JP3992706B2 - Capacitor manufacturing method - Google Patents
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- JP3992706B2 JP3992706B2 JP2004303643A JP2004303643A JP3992706B2 JP 3992706 B2 JP3992706 B2 JP 3992706B2 JP 2004303643 A JP2004303643 A JP 2004303643A JP 2004303643 A JP2004303643 A JP 2004303643A JP 3992706 B2 JP3992706 B2 JP 3992706B2
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- 239000003990 capacitor Substances 0.000 title claims description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- 239000010410 layer Substances 0.000 claims description 174
- 239000004065 semiconductor Substances 0.000 claims description 166
- 239000004020 conductor Substances 0.000 claims description 76
- 239000002243 precursor Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 48
- 239000011148 porous material Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229920001940 conductive polymer Polymers 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 8
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- -1 polyoxyphenylene Polymers 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920000128 polypyrrole Polymers 0.000 claims description 7
- 229920000123 polythiophene Polymers 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229920000414 polyfuran Polymers 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 150000002240 furans Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- 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 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 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 claims description 2
- 239000000243 solution Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005245 sintering Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROSDCCJGGBNDNL-UHFFFAOYSA-N [Ta].[Pb] Chemical compound [Ta].[Pb] ROSDCCJGGBNDNL-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- AJFGAOLLUBJXNE-UHFFFAOYSA-N iron;naphthalene-1-sulfonic acid Chemical compound [Fe].C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 AJFGAOLLUBJXNE-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PYLYNBWPKVWXJC-UHFFFAOYSA-N [Nb].[Pb] Chemical compound [Nb].[Pb] PYLYNBWPKVWXJC-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
本発明は、容量出現率が良好で低ＥＳＲであるコンデンサの製造方法に関する。 The present invention relates to a method of manufacturing a capacitor having a good capacitance appearance rate and low ESR.
パソコン等に使用される中央演算処理装置（ＣＰＵ）の回路に使用されるコンデンサは、電圧変動を抑え、高リップル（ripple）通過時の発熱を低くするために、高容量かつ低ＥＳＲ（等価直列抵抗）のものが求められていて、一般にアルミ固体電解コンデンサや、タンタル固体電解コンデンサが使用されている。 Capacitors used in central processing unit (CPU) circuits used in personal computers, etc. have high capacity and low ESR (equivalent series) in order to suppress voltage fluctuations and reduce heat generation when passing through high ripple. In general, an aluminum solid electrolytic capacitor or a tantalum solid electrolytic capacitor is used.
固体電解コンデンサは、表面層に微細な細孔を有するアルミニウム箔や、内部に微小な細孔を有するタンタル粉の焼結体を一方の電極（導電体）として、該電極の表層に形成した誘電体層と該誘電体層上に設けられた他方の電極（通常は、半導体層）とから構成されている。 Solid electrolytic capacitors consist of an aluminum foil with fine pores on the surface layer and a tantalum powder sintered body with fine pores inside as one electrode (conductor) formed on the surface of the electrode. It is composed of a body layer and the other electrode (usually a semiconductor layer) provided on the dielectric layer.
誘電体層上に半導体層が形成される割合は、半導体の代わりに電解液を含浸させた時に出現する容量に対する半導体層形成時の容量の比（１００分率）で定義される含浸率で示される。 The rate at which the semiconductor layer is formed on the dielectric layer is indicated by the impregnation rate defined by the ratio (100 fraction) of the capacity when forming the semiconductor layer to the capacity that appears when the electrolyte is impregnated instead of the semiconductor. It is.
半導体層を誘電体層の上に形成する方法として通電による方法がある。例えば、直流通電で金属酸化物からなる半導体層を形成する方法（特許第1985056号公報；特許文献１）、交流通電で導電性化合物からなる半導体層を得る方法（特許第2826341号公報；特許文献２）、導電性高分子を予め設けた化学重合層の上に別途用意した外部電極を接触させて直流通電により導電性高分子からなる半導体層を形成する方法（特許第1988457号公報；特許文献３）がある。 As a method for forming the semiconductor layer on the dielectric layer, there is a method by energization. For example, a method of forming a semiconductor layer made of a metal oxide by direct current application (Patent No. 1885056; Patent Document 1), a method of obtaining a semiconductor layer made of a conductive compound by alternating current application (Patent No. 2863441; Patent Document) 2) A method of forming a semiconductor layer made of a conductive polymer by direct current application by bringing a separately prepared external electrode into contact with a chemical polymerization layer previously provided with a conductive polymer (Patent No. 1988457; Patent Document) 3).
前記特許文献１または２の方法によれば、ＥＳＲは良好であるが、半導体層形成に長時間を有し、通常の時間内では含浸率を大きくできない。
特許文献２の方法では、多数個の導電体に同時に半導体層を形成する工業的な生産規模では対極を必要とするが、その対極にも半導体層が付着するという欠点がある。
According to the method of Patent Document 1 or 2, the ESR is good, but the semiconductor layer formation takes a long time, and the impregnation rate cannot be increased within a normal time.
The method of Patent Document 2 requires a counter electrode on an industrial production scale in which a semiconductor layer is simultaneously formed on a large number of conductors, but has a drawback that the semiconductor layer also adheres to the counter electrode.
特許文献３の方法は、多数個の導電体に同時に半導体層を形成する場合に応用すると、化学重合層が薄い時には通電によって半導体層を厚くする必要があるが、外部電極からの通電であるために導電体表層に形成された半導体層が導電体の細孔内部への半導体層形成用前駆体の拡散を邪魔するためか通電による半導体層がうまく形成されないものが出現する。化学重合層が厚い時には、通電による半導体層が容易に形成される傾向にあるが、厚い化学重合層を形成しているためにＥＳＲ値が良好でないという問題点がある。
したがって、さらにＥＳＲが改良され、かつ容量の拡大されたコンデンサ製造方法が求められている。
When the method of Patent Document 3 is applied to a case where a semiconductor layer is simultaneously formed on a large number of conductors, it is necessary to increase the thickness of the semiconductor layer by energization when the chemical polymerization layer is thin. In some cases, the semiconductor layer formed on the surface of the conductor does not successfully form the semiconductor layer due to current flow because the semiconductor layer formation precursor interferes with the diffusion of the precursor for forming the semiconductor layer into the pores of the conductor. When the chemical polymerization layer is thick, a semiconductor layer tends to be easily formed by energization, but there is a problem that the ESR value is not good because the thick chemical polymerization layer is formed.
Therefore, there is a need for a capacitor manufacturing method with further improved ESR and increased capacity.
本発明者らは、前記課題を解決するために鋭意検討した結果、通電前に細孔内に半導体層形成用前駆体を含浸し、細孔内の半導体層形成用前駆体濃度を電解液中の半導体層形成用前駆体より高濃度にして電解液中で通電することによって本課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have impregnated the semiconductor layer forming precursor in the pores before energization, and set the concentration of the semiconductor layer forming precursor in the pores in the electrolyte solution. The present inventors have found that this problem can be solved by energizing in an electrolyte solution at a concentration higher than that of the precursor for forming a semiconductor layer, and have completed the present invention.
すなわち、本発明は、以下のコンデンサの製造方法及びそのコンデンサの製造法により作製したコンデンサに関する。
１．表面に誘電体層を形成した細孔を有する導電体を一方の電極（陽極）とし、電解液中で通電手法によって導電体上に形成した半導体層を他方の電極（陰極）とするコンデンサの製造方法において、通電前に細孔内に半導体層形成用前駆体を含浸し、細孔内の半導体層形成用前駆体濃度を電解液中の半導体層形成用前駆体より高濃度にすることを特徴とするコンデンサの製造方法。
２．電解液が半導体層形成用前駆体を含まない電解液である前記１に記載のコンデンサの製造方法。
３．導電体が、金属、無機半導体、有機半導体及びカーボンから選ばれる少なくとも１種またはそれらの混合物である前記１に記載のコンデンサの製造方法。
４．導電体が、金属、無機半導体、有機半導体及びカーボンから選ばれる少なくとも１種またはそれらの混合物の導電体を表層に有する積層体である前記１に記載のコンデンサの製造方法。
５．導電体が、タンタル、ニオブ及びアルミニウムから選ばれる少なくとも１種を主成分とする金属あるいは合金、または酸化ニオブである前記３または４に記載のコンデンサの製造方法。
６．導電体が、ＣＶ値１０万μＦ・Ｖ／ｇ以上のタンタルである前記１乃至５のいずれかに記載のコンデンサの製造方法。
７．導電体が、ＣＶ値１５万μＦ・Ｖ／ｇ以上のニオブである前記１乃至５のいずれかに記載のコンデンサの製造方法。
８．導電体の大きさが、５ｍｍ3以上である前記１、３乃至７のいずれかに記載のコンデンサの製造方法。
９．導電体が箔形状であり、エッチングによる細孔深さが２００μｍ以上である前記１、３乃至８のいずれかに記載のコンデンサの製造方法。
１０．誘電体層が、Ｔａ2Ｏ5、Ａｌ2Ｏ3、ＴｉＯ2及びＮｂ2Ｏ5から選ばれる少なくとも１つを主成分とするものである前記１に記載のコンデンサの製造方法。
１１．半導体層形成用前駆体が、アニリン誘導体（ポリアニリンの原料）、フェノール誘導体（ポリオキシフェニレンの原料）、チオフェノール誘導体（ポリフェニレンサルファイドの原料）、チオフェン誘導体（ポリチオフェンの原料）、フラン誘導体（ポリフランの原料）、及びピロール誘導体（ポリピロール、ポリメチルピロールの原料）から選ばれる少なくとも１種である前記１または２に記載のコンデンサの製造方法。
１２．半導体層形成用前駆体が、ピロール、または３，４−エチレンジオキシチオフェンである前記１１に記載のコンデンサの製造方法。
１３．半導体層形成用前駆体が、通電によって酸化または還元されて、無機半導体になる化合物である前記１または２に記載のコンデンサの製造方法。
１４．半導体層が、有機半導体層及び無機半導体層から選ばれる少なくとも１種である前記１に記載のコンデンサの製造方法。
１５．有機半導体が、ベンゾピロリン４量体とクロラニルからなる有機半導体、テトラチオテトラセンを主成分とする有機半導体、テトラシアノキノジメタンを主成分とする有機半導体、下記一般式（１）または（２）
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である前記１４に記載のコンデンサの製造方法。
１６．一般式（１）で示される繰り返し単位を含む導電性高分子が、下記一般式（３）
で示される構造単位を繰り返し単位として含む導電性高分子である前記１５に記載のコンデンサの製造方法。
１７．導電性高分子が、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、及びこれらの置換誘導体及び共重合体から選択される前記１６に記載のコンデンサの製造方法。
１８．導電性高分子、ポリ（３，４−エチレンジオキシチオフェン）である前記１７に記載のコンデンサの製造方法。
１９．無機半導体が、二酸化モリブデン、二酸化タングステン、二酸化鉛、及び二酸化マンガンから選ばれる少なくとも１種の化合物である前記１４に記載のコンデンサの製造方法。
２０．半導体の電導度が１０-2〜１０3Ｓ／ｃｍの範囲である前記１４乃至１９のいずれかに記載のコンデンサの製造方法。
２１．前記１乃至２０のいずれかに記載のコンデンサの製造方法によって作製されたコンデンサ。
２２．含浸率が９０％以上である前記２１に記載のコンデンサ。
２３．前記２１または２２に記載のコンデンサを使用した電子回路。
２４．前記２１または２２に記載のコンデンサを使用した電子機器。
That is, the present invention relates to the following capacitor manufacturing method and a capacitor manufactured by the capacitor manufacturing method.
1. Manufacture of capacitors with a conductor having pores with a dielectric layer formed on the surface as one electrode (anode) and a semiconductor layer formed on the conductor in the electrolyte by an energization technique as the other electrode (cathode) In the method, the semiconductor layer forming precursor is impregnated in the pores before energization, and the concentration of the semiconductor layer forming precursor in the pores is higher than the concentration of the semiconductor layer forming precursor in the electrolyte. And a capacitor manufacturing method.
2. 2. The method for producing a capacitor as described in 1 above, wherein the electrolytic solution is an electrolytic solution containing no semiconductor layer forming precursor.
3. 2. The method for producing a capacitor as described in 1 above, wherein the conductor is at least one selected from metals, inorganic semiconductors, organic semiconductors, and carbon, or a mixture thereof.
4). 2. The method for producing a capacitor as described in 1 above, wherein the conductor is a laminate having, as a surface layer, a conductor of at least one selected from metals, inorganic semiconductors, organic semiconductors, and carbon, or a mixture thereof.
5). 5. The method for producing a capacitor as described in 3 or 4 above, wherein the conductor is a metal or alloy mainly containing at least one selected from tantalum, niobium and aluminum, or niobium oxide.
6). 6. The method for producing a capacitor according to any one of 1 to 5, wherein the conductor is tantalum having a CV value of 100,000 μF · V / g or more.
7). 6. The method for producing a capacitor according to any one of 1 to 5, wherein the conductor is niobium having a CV value of 150,000 μF · V / g or more.
8). 8. The method for manufacturing a capacitor according to any one of the above items 1, 3 to 7, wherein the conductor has a size of 5 mm 3 or more.
9. 9. The method for manufacturing a capacitor as described in any one of 1 to 3 to 8, wherein the conductor is in a foil shape, and a pore depth by etching is 200 μm or more.
10. 2. The method for producing a capacitor as described in 1 above, wherein the dielectric layer is mainly composed of at least one selected from Ta 2 O 5 , Al 2 O 3 , TiO 2 and Nb 2 O 5 .
11. The semiconductor layer forming precursors are aniline derivatives (polyaniline raw materials), phenol derivatives (polyoxyphenylene raw materials), thiophenol derivatives (polyphenylene sulfide raw materials), thiophene derivatives (polythiophene raw materials), furan derivatives (polyfuran raw materials). ) And a pyrrole derivative (raw material of polypyrrole or polymethylpyrrole). The method of producing a capacitor as described in 1 or 2 above.
12 12. The method for producing a capacitor as described in 11 above, wherein the semiconductor layer forming precursor is pyrrole or 3,4-ethylenedioxythiophene.
13. 3. The method for producing a capacitor according to 1 or 2, wherein the semiconductor layer forming precursor is a compound that is oxidized or reduced by energization to become an inorganic semiconductor.
14 2. The method for producing a capacitor as described in 1 above, wherein the semiconductor layer is at least one selected from an organic semiconductor layer and an inorganic semiconductor layer.
15. An organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
15. The method for producing a capacitor as described in 14 above, which is at least one selected from organic semiconductors mainly composed of a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula 1 with a dopant.
16. The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
16. The method for producing a capacitor as described in 15 above, wherein the capacitor is a conductive polymer containing a structural unit represented by
17. 17. The method for producing a capacitor as described in 16 above, wherein the conductive polymer is selected from polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof.
18. 18. The method for producing a capacitor as described in 17 above, which is a conductive polymer, poly (3,4-ethylenedioxythiophene).
19. 15. The method for producing a capacitor as described in 14 above, wherein the inorganic semiconductor is at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, and manganese dioxide.
20. 20. The method for producing a capacitor as described in any one of 14 to 19, wherein the conductivity of the semiconductor is in the range of 10 −2 to 10 3 S / cm.
21. 21. A capacitor produced by the method for producing a capacitor according to any one of 1 to 20 above.
22. 22. The capacitor as described in 21 above, wherein the impregnation rate is 90% or more.
23. 23. An electronic circuit using the capacitor as described in 21 or 22 above.
24. 23. An electronic device using the capacitor described in 21 or 22 above.
本発明のコンデンサの製造方法及びコンデンサの一形態を説明する。
本発明に使用される導電体の例としては、金属、無機半導体、有機半導体、カーボンから選ばれた少なくとも１種の導電体またはそれらの混合物、またはそれらの表層に導電体を積層した積層体が挙げられる。
A capacitor manufacturing method and one embodiment of the capacitor of the present invention will be described.
Examples of the conductor used in the present invention include at least one kind of conductor selected from metals, inorganic semiconductors, organic semiconductors, and carbon, or a mixture thereof, or a laminate in which conductors are laminated on the surface layer thereof. Can be mentioned.
金属として、タンタル、ニオブ及びアルミニウムから選ばれる少なくとも１種を主成分とする金属あるいは合金が挙げられる。
無機半導体として、二酸化鉛、二酸化モリブデン、二酸化タングステン、一酸化ニオブ、二酸化スズ、一酸化ジルコニウム等の金属酸化物が挙げられ、有機半導体としてポリピロール、ポリチオフェン、ポリアニリン及びこれら高分子骨格を有する置換体、共重合体等の導電性高分子、テトラシアノキノジメタンとテトラチオテトラセンとの錯体、テトラシアノキノジメタン（ＴＣＮＱ）塩等の低分子錯体が挙げられる。また、表層に導電体を積層した積層体としては、紙、絶縁性高分子、ガラス等に前記導電体を積層した積層体が挙げられる。
Examples of the metal include a metal or an alloy mainly containing at least one selected from tantalum, niobium, and aluminum.
Examples of inorganic semiconductors include metal oxides such as lead dioxide, molybdenum dioxide, tungsten dioxide, niobium monoxide, tin dioxide, and zirconium monoxide, and polypyrrole, polythiophene, polyaniline, and substituted products having these polymer skeletons as organic semiconductors, Examples thereof include conductive polymers such as copolymers, complexes of tetracyanoquinodimethane and tetrathiotetracene, and low-molecular complexes such as tetracyanoquinodimethane (TCNQ) salts. Moreover, as a laminated body which laminated | stacked the conductor on the surface layer, the laminated body which laminated | stacked the said conductor on paper, insulating polymer, glass, etc. is mentioned.
導電体として金属を使用する場合、ＬＣ値を低下させる等のコンデンサ特性の改良のために金属の一部を、炭化、燐化、ホウ素化、窒化及び硫化から選ばれる少なくとも１種の処理を行ってから使用してもよい。 When a metal is used as a conductor, a part of the metal is subjected to at least one treatment selected from carbonization, phosphation, boronation, nitridation and sulfidation in order to improve the capacitor characteristics such as lowering the LC value. You may use after.
導電体の形状は特に限定されず、箔状、板状、棒状、あるいは粉状の導電体を成形し、または成形後に焼結して用いられる。導電体表面をエッチング等で処理して、微細な細孔を有するようにしてもよい。コンデンサの単位体積当たりの容量が大きくなることから、粉状の導電体の焼結体形状のもの、または表面に微細な細孔を有するようにして導電体の表面積を増加させたものがとりわけ好ましい。粉状の導電体を成形または成形後焼結した場合には、成形時の圧力を適当に選択することによって、成形または焼結後の導電体の内部に微小な細孔を設けることができる。 The shape of the conductor is not particularly limited, and a foil-like, plate-like, rod-like, or powder-like conductor is molded, or sintered after molding. The conductor surface may be processed by etching or the like to have fine pores. Since the capacity per unit volume of the capacitor is increased, a powdery conductor-shaped sintered body or a conductor whose surface area is increased by having fine pores on the surface is particularly preferable. . When a powdery conductor is molded or sintered after molding, fine pores can be provided in the molded or sintered conductor by appropriately selecting the pressure during molding.
本発明の方法は、半導体の含浸がしにくい導電体、すなわち細孔が微小で細孔の奥行きが長い導電体に利用すると効果的である。例えば、焼結体形状の導電体の場合、タンタル金属粉材料の焼結体ではＣＶ値（電解液で測定したときの容量と化成電圧の積）が１０万μＦ・Ｖ／ｇ以上、ニオブ金属粉材料の焼結体ではＣＶ値が１５万μＦ・Ｖ／ｇ以上で、各々の大きさが５ｍｍ3以上の導電体について応用すると効果的である。また、エッチングされた箔形状の導電体の場合、1000μＦ・Ｖ／ｃｍ2以上でエッチングによる細孔深さが２００μｍ以上の導電体に応用すると効果的である。 The method of the present invention is effective when used for a conductor that is difficult to be impregnated with a semiconductor, that is, a conductor having a small pore and a long depth. For example, in the case of a sintered body-shaped conductor, the sintered body of tantalum metal powder material has a CV value (product of capacity and formation voltage when measured with an electrolytic solution) of 100,000 μF · V / g or more, niobium metal It is effective to apply to a conductor having a CV value of 150,000 μF · V / g or more and a size of 5 mm 3 or more in the sintered body of the powder material. Further, in the case of an etched foil-shaped conductor, it is effective to apply to a conductor having 1000 μF · V / cm 2 or more and a pore depth by etching of 200 μm or more.
導電体には引き出しリードを直接接続することが可能であるが、粉状の導電体を成形または成形後焼結した形状とする場合は、成形時に別途用意した引き出しリード（リード線またはリード箔）の一部を導電体と共に成形し、引き出しリードの成形外部の箇所を、コンデンサの一方の電極の引き出しリードとすることもできる。 The lead can be directly connected to the conductor, but if the powdered conductor is molded or formed into a sintered shape after forming, the lead drawn separately (lead wire or lead foil) prepared at the time of molding It is also possible to form a part of the lead with the conductor, and to place the lead lead outside of the lead lead as a lead lead for one electrode of the capacitor.
本発明の導電体表面に形成される誘電体層としては、Ｔａ2Ｏ5、Ａｌ2Ｏ3、ＴｉＯ2、Ｎｂ2Ｏ5等の金属酸化物から選ばれる少なくとも１つを主成分とする誘電体層、セラミックコンデンサやフイルムコンデンサの分野で従来公知の誘電体層が挙げられる。前者の金属酸化物から選ばれる少なくとも１つを主成分とする誘電体層の場合、金属酸化物の金属元素を有する前記導電体を鉱酸や有機酸を含有した電解液中で化成することによって誘電体層を形成すると、得られるコンデンサは、極性を持つ電解コンデンサとなる。セラミックコンデンサやフイルムコンデンサで従来公知の誘電体層の例としては、特開昭63-29919号公報、特開昭63-34917号公報に記載された誘電体層を挙げることができる。また、金属酸化物から選ばれる少なくとも１つを主成分とする誘電体層やセラミックコンデンサやフイルムコンデンサで従来公知の誘電体層を複数積層して使用してもよい。また、金属酸化物から選ばれる少なくとも１つを主成分とする誘電体やセラミックコンデンサやフイルムコンデンサで従来公知の誘電体を混合した誘電体層でもよい。 The dielectric layer formed on the surface of the conductor according to the present invention is a dielectric mainly composed of at least one selected from metal oxides such as Ta 2 O 5 , Al 2 O 3 , TiO 2 , and Nb 2 O 5. Conventionally known dielectric layers in the field of body layers, ceramic capacitors and film capacitors can be mentioned. In the case of a dielectric layer mainly composed of at least one selected from the former metal oxides, the conductor having the metal element of the metal oxide is formed in an electrolytic solution containing a mineral acid or an organic acid. When the dielectric layer is formed, the obtained capacitor becomes an electrolytic capacitor having polarity. Examples of conventionally known dielectric layers for ceramic capacitors and film capacitors include the dielectric layers described in JP-A-63-29919 and JP-A-63-34917. Further, a plurality of conventionally known dielectric layers may be used by laminating a dielectric layer mainly composed of at least one selected from metal oxides, ceramic capacitors, and film capacitors. Further, a dielectric layer in which at least one selected from metal oxides as a main component, a dielectric layer in which a conventionally known dielectric material is mixed with a ceramic capacitor, or a film capacitor may be used.
誘電体層上に電解液中で通電手法によって半導体層を形成して他方の電極とするが、本発明においては、半導体層の形成割合を高めるための前処理として、通電前に細孔内に半導体層形成用前駆体を含浸し、細孔内の半導体層形成用前駆体濃度を電解液中の半導体層形成用前駆体より高濃度にしておくことが重要である。 A semiconductor layer is formed on the dielectric layer by an energization method in an electrolyte solution to form the other electrode. In the present invention, as a pretreatment for increasing the formation ratio of the semiconductor layer, It is important to impregnate the semiconductor layer forming precursor so that the concentration of the semiconductor layer forming precursor in the pores is higher than the concentration of the semiconductor layer forming precursor in the electrolytic solution.
半導体層形成用前駆体とは、通電により半導体となる原料物質のことであり、例えば後述する有機半導体の場合、原料モノマーまたはオリゴマーであり、無機半導体の場合、通電によって酸化または還元されて、無機半導体になる化合物のことである。半導体層形成用前駆体は、２種以上を使用してもよい。また、半導体層形成用前駆体と共に、後述するドーパント（例えば、アリールスルホン酸または塩、アルキルスルホン酸または塩、各種高分子スルホン酸または塩、及び前記の各置換基を有する化合物等の公知のドーパント）を１種以上加えておいてもよい。 The precursor for forming a semiconductor layer is a raw material substance that becomes a semiconductor when energized. For example, in the case of an organic semiconductor described later, it is a raw material monomer or oligomer. A compound that becomes a semiconductor. Two or more kinds of semiconductor layer forming precursors may be used. In addition to the precursor for forming a semiconductor layer, a dopant described later (for example, arylsulfonic acid or salt, alkylsulfonic acid or salt, various polymer sulfonic acids or salts, and known dopants such as compounds having the above substituents) ) May be added in advance.
半導体層形成用前駆体を、表面に誘電体層を形成した導電体の細孔内に含浸する方法としては、例えば、半導体層形成用前駆体を適当な溶媒に溶かした溶液を含浸する方法を挙げることができる。含浸後、導電体を空気中に放置するか乾燥することにより溶媒量を任意に管理して、導電体細孔内の半導体層形成用前駆体濃度を高濃度にすることができる。溶媒を完全に飛散させてもよい。半導体層形成用前駆体が室温または加熱して液体である場合には、溶媒を完全に飛散させたものを含浸させることも可能である。 Examples of the method of impregnating the semiconductor layer forming precursor in the pores of the conductor having the dielectric layer formed on the surface include a method of impregnating a solution obtained by dissolving the semiconductor layer forming precursor in an appropriate solvent. Can be mentioned. After the impregnation, the amount of the solvent can be controlled arbitrarily by leaving the conductor in the air or drying to increase the concentration of the precursor for forming the semiconductor layer in the pores of the conductor. The solvent may be completely scattered. When the semiconductor layer forming precursor is at room temperature or heated to be liquid, it can be impregnated with a solvent completely dispersed.
電解液中での通電による従来の半導体層形成方法の場合には、半導体層形成用前駆体が溶解した電解液に導電体を浸漬して通電するために、導電体細孔内と電解液中の半導体層形成用前駆体濃度はおおよそ等しくなるが、本発明では、上述したように通電前に細孔内に半導体層形成用前駆体を高濃度に含浸しておくため細孔内の半導体層形成用前駆体濃度が、電解液中での半導体層形成用前駆体濃度よりも大きくなる。導電体細孔内の半導体層形成用前駆体濃度が大きい状態で通電手法により半導体層を形成すると、従来の方法より細孔内で半導体が多量に形成され、その結果作製されたコンデンサの半導体含浸率は８７％以上、好ましくは９０％以上という良好なものとなる。 In the case of a conventional method for forming a semiconductor layer by energization in an electrolytic solution, the conductor is immersed in the electrolytic solution in which the precursor for forming the semiconductor layer is dissolved, and the electric current is immersed in the conductor pores and in the electrolytic solution. However, in the present invention, since the semiconductor layer forming precursor is impregnated at a high concentration in the pores before energization as described above, the semiconductor layer in the pores is formed in the present invention. The forming precursor concentration is higher than the semiconductor layer forming precursor concentration in the electrolytic solution. When a semiconductor layer is formed by a current application method with a high concentration of the precursor for forming the semiconductor layer in the pores of the conductor, a larger amount of semiconductor is formed in the pores than in the conventional method. The rate is 87% or higher, preferably 90% or higher.
工業的なレベルで多数個の導電体に同時に半導体層を形成する場合、電解液の溶媒としては、通電時の火災等の安全を考慮して水が使用されるが、水への溶解度が小さな半導体層形成用前駆体、例えば有機半導体形成用の前駆体を使用する時に本発明の方法は、大きな効力を発揮することができる。一例を挙げると、ピロールや、３，４−エチレンジオキシチオフェンなどのモノマーを使用して導電性高分子からなる半導体層を形成する場合、モノマーの水への溶解度が比較的小さいので、予めアルコール等の溶解度が大きな溶媒に溶解しておき通電前に、導電体細孔内に含浸した後アルコールを飛散させて細孔内にモノマーを多量に残るようにして、引き続き行う水溶媒電解液中での通電による半導体層形成で含浸率が良好な半導体層を形成することができる。 When forming a semiconductor layer on a large number of conductors simultaneously on an industrial level, water is used as the solvent for the electrolyte in consideration of safety such as fire during energization, but the solubility in water is small. When using a precursor for forming a semiconductor layer, for example, a precursor for forming an organic semiconductor, the method of the present invention can exert a great effect. For example, when a semiconductor layer made of a conductive polymer is formed using a monomer such as pyrrole or 3,4-ethylenedioxythiophene, the solubility of the monomer in water is relatively small. In a water-solvent electrolytic solution that is continuously used, after dissolving in a solvent having a high solubility, etc. and impregnating in the pores of the conductor before passing electricity, the alcohol is scattered to leave a large amount of monomer in the pores. A semiconductor layer having a good impregnation rate can be formed by forming a semiconductor layer by energization of the above.
本発明で、通電前に細孔内に半導体層形成用前駆体を含浸した後に、通電手法により形成する半導体としては、有機半導体及び無機半導体から選ばれる少なくとも１種の化合物が挙げられる。 In the present invention, the semiconductor formed by the energization technique after impregnating the precursor for forming a semiconductor layer in the pores before energization includes at least one compound selected from an organic semiconductor and an inorganic semiconductor.
有機半導体の具体例としては、下記一般式（１）または（２）で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体が挙げられる。 Specific examples of the organic semiconductor include an organic semiconductor mainly composed of a conductive polymer obtained by doping a polymer including a repeating unit represented by the following general formula (1) or (2) with a dopant.
式（１）及び（２）において、Ｒ1〜Ｒ4はは各々独立して、水素原子、炭素数１〜６のアルキル基または炭素数１〜６のアルコキシ基を表し、Ｘは酸素、イオウまたは窒素原子を表し、Ｒ5はＸが窒素原子のときのみ存在して水素原子または炭素数１〜６のアルキル基を表し、Ｒ1とＲ2及びＲ3とＲ4は、互いに結合して環状になっていてもよい。 In the formulas (1) and (2), R 1 to R 4 each independently represents 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 a nitrogen atom, R 5 is present only when X is a nitrogen atom and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 and R 3 and R 4 are bonded to each other. It may be annular.
さらに、本発明においては、前記一般式（１）で示される繰り返し単位を含む導電性高分子は、好ましくは下記一般式（３）で示される構造単位を繰り返し単位として含む導電性高分子が挙げられる。 Furthermore, in the present invention, the conductive polymer containing a repeating unit represented by the general formula (1) is preferably a conductive polymer containing a structural unit represented by the following general formula (3) as a repeating unit. It is done.
式中、Ｒ6及びＲ7は各々独立して、水素原子、炭素数１〜６の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、または該アルキル基が互いに任意の位置で結合して、２つの酸素原子を含む少なくとも１つ以上の５〜７員環の飽和炭化水素の環状構造を形成する置換基を表す。また、前記環状構造には置換されていてもよいビニレン結合を有するもの、置換されていてもよいフェニレン構造のものも含まれる。 In the formula, R 6 and R 7 are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl group is bonded to each other at an arbitrary position. And a substituent that forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen atoms. The cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted.
このような化学構造を含む導電性高分子は、荷電されており、ドーパントがドープされる。ドーパントは特に限定されず公知のドーパントが使用できる。 A conductive polymer containing such a chemical structure is charged and doped with a dopant. A dopant is not specifically limited, A well-known dopant can be used.
式（１）〜（３）で示される繰り返し単位を含む高分子としては、例えば、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、及びこれらの置換誘導体や共重合体などが挙げられる。中でもポリピロール、ポリチオフェン及びこれらの置換誘導体（例えば、ポリ（３，４−エチレンジオキシチオフェン）等）が好ましい。 Examples of the polymer containing the repeating unit represented by the formulas (1) to (3) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof. Etc. Of these, polypyrrole, polythiophene, and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene)) are preferable.
式（１）〜（３）で示される繰り返し単位を含む高分子半導体層形成用前駆体としてはアニリン誘導体、フェノール誘導体、チオフェノール誘導体、チオフェン誘導体、フラン誘導体、及びピロール誘導体が挙げられる。これらの中でも、ピロール、１−メチルピロール、３−メチルピロール、及び３，４−エチレンジオキシチオフェンが挙げられる。 Examples of the precursor for forming a polymer semiconductor layer containing a repeating unit represented by the formulas (1) to (3) include aniline derivatives, phenol derivatives, thiophenol derivatives, thiophene derivatives, furan derivatives, and pyrrole derivatives. Among these, pyrrole, 1-methylpyrrole, 3-methylpyrrole, and 3,4-ethylenedioxythiophene are mentioned.
無機半導体の具体例として、二酸化モリブデン、二酸化タングステン、二酸化鉛、二酸化マンガン等から選ばれる少なくとも１種の化合物が挙げられる。これらの無機半導体層形成用前駆体の具体例としては、酢酸鉛、酢酸マンガン、モリブデン酸ナトリウム、タングステン酸ナトリウム等が挙げられる。 Specific examples of the inorganic semiconductor include at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, manganese dioxide and the like. Specific examples of these inorganic semiconductor layer forming precursors include lead acetate, manganese acetate, sodium molybdate, and sodium tungstate.
上記有機半導体及び無機半導体として、電導度１０-2〜１０3Ｓ／ｃｍの範囲のものを使用すると、作製したコンデンサのＥＳＲ値が小さくなり好ましい。 When the organic semiconductor and the inorganic semiconductor have a conductivity in the range of 10 −2 to 10 3 S / cm, the ESR value of the manufactured capacitor is preferably reduced.
前述した半導体層は、通電操作を行わない純粋な化学反応（溶液反応、気相反応及びそれらの組み合わせ）によって形成したり、通電手法によって形成したり、あるいはこれらの方法を組み合わせて形成するが、本発明では、半導体層形成工程で少なくとも１回は通電手法を採用する。 The semiconductor layer described above is formed by a pure chemical reaction (solution reaction, gas phase reaction and a combination thereof) without performing an energization operation, formed by an energization method, or a combination of these methods. In the present invention, the energization method is adopted at least once in the semiconductor layer forming step.
上記半導体層を導電体に形成する場合の一例について説明する。半導体層形成用前駆体が含浸された導電体を別途用意した半導体層形成溶液に漬け、導電体を陽極として、もしくは、導電体に接触してあるいは近傍に配置された外部電極を陽極として半導体層形成溶液中に設けられた陰極板に対して通電することにより半導体層が形成される。通電手法として定電圧法、定電流法またはこれらの組み合わせがあるが、多数個の導電体を同時に通電して半導体層を形成する場合は、半導体層を安定に形成するために定電流法を用いることが好ましい。 An example in which the semiconductor layer is formed on a conductor will be described. A semiconductor layer impregnated with a semiconductor layer forming solution prepared by impregnating a conductor impregnated with a precursor for forming a semiconductor layer and using the conductor as an anode or an external electrode in contact with or near the conductor as an anode A semiconductor layer is formed by energizing a cathode plate provided in the forming solution. There are a constant voltage method, a constant current method, or a combination of these as a method of energization. When a semiconductor layer is formed by simultaneously energizing a large number of conductors, the constant current method is used to stably form the semiconductor layer. It is preferable.
通電時間や所定電流値は、使用する導電体の種類、大きさ、密度、形成した誘電体層の種類、厚さ、形成する半導体層の種類等によって変化するために、予備実験によって決定される。予備実験の１手法として、半導体層の質量を管理することによって所定定電流値の良否を判断することができる。予め各定電流値で通電時間に対する半導体質量のプロットを行い、このプロットが飽和値に達した半導体質量が最大になるときの定電流値を選択する方法を挙げることができる。 The energization time and the predetermined current value vary depending on the type, size, and density of the conductor to be used, the type and thickness of the formed dielectric layer, the type of the semiconductor layer to be formed, etc., and thus are determined by preliminary experiments. . As one method of the preliminary experiment, it is possible to determine whether the predetermined constant current value is good or not by managing the mass of the semiconductor layer. A method of plotting the semiconductor mass with respect to the energization time at each constant current value in advance and selecting the constant current value when the semiconductor mass at which this plot has reached the saturation value is maximized can be mentioned.
また、定電流法を用いた場合、通電時の初期の電圧値は、所定定電流値によって決まる値をもつ。前述した化成によって形成した誘電体層の場合、初期電圧値は、化成電圧以上になることもある。 When the constant current method is used, the initial voltage value at the time of energization has a value determined by a predetermined constant current value. In the case of the dielectric layer formed by the chemical conversion described above, the initial voltage value may be equal to or higher than the chemical conversion voltage.
半導体層形成溶液には、通電により半導体となる原料や、場合によっては前述したドーパント（例えば、アリールスルホン酸または塩、アルキルスルホン酸または塩、各種高分子スルホン酸または塩、及び前記の各置換基を有する化合物等の公知のドーパント）が溶解していて通電することにより誘電体層上に半導体層が形成される。
本発明では、通電前に導電体の細孔内に半導体層形成用前駆体を高濃度で含浸させることができるので、半導体層形成溶液に半導体となる原料を入れないでおくことも可能である。
The semiconductor layer forming solution includes a raw material that becomes a semiconductor when energized, and in some cases, the above-described dopants (for example, aryl sulfonic acid or salt, alkyl sulfonic acid or salt, various polymer sulfonic acids or salts, and each of the above substituents A semiconductor layer is formed on the dielectric layer by dissolving a known dopant (such as a compound having) and applying current.
In the present invention, since a precursor for forming a semiconductor layer can be impregnated at a high concentration in the pores of the conductor before energization, it is possible not to put a raw material to be a semiconductor into the semiconductor layer forming solution. .
半導体層形成溶液の温度・ｐＨは、予備実験によって半導体層が形成しやすい条件が決定されるが、半導体層形成溶液が空気酸化されて劣化することを緩和するために低温で通電を行うことが望ましい場合がある。半導体層形成溶液中に設ける陰極板は、通電時の対陰極として使用されるもので、導電性材料、特に金属の箔や板が用いられる。複数個の導電体に同時に半導体層を形成する場合は、少なくとも１箇所の給電部に電気的に接続している複数枚の陰極板を使用して、半導体層形成溶液に漬けられた複数個の導電体全てに均一に配電できるように配置することが好ましい。 The temperature and pH of the semiconductor layer forming solution are determined under conditions that facilitate the formation of the semiconductor layer by preliminary experiments. However, it is necessary to energize the semiconductor layer forming solution at a low temperature in order to mitigate deterioration due to air oxidation. It may be desirable. The cathode plate provided in the semiconductor layer forming solution is used as an anti-cathode during energization, and a conductive material, particularly a metal foil or plate is used. In the case of simultaneously forming a semiconductor layer on a plurality of conductors, a plurality of cathode plates electrically connected to at least one power feeding portion are used, and a plurality of submersed in a semiconductor layer forming solution are used. It is preferable to arrange the conductors so that they can be evenly distributed.
半導体層形成溶液は、溶液が均一になるように撹拌して使用してもよいし、撹拌しないで用いてもよい。また、半導体層形成溶液が使用される容器は、半導体層形成溶液が常に流れ出るような大きさに設計されていてもよく、あるいは、半導体層形成溶液の体積以上であってもよい。 The semiconductor layer forming solution may be used with stirring so that the solution becomes uniform, or may be used without stirring. Further, the container in which the semiconductor layer forming solution is used may be designed to have a size such that the semiconductor layer forming solution always flows out, or may be larger than the volume of the semiconductor layer forming solution.
本発明においては、通電した後に、半導体層が形成されたことによって生じる誘電体層の微小な欠陥を修復するために、再化成（誘電体層を化成で形成しない場合は、１回目の化成）を行ってもよい。また、通電と再化成を複数回繰り返してもよいし、繰り返し時の通電条件を変更してもよい。通常、通電を止める場合、半導体層形成溶液から導電体を引き上げて洗浄・乾燥を行うが、通電・通電停止・洗浄・乾燥工程の繰り返しを複数回行ってから再化成工程に入れてもよい。理由は定かでないが、続けて通電を行うよりも通電時間を同じにして通電・通電停止・洗浄・乾燥を行うことを繰り返すほうが、半導体層質量が上昇する場合がある。前記通電を複数回行う場合は、各通電の前に、または任意の通電の前に導電体の細孔内に半導体層形成用前駆体を含浸しておくことが好ましい。 In the present invention, after energization, in order to repair a minute defect in the dielectric layer caused by the formation of the semiconductor layer, re-forming (the first forming if the dielectric layer is not formed by conversion) May be performed. Further, the energization and re-formation may be repeated a plurality of times, or the energization conditions at the time of repetition may be changed. Usually, when energization is stopped, the conductor is pulled up from the semiconductor layer forming solution to perform cleaning / drying. However, the energization / energization stop / cleaning / drying process may be repeated a plurality of times before entering the re-forming process. The reason is not clear, but the mass of the semiconductor layer may be increased by repeating energization, energization stop, cleaning, and drying with the same energization time rather than continuing energization. When the energization is performed a plurality of times, it is preferable to impregnate the semiconductor layer forming precursor in the pores of the conductor before each energization or before any energization.
再化成は、前述した化成による誘電体層の形成方法と同様にして行うことができる。再化成電圧は、化成電圧以下で行われる。 The re-chemical conversion can be performed in the same manner as the above-described dielectric layer forming method. The re-forming voltage is performed below the forming voltage.
本発明では、前述した方法等で形成された半導体層の上に電極層が設けられる。電極層は、例えば、導電ペーストの固化、メッキ、金属蒸着、耐熱性の導電樹脂フィルムの付着等により形成することができる。導電ペーストとしては、銀ペースト、銅ペースト、アルミニウムペースト、カーボンペースト、ニッケルペースト等が好ましい。これらは１種を用いても２種以上を用いてもよい。２種以上を用いる場合は混合してもよく、または別々の層として重ねてもよい。導電ペーストを適用した後、空気中に放置するか、または加熱して固化させる。固化後の導電ペースト層の厚さは、一層あたり通常約0.1〜約２００μｍである。
導電性ペーストは、通常導電粉を４０〜９７質量％含む。４０質量％未満であると作製した導電ペーストの導電性が小さく、９７質量％を超えると、導電ペーストの接着性が不良になるために好ましくない。導電ペーストに前述した半導体層を形成する導電性高分子や金属酸化物の粉を混合して使用してもよい。
In the present invention, an electrode layer is provided on the semiconductor layer formed by the above-described method or the like. The electrode layer can be formed, for example, by solidification of a conductive paste, plating, metal deposition, adhesion of a heat-resistant conductive resin film, or the like. As the conductive paste, silver paste, copper paste, aluminum paste, carbon paste, nickel paste and the like are preferable. These may be used alone or in combination of two or more. When using 2 or more types, they may be mixed or may be stacked as separate layers. After applying the conductive paste, it is left in the air or heated to solidify. The thickness of the conductive paste layer after solidification is usually about 0.1 to about 200 μm per layer.
The conductive paste usually contains 40 to 97% by mass of conductive powder. If it is less than 40% by mass, the conductivity of the produced conductive paste is small, and if it exceeds 97% by mass, the adhesiveness of the conductive paste becomes poor, which is not preferable. You may mix and use the conductive polymer and metal oxide powder which form the semiconductor layer mentioned above in the electrically conductive paste.
メッキとしては、ニッケルメッキ、銅メッキ、銀メッキ、金メッキ、アルミニウムメッキ等が挙げられる。また蒸着金属としては、アルミニウム、ニッケル、銅、銀、金等が挙げられる。 Examples of the plating include nickel plating, copper plating, silver plating, gold plating, and aluminum plating. Examples of the deposited metal include aluminum, nickel, copper, silver, and gold.
具体的には、例えば半導体層が形成された導電体の上にカーボンペースト、銀ペーストを順次積層し電極層が形成される。 Specifically, for example, an electrode layer is formed by sequentially laminating a carbon paste and a silver paste on a conductor on which a semiconductor layer is formed.
このようにして電極層まで積層して陰極部を形成したコンデンサ素子が作製される。
以上のような構成の本発明のコンデンサ素子は、例えば、樹脂モールド、樹脂ケース、金属性の外装ケース、樹脂のディッピング、ラミネートフイルムによる外装などの外装により各種用途のコンデンサ製品とすることができる。これらの中でも、とりわけ樹脂モールド外装を行ったチップ状コンデンサが、小型化と低コスト化が簡単に行えるので好ましい。
In this way, a capacitor element in which the cathode layer is formed by stacking up to the electrode layer is manufactured.
The capacitor element of the present invention having the above-described configuration can be made into a capacitor product for various uses by, for example, an exterior such as a resin mold, a resin case, a metallic exterior case, a resin dipping, or an exterior with a laminate film. Among these, a chip-shaped capacitor with a resin mold is particularly preferable because it can be easily reduced in size and cost.
樹脂モールド外装に使用される樹脂の種類としては、エポキシ樹脂、フェノール樹脂、アルキッド樹脂等固体電解コンデンサの封止に使用される公知の樹脂が採用できるが、各樹脂とも一般に市販されている低応力樹脂を使用すると、封止時におきるコンデンサ素子への封止応力の発生を緩和することができるために好ましい。また、樹脂封口するための製造機としてトランスファーマシンが好んで使用される。 As the type of resin used for the resin mold exterior, known resins used for sealing solid electrolytic capacitors such as epoxy resin, phenol resin, alkyd resin, etc. can be adopted, but each resin is generally commercially available with low stress. Use of a resin is preferable because the generation of sealing stress on the capacitor element that occurs during sealing can be reduced. A transfer machine is preferably used as a manufacturing machine for sealing the resin.
このように作製されたコンデンサは、電極層形成時や外装時の熱的及び／または物理的な誘電体層の劣化を修復するために、エージング処理を行ってもよい。エージング方法は、コンデンサに所定の電圧（通常、定格電圧の２倍以内）を印加することによって行われる。エージング時間や温度は、コンデンサの種類、容量、定格電圧によって最適値が変化するので予め実験によって決定されるが、通常、時間は、数分から数日、温度は電圧印加冶具の熱劣化を考慮して３００℃以下で行われる。エージングの雰囲気は、空気中でもよいし、Ａｒ、Ｎ2、Ｈｅ等のガス中でもよい。また、減圧、常圧、加圧下のいずれの条件で行ってもよいが、水蒸気を供給しながら、または水蒸気を供給した後に前記エージングを行うと誘電体層の安定化が進む場合がある。水蒸気の供給方法の１例として、エージングの炉中に置いた水溜めから熱により水蒸気を供給する方法が挙げられる。 The capacitor thus fabricated may be subjected to an aging treatment in order to repair the deterioration of the thermal and / or physical dielectric layer at the time of electrode layer formation or exterior. The aging method is performed by applying a predetermined voltage (usually within twice the rated voltage) to the capacitor. Aging time and temperature are determined in advance by experiment because optimum values vary depending on the type, capacity, and rated voltage of the capacitor.Normally, the time is several minutes to several days, and the temperature takes into account the thermal deterioration of the voltage application jig. At 300 ° C. or lower. The aging atmosphere may be air or a gas such as Ar, N 2 , or He. Moreover, although it may be performed under any conditions of reduced pressure, normal pressure, and increased pressure, stabilization of the dielectric layer may progress if the aging is performed while supplying water vapor or after supplying water vapor. One example of a method for supplying water vapor is a method for supplying water vapor by heat from a water reservoir placed in an aging furnace.
電圧印加方法は、直流、任意の波形を有する交流、直流に重畳した交流やパルス電流等の任意の電流を流すように設計することができる。エージングの途中に一旦電圧印加を止め、再度電圧印加を行うことも可能である。 The voltage application method can be designed to flow an arbitrary current such as a direct current, an alternating current having an arbitrary waveform, an alternating current superimposed on the direct current, or a pulse current. It is also possible to once stop the voltage application during the aging and apply the voltage again.
本発明で製造されたコンデンサは、例えば、中央演算回路や電源回路等の高容量で低ＥＳＲのコンデンサを必要とする回路に好ましく用いることができる。これらの回路は、パソコン、サーバー、カメラ、ゲーム機、ＤＶＤ、ＡＶ機器、携帯電話等の各種デジタル機器や、各種電源等の電子機器に利用可能である。本発明で製造されたコンデンサは、高容量でＥＳＲ性能がよいことから、これを用いることにより性能が良好な電子回路及び電子機器を得ることができる。 The capacitor manufactured by the present invention can be preferably used for a circuit that requires a high capacity and low ESR capacitor, such as a central processing circuit and a power supply circuit. These circuits can be used in various digital devices such as personal computers, servers, cameras, game machines, DVDs, AV devices, and mobile phones, and electronic devices such as various power supplies. Since the capacitor manufactured according to the present invention has a high capacity and good ESR performance, it is possible to obtain an electronic circuit and an electronic device with good performance by using the capacitor.
本発明は、表面に誘電体層を形成した細孔を有する導電体を一方の電極とし、電解液中で通電手法によって導電体上に形成した半導体層を他方の電極とするコンデンサの製造方法において、通電前に細孔内に半導体層形成用前駆体を含浸し、細孔内の半導体層形成用前駆体濃度を電解液中の半導体層形成用前駆体より高濃度にすることを特徴とするコンデンサの製造方法を提供したものである。 The present invention relates to a method of manufacturing a capacitor in which a conductor having pores with a dielectric layer formed on the surface is used as one electrode, and a semiconductor layer formed on the conductor by an energization technique in an electrolyte is the other electrode. The semiconductor layer forming precursor is impregnated in the pores before energization, and the concentration of the semiconductor layer forming precursor in the pores is higher than the concentration of the semiconductor layer forming precursor in the electrolyte. A method for manufacturing a capacitor is provided.
本発明によれば、容量出現率が良好なために高容量で低ＥＳＲであるコンデンサを得ることができる。 According to the present invention, a capacitor having a high capacity and a low ESR can be obtained because the capacity appearance rate is good.
以下、本発明の具体例についてさらに詳細に説明するが、以下の例により本発明は限定されるものではない。 Hereinafter, specific examples of the present invention will be described in more detail, but the present invention is not limited to the following examples.
実施例１：
ＣＶ（容量と化成電圧の積）１４万μＦ・Ｖ／ｇのタンタル粉と0.24ｍｍφのタンタルリード線を使用して成形し、大きさ4.5×1.0×1.5ｍｍの焼結体を作製した（焼結温度1300℃、焼結時間２０分、焼結体密度6.2ｇ／ｃｍ3、焼結体の1.0×1.5ｍｍの面中央部に垂直にＴａリード線が焼結体内部に４ｍｍ入り、外部に１０ｍｍ出るように植設されている。）。
別途用意した長さ２５０ｍｍ幅３０ｍｍ厚さ２ｍｍのポリイミド製樹脂板（印刷配線により、表面に３２個の導電体用の接続端子と定電流ダイオードの各アノードを接続して板左側の給電端子に至る回路、及び裏面に表面の導電体用の接続端子とのみ電気的に接続し、整流ダイオードを介して板右側の化成用給電端子に至る回路が設けられている）に左右３０ｍｍを残して前記焼結体３２個の各リード線を等間隔かつ等寸に整列接続した。このような樹脂板２０枚を５ｍｍ間隔に並列に並べ、樹脂板の左右１５ｍｍのところで電気的に接続するように金属製フレーム（左右中央部が絶縁されていて、樹脂板に設けた表裏左右の給電端子が絶縁される）に配設した。金属製フレームに焼結体が６４０個等間隔に配置されていて、各焼結体はリード線を通して金属性フレームに設けた左右の給電端子に電気的に接続されている。該金属製フレームに連なった焼結体を１ロットとして以下の各種操作を行った。
Example 1:
CV (product of capacity and conversion voltage) 140,000μF · V / g tantalum powder and 0.24mmφ tantalum lead wire were molded to produce a sintered body with a size of 4.5 × 1.0 × 1.5mm (baked) The sintering temperature is 1300 ° C, the sintering time is 20 minutes, the sintered body density is 6.2 g / cm 3 , the Ta lead wire enters 4 mm inside the sintered body perpendicularly to the center of the 1.0 x 1.5 mm surface of the sintered body, and the outside It is planted so that it can come out 10mm.)
Separately prepared polyimide resin plate with a length of 250 mm, a width of 30 mm, and a thickness of 2 mm (through printed wiring, the connection terminals for 32 conductors and the anodes of the constant current diodes are connected to the power supply terminal on the left side of the plate. The circuit and a circuit which is electrically connected only to the conductor connection terminal on the front surface on the back surface and reaches the chemical feed terminal on the right side of the plate via a rectifier diode) The 32 lead wires were aligned and connected at equal intervals and equal dimensions. Twenty such resin plates are arranged in parallel at intervals of 5 mm, and are made of metal frames (insulated at the left and right central portions, and provided on the resin plate on the front, back, left and right sides so as to be electrically connected at 15 mm on the left and right sides of the resin plate. The power supply terminal is insulated). 640 sintered bodies are arranged at equal intervals on the metal frame, and each sintered body is electrically connected to left and right power supply terminals provided on the metal frame through lead wires. The sintered body connected to the metal frame was used as one lot, and the following various operations were performed.
該焼結体を１％燐酸水溶液中にリード線の一部を除いて浸漬し、リード線を陽極とし、水溶液中に配置したＴａ陰極板との間に９Ｖを印加し、８０℃で８時間化成してＴａ2Ｏ5からなる誘電体酸化皮膜層を形成した。この焼結体のリード線を除いて、モリブデン酸アンモニウム３０ｇと硫酸ニッケル６水和物２００ｇを水８００ｇに溶解させ１Ｎ水酸化アンモニウムを２５０ｍｌ加えて作製した溶液に浸漬し、リード線側を陽極に、前記溶液中に設けたＴａ板を陰極として室温下2.2Ｖで１５０分電解反応した。
その後焼結体を溶液から引き上げ水洗乾燥した後、0.1％燐酸水溶液中で８Ｖ、８０℃、３０分の再化成を行った。再化成終了後、焼結体を水洗・乾燥を行った。
The sintered body was immersed in a 1% phosphoric acid aqueous solution except for a part of the lead wire, 9 V was applied between the lead wire as an anode and a Ta cathode plate placed in the aqueous solution at 80 ° C. for 8 hours. Then, a dielectric oxide film layer made of Ta 2 O 5 was formed. Excluding the lead wire of this sintered body, 30 g of ammonium molybdate and 200 g of nickel sulfate hexahydrate were dissolved in 800 g of water and immersed in a solution prepared by adding 250 ml of 1N ammonium hydroxide, and the lead wire side was used as the anode. The Ta plate provided in the solution was subjected to an electrolytic reaction at 2.2 V at room temperature for 150 minutes using the Ta plate as a cathode.
Thereafter, the sintered body was pulled out of the solution, washed with water and dried, and then re-formed in a 0.1% phosphoric acid aqueous solution at 8 V, 80 ° C. for 30 minutes. After completion of re-chemical conversion, the sintered body was washed with water and dried.
次にリード線を除いて焼結体を３，４−エチレンジオキシチオフェンモノマーの１５％エタノール溶液に浸漬し引き上げ、８０℃で乾燥しエタノールを飛散させ、焼結体の細孔内に半導体層形成用前駆体を含浸させた。 Next, the lead wire is removed and the sintered body is dipped in a 15% ethanol solution of 3,4-ethylenedioxythiophene monomer and pulled up, dried at 80 ° C. to disperse ethanol, and the semiconductor layer is placed in the pores of the sintered body. The forming precursor was impregnated.
続いてリード線を除いて焼結体をエチレンジオキシチオフェン（モノマーが飽和濃度以下となる水溶液として使用）とアントラキノンスルホン酸が溶解した水と２０％エチレングリコール電解液（半導体層形成溶液）に漬け、金属製フレームの表面左側の給電端子を利用しリード線から電解液中に配置した負極のタンタル電極板との間に室温で２０ｍＡの直流定電流を３０分流し、半導体層を形成するための通電を行った。引き上げ水洗・エタノール洗浄・乾燥した後、金属製フレームの裏面右側の給電端子を利用し、１％燐酸水溶液中で誘電体層の微小なＬＣ（漏れ電流）の欠陥を修復するための再化成（８０℃、３０分、８Ｖ）を行った。前記半導体層形成用前駆体の含浸と通電と再化成を１１回繰り返した（最後２回の通電は、６０分行った。）後水洗・エタノール洗浄・乾燥して半導体層を形成した。さらにリード線が植設されている面を除いて半導体層上にカーボンペーストと銀ペースト）を順に付着させ乾燥し電極層を設けて陰極部を形成し固体電解コンデンサ素子を作製した。 Subsequently, the lead wire is removed, and the sintered body is immersed in ethylenedioxythiophene (used as an aqueous solution in which the monomer is not saturated), anthraquinonesulfonic acid dissolved water, and 20% ethylene glycol electrolyte (semiconductor layer forming solution). For forming a semiconductor layer, a 20 mA DC constant current is allowed to flow for 30 minutes at room temperature between the lead wire and the negative electrode tantalum electrode plate disposed in the electrolyte using the power supply terminal on the left side of the metal frame. Energized. After pulling up, washing with water, washing with ethanol, and drying, using the power supply terminal on the back right side of the metal frame, re-formation to repair minute LC (leakage current) defects in the dielectric layer in 1% phosphoric acid aqueous solution ( 80 ° C., 30 minutes, 8V). The semiconductor layer forming precursor was impregnated, energized, and re-formed 11 times (the last two energizations were performed for 60 minutes), and then washed with water, washed with ethanol, and dried to form a semiconductor layer. Further, a carbon paste and a silver paste) were sequentially deposited on the semiconductor layer except for the surface where the lead wires were implanted, and dried to provide an electrode layer to form a cathode portion, thereby producing a solid electrolytic capacitor element.
別途用意した、厚さ１００μｍの銅合金リードフレーム（表面に厚さ平均１μｍの銅メッキさらにその上に厚さ平均７μｍの錫メッキされている。幅3.4ｍｍの一対の先端部が３２個存在し、電極層が形成された導電体が収まるように一方の先端が0.5ｍｍの段差を有するポケット加工がされている。両先端部には同一平面に投影して1.0ｍｍの隙間がある。）の一対の先端部の上面に、前記した固体電解コンデンサ素子２個の陰極部面（4.5ｍｍ×1.5ｍｍの面）と陽極リード線（一部切断除去した。）とを各々方向を揃えて隙間無く載置し、前者は陰極部と同一の銀ペーストの固化で、後者はスポット溶接で電気的・機械的に接続した。ついで前記リードフレームの一部を残してエポキシ樹脂でトランスファー成形して樹脂外装し、さらに、リードフレームの樹脂外部の所定部を切断後外装部に沿って折り曲げ加工した。引き続き１８５℃で外装樹脂を硬化させた後に、１０５℃、3.5Ｖで４時間エージング処理を行い、大きさ7.3×4.3×1.8ｍｍのチップ状固体電解コンデンサを３２０個作製した。 Separately prepared copper alloy lead frame with a thickness of 100 μm (the surface is plated with copper with an average thickness of 1 μm and further plated with tin with an average thickness of 7 μm. There are 32 pairs of tip portions with a width of 3.4 mm. , One end is pocket-processed with a step of 0.5 mm so that the conductor on which the electrode layer is formed is accommodated. On the upper surface of the pair of tip portions, the cathode part surface (4.5 mm × 1.5 mm surface) of the two solid electrolytic capacitor elements and the anode lead wire (partially cut and removed) are aligned with no gaps. The former was solidified with the same silver paste as the cathode part, and the latter was electrically and mechanically connected by spot welding. Subsequently, a part of the lead frame was left and transfer molded with epoxy resin to coat the resin, and a predetermined portion outside the resin of the lead frame was cut and then bent along the outer package. Subsequently, after the exterior resin was cured at 185 ° C., an aging treatment was performed at 105 ° C. and 3.5 V for 4 hours to produce 320 chip-shaped solid electrolytic capacitors having a size of 7.3 × 4.3 × 1.8 mm.
比較例１：
実施例１で誘電体層を形成した焼結体細孔内に半導体層形成用前駆体の含浸を行うことなしに半導体層を形成してチップ状固体電解コンデンサを３２０個作製した。
Comparative Example 1:
The semiconductor layer was formed without impregnating the precursor for forming the semiconductor layer in the sintered body pores in which the dielectric layer was formed in Example 1, and 320 chip-shaped solid electrolytic capacitors were produced.
実施例２：
実施例１でタンタル焼結体の代わりにニオブ焼結体（ＣＶ２５万μＦ・Ｖ／ｇの粉、窒化量1.1万ｐｐｍ、表面に自然酸化酸素量8.1万ｐｐｍ、焼結温度1280℃、焼結時間３０分、焼結体密度3.4ｇ／ｃｍ3）を、タンタルリード線の代わりにニオブリード線を使用して、２３Ｖの化成でＮｂ2Ｏ5からなる誘電体酸化皮膜層を形成した。次に焼結体を２％エチレンジオキシチオフェンアルコール溶液に浸漬した後引き上げ放置後１８％ナフタレンスルホン酸鉄アルコール溶液に浸漬し引き上げ４０℃で３０分放置後エタノールに浸漬するという一連の操作を７回繰り返した。次に、0.1％酢酸水溶液中で１７Ｖ、８０℃、３０分再化成し、水洗・乾燥した。
Example 2:
In Example 1, instead of tantalum sintered body, niobium sintered body (CV 250,000 μF · V / g powder, nitridation amount 11,000 ppm, natural oxygen oxidation amount 81,000 ppm, sintering temperature 1280 ° C., sintering Using a niobium lead wire for 30 minutes and a sintered body density of 3.4 g / cm 3 ) instead of a tantalum lead wire, a dielectric oxide film layer made of Nb 2 O 5 was formed by chemical conversion at 23V. Next, the sintered body was immersed in a 2% ethylenedioxythiophene alcohol solution and then left to stand, then immersed in an 18% naphthalenesulfonic acid iron alcohol solution, left to stand at 40 ° C. for 30 minutes, and then immersed in ethanol. Repeated times. Next, it was re-formed in a 0.1% acetic acid aqueous solution at 17 V, 80 ° C. for 30 minutes, washed with water and dried.
ついでリード線を除いて焼結体を３，４−エチレンジオキシチオフェンモノマーの２５％アルコール溶液に浸漬し引き上げ、８０℃で乾燥しアルコールを飛散させ、焼結体の細孔内に半導体層形成用前駆体を含浸させた。 Next, the lead wire is removed and the sintered body is dipped in a 25% alcohol solution of 3,4-ethylenedioxythiophene monomer and pulled up, dried at 80 ° C. to disperse the alcohol, and a semiconductor layer is formed in the pores of the sintered body. The precursor for use was impregnated.
その後、実施例１と同様にして通電・再化成（１４Ｖ）を繰り返して半導体層形成を行い、さらに陰極層形成・エージング（８５℃、６Ｖ、４時間）してチップ状固体電解コンデンサを３２０個作製した。 Thereafter, in the same manner as in Example 1, energization / re-formation (14V) was repeated to form a semiconductor layer, and further, cathode layer formation / aging (85 ° C., 6V, 4 hours) was performed to obtain 320 chip-shaped solid electrolytic capacitors. Produced.
比較例２：
実施例２で使用したエチレンジオキシチオフェンアルコール溶液の濃度を２０％にし、さらにアルコールに漬けることを行わずに、１８％ナフタレンスルホン酸鉄アルコール溶液との浸漬を交互に３０回行い、誘電体層を設けた導電体に化学重合層を形成したことと、焼結体細孔内に半導体層形成用前駆体の含浸を行わなかったこと以外は実施例２と同様にしてチップ状固体電解コンデンサを２１６個（半導体層形成が比較的に良好であった４３２個のコンデンサ素子から）作製した。
Comparative Example 2:
The concentration of the ethylenedioxythiophene alcohol solution used in Example 2 was set to 20%, and further immersed in 18% naphthalene sulfonic acid iron alcohol solution was performed 30 times alternately without immersing in the alcohol layer. A chip-shaped solid electrolytic capacitor was prepared in the same manner as in Example 2 except that the chemical polymerization layer was formed on the conductor provided with the above and that the sintered body pores were not impregnated with the precursor for forming the semiconductor layer. 216 pieces (from 432 capacitor elements in which the semiconductor layer formation was relatively good) were produced.
以上作製した各コンデンサについて容量、含浸率、ＥＳＲ値、及びＬＣ値を以下の方法により測定した。測定結果（平均値）を表１に示す。
コンデンサの容量：ヒューレットパッカード社製ＬＣＲ測定器を用い、室温１２０Ｈｚで測定した。
含浸率：前記コンデンサ容量を、誘電体層を形成した各導電体を３０％硫酸中で測定した容量で除した数値の百分率。
ＥＳＲ値：コンデンサの等価直列抵抗。室温１００ｋＨｚで測定した。
ＬＣ値：室温において、所定の定格電圧（実施例１及び比較例１は2.5Ｖ値、実施例２及び比較例２は４Ｖ値）を作製したコンデンサの端子間に３０秒間印加し続けた後に測定した。
The capacity, impregnation rate, ESR value, and LC value of each capacitor produced above were measured by the following methods. The measurement results (average values) are shown in Table 1.
Capacitor capacity: Measured at a room temperature of 120 Hz using an LCR measuring instrument manufactured by Hewlett-Packard Company.
Impregnation rate: Percentage of a value obtained by dividing the capacitor capacity by the capacity measured in 30% sulfuric acid for each conductor on which the dielectric layer was formed.
ESR value: Equivalent series resistance of a capacitor. Measurement was performed at room temperature of 100 kHz.
LC value: Measured after continuously applying a predetermined rated voltage (2.5 V value in Example 1 and Comparative Example 1, 4 V value in Example 2 and Comparative Example 2) between terminals of capacitors at room temperature for 30 seconds did.
実施例１と比較例１、実施例２と比較例２を比べることにより、半導体層形成の通電前に細孔内に半導体層形成用前駆体を含浸し、細孔内の半導体層形成用前駆体濃度を電解液中の半導体層形成用前駆体より高濃度にすると、容量出現率が良好で低ＥＳＲ値を示すコンデンサが得られることがわかる。 By comparing Example 1 with Comparative Example 1 and Example 2 with Comparative Example 2, the semiconductor layer forming precursor is impregnated in the pores before energization of the semiconductor layer formation, and the semiconductor layer forming precursor in the pores is impregnated. It can be seen that when the body concentration is higher than that of the precursor for forming a semiconductor layer in the electrolytic solution, a capacitor having a good capacity appearance rate and a low ESR value can be obtained.
Claims (24)
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である請求項１４に記載のコンデンサの製造方法。 An organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
The method for producing a capacitor according to claim 14, wherein the capacitor is at least one selected from organic semiconductors whose main component is a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula (1) with a dopant.
で示される構造単位を繰り返し単位として含む導電性高分子である請求項１５に記載のコンデンサの製造方法。 The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
The method for producing a capacitor according to claim 15, wherein the capacitor is a conductive polymer containing a structural unit represented by
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