WO1998038660A1 - Capacitor - Google Patents
Capacitor Download PDFInfo
- Publication number
- WO1998038660A1 WO1998038660A1 PCT/JP1998/000823 JP9800823W WO9838660A1 WO 1998038660 A1 WO1998038660 A1 WO 1998038660A1 JP 9800823 W JP9800823 W JP 9800823W WO 9838660 A1 WO9838660 A1 WO 9838660A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- niobium
- capacitor
- electrode
- dielectric
- niobium nitride
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
Definitions
- the present invention relates to a novel capacitor, in particular, a capacitor that is inexpensive and has good leakage current characteristics, and a capacitor that has high capacitance, particularly high capacitance at high frequency per unit weight and has good leakage current characteristics.
- an electrode of a condenser one using aluminum, tantalum, or an alloy thereof is known as one using a sintered metal body.
- These capacitors are used for various purposes.One of them is a capacitor used in a so-called smoothing circuit to obtain direct current from alternating current. It is said that it is desirable that As an example, the above two characteristics are required to suppress the "whisker-like voltage" that occurs when converting to DC, and to make it closer to DC.
- tantalum oxide is used as a dielectric for a capacitor using a tantalum sintered body.However, by using a material having a dielectric constant higher than that of the tantalum oxide, an ultra-small capacitor can be obtained. sell. Such materials include titanium oxide, : Niobium oxide, etc. is considered, but in reality it has not reached the level of practical use due to poor leakage current (hereinafter abbreviated as LC) characteristics.
- the present inventor has found that the sintered body of niobium nitride has a small amount of oxygen adhering to the surface and has good leakage current characteristics, and the LC failure force of a capacitor using niobium oxide as a dielectric ⁇
- the inventor has found that oxygen contributed to the dielectric has a negative effect, which has led to the completion of the present invention.
- at least one kind of compound selected from organic semiconductors and inorganic semiconductors having no excessive oxygen supply capability is used as the other electrode, it is possible to manufacture a capacitor having a large capacitance at a high frequency. I found it.
- an organic semiconductor and an inorganic semiconductor having an electric conductivity of 10 12 S cm ⁇ 1 to 10 3 S cm ⁇ 1 are used as the organic semiconductor and the inorganic semiconductor, further low impedance characteristics can be obtained. Can be manufactured.
- a capacitor composed of a pair of electrodes and a dielectric material interposed between the electrodes, a capacitor characterized in that one electrode is formed of a sintered body of niobium nitride is provided.
- the dielectric of the capacitor is preferably made of niobium oxide, more preferably niobium oxide formed by electrolytic oxidation of a niobium nitride sintered body.
- the other electrode is electrolyte above Kiko Ndenza, also made one compound with at least selected from organic semiconductors and inorganic semiconductors, more preferred properly the electric conductivity of 1 0- 2 S cm one 1-1 0 It is composed of at least one kind of compound selected from organic semiconductors and inorganic semiconductors that have 3 Scm- 1 .
- Figure 1 is a best mode for carrying out the c invention 'is a partially cutaway perspective view showing an example of a specific structure of Kondenza of the present invention
- the niobium nitride constituting one electrode of the condenser of the present invention is obtained by partially nitriding metal niobium.
- Niobium nitride for example, is obtained by displaying niobium powder in a nitrogen atmosphere. It is obtained as a powder by nitriding two sides.
- the amount of nitrogen bonded to niobium is 100 to 200,000 ppm by weight, preferably 100 to 500,000 ppm by weight.
- Nitrogenation is performed at a temperature of 2000 ° C. or less, and the time is several 10 hours. The desired amount of nitrogen can be obtained.
- Niobium nitride can be obtained. If the niobium powder is allowed to flow under nitrogen for several 10 hours even at room temperature, a niobium nitride powder having a nitrogen amount of several 10 Opm can be obtained.
- the shape of the niobium nitride powder thus obtained is not much different from the shape of the raw material niobium powder.
- the niobium powder is obtained by pulverizing a niobium lump, the obtained niobium nitride powder also has various shapes peculiar to the pulverized material.
- the niobium powder is formed into secondary particles obtained by granulating fine powder obtained by, for example, reducing niobium hydrofluoride, the obtained niobium nitride powder is also similar to the secondary particles. become.
- the particle size of the niobium nitride powder is such that if the average particle size of the niobium powder as a raw material is, for example, 0.5 zm to 100 ⁇ m,
- the sintered body of niobium nitride c having the same average particle size can be obtained, for example, by sintering niobium nitride powder at a high temperature under vacuum.
- the niobium nitride sintered body of the present invention can be obtained. If the degree of vacuum is insufficient, air is entrained during sintering and oxidation proceeds at the same time as nitridation, so that the performance of the capacitor using the target sintered body of niobium nitride as an electrode deteriorates. Generally, the sintering temperature varies depending on the particle size of the niobium nitride powder, but the smaller the particle size, the lower the temperature.
- tantalum oxide for example, tantalum oxide, niobium oxide, a polymer substance, a ceramic compound, or the like can be used.
- tantalum oxide is obtained by attaching a tantalum-containing complex, for example, an alkoxy complex, an acetyl-acetonate complex, or the like to an electrode, followed by hydrolysis and / or thermal decomposition. It can also be made.
- niobium oxide is used as the dielectric
- niobium oxide is used to form niobium nitride, which is one of the electrodes, in an electrolytic solution, or a complex containing niobium, such as an alkoxy complex or an acetyl acetate complex.
- a complex containing niobium such as an alkoxy complex or an acetyl acetate complex.
- the niobium nitride electrode is formed in an electrolytic solution, or : Others by the This hydrolysis and / or pyrolyzing niobium-containing complex on NbN electrodes, chemical conversion can be formed of niobium oxide dielectric on the surface of niobium nitride electrode (niobium in an electrolytic solution).
- the reaction is usually carried out using an aqueous solution of protonic acid, for example, 0.1% aqueous solution of phosphoric acid, or using an aqueous solution of sulfuric acid.
- This capacitor becomes an electrolytic capacitor.
- the niobium nitride side becomes the anode
- niobium nitride has no theoretical polarity and can be used either as an anode or a cathode.
- a monomer is introduced in a gaseous or liquid state into pores or voids of a metal to carry out polymerization.
- the polymer substance include fluorine resin, alkyd resin, acrylic resin, polyester resin such as polyethylene terephthalate, vinyl resin, xylylene resin, and phenol resin. are used.
- a ceramic compound as a dielectric, for example, as described in Japanese Patent Application Laid-Open No.
- a perovskite compound is added to the surface of a metal having pores or voids. Can be adopted.
- B a T i 0 3 S r T i 0, M g T i 0 3, etc.
- B a S n 0 3 is like et be.
- the other electrode of the capacitor of the present invention is not particularly limited.
- Compounds As a specific example of the electrolytic solution, a mixed solution of dimethylformamide and ethylene glycol in which 5% by weight of isobutyltripropylammoniumborofluoride electrolyte is dissolved, tetraethylammonium boronate trafluoride is used.
- a mixed solution of propylene-based water and ethylen glycol dissolved at 7% by weight is exemplified.
- organic semiconductor examples include an organic semiconductor composed of benzopyrroline tetramer and kulanilanil, an organic semiconductor composed mainly of tetrathiotetracene, and an organic semiconductor composed mainly of tetra (tetraquino) dimethane.
- Semiconductors organic semiconductors based on conductive polymers obtained by doping dopants into polymers represented by the following general formula (1) or (2), lead monoxide or manganese dioxide And inorganic semiconductors composed of triiron tetroxide. These semiconductors may be used alone or in combination of two or more.
- R 1 to R 4 represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
- X may represent an oxygen, zeo or nitrogen atom, R 5 may be present only when X is a nitrogen atom and represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R 1 and R 2 and R 3 May be bonded to each other to form a ring.
- Examples of the polymer represented by the formulas (1) and (2) include poly (aniline), polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, and polypyrrolene. And polymethylpyrrol.
- the capacitor of the present invention is composed of a pair of electrodes and a dielectric material interposed between the electrodes, and the structure itself may be the same as that conventionally used.
- FIG. 1 shows a specific example of the condenser of the present invention.
- the core part of the condenser shown in Fig. 1 is formed by forming niobium nitride sintered body 1 in an electrolytic solution or hydrolyzing diobium-containing complex and Z Of niobium oxide An electric body layer is formed, a plurality of niobium nitride sintered bodies each having the dielectric layer formed as described above are combined, and the other electrode is formed on the dielectric layer.
- a carbon paste 2 and a silver paste 3 are sequentially laminated on the other electrode, and sealed with a material such as epoxy resin to form a capacitor.
- This capacitor has a niobium lead 4 which is sintered and formed integrally with a niobium nitride sintered body or later welded.
- This capacitor is combined with an anode lead 5 and a cathode lead 6 and is surrounded by an outer resin 7 such as an epoxy resin.
- the capacitor to which the niobium lead 4 exemplified above is coupled has a rectangular parallelepiped shape, but the shape of the capacitor is not particularly limited, and may be, for example, a circular shape.
- Niobium powder having a particle size of 10 to 40 m was reacted at 400 ° C. in a nitrogen atmosphere to obtain niobium nitride powder.
- the amount of nitrogen was about 2000 weight ppm.
- the powder was sintered at 150 ° C. in a vacuum to obtain a niobium nitride sintered body (1 Om m0, thickness about lmm, porosity 45%, average pore size 3 u rn). Then, a dielectric of niobium oxide was formed on the sintered body by forming 20 V in a phosphoric acid aqueous solution.
- a plurality of niobium nitride sintered bodies formed up to the dielectric thus obtained were prepared, and the other electrode shown in Table 1 was formed on the dielectric. Further, a carbon paste and a silver paste were sequentially laminated on the other electrode, and sealed with an epoxy resin to produce a capacitor.
- Table 2 shows the capacitance (measured 100 kHz) of the fabricated capacitor and the LC value at 4 V.
- Niobium nitride powder having a particle size of 40 to 80 m was sintered in vacuum at 160 ° C to obtain a niobium nitride sintered body (1 Omm0, thickness: lmm, porosity 55%, average pore 7m).
- the sintered body of niobium nitride is immersed in a pentaethyl niobate solution, pulled up, reacted in steam at 85 ° C, and further dried at 350 ° C to be oxidized on the sintered body.
- a niobium dielectric film was formed.
- Example 8 A plurality of niobium nitride sintered bodies formed up to the dielectric material obtained in this manner were prepared, and the chloranil complex of tetrathotetracene was used as the other electrode in the same manner as in Examples 1 and 6.
- Example 8 A mixture of lead acetate and lead sulfate (Example 9) was formed on a dielectric. Subsequently, a silver paste and a silver paste were sequentially laminated on the other electrode, and sealed with an epoxy resin to produce a capacitor. Table 2 shows the performance values of the manufactured capacitors. Comparative Examples 1 and 2
- a tantalum powder having a particle size of 10 to 40 m was prepared and sintered in vacuum at 150,000 to obtain a tantalum sintered body (10 mm ⁇ , thickness of about 1 mm, pores). Rate 45%, average pore size 3 m). Then, a tanned oxide dielectric was formed on the sintered body by forming a 20 V chemical solution in a phosphoric acid aqueous solution.
- a plurality of tantalum sintered bodies formed up to the dielectric material thus obtained were prepared, and chloranil complexes of tetrathoteotetracene were used as the other electrodes in the same manner as in Example 1 and Example 6 (Comparative Example).
- a mixture of lead acetate and lead sulfate (Comparative Example 2) was formed on a dielectric. Thereafter, a carbon paste and a silver paste were sequentially laminated in the same manner as in the example, and sealed with an epoxy resin to produce a capacitor.
- Table 2 shows the performance values of the manufactured capacitors.
- Examples 1 and 6 capacitors were produced in the same manner as in Examples i and 6, except that a niobium sintered body was used without performing the nitrogen treatment.
- Table 2 shows the performance values of the produced condenser.
- a capacitor was manufactured in the same manner as in Example 10 except that a niobium sintered body was used instead of the niobium nitride sintered body in Example 10.
- Table 3 shows the characteristic values of the produced condenser.
- a capacitor was manufactured in the same manner as in Example 11 except that a niobium sintered body was used instead of the niobium nitride sintered body in Example 11.
- Table 3 shows the performance values of the manufactured capacitors.
- a capacitor was manufactured in the same manner as in Example 12, except that a niobium sintered body was used instead of the niobium nitride sintered body used in Example 12.
- Table 4 shows the performance values of the manufactured capacitors.
- a capacitor using a niobium nitride sintered body as an electrode according to the present invention is excellent in environmental stability and has little leakage current (LC) characteristic failure.
- a sintered body of niobium nitride is used as one electrode, the other electrode is at least one compound selected from organic semiconductors and inorganic semiconductors, and a dielectric between the electrodes is niobium oxide.
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/171,902 US6115235A (en) | 1997-02-28 | 1998-02-27 | Capacitor |
EP98966979A EP0953847B1 (en) | 1997-02-28 | 1998-02-27 | Capacitor with an electrode composed of a sintered body of partially nitrided niobium powder |
CNB988005042A CN1192404C (zh) | 1997-02-28 | 1998-02-27 | 部分氮化的铌粉,制备该铌粉的方法、该铌粉的烧结体,制备该烧结体的方法及电容器 |
DE69829945T DE69829945T2 (de) | 1997-02-28 | 1998-02-27 | KONDENSATOR MIT EINER ELEKTRODE AUS EINEM SINTERKöRPER AUS TEILWEISE NITRIDIERTEM NIOBPULVER |
HK00101866A HK1022948A1 (en) | 1997-02-28 | 2000-03-27 | Capacitor with an electrode composed of a sinteredbody of partially nitrided niobium powder. |
US10/012,285 US6452777B1 (en) | 1997-02-28 | 2001-12-12 | Capacitor |
US10/834,050 US7006343B2 (en) | 1997-02-28 | 2004-04-29 | Capacitor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/45650 | 1997-02-28 | ||
JP04565097A JP3254163B2 (ja) | 1997-02-28 | 1997-02-28 | コンデンサ |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/171,902 A-371-Of-International US6115235A (en) | 1997-02-28 | 1998-02-27 | Capacitor |
US62089800A Division | 1997-02-28 | 2000-07-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998038660A1 true WO1998038660A1 (en) | 1998-09-03 |
Family
ID=12725261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/000823 WO1998038660A1 (en) | 1997-02-28 | 1998-02-27 | Capacitor |
Country Status (7)
Country | Link |
---|---|
US (5) | US6115235A (ja) |
EP (1) | EP0953847B1 (ja) |
JP (1) | JP3254163B2 (ja) |
CN (1) | CN1192404C (ja) |
DE (1) | DE69829945T2 (ja) |
HK (1) | HK1022948A1 (ja) |
WO (1) | WO1998038660A1 (ja) |
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KR100799634B1 (ko) | 1999-07-15 | 2008-01-30 | 쇼와 덴코 가부시키가이샤 | 니오브분, 니오브분 소결체 및 그것을 사용한 콘덴서 |
US6960237B2 (en) | 1999-07-15 | 2005-11-01 | Showa Denko Kabushiki Kaisha | Niobium powder, sintered body thereof and capacitor using the same |
US6600646B1 (en) * | 1999-08-11 | 2003-07-29 | Showa Denko Kabushiki Kaisha | Niobium powder, sintered body thereof and capacitor using same |
US6671164B2 (en) * | 2000-04-24 | 2003-12-30 | Showa Denko Kabushiki Kaisha | Niobium powder, sintered body using the powder, and capacitor using the same |
US6855184B2 (en) | 2002-04-26 | 2005-02-15 | Showa Denko K.K. | Niobium powder, sintered body thereof and capacitor using the same |
WO2003091466A1 (en) * | 2002-04-26 | 2003-11-06 | Showa Denko K.K. | Niobium powder, sintered body thereof and capacitor using the same |
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US8264819B2 (en) | 2005-08-19 | 2012-09-11 | Avx Corporation | Polymer based solid state capacitors and a method of manufacturing them |
US8114340B2 (en) | 2005-09-02 | 2012-02-14 | Avx Corporation | Method of forming anode bodies for solid state capacitors |
US7760487B2 (en) | 2007-10-22 | 2010-07-20 | Avx Corporation | Doped ceramic powder for use in forming capacitor anodes |
US7760488B2 (en) | 2008-01-22 | 2010-07-20 | Avx Corporation | Sintered anode pellet treated with a surfactant for use in an electrolytic capacitor |
US7768773B2 (en) | 2008-01-22 | 2010-08-03 | Avx Corporation | Sintered anode pellet etched with an organic acid for use in an electrolytic capacitor |
US7852615B2 (en) | 2008-01-22 | 2010-12-14 | Avx Corporation | Electrolytic capacitor anode treated with an organometallic compound |
US8203827B2 (en) | 2009-02-20 | 2012-06-19 | Avx Corporation | Anode for a solid electrolytic capacitor containing a non-metallic surface treatment |
Also Published As
Publication number | Publication date |
---|---|
CN1192404C (zh) | 2005-03-09 |
US20020067586A1 (en) | 2002-06-06 |
US20030026061A1 (en) | 2003-02-06 |
EP0953847B1 (en) | 2005-04-27 |
US7006343B2 (en) | 2006-02-28 |
US20040202600A1 (en) | 2004-10-14 |
US6347032B2 (en) | 2002-02-12 |
US6856500B2 (en) | 2005-02-15 |
EP0953847A4 (en) | 2001-02-07 |
US6115235A (en) | 2000-09-05 |
DE69829945T2 (de) | 2006-03-23 |
JPH10242004A (ja) | 1998-09-11 |
EP0953847A1 (en) | 1999-11-03 |
JP3254163B2 (ja) | 2002-02-04 |
HK1022948A1 (en) | 2000-08-25 |
US20010024351A1 (en) | 2001-09-27 |
DE69829945D1 (de) | 2005-06-02 |
US6452777B1 (en) | 2002-09-17 |
CN1224529A (zh) | 1999-07-28 |
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