JPH0721482B2 - Ion sensor and sensor plate - Google Patents
Ion sensor and sensor plateInfo
- Publication number
- JPH0721482B2 JPH0721482B2 JP1222909A JP22290989A JPH0721482B2 JP H0721482 B2 JPH0721482 B2 JP H0721482B2 JP 1222909 A JP1222909 A JP 1222909A JP 22290989 A JP22290989 A JP 22290989A JP H0721482 B2 JPH0721482 B2 JP H0721482B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- sensor
- silver chloride
- gate electrode
- electrode
- 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.)
- Expired - Lifetime
Links
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 33
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 9
- 230000005669 field effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 58
- 239000010410 layer Substances 0.000 description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002555 ionophore Substances 0.000 description 1
- 230000000236 ionophoric effect Effects 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、出力校正を要せず、出力特性のバラツキが少
なくしたイオンセンサ及びその部分のセンサプレートに
関する。Description: TECHNICAL FIELD The present invention relates to an ion sensor that does not require output calibration and has less variation in output characteristics, and a sensor plate of that portion.
イオンセンサは、検体液中のイオン濃度を測定するため
のものであり、半導体に形成された電界効果型トランジ
スタ（FET）のゲート電極上にイオン感応膜を形成し
た、いわゆるイオン感応性電界効果型トランジスタ（IS
FET）と呼ばれるものである。このISFETは、イオン感応
膜に検体液を接触させると、イオン感応膜と溶液との界
面に生じる電界の変化に応じて半導体表面近傍の電導度
が変化することを利用し、これを外部回路で検出できる
ようにしたものである。The ion sensor is for measuring the ion concentration in the sample liquid, and is a so-called ion-sensitive field-effect type in which an ion-sensitive film is formed on the gate electrode of a field-effect transistor (FET) formed in a semiconductor. Transistor (IS
FET) is called. This ISFET utilizes the fact that when a sample liquid is brought into contact with the ion-sensitive film, the conductivity near the semiconductor surface changes in response to the change in the electric field generated at the interface between the ion-sensitive film and the solution. It can be detected.
このISFETには、FETを形成した半導体基板上ではなく、
別の絶縁性基板上に分離ゲート電極を設けこれにイオン
感応膜を設け、さらに分離比較電極を相対して設けて独
立部品とし、これをFETに接続して使用する、いわゆる
分離ゲート型ISFETも知られている。This ISFET is not on the semiconductor substrate on which the FET is formed,
A so-called separated gate type ISFET, in which a separate gate electrode is provided on another insulating substrate, an ion sensitive film is provided on it, and a separate reference electrode is provided oppositely to form an independent component, which is connected to an FET for use Are known.
このような分離ゲート型ISFETイオンセンサのイオン感
応部は、絶縁性基板、例えばガラス・エポキシ樹脂基板
上に厚さ35μｍの銅箔を接着したいわゆるプリント配線
用基板を、ホトリソグラフィック法等により所定形状の
銅導電パターンにエッチングし、ついで市販の厚付け用
銀メッキ浴等を用いて電解メッキし、その表面に数μｍ
〜20μｍ程度の厚さに銀層を形成し、さらに塩酸溶液あ
るいは塩化ナトリウム溶液中に浸漬し、電解化成処理を
することにより銀層表面に数μｍの塩化銀層を形成す
る。ついで、表層部に銀層と塩化銀層の積層構造を設け
た電極を囲むように絶縁性樹脂、例えばエポキシ樹脂で
堤体を形成した後、イオノフォアと呼ばれる大環状化合
物やイオン交換樹脂等を含むイオン感応膜を形成したも
のであり、この構造は先の出願で提案した。The ion sensitive part of such a separated gate type ISFET ion sensor is a so-called printed wiring board in which a 35 μm-thick copper foil is adhered to an insulating substrate, for example, a glass / epoxy resin substrate, by a predetermined method such as photolithography. The copper conductive pattern of the shape is etched, and then electrolytically plated using a commercially available silver plating bath for thickening, etc.
A silver layer having a thickness of about 20 μm is formed, further immersed in a hydrochloric acid solution or a sodium chloride solution, and subjected to electrolytic chemical treatment to form a silver chloride layer having a thickness of several μm on the surface of the silver layer. Then, after forming a bank with an insulating resin, for example, an epoxy resin, so as to surround the electrode having a laminated structure of a silver layer and a silver chloride layer on the surface layer portion, a macrocyclic compound called an ionophore and an ion exchange resin are included. An ion sensitive film is formed, and this structure was proposed in the previous application.
しかしながら、従来のイオンセンサは、同じ条件で同じ
ように製作されても、同じイオン濃度に対応する出力に
差異が生じ、一定のイオン濃度であるにもかかわらず、
一定の出力が得られないことが多い。そのため、個々の
イオンセンサについて校正した後使用することが行われ
ている。However, even if the conventional ion sensor is manufactured in the same manner under the same conditions, a difference occurs in the output corresponding to the same ion concentration, and despite the constant ion concentration,
In many cases, a constant output cannot be obtained. Therefore, the individual ion sensors are used after being calibrated.
その校正方法は、イオンセンサを出力回路装置に接続し
た後、予め定められた２つの異なる溶液を用意し、一方
のイオン濃度溶液中にイオンセンサを浸漬し、その出力
を読み取る。その値が所定の標準値と相違すると、出力
回路装置の回路定数を調整し、標準の出力の値と一致さ
せる。ついで、他のイオン濃度の溶液中にイオンセンサ
を浸漬し、上記と同様に出力値がそのイオン濃度に対応
する標準値と一致するように回路定数を調整する。その
後再度上記一方のイオン濃度溶液にイオンセンサを浸漬
し、出力値が対応する標準値と異なれば、再度上記と同
様にして回路定数を調整し、さらに他のイオン濃度につ
いてもこれを行い、それぞれのイオン濃度に対する出力
値が標準値になるまで校正を繰り返す。In the calibration method, after connecting the ion sensor to the output circuit device, two different predetermined solutions are prepared, the ion sensor is immersed in one of the ion concentration solutions, and the output is read. When the value is different from the predetermined standard value, the circuit constant of the output circuit device is adjusted to match the standard output value. Next, the ion sensor is immersed in a solution having another ion concentration, and the circuit constant is adjusted so that the output value matches the standard value corresponding to the ion concentration, as described above. After that, immerse the ion sensor in the one ion concentration solution again, and if the output value differs from the corresponding standard value, adjust the circuit constant again in the same manner as above, and do this for the other ion concentrations. Repeat the calibration until the output value for the ion concentration of becomes the standard value.
このような校正作業は、工程が多く、作業が煩わしく、
また労力と手間がかかり、イオンセンサとして使用しに
くいものであった。Such calibration work has many steps, and the work is troublesome.
Further, it takes labor and time and is difficult to use as an ion sensor.
そこで、電極を塩化銀を主成分とする上側層と、銀を主
成分とする下側層からなる積層構造とし、上記上側層の
表面の粗さを200μｍ以下であるようにしたイオンセン
サ及びその分割部品のセンサプレートを先を出願で提案
した。これによれば、一定イオン濃度の検体液に対する
出力のバラツキは最も少ない場合標準偏差で0.8mVにす
ることができ、これは約３％の測定誤差を生じるに過ぎ
ず、表面の粗さが200nmより大きい場合標準偏差が3.0mV
以上になるのとはかなり改良されているが、さらに測定
精度を高めようにする場合にはこれに応えることができ
ず、その改善が求められていた。Therefore, the ion sensor having a laminated structure including an upper layer containing silver chloride as a main component and a lower layer containing silver as a main component, and the surface roughness of the upper layer being 200 μm or less, and an ion sensor thereof The sensor plate of divided parts was previously proposed in the application. According to this, the standard deviation can be set to 0.8 mV when the variation of the output for the sample solution of a constant ion concentration is the smallest, which only causes a measurement error of about 3% and the surface roughness of 200 nm. If larger, standard deviation is 3.0 mV
Although the above is considerably improved, it is not possible to meet this when further improving the measurement accuracy, and the improvement has been demanded.
本発明の目的は、イオン濃度に対応する出力値を校正す
ることなく使用できるイオンセンサを提供することにあ
る。An object of the present invention is to provide an ion sensor that can be used without calibrating the output value corresponding to the ion concentration.
また、本発明の目的は、イオン濃度に対応する出力値の
バラツキをさらに少なくして測定精度を向上させること
にある。Another object of the present invention is to further reduce the variation in the output value corresponding to the ion concentration and improve the measurement accuracy.
本発明は、上記課題を解決するために、イオン感応膜を
被覆した電極を用いて検体液の感応値を電解効果型半導
体で検出できるようにしたイオンセンサにおいて、上記
イオン感応膜が被覆される電極を塩化銀を主成分とする
上側層と、銀を主成分とする下側層からなる積層構造と
し、かつ上記上側層を構成する粒子の粒子径を１μｍよ
り小さくしたことを特徴とするイオンセンサを提供する
ものである。In order to solve the above-mentioned problems, the present invention provides an ion sensor in which an electrode coated with an ion-sensitive film is used to detect a sensitive value of a sample liquid with a field effect semiconductor, and the ion-sensitive film is coated. An ion characterized in that the electrode has a laminated structure composed of an upper layer containing silver chloride as a main component and a lower layer containing silver as a main component, and the particle diameter of the particles forming the upper layer is smaller than 1 μm. A sensor is provided.
また、電界効果型半導体の基板とは別体の絶縁性基板上
に該電界効果型半導体のゲート電極と接続して使用する
分離ゲート電極と、分離比較電極を設け、上記分離ゲー
ト電極にイオン感応膜を被覆し、このイオン感応膜が被
覆される分離ゲート電極を塩化銀を主成分とする上側層
と、銀を主成分とする下側層からなる積層構造とし、か
つ上記上側層を構成する粒子の粒子径を１μｍより小さ
くしたことを特徴とするセンサプレートを提供するもの
である。Further, a separation gate electrode to be used by connecting to the gate electrode of the field effect semiconductor and a separation reference electrode are provided on an insulating substrate which is separate from the field effect semiconductor substrate, and the separation gate electrode is ion sensitive The separation gate electrode which covers the film and is covered with the ion-sensitive film has a laminated structure composed of an upper layer containing silver chloride as a main component and a lower layer containing silver as a main component, and constitutes the above-mentioned upper layer. The present invention provides a sensor plate characterized in that the particle size of the particles is smaller than 1 μm.
塩化銀を主成分とする塩化銀層の塩化銀粒子を１μｍ以
下の粒径にすると塩化銀粒子が緻密かつ高密度に充填さ
れ、この塩化銀層とイオン感応膜との間に発生する電位
のバラツキを少なくし、イオンセンサの出力のバラツキ
を減少させることができる。When the silver chloride particles in the silver chloride layer containing silver chloride as the main component have a particle size of 1 μm or less, the silver chloride particles are densely and densely packed, and the potential of the potential generated between the silver chloride layer and the ion-sensitive film is reduced. It is possible to reduce variations and reduce variations in the output of the ion sensor.
次に本発明の実施例を第１図（イ）（ロ）に基づいて説
明する。Next, an embodiment of the present invention will be described with reference to FIGS.
紙ポリエステル基板１に接着された銅箔をホトグラフィ
ック法によりパターニングし、２μｍのダイヤモンドス
ラリによって研磨し、鏡面〔触針膜厚計（テンコール社
製薄膜表面プロファイラー アルファステップ200）に
より測定した表面粗さ200nm〕に仕上げ、所定形状の銅
電極1a、1bを形成した。The copper foil adhered to the paper polyester substrate 1 was patterned by the photographic method, polished with a 2 μm diamond slurry, and the surface roughness was measured with a mirror surface [stylus film thickness meter (Tencor thin film surface profiler Alpha Step 200). 200 nm] to form copper electrodes 1a and 1b having a predetermined shape.
次に表１に示す組成のシアン系銀ストライク・メッキ浴
と定電流電源を用いて、白金メッキチタンメッシュを陽
極とし、陰極電流密度が0.5A/dm2になるようにセットし
た状態で、５秒間上記基板を浴中に浸漬し、取り出した
後水洗した。Next, using a cyan-based silver strike / plating bath having the composition shown in Table 1 and a constant current power source, a platinum-plated titanium mesh was used as an anode, and the cathode current density was set to 0.5 A / dm 2 , and 5 The above substrate was immersed in a bath for 2 seconds, taken out, and washed with water.
ついで表１に示す組成のシアン系電解銀メッキ液に温度
50℃に保持したまま浸漬し、銀線を陽極として、陰極電
流密度1.2A/dm2で15分間電解メッキを施し、銅電極1a、
1bにそれぞれ15μｍの銀層2a、2bを形成した。Then, a cyan electrolytic silver plating solution having the composition shown in Table 1
Immersion while maintaining at 50 ℃, using the silver wire as an anode, electrolytic plating is performed for 15 minutes at a cathode current density of 1.2 A / dm 2 , copper electrode 1a
Silver layers 2a and 2b having a thickness of 15 μm were formed on 1b, respectively.
その後、0.1規定（Ｎ）の塩酸（HCl）中で、上記基板を
作用極、白金電極を対極とし、銀、塩化銀電極を比較電
極とし、−150mVから350mVまで５サイクル電位を掃引
し、予備的に微粒子の塩化銀層を形成する。その後、0.
1規定の塩酸中で上記基板を陽極、白金メッキチタンメ
ッシュを陰極とし、陽極電流密度0.23A/dm2で２分40秒
間電解処理し、銀層2a、2bの表面に塩化銀層3a、3bを形
成した。この塩化銀層の塩化銀微粒子の粒子径は走査型
電子顕微鏡による観察で0.1〜0.2μｍであった。なお、
この塩化銀層の表面粗さは上記触針膜厚系による測定で
200nmであった。Then, in 0.1N (N) hydrochloric acid (HCl), the above substrate was used as a working electrode, a platinum electrode was a counter electrode, and silver and silver chloride electrodes were used as reference electrodes, and a 5-cycle potential was swept from -150 mV to 350 mV for preliminary operation. To form a fine grain silver chloride layer. Then 0.
Using the above substrate as an anode and platinum-plated titanium mesh as a cathode in 1N hydrochloric acid, electrolysis is performed at an anode current density of 0.23 A / dm 2 for 2 minutes and 40 seconds, and silver chloride layers 3a and 3b are formed on the surfaces of silver layers 2a and 2b. Was formed. The particle size of fine silver chloride particles in this silver chloride layer was 0.1 to 0.2 μm as observed by a scanning electron microscope. In addition,
The surface roughness of this silver chloride layer is measured by the above-mentioned probe thickness system.
It was 200 nm.
上記塩化銀層3aに塩化ビニル−酢酸ビニル系共重合体を
主成分とするイオン感応膜４を被覆し、このイオン感応
膜を形成した電極と、塩化銀電極3bとを囲むように、エ
ポキシ樹脂の絶縁物で堤体５を形成した。The silver chloride layer 3a is coated with an ion sensitive film 4 containing a vinyl chloride-vinyl acetate copolymer as a main component, and an epoxy resin is provided so as to surround the electrode on which the ion sensitive film is formed and the silver chloride electrode 3b. The levee body 5 was formed from the above insulator.
このようにして銅電極1a、1bにそれぞれ銀層2a、2b及び
塩化銀層3a、3bを積層し、塩化銀層3aにはイオン感応膜
４を設け、一方塩化銀層3bを分離比較電極とするセンサ
プレートができあがる。In this way, the silver layers 2a and 2b and the silver chloride layers 3a and 3b are laminated on the copper electrodes 1a and 1b, respectively, and the ion sensitive film 4 is provided on the silver chloride layer 3a, while the silver chloride layer 3b is used as a separate reference electrode. The sensor plate to be used is completed.
このようにして、80個のセンサプレートを作成した。こ
れらのセンサプレートは、イオン感応膜を設けた電極を
分離ゲートとし、これを図示省略したFETのゲート電極
と接続し、一方分離比較電極の示す電位を基準値とし
て、FETを出力回路装置に接続し、上記堤体の内側部に
検対液を滴下することにより、その含有イオン濃度をイ
オンセンサの出力値として測定することができる。In this way, 80 sensor plates were prepared. In these sensor plates, the electrode provided with the ion-sensitive film is used as a separation gate, and this is connected to the gate electrode of the FET (not shown), while the FET is connected to the output circuit device using the potential indicated by the separation comparison electrode as a reference value. Then, by dropping the test solution onto the inside of the bank, the concentration of the contained ions can be measured as the output value of the ion sensor.
このイオンセンサにカリウムイオン濃度1mM、3mM、10m
M、30mMの溶液を滴下し、それぞれの出力を測定し、出
力値がイオン濃度の対数と直線関係になることを確認す
る。その後、センサプレートをFETから分離し、以下同
様に79個のそれぞれのセンサプレートを上記と同様に接
続してこれらセンサプレートを用いたイオンセンサにつ
いて同様の測定を行った。これらの出力値のうち、カリ
ウムイオン濃度10mMの溶液を検体液とした時の出力値を
取り出し、統計的に処理し、その標準偏差を求め、表２
に示す。また、その電子顕微鏡写真を模写した図を第２
図（イ）に示し、その写真を参考資料の写真（イ）とし
て提出する。This ion sensor has potassium ion concentration of 1 mM, 3 mM, 10 m
M and 30 mM solutions are dropped, and the output of each is measured, and it is confirmed that the output value has a linear relationship with the logarithm of the ion concentration. After that, the sensor plate was separated from the FET, and each of the 79 sensor plates was connected in the same manner as described above, and the same measurement was performed on the ion sensor using these sensor plates. Of these output values, the output value when a solution having a potassium ion concentration of 10 mM was used as a sample solution was statistically processed, and the standard deviation thereof was calculated.
Shown in. In addition, a second copy of the electron micrograph is shown.
It is shown in Figure (a), and the photograph is submitted as the reference material photograph (a).
上記実施例１において、銀ストライクメッキを省略し、
表１に示す組成のシアン系電解メッキ液に常温で浸漬
し、銀線を陽極として陰極電流密度0.42A/dm2で20分間
電解メッキを施し、厚さ約15μｍの銀層を形成し、予備
的に微粒子の塩化銀層を形成することを省略して塩化銀
層を形成し、走査型顕微鏡で観察した塩化銀粒子の粒子
径を１〜２μｍとした以外は同様にして80個のセンサプ
レートを作成し、これらのそれぞれを用いてイオンセン
サを作成し、これらのそれぞれのイオンセンサについて
実施例１と同様に測定し、出力値の標準偏差を求め、そ
の結果を表２に示す。また、その電子顕微鏡写真の模写
図を第２図（ロ）に示し、その写真を参考資料の写真
（ロ）として提出する。In Example 1, omitting the silver strike plating,
It is immersed in a cyan-based electrolytic plating solution having the composition shown in Table 1 at room temperature, and electrolytically plated for 20 minutes at a cathode current density of 0.42 A / dm 2 using a silver wire as an anode to form a silver layer having a thickness of about 15 μm. 80 sensor plates in the same manner except that the silver chloride layer was formed by omitting the formation of a fine silver chloride layer, and the particle size of the silver chloride particles observed by a scanning microscope was 1 to 2 μm. Was prepared, an ion sensor was prepared using each of these, the same measurement as in Example 1 was performed for each of these ion sensors, the standard deviation of the output values was determined, and the results are shown in Table 2. A copy of the electron micrograph is shown in Fig. 2 (b), and that photo is submitted as a reference (b).
実施例２ 実施例１において、予備的に微粒子の塩化銀層を形成す
ることを省略した以外は同様にして塩化銀層を形成し、
さらに走査型電子顕微鏡で観察した塩化銀粒子の粒子径
を0.2〜0.5μｍとした以外は同様にして80個のセンサプ
レートを作成し、このそれぞれを用いてイオンセンサを
作成し、このそれぞれについて実施例１と同様に測定
し、出力値の標準偏差を求め、その結果を表２に示す。
また、その電子顕微鏡写真の模写図を第２図（ハ）に示
し、その写真を参考資料の写真（ハ）として提出する。 Example 2 A silver chloride layer was formed in the same manner as in Example 1 except that the preliminary formation of the fine grain silver chloride layer was omitted.
Further, 80 sensor plates were prepared in the same manner except that the particle size of silver chloride particles observed with a scanning electron microscope was 0.2 to 0.5 μm. Using each of these, an ion sensor was created and implemented for each. The measurement is performed in the same manner as in Example 1, the standard deviation of the output values is obtained, and the results are shown in Table 2.
In addition, a copy of the electron micrograph is shown in Fig. 2 (c), and the photo is submitted as a reference photo (c).
〔発明の効果〕 本発明によれば、イオン感応膜を設ける電極を銀を主成
分とする下側層と塩化銀を主成分とする上側層からなる
積層構造とし、上側層の粒子の粒子径を１μｍ以下にし
たので、その上側層の粒子が緻密かつ高密度に充填さ
れ、これにより電極とイオン感応膜との界面に発生する
電位のバラツキが減少し、その結果としてイオンセンサ
の出力電位のバラツキが減少する。したがって所定のイ
オン濃度で校正することなく使用できるイオンセンサを
提供することができるので、使用の際極めて便利であ
る。 EFFECT OF THE INVENTION According to the present invention, the electrode on which the ion-sensitive film is provided has a laminated structure composed of a lower layer containing silver as a main component and an upper layer containing silver chloride as a main component, and the particle size of the particles in the upper layer is Is less than 1 μm, the particles in the upper layer are densely and densely packed, and this reduces variations in the potential generated at the interface between the electrode and the ion-sensitive membrane, and as a result, the output potential of the ion sensor is reduced. Variation is reduced. Therefore, it is possible to provide an ion sensor that can be used at a predetermined ion concentration without being calibrated, which is extremely convenient in use.
第１図（イ）は本発明の一実施例のセンサプレートの平
面図、同図（ロ）はそのII−II断面図、第２図（イ）
（ハ）は本発明の実施例により作成されたセンサプレー
トの分離ゲート電極の塩化銀層の組織を示す図、第２図
（ロ）はその改良前のセンサプレートの分離ゲート電極
の塩化銀層の組織を示す図である。 図中、１は基板、2a、2bは銀層、3a、3bは塩化銀層、４
はイオン感応膜、５は堤体である。FIG. 1 (a) is a plan view of a sensor plate according to an embodiment of the present invention, FIG. 1 (b) is a sectional view taken along the line II-II, and FIG. 2 (a).
FIG. 2C is a diagram showing the structure of the silver chloride layer of the separation gate electrode of the sensor plate prepared according to the embodiment of the present invention, and FIG. 2B is the silver chloride layer of the separation gate electrode of the sensor plate before its improvement. It is a figure which shows the organization of. In the figure, 1 is a substrate, 2a and 2b are silver layers, 3a and 3b are silver chloride layers, 4
Is an ion-sensitive membrane, and 5 is a bank.
Claims (2)
液の感応値を電界効果型半導体で検出できるようにした
イオンセンサにおいて、上記イオン感応膜が被覆される
電極を塩化銀を主成分とする上側層と、銀を主成分とす
る下側層からなる積層構造とし、かつ上記上側層を構成
する粒子の粒子径を１μｍより小さくしたことを特徴と
するイオンセンサ。1. An ion sensor in which the sensitive value of a sample liquid can be detected by a field effect semiconductor by using an electrode coated with an ion sensitive film, wherein the electrode coated with the ion sensitive film is composed mainly of silver chloride. And an upper layer and a lower layer containing silver as a main component, and the particle diameter of particles constituting the upper layer is smaller than 1 μm.
基板上に該電界効果型半導体のゲート電極と接続して使
用する分離ゲート電極と、分離比較電極を設け、上記分
離ゲート電極にイオン感応膜を被覆し、このイオン感応
膜が被覆される分離ゲート電極を塩化銀を主成分とする
上側層と、銀を主成分とする下側層からなる積層構造と
し、かつ上記上側層を構成する粒子の粒子径を１μｍよ
り小さくしたことを特徴とするセンサプレート。2. A separation gate electrode used for connecting to a gate electrode of the field effect semiconductor and a separation comparison electrode are provided on an insulating substrate which is separate from the field effect semiconductor substrate, and the separation gate electrode is provided. The ion-sensitive film is coated on the isolation gate electrode, and the separation gate electrode coated with the ion-sensitive film has a laminated structure composed of an upper layer containing silver chloride as a main component and a lower layer containing silver as a main component, and the above-mentioned upper layer. A sensor plate, wherein the particle diameter of the particles constituting the is smaller than 1 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1222909A JPH0721482B2 (en) | 1989-08-31 | 1989-08-31 | Ion sensor and sensor plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1222909A JPH0721482B2 (en) | 1989-08-31 | 1989-08-31 | Ion sensor and sensor plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0387644A JPH0387644A (en) | 1991-04-12 |
| JPH0721482B2 true JPH0721482B2 (en) | 1995-03-08 |
Family
ID=16789769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1222909A Expired - Lifetime JPH0721482B2 (en) | 1989-08-31 | 1989-08-31 | Ion sensor and sensor plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0721482B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3350810B2 (en) * | 1997-12-29 | 2002-11-25 | 太陽誘電株式会社 | Ion sensor and ion sensor plate |
| CN108420427B (en) * | 2017-05-03 | 2024-09-13 | 索思（苏州）医疗科技有限公司 | Electrode material structure of wearable electrocardio sensor and processing method thereof |
| US20230024193A1 (en) * | 2020-02-26 | 2023-01-26 | The University Of Tokyo | Transistor-type sensor |
-
1989
- 1989-08-31 JP JP1222909A patent/JPH0721482B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0387644A (en) | 1991-04-12 |
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