JP4989559B2 - Electronic device and manufacturing method thereof - Google Patents

Description

  The present invention relates to an electronic device in which a conductive polymer layer is formed on a substrate and a method for manufacturing the same.

  Conductive polymers have already been applied in solid electrolytic capacitors, antistatic coatings and the like. In addition, conductive polymers are expected to be applied to organic electroluminescent devices (organic EL devices), organic solar cells, organic transistors, touch panels, battery electrodes, and the like.

  In general, a solid electrolytic capacitor uses an anode made of a valve metal such as aluminum (Al), tantalum (Ta), niobium (Nb), etc., and anodizes the surface of the anode so that a dielectric mainly made of oxide A body layer is formed on the anode. On the cathode side of the dielectric layer, those using an electrolytic solution and those using a solid conductive film are known. When the electrolytic solution is used, there is a problem that the electrolytic solution leaks or smoke is generated when the anode and the cathode are connected in the wrong polarity. At present, a solid conductive film is generally used.

  As the solid conductive film, manganese dioxide, a charge transfer complex, a conductive polymer, or the like is used. From the viewpoint of conductivity, organic conductive materials such as charge transfer complexes and conductive polymers are superior to manganese dioxide. By using a material with high conductivity, the value of equivalent series resistance (ESR), which is one of characteristic values of the solid electrolytic capacitor, can be lowered. In particular, when a conductive polymer having high conductivity such as polypyrrole or polythiophene is used, it is possible to make ESR very low. Solid electrolytic capacitors may be used in noise reduction circuits in DC power supply circuits. However, the smaller the ESR, the better the ripple (AC component) removal capability and the higher the noise reduction performance. Solid electrolytic capacitors have high added value.

  As a method of manufacturing a solid electrolytic capacitor using a conductive polymer, an anode made of a valve metal is anodized to form a dielectric layer on the surface thereof, and then, for example, a polypyrrole film formed by a chemical polymerization method is used. There has been proposed a method of sequentially forming a first conductive polymer layer and a second conductive polymer layer made of polypyrrole formed by electrolytic polymerization (Patent Document 1).

  In order to improve tan δ and leakage current characteristics, it has been proposed to form a coupling agent layer and a surfactant layer between a dielectric layer and a conductive polymer layer (Patent Document 2). In addition, for the purpose of suppressing an increase in leakage current in the reflow process, it has been proposed to form a silane coupling agent layer and a polystyrene sulfonic acid layer between the dielectric layer and the conductive polymer layer ( Patent Document 3).

However, these conventional techniques cannot sufficiently reduce the ESR.
JP-A-4-48710 JP 2001-326145 A JP 2005-322664 A

  The dielectric layer formed by anodizing an anode made of a valve metal is made of an inorganic material made of a metal oxide. On the other hand, since the conductive polymer layer is an organic material, peeling occurs at the interface between the inorganic material and the organic material due to weak adhesion due to the difference in surface energy of each material. It is easy and has problems in reliability. In addition, in a solid electrolytic capacitor, a porous metal sintered body or a metal foil is used as an anode in order to increase the capacity, and the conductive polymer layer formed on the dielectric layer is the porous metal sintered body. It is necessary to form deep inside the body. However, when the conductive polymer is poorly wetted with respect to the dielectric layer, the conductive polymer layer cannot be uniformly formed deep inside the porous metal sintered body, and the ESR is sufficiently reduced. I can't.

  An object of the present invention is to provide an electronic device in which a conductive polymer layer having excellent conductivity is uniformly formed on a substrate, and a method for manufacturing the same.

  The present invention comprises a substrate having at least a surface formed of a metal oxide, a conductive polymer layer provided on the substrate, and a thin film layer provided between the substrate and the conductive polymer layer. The thin film layer has a sulfonic acid group that interacts with the conductive polymer layer and is formed of a compound that chemically bonds to the surface of the substrate.

  In the present invention, a thin film layer is formed on a substrate, and a conductive polymer layer is formed on the thin film layer. The thin film layer is formed of a compound having a sulfonic acid group that interacts with the conductive polymer and chemically bonding to the surface of the substrate. For this reason, according to this invention, the electroconductive polymer layer excellent in electroconductivity can be formed uniformly on a base material.

  The following can be considered as the reason why the conductive polymer layer excellent in conductivity is uniformly formed on the substrate.

  The first reason is that the compound chemically bonded to the substrate surface has a sulfonic acid group, and this sulfonic acid group is present on the surface of the thin film layer, so that polymerization of the conductive polymer is likely to occur. It is thought that. Conductive polymers such as polypyrrole and polythiophene are polymerized mainly by oxidative polymerization. It is considered that the presence of a sulfonic acid group on the surface of the thin film layer increases the oxidizability, so that a conductive polymer is easily formed on the surface of the thin film layer.

  A second reason is considered to be that the conductive polymer layer interacts with the sulfonic acid group, such as bonding by Coulomb force. Conductive polymers such as polypyrrole and polythiophene have a strong donor property and easily escape electrons, and thus are easily charged positively. On the other hand, sulfonic acid groups tend to be negatively charged by releasing protons. For this reason, it is considered that the sulfonic acid group and the conductive polymer are bonded by Coulomb force. Therefore, the presence of the thin film layer makes it possible to form the conductive polymer layer uniformly on the substrate with good adhesion.

  As a third reason, it is considered that the conductivity of the conductive polymer layer is improved by the interaction of the sulfonic acid group with the dopant in the conductive polymer layer as a dopant. The conductive polymer can exhibit excellent conductivity by doping with a dopant such as sulfonic acid or halogen. Therefore, it is considered that the conductivity of the conductive polymer layer formed on the surface of the thin film layer is increased by the sulfonic acid group present on the surface. For this reason, it seems that the conductive polymer layer excellent in electroconductivity can be formed uniformly on a base material.

  The compound forming the thin film layer of the present invention is preferably a compound in which a sulfonic acid group is bonded to a phenyl group.

  In addition, the compound forming the thin film layer of the present invention is preferably a compound generated by hydrolysis or the like of a silanol group as a reactive group that chemically bonds to the surface of the substrate. For example, trimethoxysilane, triethoxysilane, It preferably contains a silane-containing group such as trichlorosilane. It is preferable that the silanol group is chemically bonded to the substrate surface by reacting with the metal oxide on the substrate surface.

  As a compound which forms the thin film layer in this invention, what is formed by making the silane coupling agent which has an amino group react with the sulfonic acid compound which has a carboxylic acid group and a sulfonic acid group is mentioned, for example. In this case, the thin film layer can be formed by reacting the silane coupling agent with the substrate surface for chemical bonding and then reacting the carboxylic acid group of the sulfonic acid compound with the amino group of the silane coupling agent.

  Other examples of the compound that forms the thin film layer include those formed by reacting a silane coupling agent having an oxirane group with a sulfonic acid compound having an amino group and a sulfonic acid group. In this case, the thin film layer can be formed by reacting the silane coupling agent with the substrate surface to cause chemical bonding and then reacting the oxirane group of the silane coupling agent with the carboxylic acid group of the sulfonic acid compound.

  As described above, the compound that forms the thin film layer includes the silane coupling agent having the first functional group, the second functional group that reacts with the first functional group, and the sulfonic acid compound having the sulfonic acid group. It can be formed by reacting.

  In the above specific compound, a silane coupling agent and a sulfonic acid compound are reacted to form a compound that forms a thin film layer, but the present invention is not limited to this, for example, A thin film layer may be formed on the surface of the substrate by a one-step reaction using a compound having a functional group that reacts with the substrate surface and a sulfonic acid group.

  In the present invention, the substrate may be porous. As such a porous substrate, for example, a sintered body obtained by sintering particles of a valve action metal or an alloy thereof used as an anode in a solid electrolytic capacitor, or a metal foil surface made of the valve action metal or an alloy thereof is used. Examples thereof include those roughened by etching or the like.

  Accordingly, examples of the electronic device of the present invention include a solid electrolytic capacitor. A solid electrolytic capacitor as an electronic device of the present invention includes an anode made of a porous substrate, a dielectric layer made of a metal oxide on the surface of the substrate, a thin film layer provided on the dielectric, and a thin film layer It is characterized by comprising a conductive polymer layer provided and a cathode provided on the conductive polymer layer.

  Examples of the valve metal that forms the anode include tantalum, niobium, aluminum, and titanium. Moreover, as these alloys, the alloy containing 50 weight% or more of at least 1 sort (s) of these valve action metals is mentioned.

  The dielectric layer formed on the anode surface can be formed by, for example, anodizing the surface of a porous sintered body made of a valve metal or an alloy thereof.

  The thin film layer formed on the dielectric layer can be formed by reacting a silane coupling agent and a sulfonic acid compound in the same manner as described above.

  As described above, the conductive polymer layer can be formed from polypyrrole, polythiophene, or the like.

  The cathode can be formed by sequentially applying a carbon layer and a silver paste.

  The production method of the present invention is a method by which the electronic device of the present invention can be produced, and includes a step of forming a thin film layer on a substrate, and a monomer constituting the conductive polymer layer on the thin film layer. And a step of forming a conductive polymer layer by supplying and polymerizing the conductive polymer layer.

  According to the production method of the present invention, a conductive polymer layer having excellent conductivity can be formed uniformly on a substrate.

  As a monomer which comprises a conductive polymer layer, the monomer which has a pyrrole ring or a thiophen ring is mentioned, for example. Therefore, examples of the conductive polymer formed from such a monomer include polypyrrole and polythiophene.

  Moreover, when supplying a monomer on a thin film layer, you may polymerize by supplying both a monomer and a polymerization agent. Examples of such a polymerization agent include an oxidant that promotes oxidative polymerization.

  Further, as described above, when a silane coupling agent having a first functional group and a sulfonic acid compound having a second functional group and a sulfonic acid group that react with the first functional group are reacted to form a thin film layer, After reacting the silane coupling agent with the substrate surface to cause chemical bonding, the second functional group of the sulfonic acid compound can be reacted with the first functional group of the silane coupling agent to form a thin film layer.

  The electronic device of the present invention is not limited to a solid electrolytic capacitor, but can be applied to an organic EL element, an organic solar cell, an organic transistor, a touch panel, and the like.

  According to the present invention, for example, a conductive polymer layer having a high conductivity of 10 S / cm or more can be formed.

  ADVANTAGE OF THE INVENTION According to this invention, it can be set as the electronic device by which the conductive polymer layer excellent in electroconductivity was uniformly formed on the base material.

  According to the production method of the present invention, a conductive polymer layer excellent in conductivity can be uniformly formed on a substrate. For example, by applying the present invention to a solid electrolytic capacitor, electrostatic capacity can be improved and ESR can be reduced.

  Hereinafter, the present invention will be described with reference to specific embodiments, but the present invention is not limited to the following embodiments.

  FIG. 1 is a schematic cross-sectional view of a solid electrolytic capacitor which is an electronic device according to an embodiment of the present invention.

  As shown in FIG. 1, in the solid electrolytic capacitor 10, a dielectric layer 2, a thin film layer 9, a conductive polymer layer 3, a carbon layer 4a, and a silver paste layer 4b are formed in this order on the surface of the anode 1. Yes. The anode 1 is formed from a porous sintered body.

  A cathode 4 is composed of the carbon layer 4a and the silver paste layer 4b. A cathode terminal 6 is connected to the silver paste layer 4 b through a conductive adhesive layer 5. An anode lead 1 a is connected to the center of the cathode 1, and the anode lead 1 a is connected to the anode terminal 7. Mold exterior resin 8 is formed so that the ends of anode terminal 7 and cathode terminal 6 are drawn out to the outside.

  The anode 1 is formed from a porous sintered body of a valve action metal or alloy, and the dielectric layer 2 is formed by oxidizing the surface of the porous sintered body by anodic oxidation or the like.

  FIG. 2 is an enlarged cross-sectional view showing the surface of the anode 1, and FIG. 3 is a further enlarged cross-sectional view. As shown in FIGS. 2 and 3, a dielectric layer 2 is formed on the surface of the anode 1 that is a porous body, and a thin film layer 9 is formed on the dielectric layer 2. A conductive polymer layer 3 is formed thereon. The conductive polymer layer 3 is made of a conductive polymer such as polypyrrole or polythiophene. The carbon layer 4a is formed by applying a carbon paste, and the silver paste layer 4b is formed by applying a silver paste containing silver particles and an organic solvent.

  As described above, the thin film layer 9 can be formed by a reaction between a silane coupling agent and a sulfonic acid. For example, the anode 1 on which the dielectric layer 2 is formed can be impregnated in a dilute solution of a silane coupling agent, and the silane coupling agent can be deposited on the dielectric layer 2. In order to remove excess silane coupling agent, the surface of the anode 1 may be washed with a solvent after impregnation and adhesion. Instead of impregnating and adhering, the silane coupling agent may be volatilized in a sealed container, and the silane coupling agent may be adhered to the surface of the dielectric layer 2 of the anode 1 in the gas phase.

  After attaching the silane coupling agent, the anode 1 is immersed in a solution in which the sulfonic acid is dissolved, and further the sulfonic acid is attached to react the first functional group of the coupling agent with the second functional group of the sulfonic acid. Let them join. In order to remove excess sulfonic acid, it may be washed with a solvent or the like.

  After the thin film layer 9 is formed on the dielectric layer 2 as described above, for example, it is immersed in a solution of a polymerization oxidant to attach the polymerization oxidant to the surface, and then the gas phase or liquid In the phase, a conductive polymer monomer such as pyrrole or thiophene is supplied, and the polymer is polymerized on the surface of the thin film layer 9 to form the conductive polymer layer 3. If necessary, after the excess monomer is washed with water or an organic solvent, the carbon layer 4a and the silver paste layer 4b are applied and formed on the outer peripheral surface of the anode 1 as described above.

  When the thin film layer 9 is formed from a reaction between a silane coupling agent having an amino group and a sulfonic acid compound having a carboxylic acid group and a sulfonic acid group, the reaction shown in the following chemical formula 1 shows that the anode 1 as a base material A thin film layer 9 can be formed thereon. In this case, for example, 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride may be used to promote the reaction between the silane coupling agent and the sulfonic acid compound (for example, sulfobenzoic acid). it can. As a solvent for preparing a solution of the silane coupling agent and the sulfonic acid compound, for example, water, alcohol, acetone, toluene, hexane, or the like can be used. The dilution concentration is generally about 1 to 8% by weight.

  Alternatively, when a silane coupling agent having an oxirane group is reacted with a sulfonic acid compound having an amino group and a sulfone group (for example, sulfanilic acid), a thin film layer can be formed by the reaction of Chemical Formula 2 shown below. The solution can have the same solvent and dilution concentration as described above.

<Solid electrolytic capacitor>
Examples of solid electrolytic capacitors as electronic devices of the present invention will be described below.

Example 1
In this example, a thin film layer was formed by the reaction shown in Chemical Formula 1 above. First, metal tantalum powder was sintered on a tantalum wire to prepare a porous tantalum sintered body (width 3.2 mm × height 4.4 mm × thickness 0.95 mm). This porous sintered body was anodized in a phosphoric acid aqueous solution, and a tantalum oxide layer as a dielectric layer was formed on the surface thereof with a thickness of about 60 nm.

  Next, 20 μl of 3-aminopropyltrimethoxysilane was diluted in 2 ml of toluene, and this solution and the anodized tantalum sintered body were placed in a sealed container, and then the silane coupling agent solution was heated to 100 ° C. For 60 minutes to volatilize and deposit a silane coupling agent on the surface of the dielectric layer.

  Next, the sintered body was immersed in an aqueous solution of p-sulfobenzoic acid and 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride (both concentrations were 2% by weight). As a result, the amino group of the silane coupling agent was reacted with the carboxylic acid group of p-sulfobenzoic acid to form a thin film layer on the surface of the sintered body. Since the sintered body is a porous body, a thin film layer is also formed on the inner surface.

  Next, the sintered body was dipped in an aqueous solution of an oxidizing agent (dilute sulfuric acid), then pulled up and dried, and an oxidizing agent was adhered on the surface thereof. Next, a thin film of polypyrrole was formed by chemical polymerization. Furthermore, electrolytic polymerization was performed in an aqueous solution containing polypyrrole and dodecylbenzenesulfonic acid using the polymer film of polypyrrole thus formed as an anode to form a polypyrrole film. As a result, a conductive polymer layer made of polypyrrole was formed on the thin film layer.

  After the electrolytic polymerization, it was dried and a carbon paste was applied on the outer peripheral surface of the sintered body. Thereafter, it was dried to form a carbon layer. Further, a silver paste was applied on the carbon layer and then dried to form a silver paste layer, thereby completing the cathode.

  The obtained capacitor element was measured for capacitance and ESR. The capacitance was 530 μF and the ESR was 7.0 mΩ.

[Measurement of conductivity of conductive polymer layer]
In order to measure the conductivity of the conductive polymer layer, a conductive polymer layer was formed in the same manner as described above on a glass substrate instead of the tantalum sintered body, and the conductivity was measured.

  Specifically, using a cleaned glass substrate (width 33 mm × height 33 mm × thickness 0.9 mm), a thin film layer is formed on the glass substrate in the same manner as described above, and then polypyrrole is formed thereon by chemical polymerization and electrolytic polymerization. A film was formed. As a result of performing electropolymerization for 2 hours, a polypyrrole film having a thickness of 15 μm was formed.

  About the formed polypyrrole film | membrane, the electrical conductivity was measured with the electrical conductivity measuring apparatus. The conductivity was 20 S / cm.

  Moreover, when the obtained polypyrrole film | membrane was observed with the optical microscope, it was confirmed that the film | membrane with very high uniformity is formed.

(Example 2)
In this example, a thin film layer was formed by the reaction shown in Chemical Formula 2 above. First, metal tantalum powder was sintered on a tantalum wire to prepare a porous tantalum sintered body (width 3.2 mm × height 4.4 mm × thickness 0.95 mm). This porous sintered body was anodized in a phosphoric acid aqueous solution, and a tantalum oxide layer as a dielectric layer was formed on the surface thereof with a thickness of about 60 nm.

  Next, 1 ml of 3-glycyridyloxypropyltrimethoxysilane was diluted in 100 ml of toluene, and the anodized tantalum sintered body was immersed in this solution and allowed to stand at room temperature for 60 minutes. Thereafter, the sintered body was pulled up from the solution and dried, and a silane coupling agent was adhered to the surface of the dielectric layer.

  Next, the sintered body is immersed in a 2% by weight aqueous solution of sulfanilic acid and heated to 50 ° C. to cause the oxirane group of the silane coupling agent to react with the amine group of sulfanilic acid. A thin film layer was formed on the surface. Since the sintered body is a porous body, a thin film layer is also formed on the inner surface.

  Next, the sintered body was dipped in an aqueous solution of an oxidizing agent (dilute sulfuric acid), then pulled up and dried, and an oxidizing agent was adhered on the surface thereof. Next, a thin film of polypyrrole was formed by chemical polymerization. Furthermore, electrolytic polymerization was performed in an aqueous solution containing polypyrrole and dodecylbenzenesulfonic acid using the polymer film of polypyrrole thus formed as an anode to form a polypyrrole film. As a result, a conductive polymer layer made of polypyrrole was formed on the thin film layer.

  After the electrolytic polymerization, it was dried, and then a carbon paste was applied on the outer peripheral surface of the sintered body and then dried to form a carbon layer. Further, a silver paste was applied on the carbon layer and then dried to form a silver paste layer, thereby completing the cathode.

  The obtained capacitor element was measured for capacitance and ESR. The capacitance was 510 μF and the ESR was 7.2 mΩ.

[Measurement of conductivity of conductive polymer layer]
In order to measure the conductivity of the conductive polymer layer, a conductive polymer layer was formed on the glass substrate in the same manner as described above instead of the tantalum sintered body, and the conductivity was measured.

  Specifically, using a cleaned glass substrate (width 33 mm × height 33 mm × thickness 0.9 mm), a thin film layer is formed on the glass substrate in the same manner as described above, and then chemical polymerization and electrolytic polymerization are performed thereon. A polypyrrole film was formed. As a result of performing electropolymerization for 2 hours, a polypyrrole film having a thickness of 15 μm was formed.

  About the formed polypyrrole film | membrane, the electrical conductivity was measured with the electrical conductivity measuring apparatus. The conductivity was 18 S / cm.

  Moreover, when the obtained polypyrrole film | membrane was observed with the optical microscope, it was confirmed that the film | membrane with very high uniformity is formed.

(Comparative Example 1)
In Example 1, after forming a dielectric layer by anodic oxidation, a polypyrrole film was formed without forming a thin film layer. Otherwise, the capacitor element was measured in the same manner as in Example 1, and the capacitance and ESR were measured. The capacitance was 480 μF and the ESR was 7.5 mΩ.

[Measurement of conductivity of conductive polymer layer]
A cleaned glass substrate (width 33 mm × height 33 mm × thickness 0.9 mm) was used, and a polypyrrole film was formed thereon without forming a thin film layer in the same manner as in Comparative Example 1. As a result of performing electropolymerization for 2 hours, a polypyrrole film having a thickness of 15 μm was formed.

  It was 11 S / cm when the electrical conductivity of this polypyrrole film | membrane was measured.

  Moreover, when the obtained conductive polymer layer was observed with an optical microscope, a three-dimensional raised portion was observed in some places, and the flatness and uniformity of the polypyrrole film were inferior to those of Examples 1 and 2. It was.

(Comparative Example 2)
[Measurement of conductivity of conductive polymer layer]
Washing was conducted in the same manner as in [Measurement of conductivity of conductive polymer layer] in Comparative Example 1 except that p-toluenesulfonic acid was used instead of dodecylbenzenesulfonic acid as a dopant agent in electrolytic polymerization. A polypyrrole film was formed on a glass substrate. As a result of performing electropolymerization for 2 hours, a polypyrrole film having a thickness of 15 μm was formed.

  When the electrical conductivity of the obtained polypyrrole film was measured, it was 10 S / cm.

  Moreover, when observed with an optical microscope, this polypyrrole film was slightly inferior in flatness and uniformity.

  As is clear from the above results, according to the present invention, a conductive polymer layer excellent in conductivity is formed by forming a thin film layer on a substrate and forming a conductive polymer layer on the thin film layer. Can be formed uniformly. Therefore, when used in a solid electrolytic capacitor, as described above, the capacitance can be increased and the ESR can be reduced.

<Organic solar cell>
(Example 3)
In this example, an organic solar cell was produced as an electronic device according to the present invention.

  FIG. 4 is a cross-sectional view showing an organic solar cell produced in this example. As shown in FIG. 4, the transparent electrode 12 is formed on the substrate 11, and the thin film layer of the present invention is formed on the transparent electrode 12. On the thin film layer 13, a hole transport layer 14 which is a conductive polymer layer of the present invention is formed. An active layer 15 is formed on the hole transport layer 14, and an electron transport layer 16 is formed on the active layer 15. An upper electrode 17 is formed on the electron transport layer 16. Specifically, the organic solar cell of the present invention was produced as follows.

  A glass substrate was used as the substrate 11, and a transparent electrode 12 on which an indium tin oxide (ITO) was formed was used. A solution prepared by diluting 1 ml of 3-aminopropyltrimethoxysilane in 100 ml of toluene is prepared, and this solution and the substrate 11 on which the transparent electrode 12 is formed are placed in a sealed container, and the silane coupling agent solution is placed at 100 ° C. The silane coupling agent was adhered to the surface of the transparent electrode 12 by heating and volatilizing for 60 minutes.

  Next, a mixed aqueous solution of p-sulfobenzoic acid and 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride (each 5% by weight) is placed on the substrate on which the silane coupling agent is attached. The thin film layer 13 was formed by reacting the amino group of the silane coupling agent with the carboxylic acid group of p-sulfobenzoic acid.

  Next, this substrate was immersed in an alcohol solution of iron p-toluenesulfonate, pulled up and dried. Next, this was exposed to vapor of ethylenedioxythiophene to form a thin film of polyethylenedioxythiophene as the hole transport layer 14. After washing away the drug remaining on the thin film, it was dried on a hot plate at 110 ° C.

  Next, a poly (3-hexylthiophene) o-dichlorobenzene solution was spin-coated on the hole transport layer 14 and then dried to form an active layer 15. Further, a C60 fullerene film was formed on the active layer 15 by vacuum vapor deposition to form an electron transport layer 16.

  An Al film was vacuum-deposited on the electron transport layer 16 using a shadow mask to form the upper electrode 17. Next, it sealed with the glass cap and completed the organic solar cell.

When the produced organic solar cell was irradiated with AM1.5 (100 mW / cm ² ) pseudo-sunlight, an electromotive force of 500 mV could be obtained as an open voltage. Compared with the case where the thin film layer 13 was not formed, a high electromotive force could be obtained.

  In the above embodiment, the solid electrolytic capacitor and the organic solar battery are shown as the electronic device of the present invention. However, the electronic device of the present invention is not limited to these, for example, an organic EL element, an organic transistor, It can also be applied to a touch panel or the like.

Sectional drawing which shows the solid electrolytic capacitor of one Embodiment according to this invention. The figure which shows the surface vicinity of an anode in the solid electrolytic capacitor shown in FIG. The figure which expands and shows the surface vicinity of an anode in the solid electrolytic capacitor shown in FIG. Sectional drawing which shows the organic solar cell of other embodiment according to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Anode 1a ... Anode lead 2 ... Dielectric layer 3 ... Conductive polymer layer 4 ... Cathode 4a ... Carbon layer 4b ... Silver paste layer 5 ... Conductive adhesive layer 6 ... Cathode terminal 7 ... Anode terminal 8 ... Mold exterior Resin 9 ... Thin film layer 10 ... Solid electrolytic capacitor 11 ... Substrate 12 ... Transparent electrode 13 ... Thin film layer 14 ... Hole transport layer 15 ... Active layer 16 ... Electron transport layer 17 ... Upper electrode

Claims (7)

A substrate having at least a surface formed of a metal oxide;
A conductive polymer layer provided on the substrate;
A thin film layer provided between the base material and the conductive polymer layer,
The electronic device, wherein the thin film layer has a sulfonic acid group that interacts with the conductive polymer layer, and is formed from a compound that chemically bonds to the surface of the substrate.   The electronic device according to claim 1, wherein the sulfonic acid group is bonded to a phenyl group in the compound.   The compound is formed by reacting a silane coupling agent having an amino group with a sulfonic acid compound having a carboxylic acid group and a sulfonic acid group, and the thin film layer is formed by reacting the silane coupling agent with the group. 3. It forms by making it react with the material surface and making it chemically bond, and making the carboxylic acid group of the said sulfonic acid compound react with the amino group of the said silane coupling agent. Electronic devices.   The compound is formed by reacting a silane coupling agent having an oxirane group and a sulfonic acid compound having an amino group and a sulfonic acid group, and the thin film layer is formed by using the silane coupling agent as the base material. 3. The electron according to claim 1, wherein the electron is formed by reacting the surface with a chemical bond and then reacting the oxirane group of the silane coupling agent with the amino group of the sulfonic acid compound. 4. device.   The electronic device according to claim 1, wherein the substrate is porous.   The anode made of the porous substrate, the dielectric layer made of the metal oxide on the surface of the substrate, the thin film layer provided on the dielectric layer, and the conductive provided on the thin film layer The electronic device according to claim 5, wherein the electronic device is a solid electrolytic capacitor comprising a conductive polymer layer and a cathode provided on the conductive polymer layer. A method for manufacturing the electronic device according to any one of claims 1 to 6,
Forming the thin film layer on the substrate;
And a step of supplying the monomer constituting the conductive polymer layer on the thin film layer and polymerizing the monomer to form the conductive polymer layer.

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