JPH0384448A - Production of ion sensor, production of sensor plate and preserving method thereof - Google Patents
Production of ion sensor, production of sensor plate and preserving method thereofInfo
- Publication number
- JPH0384448A JPH0384448A JP1220241A JP22024189A JPH0384448A JP H0384448 A JPH0384448 A JP H0384448A JP 1220241 A JP1220241 A JP 1220241A JP 22024189 A JP22024189 A JP 22024189A JP H0384448 A JPH0384448 A JP H0384448A
- Authority
- JP
- Japan
- Prior art keywords
- ion
- sensor
- electrode
- sensitive film
- atmosphere
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims description 68
- 239000012528 membrane Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 9
- 230000005669 field effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin 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
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 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
- 235000006693 Cassia laevigata Nutrition 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000735631 Senna pendula Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940124513 senna glycoside Drugs 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、出力特性のバラツキを少なくしたイオンセン
サ及びその部品のセンサプレートの製造方法並びにこり
らの保存方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ion sensor that reduces variations in output characteristics, a method for manufacturing a sensor plate as a component thereof, and a method for storing the same.
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（ＦＨＴ ）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（
ＩＳＦＥＴ）と呼ばれるものである。このｌ５ＦＥＴ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。An ion sensor is used to measure the concentration of ions in a sample liquid, and is a so-called ion-sensitive field-effect transistor in which an ion-sensitive film is formed on the gate electrode of a field-effect transistor (FHT) formed in a semiconductor. Transistor (
ISFET). This 15FET utilizes the fact that when an ion-sensitive membrane is brought into contact with a sample liquid, the conductivity near the semiconductor surface changes in response to changes in the electric field generated at the interface between the ion-sensitive membrane and the solution, and this is controlled by an external circuit. It is designed to be detectable.
このｌ５ＦＥＴ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ｌ５ＦＥＴも知られている。In this 15FET, a separate gate electrode is provided not on the semiconductor substrate on which the FET is formed, but on another insulating substrate, an ion-sensitive membrane is provided on this, and a separate comparison electrode is provided facing each other to make it an independent component. A so-called separated gate type 15FET is also known, which is used by connecting the FET to an FET.
このような分離ゲート型ｌ５ＦＥＴ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ツチングし、ついで市販の厚
付は角根メンキ浴等を用いて電解メツキし、その表面に
数μ−〜２０μ−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μ−の塩化銀層を
形成する。ついで、表層部にｕｉ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、イオノフオアと呼ばれる大
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 sensing part of such a separated gate type 15FET ion sensor is made of a so-called printed circuit board, which is made by bonding a 35-μm-thick copper foil onto an insulating substrate, such as a glass epoxy resin substrate. A copper conductive pattern of the shape is etched, and then a commercially available thick plate is electrolytically plated using a square root coating bath, etc., a silver layer is formed on the surface to a thickness of several microns to 20 microns, and then a silver layer is formed on the surface using a hydrochloric acid solution. Alternatively, a silver chloride layer of several microns is formed on the surface of the silver layer by immersing it in a sodium chloride solution and performing an electrochemical conversion treatment. Next, after forming an embankment using an insulating resin, such as an epoxy resin, to surround the electrode having a laminated structure of a ui layer and a silver chloride layer on the surface layer, an embankment containing a macrocyclic compound called an ionophore, an ion exchange resin, etc. An ion-sensitive membrane is formed, and this structure was proposed in a previous application.
しかしながら、上記のイオン感応部を構成する銀層と塩
化銀層の積層構造の電極や、この上に被覆されるイオン
感応膜は水分に対して敏感であり、吸湿により特性のバ
ラツキが大きくなることがある。ところが、従来は大気
中で上記イオン感応膜を電極に被覆する工程の作業を行
っていたため、作業日の湿度、その作業に要する時間等
により、イオンセンナとして使用された場合の出方にバ
ラツキを生じていた。However, the electrode with a laminated structure of a silver layer and a silver chloride layer that constitutes the above-mentioned ion-sensitive part, and the ion-sensitive membrane coated thereon, are sensitive to moisture, and variations in characteristics increase due to moisture absorption. There is. However, in the past, the process of coating the electrodes with the ion-sensitive membrane was carried out in the atmosphere, which resulted in variations in the output when used as an ion sensor, depending on the humidity of the working day, the time required for the work, etc. It was happening.
また、上記イオン感応部をＦＥＴと同じ基板に一体に形
成したイオンセンサ、あるいはイオン感応部からなる部
分を上記したようにＦＥＴから独立した部品のセンサプ
レートとして作威し、ＦＥＴ等と接続して使用するよう
ないずれの場合も、イオンセンサスはセンサプレートと
して製造されてから使用されるまでには保存時間があり
、この保存を大気中に開放した状態で行うと、イオン感
応膜が吸湿し、その特性が変化し、イオンセンサとして
使用された場合にその出方にバラツキが生しることにな
る。In addition, an ion sensor in which the above-mentioned ion-sensing section is integrally formed on the same substrate as the FET, or a part consisting of the ion-sensing section can be used as a sensor plate that is an independent component from the FET, and connected to the FET, etc. In any case where the ion sensor is used, there is a storage time between the time it is manufactured as a sensor plate and the time it is used, and if this storage is done in an open environment, the ion sensitive membrane will absorb moisture. Its characteristics change, and when used as an ion sensor, there will be variations in its output.
このようにイオンセンサやその部品の製造条件、保存条
件その他の原因により、イオンセンサとして使用した場
合に、同じイオン濃度に対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。In this way, due to the manufacturing conditions, storage conditions, and other causes of the ion sensor and its parts, when used as an ion sensor, there may be differences in the output for the same ion concentration. Therefore, each ion sensor is often calibrated before use.
その校正方法は、イオンセンサを出方回路装置に接続し
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、その出方
を読み取る。その値が所定の標準値と相違すると、出方
回路装置の回路定数を調整し、標準の出方の値と一致さ
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. If the value differs from a predetermined standard value, the circuit constants of the output circuit device are adjusted to match the standard output value. Next, the ion sensor is immersed in a solution with another ion concentration, and the circuit constants are adjusted in the same manner as above so that the output value matches the standard value corresponding to that ion concentration. After that, immerse the ion sensor in one of the above ion concentration solutions again, and if the output value differs from the corresponding standard value, adjust the circuit constants again in the same way as above, and repeat this for the other ion concentrations. Repeat the calibration until the output value for the ion concentration 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、イオンセンナとして使用しに
くいものであった。This kind of proofreading work involves many steps and is cumbersome.
Moreover, it required much labor and effort, and was difficult to use as an ion senna.
本発明の目的は、イオン感応膜がその製造時やこのイオ
ン感応膜を有する製品の保存時、また、電極が製品保存
時に周囲の雰囲気の湿度に影響されないで一定の特性に
制御され、イオン感応膜の吸湿性の点で校正を必要とす
ることがないようなイオンセンサの製造方法、センサプ
レートの製造方法及びこれらの保存方法を提供すること
にある。An object of the present invention is to control the ion-sensitive membrane to have constant characteristics during its manufacture, during the storage of the product having the ion-sensitive membrane, and during the storage of the product, without being affected by the humidity of the surrounding atmosphere. It is an object of the present invention to provide a method for manufacturing an ion sensor, a method for manufacturing a sensor plate, and a method for storing these, which do not require calibration in terms of membrane hygroscopicity.
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界効果型半導
体で検出できるようにしたイオンセンサの製造方法にお
いて、上記イオン感応膜を電極に被覆する工程を相対湿
度１０％以下に制御した雰囲気内で行うことを特徴とす
るイオンセンサの製造方法及びこのイオンセンサを相対
湿度１０％以下の雰囲気中に密閉保存することを特徴と
するイオンセンサの保存方法を提供するものである。In order to solve the above problems, the present invention provides a method for manufacturing an ion sensor in which a field-effect semiconductor can detect a sensitive value of a sample liquid using an electrode coated with an ion-sensitive membrane. A method for producing an ion sensor, characterized in that the step of coating the electrodes is carried out in an atmosphere controlled to a relative humidity of 10% or less, and the ion sensor is stored in a hermetically sealed atmosphere in a relative humidity of 10% or less. This invention provides a method for preserving ion sensors.
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設けて独立部品としたセンサプ
レートの製造方法において、上記イオン感応膜を電極に
被覆する工程を相対湿度１０％以下に制御した雰囲気内
で行うことを特徴とするセンサプレートの製造方法及び
このセンサプレートを相対湿度１０％以下の雰囲気中に
密閉保存することを特徴とするセンサプレートの保存方
法を提供するものである。In addition, a separate gate electrode and a separate reference electrode, which are used in connection with the gate electrode of the field effect semiconductor, are provided on an insulating substrate separate from the field effect semiconductor substrate, and an ion-sensitive electrode is provided on the separate gate electrode. A method for manufacturing a sensor plate that is provided with a membrane and made into an independent component, characterized in that the step of coating the electrode with the ion-sensitive membrane is carried out in an atmosphere with a relative humidity of 10% or less, and this method. The present invention provides a method for preserving a sensor plate, which is characterized in that the sensor plate is hermetically preserved in an atmosphere with a relative humidity of 10% or less.
イオン感応膜を電極に被覆する工程及びこのイオン感応
膜を有する製品の保存を低湿度雰囲気中で行ったので、
製造時のイオン感応膜に対する水分の影響、保存時のイ
オン感応膜及び電極に対する水分の影響を排除すること
ができ、その特性を一定化させることができる。Since the process of coating the electrode with the ion-sensitive membrane and the storage of the product containing this ion-sensitive membrane were carried out in a low-humidity atmosphere,
The influence of moisture on the ion-sensitive membrane during manufacture and the influence of moisture on the ion-sensitive membrane and electrodes during storage can be eliminated, and its characteristics can be made constant.
次に本発明の実施例を第１図及び第２図に基づいて説明
する。Next, an embodiment of the present invention will be described based on FIGS. 1 and 2.
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ＶＦｉＦＬ、鏡面（触針膜厚計（テンコー
ル社製薄膜表面プロファイラ−アルファステップ２００
）により測定した表面粗さ２００ｎｓ＋ ）に仕上げ、
所定形状の銅電極１ａ、 ｌｂを形成した。The copper foil adhered to the paper polyester substrate 1 was patterned by a photographic method, and a 2 μm diamond slurry was applied to the VFiFL, mirror surface (stylus film thickness meter (Tencor thin film surface profiler Alpha Step 200)).
) Finished to a surface roughness of 200ns+ ) measured by
Copper electrodes 1a and lb having a predetermined shape were formed.
次に１ｇ／ｌ含有する市販のシアン系銀ストライク・メ
ツキ浴と定電流電源を用いて、上記銅電極１ａ、１ｂを
陰極、白金メツキチタンメツシュを陽極とし、陰極電流
密度が０．５Ａ／ｄ ｎ？になるようにセントした状態
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 commercially available cyanide-based silver strike plating bath containing 1 g/l and a constant current power supply, the copper electrodes 1a and 1b were used as cathodes, and the platinum-plated titanium mesh was used as an anode, and the cathode current density was 0.5 A/L. dn? The substrate was immersed in the bath for 5 seconds in a state where the substrate was slanted so that the temperature was 0.5 seconds, and after taking it out, it was washed with water.
ついでｔ１２０ｇ／Ｊ含有する市販のシアン系電解銀光
沢メツキ液に温度５０℃に保持したまま浸漬し、上記銅
電極１ａ、 ｌｂを陰極、白金メッキチタンメンシェを
陽極とし、陰極電流密度１２Ａ／ｄ ｎ？で１分３０秒
間電解メツキを施し、銅電極１ａ、 ｌｂにそれぞれ厚
さ１５μ曙の銀層２ａ、 ２ｂを形成した。Then, it was immersed in a commercially available cyan-based electrolytic silver bright plating solution containing t120 g/J while maintaining the temperature at 50°C, and the copper electrodes 1a and 1b were used as cathodes, the platinum-plated titanium mensier was used as an anode, and the cathode current density was 12 A/d. n? Electroplating was performed for 1 minute and 30 seconds to form silver layers 2a and 2b with a thickness of 15 μm on the copper electrodes 1a and lb, respectively.
その後、０．１規定（Ｎ）の塩酸（ＨＣＩ）中で、上記
基板を陽極、白金メツキしたチタンメフシェ電極を陰極
とし、陽極電流密度０．２３Ａ／ｄ ｍ 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。Thereafter, in 0.1 normal (N) hydrochloric acid (HCI), the above substrate was used as an anode and the platinized titanium mesh electrode was used as a cathode, and the anode current density was 0.23 A/d m for 2 minutes and 40 minutes.
Electrolytic treatment is performed for seconds to form a silver chloride layer 3a on the surface of the silver layers 2a and 2b.
, 3b was formed.
上記塩化銀層３ａ、塩化錫電極３ｂとを囲むように、エ
ポキシ樹脂の絶縁物で堤体５を形成した後、テトラヒド
ロフラン、純水で洗浄し、真空乾燥機を用いて１００℃
、真空（−７６０ｗｒ■ｇ）の条件で２０時間乾燥させ
た。その後乾燥Ｍ棄ガス置換したデシケータ中で放冷し
た。After forming the embankment body 5 with an epoxy resin insulator so as to surround the silver chloride layer 3a and the tin chloride electrode 3b, it is washed with tetrahydrofuran and pure water, and then heated to 100°C using a vacuum dryer.
, and dried under vacuum (-760 wr g) for 20 hours. Thereafter, it was allowed to cool in a desiccator replaced with dry M waste gas.
放冷後、湿度を１０％以下に保ったクローズボックス中
で、塩化ビニル−酢酸ビニル系共重合体を含有する樹脂
液を上記塩化銀層３ａ上に塗布し、乾燥してイオン感応
膜４を形成した。After cooling, a resin solution containing a vinyl chloride-vinyl acetate copolymer is applied onto the silver chloride layer 3a in a closed box with humidity kept below 10%, and dried to form the ion-sensitive membrane 4. Formed.
このようにしてセンサプレートが作成されたが、このセ
ンサプレートを外気と遮断するため乾燥窒素ガスを封入
したアルミパンク内にシリカゲルを同封して密封した。A sensor plate was created in this manner, and in order to isolate the sensor plate from the outside air, silica gel was enclosed in an aluminum puncture filled with dry nitrogen gas and sealed.
この密封方法については接着剤を使用しても良く、また
アルさ箔にポリエチレンをう主ネートした複合材により
アルミパンクを作成し、熱シールしても良い。For this sealing method, an adhesive may be used, or an aluminum puncture may be prepared from a composite material of aluminum foil coated with polyethylene and heat sealed.
このようにして、８０個のセンサプレートを作成した。In this way, 80 sensor plates were created.
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ＦＢＴ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。These sensor plates use an electrode provided with an ion-sensitive membrane as a separation gate, which is connected to the gate electrode of an FBT (not shown), and an FET connected to an output circuit device using the potential shown by the separation comparison electrode as a reference value. However, by dropping the test liquid onto the inner side of the embankment body, the concentration of ions contained therein can be measured as an output value of the ion sensor.
上記密封保存されたセンサプレートを使用直前に開封し
、上記のように回路を形成したイオンセンサにカリウム
イオン濃度１ｓＭ 、３ｓ＋Ｍ 、１０■Ｍ、 ３０−
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ＦＩＳＴから分離し、以下同様に
１９１１Ｎ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１０−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、
表に示す。Immediately before use, the sealed sensor plate was opened, and potassium ion concentrations of 1 sM, 3s+M, 10M, and 30-
drop the solution, measure the output of each, and confirm that the output value has a linear relationship with the logarithm of the ion concentration. Thereafter, the sensor plates were separated from the FIST, and the respective sensor plates of 1911N were connected in the same manner as above, and similar measurements were performed on ion sensors using these sensor plates. Among these output values, the output value when a solution with a potassium ion concentration of 10- is used as the sample liquid is extracted, statistically processed, and its standard deviation is determined.
Shown in the table.
比較例
上記実施例１において、堤体５を形成した後、テトラヒ
ドロフラン、純水で洗浄し、乾燥機を用いて１００℃、
常圧で３０分間乾燥させ、真空デシケータ中、減圧状態
で一夜放冷し、相対湿度６０％の大気中で、イオン感応
膜を形成した以外は同様にしてセンサプレートを作成し
、これをアルミパック中に保存せず、そのまま空気中に
放置した。Comparative Example In Example 1 above, after forming the embankment body 5, it was washed with tetrahydrofuran and pure water, and dried at 100°C using a dryer.
A sensor plate was prepared in the same manner, except that it was dried for 30 minutes at normal pressure, left to cool under reduced pressure in a vacuum desiccator overnight, and an ion-sensitive membrane was formed in an atmosphere with relative humidity of 60%, and this was packed in an aluminum pack. It was not stored inside, but left in the air.
これを８０個作作成て空気中に放置し、それぞれを上記
実施例と同様に用いて測定し、出力値の標準偏差を求め
、その結果を表に示す。Eighty pieces of this were made and left in the air, and each was measured in the same manner as in the above example to determine the standard deviation of the output value, and the results are shown in the table.
本発明によれば、イオン感応膜を電極に被覆する工程や
このイオン感応膜を有する製品の保存を相対湿度１０％
以下の低湿度雰囲気中でおこなったので、イオン感応膜
の水分に対する影響を排除し、また、製品保存中の電極
に対する水分の影響を排除することができ、周囲の雰囲
気に影響されない安定したイオンセンサの出力特性が得
られる。これにより、校正の必要性を少なくすることが
できる。According to the present invention, the process of coating an electrode with an ion-sensitive membrane and the storage of a product having this ion-sensitive membrane are carried out at a relative humidity of 10%.
Since the test was carried out in the following low humidity atmosphere, it is possible to eliminate the influence of moisture on the ion-sensitive membrane and the influence of moisture on the electrodes during product storage, resulting in a stable ion sensor that is not affected by the surrounding atmosphere. output characteristics are obtained. This can reduce the need for calibration.
第１図は本発明の一実施例のセンサプレートの平面図、
第２図はそのｎ −ｎ断面図である。
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 is a plan view of a sensor plate according to an embodiment of the present invention;
FIG. 2 is a sectional view taken along line n-n. 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 an embankment body.
Claims (4)
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
センサの製造方法において、上記イオン感応膜を電極に
被覆する工程を相対湿度１０％以下に制御した雰囲気内
で行うことを特徴とするイオンセンサの製造方法。(1) In a method for manufacturing an ion sensor in which the sensitive value of a sample liquid can be detected by a field-effect semiconductor using an electrode coated with an ion-sensitive membrane, the step of coating the electrode with the ion-sensitive membrane is carried out at a relative humidity of 10%. A method for manufacturing an ion sensor, characterized in that the manufacturing method is carried out in an atmosphere controlled to % or less.
下の雰囲気中に密閉保存することを特徴とするイオンセ
ンサの保存方法。(2) A method for preserving an ion sensor, which comprises storing the ion sensor according to claim 1 in an airtight atmosphere with a relative humidity of 10% or less.
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設けて独立部品としたセンサプ
レートの製造方法において、上記イオン感応膜を電極に
被覆する工程を相対湿度１０％以下に制御した雰囲気内
で行うことを特徴とするセンサプレートの製造方法。(3) A separate gate electrode used in connection with the gate electrode of the field-effect semiconductor and a separate comparison electrode are provided on an insulating substrate separate from the field-effect semiconductor substrate, and ions are applied to the separated gate electrode. A method for manufacturing a sensor plate provided with a sensitive film and made into an independent component, characterized in that the step of coating an electrode with the ion-sensitive film is performed in an atmosphere with a relative humidity of 10% or less.
以下の雰囲気中に密閉保存することを特徴とするセンサ
プレートの保存方法。(4) The sensor plate according to claim 3 at a relative humidity of 10%.
A method for storing a sensor plate, which is characterized by storing the sensor plate in a sealed manner in the following atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220241A JP2772833B2 (en) | 1989-08-29 | 1989-08-29 | Method for manufacturing ion sensor, method for manufacturing sensor plate, and method for storing these |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220241A JP2772833B2 (en) | 1989-08-29 | 1989-08-29 | Method for manufacturing ion sensor, method for manufacturing sensor plate, and method for storing these |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0384448A true JPH0384448A (en) | 1991-04-10 |
| JP2772833B2 JP2772833B2 (en) | 1998-07-09 |
Family
ID=16748104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1220241A Expired - Lifetime JP2772833B2 (en) | 1989-08-29 | 1989-08-29 | Method for manufacturing ion sensor, method for manufacturing sensor plate, and method for storing these |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2772833B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002001215A1 (en) * | 2000-06-29 | 2002-01-03 | Yamatake Corporation | Integrated sensor device and measuring system using the same |
-
1989
- 1989-08-29 JP JP1220241A patent/JP2772833B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002001215A1 (en) * | 2000-06-29 | 2002-01-03 | Yamatake Corporation | Integrated sensor device and measuring system using the same |
| JP2002014072A (en) * | 2000-06-29 | 2002-01-18 | Yamatake Corp | Integration sensor element and measurement system using the same |
| US6798184B2 (en) | 2000-06-29 | 2004-09-28 | Yamatake Corporation | Integrated sensor device and measuring system using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2772833B2 (en) | 1998-07-09 |
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