WO2005008701A1 - Method for producing solid electrolytic capacitor - Google Patents
Method for producing solid electrolytic capacitor Download PDFInfo
- Publication number
- WO2005008701A1 WO2005008701A1 PCT/JP2004/010526 JP2004010526W WO2005008701A1 WO 2005008701 A1 WO2005008701 A1 WO 2005008701A1 JP 2004010526 W JP2004010526 W JP 2004010526W WO 2005008701 A1 WO2005008701 A1 WO 2005008701A1
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- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolytic
- electrolytic capacitor
- resin
- temperature
- earth
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 100
- 239000007787 solid Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000004065 semiconductor Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000002950 deficient Effects 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- -1 polyoxyphenylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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 a method for producing a solid electrolytic capacitor having good heat resistance.
- a tantalum solid electrolytic capacitor has a large capacitance for the size and also has good performance and therefore, this is being preferably used.
- a niobium solid electrolytic capacitor using niobium which is an inexpensive material, for the anode is recently studied.
- a capacitor element comprising a dielectric layer formed on an anode surface by electrochemical formation, a semiconductor layer sequentially stacked on the dielectric layer, and an electrically conducting layer formed on the semiconductor layer is connected to an external terminal and then jacketed to complete the solid electrolytic capacitor.
- the produced solid electrolytic capacitor is mounted together with other electronic parts on a circuit board or the like and used in practice, but in some cases, the leakage current (hereinafter, simply referred to as "LC") value of the capacitor increases due to heat of soldering at the mounting.
- LC leakage current
- JP-A-6-310382 a method of leaving the semiconductor layer to stand at a temperature higher than the curing temperature of jacketing resin and thereby preventing the increase of LC has been proposed in JP-A-6-310382 (the term "JP-A” as used herein means an "unexamined published Japanese patent application”) .
- the present invention has been accomplished based on this finding. That is, the present invention relates to a method for producing a solid electrolytic capacitor, a solid electrolytic capacitor obtained by the method, and an electronic circuit and an electronic device each using the solid electrolytic capacitor, which are described below. 1.
- a method for producing a solid electrolytic capacitor wherein a solid electrolytic capacitor element comprises an anode body composed of a material containing at least one member selected from, a group consisting of an earth-acid metal, an alloy comprising an earth-acid metal as the main component, an electrically conducting oxide of an earth-acid metal and a mixture of two or more thereof, a dielectric layer formed on the anode body by electrolytic oxidation (electrochemical formation) and comprising an oxide as the main component, a semiconductor layer formed on the dielectric layer, and an electrically conducting layer stacked on the semiconductor layer, and the solid electrolytic capacitor element is subjected to molding with a resin, curing and then voltage applying (aging) treatment, which method comprises repeating a step of leaving the resin- molded body to stand at a temperature of 225 to 305°C and a step of aging it are sequentially repeated twice or more after the above steps of molding with resin and curing.
- a resin, curing and then voltage applying (aging) treatment which method comprises
- the method for producing a solid electrolytic capacitor as described in 1 above wherein the step of leaving the resin-molded body to stand at a temperature of 225 to 305°C is a step of performing the standing at a temperature of 225 to 305°C multiple times.
- the method for producing a solid electrolytic capacitor as described in 1 above, wherein the aging step after leaving the resin-molded body to stand at a temperature of 225 to 305°C is a step of cooling the resin-molded body to a temperature of 200°C or less to cold-resistance temperature of the capacitor and then applying a voltage.
- the anode body of the electrode for the capacitor of the present invention comprises a material containing at least one member selected from a group consisting of an earth-acid metal, an alloy comprising an earth-acid metal as the main component, an oxide of an earth-acid metal, and a mixture of two or more thereof.
- the main component used herein means a component contained to a concentration of 50 mass% or more.
- the capacitor electrode used herein may have any shape of a foil, a plate, a bar and a sintered body. The surface of the electrode may be etched to enlarge the surface area.
- the electrode can be usually produced by shaping a powder (raw material powder) of the above-described metal, alloy, oxide or mixture together with a binder into an appropriate shape and after or while removing the binder, sintering the shaped article.
- the method for producing a sintered body-shaped electrode (hereinafter, simply referred to as a "sintered body") is not particularly limited, but one example thereof is described below.
- the raw material powder is press-formed into a predetermined shape to obtain a shaped article.
- This shaped article is heated at 500 to 2,000°C for a few minutes to a few hours under 10 ⁇ 4 to 10 -1 Pa to obtain a sintered body.
- a part of a metal wire comprising a valve-acting metal such as tantalum, niobium and aluminum as the main component may be embedded in the shaped article at the shaping and sintered simultaneously with the shaped article, so that the metal wire in the portion protruded from the sintered body can be used as the leading-out line of the sintered body.
- the metal wire may be connected by welding or the like after the sintering and used as the anode leading-out line.
- the diameter of such a metal wire is usually 1 mm or less.
- the above-described powder may be attached to a valve-acting metal foil such as tantalum and niobium and sintered to produce a sintered body where a part of the valve-acting metal foil is working as the anode leading-out part.
- the earth-acid metal means an element belonging to Group 5 of the Periodic Table, specifically, vanadium, tantalum or niobium.
- the earth-acid metal is preferably tantalum or niobium.
- Examples of the alloy comprising an earth-acid metal as the main component include those comprising tantalum and/or niobium as the main component and containing, as an alloy component, at least one element selected from the group consisting of elements belonging to Groups 2 to 16 of the Periodic Table.
- Examples of the electrically conducting oxide of an earth-acid metal include tantalum oxide and niobium oxide. A representative example thereof is niobium monoxide.
- a part of the earth-acid metal, alloy or electrically conducting oxide of an earth-acid metal may be subjected to at least one treatment selected from carbonization, phosphation, boronation, nitridation and sulfidation before use.
- binder examples include various acrylic resins, various vinyl resins such as polyvinyl alcohol, various butyral resins, various vinyl acetal resins, camphor and iodide.
- the binder may be used as a solid or may be used after dissolving or semi-dissolving it in an appropriate solvent.
- the amount of the binder used is usually from 0.1 to 20 parts by mass per 100 parts by mass of the earth-acid metal, alloy and/or electrically conducting oxide.
- an outgoing wire may be connected to the above-described capacitor electrode and used as anode leading-out part.
- a part of the capacitor electrode may be kept blank without forming thereon a semiconductor layer and an electrically conducting layer which are described later (while a dielectric layer may, but not necessarily, be formed on the part) , and the part may be used afterward as anode leading-out part.
- the dielectric layer formed on the surface of the capacitor electrode (anode) include a dielectric layer comprising ditantalum pentoxide or diniobium pentoxide as the main component.
- the dielectric layer comprising ditantalu pentoxide as the main component can be obtained by electrochemically forming the tantalum electrode as the capacitor electrode in an electrolytic solution.
- the tantalum electrode is electrochemically formed in an electrolytic solution usually by using an aqueous protonic acid solution, for example, an aqueous 0.1 mass% acetic acid solution, an aqueous 0.1 mass% phosphoric acid solution or an aqueous 0.01 mass% sulfuric acid solution.
- an aqueous protonic acid solution for example, an aqueous 0.1 mass% acetic acid solution, an aqueous 0.1 mass% phosphoric acid solution or an aqueous 0.01 mass% sulfuric acid solution.
- representative examples of the semiconductor layer formed on the dielectric layer of the present invention include at least one compound selected from an organic semiconductor and an inorganic semiconductor.
- organic semiconductor examples include an organic semiconductor comprising benzopyrroline tetramer and chloranil, an organic semiconductor comprising tetrathiotetracene as the main component, an organic semiconductor comprising tetracyanoquinodimethane as the main component, and an organic semiconductor comprising, as the main component, an electrically conducting polymer obtained by doping a dopant to a polymer containing a repeating unit represented by the following formula (1) or (2) :
- R 1 to R 4 which may be the same or different, each represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms or an alkoxy group having from 1 to 6 carbon atoms
- X represents an oxygen atom, a sulfur atom or a nitrogen atom
- R 5 is present only when X is a nitrogen atom
- each of the pairs R 1 and R 2 , and R 3 and R 4 may combine with each other to form a ring structure.
- the electrically conducting polymer containing a repeating unit represented by formula (1) is preferably an electrically conducting polymer containing a structure unit represented by the following formula (3) as a repeating unit:
- R 6 and R 7 each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated alkyl group having from 1 to 6 carbon atoms, or a substituent for forming at least one 5-, 6- or 7-membered saturated hydrocarbon ring structure containing two oxygen atoms when the alkyl groups are combined with each other at an arbitrary position, and the ring structure includes a structure having a vinylene bond, which may be substituted, and a phenylene structure which may be substituted.
- the electrically conducting polymer containing such a chemical structure is being electrically charged and a dopant is doped therein.
- known dopants can be used without limitation.
- Examples of the polymer containing a repeating unit represented by formula (1) , (2) or (3) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substitution derivatives and copolymers thereof.
- preferred are polypyrrole, polythiophene and substitution derivatives thereof (e.g., poly (3, 4-ethylenedioxythiophene) ) .
- the inorganic semiconductor include at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide and manganese dioxide,
- the organic or inorganic semiconductor used has an electrical conductivity of 10 "2 to 10 3 S/cm
- the capacitor produced can have a small ESR value and this is preferred.
- the organic semiconductor has a high possibility of deteriorating due to high temperatures at mounting and therefore, the production method of the present invention is particularly effective when used for a solid electrolytic capacitor using an organic semiconductor.
- an electrically conducting layer is provided on the semiconductor layer formed by the above-described method or the like.
- the electrically conducting layer can be formed, for example, by solidification of an electrically conducting paste, plating, vapor deposition of metal, or lamination of a heat-resistant electrically conducting resin film.
- Preferred examples of the electrically conducting paste include silver paste, copper paste, aluminum paste, carbon paste and nickel paste, and these may be used individually or in combination of two or more thereof. In the case of using two or more pastes, the pastes may be mixed or may be superposed one on another as separate layers.
- the electrically conducting paste applied is then solidified by leaving it to stand in air or under heating.
- the plating include nickel plating, copper plating, silver plating and aluminum plating.
- Examples of the metal vapor-deposited include aluminum, nickel, copper and silver.
- a solid electrolytic capacitor element is produced, where a dielectric layer, a semiconductor layer and an electrically conducting layer are sequentially stacked on a capacitor electrode.
- the solid electrolytic capacitor element having such a constitution of the present invention is jacketed, for example, by resin mold, resin case, metallic jacket case, resin dipping or laminate film and thereby, can be completed as a capacitor product for various uses.
- a chip solid electrolytic capacitor jacked by resin mold is particularly preferred, because the mounting can be simply performed.
- the jacketing by resin mold is specifically described below.
- a part of the electrically conducting layer of the solid electrolytic capacitor element produced as above is placed on one end part of a separately prepared lead frame having a pair of oppositely disposed end parts, the anode leading-out part (this may be used after cutting the distal end of the anode leading-out part to adjust the dimension) is further placed on the other end part of the lead frame, each is electrically or mechanically joined, for example, the former is joined by solidification of an electrically conducting paste and the latter is joined by spot-welding, the entirety is molded with a resin while leaving a part of the end part of the lead frame unmolded, and the lead frame is cut and bent at predetermined portions outside the resin mold, whereby the solid electrolytic capacitor of the present invention is produced.
- the lead frame is cut as described above and finally works out to external terminals of the solid electrolytic capacitor.
- the shape thereof is a foil or tabular form and for the material, iron, copper, aluminum or an alloy comprising such a metal as the main component is predominantly used.
- the lead frame may be partially or entirely plated with solder, tin, titanium or the like. Between the lead frame and the plating, a primer plating such as nickel or copper may be provided.
- a pair of oppositely disposed end parts are present, and a gap is provided between these end parts, so that the anode part and the cathode part of each solid electrolytic capacitor element can be insulated from each other.
- the resin used in molding of the solid electrolytic capacitor of the present invention known resins for use in molding of a solid electrolytic capacitor, such as epoxy resin, phenol resin and alkyd resin, can be used.
- the production machine used for performing the molding with resin is preferably a transfer machine.
- the solid electrolytic capacitor molded with a resin is then cured at a predetermined curing temperature of the resin used or around this temperature, usually at a temperature of 150 to 250°C (depending on the case, the curing of resin may be completed only by the molding temperature (usually from 150 to 200°C) of the transfer machine) .
- a step of leaving the resin-molded body to stand at a temperature of 225 to 305°C, preferably from 230 to 270°C, and a step of aging it are sequentially repeated twice or more to stabilize the dielectric layer, but the addition of a step of performing an aging treatment before repeating these two steps is also included in the scope of the present invention.
- the standing time at a high temperature is from a few seconds to tens of hours. After standing at a high temperature, it is necessary to once lower the temperature to 200°C or less, preferably 150°C or less, more preferably 80°C or less, still more preferably room temperature or less.
- the temperature can be lowered to a cold resistance temperature (generally -55°C) of the capacitor produced.
- the standing at a high temperature may be performed in an air atmosphere or in a gas atmosphere of Ar, N 2 , He or the like, and also may be performed under reduced pressure, atmospheric pressure or applied pressure.
- the water vapor can be supplied, for example, by a method of supplying water vapor generated due to heat from a water reservoir placed in a furnace used for the standing at a high temperature.
- the maximum temperature when leaving the solid electrolytic capacitor to stand in a high-temperature atmosphere is described. Before reaching this temperature, the temperature of the capacitor may be gradually elevated from a low temperature to reach the maximum temperature.
- the temperature elevating method can be arbitrarily selected. Incidentally, fluctuation of the above-described maximum temperature due to properties of the apparatus, for example, fluctuation within about ⁇ 30°C range, does not adversely affect the invention. Also, even if the temperature is set to give an artificial fluctuation of heat at the maximum temperature, this has fundamentally no problem.
- a temperature pattern of leaving the capacitor to stand in a high-temperature range multiple times for example, standing at a maximum temperature, once lowering to an arbitrary low temperature, and further standing at an arbitrary temperature of 225 to 305°C, may also be employed.
- the matter of importance is to leave the capacitor at least once at a temperature of 225 to 305°C.
- the temperature for the standing at a high temperature is 305°C or less. If this temperature exceeds 305°C, the dielectric layer is not stabilized but rather becomes defective and this is not preferred.
- the aging is performed by applying a predetermined voltage to the solid electrolytic capacitor. The optimal values of the aging time and temperature vary depending on the kind of capacitor, the capacitance and the voltage.
- the conditions for causing the reduction of LC value to 0.1 CV or less at the aging temperature are determined by previously performing an experiment, but the aging is usually performed for a time period of several minutes to several days at a temperature of 300°C or less in consideration for heat deterioration of the jig for applying a voltage.
- the aging may be performed in an air atmosphere or in a gas atmosphere of Ar, N 2 , He or the like, and also may be performed under reduced pressure, atmospheric pressure or applied pressure.
- the stabilization of the dielectric layer is sometimes accelerated.
- the water vapor can be supplied, for example, by a method of supplying water vapor generated due to heat from a water reservoir placed in a furnace used for the aging.
- a method of supplying water vapor generated due to heat from a water reservoir placed in a furnace used for the aging As for the method of applying a voltage, it can be designed to pass an arbitrary current such as direct current, alternating current having an arbitrary waveform and alternating current superposed on direct current. It is also possible to once stop applying a voltage on the way of aging and again apply a voltage. The reason why good heat resistance can be obtained by sequentially repeating the high-temperature standing step and the aging step twice or more in the present invention is not clearly known, but this is considered as follows.
- the deterioration of the dielectric layer due to the heat itself (and the thermal stress of resin for molding) at the mounting is severer than expected and cannot be repaired by an ordinary aging treatment.
- the capacitor produced in the present invention can be preferably used, for example, for circuits using a high- capacitance capacitor, such as electric power circuit.
- circuits can be used in various digital devices such as personal computer, sever, camera, game machine, DVD, AV equipment and cellular phone, and electronic devices such as various electric power sources.
- the capacitor produced in the present invention does not cause increase of leakage current after mounting and therefore, by using this capacitor, electronic circuits and electronic devices having a low initial failure rate can be obtained.
- BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in greater detail below by referring to Examples, however, the present invention is not limited to these Examples.
- a sintered body having a size of 4x3.2x1.7 mm was produced by using 0.12 g of tantalum powder having CV of 80,000 ⁇ F-V/g (sintering condition: temperature of 1,340°C and 30 minutes, density of sintered body: 5.5 g/cm 3 , Ta lead wire: 0.29 m ⁇ ) .
- This sintered body except for a part of the lead wire was dipped in an aqueous 0.1 mass% phosphoric acid solution and by applying a voltage of 18 V between the sintered body and a Ta plate electrode as the negative electrode, the sintered body was electrochemically formed at 80°C for 3 hours to form a dielectric layer comprising Ta 2 ⁇ 5.
- a semiconductor layer was formed on the surface of the dielectric layer according to the method described in Japanese Patent No. 2,054,506 where the sintered body is subjected to an oxidizing agent treatment by dipping it in an oxidizing agent and then to electrolytic polymerization.
- a step of sequentially performing polymerization and post-electrochemical formation that is, performing the polymerization at room temperature for 5 hours while applying a voltage of 14 V between the sintered body and the negative electrode (Ta plate electrode) at the electrolytic polymerization by using an aqueous 13 mass% anthraquinonesulfonic acid solution as the oxidizing agent, ethylenedioxythiophene (used in the form of an aqueous solution where the monomer concentration was lower than the saturated concentration) as the monomer, anthraquinone- sulfonic acid as the dopant, and water as the solvent, and then performing post-electrochemical formation at 13 V in an aqueous 0.1 mass% acetic acid solution, was repeated 6 times to form a semiconductor layer.
- Examples 6 and 7 and Comparative Examples 3 to 5 A niobium primary powder (average particle size: 0.5 ⁇ m) ground by utilizing the hydrogen embrittlement of a niobium ingot was granulated to obtain a niobium powder having an average particle size of 100 ⁇ m and containing 85,000 ppm of oxygen (this niobium power was a fine powder and therefore, naturally oxidized) .
- the obtained niobium powder was left standing in a nitrogen atmosphere at 450°C and further in Ar at 700°C to provide a partially nitrided niobium powder (CV: 150,000 ⁇ F-V/g) having a nitrided amount of 11,000 ppm.
- niobium powder was shaped together with a 0.29mm ⁇ niobium wire and then sintered at 1,300°C.
- multiple sintered bodies anodes having a size of 4.0x3.5x1.7 mm (mass: 0.08 g) were produced (30 units in each Example, 150 units in total) .
- Each sintered body was electrochemically formed in an aqueous 0.1 mass% phosphoric acid solution at 80°C and 20 V for 10 hours to form a dielectric layer comprising niobium oxide as the main component on the anode surface.
- a semiconductor layer was formed on the dielectric layer surface by a method described in International PCT Patent Application No.
- Example 2 Thereafter, the same procedure as in Example 1 was performed to obtain a chip solid electrolytic capacitor. Multiple units (30 units in each Example, 150 units in total) of the thus-produced capacitor were prepared and a step of heat-treating the capacitor and a step of aging it were performed under the conditions shown in Table 1.
- Example 8 Chip solid electrolytic capacitors were produced in the same manner as in Example 6 except that the step of heat- treating the capacitors was performed in the presence of water vapor by placing a container containing water in the furnace .
- Example 9 Chip solid electrolytic capacitors were produced in the same manner as in Example 6 except that the capacitors were left standing in moisture-controlled chamber of 90% RH at 60°C for 24 hours before the respective aging steps. In the mounting test of produced capacitor, a capacitor fixed on a substrate by a lead-less cream solder was passed
- a capacitor element comprising an anode body, a dielectric layer on the anode body, a semiconductor layer thereon and an electrically conducting layer stacked on the semiconductor layer is molded with resin and cured and thereafter, a step of leaving the resin-molded body to stand at a temperature of 225 to 305°C and a step of aging it are repeated twice of more, a solid electrolytic capacitor improved in the leakage current (LC) value after mounting can be obtained.
- LC leakage current
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CN2004800202582A CN1823397B (en) | 2003-07-18 | 2004-07-16 | Method for producing solid electrolytic capacitor |
US10/564,821 US7291537B2 (en) | 2003-07-18 | 2004-07-16 | Method for producing solid electrolytic capacitor |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54127564A (en) * | 1978-03-28 | 1979-10-03 | Matsushita Electric Ind Co Ltd | Method of producing solid electrolytic condenser |
JPH03151622A (en) * | 1989-11-08 | 1991-06-27 | Hitachi Aic Inc | Manufacture of solid electrolytic capacitor |
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2004
- 2004-07-16 WO PCT/JP2004/010526 patent/WO2005008701A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54127564A (en) * | 1978-03-28 | 1979-10-03 | Matsushita Electric Ind Co Ltd | Method of producing solid electrolytic condenser |
JPH03151622A (en) * | 1989-11-08 | 1991-06-27 | Hitachi Aic Inc | Manufacture of solid electrolytic capacitor |
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