orientation by fluctuation of molecules in the subsequent polymerization step. In particular, when the organic molecule forming the coating contains a polar functional group, if it is in a solution, even at room temperature (25 ° C.),
Fluctuations such as rotation of molecules are likely to occur. Therefore, for example, by carrying out the subsequent polymerization step in a solution, it becomes possible to orient the organic molecules constituting the film due to the fluctuation of the molecules.

Even if the above four orientation methods are applied independently,
A plurality of orientation methods may be combined and applied. By applying a plurality of alignment methods in combination, the organic molecules that form the coating can be more accurately aligned. In this case, it is preferable that the alignment of the organic molecules realized by each alignment method is substantially the same. That is, it is preferable that the rubbing direction, the polarization direction, and the liquid draining direction are substantially the same.

In this orientation treatment, the entire coating film may be oriented, or only a predetermined portion of the coating film may be oriented. As the latter form, for example,
For example, the conductive region may be oriented and the insulating region may not be oriented.

Further, the orientation direction may be different for each predetermined portion of the film. As such a form, for example, when forming a plurality of conductive regions, a form in which the orientation direction is different for each conductive region can be mentioned. in this way,
When the alignment direction is different for each predetermined portion, it is preferable to apply rubbing alignment treatment or polarized light irradiation treatment as the alignment treatment method.

As a method of applying a rubbing treatment to make the orientation direction different for each predetermined portion, for example, a first resist pattern having a predetermined pattern is formed on the surface of a base material or a coating film, and this resist pattern is used. The uncoated base material or coating surface is rubbed in a predetermined first rubbing direction, and the first resist pattern is removed after the rubbing treatment. Then, a second resist pattern in which a predetermined pattern different from the first resist pattern is formed on the surface of the base material or the coating film is formed, and the surface of the base material or the coating film not covered with this resist pattern is formed into the second predetermined pattern. Rubbing is performed in the rubbing direction, and the second resist pattern is removed after the rubbing process. 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, by repeating this with different rubbing directions, a complicated alignment pattern can be formed.

As a method of applying the polarized light irradiation treatment to make the orientation direction different for each predetermined portion, for example, a first photomask having a predetermined pattern is formed,
After irradiating the first polarized light, a second polarized light having a polarization direction different from the polarization direction of the first polarized light is passed through a second photomask on which a predetermined pattern different from the pattern of the first photomask is formed. Should be irradiated. Further, by repeating this with different polarization directions, a complicated alignment pattern can be formed.

By scanning and irradiating the coating with polarized light while changing the polarization direction, it is possible to form not only a linear conductive network but also a curved conductive network.

When a monomolecular cumulative film is formed as the above-mentioned coating, the method of orienting the coating is, for example, after repeating the step of forming the monomolecular layer to form the monomolecular cumulative film, A method of collectively orienting in a predetermined direction can be applied. This method is particularly effective when the cumulative number of layers is small. When this method is applied, it is preferable to adopt polarized light irradiation treatment or rubbing treatment as the orientation method. It is also possible to apply a method of repeating the step of orienting the monomolecular layer after forming the monomolecular layer. This method is particularly effective when the number of accumulated layers is large. When this method is applied, it is preferable to adopt polarized light irradiation treatment as the orientation method.

When a monomolecular cumulative film is formed as the coating film, the orientation directions of the layers forming the monomolecular cumulative film may be the same or different for each layer.

Next, the organic molecules forming the coating are polymerized to form a conductive organic thin film. 1A to 1C are schematic views showing an example of the structure of a film (that is, a conductive organic thin film) after polymerization.

In this step, the organic molecules in a predetermined region of the film are polymerized, and the organic molecules in the other regions are left unpolymerized. That is, the coating film is polymerized in a predetermined pattern. As a result,
As shown in A, a conductive organic thin film 3 having a conductive region 3a and an insulating region 3b is formed on the surface of the base material 1.

FIG. 1B is a schematic diagram showing an example of the structure of the conductive region 3a. As shown in this figure, the conductive region 3
In the portion to be a, the groups capable of forming a conjugated bond of the organic molecules are bonded to each other by this polymerization to form a conjugated bond chain. Then, a conductive network is formed by the formation of the conjugated bond chain, and the film exhibits conductivity. In FIG. 1B, 10 represents 1 unit of the polymer forming the conductive region, 11 represents 1 unit forming the conjugated bond chain, and 12 represents an end-bonding group chemically bonded to the surface of the base material.

For example, when the organic molecules forming the film are
In the case of the compound represented by the chemical formula (1) or (2), a polymer constituted by a unit represented by the following chemical formula (11) or (12) is used as the polymer constituting the conductive region. Can be formed. In the formulas (11) and (12) below, X, Z, E,
m, n, p and q are the same as those in the above formulas (1) and (2).

[0074]

[Chemical 6]

When the organic molecule forming the coating film is a compound represented by the chemical formula (3) or (4), the polymer forming the conductive region is represented by the following chemical formula (13) or ( A polymer composed of the unit represented by 14) can be formed. In the formulas (13) and (14) below, X, E, m, n,
p and q are the same as those in the above formulas (3) and (4).

[0076]

[Chemical 7]

When the organic molecule forming the coating is a compound represented by the chemical formula (5) or (6), the polymer forming the conductive region is represented by the following chemical formula (15) or ( A polymer composed of the unit represented by 16) can be formed. In the formulas (15) and (16) below, X, E, p, q and r are the same as those in the formulas (5) and (6).

[0078]

[Chemical 8]

When the organic molecules forming the coating film are compounds represented by the chemical formulas (7) to (10), the following chemical formulas (17) to ( A polymer composed of the unit represented by 20) can be formed. In formulas (17) to (20) below, X, E, p, q, s, and t are the same as in formulas (7) to (10).

[0080]

[Chemical 9]

FIG. 1C is a schematic view showing an example of the structure of the insulating region 3b. As shown in this figure, the insulating region 3
Polymerization between organic molecules does not occur in the portion b. Therefore, the film does not exhibit conductivity, and its insulating property is maintained. In addition, in FIG. 1C, 20 represents an organic molecule constituting the coating film, 21 represents a group capable of conjugate bonding,
22 represents an end bonding group.

In this step, "polymerization" means a reaction in which groups capable of forming a conjugated bond are bound to each other to form a conjugated bond chain. For example, when the organic molecules forming the coating are already polymerized at a site other than the conjugate bondable group, the conjugate bondable groups in the molecule (polymer) are bonded and crosslinked,
The polymerization in this step includes such crosslinking.

This polymerization step can be carried out by a method such as catalytic polymerization, energy beam irradiation polymerization, electrolytic polymerization and the like. Hereinafter, each polymerization method will be described in detail.

(I) Catalytic Polymerization Catalytic polymerization is carried out by bringing the coating film into contact with a catalyst.
It is a method of polymerizing the organic molecules constituting the coating.

FIG. 2 is a diagram showing an example of a method of polymerizing the coating film in a pattern using catalytic polymerization. This method can be carried out by forming a resist pattern 4 on the surface of the coating and bringing the coating having the resist pattern 4 into contact with a solution 5 containing a catalyst. The resist pattern 4 is patterned so as to open a portion to be the conductive region 3a and cover a portion to be the insulating region 3b. According to this method, in the portion not covered with the resist pattern (the portion corresponding to the opening portion of the resist pattern), the coating film comes into contact with the catalyst, so that the polymerization of organic molecules of the coating film occurs and the conductive region 3a is formed. Is formed. On the other hand, in the portion covered with the resist pattern, the coating film does not come into contact with the catalyst, so that organic molecules are not polymerized and become the insulating region 3b.

The resist pattern 4 is not particularly limited, but it is preferable to use a material that can be dissolved and removed by an organic solvent. Examples of such a material include photoresist. As a method of forming the photoresist, for example, in the case of using a photoresist, a method of applying a resist to the surface of the film and forming an opening corresponding to the pattern of the conductive region in the resist by photolithography is adopted. You can

This resist pattern is removed from the surface of the coating after polymerization. The method for removing the resist pattern is not particularly limited, but, for example, a method of dissolving the resist pattern with an organic solvent can be adopted. In this case, the organic solvent can be appropriately selected according to the resist pattern. For example, chloroform, acetone, xylene, etc. can be used.

The catalyst can be appropriately selected according to the organic molecules constituting the coating, but for example, a Ziegler-Natta catalyst and a metal halide catalyst can be used. As the metal halide catalyst, those containing Mo, W, Nb, Ta or the like as a metal are preferable,
Specific examples include MoCl ₅ , WCl ₆ , NbCl ₅ , and T.
aCl ₅ , Mo (CO) ₅ , W (CO) ₆ , Nb (C
O) ₅ , Ta (CO) _{5, and the} like.

As the catalyst solution, it is possible to use a solution prepared by adding a catalyst to a solvent such as chloroform, toluene, dioxane or anisole. As a method of bringing the catalyst solution into contact with the coating, as shown in FIG. 2, in addition to the method of immersing the substrate on which the coating is formed in the solution containing the catalyst, the method of applying the solution containing the catalyst to the surface of the coating, etc. Applicable. The polymerization conditions are not particularly limited, but for example, the polymerization temperature is 20 to 30 ° C. and the polymerization time is 1 to
120 minutes.

As a method of bringing the catalyst into contact with the coating, it is also possible to apply a method of exposing the coating to a gas atmosphere containing the catalyst, a method of blowing a gas containing the catalyst onto the surface of the coating, or the like.

Further, the organic molecules forming the film are oriented by flowing a solution containing the catalyst in a certain direction with respect to the film surface or by blowing a gas containing the catalyst in the same direction with respect to the film surface. It is also possible to polymerize with it.

(Ii) Energy Beam Irradiation Polymerization Energy beam irradiation polymerization is a method of polymerizing the organic molecules constituting the film by irradiating the film with an energy beam.

FIG. 3 is a diagram showing an example of a method of polymerizing the coating film in a pattern by using energy beam polymerization. In this method, a mask 6 is arranged on the surface of the coating,
An energy beam 7 is applied to the film through the mask 6.
To irradiate. The mask 6 has a conductive region 3a.
Is patterned so as to open a portion to be an insulating region 3b and a portion to be an insulating region 3b. According to this method, in the portion not covered with the mask (the portion corresponding to the opening of the mask), the coating is irradiated with the energy beam, so that the organic molecules are polymerized with each other to form the conductive region 3a. . On the other hand, in the part covered with the mask, the film is not irradiated with the energy beam, so that the polymerization of organic molecules does not occur and becomes the insulating region 3b.

As the mask 6, a material that can block the energy beam can be appropriately selected according to the type of the energy beam used. As this mask, for example, a photomask used in a photolithography method or the like can be used.

As the energy beam, for example, light rays such as infrared rays, ultraviolet rays, far ultraviolet rays, and visible rays, radiation rays such as X-rays, and particle beams such as electron beams can be applied. It is also possible to use polarized ultraviolet rays, polarized deep ultraviolet rays, polarized X-rays, etc. as the energy beam. In this case, the alignment and polymerization of the organic molecules can be performed at the same time.

Since the group capable of conjugate bonding has different absorption characteristics depending on its type, for example, the type of energy beam and irradiation conditions (irradiation amount, irradiation time, etc.) are appropriately selected depending on the type of group capable of conjugate bonding of an organic molecule. ) Should be decided. For example, when the conjugate bondable group is an ethynylene group or a diacetylene group, it is preferable to irradiate ultraviolet rays as an energy beam.

As described above, the efficiency of the polymerization reaction can be improved by determining the type and conditions of the energy beam according to the type of the group capable of conjugate bonding. Further, since many conjugate bondable groups have absorptivity for energy beams, the invention can be applied to a film made of an organic molecule having various kinds of conjugate bondable groups.

When a plurality of conductive regions are formed, the plurality of conductive regions may be formed by one irradiation process, or each conductive region may be formed by a separate irradiation process. When the irradiation step is performed for each conductive region, for example, a second mask having a predetermined pattern different from the first mask after being irradiated with an energy beam through a first mask having a predetermined pattern Through
A method of irradiating with an energy beam can be applied. In this case, the energy beam emitted through the first mask and the energy beam emitted through the second mask may not 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. By using energy beams having different polarization directions, it is possible to easily form conductive regions having different conductive network directions.

As another method of polymerizing the coating film in a pattern, it is also possible to apply a method of scanning and irradiating the surface of the coating film with an energy beam. According to this method, it is possible to more easily form the conductive region having a desired pattern. 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 networks are different from each other.
Further, if scanning irradiation is performed while keeping the polarization direction and the scanning direction (the traveling direction of the energy beam) parallel to each other, it is possible to form a conductive network that is curvilinearly continuous in a predetermined direction.

(Iii) Electropolymerization Electropolymerization is carried out by bringing an electrode pair given a potential difference into contact with the coating.

FIG. 4 is a diagram showing an example of a method for polymerizing the coating film in a pattern by using electrolytic polymerization. In this example, electrodes 8a and 8b are formed on the film and a voltage is applied between the electrodes. At this time, the electrode 8a
In the region sandwiched between and the electrode 8b, the coating film is polymerized to form the conductive region 3a. On the other hand, in other regions, the coating film does not polymerize and the insulating region 3b
Becomes

As described above, when electrolytic polymerization is used, the electrode pairs are arranged such that the portions where the conductive regions are to be formed are located between the electrodes and the portions where the insulating regions are to be formed are not located between the electrodes. By doing so, the coating film can be polymerized in a desired pattern. For example, when the pattern of the region where the conductive region is to be formed is rectangular, the electrodes may be arranged along the two sides of the pattern that face each other. It is also possible to arrange a plurality of electrode pairs for one pattern and to apply a voltage to each electrode pair so that the entire patterns are polymerized. Further, when there are a plurality of independent patterns, an electrode pair may be provided for each pattern.

The electrode is not particularly limited, but for example, a metal such as Ti, Ni, Au, Pt or the like or an alloy thereof can be used. As the forming method, a method of forming an electrode material on the surface of the base material or the coating film and patterning the electrode material can be adopted. As a film forming method, for example, a vapor deposition method, a sputtering method or the like can be adopted, and as a patterning method, for example, etching using a resist or lift-off can be adopted.

Further, the place where the electrode is formed is not particularly limited as long as the pattern-like polymerization as described above can be performed. For example, an electrode may be formed on the coating and the lower surface of the electrode may be in contact with the coating. Since such a configuration can increase the contact area between the electrode and the coating, even if some electrode peeling occurs, there is an advantage that the electrolytic polymerization of the coating in the subsequent step can be reliably performed. Have Another example is a mode in which an electrode is formed on a base material and the side surface of the electrode is in contact with the coating film.

As the electrode pair, the electrodes fixedly formed on the base material or the coating film as described above may be used. Alternatively, the electrodes may not be fixed on the base material or the coating film and may be simply attached to the coating film. Electrodes that have just been contacted may be used. In the latter case, the entire pattern is finally polymerized by repeating the operation of contacting the electrode pair to polymerize a part of the pattern, then moving the electrode pair and polymerizing the other part of the pattern. It is also possible to let.

If the magnitude of the voltage applied to the electrode pair is larger than the redox potential of the organic molecules constituting the coating,
It is not particularly limited. The applied voltage is such that the magnitude of the electric field generated between both electrodes is, for example, 1.5 to 200 V / cm,
It is preferably set to 1.5 to 20 V / cm.

As the voltage applied between the electrodes, a DC voltage or an AC voltage may be used. Further, the voltage applied between the electrodes can be a pulse wave. Usually, hydrogen is generated by electro-oxidative polymerization, but when hydrogen is locally generated, the generated hydrogen may become bubbles and peel off the electrode. It is preferable to use an AC voltage as the voltage because such local generation of hydrogen can be suppressed. When using a DC voltage, it is preferable to apply this in a pulse wave form.

The polymerization time in the electrolytic polymerization step is
The time is not particularly limited, and may be the time required for forming a conductive network between the electrodes. In this electrolytic polymerization step, since the coating film is polymerized in a state where an electric field is applied between the electrodes, whether or not the formation of the conductive network is completed can be easily determined by observing the energized state between the electrodes. That is, when the conductive network is completed, a phenomenon in which a current rapidly flows in the coating film between the electrodes can be observed.

Other electrolysis conditions are not particularly limited. For example, the electrolysis temperature is 20 to 30.
C., preferably about room temperature (25.degree. C.).

The polymerization method can be appropriately selected depending on the type of organic molecules constituting the coating.

In the case of employing the catalytic polymerization, it is preferable that the organic molecule forming the coating film contains, for example, a pyrrole group, a cylene group, an ethynylene group or a diacetylene group as a group capable of forming a conjugated bond.

When the energy beam irradiation polymerization is adopted, it is preferable that the organic molecule forming the coating film contains, for example, an ethynylene group or a diacetylene group as a group capable of forming a conjugate bond.

When electrolytic polymerization is adopted, the organic molecules constituting the film may be, for example, as a group capable of forming a conjugated bond,
It preferably contains a pyrrole group, a cenylene group, or the like.

It is also possible to use a plurality of polymerization methods in combination. In this case, it is preferable to carry out electrolytic polymerization at least in the final step of polymerization. Specifically, for example, a combination of performing catalytic polymerization or energy beam irradiation polymerization as preliminary polymerization and finally performing electrolytic polymerization is mentioned. Catalytic polymerization and energy beam irradiation polymerization have the advantage that the polymerization rate is fast.In electrolytic polymerization, polymerization is carried out while applying a voltage between the electrodes, so that a current flows between the electrodes when the conductive network is completed. It has an advantage that it can be easily detected whether or not the process is completed.

In the polymerization step, not only the organic molecule may be polymerized, but also a crosslinking reaction may be performed after the polymerization to form a conductive network. For example, when an organic molecule has two or more conjugated bondable groups, one conjugated bondable group is polymerized with another organic molecule, and then the other conjugated bondable group is further combined with another organic molecule. If crosslinked, a conductive network having a structure different from that after polymerization can be formed.

For example, when a coating film composed of an assembly group of organic molecules containing a diacetylene group as a group capable of forming a conjugate bond is formed, and the coating film is subjected to catalytic polymerization and further crosslinked by energy beam irradiation polymerization, a polyacene type Conductive networks can be formed that include conjugated bond chains.

Further, in the manufacturing method of the present invention, a step of adding a dopant to the conductive organic thin film may be carried out. In this way, the conductivity can be easily improved by doping the charge-moving dopant. As the dopant, for example, an acceptor dopant (electron acceptor) such as iodine or BF ⁻ ion, and L
Donor dopants (electron donors) such as alkali metals such as i, Na and K and alkaline earth metals such as Ca can be used.

The conductive organic thin film manufactured by the manufacturing method of the present invention has a conductive region and an insulating region. The conductive region and the insulating region are preferably in contact with each other at their boundaries.

The conductive region is a polymer of organic molecules and has a conjugated bond chain formed by polymerization of these organic molecules. Therefore, in the conductive region, a conductive network is formed by the conjugated bond chains. This conductive network is preferably directional. In this case, the conjugated bond chains forming the conductive network do not need to be strictly connected in one direction, for example, the conductive network includes conjugated bond chains connected in various directions, but if formed as a whole in a specific direction Good.

The conductivity (ρ) of the conductive region is not particularly limited, but is, for example, 1 S / cm or more, preferably 1 × 10 ³ S / cm or more, more preferably 1 × 10 ⁴ S / cm. cm or more, more preferably 5.5 × 1
It is at least 0 ⁵ S / cm, most preferably at least 1 × 10 ⁷ S / cm. Note that all the above values are in the case of no dopant at room temperature (25 ° C.). In this way, it is possible to obtain conductivity equal to or higher than that of metal.

On the other hand, in the insulating region, the organic molecules are not polymerized and the above-mentioned conjugated bond chain is not formed. Therefore, in the insulating region, the conductive network is not formed and the insulating property is maintained.

According to the manufacturing method of the present invention, it is possible to form conductive regions of various patterns depending on the use of the conductive organic thin film. Moreover, the conductive organic thin film may have a plurality of conductive regions. In this case, the direction of the conductive network of each conductive region may be the same or different for each conductive region.

FIGS. 5A to 5C are schematic views showing an example of the pattern of the conductive region and the insulating region in the conductive organic thin film. In the example of FIG. 5A, the conductive organic thin film 3 has a plurality of strip-shaped conductive regions 3a, and the conductive regions 3a are arranged in parallel with each other. Insulating regions 3b are arranged between the conductive regions 3a, whereby the conductive regions 3a are formed.
The two are insulated from each other. In the example of FIG. 5B, the conductive organic thin film 3 has a plurality of conductive regions 3a having a relatively small area, which are arranged in a matrix. The regions other than the conductive region 3a are all insulating regions 3b, which electrically insulate the conductive regions 3a from each other. In FIG. 5C, the conductive organic thin film 3 has a plurality of conductive regions 3a having different shapes. Also in this example, the regions other than the conductive region 3a are all insulating regions 3b, and the conductive regions 3a are thereby insulated from each other.

Thus, according to the manufacturing method of the present invention,
A conductive organic thin film having a desired patterned conductive region can be manufactured. Therefore, this conductive region can be applied to the manufacture of various devices that are used as conducting wires (wiring), collective wiring, electrodes, transparent electrodes, and the like. For example, semiconductor devices, electronic devices such as capacitors,
It can be applied to the manufacture of optical devices such as liquid crystal display devices, electroluminescent elements, and solar cells. In particular, according to the manufacturing method of the present invention, it is possible to accurately form a conductive region on the surface of a base material even with a fine pattern. Therefore, by applying this to manufacturing of a device, Further miniaturization and high integration are possible.

[0125]

EXAMPLES The contents of the present invention will be specifically described below based on examples. The present invention is not limited to the following examples. In the following examples, simply described as "%" means% by weight.

(Example 1) I. Synthesis of PEN Substance represented by the following chemical formula (21) (PEN: 6-pyrrol
ylhexyl-12,12,12-trichloro-12-siladodecanoate)
Was synthesized according to the following steps 1 to 5.

[0127]

[Chemical 10]

Step 1 6-Bromo-1- (tetrahydropyrra
Synthesis of (nyloxy) hexane 197.8 g (1.0 %) of 6-bromo-1-hexanol in 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 (22).

[0129]

[Chemical 11]

Step 2 N- [6- (tetrahydropyrani
Synthesis of [roxy) hexyl] pyrrole Pyrrole 38.0 in a 2 liter reaction vessel under an argon stream.
g (0.567mol), dehydrated tetrahydrofuran (THF) 200m1
Was charged and cooled to 5 ° C or lower. 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 (0.623 mol) of 6-bromo-1- (tetrahydropyranyloxy) hexane 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, hexane extraction was performed, 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 with 10/1 g of N- [6-
(Tetrahydropyranyloxy) hexyl] pyrrole was obtained. The yield was 75.2%. The reaction formula of Step 2 is shown in the following formula (23).

[0132]

[Chemical 12]

Step 3 N- (6-hydroxyhexyl) -pi
Roll synthesis 105.0 g of N- [6- (tetrahydropyranyloxy) hexyl] pyrrole obtained above in a 1 liter reaction vessel
(0.418 mol), methanol 450 ml, water 225 ml, and concentrated hydrochloric acid 37.5 ml were charged, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into 750 ml of saturated saline solution to obtain IP.
E extracted. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained residue was purified by a silica gel column with n-hexane / ethyl acetate = 3/1 to obtain 63.1 g of N- (6-hydroxyhexyl) -pyrrole. The yield was 90.3%. The reaction formula of Step 3 is shown in the following formula (24).

[0134]

[Chemical 13]

Step 4 N- [6- (10-undecenoyl
Synthesis of ( oxy) hexyl] -pyrrole N- (6-hydroxyhexyl) -in a 2 liter reaction vessel.
Pyrrole 62.0 g (0.371 mol) and dry pyridine 33.2
g (0.420 mol), dry toluene 1850 ml
, 10-undecenoyl chloride 75.
7 g (0.373 mol) of dry toluene 300 ml solution 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 by a silica gel column with n-hexane / acetone = 20/1, and 99.6 g of N- [6- (1
0-undecenoyloxy) hexyl] -pyrrole was obtained. The yield was 80.1%. The reaction formula of Step 4 is shown in the following formula (25).

[0136]

[Chemical 14]

Step 5 Synthesis of PEN N- [6- (10-
Undecenoyloxy) hexyl] -pyrrole 2.0 g
(6.0 × 10 ^-3 mo1), trichlorosilane 0.98g
(7.23 × 10 ^-3 mol), was charged with 5% isopropyl alcohol solution 0.01g of _{H 2 PtC1 6 · 6H 2 0} , 100 ℃
And reacted for 12 hours. After treating this reaction solution with activated carbon, low-boiling components were distilled off under reduced pressure of 2.66 × 10 ³ Pa (20 Torr). 2.3 g of PEN was obtained. The yield was 81.7%. The reaction formula of Step 5 is shown in the following formula (26).

[0138]

[Chemical 15]

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.

FIG. 8 shows an NMR chart and FIG. 9 shows an IR chart of the obtained PEN. (NMR) (1) Measuring device: device name AL300 (manufactured by JEOL Ltd.) (2) Measuring condition: ¹ H-NMR (300 MHz), 30 mg of sample was dissolved in CDCl ₃ and measured. (Infrared absorption spectrum: IR) (1) Measuring device: Device name 270-30 type (manufactured by Hitachi, Ltd.) (2) Measuring condition: neat (sample is sandwiched between two NaCl plates)

II. Formation of Monomolecular Film Using PEN of the above chemical formula (21), a chemically adsorbed liquid was prepared by diluting it to 1 wt% with dehydrated dimethyl silicone solvent. Further, a silica film was formed on the surface of the polyimide substrate by plasma polymerization using a mixed gas of SiH ₄ and O ₂ gas.

The substrate was immersed in a chemical adsorbent at room temperature (25 ° C.) for 1 hour to cause a desalting reaction on the surface of the substrate to form a thin film on the entire surface of the substrate. Next, the unreacted substance remaining on the substrate was washed off with anhydrous chloroform.

At this time, since a large number of hydroxyl groups containing active hydrogen are present on the surface of the polyimide substrate coated with the silica film, the chlorosilyl group (-SiCl) of the substance causes a dehydrochlorination reaction with the hydroxyl groups, and the substrate surface Covalently bound to.
As a result, a monomolecular film composed of molecules represented by the following chemical formula (27) was formed.

[0144]

[Chemical 16]

III. Alignment of Monolayer Next, the polyimide substrate on which the monolayer is formed is immersed in a chloroform solution for cleaning, and when the polyimide substrate is pulled up from the chloroform solution, the first electrode to be formed into a second electrode in a later step. The polyimide substrate was lifted upright so that it could be drained parallel to the direction in which it was directed. As a result, a monomolecular film that was primarily oriented from the first electrode to the second electrode was formed.

IV. Formation of Electrodes Next, a nickel film was formed by vapor deposition on the entire surface of the substrate, and then a first electrode and a second electrode were formed on the monomolecular film by applying photolithography and etching. Figure 6
, The first electrode 8a and the second electrode 8b
Are arranged so as to face each other with the region 9 where the conductive region is to be formed sandwiched therebetween. Note that the first electrode and the second
The dimensions of the electrodes are (a x b) 10 μm x 100 μ
m, and the distance (c) between the electrodes was 100 μm.

V. Electrolytic Polymerization Then, in a pure aqueous solution, a voltage was applied between the first electrode and the second electrode to electrolytically polymerize the molecules forming the monomolecular film. The electrolytic polymerization conditions were an electric field of 5 V / cm, a reaction temperature of 25 ° C., and a reaction time of 5 hours.

By this electrolytic polymerization, the monomolecular film between the first electrode and the second electrode was polymerized. As a result, a conductive organic thin film having a rectangular pattern of conductive regions was formed.
The dimensions of the conductive region were 100 μm × 100 μm.
In the area other than the conductive area, the monomolecular film did not polymerize and an insulating area was formed. The thickness of the obtained conductive organic thin film was about 2.0 nm, and the thickness of the polypyrrole portion in the conductive region was about 0.2 nm. Further, the obtained organic conductive film was transparent under visible light.

The chemical formula (28) below shows one unit of the polymer constituting the conductive region.

[0150]

[Chemical 17]

VI. Measurement Using a commercially available atomic force microscope (AFM) (SAP3800N manufactured by Seiko Instruments Inc.), AFM-CI
The conductivity (ρ) of the conductive region in the obtained conductive organic thin film was measured under the conditions of voltage: 1 mV and current: 160 nA in the TS mode. As a result, at room temperature (25 ° C.), ρ> 1 × 10 ⁷ S / cm without doping. This is because the ammeter can measure only up to 1 × 10 ⁷ S / cm, and the needle is over and shaken out. Gold, which is a metal with good conductivity, has room temperature (2
5.2 × 10 ⁵ S / cm at 5 ° C., 5.4 × for silver
Based on 10 ⁵ S / cm, the conductivity of the conductive region formed in this example is surprisingly high. From the above values, the conductive region of the present invention can be referred to as a "supermetal conductive region".

Example 2 I.D. Synthesis of TEN A substance represented by the following chemical formula (29) (TEN: 6-[(3-th
ienyl) hexyl-12,12,12-trichloro-12-siladodecanoat
e]) was synthesized according to steps 1-5 below.

[0153]

[Chemical 18]

Step 1 6-Bromo-1- (tetrahydro
Synthesis of pyranyloxy) hexane 6-Bromo-1-
(Tetrahydropyranyloxy) hexane was synthesized.
First, 197.8 g (1.09 mol) of 6-bromo-1-hexanol was charged into a 500 mL reaction vessel, and the temperature was 5 ° C.
After cooling to below, dihydropyran 102.1
g (1.21 mol) was added dropwise at 10 ° C or lower. After completion of dropping, the mixture was returned to room temperature and stirred for 1 hour.

[0155]

[Chemical 19]

The resulting residue was applied to a silica gel column,
Hexane / diisopropyl ether (I
PE) purified with a mixed solvent (volume ratio 5: 1), 26
3.4 g of 6-bromo-1 (tetrahydropyranyloxy) hexane was obtained. The yield at this time was 90.9%.

Step 2 3- [6- (tetrahydropyranyloxy
Synthesis of ( si) hexyl] thiophene 3- [6- (tetrahydropyranyloxy) hexyl] thiophene was synthesized by performing the reaction represented by the following chemical formula (31).

[0158]

[Chemical 20]

First, 25.6 g (1.06 m.1) of ground magnesium was charged into a 2-liter reaction vessel under an argon stream, and further, 140.2 g (0..0) of 6-bromo-1- (tetrahydropyranyl) hexane. 4 L of a dry tetrahydrofuran (dry THF) solution containing 529 mol) was added dropwise at room temperature. The dropping time at this time was 1 hour and 50 minutes, and an exothermic reaction occurred. Then, the mixture was stirred at room temperature for 1.5 hours to prepare a Grignard reagent.

Next, under a stream of argon, a new 2 L reaction vessel was charged with 88.2 g (541 mo) of 3-bromothiophene.
1) and 3.27 g of dichlorobis (triphenylphosphine) nickel (II) were charged, and the entire amount of the Grignard reagent prepared above was added dropwise at room temperature. At this time, the temperature in the reaction vessel was kept at room temperature (50 ° C. or lower), and the dropping time was
30 minutes. After dropping, the mixture was stirred at room temperature for 23 hours.

The reaction mixture was kept at 0 ° C. with 0.5N.
It was added to 1.3 L of HCl and IPE extraction was performed. The obtained organic layer was washed with water and further washed with saturated saline, and then anhydrous magnesium sulfate was added and dried. Then, the solvent was distilled off to obtain 199.5 g of a crude product containing 3- [6- (tetrahydropyranyloxy) hexyl] -thiophene. This crude product was subjected to the next step 3 without purification.

Step 3 3- (6-Hydroxyhexyl)
-Synthesis of thiophene The reaction represented by the following chemical formula (32) was performed to synthesize 3- (6-hydroxyhexyl) -thiophene.

[0163]

[Chemical 21]

In a 1 L reaction vessel, the crude 3- [6- (tetrahydropyranyloxy) hexyl] -obtained in the above step 2 was used.
Thiophene 199.5 g, methanol 450 mL, water 2
Charge 25 mL and concentrated hydrochloric acid 37.5 mL, and add 6 at room temperature.
Stir for a reaction to react. This reaction mixture was added to 750 mL of saturated saline, and IPE extraction was performed. Then, the obtained organic layer was washed with saturated saline and further dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain a crude body 148.8 containing 3- (6-hydroxyhexyl) -thiophene.
g was obtained. This crude product was subjected to a silica gel column and purified using an n-hexane / ethyl acetate mixed solvent (volume ratio 3: 1) as an elution solvent to obtain 84.8 g of 3- (6-hydroxyhexyl) -thiophene. It was The yield in this case was 87.0 based on the crude product containing 3- [6- (tetrahydropyranyloxy) hexyl] -thiophene obtained in step 2.
%Met.

Step 4 3- [6- (10-Undecenoyloxy
Synthesis of ( Ci) hexyl] -thiophene 3- (6- (10
-Undecenoyloxy) hexyl) -thiophene was synthesized.

[0166]

[Chemical formula 22]

In a 2 L reaction vessel, the 3-
Crude 8 containing (6-hydroxyhexyl) -thiophene
4.4 g (0.458 mol), dry pyridine 34.
9 g (0.442 mol) and dry toluene 145
0 mL was charged, and 79.1 g (0.390 mol) of 10-undecenoyl chloride was added at 20 ° C or lower.
250 mL of a dry toluene solution containing P was added dropwise.
The dropping time was 30 minutes, and then the mixture was stirred at the same temperature for 23 hours for reaction. The obtained reaction mixture was added to 2 L of ice water, and further 75 mL of 1N hydrochloric acid was added. The mixture was extracted with ethyl acetate, the obtained organic layer was washed with water, further washed with saturated saline, and then dried by adding anhydrous magnesium sulfate. By removing the solvent, 3- [6-
161.3 g of a crude product containing (10-undecenoyloxy) hexyl] -thiophene was obtained. This crude product was applied to a silica gel column and purified using an n-hexane / acetone mixed solvent (volume ratio 20: 1) as an elution solvent, and 157.
6 g of 3- [6- (10-undecenoyloxy) hexyl] -thiophene was obtained. The yield at this time was 98.2% with respect to the crude product containing 3- (6-hydroxyhexyl) -thiophene obtained in the above step 3.

Step 5 Synthesis of TEN The reaction shown in the following chemical formula (34) was performed to synthesize TEN.

[0169]

[Chemical formula 23]

(A) First, in a 100 mL pressure-proof test tube with a cap, 10.0 g of 3- [6- (10-undecenoyloxy) hexyl] -thiophene (2.86 × 1012 m)
ol), trichlorosilane 4.65 g (3.43 x 10)
4 mol) and 0.05 g of isopropyl alcohol solution containing H ₂ PtC1 ₆ · 6H ₂ 0 at a ratio of 5% by weight.
Was charged and reacted at 100 ° C. for 14 hours. After treating this reaction solution with activated carbon, low-boiling components were distilled off under reduced pressure. The reduced pressure condition was 2.66 × 10 ³ Pa (20 Torr).

(B) Similarly, 39.0 g (1.11 × 10 ^-1 mo) of 3- [6- (10-undecenoyloxy) hexyl] -thiophene was placed in a 100 mL pressure-proof test tube with a cap.
l), trichlorosilane 18.2 g (1.34 × 10 ⁻¹⁾
mol) and 0.20 g of an isopropyl alcohol solution containing H ₂ PtCl ₆ .6H ₂ 0 at a ratio of 5% by weight, and the mixture was reacted at 100 ° C. for 12 hours. After treating this reaction solution with activated carbon, low-boiling components were distilled off under reduced pressure. The reduced pressure conditions are as described above.

The residues obtained in (a) and (b) are mixed,
Argon gas was passed through this for 1 hour to remove hydrochloric acid gas, thereby obtaining 65.9 g of the desired product TEN. The yield of TEN in this case is 3- [6- (10-
It was 97.2% based on the crude product containing undecenoyloxy) hexyl] -thiophene.

The TEN obtained was subjected to IR analysis and NMR analysis. The conditions and results are shown below. Note that FIG. 10 shows an NMR chart and FIG. 11 shows an IR chart.

(NMR) (1) Measuring device: device name AL300 (manufactured by JEOL Ltd.) (2) Measuring condition: ¹ H-NMR (300 MHz), 30 mg of sample was dissolved in CDCl ₃ and measured.

(Infrared absorption spectrum: IR) (1) Measuring device: device name 270-30 type (manufactured by Hitachi, Ltd.) (2) Measuring condition: neat (sample sandwiched between two NaCl plates)

II. Monolayer formation, orientation treatment, electrode formation and electropolymerization The monolayer formation, orientation treatment, electrode formation and electropolymerization were performed in the same manner as in Example 1 except that the obtained TEN was used. Carried out.

As a result, a conductive organic thin film having a rectangular pattern conductive region was formed. The size of the conductive area is 1
It was 00 μm × 100 μm. In the area other than the conductive area, the monomolecular film did not polymerize and an insulating area was formed. The thickness of the obtained conductive organic thin film was about 2.
The thickness of the polythiophene portion in the conductive region was about 0.2 nm. Further, the obtained organic conductive film was transparent under visible light.

The chemical formula (35) below shows one unit of the polymer constituting the conductive region.

[0179]

[Chemical formula 24]

III. Measurement The conductivity (ρ) of the conductive region in the obtained conductive organic thin film was measured by the same method as in Example 1.
As a result, ρ> 1 at room temperature (25 ° C) without doping.
It was × 10 ⁷ S / cm, which showed a surprisingly high conductivity, similar to the conductive region in Example 1 above.

(Example 3) A substrate having a monomolecular film formed thereon is immersed in a chloroform solution for cleaning, the substrate is pulled up from the chloroform solution in a predetermined direction, and then polarized visible light is irradiated. A conductive organic thin film was formed in the same manner as in Example 1 and Example 2 except that the alignment treatment was performed. The draining direction is
The direction from the first electrode to the second electrode was set, and the polarization direction was set to intersect with the direction from the first electrode to the second electrode at 45 °. Also, polarized light irradiation is about 500 m
It was performed under the condition of J / cm ² .

As a result, the organic molecules constituting the monomolecular film were oriented substantially parallel to the polarization direction from the orientation in the liquid draining direction.

Then, when the monomolecular organic thin film was subjected to the liquid draining alignment treatment and the alignment treatment by polarized light irradiation and then polymerized to form a conductive region, it was excellent as in Examples 1 and 2 above. It was possible to form a conductive region exhibiting conductivity.

Example 4 A conductive organic thin film was prepared in the same manner as in Example 1 except that the compound represented by the chemical formula (36) below was used.

[0185]

[Chemical 25]

As a result, a conductive organic thin film having a rectangular conductive region was formed. The size of the conductive area is 1
It was 00 μm × 100 μm. In the area other than the conductive area, the monomolecular film did not polymerize and an insulating area was formed. The thickness of the obtained conductive organic thin film was about 2.
The thickness of the polypyrrole portion in the conductive region was about 0.2 nm. Further, the obtained organic conductive film was transparent under visible light.

The following chemical formula (37) shows one unit of the polymer constituting the conductive region.

[0188]

[Chemical formula 26]

The electric conductivity (ρ) of the conductive region in the obtained conductive organic thin film was measured by the same method as in Example 1 above. As a result, it was 1 × 10 ³ S / cm without doping at room temperature (25 ° C.).

Example 5 A conductive organic thin film was prepared using the compound of the following chemical formula (38).

[0191]

[Chemical 27]

First, the compound of the chemical formula (38) was diluted to 1 wt% with dehydrated dimethyl silicone solvent to prepare a chemical adsorbent. Next, the glass substrate was immersed in a chemical adsorbent at room temperature (25 ° C.) for 1 hour to cause a desalting reaction on the substrate surface to form a monomolecular film on the entire surface of the substrate. Next, the unreacted substance remaining on the substrate was washed off with anhydrous chloroform.

Next, rubbing treatment was performed on the monomolecular film formed on the surface of the substrate. In this step, as shown in FIG. 7, while the roll 42 around which the rubbing cloth 41 is wound is rotated at a predetermined speed, the surface of the substrate 1 provided with the monomolecular film 2 is brought into contact with the substrate 1 at a predetermined speed. It is carried out by moving. The rubbing treatment was performed by using a rubbing roll having a diameter of 7 cm wrapped with a rayon-made rubbing cloth (Yoshikawa Kako Co., Ltd .: YA-20-R).
It was carried out under the conditions of 1.7 mm, the rotation speed of the roll was 1200 rotations / sec, and the substrate transfer speed was 40 mm / sec.

Next, a photoresist (“OEPR5000 (trade name)” manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the surface of the monomolecular film, and the resist was patterned by the photolithography method. As a result, a resist pattern was formed on the surface of the monomolecular film so as to open a portion to be a conductive region and cover a portion to be an insulating region. The opening of the resist pattern was a rectangle of 10 μm × 100 μm.

Then, the substrate on which the resist pattern was formed was treated with toluene containing Ziegler-Natta catalyst (5 × 10 ^-2 mol / liter solution of triethylaluminum and 2.5 × 10 ^-2 mol / liter solution of tetrabutyl titanate). Immersed in the solvent. As a result, the ethynylene groups of the molecules forming the monomolecular film were polymerized in the openings of the resist pattern. As a result, a conductive organic thin film having a rectangular pattern of conductive regions was formed. The dimensions of the conductive region were 10 μm × 100 μm. In the area other than the conductive area, the monomolecular film did not polymerize and an insulating area was formed. The thickness of the obtained electroconductive courage thin film was about 2.0 nm.

The chemical formula (39) below shows one unit of the polymer constituting the conductive region.

[0197]

[Chemical 28]

The conductivity (ρ) of the conductive region in the obtained conductive organic thin film was measured by the same method as in Example 1 above. As a result, it was 1 × 10 ³ S / cm without doping at room temperature (25 ° C.).

Example 6 A monomolecular film was formed on the surface of a substrate and a rubbing treatment was applied to the monomolecular film in the same manner as in Example 5 except that the compound represented by the following chemical formula (40) was used. .

[0200]

[Chemical 29]

Next, the surface of the monomolecular film was irradiated with ultraviolet rays, which is an energy beam, through a photomask which has openings for conductive areas and covers for insulating areas. The opening of the mask was rectangular with a size of 10 μm × 100 μm. The energy density of ultraviolet rays is 100m
It was set to J / cm ² .

As a result, the diacetylene groups of the molecules composing the monomolecular film were polymerized in the openings of the mask. As a result, a conductive organic thin film having a rectangular pattern of conductive regions was formed. The size of the conductive area is 10 μm × 100
was μm. In the area other than the conductive area,
The monolayer did not polymerize and an insulating region was formed. The thickness of the obtained conductive organic thin film was about 2.0 nm.

The following chemical formula (41) shows one unit of the polymer constituting the conductive region.

[0204]

[Chemical 30]

The conductivity (ρ) of the conductive region in the obtained conductive organic thin film was measured by the same method as in Example 1 above. As a result, it was 1 × 10 ⁴ S / cm without doping at room temperature (25 ° C.).

[0206]

As described above, according to the production method of the present invention, a terminal bondable group capable of forming a covalent bond with the surface of the base material and a conjugate capable of being polymerized with another molecule are formed on the surface of the base material. A film of an organic molecule containing a bondable group is formed, and a conjugated bond chain is formed by polymerizing the conjugated bondable group in the part which becomes the conductive region of the film, and in the part which becomes the insulating region of the film. By leaving the group capable of conjugate bonding in an unpolymerized state, a conductive region having a desired pattern can be easily and accurately formed in the conductive organic thin film.

[Brief description of drawings]

FIG. 1A is a cross-sectional view showing an example of a conductive organic thin film obtained by the manufacturing method of the present invention. FIG. 1B is a schematic diagram showing the outline of the structure of the conductive region, and FIG. 1C is a schematic diagram showing the outline of the structure of the insulating region.

FIG. 2 is a diagram for explaining an example of a method of polymerizing a coating film in a pattern using catalytic polymerization.

FIG. 3 is a diagram for explaining an example of a method for polymerizing a coating film in a pattern using energy beam irradiation polymerization.

FIG. 4 is a diagram for explaining an example of a method for polymerizing a coating film in a pattern using electrolytic polymerization.

5A and 5B are diagrams each showing an example of a pattern of a conductive region in a conductive organic thin film obtained by the manufacturing method of the present invention.

FIG. 6 is a diagram showing an electrode arrangement for electrolytic polymerization in an example of the present invention.

FIG. 7 is a diagram illustrating a rubbing method according to an embodiment of the present invention.

FIG. 8 is an NMR chart of a pyrrolyl compound obtained according to an example of the present invention.

FIG. 9 is an IR chart of the pyrrolyl compound.

FIG. 10 is an NMR chart of a cenyl compound obtained according to another example of the present invention.

FIG. 11 is an IR chart of the cenyl compound.

[Explanation of symbols]

1 base material 2 monolayer 3 Conductive organic thin film 3a conductive area 3b Insulation area 4 Resist pattern 5 catalyst solution 6 masks 7 energy beam 8a, 8b electrodes

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Yamamoto             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F term (reference) 4J011 AC04 CA02 CC10 UA01 UA03                       UA04 VA01 WA01 XA01                 4M104 AA01 AA10 BB05 BB36 DD22                       DD51 DD77 HH20                 5G307 GA05 GC02

Claims (13)

[Claims] 1. A method for producing a conductive organic thin film including a conductive region selectively formed in a predetermined region of a substrate surface and an insulating region formed in a region of the substrate surface excluding the predetermined region. A method comprising: a surface of the substrate having active hydrogen on the surface thereof or having an active hydrogen added thereto, comprising at one end of a molecule an end-bondable group capable of forming a covalent bond with the surface of the substrate; An organic molecule containing a conjugated bondable group capable of polymerizing with another molecule is brought into contact with any part of the above, and the terminal bondable group of the organic molecule is reacted with active hydrogen on the surface of the substrate to form a covalent bond. By forming a coating film on the surface of the base material, in the portion which becomes the conductive region of the coating film, the conjugated bondable group is polymerized with the conjugated bondable group of another organic molecule to form a conjugated bond chain. And the insulating region of the coating That in the portion, the manufacturing method of the conductive organic thin film characterized in that to leave the conjugated bondable groups in the form of unpolymerized. 2. The method for producing a conductive organic thin film according to claim 1, wherein the polymerization is carried out by at least one polymerization method selected from electrolytic polymerization, catalytic polymerization and energy beam irradiation polymerization. 3. The method for producing a conductive organic thin film according to claim 1, wherein the organic molecules forming the coating film are oriented in at least the conductive region of the coating film. 4. The orientation is an orientation by rubbing treatment, an orientation by a treatment of draining a liquid in a predetermined direction from the surface of the substrate having the coating film, an orientation by a polarized light irradiation treatment, and a molecule at the time of polymerization. The method for producing a conductive organic thin film according to claim 3, which is realized by at least one selected from orientations due to fluctuations. 5. The method for producing a conductive organic thin film according to claim 1, wherein the coating film is a monomolecular film or a monomolecular cumulative film. 6. The group capable of conjugate bonding is at least one group selected from a pyrrolyl group, a cenyl group, an ethynylene group (—C≡C—) and a diacetylene group (—C≡C—C≡C—). The method for producing a conductive organic thin film according to claim 1, which comprises. 7. The terminal bondable group is a halogenated silyl group, an alkoxysilyl group or an isocyanate silyl group, and the reaction between the terminal bondable group and active hydrogen on the surface of the substrate is a dehydrohalogenation reaction. The method for producing a conductive organic thin film according to any one of claims 1 to 6, wherein the method is a dealcoholization reaction or a deisocyanation reaction. 8. The covalent bond formed by the reaction between the end-bondable group and active hydrogen on the surface of the substrate is at least one bond selected from a siloxane bond (—SiO—) and a —SiN— bond. A method for producing a conductive organic thin film according to claim 1. 9. The conductive material according to claim 1, wherein the organic molecule contains a polar functional group containing no active hydrogen between the terminal bondable group and the conjugated bondable group. Method for manufacturing organic thin film. 10. The polar functional group is an ester group (-
COO-), an oxycarbonyl group (-OCO-), a carbonyl group (-CO-) and a carbonate (-OCOO).
-) At least one group selected from the group
A method for producing a conductive organic thin film as described in 1. 11. The method for producing a conductive organic thin film according to claim 1, wherein the organic molecule contains a photoresponsive functional group between the terminal bondable group and the conjugate bondable group. . 12. The photoresponsive functional group is an azo group (—N =
N-), The method for producing a conductive organic thin film according to claim 11. 13. The method for producing a conductive organic thin film according to claim 1, wherein the organic molecule is represented by the following chemical formula (1) or (2). [Chemical 1] (However, X is hydrogen, an organic group containing an ester group or an organic group containing an unsaturated group, q is an integer of 0 to 10, Z is an ester group (-COO-), an oxycarbonyl group (-OCO).
-), A carbonyl group (-CO-) or a carbonate (-OCOO-) group, D is a halogen, an isocyanate group or an alkoxyl group having 1 to 3 carbon atoms, E is hydrogen or an alkyl group having 1 to 3 carbon atoms, m and n is 2 ≦ (m +
n) an integer satisfying ≦ 25, and p is an integer of 1 to 3. )