WO2005050721A1 - Method for preparing ruthenium oxide-thin film using electrodeposition - Google Patents

Method for preparing ruthenium oxide-thin film using electrodeposition Download PDF

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Publication number
WO2005050721A1
WO2005050721A1 PCT/KR2003/002891 KR0302891W WO2005050721A1 WO 2005050721 A1 WO2005050721 A1 WO 2005050721A1 KR 0302891 W KR0302891 W KR 0302891W WO 2005050721 A1 WO2005050721 A1 WO 2005050721A1
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WO
WIPO (PCT)
Prior art keywords
plate
thin film
electrode
ruthenium oxide
working electrode
Prior art date
Application number
PCT/KR2003/002891
Other languages
English (en)
French (fr)
Inventor
Oh Shim Joo
Kwang-Deog Jung
C. D. Lokhande
Bong-Ok Park
Original Assignee
Korea Institute Of Science And Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Institute Of Science And Technology filed Critical Korea Institute Of Science And Technology
Priority to AU2003288772A priority Critical patent/AU2003288772A1/en
Publication of WO2005050721A1 publication Critical patent/WO2005050721A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes
    • H01L28/65—Electrodes comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes

Definitions

  • the present invention relates to a novel method for preparing a ruthenium oxide-thin film by electrodeposition, which can be advantageously used in the fabrication of an electrode for an electrochemical capacitor.
  • Ruthenium oxide (Ru0 2 ) is an attractive electrode material for electrochemical capacitors, since it exhibits a low electric resistance, excellent stability when exposed to thermal or chemical stress, high charge storage capacity which is ten times higher than that of a carbon electrode, and highly reversible redox reaction at a wide range of potential.
  • a sputtering process see [M. Takeuchi, K. Miwada and H. Nagasako, Appl. Surf. Sci. 12/13 (1982) 298]
  • a sol-gel process see [J.P. Zheng, P. J. Cygan and T.R. Jow, J. Electrochem.
  • a method for preparing an amorphous ruthenium oxide-thin film having a high specific capacitance under the mild conditions which is suited for an electrode for an electrochemical capacitor.
  • a method for preparing a ruthenium oxide-thin film which comprises the steps of: a) mtmersing a working electrode-plate and a counter electrode in an electrodeposition bath containing 0.001 to 0.1 M aqueous ruthenium salt solution having a pH of 1.0 to 2.5, and b) applying an electric current of 1 to 50 mA/cm 2 between the working electrode-plate and the counter electrode.
  • FIG. 1 scanning electron microscope (SEM) scan of the Ru0 2 thin film obtained in Example.
  • the inventive method is characterized in that ruthenium oxide particles are electodeposited on a substrate plate by way of using an electrolyte having a specific concentration of a ruthenium salt at a controlled pH range, which leads to the formation of an amorphous Ru0 2 thin film suitable for use as an electrode for an electrochemical capacitor having a high capacitance per unit mass (F/g).
  • the electrodeposition process as used in the present invention is generally suitable for forming a uniform film on a substrate having a complex shape and porosity. The thickness of such a Ru0 2 film can be easily controlled by adjusting the deposition rate, and the process does not require a separate heat-treatment step.
  • the process of the present invention may be conducted as follows: A conductive working electrode-plate, an anode, which is to be coated with Ru0 2 particles and a counter electrode, a cathode, are immersed in an electrodeposition bath containing a ruthenium salt, and then an electric current is applied across the anode and the cathode, while stirring the electrodeposition bath, to electrodeposit ruthenium oxide particles on the substrate plate.
  • the ruthenium salts are present at a concentration ranging from 0.001 to 0.1 M in the aqueous electrolyte of the present invention.
  • the pH of the electrolyte is adjusted to 1.0 to 2.5 with an acid such as hydrochloric acid. When the pH and the concentration of the electrolyte is out of the specified ranges, the electrodeposition of ruthenium oxide does not occur.
  • the electrolyte does not contain a complexing agent, and if necessary, it may be deaerated prior to use.
  • Suitable for use as the working electrode-plate of the present invention is a conductive material having an electrochemical stability, and representative examples thereof include titanium (Ti), indium-tin-oxide (ITO) coated glass, stainless steel, nickel (Ni) and a carbonaceous material.
  • the surface of the working-electrode plate may be coated by chemical vapor deposition with a carbon nanomaterial such as carbon nanotubes, carbon nanofibers and amorphous carbons in order to obtain an electrode having a higher specific capacitance.
  • Such the coating of a carbon nanomaterial may be carried out by contacting the surface of the working-electrode plate with a mixture of hydrogen and a hydrocarbon at a temperature ranging from 400 to 1200 ° C, and representative examples of the hydrocarbon include acetylene, ethylene, methane, propane, butane and the like.
  • the working-electrode plate is pre-treated prior to the deposition thereon of Ru0 2 , e.g., by mechanically scrubbing with a polishing-paper, washing with distilled water, etching with a HC1 solution, and then ultrasonically cleaning.
  • the counter electrode plate used in the present invention may be a conventional platinium electrode.
  • the electrodeposition of step b) may be performed by applying an electric current ranging from 1 to 50 mA/cm , more preferably from 2 to 10 mA cm 2 at a temperature ranging from 0 to 100 ° C, preferably from 25 to
  • the resulting Ru0 2 thin film may be dried at a temperature ranging from 25 to 100 ° C under an inert gas atmosphere.
  • continuous current electrodeposition occurs within the specified pH and concentration ranges, which results in electrodeposition of ruthenium oxide formed from ruthenium hydroxide generated by the hydrolysis of a ruthenium salt.
  • the Ru0 2 thin film prepared in accordance with the present invention is amorphous and has a high specific capacitance, and thus it can be advantageously used, besides as an electrode for an electrochemical capacitor, in the hybrid system of electric motorcar, camera flash, laser and pulse beam generator.
  • the following Example is intended to illustrate the present invention more specifically, without limiting the scope of the invention.
  • a Ti plate (1cm x 1cm) was scrubbed with a polishing-paper, washed with distilled water, etched using 3% hydrochloric acid, and then ultrasonically cleaned.
  • the surface-treated Ti plate and a Pt plate were immersed in an electrodeposition bath containing 0.04 M deaerated aqueous RuCl 3 - xH 2 0 solution whose pH was 2.15.
  • an electrodeposition process was performed by applying a current of 5 mA cm 2 between the Ti and Pt electrodes for about 1 hour, while maintaining the electrodeposition bath at 55 ° C, to obtain a uniform blackish ruthenium oxide-thin film formed on the Ti plate, which had a thickness of 1.3 to 1.5 j_m.
  • Ru0 thin film prepared in accordance with the present invention exhibits a high specific capacitance and thus can be advantageously used as an electrode for an electrochemical capacitor having high performance characteristics.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
PCT/KR2003/002891 2003-11-19 2003-12-30 Method for preparing ruthenium oxide-thin film using electrodeposition WO2005050721A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003288772A AU2003288772A1 (en) 2003-11-19 2003-12-30 Method for preparing ruthenium oxide-thin film using electrodeposition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2003-0082026 2003-11-19
KR1020030082026A KR100578734B1 (ko) 2003-11-19 2003-11-19 전착법을 이용한 루테늄 산화물 박막의 제조방법

Publications (1)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100521014C (zh) * 2006-05-30 2009-07-29 中南大学 超级电容器RuO2涂层阴极薄膜材料的制备工艺
CN101525760B (zh) * 2009-04-17 2011-03-23 中南大学 一种用于制备超级电容器RuO2电极材料的电沉积工艺
EP2581971A1 (de) 2011-10-11 2013-04-17 Bayer Intellectual Property GmbH Katalysatorbeschichtung und Verfahren zu ihrer Herstellung
WO2020148754A1 (en) * 2019-01-14 2020-07-23 B.G. Negev Technologies & Applications Ltd., At Ben-Gurion University An electrode and a pseudo-capacitor based on the electrode

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100806678B1 (ko) * 2006-07-13 2008-02-26 연세대학교 산학협력단 전기화학법으로 제조된 탄소나노튜브／금속산화물 나노복합전극의 제조방법
KR100970575B1 (ko) 2008-05-07 2010-07-16 인하대학교 산학협력단 전기화학적 증착법에 의한 중간세공 구조를 갖는이산화루테늄 박막의 제조방법 및 이를 이용하여 제조되는이산화루테늄 박막
KR101391136B1 (ko) * 2012-05-17 2014-06-19 아주대학교산학협력단 그라파이트에 금속 산화물이 전착된 슈퍼커패시터 전극의 제조방법 및 이를 이용한 슈퍼커패시터
KR101583701B1 (ko) 2014-04-25 2016-01-08 국민대학교산학협력단 수퍼캐패시터용 투명전극, 그 제조방법 및 상기 투명전극을 포함한 수퍼캐패시터

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511442A (en) * 1982-03-26 1985-04-16 Oronzio De Nora Impianti Elettrochimici S.P.A. Anode for electrolytic processes
JPH031519A (ja) * 1989-05-29 1991-01-08 Nichicon Corp 固体電解コンデンサの製造方法
JPH06146054A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JP2000243453A (ja) * 1999-02-24 2000-09-08 Nissan Motor Co Ltd 非水電気化学キャパシタ
KR20020032053A (ko) * 2000-10-25 2002-05-03 김광범 루테늄 옥사이드 수화물 박막 전극 제조 방법 및 장치
US6649211B2 (en) * 2002-02-28 2003-11-18 The United States Of America As Represented By The Secretary Of The Navy Selective deposition of hydrous ruthenium oxide thin films

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511442A (en) * 1982-03-26 1985-04-16 Oronzio De Nora Impianti Elettrochimici S.P.A. Anode for electrolytic processes
JPH031519A (ja) * 1989-05-29 1991-01-08 Nichicon Corp 固体電解コンデンサの製造方法
JPH06146054A (ja) * 1992-11-06 1994-05-27 Japan Energy Corp ルテニウムめっき液
JP2000243453A (ja) * 1999-02-24 2000-09-08 Nissan Motor Co Ltd 非水電気化学キャパシタ
KR20020032053A (ko) * 2000-10-25 2002-05-03 김광범 루테늄 옥사이드 수화물 박막 전극 제조 방법 및 장치
US6649211B2 (en) * 2002-02-28 2003-11-18 The United States Of America As Represented By The Secretary Of The Navy Selective deposition of hydrous ruthenium oxide thin films

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100521014C (zh) * 2006-05-30 2009-07-29 中南大学 超级电容器RuO2涂层阴极薄膜材料的制备工艺
CN101525760B (zh) * 2009-04-17 2011-03-23 中南大学 一种用于制备超级电容器RuO2电极材料的电沉积工艺
EP2581971A1 (de) 2011-10-11 2013-04-17 Bayer Intellectual Property GmbH Katalysatorbeschichtung und Verfahren zu ihrer Herstellung
WO2020148754A1 (en) * 2019-01-14 2020-07-23 B.G. Negev Technologies & Applications Ltd., At Ben-Gurion University An electrode and a pseudo-capacitor based on the electrode
US11791108B2 (en) 2019-01-14 2023-10-17 B.G. Negev Technologies & Applications Ltd., At Ben-Gurion University Electrode and a pseudo-capacitor based on the electrode

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KR20050048173A (ko) 2005-05-24
AU2003288772A1 (en) 2005-06-08
KR100578734B1 (ko) 2006-05-12

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