JPS6070348A - Fet chemical sensor - Google Patents

Fet chemical sensor

Info

Publication number
JPS6070348A
JPS6070348A JP58177961A JP17796183A JPS6070348A JP S6070348 A JPS6070348 A JP S6070348A JP 58177961 A JP58177961 A JP 58177961A JP 17796183 A JP17796183 A JP 17796183A JP S6070348 A JPS6070348 A JP S6070348A
Authority
JP
Japan
Prior art keywords
ion
metal
electrode
sensor
membrane
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
JP58177961A
Other languages
Japanese (ja)
Inventor
Hiroyuki Miyagi
宮城 宏行
Takuya Maruizumi
丸泉 琢也
Keiji Tsukada
啓二 塚田
Teruaki Kobayashi
映章 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
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 Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP58177961A priority Critical patent/JPS6070348A/en
Publication of JPS6070348A publication Critical patent/JPS6070348A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

PURPOSE:To attain to prolong the life of an FET chemical sensor, by connecting a specific metal indication electrode having an ion responsive part at the leading end thereof to a gate electrode. CONSTITUTION:MOSFET 2 is provided to one end of a support substrate 1 and a metal indication electrode 3 is connected thereto. The porous electrode 4 provided to the leading end of the indication electrode 3 is formed by providing fine perforations 5 to a sintered metal such as stainless steel or silver or a metal such as gold, silver or platinum by chemically etching due to aqua regia and the surface thereof is coated with a high-molecular membrane 6 having ion selective response. The ion selectively responsive membrane 6 can be formed by using a composition wherein an ion responsive substance is dispersed in PVC as a plasticizer or a composition prepared by dispersing the ion responsive substance in a silicone rubber or epoxy resin film. Because the film 6 is penetrated into the fine perforations 5 and adhered thereto and no peel-off is generated, the life of a sensor is elongated.

Description

【発明の詳細な説明】 〔発明の利用分野〕 本発明は、MOSFETを利用するFET化学センサに
係り、特に、長寿命化を図るに好適なFET化学センサ
に係る。
DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a FET chemical sensor using a MOSFET, and particularly to a FET chemical sensor suitable for achieving a long life.

〔発明の背景〕[Background of the invention]

MOSFETのゲート電極に、白金などの金属指示電極
を接続し、その先端に有機高分子支持膜形イオン選択感
応膜を塗布したF E TイオンセンサはIt Tho
mpsonらによって報告されている((Talant
a、26. ppl、015−1018.1979)。
It Tho is an FET ion sensor in which a metal indicator electrode such as platinum is connected to the gate electrode of a MOSFET, and an organic polymer-supported ion-selective membrane is coated on the tip of the indicator electrode.
As reported by mpson et al.
a, 26. ppl, 015-1018.1979).

このFETセンサは、極めて簡単に製作することができ
、また微小センサを構成するに適している。
This FET sensor can be manufactured extremely easily and is suitable for constructing a minute sensor.

通常、金属指指示′電極としては白金線が用いられてい
るが、この種のセンサは白金線に塗布した上記の有機高
分子膜が剥離し、性能劣化の原因となっている。
Usually, a platinum wire is used as the metal finger indicator electrode, but in this type of sensor, the organic polymer film coated on the platinum wire peels off, causing performance deterioration.

〔発明の目的〕[Purpose of the invention]

本発明の主たる目的は、MOSFET を利用した化学
センサ、特にイオンセンサの長寿命化を図るに適するセ
ンサを提供することである。
The main object of the present invention is to provide a chemical sensor using MOSFET, particularly a sensor suitable for extending the life of an ion sensor.

〔発明の概要〕[Summary of the invention]

上記した、本発明の目標を達成するために、金属指示電
極を多孔性金属とし、イオン感応膜などの有機高分子膜
の剥離を防ぐ方法を採用した。
In order to achieve the above-mentioned goals of the present invention, a method was adopted in which a porous metal was used as the metal indicator electrode to prevent peeling of an organic polymer film such as an ion-sensitive film.

〔発明の実施例〕[Embodiments of the invention]

以下、本発明金実施例に基づき詳細に説明する。 Hereinafter, the present invention will be explained in detail based on examples of the present invention.

第1図は、本発明の第1の実施例である。支持基板1の
一端にはMOSFET 2が設置されておシ、そのゲー
ト電極に金属製指示電極3が接続された構造となってい
る。この指示電極の先端は多孔性電極4になっておシ、
その表面に有機高分子膜として有機高分子支持膜形イオ
ン感応膜が塗布される。
FIG. 1 shows a first embodiment of the invention. A MOSFET 2 is installed at one end of the support substrate 1, and a metal indicator electrode 3 is connected to the gate electrode of the MOSFET 2. The tip of this indicator electrode becomes a porous electrode 4.
An organic polymer-supported ion-sensitive membrane is coated on the surface thereof as an organic polymer membrane.

上記した金属製指示゛電極3は白金、金、アルミニウム
、銅、不純物をドープしたポリシリコンなど電気伝導性
の良い金属ならいかなるものでも使用できる。捷た、指
示電極3の先端部の多孔性電極4はステンレススチール
おるいは銀などの焼結金属、あるいは、金、銀、白金な
どの薄膜を王水などによる化学的エツチング、おるいは
ホトリソグラフィーなどの物理的エツチングによシ細孔
をあけたものなどが使用できる。該指示電極3と多孔性
指示電極4は第1図のように支持基板l上に設けた構造
の他、支持基板を取ジ除いて用いてもよい。
The metal indicator electrode 3 described above can be made of any metal with good electrical conductivity, such as platinum, gold, aluminum, copper, or polysilicon doped with impurities. The porous electrode 4 at the tip of the cut indicator electrode 3 is made of stainless steel or sintered metal such as silver, or a thin film of gold, silver, platinum, etc., by chemical etching with aqua regia, or by photo-etching. A material with pores formed by physical etching such as lithography can be used. The indicator electrode 3 and the porous indicator electrode 4 may have a structure provided on a support substrate l as shown in FIG. 1, or may be used by removing the support substrate.

第1図に示した実施例のイオン感応部の断面図を第2図
に示す。支持基板1上に凹部を設け、その中に多孔性電
極4が設置されており、その上にイオン選択感応膜6を
頭布した構造となっている。
FIG. 2 shows a cross-sectional view of the ion sensing portion of the embodiment shown in FIG. 1. A concave portion is provided on the support substrate 1, a porous electrode 4 is placed in the concave portion, and an ion selective sensitive membrane 6 is placed on top of the concave portion.

イオン選択感応膜としては、ポリ塩化ビニル(PVC)
中に可塑剤とイオン感応物質を分散させたもの、シリコ
ンゴム、エポキシ樹脂中にイオン感応物質を分散させた
ものなどが使用できるが、膜材料物質を溶媒に俗解し、
ディップコート法あるいはキャスティング法で塗布でき
るものが多孔性電極4に密着しやすい点で好ましい。
As an ion selective sensitive membrane, polyvinyl chloride (PVC)
Materials with a plasticizer and ion-sensitive substance dispersed in them, silicone rubber, or epoxy resin with an ion-sensitive substance dispersed in them can be used, but the membrane material substance is commonly understood as a solvent.
It is preferable to use a material that can be applied by dip coating or casting because it can easily adhere to the porous electrode 4.

本発明によるイオンセンサの実施例では、イオン感応膜
が多孔性電極4のl1ll孔5に浸透して接着されるた
め、剥離が生じに<<、細孔のない金属に直接塗布した
。場合に比較し、センサ寿命は一段と長くなる。
In the embodiment of the ion sensor according to the present invention, the ion-sensitive membrane penetrates into the pores 5 of the porous electrode 4 and is adhered to it, so that it is applied directly to the metal without pores, which causes peeling. The sensor life is much longer than in the case of

本発明で採用した多孔性電極4の形状は、第2図のよう
な平板状の他、棒状おるいは棒の先端に涼秋の金属を爆
接したものなどでもよい。また、電極としてもよい。
The shape of the porous electrode 4 employed in the present invention may be in addition to a flat plate shape as shown in FIG. 2, or a rod shape, or a rod in which cool metal is explosively bonded to the tip of the rod. It may also be used as an electrode.

本発明の第2の実施例断面図を第3図に示すが、この例
では、多孔性電極4は支持基板lの凹部に浮いた構造と
なっておシ、イオン感応膜6を多孔性電極の上方及び下
方にも塗布した。この実施例では、第1の実施例に比較
し、更にセンサ寿命を長くすることができた。
A cross-sectional view of a second embodiment of the present invention is shown in FIG. It was also applied above and below. In this example, the sensor life could be further extended compared to the first example.

第4図は、本発明の第3の実施例断面図でろシ、固定化
酵素膜と組合せた謂わゆるFET酵素センサを構成した
ものでめる。多孔性電極4として、焼結銀板を用い、そ
の表面に、PVC膜中に可塑材であるジオクチルセバケ
ートとノナクチ/を分散したNHa+イオン選択膜を塗
布し、更に、その上部にアルブミンにグルグルアルデヒ
ドを介して12レアーゼを固定化した酵素膜を塗布した
。この尿素センサは、1ケ月以上に渡シ、血清中の尿素
の測定に供し得た。
FIG. 4 is a sectional view of a third embodiment of the present invention, which is a so-called FET enzyme sensor in combination with a filter and an immobilized enzyme membrane. A sintered silver plate is used as the porous electrode 4, and on its surface is coated an NHa+ ion-selective membrane in which plasticizers dioctyl sebacate and nonacti are dispersed in a PVC membrane, and on top of that is coated with albumin. An enzyme membrane in which 12-rease was immobilized via aldehyde was applied. This urea sensor could be used to measure urea in serum for more than one month.

第1図に示した実施例で、K+イオンセ/すを構成し、
スロープ感度の経日変化を測定した例を第5図に示す。
In the embodiment shown in FIG. 1, a K+ ion cell is configured,
FIG. 5 shows an example of measuring the change in slope sensitivity over time.

ここで、スロープ感展は濃度を1桁変化させた際の出力
電位の差である。この実験に用いたイオンセンサは、サ
ファイア基板上に銀を蒸着し、これを化学的にエツチン
グして1〜10μの細孔をあけ多孔質とした電極を用い
た。
Here, the slope sensitivity is the difference in output potential when the concentration is changed by one order of magnitude. The ion sensor used in this experiment used a porous electrode in which silver was deposited on a sapphire substrate and chemically etched to form pores of 1 to 10 microns.

K+イオン選択膜はpvc、ジオクチルアジペート及び
パリノマイシンをテトラヒドロフランに俗解したキャス
ティング溶液を調製し、これを直接指示電極上に滴下し
た後、テトラヒドロフラン全蒸発させる方法により調製
した。第5図には、同様のに+イオン感応族を化学エツ
チングを施さない従来の銀指示電極に塗付した場合(B
)と本発明の多孔性指示電極に塗付した場合(A)とを
比較して図示した。従来の方式では、感応膜の剥離及び
ピンホールの生成などにより、短期間で使用できなくな
るが、本発明のイオンセンサは1ケ月以上の使用に耐え
る。
The K + ion selective membrane was prepared by preparing a casting solution of PVC, dioctyl adipate, and palinomycin in tetrahydrofuran, dropping this directly onto the indicator electrode, and then completely evaporating the tetrahydrofuran. Figure 5 shows a case in which a similar + ion-sensitive group is applied to a conventional silver indicator electrode that is not chemically etched (B
) is compared with (A) when applied to the porous indicator electrode of the present invention. The conventional method becomes unusable in a short period of time due to peeling of the sensitive membrane and formation of pinholes, but the ion sensor of the present invention can withstand use for more than one month.

本発明の多孔性指示電極としては、銀粉などをフェノー
ル樹脂フェス等に混合した導電性塗料を支持基板上に塗
布し、これを熱処理して多孔銀電極としたものなども便
利に使用できる。
As the porous indicator electrode of the present invention, a porous silver electrode prepared by coating a support substrate with a conductive paint containing silver powder or the like mixed with a phenol resin face or the like and heat-treating the resultant material can also be conveniently used.

〔発明の効果〕〔Effect of the invention〕

本発明のFET化学センサは、イオン感応膜や固定化酵
素膜が指示電極から剥離することを防ぐ上で極めて効果
的である。したがって、有機高分子イオン感応膜、固定
化酵素膜などを利用するF E ’1’化学七ンサの安
定化及び長寿命化に適するものである。
The FET chemical sensor of the present invention is extremely effective in preventing the ion-sensitive membrane and the immobilized enzyme membrane from peeling off from the indicator electrode. Therefore, it is suitable for stabilizing and extending the life of F E '1' chemical sensors that utilize organic polymer ion-sensitive membranes, immobilized enzyme membranes, and the like.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は、本発明の第1の実施例の平面図、第2図はそ
の断面図、第3図は第2の実施例の断面図、第4図は本
発明を酵素センサに適用した例の断面図、第5図は本発
明のイオン感応膜の特性を示す図である。 l・・・支持基板、2・・・MO8FE’l” 、3・
・・指示電極、4・・・多孔性電極、5・・・細孔、6
・・・イオン選択感応膜、10・・・NH4+イオン感
応族、11・・・固定化ウレアーゼ膜。 代理人 弁理士 高橋明未 I i 図
Fig. 1 is a plan view of the first embodiment of the present invention, Fig. 2 is a sectional view thereof, Fig. 3 is a sectional view of the second embodiment, and Fig. 4 is a plan view of the first embodiment of the present invention. An example cross-sectional view, FIG. 5, is a diagram showing the characteristics of the ion-sensitive membrane of the present invention. l...Supporting substrate, 2...MO8FE'l", 3.
... Indicator electrode, 4 ... Porous electrode, 5 ... Pore, 6
... Ion selective sensitive membrane, 10... NH4+ ion sensitive group, 11... Immobilized urease membrane. Agent Patent Attorney Akemi Takahashi I Figure

Claims (1)

【特許請求の範囲】 1、MOSFETのゲート電極に、先端部にイオン感応
部を有する金属指示電極を接続して構成するFETイオ
ンセンサにおいて、該金属指示電極のイオン感応部が多
孔性であシ、その表面に有機高分子膜を塗布したことを
特徴とするFET化学センサ。 2、該多孔性金属が、電気伝導性の金属あるいは金属化
合物、合金のいずれかであシ、かつ、それらの焼結体、
あるいは物理的又は化学的エツチングによ1ift孔が
形成されたものであることを特徴とする特許請求の範囲
第1項記載のFET化学センサ。
[Claims] 1. In an FET ion sensor configured by connecting a metal indicator electrode having an ion-sensing part at the tip to a gate electrode of a MOSFET, the ion-sensing part of the metal indicator electrode is porous and non-porous. , an FET chemical sensor characterized by having an organic polymer film coated on its surface. 2. The porous metal is an electrically conductive metal, a metal compound, or an alloy, and a sintered body thereof;
Alternatively, the FET chemical sensor according to claim 1, wherein the 1ift hole is formed by physical or chemical etching.
JP58177961A 1983-09-28 1983-09-28 Fet chemical sensor Pending JPS6070348A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58177961A JPS6070348A (en) 1983-09-28 1983-09-28 Fet chemical sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58177961A JPS6070348A (en) 1983-09-28 1983-09-28 Fet chemical sensor

Publications (1)

Publication Number Publication Date
JPS6070348A true JPS6070348A (en) 1985-04-22

Family

ID=16040102

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58177961A Pending JPS6070348A (en) 1983-09-28 1983-09-28 Fet chemical sensor

Country Status (1)

Country Link
JP (1) JPS6070348A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270749A (en) * 1985-09-25 1987-04-01 Toshiba Corp Fet sensor and its preparation
JPH07234200A (en) * 1994-02-24 1995-09-05 Nec Corp Flat metal electrode for qualification electrode and its manufacturing method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270749A (en) * 1985-09-25 1987-04-01 Toshiba Corp Fet sensor and its preparation
JPH07234200A (en) * 1994-02-24 1995-09-05 Nec Corp Flat metal electrode for qualification electrode and its manufacturing method

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