JP4694642B2 - Capacitor and manufacturing method thereof - Google Patents
Capacitor and manufacturing method thereof Download PDFInfo
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- JP4694642B2 JP4694642B2 JP2010000476A JP2010000476A JP4694642B2 JP 4694642 B2 JP4694642 B2 JP 4694642B2 JP 2010000476 A JP2010000476 A JP 2010000476A JP 2010000476 A JP2010000476 A JP 2010000476A JP 4694642 B2 JP4694642 B2 JP 4694642B2
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- 239000003990 capacitor Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 61
- 229910052758 niobium Inorganic materials 0.000 claims description 50
- 239000010955 niobium Substances 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 7
- 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 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims 1
- 238000005121 nitriding Methods 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001257 Nb alloy Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YMUICPQENGUHJM-UHFFFAOYSA-N 2-methylpropyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)CC(C)C YMUICPQENGUHJM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ROSDCCJGGBNDNL-UHFFFAOYSA-N [Ta].[Pb] Chemical compound [Ta].[Pb] ROSDCCJGGBNDNL-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- -1 polyoxyphenylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Powder Metallurgy (AREA)
Description
本発明は、コンデンサおよびその製造方法に関する、特に容量を低下させずに漏れ電流（以下「ＬＣ」と略す。）値が低くまたはそのバラツキが小さく、あるいは耐熱性が良好であるコンデンサおよびその製造方法に関する。 The present invention relates to a capacitor and a method for manufacturing the same, and in particular, a capacitor having a low leakage current (hereinafter abbreviated as “LC”) without reducing the capacitance, a small variation thereof, or a good heat resistance, and a method for manufacturing the same About.
携帯電話やパーソナルコンピューター等の電子機器に使用されるコンデンサは、小型で大容量のものが望まれている。このようなコンデンサの中でもタンタル電解コンデンサは、大きさの割には容量が大きくしかも性能が良好なため、好んで使用されている。通常タンタル電解コンデンサの誘電体として酸化タンタルが使用されているがさらに容量を大きくするために、誘電率のより大きい酸化ニオブを誘電体としたニオブ電解コンデンサが検討されている。 Capacitors used in electronic devices such as mobile phones and personal computers are desired to be small and have a large capacity. Among such capacitors, a tantalum electrolytic capacitor is favorably used because of its large capacity and good performance for its size. In general, tantalum oxide is used as a dielectric of a tantalum electrolytic capacitor, but in order to further increase the capacity, a niobium electrolytic capacitor using niobium oxide having a higher dielectric constant as a dielectric has been studied.
ニオブからなる一方の電極を陽極として電解液中で電解酸化を行う従来の方法で得られたニオブ誘電体を用いたニオブ電解コンデンサの容量は大きくなるが、ＬＣ値が大きくなる場合がありまたはそのバラツキが大きくなる場合がありあるいは耐熱性も不充分である場合があり、より信頼性の向上が求められている。
本発明は、上記状況を鑑みてなされたものであり、その目的は容量を低下させずにＬＣ値が低くまたはそのバラツキを小さくしあるいは耐熱性が良好であるコンデンサおよびその製造方法を提供することにある。
Although the capacity of a niobium electrolytic capacitor using a niobium dielectric obtained by a conventional method in which electrolytic oxidation is performed in an electrolytic solution using one electrode made of niobium as an anode, the LC value may increase or In some cases, the variation may increase or the heat resistance may be insufficient, and further improvement in reliability is required.
The present invention has been made in view of the above situation, and an object of the present invention is to provide a capacitor having a low LC value or a small variation without reducing the capacity, or having a good heat resistance, and a method for manufacturing the same. It is in.
本発明者等は、前記課題を解決する為に鋭意研究した結果、酸化ニオブの誘電体を形成する時の製造方法として特異な電解酸化方法を用いることにより上記課題が解決できることを見出し本発明を完成するに至った。
１）上記課題を解決する第１の発明は、二つの電極と少なくともその間に介在した誘電体とから構成され、該電極の一方の電極がニオブ焼結体からなり、該誘電体が前記ニオブ焼結体からなる電極の上に形成された酸化ニオブからなるコンデンサの製造方法において、一方の電極のニオブ焼結体はニオブ粉体を加圧成型した後１０0×１３３〜１０-6×１３３［Ｐａ］の条件下で５００〜２０００℃で焼結したものであり、該ニオブ焼結体からなる一方の電極を陽極として電解液中で電解酸化を行うに際して、初期に電流値をニオブ焼結体からなる一方の電極の重量あたり２００［ｍＡ］以上とした定電流状態で電解酸化を開始しその後定電圧で電解酸化を継続することによって該誘電体を作製することを特徴とするコンデンサの製造方法。
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific electrolytic oxidation method as a manufacturing method when forming a dielectric of niobium oxide. It came to be completed.
1) A first invention for solving the above-described problem is composed of two electrodes and at least a dielectric interposed between the electrodes, and one of the electrodes is made of a niobium sintered body, and the dielectric is made of the niobium sintered body. In the method of manufacturing a capacitor made of niobium oxide formed on an electrode made of a bonded body, the niobium sintered body of one electrode is 10 0 × 133 to 10 −6 × 133 [ Pa] and sintered at 500 to 2000 ° C., and when performing electrolytic oxidation in an electrolytic solution using one electrode made of the niobium sintered body as an anode, the current value is initially set to the niobium sintered body. A method of manufacturing a capacitor comprising producing the dielectric by starting electrolytic oxidation in a constant current state of 200 [mA] or more per weight of one of the electrodes, and then continuing electrolytic oxidation at a constant voltage .
２）上記課題を解決する第２の発明は、一方の電極のニオブが一部窒化されていることを特徴とする上記１）に記載のコンデンサの製造方法である。
３）上記課題を解決する第３の発明は、一方の電極のニオブの窒素量が５０〜１５００００重量ｐｐｍであることを特徴とする上記２）に記載のコンデンサの製造方法である。
４）上記課題を解決する第４の発明は、電解液がりん酸からなる水溶液で、その濃度が０．０１重量％以上５重量％以下であることを特徴とする上記１）〜３）のいずれか１項に記載のコンデンサの製造方法である。
５）上記課題を解決する第５の発明は、電解酸化時の温度が６０℃以上であることを特徴とする上記１）〜４）いずれか１項に記載のコンデンサの製造方法である。
６）上記課題を解決する第６の発明は、一方の電極の構造が焼結体であって、ＣＶ値が少なくとも５００００［ＣＶ／ｇ］以上であることを特徴とした上記１）〜５）のいずれか一項に記載のコンデンサの製造方法である。
2) A second invention for solving the above problem is the method for manufacturing a capacitor as described in 1) above, wherein niobium of one electrode is partially nitrided.
3) A third invention for solving the above problem is the method for producing a capacitor as described in 2) above, wherein the nitrogen content of niobium in one electrode is 50 to 150,000 ppm by weight.
4) A fourth invention for solving the above-mentioned problems is that the electrolytic solution is an aqueous solution made of phosphoric acid, the concentration of which is 0.01 wt% or more and 5 wt% or less. It is a manufacturing method of the capacitor given in any 1 paragraph.
5) A fifth invention for solving the above-mentioned problems is the method for producing a capacitor as described in any one of 1) to 4) above, wherein the temperature during electrolytic oxidation is 60 ° C. or higher.
6) The sixth invention for solving the above-mentioned problems is characterized in that the structure of one of the electrodes is a sintered body, and the CV value is at least 50000 [CV / g] or more. The method for producing a capacitor according to any one of the above.
７）上記課題を解決する第７の発明は、二つの電極と少なくともその間に介在した誘電体とから構成され、該電極の一方の電極がニオブからなり、該誘電体が前記ニオブからなる電極の上に形成された酸化ニオブからなるコンデンサにおいて、ニオブからなる一方の電極を陽極として電解液中で電解酸化を行うに際して、初期に電流値をニオブからなる一方の電極の重量あたり２００［ｍＡ］以上とした定電流状態で電解酸化を開始しその後定電圧で電解酸化を継続することによって形成された該誘電体を有するコンデンサである。
８）上記課題を解決する第８の発明は、一方の電極のニオブが一部窒化されていることを特徴とする上記７）に記載のコンデンサである。
９）上記課題を解決する第９の発明は、一方の電極の構造が焼結体であって、ＣＶ値が少なくとも５００００［ＣＶ／ｇ］以上であることを特徴とした上記７）または８）に記載のコンデンサである。
7) A seventh invention for solving the above-mentioned problems is composed of two electrodes and at least a dielectric interposed therebetween, one of the electrodes being made of niobium, and the dielectric being made of the niobium. In the capacitor made of niobium oxide formed above, when electrolytic oxidation is performed in an electrolytic solution using one electrode made of niobium as an anode, an initial current value is 200 mA or more per weight of the one electrode made of niobium. The capacitor having the dielectric formed by starting electrolytic oxidation in a constant current state as described above and then continuing electrolytic oxidation at a constant voltage.
8) An eighth invention for solving the above problem is the capacitor as described in 7) above, wherein niobium of one electrode is partially nitrided.
9) The ninth invention for solving the above-mentioned problems is that the structure of one of the electrodes is a sintered body, and the CV value is at least 50000 [CV / g] or more, 7) or 8) above It is a capacitor | condenser described in.
本発明のコンデンサの製造方法に従えば、ニオブからなる一方の電極を陽極として電解液中で電解酸化を行うに際して、初期に電流値をニオブからなる一方の電極の重量あたり２００［ｍＡ］以上とした定電流状態で電解酸化を開始しその後定電圧で電解酸化を継続することによって該誘電体を作製しているので、容量を低下させずにＬＣ値が低くまたはそのバラツキが小さく、あるいは耐熱性が良好なコンデンサを製造することが出来る。
［作用］
本発明の作用は必ずしも明確ではないが以下のように推定できる。通常ニオブはタンタルより酸素親和力が大きいため誘電体を作製中に誘電対中の酸素が内部の電極側に引き抜かれるが、この現象よりも速く誘電体を作製することによって安定な誘電体を形成できると推定できる。つまり一般に良好な誘電体が形成されると思われる電流値よりもはるかに高い値の定電流状態で速く誘電体を形成する方法によってより安定な誘電体が形成されていると推定している。さらには誘電体を形成する電解酸化時の電解液の濃度、誘電体を形成する電解酸化時の温度を調整するなどの方法によって高容量でより安定な誘電体が形成されていると推定している。
According to the method for manufacturing a capacitor of the present invention, when electrolytic oxidation is performed in an electrolytic solution using one electrode made of niobium as an anode, an initial current value is 200 mA or more per weight of the one electrode made of niobium. Since the dielectric is produced by starting electrolytic oxidation in a constant current state and then continuing electrolytic oxidation at a constant voltage, the LC value is low or its variation is small without reducing the capacity, or heat resistance Can produce a good capacitor.
[Action]
Although the operation of the present invention is not necessarily clear, it can be estimated as follows. Niobium usually has a higher oxygen affinity than tantalum, so oxygen in the dielectric pair is extracted to the internal electrode side during fabrication of the dielectric, but a stable dielectric can be formed by fabricating the dielectric faster than this phenomenon. Can be estimated. That is, it is estimated that a more stable dielectric is formed by a method of forming a dielectric faster in a constant current state of a value much higher than a current value that is generally considered to form a good dielectric. In addition, it is estimated that a high-capacity and more stable dielectric is formed by adjusting the concentration of the electrolyte during electrolytic oxidation that forms the dielectric and the temperature during electrolytic oxidation that forms the dielectric. Yes.
本発明のコンデンサを得るための一実施形態を説明する。本発明のコンデンサの製造方法において用いられる一方の電極を構成するニオブはニオブの合金を含みその形状は板状、箔状、棒状、焼結体などとすることができる。大きさは作製するコンデンサの容量を勘案して任意に決定できる。箔状、棒状の場合は、折り曲げたり巻き回したり、表面をエッチングしたりして、容量を大きくするために単位体積当たりの表面積を増大させて使用しても良い。焼結体を作製する場合は例えば前述した材料の粉体を加圧成型した後１０0×１３３〜１０-6×１３３［Ｐａ］の条件下で５００〜２０００℃、数分間〜数時間放置する方法を用いることが出来る。 One embodiment for obtaining the capacitor of the present invention will be described. Niobium constituting one of the electrodes used in the method for manufacturing a capacitor of the present invention includes an alloy of niobium, and the shape thereof can be a plate shape, a foil shape, a rod shape, a sintered body, or the like. The size can be arbitrarily determined in consideration of the capacity of the capacitor to be manufactured. In the case of foil shape or rod shape, the surface area per unit volume may be increased to be used by bending or winding or etching the surface to increase the capacity. In the case of producing a sintered body, for example, the above-mentioned powder of the material is pressure-molded and then left under conditions of 10 0 × 133 to 10 -6 × 133 [Pa] at 500 to 2000 ° C. for several minutes to several hours. Method can be used.
上記、電極の表面には電解酸化によって酸化ニオブからなる誘電体が形成される。本発明においてはニオブからなる電極を陽極として電解液中で別途用意した対極との間で電圧印加することで該誘電体はニオブからなる電極上に形成される。ここで、誘電体を形成する電解酸化の方法は以下のようにする。まず初期に、一般に良好な誘電体が形成されると思われる電流値よりもはるかに高い値（例えば１０倍以上）の定電流状態で電解酸化を開始する。その後所定の電圧になった時点でその所定の電圧を維持した定電圧状態にて電解酸化を継続して行う。このように電解酸化を実施することにより所定の電圧に短時間で到達する。このように形成した誘電体膜を形成された電極を用いると漏れ電流値（以下「ＬＣ値」という。）が低くまたはそのバラツキが小さく、あるいは耐熱性が良好なコンデンサを得ることができる。例えば定電流値を、ニオブからなる一方の電極の重量あたり２００［ｍＡ］以上、好ましくは４００［ｍＡ］以上とする。定電流値が２００［ｍＡ］未満であると、漏れ電流値が低くまたはそのバラツキが小さく、あるいは耐熱性が良好なコンデンサを得ることは困難である。 A dielectric made of niobium oxide is formed on the surface of the electrode by electrolytic oxidation. In the present invention, the dielectric is formed on the electrode made of niobium by applying a voltage between the electrode made of niobium as an anode and a counter electrode separately prepared in the electrolyte. Here, the electrolytic oxidation method for forming the dielectric is as follows. First, electrolytic oxidation is started in a constant current state of a value much higher (eg, 10 times or more) than a current value at which a good dielectric is generally expected to be formed. Thereafter, when a predetermined voltage is reached, electrolytic oxidation is continuously performed in a constant voltage state in which the predetermined voltage is maintained. Thus, by performing electrolytic oxidation, a predetermined voltage is reached in a short time. When an electrode formed with a dielectric film formed in this way is used, a capacitor having a low leakage current value (hereinafter referred to as “LC value”) or a small variation, or a good heat resistance can be obtained. For example, the constant current value is set to 200 [mA] or more, preferably 400 [mA] or more per weight of one electrode made of niobium. When the constant current value is less than 200 [mA], it is difficult to obtain a capacitor having a low leakage current value, a small variation thereof, or a good heat resistance.
対極としてはタンタル、ニオブ、白金、鉄ニッケル合金などが従来公知の金属を使用することが出来る。また、印加する前述した所定の電圧値は作製するコンデンサの作動電圧と容量値を考慮して任意に決定することが出来る。たとえば、作動電圧が１０Ｖのコンデンサでは印加電圧４０Ｖ、作動電圧が６．３Ｖのコンデンサでは印加電圧２０〜２２Ｖが用いられる。
電解液の種類としては、鉱酸、有機酸、それらの酸の塩を１種以上使用した水溶液、それらの酸の塩を１種以上使用した非水溶液などを使用できる。とりわけ、作業の容易性安全性など実用性の点から、りん酸からなる水溶液を用いその濃度を０．０１重量％以上５重量％以下、さらに好ましくは０．１重量％以上４重量％以下にしておくおくことが好ましい。０．０１重量％未満であると所定電圧になるまでに長時間必要となり、本発明の作用の効果が得られにくくなるおそればあるばかりでなく生産効率の面からも不利である。また５重量％を越えると作製したコンデンサの容量が減少する場合がある。
As the counter electrode, a conventionally known metal such as tantalum, niobium, platinum, iron nickel alloy or the like can be used. The predetermined voltage value to be applied can be arbitrarily determined in consideration of the operating voltage and capacitance value of the capacitor to be manufactured. For example, an applied voltage of 40V is used for a capacitor having an operating voltage of 10V, and an applied voltage of 20 to 22V is used for a capacitor having an operating voltage of 6.3V.
As the kind of the electrolytic solution, a mineral acid, an organic acid, an aqueous solution using one or more salts of those acids, a non-aqueous solution using one or more salts of these acids, and the like can be used. In particular, from the viewpoint of practicality such as ease of work and safety, an aqueous solution made of phosphoric acid is used, and its concentration is 0.01 wt% or more and 5 wt% or less, more preferably 0.1 wt% or more and 4 wt% or less. It is preferable to keep it. If it is less than 0.01% by weight, it takes a long time to reach a predetermined voltage, which may be difficult to obtain the effects of the present invention, and is disadvantageous in terms of production efficiency. On the other hand, if it exceeds 5% by weight, the capacity of the produced capacitor may decrease.
電解温度は好ましくは６０℃以上、さらに好ましくは８０℃以上である。６０℃未満であると本発明の作用の効果が得られにくくなるおそれがあるばかりでなく作製したコンデンサのＬＣ値がばらつきが大きくなる場合がある。
本発明の一方の電極であるニオブはその一部を窒素化したものであっても良い。ＬＣ値をより低下させる点から、窒素量は５０〜１５００００重量ｐｐｍ、好ましくは１００〜７０００重量ｐｐｍ、更に好ましくは５００〜７０００重量ｐｐｍとすることが出来る。窒化方法としては、ガス窒化、液体窒化、イオン窒化、ガス窒化などのうちいずれかあるいはそれらの組み合わせた方法で実施することができる。
The electrolysis temperature is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. If the temperature is lower than 60 ° C., the effect of the present invention may not be easily obtained, and the LC value of the manufactured capacitor may vary greatly.
Niobium which is one electrode of the present invention may be a part of which is nitrogenated. From the viewpoint of further reducing the LC value, the nitrogen amount can be 50 to 150,000 ppm by weight, preferably 100 to 7000 ppm by weight, and more preferably 500 to 7000 ppm by weight. As the nitriding method, any one of gas nitriding, liquid nitriding, ion nitriding, gas nitriding, etc., or a combination thereof can be used.
窒素ガス雰囲気に放置することによるガス窒化処理は、装置が簡便で操作が容易なため好ましい。窒素化する温度は２０００℃以下で時間は数１０時間で目的とする窒素量の一部窒化したニオブが得られるが一般に高温ほど短時間で所定量の窒素量のものを得ることが出来る。また、室温下でも窒素雰囲気中に数１０時間ニオブを放置しておくと数１００重量ｐｐｍの窒素量の一部窒化したニオブを得ることが出来る。また、窒素を加圧導入することにより窒化を時間短縮することが可能である。逆に窒素を減圧下に導入すると窒化の時間が遅くなる。たとえば、０．０１×１３３［Ｐａ］等の極端な減圧下に前記ニオブを放置しても工業的な数１０時間の範囲では窒化はほとんど起こらない。 Gas nitriding treatment by leaving in a nitrogen gas atmosphere is preferable because the apparatus is simple and easy to operate. Nitrogen is obtained by nitriding at a temperature of 2000 ° C. or less and for several tens of hours to obtain a partially nitrided niobium having a desired amount of nitrogen. In general, a higher amount of nitrogen can be obtained in a shorter time. Further, if niobium is left in a nitrogen atmosphere for several tens of hours at room temperature, a partially nitrided niobium having a nitrogen content of several hundred weight ppm can be obtained. Further, it is possible to shorten the nitriding time by introducing nitrogen under pressure. Conversely, when nitrogen is introduced under reduced pressure, the nitriding time is delayed. For example, even if the niobium is allowed to stand under an extremely reduced pressure of 0.01 × 133 [Pa] or the like, nitriding hardly occurs in an industrial range of several tens of hours.
さらに、電極の構造を焼結体とした場合、ニオブやニオブ合金またはそれらの一部窒化された粉体を使用して焼結体を作製し、ＣＶ値（容量と電解酸化時の印加電圧との積を電極重量で割った値）を少なくとも５００００［ＣＶ／ｇ］以上としたものが大容量のコンデンサを得ることが出来るので好ましい。たとえば平均粒径が３〜５［μｍ］の粉体を用いることでそのＣＶ値を得ることができる。さらに焼結体を作製する粉体の形状の平均粒径を小さくすることにより大きなＣＶ値を得ることができる。１０００００［ＣＶ／ｇ］以上を得るためには例えば０．３〜２［μｍ］にすることにより、さらに６０００００［ＣＶ／ｇ］以上を得るためには例えば０．２［μｍ］以下にすることにより、より大高容量のコンデンサを得るために要求されるより大きなＣＶ値を有する焼結体とすることが出来る。 Further, when the electrode structure is a sintered body, a sintered body is prepared using niobium, a niobium alloy, or a partially nitrided powder thereof, and a CV value (capacity and applied voltage during electrolytic oxidation) (Product obtained by dividing the product of (1) by electrode weight) at least 50000 [CV / g] is preferable because a large-capacity capacitor can be obtained. For example, the CV value can be obtained by using a powder having an average particle diameter of 3 to 5 [μm]. Furthermore, a large CV value can be obtained by reducing the average particle size of the shape of the powder forming the sintered body. In order to obtain 100000 [CV / g] or more, for example, 0.3 to 2 [μm], and in order to obtain 600000 [CV / g] or more, for example, 0.2 [μm] or less. Thus, a sintered body having a larger CV value required for obtaining a capacitor having a larger capacity can be obtained.
このような平均粒径を有するニオブ粉は、たとえばフッ化ニオブ酸カリのナトリウム還元物の粉砕による方法、ニオブインゴットの水素化物の粉砕および脱水素による方法、酸化ニオブの炭素還元による方法等によって得ることができる。たとえばニオブインゴットの水素化物の粉砕および脱水素から得る方法の場合、ニオブインゴットの水素化量と粉砕時間、粉砕装置などを調製することにより、希望の平均粒径を有するニオブ粉を得ることができる。 The niobium powder having such an average particle size is obtained by, for example, a method by pulverization of sodium reduced product of potassium fluoride niobate, a method by pulverization and dehydrogenation of hydride of niobium ingot, a method by carbon reduction of niobium oxide, or the like. be able to. For example, in the case of a method obtained by pulverization and dehydrogenation of a hydride of niobium ingot, niobium powder having a desired average particle diameter can be obtained by adjusting the hydrogenation amount and pulverization time of the niobium ingot, the pulverizer, etc. .
焼結体を作製後窒化する方法を用いて、一部窒化した電極を得ることも出来る。例えば、ニオブ粉を成型して焼結後、該焼結体を前述した窒化処理方法を用いて窒化することが出来る。
ここで本明細書中でニオブ、ニオブ粉体への窒素量とはこれらの材料に吸着した状態のものではなく確実に結合し窒化したものである。
A partially nitrided electrode can be obtained by using a method of nitriding after producing a sintered body. For example, after the niobium powder is molded and sintered, the sintered body can be nitrided using the nitriding method described above.
Here, in this specification, the amount of nitrogen in niobium and niobium powder is not in a state of being adsorbed by these materials, but is bonded and nitrided reliably.
一方、本発明のコンデンサの他方の電極は格別限定されるものではなく、例えば、アルミ電解コンデンサ業界で公知である電解液、有機半導体および無機半導体から選ばれた少なくとも一種の化合物が挙げられる。電解液の具体例としてはイソブチルトリプロピルアンモニウムボロテトラフルオライド電解質を５重量％溶解したジメチルホルムアミドとエチレングリコールの混合溶液、テトラエチルアンモニウムボロテトラフルオライドを７重量％溶解したプロピレンカーボネートとエチレングリコールの混合溶液等が挙げられる。有機半導体の具体例としては、ベンゾピロリン四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）で表される高分子にドーパントをドープした電導性高分子を主成分とした有機半導体が挙げられる。無機半導体の具体例としては二酸化鉛または二酸化マンガンを主成分とする無機半導体、四三酸化鉄からなる無機半導体などが挙げられる。このような半導体は単独でも、または二種以上組み合わせて使用しても良い。 On the other hand, the other electrode of the capacitor of the present invention is not particularly limited, and examples thereof include at least one compound selected from an electrolytic solution, an organic semiconductor, and an inorganic semiconductor known in the aluminum electrolytic capacitor industry. Specific examples of the electrolyte include a mixed solution of dimethylformamide and ethylene glycol in which 5% by weight of isobutyltripropylammonium borotetrafluoride electrolyte is dissolved, and a mixture of propylene carbonate and ethylene glycol in which 7% by weight of tetraethylammonium borotetrafluoride is dissolved. Examples include solutions. Specific examples of the organic semiconductor include an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, and the following general formula (1) Or the organic semiconductor which has as a main component the electroconductive polymer which doped the dopant to the polymer represented by (2) is mentioned. Specific examples of the inorganic semiconductor include an inorganic semiconductor mainly composed of lead dioxide or manganese dioxide, and an inorganic semiconductor composed of iron trioxide. Such semiconductors may be used alone or in combination of two or more.
式（１）および（２）において、Ｒ１〜Ｒ４は水素、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、これらは互いに同一であっても相違してもよく、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または炭素数１〜６のアルキル基を表し、Ｒ１とＲ２およびＲ３とＲ４は互いに結合して環状になっていても良い。式（１）または（２）で表される高分子としては、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、およびこれらの高分子の誘導体などが挙げられる。 In the formulas (1) and (2), R1 to R4 represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, which may be the same or different from each other, X represents an oxygen, sulfur or nitrogen atom, R5 is present only when X is a nitrogen atom and represents hydrogen or an alkyl group having 1 to 6 carbon atoms; R1 and R2 and R3 and R4 are bonded to each other to form a ring It may be. Examples of the polymer represented by the formula (1) or (2) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and derivatives of these polymers.
上記の有機半導体および無機半導体として、電導度１０-2Ｓ・ｃｍ-1〜１０3Ｓ・ｃｍ-1の範囲のものを使用すると、作製したコンデンサのインピーダンス値がより小さくなり、高周波での容量をさらに一層大きくすることができる。 When the organic semiconductor and the inorganic semiconductor having a conductivity in the range of 10 −2 S · cm −1 to 10 3 S · cm −1 are used, the impedance value of the produced capacitor becomes smaller and the capacitance at high frequency is increased. Can be further increased.
さらに他方の電極が固体の場合には、例えば他方の電極上にカーボンペースト、銀ペーストを順次積層し、エポキシ樹脂のような材料で封口してコンデンサが構成される。このコンデンサはニオブと一体に成型された、または後から電極に溶接されたニオブまたはタンタルのリード線を有していても良い。また他方の電極が液体の場合には、前記両極と誘電体から構成されたコンデンサを、例えば、他方の電極と電気的に接続した缶に収納してコンデンサが形成される。この場合、ニオブの電極側はたとえば前記したニオブまたはタンタルリード線を介して外部に導出されると同時に、絶縁性ゴム等により、缶との絶縁がはかられるように設計されている。 Further, when the other electrode is solid, for example, a carbon paste and a silver paste are sequentially laminated on the other electrode and sealed with a material such as an epoxy resin to form a capacitor. The capacitor may have niobium or tantalum leads that are molded integrally with niobium or later welded to the electrode. When the other electrode is a liquid, a capacitor formed of the two electrodes and the dielectric is housed in, for example, a can electrically connected to the other electrode to form a capacitor. In this case, the electrode side of niobium is designed to be insulated from the can by insulating rubber or the like at the same time as being led out to the outside through, for example, the above-described niobium or tantalum lead wire.
以上説明した本発明に従って、コンデンサを作製することにより、容量を低下させずにＬＣ値が低くまたはそのバラツキを小さく、あるいは耐熱性が良好なコンデンサを製造することが出来る。 By manufacturing a capacitor according to the present invention described above, it is possible to manufacture a capacitor having a low LC value, a small variation, or good heat resistance without reducing the capacitance.
以下本発明の具体例についてさらに詳細に説明する。粉体の窒化量は次のように測定した。熱伝導度から窒素量を求めるＬＥＣＯ社製酸素窒素量測定器を用いて粉体の窒素量を求め、別途測定した粉体の質量との比を窒化量とした。 Hereinafter, specific examples of the present invention will be described in more detail. The nitriding amount of the powder was measured as follows. The amount of nitrogen in the powder was determined using an oxygen / nitrogen amount measuring device manufactured by LECO that obtains the amount of nitrogen from the thermal conductivity, and the ratio of the measured amount to the mass of the powder was used as the amount of nitriding.
焼結体の容量は次のように測定した。室温において、３０％硫酸中に浸漬させた焼結体と硫酸液中に入れたタンタル材の電極と間にＨＰ製ＬＣＲ測定器を接続して測定した１２０Ｈｚでの容量を焼結体の容量とした。 The capacity of the sintered body was measured as follows. At room temperature, the capacity at 120 Hz measured by connecting an LCR measuring instrument made of HP between a sintered body immersed in 30% sulfuric acid and an electrode of a tantalum material placed in a sulfuric acid solution is the capacity of the sintered body. did.
焼結体の漏れ電流値（ＬＣ値）は次のように測定した。室温において、２０％りん酸水溶液中に浸漬させた焼結体とりん酸水溶液中に入れた電極と間に誘電体作製時の化成電圧の７０％の電圧の直流電圧を３分間印可し続けた後に測定された電流値を焼結体の漏れ電流値とした。本発明では、１４［Ｖ］の電圧を印加した。 The leakage current value (LC value) of the sintered body was measured as follows. At room temperature, a DC voltage of 70% of the formation voltage at the time of producing the dielectric was continuously applied for 3 minutes between the sintered body immersed in a 20% phosphoric acid aqueous solution and the electrode placed in the phosphoric acid aqueous solution. The current value measured later was taken as the leakage current value of the sintered body. In the present invention, a voltage of 14 [V] was applied.
チップに加工したコンデンサの容量は次のように測定した。室温において、作製したチップの端子間にＨＰ製ＬＣＲ測定器を接続して測定した１２０Ｈｚでの容量をチップに加工したコンデンサの容量とした。 The capacitance of the capacitor processed into the chip was measured as follows. At room temperature, the capacity at 120 Hz measured by connecting an HP LCR measuring device between the terminals of the manufactured chip was taken as the capacity of the capacitor processed into the chip.
チップに加工したコンデンサの漏れ電流は以下のように測定した。定格電圧値（２．５［Ｖ］、４［Ｖ］、６．３［Ｖ］、１０［Ｖ］、１６［Ｖ］、２５［Ｖ］等）のうち誘電体作製時の化成電圧の約１／３〜約１／４に近い直流電圧を、室温において、作製したチップの端子間に１分間印可し続けた後に測定された電流値をチップに加工したコンデンサの漏れ電流値とした。本発明では、６．３［Ｖ］の電圧を印加した。 The leakage current of the capacitor processed into the chip was measured as follows. Of rated voltage values (2.5 [V], 4 [V], 6.3 [V], 10 [V], 16 [V], 25 [V], etc.) The current value measured after a DC voltage close to 1/3 to about 1/4 was continuously applied for 1 minute between the terminals of the manufactured chip at room temperature was taken as the leakage current value of the capacitor processed into the chip. In the present invention, a voltage of 6.3 [V] was applied.
コンデンサの耐熱特性は以下のように測定した。作製したコンデンサを厚さ１．５ｍｍの積層基板に半田と共に搭載してリフロー炉を３回通した後ＬＣ値が５００μＡ以上になった個数をカウントした。ここでコンデンサはリフロー炉通過時に約２３０℃×３０秒×３回加熱されることになるので、実用的な熱履歴（たとえば、基板の表面に実装した部品の半田付け、裏面に実装した部品の半田付け、後付け部品の半田付けを実施した場合の３回の半田付けの熱履歴等）に対しての評価をすることが出来る。 The heat resistance characteristics of the capacitor were measured as follows. The produced capacitors were mounted on a 1.5 mm thick laminated substrate together with solder, passed through a reflow furnace three times, and then the number of LC values of 500 μA or more was counted. Here, since the capacitor is heated about 230 ° C. × 30 seconds × 3 times when passing through the reflow furnace, a practical thermal history (for example, soldering of the component mounted on the surface of the substrate, It is possible to evaluate the soldering, the heat history of the soldering three times when the soldering of the retrofitted parts is performed, and the like.
試験例１〜２３平均粒径１μｍの一部窒化されたニオブ粉からなるニオブ粉末（ニオブ粉を３００℃の条件下で２時間、窒素ガス雰囲気中に放置して得た。結合した窒素量２５００重量ｐｐｍ。）を０．１ｇとり、大きさおおよそ１．８×３．５×４．５ｍｍの成型体を作製し、温度１１５０℃で焼結した。得られた一部窒化したニオブの焼結体を、表１に示した電解液中に浸漬して、タンタル板を対極として表１に示した条件下で化成電圧２０Ｖを６００分間印加して化成処理をおこなった。ここで印加時間は、印加電圧が２０Ｖの定電圧に安定してからの経過時間である。この電極のＣＶ値を表１に示した。 Test Examples 1 to 23 Niobium powder made of partially nitrided niobium powder having an average particle diameter of 1 μm (obtained by leaving niobium powder in a nitrogen gas atmosphere at 300 ° C. for 2 hours. The amount of nitrogen bonded 2500 0.1 g of weight ppm.) Was taken, and a molded body having a size of approximately 1.8 × 3.5 × 4.5 mm was prepared and sintered at a temperature of 1150 ° C. The obtained partially nitrided niobium sintered body was immersed in the electrolytic solution shown in Table 1, and a chemical voltage of 20 V was applied for 600 minutes under the conditions shown in Table 1 using a tantalum plate as a counter electrode. Processed. Here, the application time is an elapsed time after the applied voltage is stabilized at a constant voltage of 20V. The CV value of this electrode is shown in Table 1.
次に、誘電体を形成した前記した焼結体に対して硝酸マンガン水溶液に浸漬した後に２２０℃で３０分間加熱反応させるという処理を複数回繰り返して、誘電体酸化皮膜上に他方の電極層として二酸化マンガン層を形成した。引き続き、その上に、カーボン層、銀ペースト層を順次に積層し、次に、リードフレームに載せた後、全体をエポキシ樹脂で封止して、大きさ７．３×４．３×２．８ｍｍのチップ型コンデンサを作製した。 Next, the above-mentioned sintered body on which the dielectric is formed is dipped in a manganese nitrate aqueous solution and then subjected to a heat reaction at 220 ° C. for 30 minutes, so that the other electrode layer is formed on the dielectric oxide film. A manganese dioxide layer was formed. Subsequently, a carbon layer and a silver paste layer are sequentially laminated thereon, and then placed on a lead frame, and then the whole is sealed with an epoxy resin, and the size is 7.3 × 4.3 × 2. An 8 mm chip type capacitor was produced.
表１に作製したコンデンサの容量、ＬＣ値の平均値及びバラツキ（２σ：標準偏差値の２倍）、および耐熱特性を示した。なお各試験例につき２０個の試料を作製し測定した平均値および標準偏差値を示した。 Table 1 shows the capacitance, average LC value and variation (2σ: twice the standard deviation value), and heat resistance characteristics of the capacitors produced. In addition, the average value and standard deviation value which produced and measured 20 samples for each test example were shown.
試験例２４〜２９
次ぎに、平均粒径０．７μｍの一部窒化されたニオブ粉からなるニオブ粉末（ニオブ粉を３００℃の条件下で９０分間、窒素ガス雰囲気中に放置して得た。結合した窒素量１８００重量ｐｐｍ。）を用いて、試験例１〜６と同様にして焼結体を得た。さらに他方の電極をピロールとアンソラキノンスルフォン酸と過硫酸アンモニウム水溶液とから作製したポリピロールを用いた以外は試験例１〜６と同様にしてコンデンサを作製した。作製したコンデンサの諸性能を表２に示した。
Test Examples 24-29
Next, niobium powder composed of partially nitrided niobium powder having an average particle size of 0.7 μm (obtained by leaving niobium powder in a nitrogen gas atmosphere at 300 ° C. for 90 minutes. Amount of bound nitrogen 1800 In the same manner as in Test Examples 1 to 6, a sintered body was obtained. Further, a capacitor was produced in the same manner as in Test Examples 1 to 6 except that the other electrode was polypyrrole produced from pyrrole, anthoraquinone sulfonic acid and an ammonium persulfate aqueous solution. Table 2 shows various performances of the manufactured capacitor.
本願発明によれば容量を低下させずにＬＣ値が低くまたはそのバラツキが小さく、あるいは耐熱性が良好なコンデンサを製造することが出来るので、産業上利用できる。 According to the present invention, a capacitor having a low LC value or a small variation or good heat resistance can be produced without reducing the capacity, and thus it can be used industrially.
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| JPH02267915A (en) * | 1989-04-07 | 1990-11-01 | Hitachi Aic Inc | Manufacture of solid-state electrolytic capacitor |
| JPH033311A (en) * | 1989-05-31 | 1991-01-09 | Hitachi Aic Inc | Manufacture of solid electrolytic capacitor |
| JPH09306793A (en) * | 1996-05-14 | 1997-11-28 | Matsushita Electric Ind Co Ltd | Manufacture of capacitor |
| JPH10242004A (en) * | 1997-02-28 | 1998-09-11 | Showa Denko Kk | Capacitor |
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| JPH02267915A (en) * | 1989-04-07 | 1990-11-01 | Hitachi Aic Inc | Manufacture of solid-state electrolytic capacitor |
| JPH033311A (en) * | 1989-05-31 | 1991-01-09 | Hitachi Aic Inc | Manufacture of solid electrolytic capacitor |
| JPH09306793A (en) * | 1996-05-14 | 1997-11-28 | Matsushita Electric Ind Co Ltd | Manufacture of capacitor |
| JPH10242004A (en) * | 1997-02-28 | 1998-09-11 | Showa Denko Kk | Capacitor |
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