Electrochemistry, Vol. 74. No.01, 2006


p2

Advanced Plating Technology for Electronic Devices

Hideo HONMA,a, b, c Kimiko OYAMADA,b and Ichiro KOIWAa, c

aSurface Engineering Research Institute, Kanto Gakuin University (4-4-1 Ikeda-cho, Yokosuka,Kanagawa 239-0806,Japan)
bGraduate School of Engineering, Kanto Gakuin University (1-50-1 Mutuurahigashi Kanazawa-ku Yokohama 236-8501, Japan)
cDepertment of Applied Material and Life Science, Faculty of Engineering, Kanto Gakuin University (1-50-1 Mutuurahigashi Kanazawa-ku Yokohama 236-8501, Japan)

Received August 31, 2005 ; Accepted November 11, 2005

Many electronic devices have been requested to downsize with improving their functionality. Improved semiconductor technologies have been main routes to realize these requests. However, the further improvement of semiconductor technologies has become difficult and costly. The next main technologies to be used are the improvement of printed circuit boards (PCBs) and their connection with integrated circuits (ICs), especially bump formation and their connection methods. For these two technologies, both electroplating and electroless plating are employed as the main methods employed. In this paper, primarily PCBs and their connection methods are reviewed. For PCBs, copper plating technologies are mainly reviewed, especially the selection of additives and current waveforms which are most effective for via-filling. For connections, the formation of bumps and their connecting are reviewed. Two new technologies, nickel bump formation on an aluminum pad and, microbump formation by non-cyanide gold electroplating, were mainly demonstrated. Finally, the production of anisotropic conductive particles by electroless nickel plating are demonstrated. The discovery of new plating technologies is necessary for future development, especially the use of new additives and new agitating methods for copper plating as well as new formation methods and their connection technologies for bump formation.



p12

High Throughput Microinjection Technology toward Single-cell Bioelectrochemistry

Hideaki MATSUOKAa, b * and Mikako SAITOa, b

aDepartment of Biotechnology and Life Science, Tokyo University of Agriculture and Technology (Koganei, Tokyo184-8588, Japan)
bCREST, Japan Science and Technology Agency (Honcho 4-1-8, Kawaguchi, Saitama 332-0012, Japan)

Received September 29, 2005 ; Accepted October 12, 2005

Microinjection has long been regarded as an unusually difficult method but its potential usefulness has been well understood. In order to overcome its difficulty, a single-cell manipulation supporting robot (SMSR) has recently been developed. SMSR has enabled high throughput microinjection into any type of cell. Its excellent performance was demonstrated by the high success rate of simultaneous introduction of two genes into mouse ES cells. The size of an ES cell is only 20 μm in diameter. With use of a multichannel microelectrode, electrophoretic introduction and automatic positioning of microinjector have been successfully demonstrated. Owing to these studies, single-cell analysis is now recognized as a practical method for the dynamic analysis of functional role of genes, gene expression products, and other molecules in living cells. For instance, the specific role of a protein Sar1p in the trafficking in BY-2 cells could be analyzed by microinjection experiment of a Sar1p dominant negative. Further advancing study is focused on the development of novel electric/electrochemical devices with submicro or nano size and the analytical methods using these devices.



p19

Pioneer Works in Development of In Situ Scanning Tunneling Microscopy for Electrochemical Surface Science

Kingo ITAYA

Department of Applied Chemistry, Graduate School of Engineering, Tohoku University (Aoba-yama 04, Sendai 980-8579, Japan)

Received October 12, 2005 ; Accepted October 19, 2005

Since its invention by Binnig and Rohrer, scanning tunneling microscopy (STM) was immediately established as an invaluable and powerful surface analysis technique with atomic resolution in ultra-high vacuum (UHV). Belatedly, but assuredly, developments in STM operated at solid-liquid interfaces led to its valuation as arguably the premier technique for atomic-level surface structural investigations of chemical processes taking place at solid-liquid interfaces. It has been demonstrated that in situ STM makes it possible to monitor, under reaction conditions, a wide variety of electrode processes such as the adsorption of inorganic and organic species, the reconstruction of electrode surfaces, the dissolution and deposition of metals and semiconductors.



p28

高温焼成によるCo 含有バーネサイト型二酸化マンガンの合成とリチウム二次電池正極特性

尾形  敦a,駒場 慎一a,*,熊谷 直昭b

a東京理科大学理学部応用化学科(〒162-8601 東京都新宿区神楽坂1-3)
b岩手大学大学院工学研究科フロンティア材料機能工学専攻(〒020-8551 盛岡市上田4-3-5)

Calcination Synthesis of Birnessite Type Manganese Dioxides Doped with Cobalt for Rechargeable Li Batteries

Atsushi OGATA,a Shinichi KOMABA,a and Naoaki KUMAGAIb

a Department of Applied Chemistry, Faculty of Science, Tokyo University of Science (Tokyo 162-8601, Japan)
b Department of Frontier Materials and Functional Engineering, Graduate School of Engineering, Iwate University (Iwate 020-8551, Japan)

Received September 19, 2005 ; Accepted October 18, 2005

Birnessite type manganese dioxides doped with cobalt were synthesized by calcination of a mixture of KMnO4 and Co(NO3)2・6H2O at 600 ℃ in air. The artificial birnessite was consisted of differently stacked slab phases depending on the cobalt content. These birnessites doped with Co exhibited different ratio of two phases; twolayer hexagonal (2H) and three-layer rhombohedral (3R) whose stacking sequences are different but belong to birnessite. The ratio of 3R/2H phases increased with increasing the Co quantity. Their electrochemical performances in Li cells were investigated in a LiClO4-propylene carbonate solution. As a result, the Co-doped birnessite demonstrated the smaller charge transfer resistance and higher reversible capacities than Co-free birnessite.



p32

Electrocatalytic Activity of Electropolymerized Meldola’s Blue toward Oxidation of Dopamine

Takahiro YAMAGUCHI, Teruhisa KOMURA, Sayomi HAYASHI, Manabu ASANO, Guang Yao NIU, and Kohshin TAKAHASHI

Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University(Kakumamachi, Kanazawa 920-1192, Japan)

Received July 30, 2005 ; Accepted October 14, 2005

To understand the kinetics of charge transfer from chemically modified electrodes to solution species, the authors have investigated the influence of poly (Meldola’s blue) on the kinetic parameters of dopamine oxidation by rotating disc electrode voltammetry. The polymer film fixed on electrode surfaces raised the dopamine peak current by a factor of 10 in a 0.1 mM solution; this electrocatalytic effect enables one to detect dopamine at concentrations of the order of 5 μM. The polymer film increased the standard heterogeneous rate constant of dopamine oxidation more than 10-fold and favored a two-electron transfer step, thus raising the dependence of the kinetic current on the electrode potential. These effects were independent of electron self-exchange between redox-active sites in the film. They arose from the incorporation of dopamine with the polymer. This binding interaction decreased with protonation of the polymer, because of electrostatic repulsion between the positively charged species.



p42

Effect of Anions and Added Organic Solvents of Polymerizing
Solutions on the Conductivity of Poly ( N-methylaniline)

Jun YANO,a* Hiroko YOSHIKAWA,b Tomomi MUKAI,b Sumio YAMASAKI,b and Akira KITANIc

aDepartment of Engineering Science, Niihama National College of Technology (7-1 Yagumocho, Niihama, Ehime 792-8580, Japan)
bFaculty of Engineering, Kyushu Sangyo University (2-3-1 Matsukadai, Higashi-ku, Fukuoka 813-8503, Japan)
cFaculty of Engineering, Hiroshima University (1-4-1 Kagamiyama, Higashihiroshima, Hiroshima 739-8521, Japan)

Received August 8, 2005 ; Accepted October 18, 2005

Poly (N-methylaniline) (PNMA) is prepared by the electro-oxidation of N-methylaniline in aqueous acid solutions. To prepare highly conductive PNMA, N-methylaniline was electropolymerized in several aqueous acidic solutions containing different organic solvents (acetonitrile, N,N-dimethylformamide an dimethylsulfoxide) and anions (ClO4, Cl, NO3 and SO42−). After the initial stage of the electropolymerization for the polymerizing solutions without the organic solvents, the anodic current linearly increased for the Cl, NO3 and SO42 solutions, while it decreased for the ClO4 solution. The decreasing current for the ClO4 solution meant that the polymerization proceeded by oligomer-coupling reactions. The linear increasing current for the Cl, NO3 and SO42− solutions implied one-dimensional nucleation growth of PNMA on the electrode surface. The polymerization rate estimated from the slope values of the i-t curves was in the order of SO42−> NO3>Cl. The conductivity of the obtained PNMAs was of the same order and the highest conductivity of 2.2 × 103 S cm−1 was seen for the SO42− doped PNMA. The order was explained by the Hofmeister series of the anions which are based on lyophilicity. During the polymerization, both the anion release from the monomer-anion and oligomer-anion ion pairs and the anion doping of the polymer occurred most frequently for SO42− with the lowest lyophilicity. The organic solvents were added to the SO42− polymerizing solution and the electropolymerization was performed. The conductivity of the obtained PNMAs was further enhanced. The most conductive PNMA was obtained when dimethylsulfoxide was added (σ = 1.0 × 10−2 S cm−1). The PNMA polymer chains were tangled and stacked with each other by electron-donating association, and the tangling and stacking prevented the anion doping reaction. The addition of the organic solvents suppressed the tangling and stacking and the anion doping reaction was effectively promoted.



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Ion Pairing of Electrochemically Generated Fluorenyl Anions with Tetraalkylammonium Counter Cations

Mitsutoshi OKANO, a* Shinobu HINOa, and Tsuyoshi KUGITAb

aDepartment of Nanochemistry, Tokyo Polytechnic University (1583 Iiyama, Atsugi, Kanagawa 243-0297, Japan)
bDepartment of Environmental & Material Science, Teikyo University of Science and Technology (2525 Yatsusawa, Uenohara, Yamanashi 409-0193, Japan)

Received August 18, 2005 ; Accepted October 14, 2005

Fluorenyl anions were successfully accumulated in the cathode compartment of a two-compartment cell by electrochemical reduction of fluorene in various solvents. Examination of the anions by UV-visible absorption spectroscopy and NMR spectroscopy revealed that all the obtained fluorenyl anions with tetraalkylammonium counter cations were contact ion pairs. Their electronic states were close to those of solvent-separated ion pairs. These observations were understood as that, in the contact ion pairs with tetraalkylammonium counter cations, anion and cation centers were far apart, for the alkyl chains of the cations prevented the cation centers to get closer to the anion centers. Among the contact ion pairs, those in dimethyl sulfoxide (solvent with the largest dielectric constant) showed their electronic states closest to those of the solvent-separated ion pairs. The influence of alkyl chain length and that of temperature on the electronic state of the anions were both small.



p53

イオン液体メディアを用いたナノポーラスタンタル細孔中へのポリピロール形成

直井 勝彦,太田 陽介,町田 健治

東京農工大学大学院共生科学技術研究院ナノ未来科学拠点(〒184-8588 小金井市中町2-24-16)

Pulse Anodization of Tantalum Oxide/Polypyrrole Film on Nanoporous Tantalum Anode in Ionic Liquid Media

Katsuhiko NAOI, Yosuke OTA, and Kenji MACHIDA

Center of Future Nanomaterials Science, Institute of Symbiotic Science and Technology, Tokyo University of Agriculture andTechnology (2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan)

Received July 1, 2005 ; Accepted October 7, 2005

In an ionic liquid electrolyte, namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4), a compact and dense polypyrrole film was formed on a nano-porous Ta pellet anode (average pore diameter: 250 nm, specific surface area: 4,000 cm2 g-1, and specific capacitance: 50,000 μFV g-1) under a pulse anodization. In the EMI-BF4 electrolyte, polypyrrole film was uniformly deposited at a pellet surface (thickness: 240 nm) and a nano-porous domain (thickness: 240 nm). However, in a conventional aqueous electrolyte (0.1 M sodium dodecylbenzenesulfonate aqueous solution), deposition thickness was different at the pellet surface (3000 nm) and at the nano-porous domain (230 nm). The resistivity of polypyrrole film formed in the EMI-BF4 was found as low as 2 × 10-2Ω/□.



p59

アミノ基を末端に有するチオール単分子膜電極を用いたインジゴイオンの酸化還元挙動

山口 孝浩*,遠藤 佑太,小村 照寿,高橋 光信

金沢大学大学院自然科学研究科物質科学専攻(〒920-1192 金沢市角間町)

Voltammetric and Impedance Study of Interaction of Indigo Ion with Thiol Monolayers having Terminal Amino Groups Modified Gold Electrode

Takahiro YAMAGUCHI, Yuta ENDO, Teruhisa KOMURA, and Kohshin TAKAHASHI

Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University (Kakumamachi,Kanazawa 920-1192, Japan)

Received July 6, 2005 ; Accepted October 16, 2005

The influences of thiol monolayers having terminal amino groups on the electron transfer rate for indigotetrasulfonate have been examined by cyclic voltammetry and ac impedance spectroscopy. The electron transfer rate for indigotetrasulfonate decrease with increasing pH at a bare Au electrode. The adsorption of indigotetrasulfonate ion onto 4-aminothiophenol monolayer, at low pH values, resulted primarily from an electrostatic attraction between the protonated terminal amino groups and the anions. An increase in solution pH, however, 4-aminothiophenol, cystamine, and 4-mercaptopyridine monolayer-modified electrode showed a increase in electrochemical reversibility with deprotonation of the terminal amino groups. Whereas 11-amino-1-undecanethiol, which is longchain thiol having terminal amino groups impedes the electrode reaction of[Co (phen)33+, this monolayer raised the apparent rate constant for indigotetrasulfonate to twice that observed at a bare Au in pH 6. Furthermore, in the presence of ethylenediamine or triethylenetetramine at pH 8, indigotetrasulfonate was obtained the reversible wave using at a bare Au. We propose a chemical interaction between the amine groups of the thiol monolayer and the carbonyl groups of indigotetrasulfonate. We postulate that protons transfer from the reduced indigo ion to the unprotonated terminal amino groups of thiols.



p65

Analysis of Electrochemical Reaction of Ferrocenylnaphthalene Diimide Captured by Double-Stranded DNA during the Electrochemical Detection of DNA Hybridization

Masaharu KOMATSU, Takahiko NOJIMA, and Shigeori TAKENAKA

Department of Applied Chemistry, School of Engineering, Kyushu University (744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan)

Received January 20, 2005 ; Accepted October 7, 2005

Recently, studies of electrochemical DNA sensors are attracting considerable attention, because they will be developed for an electrochemical DNA chip using integration, etc. The response current that originated from the formation of the DNA duplex was clearly observed using differential pulse voltammetry for a DNA-immobilized gold electrode in an electrolyte solution containing ferrocenylnaphthalene diimide as the hybridization indicator. A mismatch- discrimination was also exhibited. The authors carried out fundamental electrochemical analyses to obtain each parameter controlling the electrochemical response of the electrode system and to more qualitatively characterize.



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