TW200525567A - Chip solid electrolyte capacitor and production method of the samE - Google Patents

Abstract

The present invention relates to a chip solid electrolyte capacitor obtained by connecting a part of the anode part and a part of the cathode part of a capacitor element to an anode terminal and a cathode terminal, respectively, and jacket-molding the capacitor element excluding a part or the whole of respective bottom faces or bottom and side faces of the anode and cathode terminals, wherein the connection face of the cathode terminal to the capacitor element is larger than the entire face of the capacitor element in the side connected to the cathode terminal, having large capacitance and low equivalent series resistance (ESR); a production method of the capacitor and an electronic device using the capacitor.

Description

200525567 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a wafer-shaped solid electrolytic capacitor having a large capacity per unit volume, a low isoelectric series resistance (ESR), and good characteristics, and a method for manufacturing the same. [Prior art] In order to suppress voltage fluctuations and reduce heat generation when high fluctuations (r i p p 1 e) are passed, capacitors used in central computing processing units (CPUs) such as computers are expected to have high capacity and low ESR. Such capacitors include wafer-shaped aluminum solid electrolytic capacitors or wafer-shaped molybdenum solid electrolytic capacitors. Wafer-shaped solid electrolytic capacitors are formed by a valve-acting metal foil with fine holes in the surface layer or a sintered body with fine holes in the inside. The anode substrate or the surface on which the anode portion of one end of the anode substrate formed by the connection of the sintered body and the metal wire is removed, and the dielectric oxide film layer, the semiconductor layer and the conductor layer are laminated in this order to form a solid electrolytic capacitor element at the cathode portion. A part of the anode part and a part of the cathode part are respectively connected to the anode terminal and the cathode terminal, and a part of the foregoing two terminals of the anode and the anode is left to be externally sealed. Recently, the method of increasing the capacity of this solid electrolytic capacitor and reducing ESR 値 is to arrange the aforementioned two terminals of the cathode and anode below the wafer-shaped solid electrolytic capacitor, leaving only the lower sides of the cathode and anode terminals and externally mounting them. Sealed capacitors are well known. By placing the two terminals of the cathode and anode below the exterior sealing body, the exterior sealing body is set to be full -4- 200525567 (2) The anode base body expands the capacity, and the cathode and anode terminals and the anode and cathode portions of the capacitor element are enlarged. The distance is the shortest, and low ESR can be expected. For example, the structure of an example of a conventional wafer-shaped solid electrolytic capacitor is shown in the schematic diagram (oblique view) of FIG. 3, in which a sintered body formed of a valve-acting metal having a dielectric oxide film layer on a surface is sequentially laminated with a semiconductor layer and A part of the cathode part of the solid electrolytic capacitor element (1) provided with the cathode part (3) on the conductor layer is placed on the cathode terminal (4), and the anode lead (2) (anode part) connected to the sintered body A part is placed on the anode terminal (5). After the respective electrical and mechanical connections are made, only the underside (4a, 5a) of each cathode and anode terminal is left with an external resin seal to form an exterior (6). (KOKAI Publication No. 2003-68576) (In FIG. 3, the size of the two terminals of the cathode and the anode is exaggerated for easy understanding). Furthermore, Japanese Unexamined Patent Publication No. 8-1, 4 8 3 8 6 describes the use of a lower electrode on an electrode surface provided above and below the substrate. [Summary of the Invention] In the method of the aforementioned Japanese Patent Application Laid-Open No. 2 03-6 8 5 7 6, the lower surface of the cathode layer of the capacitor element is not connected to the cathode terminal at all, so the method is reduced. In the method described in Japanese Unexamined Patent Publication No. 8.14 83.6, it is necessary to pass conductive members above and below the substrate, so ESR is not available, and the substrate thickness is large. The size of the capacitor element changes to the disadvantage that the capacity cannot be obtained. Therefore, to further improve the ESR and capacity expansion > $ a chip-shaped solid electrolytic capacitor is expected. -5- 200525567 (3) The present inventors have discovered that in order to solve the foregoing problems, the present inventors have solved the problems by improving the shape of the terminals, and thus completed the present invention. That is, the present invention relates to the following wafer-shaped solid electrolytic capacitors, a method for manufacturing the same, and an electronic device using the wafer-shaped solid electrolytic capacitors. A wafer-shaped solid electrolytic capacitor is one of the anode portions of a capacitor element. A part is connected to a part of the cathode part, each anode terminal and the cathode terminal, and a part or all of the lower or lower side and the side of the foregoing anode and cathode terminals are removed, and a sealed solid electrolytic chip capacitor is externally installed. It is characterized in that the connection surface of the capacitor element with the cathode terminal is larger than the entirety of the connection surface side of the capacitor element with the cathode terminal. 2 · The wafer-shaped solid electrolytic capacitor according to item 1 of the patent application, wherein the size of the lower surface of the cathode terminal and the lower surface of the anode terminal are approximately the same. 3. For example, the wafer-shaped solid electrolytic capacitor of item 1 or 2 of the patent application, wherein the surface of the anode substrate formed of a sintered body of a valve-acting metal or a conductive oxide is laminated with a dielectric oxide film layer in order. And a conductor layer to form a cathode portion. 4 · The solid electrolytic capacitor in the form of a wafer, as in item 1 of the patent application, is formed at the end of the anode base. 5. The wafer-shaped solid electrolytic capacitor according to item 1 of the patent application, wherein the anode portion is formed by a metal wire or a metal foil connected to a sintered body. 6. The wafer-shaped solid electrolytic capacitor according to item 5 of the scope of the patent application, wherein the metal wire is selected from the group consisting of giant, niobium, aluminum, titanium, and these metals are -6-200525567 (4) The main component of the alloy and the Such as metal or a part of the foregoing alloy to be oxidized and / or nitrided. 7 · The wafer-shaped solid electrolytic capacitor according to item 1 of the scope of the patent application, wherein the material of the two terminals of the cathode and anode is selected from the group consisting of iron, copper, aluminum, and alloys containing these metals as main components. 8 · As for the wafer-shaped solid electrolytic capacitor in the first item of the scope of patent application, ‘wherein’ a part or all of the two terminals of the cathode and anode are electroplated selected from solder, tin and titanium. 9. If the wafer-shaped solid electrolytic valley device of the patent application scope item 7 or 8 is used, the materials of the two terminals of the cathode and anode are different. 10. The wafer-shaped solid electrolytic capacitor according to item 3 of the scope of the patent application, wherein the valve-acting metal or conductive oxide system, giant, aluminum, niobium, titanium, an alloy mainly composed of such valve action, or niobium oxide Or a mixture of two or more selected from the aforementioned valve-acting metal 'alloys and conductive oxides. 11. For example, the wafer-shaped solid electrolytic capacitor of item 10 of the patent application, in which the aforementioned valve-acting metal alloys and conductive compounds are used, and one of these tools is self-carbonizing, phosphating, boronizing, and nitrogen. At least chemical, vulcanization-the kind of processor. 1 2. The wafer-shaped solid electrolytic capacitor according to item 3 of the patent application, wherein the surface of the aforementioned sintering system is chemically and / or electrically etched. 13. The wafer-shaped solid electrolytic capacitor according to item 1 of the scope of the patent application, wherein the boundary portion of the anode portion of the anode substrate and the portion except the anode portion are insulated by an insulating resin. 200525567 (5) 1 4. The wafer-shaped solid electrolytic capacitor according to item 3 of the patent application scope, wherein the dielectric oxide layer is at least one selected from the group consisting of Ta2 0 5, Al2O3, Ti02, and Nb2 0 5 Those who are the main component. 15. The wafer-shaped solid electrolytic capacitor according to item 3 of the scope of patent application, wherein the semiconductor layer is at least one selected from the group consisting of an organic semiconductor layer and an inorganic semiconductor layer. 16. The wafer-shaped solid electrolytic capacitor according to item 15 of the patent application scope, wherein the organic semiconductor is contained in an organic semiconductor selected from the group consisting of a benzopyrroline tetramer and chloroquinone, and tetrathiotetrahydrofuran is the main component. Organic semiconductors, organic semiconductors with tetrahydroparaquinone dimethane as the main component, the following general formula (1) or (2) R * R2 Ί Γ R1 R2

(In the formulae (1) and (2), R to R4 are each independently a hydrogen atom, a radical having 1 to 6 carbon atoms or a radical having 1 to 6 carbon atoms, and X represents oxygen, sulfur, or nitrogen. Atom 'R5 is X when it is only a nitrogen atom. It is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms. R1 and R2 and R3 and R4 can be bonded to each other to form a ring.) The polymer is at least one kind of organic semiconductor mainly composed of a conductive polymer doped with a dopant. 17. The wafer-shaped solid electrolytic capacitor according to item 16 of the patent application-8-200525567 (6), wherein the conductive polymer of the repeating unit represented by the general formula (1) contains the following general formula ( 3) r6〇OR7

(In the formula, 'R6 and r7 are independent hydrogen atoms, linear or branched saturated or unsaturated alkyl groups having 1 to 6 carbon atoms, or the alkyl groups are bonded to each other at any position to form A substituent having a cyclic structure of a saturated warp group of at least one 5 to 7 ring containing two oxygen atoms. In addition, the aforementioned cyclic structure contains a substitutable vinylidene bond and a substitutable sub-group. Phenyl structure), the structural unit shown as a repeating unit of a conductive polymer. 18. The wafer-shaped solid electrolytic capacitor according to item 17 of the scope of patent application, wherein the conductive polymer system is selected from the group consisting of polyaniline, polyepoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, Each of polypyrrole, polymethylpyridine, and substituted derivatives or copolymers thereof. 19. The wafer-shaped solid electrolytic capacitor according to item 18 of the patent application scope, wherein the conductive polymer is poly (3, cardiodiethylenethiophene). 20. The wafer-shaped solid electrolytic capacitor according to item 15 of the application, wherein the inorganic semiconductor is a compound selected from at least one of molybdenum dioxide, tungsten dioxide, lead dioxide, and manganese dioxide. 2 1. If the wafer-shaped solid electrolytic capacitor of item 3 of the scope of patent application, -9-200525567 (7) Among them, the conductivity of the semiconductor is in the range of 10 · 2 ~ I03s / cm. 22. A method for manufacturing a wafer-shaped solid electrolytic capacitor, which connects a portion of an anode portion and a portion of a cathode portion of a capacitor element to each anode terminal and the cathode terminal, and connects the foregoing anode and the cathode below each terminal The chip-shaped solid electrolytic capacitor, which is partially or completely removed from the lower surface and the side surface, and is externally sealed, is characterized in that the connection surface with the capacitor element of the cathode terminal is larger than the overall surface side of the cathode terminal with the capacitor element. A method for manufacturing a wafer-shaped solid electrolytic capacitor is characterized by using a lead frame pair having a lower portion which becomes a part of both terminals of a cathode and an anode, and the lead frame corresponding to the cathode terminal will constitute a cathode of the capacitor element. Those with a larger area of the terminal connection surface are bonded with the metal material of the yin and yang terminals. 203. A manufacturing method of a wafer-shaped solid electrolytic capacitor, which is a part of the anode part and the cathode part of the capacitor element , Connected to each anode terminal and cathode terminal, the lower or lower and side of each of the foregoing anode and cathode terminals In a wafer-shaped solid electrolytic capacitor that is partially or completely removed and sealed, the connection surface of the capacitor element with the cathode terminal is larger than that of the connection surface side of the cathode terminal of the capacitor element. A method for manufacturing a wafer-shaped solid electrolytic capacitor having a lower surface portion and an anode terminal portion having substantially the same size is characterized in that a lead frame pair having approximately the same lower surface portion as a part of the two terminals of the anode and the anode is used. On the lead frame of the aforementioned cathode terminal, a metal material constituting a yin-yang terminal having a larger area than the cathode terminal connection surface of the capacitor element is pasted, and the lead frame corresponding to the aforementioned anode terminal is formed with -10- 200525567 (8) The metal material of the anode terminal bonded to the anode portion of the capacitor element is given to S. 2 4. — An electronic circuit using a wafer-shaped solid electrolytic capacitor such as the scope of patent application No. 丨 or 21. 2 5. An electronic device using a wafer-shaped solid electrolytic capacitor such as those in the scope of application for patents I to 21. One aspect of the wafer-shaped solid electrolytic capacitor of the present invention will be described with reference to the drawings. Fig. 1 is a schematic view (an oblique view) of an example of a wafer-shaped solid electrolytic capacitor of the present invention, Fig. 2 (A) is a plan sectional view of Fig. 1, and (B) is a side sectional view (in Figure 2 is an exaggerated drawing of the size of the two terminals of the cathode and anode). This example is made of a valve-acting metal or a conductive oxide, and the surface of the anode substrate connected to the anode lead wire (2) is sequentially laminated with a dielectric oxide film layer, a semiconductor layer on top, and a conductor layer on the cathode A part of the cathode part of the solid electrolytic capacitor element (1) formed by the part (3) is placed on the cathode terminal (4), and a part of the anode wire (2) is placed on the anode terminal (5). After the respective electrical and mechanical bondings are performed, the structure of the resin-sealed exterior (6) remains on the lower surface (4a, 5a) and the side surface (4c) of the two anode and anode terminals. The capacitor element used in the present invention is manufactured based on an anode substrate of a valve-acting metal or a conductive oxide. In terms of valve-acting metals or conductive oxides, examples include giant, aluminum, vanadium, rhenium, alloys or niobium oxide based on these valve-acting components, or selected from the group of valve-acting metals and conductive oxides. A mixture of two or more kinds of substances (11-200525567). A part of the valve action metal, the aforementioned alloy, or the conductive compound may be used by subjecting it to at least one treatment selected from the group consisting of 'carbonization, phosphation', boronization, nitriding, and sulfurization. The anode substrate used in the present invention is a foil or plate of valve-acting metal having fine pores on the surface layer, and the powder of the valve-acting metal or conductive oxide is formed into a sintered body after being formed into a sintered body. In this case, the surface pressure of the sintered body can be changed by appropriately selecting the molding pressure and the sintering conditions (temperature and time). In order to further increase the surface area of the sintered body after sintering, the surface of the sintered body can be chemically and / or electrically etched. In the present invention, a part of the anode base can be used as the anode portion. The anode base may be provided as the anode part at the end, or as shown in FIG. 1, a metal wire (2) or a metal foil (not shown) may be connected as the anode part in a part of the anode base. The connection of the metal wire (or metal foil) may be performed after the sintered body is manufactured, and a part of the metal wire (or metal foil) is buried and sintered during the forming before the sintered body is manufactured, or the connection method may be adopted. As for the type of the metal wire (or metal foil), giant, niobium, aluminum, titanium, alloys of which these metals are the main component, and those metals or a part of the foregoing alloys are oxidized and / or nitrided. . The wire diameter is usually 1 mm or less, and in the case of metal foil, the thickness is usually 1 mm or less. The anode portion has a semiconductor layer to be described later. In order to prevent short circuit of the capacitor, an insulating resin may be attached in a turban shape at the boundary between the anode portion and the anode base of the stub before the semiconductor layer is formed. In terms of the entire surface of the anode substrate from which the anode portion of the present invention is removed, or the dielectric oxide film layer formed in a part of -12-200525567 (10), it may be selected from the group consisting of T a205, Al203, and Ti. 2. At least one of the metal oxides of Nb205 and the like is a dielectric layer having a main component. The dielectric layer can be obtained by chemically synthesizing the anode substrate in an electrolytic solution. Further, a dielectric layer in which a dielectric layer containing at least one selected from metal oxides as a main component and a dielectric layer used in a ceramic capacitor are mixed may be used (WOOO / 7 5 94 3). On the one hand, as a representative example of the semiconductor layer formed on the dielectric layer of the present invention, a compound selected from at least one of an organic semiconductor and an inorganic semiconductor may be mentioned. In terms of specific examples of organic semiconductors, organic semiconductors composed of benzopyrroline tetramers and chloroquinones, organic semiconductors with tetrathio four strings as main components, and organic semiconductors with tetrahydroparaquinone dimethane as main components can be cited. In the following formula (1) or (2), the polymer of the repeating repeating unit will be doped with r dioxin.

The main body of the guide is divided into subordinates.

R

V7V3R

R y \ / \

X —— R

R In the formulae (1) and (2), R1 to R4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and X represents oxygen, sulfur, or nitrogen. The atom 'R5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms when X is only a nitrogen atom. R1 and R2 and R3 and R4 may be bonded to each other to form a ring. Furthermore, in the present invention, among the conductive polymers containing a repeating unit of -13-200525567 (11) yuan represented by the aforementioned general formula (i), it is preferable to include a structure represented by the following general formula (3) The unit serves as a conductive polymer of a repeating unit.

In the formula, R6 and R7 are independent hydrogen atoms, 1 to 6 carbon atoms or straight or branched saturated or unsaturated alkyl groups, or the alkyl groups may be bonded to each other at any position, including Substituent formed by the cyclic structure of saturated hydroxyl groups of at least one 5-7 ring of two oxygen atoms. The cyclic structure contains a vinylene bond that can be substituted and a phenylene structure that can be substituted. The conductive polymer containing this chemical structure is doped with a dopant because it is electrically charged. As the dopant, a known dopant can be used without limitation. As for the polymer containing the repeating unit represented by the formula (1) to (3), for example, polyaniline, polyepoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, Polymethylpyrrole, and its derivatives: biological or copolymers. Among them, polypyrrole, polythiophene, and the like are substituted;% biological (such as poly (3,4-ethylenedioxythiophene), etc.) is preferred. As a specific example of the inorganic semiconductor, a compound selected from at least one selected from the group consisting of dioxide, tungsten dioxide, lead dioxide, and manganese dioxide can be mentioned. When the above-mentioned organic semiconductor and inorganic semiconductor are used with a conductivity in the range of 103 S / cm, the ESR of the capacitor produced is preferably small. In terms of the method for forming the above semiconductor layer, a method using electrolytic polymerization $ -14-200525567 (12) can be adopted (Japanese Patent Laid-Open No. 6 0-3 7 1 1 4), and the anode substrate treated with the oxidant is electrolyzed. A well-known method such as a method of polymerization (Patent No. 2 05 4 5 q 6) such as a chemical precipitation method (Patent No. 2 4 4 3 3 4), etc. In the present invention, the semiconductor formed by the aforementioned method or the like is used. A conductor layer is provided on the layer. The conductor layer can be formed by, for example, curing of a conductive solder paste, electroplating, metal evaporation, and adhesion of a heat-resistant conductive resin film. As for the conductive solder paste, silver solder paste, copper solder paste, aluminum solder paste, carbon solder paste, nickel solder paste, etc. are preferable, and i or two or more kinds can be used. When two or more types are used, they may be mixed or overlapped with other layers. After applying conductive solder, it can be left in the air, or it can be cured by heating. Conductive solder paste is mainly composed of conductive powders such as resin and metal. However, depending on the situation, a solvent for dissolving the resin or a hardener for the resin will be added. However, the solvent will scatter during curing. As for the resin, well-known resins such as alkyd resin, acrylic resin, epoxy resin, phenol resin, ammonium resin, fluororesin, ester resin, iminoamidine-based resin, ammonium resin, and styrene resin can be used. . As for the conductive powder, powders of silver, copper, aluminum, gold, carbon, nickel, and alloys containing these metals as main components can be used. At least one of the powder of the coating film of the metal on the surface or the powder of the mixture. The conductive powder usually contains 40 to 97.7% by mass. The conductive solder paste produced when the content is less than 40% by mass has a small conductivity, and when it exceeds 97% by mass, the conductive solder paste has poor adhesion and is not good. 200525567 (13) The aforementioned semiconductor will be formed in the conductive solder paste A layer of conductive polymer or metal oxide powder may be mixed and used. As for the plating, nickel plating, copper plating, silver plating, aluminum plating, and the like can be exemplified. As for the metal to be vapor-deposited, aluminum, nickel, copper, and silver can be exemplified. Specifically, for example, a carbon solder paste and a silver solder paste are sequentially laminated on an anode substrate capable of forming a semiconductor layer to form a conductor layer. In this way, a solid electrolytic capacitor element in which the cathode portion of the anode substrate is laminated to the conductor layer can be produced. After a part of the anode part and a part of the cathode part of the solid electrolytic capacitor element are respectively connected to the anode terminal and the cathode terminal described later, a part or all of the lower part or the lower part and the side face of the foregoing terminals are provided. Residuals are sealed with an exterior to produce a wafer-shaped solid electrolytic capacitor. In the present invention, the size of the upper surface (4b) of the cathode terminal that is actually connected to the capacitor element is necessary to be above the cathode terminal connection surface of the solid electrolytic capacitor element, and it is preferable that the size of the lower surface of the two terminals of the cathode and anode is approximately the same. . Here, the cathode terminal connection surface of the solid electrolytic capacitor element refers to the comprehensive meaning of the side of the capacitor element formed by the cathode layer connected to the side of the cathode terminal. By making the size of the cathode terminal larger than that of the cathode terminal connection surface of the solid electrolytic capacitor element, the ESR of the solid electrolytic capacitor can be minimized. Further, in the present invention, only the size above and below the cathode terminal is changed. That is, the capacitor method of Japanese Unexamined Patent Application Publication No. 8-148386 does not use an excess material that restricts the height direction, so that the aforementioned wafer-shaped solid electrolytic capacitor is used. It is not necessary to reduce the height direction of the capacitor element contained in -16-200525567 (14) in the outer package. As a result, the capacitor capacity can reach its maximum limit. Cathode terminals with different shapes on the top and bottom can be made of metal materials, but in the case of manufacturing multiple wafer-shaped solid electrolytic capacitors at the same time, the two terminals of the cathode and anode are usually made by repeating the pattern of the cathode and anode two terminals. To make a frame “cut to a desired shape after mounting” to make the cutting easier, only thicken the lead frame part corresponding to the two terminals of the anode and cathode. For example, a flat lead frame with the same thickness It is manufactured by subjecting the opened metal to an adhesive process. In addition, as a method for producing a thin portion, a method of thinning a desired portion by press working can be adopted. As for the material of the two terminals of the anode and the anode, for example, iron, copper, aluminum, or an alloy whose main component is these metals can be used. One or all of the two terminals of the anode and the anode can be plated with solder, tin, titanium, silver, gold, etc. Between the anode and cathode terminals and the plating, a substrate such as nickel or copper can be plated. In addition, if the materials of the two terminals of the yin and yang poles are made of other materials, and the wafer-shaped solid electrolytic capacitors used in the audio equipment are used, the ones corresponding to the diversified sound quality are used. By making the size of the lower face of the two terminals of the cathode and anode approximately the same, the interchangeability of the lower face of the conventional wafer-shaped solid electrolytic capacitor can be generated ^, and there will be a contact surface of the circuit board on which these capacitors are combined ( (land) There is no need to change the state. In the present invention, the number of solid electrolytic capacitor elements placed on the two terminals of the cathode and the anode may be a plurality. In this case, the size of the upper surface of the cathode terminal is larger than the connection surface of the cathode terminals of the plurality of capacitor elements. Yue-17-200525567 (15) The solid electrolytic capacitor element of the present invention is packaged with, for example, a resin mold, a resin case, a metallic case, and the like, and various types of capacitor products can be manufactured. Among these, since miniaturization and low cost can be easily performed, wafer-shaped solid electrolytic capacitors for externally mounting resin molds are preferable. The types of resins used in the exterior of resin molds can be adopted. Epoxy resins, phenol resins, alkyd resins, and other well-known resins used in the sealing of solid electrolytic capacitors can be used. When each resin is a low-stress resin, it is preferable to reduce the occurrence of the sealing stress of the capacitor element generated during sealing. Moreover, a transmission device can be used suitably for the manufacturing machine for resin sealing. The solid electrolytic capacitor thus produced may be subjected to an aging treatment to repair the deterioration of the thermal and / or physical dielectric layer during the formation of the conductor layer or the exterior. The method of aging is carried out by applying a fixed voltage (less than twice the voltage of the suspension's voltage) to the solid electrolytic capacitor. The aging time or temperature will depend on the type, capacity, and rated voltage of the capacitor. The optimum change can be determined by experiments in advance, but usually, the time is a few minutes to several days. The temperature takes into account the voltage plus the thermal degradation of the mold. Then it is carried out below 300 ° C. The aging atmosphere can be in the air or in argon, nitrogen, helium and other gases. In addition, it may be performed under any conditions of reduced pressure, normal pressure, and increased pressure. 'When the aging is performed at the same time as the water vapor is supplied or after the water vapor is supplied, the stability of the dielectric layer may progress. . As for the method of supplying water vapor, for example, a method of supplying water vapor by heating pits placed in an aging furnace by heat -18-200525567 (16) can be cited. In terms of voltage application method, it can be designed as direct current, alternating current with arbitrary waveform, alternating current or pulse current that overlaps with direct current. During the aging process, the voltage application at one end is stopped, and the voltage application can be performed again. The wafer-shaped solid electrolytic capacitor manufactured by the present invention has a high capacity such as a central calculation circuit or a power supply circuit, and a capacitor having a low ESR is necessary and can be used appropriately. As these circuits, various digital devices such as computers, servers, cameras, game consoles, DVDs, AV devices, and mobile phones, or electronic devices such as various power sources can be used. The wafer-shaped solid electrolytic capacitor manufactured by the present invention has a high capacity and good ESR performance. Therefore, it can be used to obtain electronic circuits and electronic devices with high reliability. Effects of the Invention The present invention provides that the connection surface of the capacitor element with the cathode terminal is larger than that of the connection surface side of the cathode terminal of the capacitor element, and the size of the lower surface of the two terminals of the cathode and anode is approximately the same, so that the foregoing cathode and anode terminals Wafer-shaped solid electrolytic capacitors with external seals are left under or under one of the sides and sides. According to the present invention, a chip solid electrolytic capacitor having a large capacity and a good E S R can be obtained. [Embodiment] Hereinafter, specific examples of the present invention will be described in detail, but the following -19-200525567 (17) examples are not intended to limit the present invention. Example 1 and Comparative Example 1: CV (product of capacity and chemical synthesis voltage) of 130,000 gF V / 9 tantalum powder was used to produce a sintered body having a size of 4.5 × 0.95 × 3.0mm (sintering temperature 1 300 ° C 'The sintering time is 20 minutes, the density of the sintered body is 6.3 g / cm3, and the Ta introduction line is 0.2 4 mm (D, parallel to the long side of the 4.5 mm dimension of the sintered body, and a part of the T introduction line is embedded to sinter the body. The protruding lead wire part becomes the anode part.) The sintered body that becomes the anode is immersed in 1 ° /. Phosphoric acid aqueous solution is removed by immersing a part of the lead wire, and 9V is applied between the Ta electrode of the cathode at 8 (TC Chemical synthesis was performed for 8 hours to form a dielectric oxide film layer made of Ta205. After removing the lead of this sintered body, immerse it in a 1: 1 mixed solution of 20% lead acetate aqueous solution and 35% ammonium persulfate aqueous solution at 40 ° C. After being left for 1 hour, it was washed with water, dried, and washed with a 15% ammonium acetate aqueous solution, and repeated 3 to 5 times to form a mixture of lead dioxide and lead acetate (96% lead dioxide) on the dielectric oxide film layer. A semiconductor layer, and a carbon solder paste epoxy is sequentially laminated on the semiconductor layer 10 mass parts of grease and 90 mass parts of silver powder were used to form the cathode part to form a solid electrolytic capacitor element. A copper alloy lead frame (thickness of 3.4 μm in thickness with a width of 3.4 μm) was prepared on the surface. There are 32 pairs of the front end of one mm. The front end is placed on the cathode, so that a lead frame with a width of 3.4 mm, a length of 5.4 mm, and a thickness of 100 μm and a metal sheet of the same material are at the front end. The width is uniform. The tip is welded to make the head protrude 4.0 mm, and placed on the anode. -20- 200525567 (18)

The front end has a defect of 3.4mm in width, 1.4mm in length, and a thickness of 500μη in one corner, with a defect of 3.4mm in width, 0.4mm in length, and 400μm in thickness. The metal sheet of the same material as the lead frame is attached to the front end and is in a non-defective direction. The width makes the head consistent and welded. The lower face of both the cathode and anode terminals are 3.4mm wide and 1.4mm long. The two front ends are projected into the same plane with a gap of 0.5mm. ) A pair of upper surfaces of the front end portions are respectively placed, and the solidification of the silver solder paste of the cathode portion surface (4.5 mm X 3.0 mm surface) of the solid electrolytic capacitor element and the anode portion is the same as that of the cathode portion, In the latter case, electrical and mechanical connections are made by spot welding. Next, all the bottom and side surfaces of the two anode and anode terminals are die-casted with epoxy resin and externally packaged, and then the lead frame is cut by the flat portion of the lead frame, that is, the side surface of the external package. A wafer-shaped solid electrolytic capacitor having a size of 7.3 X 4.3 X 1.8 mm was produced (Example 1).

At the front end of the lead frame on which the cathode part of the capacitor element is placed in Example 1, a lead frame with a width of 3.4 mm, a length of 1.4 mm, and a thickness of 100 μm and a metal sheet of the same material are used to make the width consistent with the head. (At this time, the two front ends are projected on the same plane with a gap of 4.5 mm.) Except for welding, a wafer-shaped solid electrolytic capacitor was produced in the same manner as in Example 1 (Comparative Example 1). Example 2 and Comparative Example 2: A part of nitrided niobium powder with CV 220,000 pF V / 9 (nitrogen content I 0,000 ppm, the surface is naturally oxidized and the total oxygen content is 91,000 ppm) 〇48 g, Making multiple sintered bodies with a size of 4.5x.94x3.0mm (sintering temperature -21-200525567 (19) 1 2 8 0 ° C sintering time 30 minutes, sintered body density 3.8g / cm3, Nb wire 0.2 4 mm Φ) . The sintered body was immersed in a 0.1% phosphoric acid aqueous solution except for a part of the lead-in wire. 20 V was applied between the sintered body and the Ta plate electrode of the negative electrode, and chemical synthesis was performed at 80 ° C for 5 hours. The dielectric layer of the main component. This sintered body was immersed in 3% 3,4-ethylenedioxythiophene alcohol solution at 1.5 ° /. A 13% anthraquinone sulfonic acid aqueous solution dissolved in ammonium persulfate was repeated seven times so that a plurality of minute contacts with ethylenedioxy polymer as a main component were adhered on the dielectric layer, and a plurality of electrically minute ones were produced on the dielectric layer. Defective part. The micro-contact system was observed with a scanning electron microscope (SEM), and approximately 8% of the dielectric layer was covered with dots. Next, the sintered body was impregnated with ethylenedioxythiophene (the monomer is used as an aqueous solution with a saturation concentration below) and water with anthraquinone sulfonic acid dissolved in a 20% ethylene glycol electrolyte, so that the lead of the sintered body became the anode. Between the giant electrodes of the negative electrode arranged in the electrolytic solution, a direct current of 30 μA was passed at room temperature for 45 minutes to conduct electricity for forming a semiconductor layer. After washing and drying, rechemical synthesis was performed to repair the tiny LC defects in the dielectric layer in a 0.1% acetic acid aqueous solution (80 ° C, 30 minutes, 14V). The aforementioned electrification and rechemical synthesis were repeated 15 times, and then washed and dried with water to form a cathode semiconductor layer. Then, a carbon solder paste, 10 parts by mass of acrylic resin, and 90 parts by mass of silver powder of silver powder were sequentially laminated. A cathode layer is formed and a solid electrolytic capacitor element is produced. Then, in the same manner as in Example 1 and Comparative Example 1, wafer-shaped solid electrolytic capacitors (capacitors of Example 2 and Comparative Example 2) were produced. Regarding each of the wafer-shaped solid electrolytic capacitors prepared above, 200525567 (20) The capacity, E S R ′ ′ and L C 値 were measured by the following method. The measurement results (average 値) are shown in Table 1. Capacitor capacity: The capacity was measured at room temperature '120 Hz using an LCR tester manufactured by Hewlett-Packard Company. ESR 値: The series resistance of capacitors is measured at 100kHZ. L · C 値: At room temperature, a constant DC voltage (2.5 V 値 in Example 1 and Comparative Example 1 and 4 V 値 in Example 2 and Comparative Example 2) is continuously applied between the terminals of the capacitor. Seconds were determined later. Table 1 Capacity (μP) ESR (m Ω) LC (μΑ) Example 1 966 6 18 2 433 11 2 7 Comparative example 1 96 1 9 16 2 42 5 16 29

From the comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, it can be seen that if the connection surface of the capacitor element to the cathode terminal is larger than the entire surface of the cathode terminal connection surface of the capacitor element, ESR 値 is good. [Brief description of the drawings] In the first figure, a part of an anode part and a part of a cathode part of a solid electrolytic capacitor element having an anode lead (anode part) are placed on a yin-yang-23- 200525567 (21) electrode A perspective view of the wafer-shaped solid electrolytic capacitor of the present invention in a two-terminal state. FIG. 2 is a plan sectional view (A) and a side sectional view (B) of the solid electrolytic capacitor of FIG. FIG. 3 is a perspective view of a conventional wafer-shaped solid electrolytic capacitor

[Description of Symbols of Main Components] 1: Capacitor element 2: Anode lead 3: Cathode part 4: Cathode terminal 4a, 5a: Below 5: Anode terminal

6: Exterior 4 c: Side -24-

Claims (1)

200525567 (1) X. Patent application scope 1 · A wafer-shaped solid electrolytic capacitor, in which a part of an anode portion and a portion of a cathode portion of a capacitor element are connected, each anode terminal and the cathode terminal connect the foregoing anode In a wafer-shaped solid electrolytic capacitor which is externally sealed with a part or all of the lower or lower sides of the cathode terminals, or a part other than the side, the connection surface of the cathode terminal and the capacitor element is characterized by The full side of the connection surface is the larger one. 2. The wafer-shaped solid electrolytic capacitor according to item 1 of the scope of patent application, wherein the size of the lower surface portion of the cathode terminal and the lower surface portion of the anode terminal are approximately the same. 3. The wafer-shaped solid electrolytic capacitors according to item 1 or 2 of the patent application scope, wherein the surface of the anode substrate formed of the sintered body of the valve action metal or conductive oxide is laminated with a dielectric oxide film layer in order, the semiconductor And a conductor layer to form a cathode portion. 4 · The solid electrolytic capacitor in the form of a wafer as described in the first item of the patent application, in which the 'anode portion is formed at the end of the anode base. 5. The wafer-shaped solid electrolytic capacitor according to item 1 of the patent application scope, wherein the 'anode portion is formed by a metal wire or a metal foil connected to a sintered body. 6. The wafer-shaped solid electrolytic capacitor according to item 5 of the application, wherein the metal wire is selected from the group consisting of giant, niobium, aluminum, and titanium, an alloy containing these metals as the main component, and these metals or one of the foregoing alloys Partially oxidized and / or nitrided. 7 · For the wafer-shaped solid electrolytic capacitors under the scope of the patent application, the material of the two terminals of the cathode and anode is selected from the group consisting of iron, copper, aluminum, and alloys containing metals such as -25-200525567 (2) as the main component. . 8. The chip-shaped solid electrolytic capacitor according to item 1 of the scope of patent application, wherein one or all of the two terminals of the cathode and the anode are electroplated selected from solder, tin and titanium. 9. The wafer-shaped solid electrolytic capacitor according to item 7 or 8 of the patent application scope, wherein the materials of the two terminals of the cathode and anode are different. 10. The wafer-shaped solid electrolytic capacitor according to item 3 of the scope of patent application, wherein the valve-acting metal or conductive oxide is molybdenum, aluminum, niobium, titanium, an alloy containing these valve-acting metals as the main component, or niobium oxide. Or a mixture of two or more kinds selected from the aforementioned valve-acting metals, alloys, and conductive oxides. 11. A chip-shaped solid electrolytic capacitor, such as the scope of application for item 10, wherein the aforementioned valve-acting metals, alloys, and conductivity Compounds, one of which is treated by at least one selected from the group consisting of carbonization, phosphating, boronizing, nitriding, and sulfurizing. 1 2. The wafer-shaped solid electrolytic capacitor according to item 3 of the patent application scope, wherein the surface of the aforementioned sintering system is chemically and / or electrically etched. 1 3 · For the wafer-shaped solid electrolytic capacitor according to item 1 of the patent application scope, wherein the boundary portion between the anode portion of the anode base and the external portion of the anode portion is insulated by an insulating resin. 14 · The wafer-shaped solid electrolytic capacitor according to item 3 of the application, wherein the dielectric oxide layer is composed of at least one selected from Ta205, Al203, Ti02, and Nb205. -26- 200525567 (3) 1 5 · The wafer-shaped solid electrolytic capacitor according to item 3 of the patent application 'wherein' the semiconductor layer is at least one selected from the group consisting of an organic semiconductor layer and an inorganic semiconductor layer. 16. The wafer-shaped solid electrolytic capacitor according to item 15 of the scope of patent application, wherein the organic semiconductor is selected from organic semiconductors composed of benzopyrroline tetramer and chloroquinone, and organic compounds with tetrathio $ as the main components. Semiconductors, organic semiconductors with tetraCyanoquinodimethane as the main component, containing the following general formula (1) or (2) Γ R1 R2 Ί Γ r1 R2 Ί V / V. X —— RX 丨 RR (In the formulae (1) and (2), Ri to R4 are each independently a hydrogen atom, a radical having 1 to 6 carbon atoms, or a radical having 1 to 6 carbon atoms, and X represents an oxygen, sulfur, or nitrogen atom. , R5 is only a nitrogen atom when it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R1 and R2 and trans 3 and R4 systems can be bonded to each other to form a ring), as shown in the repeating unit In the polymer, at least one of organic semiconductors doped with a conductive polymer as a main component is doped with a dopant. 17. The wafer-shaped solid electrolytic capacitor according to item 16 of the application for a patent, wherein the conductive polymer containing a repeating unit represented by the general formula (1) contains the following general formula (3) -27-200525567 ( 4) (3) (In the formula, R6 and R7 are each independently hydrogen atom, linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl groups are bonded to each other at any position. It can form a substituent of a cyclic structure of a saturated hydroxyl group of 5 to 7 rings containing at least one of two oxygen atoms. In addition, the cyclic structure described above contains a vinylidene bond that can be substituted and can be substituted. The phenylene structure), the structural unit shown as a repeating unit of a conductive polymer. 18. The wafer-shaped solid electrolytic capacitor according to item 17 of the scope of patent application, wherein the conductive polymer system is selected from the group consisting of polyaniline, polyepoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, Polypyrrole, polymethylpyrrole, and substituted derivatives or copolymers thereof. 19. The wafer-shaped solid electrolytic capacitor according to claim 18, wherein the conductive polymer is poly (3,4-ethylenedioxythiophene). 20. The wafer-shaped solid electrolytic capacitor according to item 15 of the patent application scope, wherein the inorganic semiconductor is a compound selected from at least one of molybdenum dioxide, tungsten dioxide, lead dioxide, and manganese dioxide. 2 1. The wafer-shaped solid electrolytic capacitor according to item 3 of the scope of patent application, wherein the conductivity of the semiconductor is in the range of 1CT2 to 103S / cm. 22. A method for manufacturing a wafer-shaped solid electrolytic capacitor, which connects -28- 200525567 (5) a part of the anode part and a part of the cathode part of the capacitor element to each anode terminal and the cathode terminal, and A wafer-shaped solid electrolytic capacitor in which the bottom or the bottom of each of the anode and cathode terminals and a part or all of the side surfaces are sealed outside is characterized in that the connection surface of the cathode terminal and the capacitor element is connected to the capacitor element and the cathode terminal. A method for manufacturing a larger and larger wafer-shaped solid electrolytic capacitor on the side is characterized by using a lead frame pair having a lower surface portion which becomes a part of two terminals of a cathode and an anode. A metal material constituting a yin and yang terminal having a larger area than the cathode terminal connection surface of the capacitor element is adhered. 23. A method for manufacturing a wafer-shaped solid electrolytic capacitor, which connects a portion of an anode portion and a portion of a cathode portion of a capacitor element to each anode terminal and the cathode terminal, and connects the foregoing anode and cathode terminals In a wafer-shaped solid electrolytic capacitor whose outer surface is sealed below or below and a part or all of the side, the connection surface between the cathode terminal and the capacitor element is larger than that on the connection surface side between the capacitor element and the cathode terminal. A method for manufacturing a wafer-shaped solid electrolytic capacitor having a substantially lower size of a lower surface of a cathode terminal and a lower surface of an anode terminal, which is characterized in that a portion having substantially the same lower surface having a portion that becomes one of the two terminals of the anode and the cathode is used. For the lead frame pair, a metal material constituting a yin and yang terminal having a larger area than the cathode terminal connection surface of the capacitor element is pasted on the lead frame corresponding to the cathode end, and the lead frame corresponding to the anode terminal is pasted. A metal material constituting an anode terminal joined to an anode portion of a capacitor element is adhered. -29- 200525567 (6) 2 4. — An electronic circuit that uses a chip-shaped solid electrolytic capacitor such as those in the scope of patent applications No. 1 to 21. 2 5. — An electronic device using a wafer-shaped solid electrolytic capacitor such as the scope of claims 1 to 21 of the patent application. -30-