WO2010058552A1 - Corps d'électrode pour condensateur et condensateur - Google Patents

Corps d'électrode pour condensateur et condensateur Download PDF

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Publication number
WO2010058552A1
WO2010058552A1 PCT/JP2009/006151 JP2009006151W WO2010058552A1 WO 2010058552 A1 WO2010058552 A1 WO 2010058552A1 JP 2009006151 W JP2009006151 W JP 2009006151W WO 2010058552 A1 WO2010058552 A1 WO 2010058552A1
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WO
WIPO (PCT)
Prior art keywords
layer
capacitor
insulating film
high dielectric
electrode body
Prior art date
Application number
PCT/JP2009/006151
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English (en)
Japanese (ja)
Inventor
藤原英明
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三洋電機株式会社
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Filing date
Publication date
Application filed by 三洋電機株式会社 filed Critical 三洋電機株式会社
Priority to US13/129,983 priority Critical patent/US8587928B2/en
Priority to JP2010539139A priority patent/JP5445464B2/ja
Publication of WO2010058552A1 publication Critical patent/WO2010058552A1/fr

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    • 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
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • 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
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer
    • 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
    • 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
    • H01G9/07—Dielectric layers

Definitions

  • the present invention relates to a capacitor electrode body suitable for use in a large capacity capacitor and a capacitor using the same.
  • the electronic circuits mounted on these electronic devices are required to be smaller, faster and more highly integrated each year.
  • the passive components that form the electronic circuit For example, capacitors are also required to be as short as possible and to have a large capacity.
  • a powder of a valve metal such as aluminum (Al), tantalum (Ta), niobium (Nb), titanium (Ti) or the like capable of anodic oxidation capable of rectifying is added.
  • a powder of a valve metal such as aluminum (Al), tantalum (Ta), niobium (Nb), titanium (Ti) or the like capable of anodic oxidation capable of rectifying.
  • an electrolytic capacitor in which porous pellets obtained by pressure forming and firing are used as an anode body, and dielectric layers made of these metal oxides are formed on the surface of the anode body (see, for example, Patent Document 1) ).
  • an anode body by using a powder at a submicron level for the powder to be used, an anode body having a very large surface area can be obtained, whereby the capacity of the capacitor can be increased.
  • the metal oxide film formed on the surface has a high relative dielectric constant (relative dielectric constant of tantalum oxide: 20 to 30, relative dielectric constant of tantalum oxide) Rate: 83 to 183) It is a high dielectric constant insulating film.
  • the electron affinity of the high dielectric constant insulating film tends to increase as the dielectric constant increases.
  • the present invention has been made in view of such problems, and an object thereof is to realize a large capacity of a capacitor while suppressing a leak current caused by a high dielectric constant insulating film constituting a dielectric layer.
  • One embodiment of the present invention is a capacitor electrode body.
  • the capacitor electrode body is characterized by including a core portion containing nickel and a high dielectric insulating film covering the periphery of the core portion.
  • the presence of the core portion containing nickel having a large work function inside the high dielectric constant insulating film makes it possible to use the high dielectric constant insulating film having a high electron affinity from the core portion.
  • a capacitor with a large capacitance density can be realized while suppressing the occurrence of leakage current to the high dielectric constant insulating film.
  • the capacitor is characterized in that the capacitor electrode body of the above-mentioned embodiment is used on the anode side, and a cathode body formed on the opposite side of the core portion with the high dielectric insulating film interposed therebetween.
  • capacitor electrode body of the above-described embodiment is used on the cathode side, and an anode body formed on the opposite side of the core portion with the high dielectric insulating film interposed therebetween.
  • FIG. 1 is a cross-sectional view showing a structure of a capacitor including a capacitor electrode body according to Embodiment 1. It is a Rutherford backscattering spectrum of the sample which oxidized the surface of the NiTi (alloy) layer provided on the silicon dioxide substrate.
  • FIG. 7 is a cross-sectional view showing a structure of a capacitor including a capacitor electrode body according to Embodiment 2.
  • FIG. 10 is a cross-sectional view showing a structure of a capacitor including the capacitor electrode body according to Embodiment 3.
  • FIG. 1 is a cross-sectional view showing the structure of a capacitor including the capacitor electrode body according to the first embodiment.
  • the capacitor 10 includes an anode substrate 20, a dielectric layer 22, an anode body 30, a dielectric layer 32, a cathode body 40, and a cathode substrate 50.
  • the anode substrate 20 constitutes the anode of the capacitor 10 together with the anode body 30.
  • An anode terminal (not shown) for external extraction is connected to the anode substrate 20.
  • the form of the anode substrate 20 is not particularly limited.
  • a thin film (foil), a lead wire or the like is used.
  • the thickness of the anode substrate 20 is, for example, about 50 to 100 ⁇ m.
  • the anode body 30 is formed on the anode substrate 20, and a part of the anode body 30 is in contact with the anode substrate 20.
  • the anode body 30 is formed by bonding a large number of metal particles, and the bonded metal particles form a network like a network.
  • the anode substrate 20 and the anode body 30 correspond to the “core portion” of the capacitor electrode body according to the first embodiment.
  • the anode substrate 20 and the anode body 30 are formed of a NiTi alloy containing Ni having a large work function (about 5.2 eV).
  • a metal such as Ru, Pt, or Ir may be used.
  • Dielectric layers 22 and 32 are formed on the surfaces of the anode substrate 20 and the anode body 30, respectively.
  • the film thickness of each of the dielectric layers 22 and 32 is 10 nm.
  • the dielectric layers 22 and 32 are formed of titanium oxide.
  • the relative dielectric constant of titanium oxide is about 100, and titanium oxide is a high dielectric constant oxide. That is, the dielectric layers 22 and 32 correspond to the “high dielectric constant insulating film” of the capacitor electrode body according to the first embodiment.
  • metal oxides such as Hf, Zr, Ta, Nb and the like may be used as the high dielectric constant oxide constituting the dielectric layers 22 and 32.
  • the composite material comprising the anode body 30 and the dielectric layer 32 is porous and has a very large specific surface area.
  • At least one Ni atomic layer be formed at the interface between the high dielectric constant insulating film and the core portion.
  • the Ni atomic layer is more preferably formed on the entire interface, but may be partially formed on the interface.
  • a layer of Ni-rich NiTi alloy may be formed at the interface between the high dielectric constant insulating film and the core part compared to the core part.
  • the cathode body 40 constitutes the cathode of the capacitor 10 together with the cathode substrate 50.
  • the cathode body 40 functions as an electrolyte layer, and as the cathode body 40, for example, conductive polymers such as polythiophene, polypyrrole, polyaniline, etc., TCNQ (7,7,8,8-tetracyanoquinodimethane) complex salt, etc. A conductive polymer is used.
  • the cathode body 40 is provided so as to fill the space between the anode substrate 20 and the cathode substrate 50, and is also filled in the gap portion formed by the composite of the anode body 30 and the dielectric layer 32. ing.
  • the base material 50 for the cathode comprises a carbon paste layer 52 laminated on the cathode body 40 and a silver paste layer 54 laminated on the carbon paste layer 52.
  • a cathode terminal (not shown) for external extraction is connected to the cathode substrate 50.
  • a method of manufacturing the capacitor electrode used in the first embodiment will be described.
  • a NiTi alloy with a particle size of 10 nm to 1 ⁇ m is deposited on a NiTi thin film (corresponding to the anode substrate 20) using a cold spray method.
  • the NiTi alloys are connected to each other to form a porous, high surface area network structure, and a NiTi alloy layer (corresponding to the anode body 30) having a high porosity (porosity) is formed.
  • the cold spray method material particles or material powder are sprayed on the surface of the object to be coated in a flow of high temperature and high speed, and material particles are deposited on the surface of the object to be coated to coat the object to be coated Processing method.
  • the cold spray method can form a porous layer having a large surface area as compared with the sintering method, so that the capacity density of the capacitor can be increased.
  • the surfaces of the NiTi alloy layer and the NiTi thin film are oxidized by high temperature oxidation treatment in an environment with a low oxygen partial pressure (for example, under an atmosphere of 20% O 2 and 80% N 2 ).
  • a low oxygen partial pressure for example, under an atmosphere of 20% O 2 and 80% N 2 .
  • the Ni forming the alloy is driven to the inside of the high dielectric constant insulating film made of titanium oxide, the surface of the NiTi alloy layer and the NiTi thin film becomes Ni rich, and the high dielectric constant insulating film and the core portion (NiTi alloy layer and NiTi alloy layer).
  • the nickel concentration at the interface with the NiTi thin film increases.
  • at least one Ni atomic layer is formed.
  • the Ni atomic layer may be formed on the entire interface between the high dielectric constant insulating film and the core part, it may be formed on part of the interface between the high dielectric insulating film and the core part.
  • the capacitor electrode body used in the first embodiment is manufactured by the above steps.
  • FIG. 2 is a Rutherford backscattering spectrum of a sample obtained by oxidizing the surface of a NiTi (alloy) layer provided on a silicon dioxide substrate.
  • the NiTi layer corresponds to the NiTi alloy layer or the NiTi thin film of the first embodiment.
  • the Rutherford backscattering spectrum was measured using an RBS (Rutherford Backscattering Spectrum) measurement apparatus. The main measurement conditions are shown below.
  • Region A titanium oxide layer region B: intermediate layer region changing from titanium oxide layer to NiTi layer C: NiTi layer region D: intermediate layer region changing from NiTi layer to silicon dioxide layer E: silicon dioxide layer (silicon dioxide substrate)
  • the NiTi layer on the silicon dioxide substrate has the same composition in the depth direction before oxidizing the NiTi layer.
  • a titanium oxide layer (region A) is formed on the surface of the NiTi layer (region C) via the intermediate layer (region B) Ni in the titanium layer (region A) and in the intermediate layer (region B) migrate to the silicon dioxide substrate side and concentrate in the NiTi layer (region C). Therefore, the Ni concentration is higher at the outermost surface of the NiTi layer (region C) than at the deepest portion of the NiTi layer (region C).
  • a Ni-rich region was formed on the surface (the titanium oxide layer side) of the NiTi layer by oxidizing the NiTi layer.
  • a Ni layer or Ni-rich NiTi alloy having a large work function is formed at the interface between the core portion to be an anode and the high dielectric constant insulating film. Existing. As a result, even when a high dielectric constant insulating film having a high electron affinity is used, it is possible to realize a capacitor having a large capacitance density while suppressing the occurrence of a leak current.
  • the material used for the core portion is a cheaper NiTi alloy instead of Ta used in the conventional solid electrolytic capacitor, a large capacity capacitor can be manufactured at lower cost.
  • the film thickness of the high dielectric constant insulating film obtained by oxidizing the surface without changing the composition of the NiTi alloy to be the core portion it is possible to easily suppress the leakage current to various breakdown voltages required for the capacitor. It can correspond.
  • the energy difference between the Fermi level of Ni or Ni rich NiTi alloy and the conduction band of the high dielectric constant insulating film at the interface between the core portion and the high dielectric constant insulating film Is about 1 eV or more. Therefore, when the effective work function of the cathode body 40 (conductive polymer) is large, the capacitor electrode side composed of the core portion and the high dielectric constant insulating film is used as a cathode, and the cathode body 40 is used as an "anode body". By using it, leakage current can be suppressed.
  • FIG. 3 is a cross-sectional view showing a structure of a capacitor including the capacitor electrode body according to the second embodiment.
  • Ni is used as the material of the core portion, that is, the base material 20 for the anode and the anode body 30. More specifically, the anode body 30 is formed by bonding a large number of Ni particles.
  • a metal such as Ru, Pt, or Ir may be used.
  • a Ta layer 31 containing Ta intervenes in the bonding portion between Ni particles, and the Ta layer 31 is a part of the anode body 30. Similarly, a Ta layer 31 intervenes in the connection portion between the anode substrate 20 and the anode body 30. More specifically, the Ta layer 31 is formed of a Ta layer, a NiTa alloy layer, or a mixed layer of a Ta layer and a NiTa alloy layer.
  • the high dielectric constant insulating film that is, the dielectric layers 22 and 32 are formed of tantalum oxide.
  • the relative dielectric constant of tantalum oxide is about 28, and tantalum oxide is a high dielectric constant oxide.
  • metal oxides such as Hf, Zr, Ti, Nb and the like may be used as the high dielectric constant oxides constituting the dielectric layers 22 and 32.
  • a Ta layer is formed on a Ni thin film (corresponding to the anode substrate 20) using a CVD method or the like.
  • Ni particles covered with a Ta film with a particle size of 10 nm to 1 ⁇ m are deposited on the Ta layer using a cold spray method.
  • the Ni particles are connected to each other through the Ta film to form a porous, high surface area network structure, and a Ni-gold layer (corresponding to the anode body 30) having a high porosity is formed.
  • the Ta film present between the Ni particles is thinner than before the deposition due to the pressure when the Ni particles collide with each other.
  • the Ni particles and the Ni thin film are connected via a Ta film and a Ta layer.
  • anodizing treatment is performed to oxidize the exposed portions of the Ta film and the Ta layer, thereby forming a covering layer made of tantalum oxide, that is, a high dielectric constant insulating film.
  • the Ta film interposed between the Ni particles and the Ta layer interposed between the Ni particles and the Ni thin film (hereinafter collectively referred to as a residual Ta layer) are not oxidized and remain as metals.
  • Ni is diffused from the Ni particles or the Ni thin film into the remaining Ta layer by thermal oxidation. For this reason, the remaining Ta layer contains Ni. That is, the remaining Ta layer (Ta layer 31 in FIG. 3) is formed of a Ta layer, a NiTa alloy layer, or a mixed layer composed of a Ta layer and a NiTa alloy layer.
  • the capacitor electrode body used in the second embodiment is manufactured by the above steps.
  • the core portion made of Ni having a large work function exists inside the high dielectric constant insulating film.
  • a high dielectric constant insulating film having a large electron affinity is used, it is possible to realize a capacitor having a large capacity density while suppressing the generation of a leak current from the core portion to the high dielectric constant insulating film. it can.
  • the material used for the core part is replaced with Ta used in the conventional solid electrolytic capacitor, and Ni which is less expensive is used, and the part where Ta is used is only the Ta film.
  • the amount of use of Ta is reduced compared to the conventional case, and a large capacity capacitor can be manufactured at lower cost.
  • the oxidation of the Ta film can be carried out by anodic oxidation which has been used in the manufacture of conventional solid electrolytic capacitors. For this reason, it is possible to reduce the manufacturing cost of the capacitor without requiring special manufacturing.
  • the energy difference between the Fermi level of Ni and the conduction band of the high dielectric constant insulating film is about 1 eV or more at the interface between the core portion and the high dielectric constant insulating film. . Therefore, when the effective work function of the cathode body 40 (conductive polymer) is not large, the leakage current is suppressed by using the capacitor electrode side including the core portion and the high dielectric constant insulating film as a cathode. Can.
  • FIG. 4 is a cross-sectional view showing a structure of a capacitor including the capacitor electrode body according to the third embodiment.
  • Ni is used as the material of the core portion, that is, the base material 20 for the anode and the anode body 30. More specifically, the anode body 30 is formed by bonding a large number of Ni particles.
  • a metal such as Ru, Pt, or Ir may be used.
  • the high dielectric constant insulating film that is, the dielectric layers 22 and 32 are formed of titanium oxide.
  • metal oxides such as Hf, Zr, Ta, Nb and the like may be used as the high dielectric constant oxide constituting the dielectric layers 22 and 32.
  • the core portion made of Ni is formed inside the high dielectric constant insulating film made of titanium oxide.
  • the outermost layer of the core portion may be oxidized to form a nickel oxide layer, but also in this case, the effective work function of the Ni electrode is large, and the leak current can be effectively suppressed.
  • Ni particles with a particle size of 10 nm to 1 ⁇ m are deposited on a Ni thin film (corresponding to the anode substrate 20) using a cold spray method. Thereby, the Ni particles are connected to each other to form a porous and high surface area network structure, and a Ni layer (corresponding to the anode body 30) having a high porosity is formed.
  • a Ti film made of Ti is formed on the surfaces of the Ni layer and the Ni thin film using a plating method, an ion plating method, or the like.
  • the film thickness of the Ti film is, for example, 10 nm.
  • the Ti film is rapidly oxidized by high temperature oxidation treatment in a low oxygen partial pressure environment (for example, under an atmosphere of 20% O 2 and 80% N 2 ).
  • a low oxygen partial pressure environment for example, under an atmosphere of 20% O 2 and 80% N 2 .
  • the Ni layer and the Ni thin film are covered with the high dielectric constant insulating film made of titanium oxide.
  • the outermost layer of the core may be oxidized to form a nickel oxide layer, but also in this case, the effective work function of the Ni electrode is large, and the leakage current can be effectively suppressed. it can.
  • the capacitor electrode body used in the third embodiment is manufactured by the above steps.
  • the core portion made of Ni having a large work function exists inside the high dielectric constant insulating film.
  • a high dielectric constant insulating film having a large electron affinity is used, it is possible to realize a capacitor having a large capacity density while suppressing the generation of a leak current from the core portion to the high dielectric constant insulating film. it can.
  • the material used for the core part is Ni which is cheaper instead of Ta used in the conventional solid electrolytic capacitor, a large capacity capacitor can be manufactured at lower cost.
  • the film thickness of the high dielectric constant insulating film obtained by oxidation can be changed. As described above, by changing the thickness of the high dielectric constant insulating film, various withstand voltages required for the capacitor can be easily coped with.
  • the energy difference between the Fermi level of Ni and the conduction band of the high dielectric constant insulating film is about 1 eV or more at the interface between the core portion and the high dielectric constant insulating film. .
  • the electrode body for the capacitor comprising the core portion and the high dielectric constant insulating film is used as a cathode, and the cathode body 40 is an "anode body". Leakage current can be suppressed by using as.
  • the cold spray method is used to deposit the particles containing Ni, but as a process for depositing the particles containing Ni, the sintering method, the aerosol deposition method, and the powder are used.
  • Other methods such as jet method and CVD method may be used.
  • the present invention has industrial applicability in the field of a capacitor electrode body suitable for use in a large capacity capacitor and a capacitor using the same.

Abstract

L’invention concerne un condensateur (10) qui comprend un substrat d'électrode positive (20), une couche diélectrique (22), un corps d'électrode positive (30), une couche diélectrique (32), un corps d'électrode négative (40) et un substrat d'électrode négative (50). Le corps d'électrode positive (30) est formé sur le substrat d'électrode positive (20), de telle manière qu'une partie du corps d'électrode positive (30) est en contact avec le substrat d'électrode positive (20). Le corps d'électrode positive (30) est formé par combinaison d'une pluralité de particules métalliques, de telle sorte que les particules métalliques combinées forment un réseau maillé. Le substrat d'électrode positive (20) et le corps d'électrode positive (30) (une partie centrale) sont formés à partir d'un alliage NiTi contenant Ni qui présente un travail d'extraction important. Les couches diélectriques (22) et (32) (films isolants à constante diélectrique élevée) sont formées à partir d'oxyde de titane. Il est souhaitable qu'au moins une couche atomique de Ni soit formée à l'interface entre les films isolants à constante diélectrique élevée et la partie centrale. Il est davantage désirable que la couche atomique de Ni soit formée sur la totalité de l'interface, mais la couche atomique de Ni peut être formée sur une partie de l'interface.
PCT/JP2009/006151 2008-11-19 2009-11-17 Corps d'électrode pour condensateur et condensateur WO2010058552A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/129,983 US8587928B2 (en) 2008-11-19 2009-11-17 Electrode for capacitor and capacitor
JP2010539139A JP5445464B2 (ja) 2008-11-19 2009-11-17 コンデンサ用電極体およびコンデンサ

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JP2008-296069 2008-11-19
JP2008296069 2008-11-19

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WO2010058552A1 true WO2010058552A1 (fr) 2010-05-27

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JP (1) JP5445464B2 (fr)
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2019169715A (ja) * 2015-08-12 2019-10-03 株式会社村田製作所 コンデンサおよびその製造方法
WO2020161832A1 (fr) * 2019-02-06 2020-08-13 朝日インテック株式会社 Fil-guide

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Publication number Priority date Publication date Assignee Title
KR20130076793A (ko) * 2010-04-07 2013-07-08 도요 알루미늄 가부시키가이샤 전극 구조체의 제조 방법, 전극 구조체 및 콘덴서
TWI801222B (zh) * 2022-04-26 2023-05-01 國立成功大學 多元合金材料層、其製造方法及半導體裝置的電容結構

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US20070127189A1 (en) * 2005-12-02 2007-06-07 Vishay Sprague, Inc. Surface mount chip capacitor
JP2007317784A (ja) * 2006-05-24 2007-12-06 Tdk Corp 固体電解コンデンサ

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JP2003257787A (ja) 2002-03-01 2003-09-12 Sanyo Electric Co Ltd 固体電解コンデンサ及びその製法
US7190016B2 (en) * 2004-10-08 2007-03-13 Rohm And Haas Electronic Materials Llc Capacitor structure

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US20070127189A1 (en) * 2005-12-02 2007-06-07 Vishay Sprague, Inc. Surface mount chip capacitor
JP2007317784A (ja) * 2006-05-24 2007-12-06 Tdk Corp 固体電解コンデンサ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019169715A (ja) * 2015-08-12 2019-10-03 株式会社村田製作所 コンデンサおよびその製造方法
WO2020161832A1 (fr) * 2019-02-06 2020-08-13 朝日インテック株式会社 Fil-guide
JPWO2020161832A1 (ja) * 2019-02-06 2021-11-25 朝日インテック株式会社 ガイドワイヤ
JP7183308B2 (ja) 2019-02-06 2022-12-05 朝日インテック株式会社 ガイドワイヤ

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US8587928B2 (en) 2013-11-19
JPWO2010058552A1 (ja) 2012-04-19
US20110222210A1 (en) 2011-09-15
JP5445464B2 (ja) 2014-03-19

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