WO2015029344A1 - 電解コンデンサおよびその製造方法 - Google Patents
電解コンデンサおよびその製造方法 Download PDFInfo
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- WO2015029344A1 WO2015029344A1 PCT/JP2014/004097 JP2014004097W WO2015029344A1 WO 2015029344 A1 WO2015029344 A1 WO 2015029344A1 JP 2014004097 W JP2014004097 W JP 2014004097W WO 2015029344 A1 WO2015029344 A1 WO 2015029344A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0032—Processes of manufacture formation of the dielectric layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/07—Dielectric layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Definitions
- the present invention relates to an electrolytic capacitor having a dielectric layer and a method for manufacturing the same.
- a solid electrolytic capacitor includes an anode formed of a valve metal such as tantalum, niobium, titanium, and aluminum, a dielectric layer formed on the surface of the anode, and a solid electrolyte layer formed on the surface of the dielectric layer. It has.
- a conductive polymer layer as a solid electrolyte layer on the surface of the dielectric layer (for example, Patent Documents 1 and 2).
- a solution containing a monomer, a dopant and an oxidant is applied on the dielectric layer and chemically polymerized in situ, or a solution or dispersion of a conductive polymer. Can be applied to the dielectric layer.
- the dielectric layer cannot be sufficiently covered by the conductive polymer layer, and it is not possible to sufficiently increase the capacitance. It was difficult.
- An object of the present invention is to increase the capacitance of an electrolytic capacitor having a dielectric layer.
- one aspect of the present invention includes an anode, a dielectric layer formed on the anode, and an organic semiconductor layer covering at least a part of the dielectric layer, and the organic semiconductor layer has a number average.
- Another aspect of the present invention is a step of preparing an anode having a dielectric layer, and an organic semiconductor compound having a number average molecular weight of 100 to 10,000 and having a ⁇ electron cloud on the surface of the dielectric layer And a step of forming an organic semiconductor layer covering at least a part of the surface of the dielectric layer by applying a solution in which is dissolved.
- Still another aspect of the present invention is a step of preparing an anode having a dielectric layer, and an organic semiconductor having a number average molecular weight of 100 to 10,000 on the surface of the dielectric layer and having a ⁇ electron cloud
- An electrolysis comprising: providing a solution in which a precursor of the compound is dissolved; and forming the organic semiconductor compound from the precursor and forming an organic semiconductor layer covering at least a part of a surface of the dielectric layer.
- the present invention relates to a method for manufacturing a capacitor.
- the capacitance of an electrolytic capacitor having a dielectric layer can be increased.
- FIG. 2 is an enlarged view of a region surrounded by a solid line ⁇ in FIG. 1. It is a cross-sectional schematic diagram of the principal part of the electrolytic capacitor which concerns on other embodiment of this invention. It is a cross-sectional schematic diagram of the principal part of the electrolytic capacitor which concerns on further another embodiment of this invention. It is a cross-sectional schematic diagram of the principal part of the electrolytic capacitor which concerns on further another embodiment of this invention.
- the electrolytic capacitor of the present invention includes an anode, a dielectric layer formed on the anode, and an organic semiconductor layer covering at least a part of the dielectric layer.
- the organic semiconductor layer includes an organic semiconductor compound having a number average molecular weight of 100 to 10,000 and having a ⁇ electron cloud (hereinafter referred to as a low molecular organic semiconductor compound). Carriers move between the molecules of the low molecular organic semiconductor compound via the ⁇ electron cloud.
- the low molecular organic semiconductor compound can penetrate into the holes of the dielectric layer or the inner wall surface of the etching pit. Therefore, compared to the conductive polymer, the details of the dielectric layer can be easily covered, and the capacitance of the electrolytic capacitor can be increased.
- At least a part of the organic semiconductor layer may be covered with a conductive polymer layer.
- ESR of an electrolytic capacitor can be reduced.
- the dielectric layer is not covered with the conductive polymer layer and covered with the organic semiconductor layer, and the portion not covered with the organic semiconductor layer and covered with the conductive polymer layer; , May be included. Thereby, a larger electrostatic capacity can be obtained in the electrolytic capacitor.
- the low molecular weight organic semiconductor compound is preferably a compound containing at least one selected from the group consisting of a condensed ring and a heterocyclic ring. Thereby, the crystallinity of the organic semiconductor layer is improved.
- the organic semiconductor layer preferably contains a dopant. Thereby, the electroconductivity of an organic-semiconductor layer improves.
- the dopant may be at least one selected from the group consisting of an electron donating molecule and an electron accepting molecule.
- FIG. 1 is a schematic cross-sectional view of an electrolytic capacitor 20 according to this embodiment.
- the electrolytic capacitor 20 includes a capacitor element 10 having a substantially rectangular parallelepiped shape, a resin sheathing body 11 that seals the capacitor element 10, and an anode terminal 7 and a cathode terminal 9 that are exposed to the outside of the resin sheathing body 11, respectively. ing. Similar to the capacitor element 10, the electrolytic capacitor 20 has a substantially rectangular parallelepiped outer shape.
- the capacitor element 10 includes a substantially rectangular parallelepiped anode 1, an anode lead 2 in which a first end 2 a is embedded in the anode 1, and a second end 2 b drawn from the anode 1, and a dielectric layer that covers the surface of the anode 1. 3, an organic semiconductor layer 4 covering at least a part of the dielectric layer 3, and a cathode layer 5 covering the surface of the organic semiconductor layer 4. Furthermore, you may have the conductive polymer layer 6 which covers at least one part of the dielectric material layer 3 or the organic-semiconductor layer 4.
- FIG. 1 and 2 show a case where a porous body is used as the anode 1.
- FIG. 1 schematically shows the dielectric layer 3, the organic semiconductor layer 4, and the conductive polymer layer 6 formed on the outer peripheral side of the anode 1. Omitted.
- the second end 2b of the anode lead 2 is electrically connected to the first end 7a of the anode terminal 7 sealed with the resin sheathing body 11 by welding or the like.
- the cathode layer 5 is provided via the first end 9a of the cathode terminal 9 sealed with the resin sheathing body 11 and the conductive adhesive 8 (for example, a mixture of thermosetting resin and metal particles). Electrically connected.
- the second end portion 7b of the anode terminal 7 and the second end portion 9b of the cathode terminal 9 are drawn from different side surfaces of the resin sheathing body 11, respectively, and are exposed to one main flat surface (the lower surface in FIG. 1). is doing.
- the exposed portions of the terminals on the flat surface are used for solder connection with a substrate (not shown) on which the solid electrolytic capacitor 20 is to be mounted.
- the anode 1 is a porous body of valve action metal particles.
- the anode lead 2 is made of, for example, a conductive wire.
- the anode 1 is formed by, for example, embedding the first end 2a of the anode lead 2 in a valve metal or an alloy particle containing a valve metal, forming the metal particles into a rectangular parallelepiped in this state, and sintering the molded body. Produced. That is, the anode 1 is a combined body (sintered body) of valve action metal or alloy particles containing the valve action metal. Thereby, it pulls out from the outer peripheral surface of the anode 1 so that the 2nd end part 2b of the anode lead 2 may be planted.
- the anode 1 may be formed of a valve metal or an alloy foil containing the valve metal.
- the foil is roughened by etching or the like in order to increase its surface area.
- the same kind or different kinds of materials are used.
- the conductive material titanium (Ti), tantalum (Ta), aluminum (Al), niobium (Nb), or the like, which is a valve action metal, is used. Since these metal oxides have a high dielectric constant, they are suitable as a constituent material of the anode 1.
- the conductive material may be an alloy made of two or more metals. For example, an alloy containing a valve action metal and silicon, vanadium, boron, or the like can be used. A compound containing a valve metal and a typical element such as nitrogen may be used.
- the valve metal alloy is preferably composed mainly of the valve metal and contains 50 atomic% or more of the valve metal.
- the anode 1 and the anode lead 2 may be made of different conductive materials.
- the dielectric layer 3 can be formed as an oxide film by oxidizing the surface of the conductive material constituting the anode 1. Therefore, the dielectric layer 3 is uniformly formed along the surface of the porous body or foil (including the inner wall surface of the hole or etching pit) constituting the anode 1.
- the thickness of the dielectric layer 3 is, for example, 10 nm to 200 nm.
- Organic semiconductor layer 4 is formed so as to cover the surface of the dielectric layer 3. Specifically, the organic semiconductor layer 4 is formed along a surface including a recess (hole or inner wall surface of an etching pit) derived from a porous body or foil constituting the anode 1.
- a conductive polymer layer is formed by chemically polymerizing a raw material monomer on a dielectric layer.
- the raw material monomer is polymerized so as to block the inner surface of the hole or the etching pit and polymerizes so as to block the film earlier. Therefore, the surface of the dielectric layer formed on the inner wall surface of the hole or the etching pit cannot be covered with the conductive polymer layer, and a large electrostatic capacity cannot be obtained. Further, the unreacted raw material monomer remains on the dielectric layer, which may reduce the reliability of the electrolytic capacitor, such as an increase in equivalent series resistance (ESR) of the electrolytic capacitor.
- ESR equivalent series resistance
- conductive polymer layer Other methods for forming the conductive polymer layer include a method of applying a conductive polymer solution onto the dielectric layer.
- the conductive polymer has a large molecule and, in many cases, has a rigid molecular skeleton.
- the viscosity of the solution tends to increase. Therefore, the conductive polymer cannot sufficiently enter the hole or the etching pit.
- a conductive polymer layer is also formed by applying a dispersion containing conductive polymer particles on a dielectric layer.
- the conductive polymer particles are large, they cannot sufficiently enter the holes or the etching pits.
- the conductive polymer layer cannot be uniformly formed to the details of the dielectric layer including the inner wall surface of the hole or etching pit, and a sufficiently large capacitance can be obtained. Was difficult.
- the organic semiconductor layer 4 contains a low molecular organic semiconductor compound having a number average molecular weight of 100 to 10,000.
- the number average molecular weight of the low molecular weight organic semiconductor compound is preferably 100 to 2,000.
- the low molecular weight organic semiconductor compound Since the low molecular weight organic semiconductor compound has a low molecular weight, its molecular chain is short, and it can easily enter the holes or etching pits of the dielectric layer 3, and the organic semiconductor layer 4 is formed on the dielectric layer 3 on the inner wall surface thereof. Can be formed. Therefore, the obtained electrolytic capacitor has an improved capacity appearance rate and can obtain a large capacitance. Moreover, since the solution in which the low molecular organic semiconductor compound is dissolved has a low viscosity, it can easily reach the inside of the hole or the etching pit. Therefore, it becomes easy to form the organic semiconductor layer 4 on the dielectric layer 3 on the inner wall surface of the hole or the etching pit.
- the low molecular weight organic semiconductor compound since the low molecular weight organic semiconductor compound has a low molecular weight as described above, it is easily dissolved in a solvent. Therefore, as in the case of using a conductive polymer, it is less necessary to introduce a substituent such as an alkyl chain in order to dissolve in a solvent. Since the introduced substituent inhibits packing between molecules, the crystallinity tends to decrease and the carrier mobility tends to decrease.
- a low molecular weight organic semiconductor compound has a short molecular chain and is a uniform molecular assembly, so that packing between molecules is dense and crystallinity is high. As a result, carrier mobility is improved.
- the electrolytic capacitor including the organic semiconductor layer 4 on the dielectric layer 3 is not easily affected by the raw material monomer remaining after the polymerization reaction for forming the conductive polymer layer 6. Therefore, the reliability of the electrolytic capacitor is improved.
- the low molecular organic semiconductor compound has a ⁇ electron cloud.
- the organic semiconductor layer 4 exhibits semiconductor characteristics by performing carrier transfer between molecules of the low molecular weight organic semiconductor compound as well as within the molecule of the low molecular weight organic semiconductor compound via the ⁇ electron cloud.
- TCNQ 7,7,8,8-tetracyanoquinodimethane
- TCNQ complex salt is composed of one molecule of a salt composed of a cation such as tetrathiafulvalene (TTF, electron donor) and an anion of TCNQ (electron acceptor), and about one molecule of neutral TCNQ.
- TTF tetrathiafulvalene
- ECNQ electron acceptor
- the TCNQ salt is called a charge transfer complex because electrons move from TTF to TCNQ to form a salt.
- each planar TTF and TCNQ form a laminated structure. Electrons move between these layers to exhibit conductivity.
- the organic semiconductor layer 4 can be expected to have high carrier mobility between molecules.
- the low molecular weight organic semiconductor compound contained in the organic semiconductor layer 4 has high crystallinity due to high molecular orientation, and the distance between molecules constituting the organic semiconductor layer 4 can be shortened. Therefore, a large number of overlapping portions of ⁇ electron clouds of molecules of the low molecular organic semiconductor compound are formed between the molecules.
- the charge transfer complex (TCNQ salt) is difficult to dissolve in the solvent, it is difficult to reach the inside of the hole or the etching pit. Therefore, a high capacity appearance rate cannot be expected.
- the low molecular weight organic semiconductor compound is preferably a compound containing at least one selected from the group consisting of a condensed ring and a heterocyclic ring.
- a part of the compound has a planar structure such as a condensed ring or a heterocyclic ring, crystallinity is improved and carrier mobility is increased.
- the compound containing a condensed ring or a heterocyclic ring is not particularly limited, but polyacenes having a structure in which a plurality of benzene rings are condensed linearly as shown in Formula 1 and derivatives thereof, and a plurality of benzene rings are nonlinear.
- Compounds having a condensed structure and derivatives thereof, oligothiophenes and derivatives thereof in which a plurality of thiophenes are bonded as shown in Formula 2, thienoacenes and derivatives thereof containing thiophene-containing condensed polycyclic aromatics as shown in Formulas 3 to 5 and the like Is mentioned.
- Such a compound has a low molecular weight, but has developed a ⁇ -conjugated system.
- the compound containing a condensed ring or a heterocyclic ring is not limited to the following chemical formula.
- examples of the compound containing a condensed ring include anthracene, tetracene, pentacene, rubrene, picene, benzopyrene, chrysene, pyrene, and triphenylene.
- examples of the derivative include (6,13-bis (triisopropylsilylethynyl) pentacene, TIPS-pentacene).
- 2,7-dioctylbenzothieno [3,2-b] benzothiophene 2,7-dioctylbenzothieno [3,2-b] benzothiophene (2,7-dioctylbenzothieno [3,2-b] BTBT derivatives such as benzothiophene, C8-BTBT), dinaphtho [2,3-b: 2 ', 3'-f] thiopheno [3,2-b] thiophene (dinaphtho [2,3-b: 2', 3 ' -f] thieno [3,2-b] thiophene, DNTT), dianthra [2,3-b: 2 ', 3'-f] thiopheno [3,2-b] thiophene (dianthra [2,3-b: 2', 3'-f] thieno [3,2-b] thiophene, DATT) and 5,5'-bis (7-hexy
- Other compounds include tris (8-hydroxyquinolinato) aluminum (Alq3), 1,1,2,2-tetraphenyldisilane (TPDS), and the like.
- the low molecular weight organic semiconductor compound is preferably soluble in a solvent having a boiling point of 100 ° C. or lower.
- a low molecular organic semiconductor compound or a precursor thereof is dissolved in a solvent, and the obtained solution is applied onto the dielectric layer 3. Thereafter, the solvent is removed by heat treatment or the like, but if the boiling point of the solvent is 100 ° C. or lower, the solvent is easily removed. If the solvent remains, the solvent becomes a resistance component and the internal resistance increases. Further, the solvent expands during the reflow process performed for mounting the electrolytic capacitor on the substrate, and stress is applied to the dielectric layer 3. As a result, defects such as cracks occur in the electrolytic capacitor, which may increase the leakage current. Conventionally, the conductive polymer used is difficult to dissolve in a low boiling point solvent. For this reason, the solvent tends to remain, which may affect the performance of the electrolytic capacitor.
- Examples of the solvent having a boiling point of 100 ° C. or lower include halogenated solvents such as tetrahydrofuran (THF), methanol, isopropyl alcohol, trichloroethylene, and chloroform.
- halogenated solvents such as tetrahydrofuran (THF), methanol, isopropyl alcohol, trichloroethylene, and chloroform.
- the thickness of the organic semiconductor layer 4 is preferably 1 ⁇ m or less. When the thickness of the organic semiconductor layer 4 is 1 ⁇ m or less, high conductivity can be expected. When it is thicker than this, there is a possibility that the movement between the molecules of the carrier increases and the conductivity is lowered.
- the organic semiconductor layer 4 functions as an electrolyte even when a dopant is not added separately and actively.
- an electric field for example, carriers are injected from the adjacent conductive polymer layer 6 into the organic semiconductor layer 4 to solve the ⁇ electron cloud of the low molecular organic semiconductor compound forming the organic semiconductor layer 4. This is because the carrier can be transported.
- film quality deterioration of the organic semiconductor layer 4 due to the dopant for example, due to dedoping or diffusion of the dopant does not occur, and the reliability of the electrolytic capacitor can be improved.
- a dopant may be added to the organic semiconductor layer 4. Doping increases the carrier concentration of the organic semiconductor layer 4, so that the conductivity of the organic semiconductor layer 4 can be increased. Even when the organic semiconductor layer 4 has a dopant, intra- and inter-molecular carrier movement is performed via a ⁇ electron cloud of the low-molecular organic semiconductor compound.
- the dopant is at least one selected from the group consisting of an electron donating molecule and an electron accepting molecule.
- the dopant is not particularly limited, and examples thereof include TCNQ derivatives such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, and tetrathiafulvalene.
- the organic semiconductor layer 4 may be formed after treating the surface of the dielectric layer 3. Since the low molecular organic semiconductor compound is hydrophobic, it is preferable to make the surface of the dielectric layer 3 hydrophobic. Specifically, for example, the organic semiconductor layer 4 can be formed after treating the surface of the dielectric layer 3 with a silane coupling agent.
- silane coupling agent an silane coupling agent having an epoxy group, a silane coupling agent having an acrylic group, and the like are preferable because they are advantageous in reducing ESR and increasing the capacity.
- examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane and the like can be mentioned.
- silane coupling agent having an acrylic group examples include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples thereof include 3-acryloxypropyltrimethoxysilane ( ⁇ -acryloxypropyltrimethoxysilane).
- silane couplings include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Hydrochloride of silyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxy
- the conductive polymer layer 6 is formed on the organic semiconductor layer 4.
- the conductive polymer layer 6 can be formed by chemically polymerizing the raw material monomer on the organic semiconductor layer 4.
- the conductive polymer layer 6 can be formed by applying a solution in which the conductive polymer is dissolved or a dispersion liquid in which the conductive polymer is dispersed to the organic semiconductor layer 4.
- the thickness of the conductive polymer layer 6 is, for example, 1 to 50 ⁇ m.
- Examples of the conductive polymer include polypyrrole, polythiophene, polyfuran, polyaniline, polyacetylene, polyphenylene, polyparaphenylene vinylene, polyacene, polythiophene vinylene, polyfluorene, polyvinyl carbazole, polyvinyl phenol, polypyridine, and derivatives of these polymers. . These may be used alone or in combination of two or more. Moreover, the copolymer of 2 or more types of monomers may be sufficient. Among these, polyaniline and polypyrrole are preferable because they are excellent in solubility in solvents and conductivity.
- polypyrrole, polythiophene, polyfuran, polyaniline and the like mean polymers having a basic skeleton of polypyrrole, polythiophene, polyfuran, polyaniline and the like, respectively. Accordingly, polypyrrole, polythiophene, polyfuran, polyaniline and the like can also include respective derivatives.
- polythiophene includes poly (3,4-ethylenedioxythiophene) and the like.
- the weight average molecular weight of the conductive polymer is not particularly limited, but preferably exceeds 10,000, for example. More preferably, the weight average molecular weight of the conductive polymer is more than 10,000 and 1,000,000 or less. Such a conductive polymer tends to form a homogeneous electrolyte layer.
- the average particle diameter D50 of the particles or powder is preferably 0.01 to 0.5 ⁇ m, for example.
- the average particle diameter D50 is a median diameter in a volume particle size distribution obtained by a laser diffraction particle size distribution measuring apparatus.
- the solvent water or the like can be used.
- Various dopants may be added to the conductive polymer solution or dispersion in order to improve the conductivity of the conductive polymer.
- the dopant is not particularly limited. 2,7-naphthalenedisulfonic acid, 2-methyl-5-isopropylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, 4-nitrotoluene-2-sulfonic acid, m-nitrobenzenesulfonic acid, n-octylsulfonic acid, n-butane Sulfonic acid, n-hexanesulfonic acid, o-nitrobenzenesulfonic acid, p-ethylbenzenesulfonic acid, trifluoromethanesulfonic acid, hydroxybenzenesulfonic acid, butylnaphthalenesulfonic acid, benzenesulfonic acid, polystyrenesulfonic acid, polyvinylsulfone Acid, me
- the cathode layer 5 is formed so as to cover the surface of the conductive polymer layer 6.
- the cathode layer 5 has a carbon layer 5a and a silver paste layer 5b formed on the surface of the carbon layer 5a.
- the carbon layer 5a is composed of a composition containing a conductive carbon material such as graphite.
- the silver paste layer 5b is composed of a composition containing silver particles and a resin.
- the structure of the cathode layer 5 is not restricted to this, What is necessary is just a structure which has a current collection function.
- the anode 1 and the anode lead 2 constitute the anode member of the capacitor element 10
- the organic semiconductor layer 4 constitute the cathode member of the capacitor element 10
- the dielectric layer 3 constitutes a dielectric member of the capacitor element 10.
- Anode preparation step An anode 1 having a dielectric layer 3 is prepared. Specifically, the anode 1 is immersed in a chemical conversion tank filled with an electrolytic aqueous solution (for example, phosphoric acid aqueous solution), and the second end 2b of the anode lead 2 is connected to the anode of the chemical conversion tank to perform anodization. As a result, the dielectric layer 3 made of an oxide film of the valve action metal can be formed on the surface of the anode 1.
- an electrolytic aqueous solution for example, phosphoric acid aqueous solution
- the electrolytic aqueous solution is not limited to a phosphoric acid aqueous solution, and nitric acid, acetic acid, sulfuric acid, and the like can be used.
- (Ii) Hydrophobizing step of dielectric layer This step is performed as necessary, and is performed by applying a solution containing a silane coupling agent to the dielectric layer 3 and then drying it. Although it does not specifically limit as a solvent, Monohydric alcohols, such as water or ethanol, propanol, butanol, can be used.
- Step of forming organic semiconductor layer A solution in which a low molecular organic semiconductor compound is dissolved in a low boiling point solvent (boiling point 66 ° C.) such as tetrahydrofuran (THF) is applied to the dielectric layer 3, and the solvent is removed by heat treatment or the like. By removing, the organic semiconductor layer 4 is formed.
- a low boiling point solvent such as tetrahydrofuran (THF)
- THF tetrahydrofuran
- the concentration of the low molecular organic semiconductor compound solution is preferably 0.01 to 5% by weight. If the concentration is within this range, an organic semiconductor layer having a sufficient thickness can be formed on the dielectric layer.
- the heat treatment may be performed at 100 to 180 ° C. for 1 to 60 minutes.
- the boiling point of the solvent for dissolving the low molecular organic semiconductor compound is preferably 100 ° C. or lower.
- a solution in which the precursor of the low molecular organic semiconductor compound is dissolved may be applied to the dielectric layer 3.
- a low molecular organic semiconductor compound is produced from the precursor by applying a solution in which the precursor of the low molecular organic semiconductor compound is dissolved and then performing a heat treatment or the like.
- the precursor refers to a compound that generates a low molecular organic semiconductor compound by heat treatment.
- pentacene 13,6-N-sulfinylacetamidopentacene 13,6-N-Sulfinylacetamidopentacene, NSFAAP
- pentacene-N-sulfinyl-tert-butylcarbamic acid pentacene-N -sulfinyl-tert-butylcarbamate
- the precursor is also preferably soluble in a solvent having a boiling point of 100 ° C. or lower.
- the concentration of the precursor in the solution is preferably 0.01 to 5% by weight. If the concentration is within this range, the organic semiconductor layer 4 having a sufficient thickness can be formed on the dielectric layer 3.
- the heat treatment for generating the low molecular weight organic semiconductor compound from the precursor may be performed as a heat treatment for removing the solvent.
- Step of forming conductive polymer layer Conductor is formed by a method in which a monomer or oligomer is impregnated into a capacitor element precursor on which organic semiconductor layer 4 is formed, and then the monomer or oligomer is polymerized by chemical polymerization or electrolytic polymerization.
- the functional polymer layer 6 can be formed.
- the concentration of the raw material monomer in the solution is, for example, 0.1 to 2.0 mol / L (liter).
- the conductive polymer layer 6 can be formed by applying a solution or dispersion of a conductive polymer to the organic semiconductor layer 4 formed in the capacitor element and drying it.
- the concentration of the conductive polymer in the solution is, for example, 0.5 to 6 g / L (liter).
- the conductive polymer layer 6 may be formed after the organic semiconductor layer 4 is formed, or may be formed before the organic semiconductor layer 4 is formed. In the former case, a void 12 surrounded by the organic semiconductor layer 4 and the conductive polymer layer 6 may be formed. In the latter case, the dielectric layer 3 is not covered with the conductive polymer layer 6 and is covered with the organic semiconductor layer 4, and is not covered with the organic semiconductor layer 4, and the conductive polymer layer. 6 and a portion covered with 6.
- the second conductive polymer layer 6b may be formed in an overlapping manner.
- the second conductive polymer layer 6b can be formed electrochemically by electrolytic polymerization. Electropolymerization is suitable for synthesizing thin film polymers.
- the capacitor element precursor on which the first conductive polymer layer 6a is formed is immersed in a solution containing a raw material monomer and a dopant, and a current is passed as an electrode, or a potential is scanned across the electrode.
- the concentration of the raw material monomer in the solution is, for example, 0.1 to 2.0 mol / L (liter).
- Step of forming cathode layer Carbon layer 5a and silver paste layer 5b are formed by sequentially applying a carbon paste and a silver paste onto the surface of conductive polymer layer 6 (or second conductive polymer layer 6b).
- the cathode layer 5 comprised by these can be formed.
- the configuration of the cathode layer 5 is not limited thereto, and any configuration having a current collecting function may be used.
- the conductive polymer layer 6 includes a first conductive polymer layer 6a and a second conductive polymer layer 6b.
- the first conductive polymer layer 6 a covers a part of the organic semiconductor layer 4. Therefore, a gap 12 surrounded by the organic semiconductor layer 4 and the first conductive polymer layer 6a or the second conductive polymer layer 6b is formed.
- This void 12 was formed because the conductive polymer forming the first conductive polymer layer 6a or the second conductive polymer layer 6b could not enter the concave and convex recesses derived from the anode 1. Is. Even in this case, since the organic semiconductor layer 4 is formed along the recess, the capacity appearance rate can be improved and a large capacitance can be obtained.
- the first conductive polymer layer 6a and the second conductive polymer layer 6b may be formed of the same polymer or may be formed of different polymers. Similarly, when a dopant is included, the same dopant may be included or different dopants may be included.
- the first conductive polymer layer 6a can be formed by, for example, chemical polymerization.
- the second conductive polymer layer 6b can be formed by, for example, electrolytic polymerization.
- the conductive polymer layer 6 covers a part of the organic semiconductor layer 4. Therefore, a void 12 surrounded by the organic semiconductor layer 4 and the conductive polymer layer 6 is formed.
- the void 12 is formed because the conductive polymer could not enter the concave and convex portions derived from the anode 1.
- the conductive polymer layer 6 of this embodiment is formed by applying a polymer dispersion dispersed in a dispersion medium to the organic semiconductor layer 4. Even in the case where the gap 12 is formed in this way, the organic semiconductor layer 4 is formed along the recess, so that the capacity appearance rate can be improved and a large capacitance can be obtained. it can.
- Embodiment 4 >> Embodiment 4 of the present invention will be described with reference to FIG.
- the dielectric layer 3 is not covered with the first conductive polymer layer 6a, is covered with the organic semiconductor layer 4, and is not covered with the organic semiconductor layer 4. And a portion covered with the conductive polymer layer 6a.
- the organic semiconductor layer 4 is formed, for example, after the first conductive polymer layer 6a is formed.
- the second conductive polymer layer 6 b is formed, but the second conductive polymer layer 6 b is not formed in the recess on the dielectric layer 3.
- the electrolytic capacitor of the present embodiment includes a wound capacitor element.
- a wound capacitor element is manufactured from a wound body.
- a wound body is a semi-finished product of a capacitor element, and includes an anode connected to a lead tab, a cathode connected to another lead tab, and a separator. The anode and the cathode are wound through a separator. The outermost periphery of the wound body is fixed by a winding tape.
- the anode is a metal foil roughened so that the surface has irregularities, and a dielectric layer is formed on the metal foil having irregularities.
- a metal foil can be used for the cathode.
- valve action metals such as aluminum, a tantalum, niobium, or the alloy containing a valve action metal. If necessary, the surface of the cathode may be roughened.
- a capacitor element can be obtained by providing an organic semiconductor layer between the anode and the cathode.
- the anode and the cathode are wound by impregnating a wound body in which the anode, the separator, and the cathode are wound into a solution in which the low molecular organic semiconductor compound is dissolved or a solution in which the precursor of the low molecular organic semiconductor compound is dissolved.
- An organic semiconductor layer can be formed between the two.
- the anode before winding is impregnated with a solution in which a low molecular organic semiconductor compound is dissolved or a solution in which a precursor of a low molecular organic semiconductor compound is dissolved, and an organic semiconductor layer is formed on the surface of the anode. By winding these, an organic semiconductor layer can be provided between the anode and the cathode. At this time, the organic semiconductor layer may be similarly formed on the separator and the cathode before winding.
- the electrolyte is preferably an organic solvent, and examples thereof include propylene glycol, sulfolane, ⁇ -butyrolactone, and ethylene glycol.
- the conductive polymer may be used, or a solution or dispersion of a conductive polymer containing an organic solvent may be used.
- anode 1 Formation of anode 1>
- tantalum metal particles having a primary particle size of about 0.5 ⁇ m and a secondary particle size of about 100 ⁇ m were used.
- the tantalum metal particles were formed into a rectangular parallelepiped so that the first end 2a of the anode lead 2 made of tantalum was embedded in the tantalum metal particles, and then the formed body was sintered in vacuum.
- an anode 1 made of a tantalum porous sintered body was obtained.
- the anode 1 is a rectangular parallelepiped having a length of 4.4 mm, a width of 3.3 mm, and a thickness of 0.9 mm.
- Step 2 Formation of dielectric layer 3> A part of the anode 1 and the anode lead 2 is immersed in a chemical conversion tank filled with 0.01 to 0.1 wt% phosphoric acid aqueous solution, which is an electrolytic aqueous solution, and the second end 2b of the anode lead 2 is formed in the chemical conversion tank. Connected to the anode.
- a dielectric layer 3 of tantalum oxide (Ta 2 O 5 ) was formed on the surface of the anode 1 and a part of the surface of the anode lead 2 as shown in FIG.
- a uniform dielectric layer 3 was formed on the surface of the porous body (including the inner wall surface of the hole) constituting the anode 1 and a part of the anode lead 2.
- Hydrophobization treatment The silane coupling agent was dissolved in water to prepare a silane coupling agent solution. This solution was applied to the dielectric layer 3 and dried at 100 ° C. for 10 minutes.
- Step 4 Formation of Organic Semiconductor Layer 4> A solution (concentration 0.05% by weight) of C8-BTBT represented by the following formula 6 in THF was applied onto the hydrophobized dielectric layer 3 and dried at 100 ° C. for 10 minutes.
- ⁇ Step 5 Formation of conductive polymer layer 6>
- the conductive polymer layer 6 was formed by immersing the precursor of the capacitor element in which the organic semiconductor layer 4 was formed in a solution containing a pyrrole monomer, and performing chemical polymerization.
- ⁇ Step 6 Formation of cathode layer 5>
- a carbon layer 5 a was formed by applying a carbon paste on the surface of the conductive polymer layer 6.
- the silver paste layer 5b was formed by apply
- the cathode layer 5 composed of the carbon layer 5a and the silver paste layer 5b was formed.
- Step 7 Production of electrolytic capacitor> The obtained capacitor element was sealed to complete the electrolytic capacitor of Example 1 shown in FIG.
- Example 2 In order to form the organic semiconductor layer 4, a solution was prepared by dissolving NSFAAP (formula 7 below), which is a precursor of pentacene, and F4TCNQ as a dopant of the organic semiconductor layer 4 in THF.
- NSFAAP formula 7 below
- F4TCNQ F4TCNQ
- the molar ratio of NSFAAP to F4TCNQ was 1: 3.
- the concentration of F4TCNQ was 0.5% by weight.
- This solution was applied on the dielectric layer 3 and dried at 100 ° C. for 10 minutes to produce pentacene as a low molecular weight organic semiconductor compound on the dielectric layer 3 to form the organic semiconductor layer 4.
- Example 3 An electrolytic capacitor was obtained in the same manner as in Example 2 except that F4TCNQ was not used as the dopant of the organic semiconductor layer 4.
- Example 4 Instead of the silane coupling agent treatment, a conductive polymer layer containing polypyrrole was formed on the dielectric layer 3 by chemical polymerization, and then the organic semiconductor layer 4 was formed. An electrolytic capacitor was obtained.
- Comparative Example 1 An electrolytic capacitor was obtained in the same manner as in Example 4 except that the second conductive polymer layer 6b containing polypyrrole was further formed by electrolytic polymerization without forming the organic semiconductor layer 4. [Evaluation] ⁇ Capacitance> Measurement was performed at 120 Hz using an LCR meter.
- Table 1 shows the evaluation results. Examples 1 to 4 show values when the numerical value of Comparative Example 1 is 1.000.
- Example 4 In each of Examples 1 to 3 in which the organic semiconductor layer 4 is formed on the dielectric layer 3, compared to Comparative Example 1, the capacitance and the capacity appearance rate are all improved, and the leakage current is reduced.
- Example 4 after forming the first conductive polymer layer 6a directly on the dielectric layer 3, the organic semiconductor layer 4 and the second conductive polymer layer 6b are sequentially formed. Also in this case, the capacity appearance rate is improved as compared with Comparative Example 1. This is presumably because the gap on the dielectric layer 3 where the first conductive polymer layer 6a was not formed was covered with the organic semiconductor layer 4 formed later.
Abstract
Description
と、を備える電解コンデンサの製造方法に関する。
≪実施形態1≫
本発明の一実施形態に係る電解コンデンサについて、図1および図2を参照しながら説明する。図1は、本実施形態に係る電解コンデンサ20の断面模式図である。
<電解コンデンサ>
電解コンデンサ20は、ほぼ直方体の外形を有するコンデンサ素子10と、コンデンサ素子10を封止する樹脂外装体11と、樹脂外装体11の外部にそれぞれ露出する陽極端
子7および陰極端子9と、を備えている。電解コンデンサ20は、コンデンサ素子10と同じく、ほぼ直方体の外形を有する。
<陽極>
本実施形態においては、陽極1は弁作用金属の粒子の多孔質体である。陽極リード2は、例えば導電性を有するワイヤから構成されている。陽極1は、例えば、陽極リード2の第一端部2aを弁作用金属又は弁作用金属を含む合金の粒子に埋め込み、その状態で金属粒子を直方体に成形し、成形体を焼結させることにより作製される。すなわち、陽極1は、弁作用金属又は弁作用金属を含む合金の粒子の結合体(焼結体)である。これにより、陽極1の外周面から、陽極リード2の第二端部2bが植立するように引き出される。
<誘電体層>
誘電体層3は、陽極1を構成する導電性材料の表面を酸化することにより、酸化被膜として形成することができる。従って、誘電体層3は、陽極1を構成する多孔質体または箔の表面(孔またはエッチングピットの内壁面を含む)に沿って均一に形成されている。誘電体層3の厚さは、例えば、10nm~200nmである。
<有機半導体層>
有機半導体層4は、誘電体層3の表面を覆うように形成されている。具体的には、有機半導体層4は、陽極1を構成する多孔質体または箔に由来する凹部(孔またはエッチングピットの内壁面)を含む表面に沿って形成されている。
具体的には、縮合環を含む化合物としては、アントラセン、テトラセン、ペンタセン、ルブレン、ピセン、ベンゾピレン、クリセン、ピレンおよびトリフェニレンなどが挙げられる。その誘導体としては、(6,13-ビス(トリイソプロピルシリルエチニル)ペンタセン(6,13-Bis(triisopropylsilylethynyl)pentacene、TIPS-pentacene)などが挙げられる。
benzothiophene、C8-BTBT)などのBTBT誘導体、ジナフト[2,3-b:2',3'-f]チオフェノ[3,2-b]チオフェン(dinaphtho[2,3-b:2',3'-f]
thieno [3,2-b] thiophene、DNTT)、ジアントラ[2,3-b:2',3'-f]チオフェノ[3,2-b]チオフェン(dianthra [2,3-b:2',3'-f] thieno [3,2-b] thiophene、DATT)および、5,5'-ビス(7-ヘキシル-9H-フルオレン-2-イル)-2,2'-ビチオフェン(5,5'-Bis(7-hexyl-9H-fluoren-2-yl)-2,2'-bithiophene、DHFTTF)などのチオフェン化合物が挙げられる。
<導電性高分子層>
本実施形態においては、導電性高分子層6が、有機半導体層4上に形成されている。具体的には、例えば、原料モノマーを有機半導体層4上で化学重合することにより、導電性高分子層6を形成することができる。あるいは、導電性高分子が溶解した溶液、または、導電性高分子が分散した分散液を有機半導体層4に塗布することにより、導電性高分子層6を形成することができる。導電性高分子層6の厚さは、例えば1~50μmである。
<陰極層>
陰極層5は、導電性高分子層6の表面を覆うように形成されている。陰極層5は、カーボン層5aと、カーボン層5aの表面に形成された銀ペースト層5bと、を有している。カーボン層5aは、黒鉛などの導電性炭素材料を含む組成物により構成される。銀ペースト層5bは、銀粒子と樹脂とを含む組成物により構成される。なお、陰極層5の構成は、これに限られず、集電機能を有する構成であればよい。
≪電解コンデンサの製造方法≫
(i)陽極の準備工程
誘電体層3を有する陽極1を準備する。具体的には、電解水溶液(例えばリン酸水溶液)が満たされた化成槽に、陽極1を浸漬し、陽極リード2の第二端部2bを化成槽の陽極に接続して、陽極酸化を行うことにより、陽極1の表面に弁作用金属の酸化被膜からなる誘電体層3を形成することができる。電解水溶液としては、リン酸水溶液に限らず、硝酸、酢酸、硫酸などを用いることができる。
(ii)誘電体層の疎水化工程
この工程は必要に応じて行われ、シランカップリング剤を含む溶液を、誘電体層3に塗布し、その後、乾燥させることにより行われる。溶媒としては、特に限定されないが、水またはエタノール、プロパノール、ブタノールなどの1価アルコールを用いることができる。
(iii)有機半導体層の形成工程
テトラヒドロフラン(THF)などの低沸点(沸点66℃)の溶媒に低分子系有機半導体化合物が溶解した溶液を、誘電体層3に付与し、熱処理などにより溶媒を除去することにより、有機半導体層4を形成する。付与の方法としては、低分子系有機半導体化合物の溶液を誘電体層3に塗布する方法や、低分子系有機半導体化合物の溶液に、誘電体層3が形成されたコンデンサ素子の前駆体を含浸する方法などが挙げられる。低分子系有機半導体化合物が低分子であるため、溶液を付与するという簡単な方法により、誘電体層3の表面に高い被覆率で有機半導体層4を形成することができる。
(Pentacene-N
-sulfinyl-tert -butylcarbamate)などが挙げられる。
(iv)導電性高分子層の形成工程
有機半導体層4が形成されたコンデンサ素子の前駆体にモノマーやオリゴマーを含浸させ、その後、化学重合や電解重合によりモノマーやオリゴマーを重合させる方法により、導電性高分子層6を形成することができる。溶液中の原料モノマーの濃度は、例えば、0.1~2.0mol/L(リットル)である。あるいは、コンデンサ素子に形成された有機半導体層4に、導電性高分子の溶液または分散液を塗布し、乾燥させることにより、導電性高分子層6を形成することができる。溶液中の導電性高分子の濃度は、例えば、0.5~6g/L(リットル)である。
(v)陰極層の形成工程
導電性高分子層6(または第2導電性高分子層6b)の表面に、カーボンペーストおよび銀ペーストを順次、塗布することにより、カーボン層5aと銀ペースト層5bとで構成される陰極層5を形成することができる。陰極層5の構成は、これに限られず、集電機能を有する構成であればよい。
≪実施形態2≫
本発明の実施形態2について、図3により説明する。
≪実施形態3≫
本発明の実施形態3について、図4により説明する。
≪実施形態4≫
本発明の実施形態4について、図5により説明する。
《実施形態5》
本実施形態の電解コンデンサは、巻回体のコンデンサ素子を具備する。巻回型のコンデンサ素子は、巻回体から作製される。巻回体とは、コンデンサ素子の半製品であり、リードタブと接続された陽極と、他のリードタブと接続された陰極と、セパレータとを備える。陽極および陰極は、セパレータを介して巻回されている。巻回体の最外周は、巻止めテープにより固定される。
[実施例]
以下、実施例に基づいて、本発明をより詳細に説明するが、本発明は実施例に限定されるものではない。
《実施例1》
下記の要領でコンデンサ素子を作製し、その特性を評価した。
<工程1:陽極1の形成>
弁作用金属として、一次粒子径が約0.5μm、二次粒子径が約100μmであるタンタル金属粒子を用いた。タンタルからなる陽極リード2の第一端部2aがタンタル金属粒子に埋め込まれるように、タンタル金属粒子を直方体に成形し、その後、成形体を真空中で焼結した。これにより、タンタルの多孔質焼結体からなる陽極1を得た。陽極1は、長さ4.4mm、幅3.3mm、厚さ0.9mmの直方体である。陽極1の一側面(3.3mm×0.9mm)からは、陽極リード2の第二端部2bが突出した状態で固定されている。
<工程2:誘電体層3の形成>
電解水溶液である0.01~0.1重量%のリン酸水溶液が満たされた化成槽に、陽極1と陽極リード2の一部を浸漬し、陽極リード2の第二端部2bを化成槽の陽極に接続した。そして、陽極酸化を行うことにより、図1に示すように、陽極1の表面および陽極リード2の一部の表面に、酸化タンタル(Ta2O5)の誘電体層3を形成した。この陽極酸化により、図2に示すように、陽極1を構成する多孔質体の表面(孔の内壁面を含む)および陽極リード2の一部に、均一な誘電体層3が形成された。
<工程3:疎水化処理>
シランカップリング剤を水に溶解して、シランカップリング剤の溶液を調製した。この溶液を、誘電体層3に塗布し、100℃で10分間乾燥させた。
<工程4:有機半導体層4の形成>
疎水化処理された誘電体層3上に、下記式6に示すC8-BTBTをTHFに溶解した溶液(濃度0.05重量%)を塗布し、100℃で10分間乾燥した。
ピロールモノマーを含む溶液に、有機半導体層4が形成されたコンデンサ素子の前駆体を浸漬し、化学重合することにより、導電性高分子層6を形成した。
<工程6:陰極層5の形成>
導電性高分子層6の表面に、カーボンペーストを塗布することにより、カーボン層5aを形成した。次に、カーボン層5aの表面に、銀ペーストを塗布することにより、銀ペースト層5bを形成した。こうして、カーボン層5aと銀ペースト層5bとで構成される陰極層5を形成した。
<工程7:電解コンデンサの作製>
得られたコンデンサ素子を封止して、図1に示す実施例1の電解コンデンサを完成させた。
《実施例2》
有機半導体層4を形成するため、ペンタセンの前駆体であるNSFAAP(下記式7)と、有機半導体層4のドーパントとしてF4TCNQとを、THFに溶解させた溶液を調製した。NSFAAPとF4TCNQとのモル比(NSFAAP:F4TCNQ)は、1:3とした。F4TCNQの濃度は、0.5重量%であった。この溶液を誘電体層3上に塗布し、100℃で10分間乾燥し、誘電体層3上に、低分子系有機半導体化合物としてペンタセンを生成させ、有機半導体層4を形成した。
有機半導体層4のドーパントとしてF4TCNQを用いなかったこと以外は、実施例2と同様にして、電解コンデンサを得た。
《実施例4》
シランカップリング剤処理に変えて、誘電体層3上に、化学重合によりポリピロールを含む導電性高分子層を形成した後、有機半導体層4を形成したこと以外は、実施例1と同様にして、電解コンデンサを得た。
《比較例1》
有機半導体層4を形成せずに、さらに電解重合によりポリピロールを含む第2導電性高分子層6bを形成したこと以外は、実施例4と同様にして、電解コンデンサを得た。
[評価]
《静電容量》
LCRメータを用いて、120Hzで測定した。
《容量出現率》
得られた電解コンデンサの静電容量を、陽極に誘電体層のみを形成したコンデンサ素子を用いた電解コンデンサを酸液中に浸漬して測定した静電容量(水中容量)で除して容量出現率(静電容量/水中容量)を求めた。
《漏れ電流》
陽極と陰極との間に6.3Vの電圧を印加し、40秒後の漏れ電流(LC40)を測定した。
Claims (10)
- 陽極と、
前記陽極上に形成された誘電体層と、
前記誘電体層の少なくとも一部を覆う有機半導体層と、を備え、
前記有機半導体層は、数平均分子量が100~10,000であり、かつ、π電子雲を有する有機半導体化合物を含み、
前記有機半導体化合物が、前記π電子雲を介して、前記有機半導体化合物の分子間のキャリア移動を行う、電解コンデンサ。 - 前記有機半導体層の少なくとも一部を覆う導電性高分子層を有する、請求項1に記載の電解コンデンサ。
- 前記有機半導体層と前記導電性高分子層とで囲まれた空隙を有する、請求項2に記載の電解コンデンサ。
- 前記誘電体層が、導電性高分子層で覆われず、かつ、前記有機半導体層で覆われた部分と、前記有機半導体層で覆われず、かつ、前記導電性高分子層で覆われた部分と、を有する、請求項1に記載の電解コンデンサ。
- 前記有機半導体化合物が、縮合環およびヘテロ環よりなる群から選択される少なくとも1種を含む化合物である、請求項1~4いずれか1項に記載の電解コンデンサ。
- 前記有機半導体層が、ドーパントを含む、請求項1~5のいずれか1項に記載の電解コンデンサ。
- 前記ドーパントが、電子供与性分子および電子受容性分子よりなる群から選択される少なくとも1種である、請求項6に記載の電解コンデンサ。
- 前記有機半導体化合物が、100℃以下の沸点を有する溶媒に可溶である、請求項1~7のいずれか1項に記載の電解コンデンサ。
- 誘電体層を有する陽極を準備する工程と、
前記誘電体層の表面に、数平均分子量100~10,000であり、かつ、π電子雲を有する有機半導体化合物が溶解した溶液を付与することにより、前記誘電体層の表面の少なくとも一部を覆う有機半導体層を形成する工程と、を備える電解コンデンサの製造方法。 - 誘電体層を有する陽極を準備する工程と、
前記誘電体層の表面に、数平均分子量100~10,000であり、かつ、π電子雲を有する有機半導体化合物の前駆体が溶解した溶液を付与する工程と、
前記前駆体から前記有機半導体化合物を生成させ、前記誘電体層の表面の少なくとも一部を覆う有機半導体層を形成する工程と、を備える電解コンデンサの製造方法。
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WO2019131477A1 (ja) * | 2017-12-28 | 2019-07-04 | パナソニックIpマネジメント株式会社 | 電解コンデンサおよびその製造方法 |
US11056285B2 (en) * | 2018-04-13 | 2021-07-06 | Avx Corporation | Solid electrolytic capacitor containing an adhesive film |
JP7167344B2 (ja) * | 2018-11-29 | 2022-11-08 | キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション | 順次蒸着誘電体膜を含む固体電解キャパシタ |
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