Digest of the 9th Chemical Sensor Symposium
October 21-22, 1989
Aoyama Gakuin University
Abstracts
1
導電性ADH膜で被覆した白金黒電極によるアルコールセンシング
石塚俊博*・篠原寛明・碇山義人・相澤益男
オリエンタル電気*・東工大工
AMPEROMETRIC SENSING OF ALCOHOL USING ELECTROCONDUCTIVE ADH FILM-COATED PLATINIZED ELECTRODE
Toshihiro ISHIZUKA*, Hiroaki SHINOHARA, Yoshihito IKARIYAMA and Masuo AIZAWA
Department of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan
*Oriental Electric Co. Ltd.
3-9-7 Nobidome Niiza-shi, Saitama 352, Japan
A new type enzyme sensor for the determination of alcohol was fabricated by coating a platinized electrode with a electroconductive ADH (Alcohol dehydrogenase) film, in which ADH, NAD, and Meldola's blue were co-immobilized. Alcohol as low as 5×10-5 mol・dm-3 was determined with the sensor. By taking advantages of a platinized electrode and an electron transfer system, high sensitivity and wide dynamic range were obtained. The sensor characteristics were investigated in connection with effective electron transfer in the sensing unit.
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2
アルコールデヒドロゲナーゼとNAD+を同時固定化したアルコールセンサ
宮本重幸・村上 徹・齋藤 敦・木村 純
日本電気中研
DEVELOPMENT OF AN AMPEROMETRIC ALCOHOL SENSOR BASED ON CO-IMMOBILIZED ALCOHOL DEHYDROGENASE AND NAD+
Shigeyuki MIYAMOTO, Toru MURAKAMI, Atsushi SAITO and Jun KIMURA
NEC Corporation, Central Research Laboratories
1-1 Miyazaki 4-chome Miyamae-ku, Kawasaki, Kanagawa 213, Japan
An amperometric alcohol sensor based on co-immobilized alcohol dehydrogenase (ADH) and nicotine adenine dinucleotide (NAD+) was developed and evaluated. Various factors for the sensor membrane, such as the membrane thickness and crosslinking regent concentration, were determined, then an ADH-immobilized sensor was fabricated. By employing a denser BSA membrane on the co-immobilized membrane of ADH and NAD+, sensor responses for ethanol were observed.
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3
ポリ（N-メチルピロール）に固定化したグルコースオキシダーゼの直接電子移動
ﾌｨﾘｯﾌﾟ･ﾃﾞｭ･ﾀｸｼｰ･ﾃﾞｭ･ﾎﾟｴｯﾄ・宮本重幸*・木村 純*・軽部征夫
東大先端研・日本電気中研*
DIRECT ELECTRON TRANSFER WITH GLUCOSE OXIDASE IMMOBILIZED IN ELECTROPOLYMERIZED POLY (N-METHYLPYRROLE) FILM ON GOLD MICROELECTRODE
Philippe De Taxis Du Poet, Shigeyuki MIYAMOTO, Jun KIMURA and Isao KARUBE
The University of Tokyo, R. C. A. S. T.,
4-6-1 Komaba Meguro-ku, Tokyo 153, Japan
NEC Corporation, Central Research Laboratories
1-1 Miyazaki 4-chome Miyamae-ku, Kawasaki, Kanagawa 213, Japan
Direct electron transfer between flavin cofactors and a gold electrode has been obtained when glucose oxidase was immobilized in poly (N-methylpyrrole) electrochemically prepared on the gold electrode. When electropolymerization was accomplished at 50℃, cyclic voltammogram showed, after addition of glucose, an increasing oxidation peak at approximately -0.45 V vs. Ag/AgCl reference electrode. This potential corresponds to the oxidation potential for FADH2. Although the specificity of glucose oxidase was affected, glucose-dependent current response was obtained.
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4
電極型アレルギーセンサの開発
福田邦昭・高野 亮・北島洋二・中村徳幸・松永 是
東農工大工
DEVELOPMENT OF ELECTRODE TYPE ALLERGY SENSOR
Kuniaki FUKUDA, Ryo TAKANO, Youji KITAJIMA, Noriyuki NAKAMURA and Tadashi MATSUNAGA
Department of Biotechnology, Tokyo University of Agriculture & Technology
Koganei, Tokyo 184, Japan
We have investigated the allergic reaction with rat basophilic leukemia (RBL-1) cells and a basalplane pyrolytic graphite (BPG) electrode. Addition of the appropriate allergen to the stimulated RBL-1 cells causes degranulation, thereby releasing histamine and serotonin. In this investigation, the allergy sensor cosisting of a liquid membrane type ammonia electrode and enzyme has been developed for the determination of released histamine. The response time of the sensor system was 7-9 min. A linear relationship was obtained between the potential decrease of the sensor and the histamine concentration in the range of 0.01-1 mM.
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5
EEE型高性能コレステロールセンサの作製
長井律子・矢尾板仁**・吉田泰彦・碇山義人*・山内 繁**
東洋大工・東工大工*・国立リハ研**
HIGH PERFORMANCE BIOSENSOR FOR CHOLESTEROL
Ritsuko NAGAI, MasashiYAOITA**, Yasuhiko YOSHIDA, Yoshihito IKARIYAMA* and Shigeru YAMAUCHI**
Dept. of Applied Chemistry, Faculty of Engineering, Toyo University
2100 Kujirai Kawagoe, Saitama 350, Japan
*Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, Tokyo 152, Japan
**Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
We have already reported that the Enzyme Embodied Electrode (EEE) Sensor, which is fabricated by an immobilization of enzyme on platinized platinum surface, can also be applied to cholesterol sensing , other than glucose sensing. To this end we have fabricated EEE sensors immobilizing three different types of cholesterol oxidase on a platinum surface of 100 μm in diameter. The response characteristic largely depends on the type of the enzyme. The highest sensitivity was observed on the cholesterol sensor fabricated by using Toyo Jozo Enzyme T-19, exhibiting a sensitivity of 0.5 nA at 13 μM in phosphate buffer solution with 0.1% Triton X-100. The dynamic range was from 0.52 to 52 μM.
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6
電極表面処理によるEEEセンサの非特異応答の抑制
矢尾板仁・碇山義人*・山内 繁
国立リハ研・東工大工*
OXIDATION OF PLATINIZED PLATINUM SURFACE AND NON-SPECIFIC RESPONSE OF ENZYME EMBODIED ELECTRODE (EEE) SENSOR
Masashi YAOITA, Yoshihito IKARIYAMA* and Shigeru YAMAUCHI
Research Institute of National Rehabilitation Center
4-1 Namiki Tokorozawa, Saitama 359, Japan
*Dept. of Bioengineering, Tokyo Institute of Technology
2-12-1 O-okayama Meguro-ku, tokyo 152, Japan
In order to decrease non-specific response of EEE sensors to saccarides and/or ascorbate, we have tried to de-activate platinized platinum surface by gaseous oxidation in air at 70-200℃. Those heated above 100℃ gave negligible current to saccarides, while appreciable decrease in current response was observed to ascorbate. Glucose sensor fabricated by immobilization of glucose oxidase or the oxidized surface gave little response to saccarides other than glucose. Response to ascorbate relative to that of glucose was remarkably smaller than those fabricated on the as-deposited platinized platinum electrode.
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7
メディエータを用いるアンペロメトリックフルクトースセンサ
池田篤治・千田 貢
京大農
MEDIATED AMPEROMETRIC FRUCTOSE SENSOR
Tokuji IKEDA and Mitsugi SENDA
Department of Agricultural Chemistry, Kyoto University
Sakyo-ku, Kyoto 606, Japan
Fructosedehydrogenase (FDH, EC 1.1.99.11) was immobilized behind a dialysis membrane on a carbon paste electrode. The FDH-modified electrode could oxidize D-fructose electro-enzymically in the presence of artificial electron acceptors such as p-benzoquinone, BQ, in which the electron acceptors functioned as mediators of electron transfer between the electrode and the immobilized enzyme. When BQ was mixed in the carbon paste, the BQ containing carbon paste electrode carrying immobilized FDH served as a reagentless fructose sensor which was stable for more than a week. Some characteristics of the fructose sensor were studied.
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8
酵素単分子層化学修飾型バイオセンサ
大川祐輔・立間 徹*・渡辺 正*・小林裕幸・大野隆司・水澤伸也
千葉大工・東大生研*
BIOSENSORS CARRYING ENZYME MONOMOLECULAR LAYER
Yusuke OKAWA, Tetsu TATSUMA*, Tadashi WATANABE*, Hiroyuki KOBAYASHI, Takashi OHNO and Shinya MIZUSAWA
Department of Image Science and Engineering, Faculty of Engineering, Chiba University
Yayoi-cho Chiba-shi 260, Japan
*Institute of Industrial Science, University of Tokyo
Roppongi Minato-ku, Tokyo 106, Japan
The response of amperometric biosensors carrying an enzyme monomolecular layer was studied with the digital simulation method on a 1-dimensional semiinfinite diffusion model including surface catalytic and electrode reactions. The simulation showed that the diffusion of the substrates to the surface was fast relative to the enzymatic reaction and that the sensor response strongly depended on the electrode kinetics. The simulated results were compared with experimentally obtained results for the previously reported sensors.
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9
タバコの葉の匂い応答における定量性の検討
松岡英明・川鍋健志・武川征弘
東農工大工
PRELIMINARY STUDY ON THE QUANTITATIVE RESPONSE OF TOBACCO LEAF TO ODOUR COMPOUND
Hideaki MATSUOKA, Takeshi KAWANABE and Yukihiro TAKEKAWA
Department of Biotechnology, Faculty of Technology, Tokyo University of Agriculture and Technology
Nakamachi Koganei, Tokyo 184, Japan
The responsive properties of a tobacco leaf (Nicotiana tabacum "Xanthi nc") to benzyl acetate (BA) were investigated. A flow system for the quantitative supply of odour compounds was developed using a diffusion tube. Acutual concentration of odour in the reaction gas was checked by gas chromatography. A sample leaf showed a characteristic pattern in response to 100% CO2 gas as detected with a microelectrode. When CO2 gas containing BA. Was supplied on the leaf, the response was suppressed. This suppression effect was observed in the range of 3.8〜9.8 ppb of BA. It was also suggested that the suppression effect did not completely disappear within 2 hr.
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10
アポ酵素サーミスタ ―微量亜鉛（II）イオンのバイオセンシング―
佐藤生男・長瀬 誠・渡辺尚哉
神奈川工科大
AN APPOENZYME THERMISTOR
-BIOSENSING OF TRACE AMOUNT OF Zinc(II) IONS-
Ikuo SATOH, Makoto NAGASE and Naoya WATANABE
Department of Chemical Technology, Faculty of Engineering, Kanagawa Institute of Technology
1030 Shimo-Ogino Atsugi-shi, Kanagawa 243-02, Japan
A novel calorimetric biosensing with use of an apoenzyme sensor is proposed for flow-injection microdetermination of zinc(II) ions. The biosensing system was assembled with the immobilized alkaline phosphatase reactor and a thermistor device for monitoring of the enzymatic activity. Zinc(II) ions were calorimetrically determined in the range of 0.01 to 1.0 mM through its activation of the immobilized metal-free alkaline phosphatase(apoenzyme) reactor. The activity of the reactor was assessed by injecting a 0.1 mL of 100 mM p-nitrophenyl phosphate solution and then the heat evolved in the hydrolytic reaction was measured. Regeneration of the reactor was made by pumping 20 mM 2,6-pyridine dicarboxylate solution (pH 6.0).
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11
オプティカルイオンセンサと電気化学イオンセンサの応答特性の比較
鈴木孝治・遠田浩司・大空弘幸・渡辺一彦・宮崎京太・岡 等・白井恒雄
慶大理工
COMPARISON OF THE RESPONSE CHARACTERISTICS OF OPTICAL-AND ELECTROCHEMICAL-ION SENSORS BASED ON NEUTRAL IONOPHORES
Koji SUZUKI, Koji TOHDA, Hiroyuki OHZORA, Kazuhiko WATANABE, Kyota MIYAZAKI, Hitoshi OKA and Tsuneo Shirai
Department of Applied Chemistry, Keio University
3-14-1 Hiyoshi Kohoku-ku, Yokohama 223, Japan
A comparison of the response characteristics of an optical ion sensor and an electrochemical ion sensor (potentiometric ion-selective electrode) based on valinomycin as a potassium ion-selective neutral ionophore was investigated. Though the ion selectivities of both sensors were almost the same, the optical sensor based on an absorbance change was able to be designed and prepared with a higher sensitivity in comparison to the electrochemical sensor. Other important characteristics for sensor response were experimentally and theoretically discussed.
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12
強酸性電解液中溶存塩素ガスセンサの開発
佐藤秀行・三沢義男・墨井 勉
古河電工・東北電力
RESEARCH AND DEVELOPMENT ON A SENSOR FOR A DISSOLVED CHLORINE IN A STRONG ACIDIC ELECTROLYTE
Hideyuki SATO, Yoshio MISAWA and Tsutomu SUMII
Yokohama Laboratories, The Furukawa Electric Co. Ltd.
Nishi-ku Yokohama, Kanagawa 220, Japan
Electric Power Technical Laboratories, Tohoku Electric Power Co. Ltd.,
Nakayama, Sendai, Miyagi 981, Japan
A cyclicvoltammogram was measured in an electrolyte with and without a reducible species (Oxd1) having the same UV absorption wave length that an aqueous chlorine at a porous carbon electrode coated with RuO2. The probable potential range of an electrochemical quantitative analysis of a dissolved chlorine was determined to be ca. 0.50-ca. 0.80 V vs. 3.3 mol・dm-3 KCl/AgCl/Ag. At a potential in the region, using a sensor constructed by us, into which an electrolyte containing chlorine with and without Oxd1 was flowed, the detected current was proportional to the concentration of a dissolved chlorine irrespectively of the inclusion of Oxd1.
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13
電極法による高分子膜の酸素透過係数の測定法に関する研究
小林裕幸・大川祐輔・大野隆司・水澤伸也
千葉大工
STUDIES ON ELECTROCHEMICAL METHOD OF MEASURING OXYGEN PERMEABILITY OF POLYMER MEMBRANES
Hiroyuki KOBAYASHI, Yusuke OKAWA, Takashi OHNO and Shinya MIZUSAWA
Department of Image Science and Engineering, Faculty of Engineering, Chiba University
1-33 Yayoi-cho, Chiba 260, Japan
Two electrode system has been used in the current electrode method of measuring oxygen permeability of polymer membranes. This leads to a large error in the case of samples with large permeability because of large iR drop between the two electrodes. Further the lateral diffusion of oxygen from the anterior sample surface outside the electrode area contributes to the cathodic current and results in an overestimation (idge effect). In the present paper, it was attempted to solve these problems using a three electrodes system and a supporting screen on the anterior sample surface.
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14
ISFET型グルコースセンサによる血清の無希釈測定
齋藤 敦・宮本重幸・木村 純・栗山敏秀
日本電気中研
ISFET GLUCOSE SENSOR FOR SERUM SAMPLE MEASUREMENT WITHOUT DILUTION
Atsushi SAITO, Shigeyuki MIYAMOTO, Jun KIMURA and Toshihide KURIYAMA
NEC Corporation, Central Research Laboratories
1-1 Miyazaki 4-chome, Miyamae-ku Kawasaki, Kanagawa 213, Japan
An ISFET glucose sensor for serum sample measurement without dilution was fabricated and discussed. An ISFET glucose sensor, whose enzyme membrane has a certain buffer capacity around pH 7.5 and a restrict permeable membrane covering an enzyme membrane, was realized. As a restrict permeable membrane, an albumin crosslinking membrane was selected, because it has good properties in restricted permeability and adhesion with an enzyme membrane. A good linear relationship between glucose concentration and sensor response was obtained in the range from 90 to 430 mg/dl.
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15
ISFETを用いた酵素標識IgG免疫センサの特性
坂井宏光・金木則明・原 弘
室蘭工大
CHARACTERISTICS OF ENZYME IMMUNOSENSOR USING ISFET FOR HUMAN IgG
Hiromitsu SAKAI, Noriaki KANEKI and Hiroshi HARA
Department of Chemical Engineering, Faculty of Engineering, Muroran Institute of Technology
27-1 Mizumoto-cho, Muroran 050, Japan
We have demonstrated that as an effective and simple potentiometric sensor for detecting human IgG. The immuno-ISFET sensor was constructed using as immobilized human IgG membrane and a ISFET. The assay procedure involves the competitive immuno-chemical reaction of urease labeled anti-human IgG with human IgG in samples and the membrane bound IgG and the electrochemical determination of membrane bound urease activity. The analytical result is directly displayed by the output voltage of the sensor.
In this study, a linear relationship was obtained between the response and the human IgG concentration from 0.1-2.0 mg/ml. The response of ISFET with the membrane was kept for two weeks.
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16
プレーナ型pHセンサの制作と微少酵素電極への応用
荒井真人・遠藤英樹・中島 聡・滝沢耕一・楓 邦男
立石ライフサイエンス研
DEVELOPMENT OF A PLANER-TYPE pH SENSOR AND ITS APPLICATION TO ENZYME ELECTRODE
Masato ARAI, Hideki ENDO, Satoshi NAKAJIMA, Koichi TAKIZAWA and Kunio KAEDE
Tateishi Institute of Life Sciences
17 Minami-cho Chudoji Shimogyo-ku, Kyoto 600, Japan
A planer-Ttype pH sensor based on TiN onto a ceramic plate were developed and its applicability was investigated. This newly solid-state pH sensor was found to 57 mV/pH, following Nernst's equation. Urease was immobilized on TiN electrode using G. A. and BSA. A linear calibration curve was obtained for urea concentrations between 0.5 mM and 5 mM.
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17
リチウムイオン伝導体を用いたCO2センサ
河里 健・今中信人・足立吟也
阪大工
A CARBON DIOXIDE GAS SENSOR BASED ON LITHIUM IONIC CONDUCTOR
Takeshi KAWASATO, Nobuhito IMANAKA and Gin-ya ADACHI
Department of Applied Chemistry, Faculty of Engineering, Osaka University
2-1 Yamadaoka Suita, Osaka 565, Japan
A compact carbon dioxide gas sensor probe was fabricated with lithium titanium phosphate and calcium carbonate- calcium oxide mixture as a solid electrolyte and a solid reference electrode, respectively. Lithium carbonate pellet was fixed on both surface of the electrolyte. The reference CO2 gas concentration was determined from the calculation of the standard Gibbs' free energy change for the dissociation of CaCO3 into CaO and CO2. The probe could detect the CO2 gas continuously with a rapid response. A good accordance between the measured and the calculated EMF from the Nernst's equation was obtained in the CO2 gas concentration range from 233 ppm to 1330 ppm.
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18
固体基準物質を用いた起電力式高温湿度センサの試作とその特性
矢嶋 保・小出邦博・岩原弘育*
TYK・名大工*
TRIAL FABRICATION OF GALVANIC CELL TYPE HIGH TEMPERATURE HUMIDITY SENSOR USING STANDARD MATERIALS AND ITS SENSING CHARACTERISTICS
Tamotsu YAJIMA, Kunihiro KOIDE and Hiroyasu IWAHARA*
Research and Development Center, TYK Corporation
*Synthetic Crystal Research Laboratory, Faculty of Engineering, Nagoya University
A galvanic cell type high temperature humidity sensor was constructed using SrCe0.95Yb0.05O3-α ceramic as a solid electrolyte and AlPO4-LaCoO3 mixture as a solid state standard material. This sensor showed stable emf in correspondence to partial pressure of water vapor. The portable sensors of this type were fabricated and their characteristics were examined. The sensor gave rise to stable emf and its response speed was fast. The relation between emf and logarithms of the water vapor pressure was linear.
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19
プロトン導電体厚膜を用いた常温作動型酸素センサ
吉田宣昭・清水陽一・桑田茂樹*・三浦則雄・山添 f
九大総合理工・新居浜高専*
OXYGEN SENSOR USING PROTON-CONDUCTOR THICK-FILM WORKABLE AT ROOM TEMPERATURE
Nobuaki YOSHIDA, Youichi SHIMIZU, Shigeki KUWATA*, Norio MIURA and Noboru YAMAZOE
Department of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816, Japan
*Department of Industrial Chemistry, Niihama National College of Technology
Niihama, Ehime 792, Japan
An amperometric solid-state oxygen sensor using a proton-conductor thick-film was investigated as an approach to miniaturized and integrated oxygen sensor operative at room temperature. The thick-film was formed on a porous alumina substrate by a spin-coating method. The sensor element had a laminated-type structure: (counter Pt electrode | proton-conductor thick-film | sensing Pt electrode, gas-diffusion layer). At an applied voltage of 1.6 V, a limiting current, controlled by the rate of oxygen permeation through the gas diffusion layer, increased linearly with an increase in oxygen partial pressure in the sample gas. The 90% response time was about 40 s at room temperature. Furthermore, when the element was coated with a sensor using a hydrophobic gas-diffusion layer based on a polystyrene binder, the limiting current was linear to the dissolved oxygen concentration in water up to 20 ppm at 30℃.
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20
NAFION膜を用いた表面型酸素センサ
桑田茂樹*・三浦則雄・山添 f
新居浜高専*・九大総合理工
A PLANAR-TYPE OXYGEN SENSOR USING NAFION MEMBRANE
Shigeki KIWATA, Norio MIURA, and Noboru YAMAZOE
Department of Industrial Chemistry, Niihama National College of Technology
Niihama-shi, Ehime 792, Japan
Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoka 816,Japan
A planar-type oxygen sensor using a NAFION thick-film was developed for monitoring the oxygen partial pressure at ambient temperature. The NAFION thick-film was formed on an alumina substrate, and on top of it the counter Au electrode and the sensing Pt electrode were deposited, leaving a space 0.5 mm in between, by means of RF sputtering. No reference gas flow was necessary for this sensor. The e. m. f. and the short-circuit current of the sensor were found to vary logarithmically and almost linearly, respectively, with the oxygen partial pressure at 25℃. The 90% response time in amperometric sensing was about 1 min during increasing oxygen partial pressure.
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21
常温で作動する半導体マイクロ酸素センサ
南 海玉・原 正史・勝部昭明・芹沢和泉*・石橋紀雄*・安達伸雄*・三浦則雄**・山添 f**
埼玉大工・オーク*・九大総合理工**
SEMICONDUCTOR MICRO OXYGEN SENSOR WORKABLE AT ROOM TEMPERATURE
Kaigyoku NAN, Masashi HARA, Teruaki KATSUBE, Izumi SERIZAWA*, Norio ISHIBASHI*, Nobuo ADACHI*, Norio MIURA** and Noboru YAMAZOE**
Saitama University
Shimo-okubo, Urawa-shi 338, Japan
*ORK Co.,
Chofu-ga-oka, Chofu-shi 182, Japan
**Kyushu University
Kasuga-shi, Fukuoka 816, Japan
A sputtered LaF3 film was applied to construct a semiconductor micro oxygen sensor consisting of Pt/LaF3/SiO2/n-Si/Al structure. It was shown that the sensor had a stable response in the oxygen concentration range from 10 to 100% at room temperature. The sensitivity and response time strongly depended on the fabrication conditions of LaF3 and Pt films and the optimum sputtering conditions to prepare the films were investigated.
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22
MOSFETによるポテンシオメトリックセンサ
伊藤善孝・堤 和夫・平井 実
新電元工業
POTENTIONMETRIC SENSOR WITH MOSFET(MNOSFET)
Yoshitaka ITOH, Kazuo TSUTSUMI and Minoru HIRAI
Research & Development Division, Shindengen
Hanno-shi, Saitama 357, Japan
In this paper a potentiometric sensing with metal gate type FET is reported and discussed the possibilities of a new type of gas sensor operating at room temperature. The Metal Nitride Oxide Silicon Field Effect Transistor (MNOSFET) is fabricated by using conventional bipolar and MOS monolithic IC processes, electrically protected well from solutions. A differential configuration of a platinum gate MNOSFET and gold gate MNOSFET can be a sensing system, operating at room temperature, without saturated KCl reference electrode. A oxygen sensor consists of a dual MNOSFET, coated with a polymeric gel and covered with a gas permeable membrane. Differential output voltage of about 160 mV is obtained with nonlinearity from 0.01 to 1.0 of oxygen partial pressure. The response times of the sensor upon an increase and a decrease in oxygen partial pressure are approximately 30 sec. and 2 min., respectively.
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23
インラインマイクロフローセンサによる磁気式酸素センサ
山田 誠・江刺正喜*・庄子習一*・大場利三郎
東北大流体研・東北大工*
INTEGRATED MAGNETIC OXYGEN SENSOR USING A INLINE MICRO FLOW SENSOR
Makoto YAMADA, Masayoshi ESASHI*, Shuichi SHOJI *and Risaburo OBA
Institute of Fluid Science, Tohoku University
Katahira Aobaku, Sendai 980, Japan
*Department of Electronic Engineering, Tohoku University
Aza Aoba, Aramaki, Aobaku, Sendai 980, Japan
A magnetic oxygen sensor is fabricated on a silicon wafer using micromachining techniques. The performance of a micro flow sensor is improved for high reliability. The micro flow sensor is based on titanium heaters, formed on a Pyrex glass and its base-line stability was studied.
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24
シリコン基板上へ集積化した微量化学分析システム
中川 茂・庄子習一・江刺正喜
東北大工
A MICRO CHEMICAL ANALYZING SYSTEM INTEGRATED ON A SILICON WAFER
Shigeru NAKAGAWA, Shuichi SHOJI and Masayoshi ESASHI
Department of Electronic Engineering, Tohoku University
Aza Aoba Aramaki Aobaku, Sendai 980, Japan
To integrate flow injection chemical analyzing (FIA) systems, micropumps and three-way valves were fabricated on silicon wafers with micromachining techniques. Micropumps must be rippleless not to cause a noise at the detector. To realize rippleless flow, a dual pump and a buffer pump were fabricated on a silicon wafer. The three-way valve was confirmed to operate satisfactorily. Leakage at the valve seats could be less than 0.1 ul/min using a nickel valve seat.
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25
煙道用NOxセンサ
佐竹和子・小林 愛・中原 毅・武内 隆
徳山曹達
NOx SENSORS FOR EXHAUST MONITORING
Kazuko SATAKE, Ai KOBAYASHI, Takeshi NAKAHARA and Takashi TAKEUCHI
TOKUYAMA SODA CO., LTD
2051 Endo, Fujisawa-city, Kanagawa 252, Japan
NOx sensors composed of oxide semiconductors have been examined for the use of exhaust monitoring. Titania, especially doped with 3 valent elements, such as, Al3+, Sc3+, Ga3+ and In3+ has a good sensitivity and selectivity to NO and high responsibility.
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26
In2O3系NOxセンサ
菅井 孝・松沢隆嗣・村山義彦・佐藤峰夫*・坂口雅一*
根本特殊化学・新潟大自然研*
In2O3-BASED NOx GAS SENSOR
Takashi SUGAI, Takashi MATSUZAWA, Yoshihiko MURAYAMA, Mineo SATO* and Masakazu SAKAGUCHI*
Nemoto & Co., Ltd.,
Takaido-higashi Suginami-ku, Tokyo 168, Japan
*Division of Fundamental Science and Technology, Niigata University
Ikarashi-2nocho Niigata-shi, Niigata 950-21, Japan
A NOx gas sensor based on Indium Oxide (In2O3) has been newly developed. The sensor is highly sensitive to NO and NO2 gases caused by the combustion of fuels. The important characteristics for practical use including gas selectivity; sensitivity to various reducing gases, speed of response, stability, etc. are described. Furthermore, the adsorption mechanism of a nitrogen oxide gas and resulting conductivity changes are discussed.
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27
SnO2系ガスセンサにおけるNOxの吸着と素子抵抗への影響
秋山守人・玉置 純・三浦則雄・山添 f
九大総合理工
INFLUENCE OF NOx ADSORBATES ON ELECTRICAL CONDUCTIVITY OF SnO2 AND Pd-SnO2
Morito AKIYAMA, Jun TAMAKI, Norio MIURA and Noboru YAMAZOE
Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu university
Kasuga-shi, Fukuoka 816, Japan
Adsorption behavior of NOx on SnO2 and Pd-SnO2 was investigated under various conditions by means of a temperature programmed desorption (TPD) technique. The effects of NOx adsorbates on the electrical resistivity of SnO2 and Pd-SnO2 were also investigated. TPD experiments revealed that both NO on heating. In addition, electrical resistivity measurements coupled with NO pulse injection at 100℃ suggested the existence of a quick, reversible NO adsorption which decreased the electrical resistance. The addition of Pd to SnO2 influenced markedly the amounts of these adsorbates through the electronic interaction between Pd and SnO2.
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28
YBa2Cu3O6系化合物のガス感応特性
越崎直人・菅 和生*・安本勝哉
製品科学研・横浜ゴム*
GAS SENSING CHARACTERISTICS OF YBa2Cu3O6 AND RELATED COMPOUNDS
Naoto KOSHIZAKI, Kazuo SUGA *and Katsuya YASUMOTO
Indutrial Products Research Institute
*Yokohama Rubber Co., Ltd.
Tsukuba-shi, Ibaraki 305, Japan
Gas sensing characteristics of YBa2Cu3O7-y and related compounds having oxygen deficient triperovskite structure are investigated. These compounds with larger y like YBa2Cu3O6 obtained by quenching into liquid N2 or annealing in N2 at 650℃ are semiconducting and change their resistivity by NO and NO2. Larger and faster response of resistivity changes by NO takes place at 150-200℃. Substitution of Y on A-site by La and Cu on B-site by Co in 20% in YBa2Cu3O7-y causes high sensitivity. The effect of sensitizer is also investigated to obtain higher sensitivity.
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特別講演１
TANDEM CHEMICAL SENSORS
Simon. Middelhoek
Delft University of Technology
Department of Electrical Engineering
P. O. Box 5031, Delft, The Netherlands
For many applications low-cost miniature sensors are needed for in-line control of chemical substances. Possible candidates, like the ISFET and the Pd-gate FET have been studied for almost twenty years, but up to now this has not led to commercially successful devices. This probably is caused by the fact that the action of a FET is based on the large sensitivity of silicon surfaces to electrical fields, and that in a FET based chemosensor the same surface have to be also exposed to the chemical measurand.
In contrast to direct sensors, in a tandem sensor the transducing elements are not in contact with the chemical measurand and, therefore, such devices stand a larger chance of leading to satisfactory chemical sensors. This is illustrated with a few examples.
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特別講演２
MICROFABRICATED CHEMICAL SENSORS
Nico. F. de Rooij
Institute of Microtechnology, University of Neuchatel
2007 Neuchatel, Switzerland
Silicon micromachining techniques can be considered as key processing steps in the fabrication of chemical sensors. In this paper examples of various types of chemical sensors using microfabrication techniques are presented. In particular the processing steps, characteristics and applications of pH-ISFETs with backside contacts, a combined pH-pressure sensor, a flow-through cell for multi-ion detection and a planar glucose sensor will be outlined.
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29
半導体ガスセンサにおけるイカの鮮度判定
高尾雄二・清水康博・江頭 誠
長崎大工
DETECTION OF FRESHNESS OF SQUID BY SEMICONDUCTOR GAS SENSORS
Yuji TAKAO, Yasuhiro SHIMIZU and Makoto EGASHIRA
Department of Materials Science and Engineering, Faculty of Engineering, Nagasaki University
1-14 Bunkyo-machi, Nagasaki 852, Japan
An attempt has been made to detect freshness of squid by nine kinds of semiconductor gas sensors; Ru/TiO2, Pt/TiO2, Rh/TiO2, Au/TiO2, In/TiO2, Mg2+-doped In2O3, W6+-doped Nb2O5, Ti4+-doped Cr2O3, Ru/Ti4+-doped Cr2O3. Electrical resistance of all the sensor elements well responded to the deterioration of squid after death, and the resistance change became large at the time of strong evolution of bad smell. Among the sensors examined, Ru/TiO2+ exhibited the earliest and highest response to the smell. Thus, the present results suggested that the semiconductor gas sensor method is promising to detect the freshness of squid which cannot be detected by the usual K-value method.
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30
接触燃焼式COセンサ
荻野 薫・安形和俊・二田穂積
矢崎計器
CATALYTIC COMBUSTION SENSOR TO DETECT CARBON-MONOXIDE GAS
Kaoru OGINO, Kazutoshi ANGATA and Hozumi FUTATA
Yazaki Meter Co., Ltd Gas Appliance Laboratory
23 Minamikashima Futamata Tenryu-shi, Shizuoka 431-33, Japan
Generally speaking, gas sensors of the catalytic combustion type have acceptable levels of sensitivity, including functional linearity to a wide range of gas concentration. Moreover sensitivity is reliable under changing environmental conditions. In contrast, their sensitivity to diluted concentrations of gas is considered poor. An improved version of this kind of sensor, capable of detecting the presence of carbon-monoxide while retaining its selective-sensing capability, has been developed. This type of sensor displaces only a small quantity of power and has a wide range of applications, including complete combustion alarms, portable carbon-monoxide detectors and smoke detectors.
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31
Pt/TiO2粒状金属膜の酸素応答特性（IV）
小野 洋・堀池彰夫・森崎 弘・矢澤一彦
電通大
Pt/TiO2 GRANULAR METAL FILMS AS AN OXYGEN SENSOR (IV)
Hiroshi ONO, Akio HORIIKE, Hiroshi MORISAKI and Kazuhiko YAZAWA
The University of Electro-communications
Chofu-shi, Tokyo 182, Japan
It has been found that apparent in-plane resistance of Pt/TiO2 composite films is sensitive to oxygen gas at temperatures higher than 130℃. Measurement of in-plane potential distribution across the film has shown that there are oxygen-sensitive high resistance region underneath two metal electrodes. According to an ESCA depth profile, the high resistance is originated from the heterogenous film structure composed of Pt/TiO2 granular metal and the highly resistive surface TiO2 layer. It has also been observed that the response time of the sample is improved very much by thermal treatment in hydrogen atmosphere.
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32
薄膜空燃比センサ
近藤春義・佐治啓市・高橋英昭・五十嵐伊勢美
豊田中研
THIN FILM AIR-FUEL RATIO SENSOR
Haruyoshi KONDO, Keiichi SAJI, Hideaki TAKAHASHI and Isemi IGARASHI
Toyota central research and development laboratories, Inc.
Nagakute-cho Aichi-gun, Aichi 480-11, Japan
An air-fuel ratio sensor has been developed. The sensor consists of two detective parts and a heating part. One of the detective parts is a limiting current-type oxygen sensor for detecting lean air-fuel ratios and the other is a resistive-type oxygen sensor for detecting the stoichiometric air-fuel ratio. The whole sensor has such a simple structure that both detective parts and the heating part are fabricated on a porous substrate by a thin film technique. The outputs from the detective parts are converted to a single output by an external electric circuit.
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33
水晶振動子を用いたマイクロバランスの応用
吉開正彰・町田正人・江口浩一・荒井弘通
九大総合理工
APPLICATION OF QUARTZ CRYSTAL MICROBALANCE TO GRAVIMETRIC CHARACTERIZATION OF POROUS CERAMIC THIN FILMS
Masaaki YOSHIKAI, Masato MACHIDA, Koichi EGUCHI and Hiromichi ARAI
Department of Materials Science and Technology, Graduate School of engineering Sciences, Kyushu university
Kasuga-shi, Fukuoka 816, Japan
Direct measurement of N2 adsorption onto porous Al2O3 films was examined with a quartz crystal microbalance at 77 K. Nitrogen adsorption led to the change in resonant frequency (ΔF) of the Al2O3 coated quartz crystal. A cumulative plot of ΔF at the relative pressure corresponds to the N2 adsorption isotherm, from which pore size distribution and surface area of the Al2O3 thin films (ca. 0.1 mg) were successfully obtained.
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34
ピエゾ素子の温度特性を利用した新しいガスセンサ
湊本裕彦・三浦則雄・山添 f
九大総合理工
NEW TYPE GAS SENSOR USING TEMPERATURE CHARACTERISTICS OF PIEZOELECTRIC CRYSTAL
Hirohiko MINAMOTO, Norio MIURA and Noboru YAMAZOE
Department of Materials Science and Technology, Graduate School of Engineering Sciences, Kyushu University
Kasuga-shi, Fukuoke 816, Japan
A new type quartz piezoelectric sensor coated with a sputtered Pt (or Pd) film was proposed for the detection of inflammable gases such as H2 and CO in air. The sensing signal of the new sensor is provided by an increase in resonance frequency of the crystal (ΔF) due to a temperature increase upon contact with the sample gas. The frequency change of the sensor was found to be opposite in direction to that of the conventional adsorption-type piezoelectric sensor.
The temperature change of the present sensor resulted from the oxidation of the inflammable gas on the surface of the catalyst film. A linear dependence between ΔF and H2 concentration (0-0.4 vol%) was observed at 140℃. The sensitivity of the sensor to H2 in air increased sharply with increasing temperature in the range from ca. 50℃ to 400℃.
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35
酸化物薄膜のCata-Chromismとオプティカルガスセンサの可能性
小林哲彦・春田正毅・佐野 寛
大工試
CATALYTIC CHROMISM OF METAL-OXIDE THIN FILMS APPLICABLE TO OPTICAL GAS-DETECTION
Tetsuhiko KOBAYASHI, Masatake HARUTA and Hiroshi SANO
Government Industrial Research Institute of Osaka
1 Midorigaoka Ikeda, Osaka 563, Japan
The visible-light absorption of a Co3O4 thin film was found to change with the concentration of CO contained in air at temperatures above 100℃. At temperatures above 200℃ where the catalytic oxidation of CO took place, this absorption change occurred reversibly and was proved to be applicable to the optical detection of combustible gases.
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36
マイクロブリッジ型絶対湿度センサ
宇田和孝・杉原孝志・田渕宏樹・古林久敏・実吉秀治・井波靖彦・橋爪信郎
シャープ
MICRO-BRIDGE TYPE ABSOLUTE HUMIDITY SENSOR
Kazutaka UDA, Takashi SUGIHARA, Hiroki TABUCHI, Hisatoshi FURUBAYASHI, Shuji MIYOSHI, Yasuhiko INAMI and Nobuo HASHIZUME
Corporate Research and Development Group, Sharp Corporation
Tenri-shi, Nara 632, Japan
Micro-bridge type absolute humidity sensor was fabricated on silicon wafer by micromachining techniques. It has two micro-bridges for sensor and reference which are enclosed in each cavity formed between the substrate and the cap. Low thermal capacitance of the micro-bridge realized high sensitivity by high temperature operation and rapid response to humidity change.
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37
ポリメタクリル酸メチルを用いた容量型湿度センサ
松口正信・酒井義郎・定岡芳彦・黒岩孝朗*・伊藤昭彦*
愛媛大工・山武ハネウェル*
CAPACITIVE-TYPE HUMIDITY SENSOR USING POLY (METHYL METHACRYLATE)
Masanobu MATSUGUCHI, Yoshiro SAKAI, Yoshihiko SADAOKA, Takaaki KUROIWA* and Akihiko ITO*
Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama-shi, Ehime 790, Japan
*Fujisawa Factory, Yamatake-Honeywell Co., Ltd.,
Fujisawa, Kanagawa 251, Japan
The thin film of poly (methyl methacrylate) was examined to fabricate the capacitive-type humidity sensor without any apparent hysteresis. The amount of sorbed water of PMMA was about 1/3 of cellulose acetate butyrate and the humidity dependence of capacitance was also low. The degree of hysteresis for PMMA was small compared with that for CAB. The temperature coefficient of sensitivity was hardly influenced by sorbing water, though the capacitance at a certain relative humidity increased with increasing the temperature. This is due to the temperature dependence of permittivity of PMMA itself.
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38
四級化ビニルピリジンをグラフト重合したポリエチレン多孔膜を用いた湿度センサ
酒井義郎・松口正信・須本勇治・定岡芳彦
愛媛大工
HUMIDITY SENSOR USING MICROPOROUS POLYETHYLENE FILM GRAFTED WITH QUATERNIZED POLYVINYLPYRIDINE
Yoshiro SAKAI, Masanobu MATSUGUCHI, Yuji SUMOTO and Yoshihiko SADAOKA
Department of Industrial Chemistry, Faculty of Engineering, Ehime University
Matsuyama 790, Japan
A humidity sensor was prepared using a microporous polyethylene film grafted with quaternized vinylpyridine. The impedance of the device is lower when the films of higher grafting ratio were used. The impedance of the film depends on the counter anion of the pyridinium group, according to the order Cl- < Br- < I-. The films of higher grafting ratio adsorb more water vapor than those of lower grafting ratio. The parallel resistance RP, which was estimated by complex impedance analysis, also depends on the species of counter ion, according to the order Cl- < Br- < I-, when the films containing the same amount of water were compared. The sensor thus developed is water resistive and its response time is very short.
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39
PbCrO4-CuO系厚膜素子の感湿特性と微細構造
金子文隆・難波典之*
相模工大・関東学院大*
HUMIDITY-SENSITIVE CHARACTERISTICS AND MICROSTRUCTURE OF THICK FILM ELEMENTS IN THE SYSTEM PbCrO4-CuO
Fumitaka KANEKO and Noriyuki NANBA*
Department of Electrical Engineering, Sagami Institute of Technology
Fujisawa 251, Japan
*Department of Electrical Engineering, Faculty of Engineering, Kanto-Gakuin University
Yokohama 236, Japan
Humidity-sensitive characteristics in electrical resistivity of the thick film elements with the main component PbCrO4 are different between mixed oxides. The various microstructures depending on the mixed oxides were observed by SEM figure on the surface of the sintered body with the same composition as the thick film element.
In the film elements mixed with copper oxide CuO, the same microstructure as the surface of sintered body was obtained SEM observation.
Here the results of humidity-sensitive characteristics and microstructures in thick film elements examined for the various mixing ratio of cupric oxide CuO to PbCrO4 are reported.
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40
希土類金属酸化物焼結体の電気的特性に及ぼす湿度の影響
小川充茂・林 太郎・前河内修治・東 正志・南 晋一
阪工大工
EFFECT OF HUMIDITY ON ELECTRICAL PROPERTIES OF SINTERED RARE-EARTH OXIDES
Mitsushige OGAWA, Tarou HAYASHI, Syuuji MAEKAWAUCHI, Masashi AZUMA and Shin-ichi MINAMI
Department of Applied Chemistry, Osaka Institute of Technology
Asahi-ku, Osaka 535, Japan
Electrical properties of rare-earth (Ln) oxides were investigated by using complex impedance measurements with various relative humidities. The impedance of rare-earth (Ln= Y, Nd, Sm, Eu, Gd, Dy) sesquioxides (Ln2O3) having insulating properties decreases exponentially with increasing relative humidities owing to ionic conductivity. The results of complex impedance plots suggested that the impedance decrease of Ln2O3 with increasing relative humidities depends on bulk resistance decreases owing to increasing absorbed water. On the other hand, for non-stoichometric rare-earth oxides (Pr6O11), the conduction is mainly due to electronic conductivity explained in terms of the hopping mechanism in the low humidity region, and in high one there are both some contribution from electronic conductivity and major one from ionic conductivity.
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To Record of Chemical Sensor Symposium (Japanese)
To Record of Chemical Sensor Symposium (English)