JPH01282456A - Biosensor and divided parts thereof - Google Patents
Biosensor and divided parts thereofInfo
- Publication number
- JPH01282456A JPH01282456A JP63110440A JP11044088A JPH01282456A JP H01282456 A JPH01282456 A JP H01282456A JP 63110440 A JP63110440 A JP 63110440A JP 11044088 A JP11044088 A JP 11044088A JP H01282456 A JPH01282456 A JP H01282456A
- Authority
- JP
- Japan
- Prior art keywords
- gate electrode
- ion
- electrode
- biosensor
- sensitive 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000005669 field effect Effects 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 238000005476 soldering Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 37
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002555 ionophore Substances 0.000 description 2
- 230000000236 ionophoric effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VJFPVACZAZLCCM-UAIGNFCESA-N (z)-but-2-enedioic acid;chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C.OC(=O)\C=C/C(O)=O VJFPVACZAZLCCM-UAIGNFCESA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RMIXHJPMNBXMBU-QIIXEHPYSA-N Nonactin Chemical compound C[C@H]([C@H]1CC[C@H](O1)C[C@@H](OC(=O)[C@@H](C)[C@@H]1CC[C@@H](O1)C[C@@H](C)OC(=O)[C@H](C)[C@H]1CC[C@H](O1)C[C@H](C)OC(=O)[C@H]1C)C)C(=O)O[C@H](C)C[C@H]2CC[C@@H]1O2 RMIXHJPMNBXMBU-QIIXEHPYSA-N 0.000 description 1
- RMIXHJPMNBXMBU-UHFFFAOYSA-N Nonactin Natural products CC1C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC2CCC1O2 RMIXHJPMNBXMBU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- -1 Tridodecylamine Chlor Chemical compound 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJSZDECKJYYBGE-UHFFFAOYSA-N bis(1,4,7,10-tetraoxacyclododec-2-ylmethyl) 2-dodecyl-2-methylpropanedioate Chemical compound C1OCCOCCOCCOC1COC(=O)C(C)(CCCCCCCCCCCC)C(=O)OCC1COCCOCCOCCO1 FJSZDECKJYYBGE-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、イオン感応膜を改善したバイオセンサ及びそ
の分割部品に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a biosensor with an improved ion-sensitive membrane and divided parts thereof.
バイオセンサは、生体関連物質を固定化した膜を用いて
化学物質を検出するものであるが、検出する化学物質の
特異性に優れている。その１つとして、検体中のイオン
濃度を測定するために、イオン感応性電界効果型トラン
ジスタ（以下ＩＳＦＥＴと称する）を用いたイオンセン
サがある。Biosensors detect chemical substances using a membrane on which biological substances are immobilized, and are excellent in the specificity of the chemical substances they detect. One of them is an ion sensor that uses an ion-sensitive field effect transistor (hereinafter referred to as ISFET) to measure the ion concentration in a sample.
このｌ５ＦＥＴは、半導体表面上に設けた感応膜と溶液
との界面にＢＥし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たものである。This 15FET utilizes the fact that the conductivity near the semiconductor surface changes in accordance with the change in the electric field applied to the interface between a solution and a sensitive film provided on the semiconductor surface.
このｆｓＦｌ’Ｔには、電界効果型トランジスタ（ＦＥ
Ｔ）のゲート絶縁膜上にイオン感応膜を設けたものが使
用されているが、イオン感応膜とＦＥＴを同一半導体基
板上で分離した構造の分離ゲート式％式％
これらのｌ５ＦＥＴのイオン感応膜としては、無機系材
料、例えば窒化ケイ素膜、酸化アルミニウム膜、酸化イ
ンジウム膜からなる水素イオン感応膜が知られている。This fsFl'T includes a field effect transistor (FE).
The ion sensitive film of these 15 FETs is a separated gate type with a structure in which the ion sensitive film and the FET are separated on the same semiconductor substrate. Hydrogen ion sensitive films made of inorganic materials such as silicon nitride films, aluminum oxide films, and indium oxide films are known as such.
一方、有機系材料からなるイオン感応膜も用いられてお
り、これには高分子膜中にイオノフオアと呼ばれる、イ
オンを選択的に取り込む活性物質を担持させたものが用
いられている。イオノフオアとしてパリノマイシンを用
いるとカリウムイオン感応膜、ビス−（１２−クラウン
−４）を用いるとナトリウムイオン感応膜がそれぞれで
きる。On the other hand, ion-sensitive membranes made of organic materials are also used, in which a polymer membrane supports an active substance called an ionophore that selectively takes in ions. When palinomycin is used as the ionophore, a potassium ion-sensitive membrane is produced, and when bis-(12-crown-4) is used, a sodium ion-sensitive membrane is produced.
この高分子膜としては、可塑剤を含んだポリ塩化ビニル
が用いられている。As this polymer membrane, polyvinyl chloride containing a plasticizer is used.
しかしながら、ポリ塩化ビニルフィルムは、塗布される
電極面に対する密着性が劣り、イオン感応膜を安定動作
させるために必要なこととされている製造直後から検出
しようとするイオン水溶液中に浸漬保存することにより
、イオン感応膜の剥離が生じたり、塗布面との界面に小
泡ができたりすることがあり、これらがイオンセンサと
しての特性を劣化させる原因となるという問題がある。However, polyvinyl chloride film has poor adhesion to the electrode surface on which it is coated, and it is necessary to store it immersed in an aqueous ion solution immediately after production, which is considered necessary for stable operation of an ion-sensitive membrane. This may cause peeling of the ion-sensitive membrane or the formation of small bubbles at the interface with the coated surface, which poses a problem of causing deterioration of the characteristics as an ion sensor.
特に、分離ゲート式ｒｓＦＥＴ構造のイオンセンサは、
ＦＥＴのゲート電極を延長しＦＥＴ本体と、離れたとこ
ろに検体と接する部分を設け、検体の水分等がＦＥＴの
性能に影響を及ぼさないよ−うにしており、この延長部
分のゲート電極は例えば銀のメツキにより形成されるの
で、その表面には凹凸が多く、ポリ塩化ビニルフィルム
の密着性が良くないという問題点を有する。In particular, ion sensors with separated gate rsFET structure,
The gate electrode of the FET is extended to provide a part that comes into contact with the specimen at a distance from the FET main body to prevent moisture in the specimen from affecting the performance of the FET. Since it is formed by silver plating, its surface has many irregularities and has a problem that the adhesion of polyvinyl chloride film is not good.
Ｃ課題を解決するための手段〕
本発明は、上記問題点を解決するために、イオン感応膜
による検体液の感応値を電界効果型トランジスタで検出
できるようにしたバイオセンサにおいて、上記イオン感
応膜に水酸基及び／又はカルボキシル基を有するビニル
系高分子を含有することを特徴とするバイオセンサを提
供するものである。また、バイオセンサ機能を同一基板
に組み込み、ゲート電極を延長して分離ゲート電極を形
成し、これにイオン感応膜を設け、これと比較電極を相
対したバイオセンサ、また、これから比較電極を除いた
部品、さらには比較電極とイオン感応膜を有する分離ゲ
ート電極を分割して独立させた部品を提供するものであ
る。Means for Solving Problem C] In order to solve the above-mentioned problems, the present invention provides a biosensor in which a field-effect transistor can detect the response value of a sample liquid by an ion-sensitive membrane. The present invention provides a biosensor characterized by containing a vinyl polymer having a hydroxyl group and/or a carboxyl group. In addition, the biosensor function was built into the same substrate, the gate electrode was extended to form a separate gate electrode, an ion-sensitive membrane was provided on this, and a reference electrode was placed opposite the biosensor. The present invention provides a component in which a reference electrode and a separation gate electrode having an ion-sensitive membrane are separated and made independent.
本発明において使用される水酸基及び／又はカルボキシ
ル基を有するビニル系高分子は、後述の実施例に示した
もののほかに、水酸基とカルボキシル基の両方を含むも
のでも良く、また、これらを別々に含む高分子の混合物
でも良く、また、ポリ塩化ビニル、塩化ビニル−酢酸ビ
ニル共重合体、その池水酸基、カルボキシル基以外の七
ツマ−を共重合したビニル系高分子を併用することもで
きる。The vinyl polymer having a hydroxyl group and/or a carboxyl group used in the present invention may contain both a hydroxyl group and a carboxyl group, or may contain these separately, in addition to those shown in the examples below. A mixture of polymers may be used, and vinyl polymers obtained by copolymerizing polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and heptads other than hydroxyl groups and carboxyl groups can also be used in combination.
本発明に係わる水酸基及び／又はカルボキシル基を有す
るビニル系高分子としては、塩化ビニル−酢酸ビニル−
ビニルアルコールの共重合体、塩化ビニル−酢酸ビニル
の部分ケンカ物、塩化ビニル−酢酸ビニル−マレイン酸
く又は無水マレイン酸）等の不飽和カルボン酸を共重合
させたもの等が挙げられる。これらのビニル系高分子に
は、さらに他の七ツマ−も共重合させることができる。The vinyl polymer having a hydroxyl group and/or carboxyl group according to the present invention includes vinyl chloride-vinyl acetate-
Copolymers of vinyl alcohol, partially oxidized vinyl chloride-vinyl acetate, and copolymers of unsaturated carboxylic acids such as vinyl chloride-vinyl acetate-maleic acid or maleic anhydride may be mentioned. Other hexamers can also be copolymerized with these vinyl polymers.
また、本発明で使用されるビニル系高分子には可塑剤等
の添加剤も併用することができ、例えば可塑剤としては
ビニル樹脂用の可塑剤として使用されているものが用い
られる。Moreover, additives such as plasticizers can also be used in combination with the vinyl polymer used in the present invention. For example, as the plasticizer, those used as plasticizers for vinyl resins can be used.
また、上記ビニル系高分子を含有する担体に担持させる
活性物質として、例えばパリノマイシンを用いると、カ
リウムイオンを検出できるが、下記の活性物質を用いれ
ば検体中からそれぞれに特有な右側のイオンを検出でき
る。In addition, potassium ions can be detected by using palinomycin, for example, as an active substance supported on a carrier containing the above-mentioned vinyl polymer, but if the following active substances are used, the ions on the right side, which are unique to each, can be detected from the sample. can.
■ ｂｉｓ−１２−ｃｒｏｗｎ−４ナトリウムイオン■
トリドデシルアミン クロールイオン■ ノナク
チン アンモニウムイオンまた、本発明に係わ
るイオン感応膜は、イオン感応膜をＦＥＴのゲート絶縁
膜上に構成した構造のイオンセンサ、ゲートを延長して
ＦＥＴ本体より分離しかつ比較電極を同一基板上に組み
込んだ分離ケ−＋［ＦＥｒ構造のイオンセンサ（実願昭
６２−１５５６２５号明１［１Ｍに記載されたもの）、
また、これからさらに比較電極を別体に構成した完全分
離ゲート型ＦＥＴ構造のイオンセンサ、さらにはＦＥＴ
等と組み合わせて使用する別体の検体液に接触する電極
部分のみを分離した感応膜センサープレート（実願昭６
３−７１０３号明細書に記載されているもの）等固体電
極上に感応膜を形成するいずれのものにも使用できる。■ bis-12-crown-4 sodium ion ■
Tridodecylamine Chlor ion ■ Nonactin Ammonium ion In addition, the ion-sensitive membrane according to the present invention is an ion sensor with a structure in which the ion-sensitive membrane is constructed on the gate insulating film of the FET, and the gate is extended and separated from the FET body for comparison. Ion sensor with FEr structure (described in Utility Application No. 155625/1983 [1M)]
In addition, from now on, ion sensors with a completely separated gate type FET structure with a separate reference electrode, and even FET
Sensitive membrane sensor plate with only the electrode part that comes into contact with a separate sample liquid used in combination with
It can be used in any method that forms a sensitive film on a solid electrode, such as the method described in No. 3-7103.
また、ソース、ドレイン、ゲート、分離ゲート等のイオ
ン感応膜が形成される電極の電極材料としては、銀、白
金・パラジウム、金、白金、銀、クロム、銅等の金属、
１ｒ０２．５ｎ０２等の酸化物導電体を使用しても良く
、これらはメツキ、蒸着、あるいはペーストにして塗布
し、焼付けるようにしても良い。In addition, electrode materials for electrodes on which ion-sensitive films such as sources, drains, gates, and isolation gates are formed include metals such as silver, platinum/palladium, gold, platinum, silver, chromium, copper, etc.
An oxide conductor such as 1r02.5n02 may be used, and these may be plated, vapor-deposited, or applied as a paste and baked.
また、上記の電極を形成する基板には、ガラス坂、樹脂
板、セラミック板も使用できる。Moreover, a glass plate, a resin plate, or a ceramic plate can also be used for the substrate forming the above-mentioned electrodes.
ビニル系高分子に水酸基、カルボキシル基を導入するこ
とにより、特に金属等に対する親和性が増大するものと
考えられる。It is believed that the introduction of hydroxyl groups and carboxyl groups into vinyl polymers increases the affinity for metals and the like.
次ぎ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.
まず、第１図に示すようにガラス基板１上に蒸着により
形成したソース電極２）ドレイン電極３及びゲート電極
４にＦＥＴ ５をハンダ付けにより固定する。ゲート電
極を延長してその端部に分離デー４電極４ａを形成して
おき、その周囲にエポキシ樹脂等の絶縁材からなる堤体
６を形成して検体液滴下窓部７を形成する。さらに上記
検体液滴下窓部７に臨ませられた分離ゲート用電極４ａ
に下記実施例、比較例で得られる塗液を塗布・乾燥して
イオン感応膜８を形成する。なお、９は耐水性の絶縁膜
である。First, as shown in FIG. 1, the FET 5 is fixed by soldering to the source electrode 2) drain electrode 3 and gate electrode 4 formed by vapor deposition on a glass substrate 1. A separation electrode 4a is formed at the end of the gate electrode by extending it, and a dike body 6 made of an insulating material such as epoxy resin is formed around it to form a sample liquid dropping window 7. Further, a separation gate electrode 4a facing the sample liquid dropping window 7
A coating liquid obtained in the following Examples and Comparative Examples is applied and dried to form an ion-sensitive membrane 8. Note that 9 is a water-resistant insulating film.
このようにして得られたものは別の比較電極と組みあわ
されてイオンセンサとして使用することができる。これ
は完全分離ゲー） ＦＥＴ型構造の例である。The product thus obtained can be combined with another reference electrode and used as an ion sensor. This is an example of a completely isolated G/FET type structure.
実施例１
塩化ビニル；酢酸ビニル；ビニルアルコールの重量組成
比が９１：３：６、平均重合度が４２０である高分子粉
末０．２ｇ、ジオクチルアジペート０．１５ｍβ、パリ
ノマイシン２．５ｍｇを３ｍｊ２のテトラヒドロフラン
に溶解した溶液を第１図に示す分離ゲート４ａ上に１０
μ２滴下し、自然乾燥により成膜化し、イオン感応１ｔ
！！！８としてカリウムイオン感応膜を形成した。この
膜厚は約８０μ巾であった。Example 1 0.2 g of polymer powder with a weight composition ratio of vinyl chloride, vinyl acetate, and vinyl alcohol of 91:3:6 and an average degree of polymerization of 420, 0.15 mβ of dioctyl adipate, and 2.5 mg of palinomycin were added to 3 mj2 of tetrahydrofuran. The solution dissolved in
Add μ2 drops, form a film by air drying, and ion-sensitize 1t.
! ! ! A potassium ion sensitive membrane was formed as No. 8. This film thickness was about 80 μm wide.
このようにして得られたものを第３図に示されるソース
ホロワ−回路１０により、Ｋ（Ｊ飽和Ａｇ／へｇＣＡ比
較電極１１を用い、カリウムイオン感応膜表面における
電位を測定し、溶液のカリウムイオン濃度を変化させた
時の電位変化によりカリウムイオン感応膜の感度を求め
た。Using the source follower circuit 10 shown in FIG. The sensitivity of the potassium ion-sensitive membrane was determined from the potential change when the concentration was changed.
この感度を上記作製直後と、作製後イオン感応膜を１０
ｍＭのＫＣｌ中に浸漬保存して７日経過した後、さらに
同様に１４日経過した後に求めた結果をそれぞれ表に示
す。This sensitivity was measured immediately after the above fabrication and after fabrication at 10
The results obtained after 7 days of immersion preservation in mM KCl and after 14 days in the same manner are shown in the table.
また、カリウムイオン感応膜の分離ゲート電極４ａとの
間に小泡が発生するかどうかを目視調べた結果、７日後
ののみならず１４日後のものにも小〆包は見られなかっ
た。Further, as a result of visual inspection to see whether small bubbles were generated between the potassium ion sensitive membrane and the separation gate electrode 4a, no small bubbles were observed not only after 7 days but also after 14 days.
実施例２
実施例１において使用した高分子の代わりに、塩化ビニ
ル：酢酸ビニル：マレイン酸の重量組成比が８６：１３
：１ 、平均重合度が４２０である高分子粉末を用いた
以外は実施例１と同様にしてカリウムイオン感応膜を形
成したものを作製し、これを用いて実施例１と同様に測
定した結果を表に示す。Example 2 Instead of the polymer used in Example 1, the weight composition ratio of vinyl chloride: vinyl acetate: maleic acid was 86:13.
:1 A potassium ion-sensitive membrane was prepared in the same manner as in Example 1 except that a polymer powder with an average degree of polymerization of 420 was used, and the results were measured in the same manner as in Example 1 using this membrane. are shown in the table.
なお、小泡の発生を実施例１と同様に調べたところ、小
泡は７日後のもののみならず、１４日後のものにも見ら
れなかった。When the generation of small bubbles was examined in the same manner as in Example 1, no small bubbles were observed not only after 7 days but also after 14 days.
比較例
実施例１において使用した高分子の代わりに、アルドリ
ソ千社製塩化ビニル０．２ｇを用いた以外は実施例１と
同様にしてカリウムイオン感応膜を形成したものを作製
し、これについても実施例１と同様にし測定した結果を
表に示す。また、小泡の発生を実施例１と同様に調べた
ところ、７日後、１４日後のものに小泡が見られた。Comparative Example A potassium ion-sensitive membrane was prepared in the same manner as in Example 1, except that 0.2 g of vinyl chloride manufactured by Aldriso Sensha was used instead of the polymer used in Example 1. The results were measured in the same manner as in Example 1 and are shown in the table. Further, when the generation of small bubbles was examined in the same manner as in Example 1, small bubbles were observed after 7 days and after 14 days.
ゲート電極によく密着しているが、比較例のものはその
密着力が弱いことがわかる。Although it adheres well to the gate electrode, it can be seen that the adhesive strength of the comparative example is weak.
本発明は、以上説明したように、イオン感応膜に水酸基
及び／又はカルボキシル基を有するビニル系高分子を含
有させたので、その電極等に対する密着性を増大するこ
とができる。これによりイオン感応膜がＦＥＴの絶縁膜
上に形成されているもののみならず、分離ゲート型ＦＥ
Ｔ構造のもので電極が金属材料から構成されこれにイオ
ン感応膜が形成されているようなものでも、イオンセン
サを安定動作させるために検出しようとするイオンを含
んだ溶液にイオン感応膜を浸漬することによってイオン
感応膜の剥離を生じるようなことがなく、イオンセンサ
の特性を長く損なわないように維持できる。As explained above, in the present invention, since the ion-sensitive membrane contains a vinyl polymer having a hydroxyl group and/or a carboxyl group, its adhesion to an electrode or the like can be increased. As a result, the ion-sensitive film is not only formed on the insulating film of the FET, but also the isolated gate type FE.
Even if the ion sensor has a T-structure and the electrode is made of a metal material and an ion-sensitive membrane is formed on it, the ion-sensitive membrane must be immersed in a solution containing the ions to be detected in order to ensure stable operation of the ion sensor. By doing so, the ion-sensitive membrane does not peel off, and the characteristics of the ion sensor can be maintained for a long time without being impaired.
第１図は完全分離ゲートＦＥＴ型イオンセンサの主要部
を示す平面図、第２図はそのｎ −ｎ断面図、第３図は
このイオンセンサを使用した測定回路図である。
図中、１は基板、２はソース電極、３はドレイン電極、
４はゲート電極、４ａは分離ゲート電極、５はＦｌｌ：
Ｔ 、７は検体滴下部、８はイオン感応膜、１１は比較
電極である。
第１図
第２図FIG. 1 is a plan view showing the main parts of a completely isolated gate FET type ion sensor, FIG. 2 is a sectional view taken along line n--n, and FIG. 3 is a measurement circuit diagram using this ion sensor. In the figure, 1 is a substrate, 2 is a source electrode, 3 is a drain electrode,
4 is a gate electrode, 4a is a separated gate electrode, 5 is Fll:
T, 7 is a sample dropping part, 8 is an ion-sensitive membrane, and 11 is a reference electrode. Figure 1 Figure 2
Claims (4)
トランジスタで検出できるようにしたバイオセンサにお
いて、上記イオン感応膜に水酸基及び／又はカルボキシ
ル基を有するビニル系高分子を含有することを特徴とす
るバイオセンサ。(1) A biosensor in which the sensitivity value of a sample liquid by an ion-sensitive membrane can be detected by a field-effect transistor, characterized in that the ion-sensitive membrane contains a vinyl polymer having a hydroxyl group and/or a carboxyl group. biosensor.
って、ソース電極、ドレイン電極、ゲート電極及びゲー
ト電極を延長して形成した分離ゲート電極、さらにこの
分離ゲート電極に相対する比較電極を同一基板に有し、
分離ゲート電極にイオン感応膜を設けて上記比較電極と
ともに検体滴下部を形成し、この検体滴下部に滴下した
検体の化学物質を検出する上記ソース電極、ドレイン電
極、ゲート電極及びゲート電極に接続して固定した電界
効果型半導体を有することを特徴とするバイオセンサ。(2) The biosensor according to claim 1, which includes a source electrode, a drain electrode, a gate electrode, a separated gate electrode formed by extending the gate electrode, and a comparison electrode facing the separated gate electrode. on the same board,
An ion-sensitive membrane is provided on the separation gate electrode to form a sample dropping part together with the reference electrode, and connected to the source electrode, drain electrode, gate electrode, and gate electrode for detecting the chemical substance of the sample dropped into the sample dropping part. A biosensor characterized by having a field-effect semiconductor fixed thereon.
較電極を除いたバイオセンサ部品であって、別体に設け
た比較電極と組み合わせて使用することを特徴とするバ
イオセンサ分割部品。(3) A biosensor component obtained by removing the comparison electrode from the biosensor according to claim 2, and characterized in that it is used in combination with a separately provided comparison electrode.
体滴下部を構成する比較電極とイオン感応膜を有する分
離ゲート電極を分割して検体滴下部を独立させた部品で
あって、分割された他の構成体に接続して使用可能とし
たことを特徴とするバイオセンサ分割部品。(4) A component in which the reference electrode and the separation gate electrode having an ion-sensitive membrane, which constitute the sample dripping part of the biosensor described in claim 2, are divided to make the sample dripping part independent; A biosensor divided part characterized in that it can be used by being connected to other components.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63110440A JPH0786500B2 (en) | 1988-05-09 | 1988-05-09 | Electrode parts for sample dropping of ion sensor |
| DE8888117028T DE3876602T2 (en) | 1987-10-13 | 1988-10-13 | ION SENSOR. |
| EP88117028A EP0315788B1 (en) | 1987-10-13 | 1988-10-13 | Ion sensor |
| US07/257,439 US4921591A (en) | 1987-10-13 | 1988-10-13 | Ion sensors and their divided parts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63110440A JPH0786500B2 (en) | 1988-05-09 | 1988-05-09 | Electrode parts for sample dropping of ion sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01282456A true JPH01282456A (en) | 1989-11-14 |
| JPH0786500B2 JPH0786500B2 (en) | 1995-09-20 |
Family
ID=14535774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63110440A Expired - Lifetime JPH0786500B2 (en) | 1987-10-13 | 1988-05-09 | Electrode parts for sample dropping of ion sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0786500B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023042657A1 (en) * | 2021-09-16 | 2023-03-23 | 株式会社デンソー | Ion sensor, and method for detecting substance being detected |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5570733A (en) * | 1978-11-21 | 1980-05-28 | Kuraray Co Ltd | Stable fet sensor |
| JPS62220854A (en) * | 1986-03-24 | 1987-09-29 | Toshiba Corp | Fet ion sensor |
| JPS63265154A (en) * | 1986-12-25 | 1988-11-01 | Tokuyama Soda Co Ltd | Ion sensitive film |
-
1988
- 1988-05-09 JP JP63110440A patent/JPH0786500B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5570733A (en) * | 1978-11-21 | 1980-05-28 | Kuraray Co Ltd | Stable fet sensor |
| JPS62220854A (en) * | 1986-03-24 | 1987-09-29 | Toshiba Corp | Fet ion sensor |
| JPS63265154A (en) * | 1986-12-25 | 1988-11-01 | Tokuyama Soda Co Ltd | Ion sensitive film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023042657A1 (en) * | 2021-09-16 | 2023-03-23 | 株式会社デンソー | Ion sensor, and method for detecting substance being detected |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0786500B2 (en) | 1995-09-20 |
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