JPH0544986B2 - - Google Patents
Info
- Publication number
- JPH0544986B2 JPH0544986B2 JP60021749A JP2174985A JPH0544986B2 JP H0544986 B2 JPH0544986 B2 JP H0544986B2 JP 60021749 A JP60021749 A JP 60021749A JP 2174985 A JP2174985 A JP 2174985A JP H0544986 B2 JPH0544986 B2 JP H0544986B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- sensitive
- film
- field effect
- effect transistor
- 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
- 150000002500 ions Chemical class 0.000 claims description 72
- 239000012528 membrane Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910010272 inorganic material Inorganic materials 0.000 claims description 10
- 239000011147 inorganic material Substances 0.000 claims description 10
- 230000005669 field effect Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011882 ultra-fine particle Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 42
- 229920000052 poly(p-xylylene) Polymers 0.000 description 7
- -1 polyparaxylylene Polymers 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910002012 Aerosil® Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 108010067973 Valinomycin Proteins 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/414—Ion-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)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は溶液中のイオン濃度を測定するマルチ
イオン感応性電界効果型トランジスタ（以下
ISFETと略す）に係る。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a multi-ion sensitive field effect transistor (hereinafter referred to as
(abbreviated as ISFET).
最近、同一基板上に複数のゲート絶縁領域を形
成したマルチISFETが開発されている。（例えば
ダブリユー・エツチ・コウ（W.H.Ko）等、プロ
シーデイング オブ ザ インターナシヨナル
ミーテイング オン ケミカル センサース
（Proceding of the International Meeting on
Chemical Sensors）、496頁（P.496）、講談社
（Kodansha LTD）、東京（Tokyo）（1983））。こ
れらのマルチISFETにおいては、下地FETは自
身のMOS構造により夫々電気的に絶縁分離され
ているため、特定下地FETの電気特性変化が他
の下地FET特性に影響を及ぼすことはない。然
し、これら複数個のISFETゲート絶縁膜上にイ
オン感応膜が連続して全面に形成されている場合
には、特定ISFETゲート領域上のイオン感応膜
の特性変化により残りのISFET特性が影響を受
け、１ケのISFETの劣化により残り全ての
ISFETの正常動作が妨げられる。この現象はイ
オン感応膜に有機イオン感応膜を用いた場合、無
機感応膜に比べて顕著に見られる現象である。こ
れを防ぐには、個々のISFETゲート絶縁膜上に
イオン感応膜を分離形成すれば良い。従来、有機
イオン感応膜の形成には、膜母材、イオン感応物
などを溶解に溶媒したキヤスト液をISFETゲー
ト絶縁領域上に滴下乾燥したイオン感応膜を形成
するキヤステイング法が用いられている。このキ
ヤステイング法により、マルチISFETのイオン
感応膜を個々のISFETゲート絶縁領域上に分離
形成する場合、キヤスト液の流延により隣接イオ
ン感応膜が接触、混合し、１つのISFETの性能
変化が、他のISFET性能に影響を与えるという
欠点があつた。
Recently, multi-ISFETs in which multiple gate insulating regions are formed on the same substrate have been developed. (For example, WHKo, etc., Proceedings of the International
Proceedings of the International Meeting on Chemical Census
Chemical Sensors), 496 pages (P.496), Kodansha LTD, Tokyo (1983)). In these multi-ISFETs, the base FETs are electrically isolated from each other by their own MOS structure, so changes in the electrical characteristics of a specific base FET do not affect the characteristics of other base FETs. However, if an ion-sensitive film is continuously formed over the entire surface of these multiple ISFET gate insulating films, changes in the characteristics of the ion-sensitive film on a specific ISFET gate region will affect the characteristics of the remaining ISFETs. , due to deterioration of one ISFET, all remaining
Normal operation of ISFET is disturbed. This phenomenon is more noticeable when an organic ion-sensitive membrane is used as the ion-sensitive membrane, compared to an inorganic membrane. To prevent this, it is sufficient to separately form an ion-sensitive film on each ISFET gate insulating film. Conventionally, to form organic ion-sensitive films, a casting method has been used in which a casting liquid containing a membrane base material, an ion-sensitive material, etc. as a solvent is dropped onto the ISFET gate insulating region to form a dried ion-sensitive film. . When the ion-sensitive films of multiple ISFETs are formed separately on the gate insulating regions of individual ISFETs using this casting method, adjacent ion-sensitive films come into contact and mix due to the casting liquid, and the performance change of one ISFET is caused by The drawback was that it affected the performance of other ISFETs.
本発明は、複数のゲート絶縁膜上イオン感応膜
が分離形成され、特定のイオン感応膜の劣化が他
にISFETの性能変化をひきおこさないマルチ
ISFETの製造方法を提供することにある。
In the present invention, multiple ion-sensitive films on gate insulating films are formed separately, and the deterioration of a specific ion-sensitive film does not cause a change in the performance of other ISFETs.
The purpose of the present invention is to provide a method for manufacturing ISFET.
上記目的を達成するために本発明では、同一基
板上に複数のゲート絶縁領域を形成し、該ゲート
絶縁領域上にイオン感応膜を形成するマルチ
ISFETにおいて、膜母材、イオン感応物質、溶
媒および粘度調整用不活性無機材料よりなるペー
ストを、所定の開口パターンが形成された治具を
介してゲート絶縁領域上に塗布することにより、
複数のゲート絶縁膜上イオン感応膜を分離形成す
るようにした。
In order to achieve the above-mentioned object, the present invention provides a multilayer multilayer film that forms a plurality of gate insulating regions on the same substrate and forms an ion-sensitive film on the gate insulating regions.
In an ISFET, a paste consisting of a membrane base material, an ion-sensitive material, a solvent, and an inert inorganic material for viscosity adjustment is applied onto the gate insulating region through a jig in which a predetermined opening pattern is formed.
A plurality of ion sensitive films on the gate insulating films are formed separately.
次に本発明の実施例を図面とともに説明する。
第１図は、本発明によるイオン感応膜が分離形成
されたマルチISFETの一実施例の平面図である。
２mm角のシリコンチツプ１を用い、ソース領域
７，８，９，１０，１１とドレイン領域７′，
８′，９′，１０′，１１′ではさみ込まれる５ケの
ゲート絶縁領域上に５ケの同種のイオン感応膜１
２，１３，１４，１５，１６を分離形成してい
る。本実施例ではイオン感応膜１２，１３，１
４，１５，１６に同一組成を持つK+イオン感応
膜を同時に塗布した。以下塗布工程について述べ
る。まず膜母材ポリ塩化ビニル240mg、可塑剤ジ
オクチルアジペート540mg、イオン感応物質とし
てニユートラルキヤリヤ型の抗生物質バリノマイ
シン50mgを溶媒シクロヘキサノン２mlに溶解した
イオン感応膜組成物を調製した。次に粘度調整用
無機材料として超微粒子状無水シリカ（商品名ア
エロジル）250mgを先に調製したイオン感応膜組
成物に添加、混合してイオン感応ペーストを調製
した。次に第１図イオン感応膜１２，１３，１
４，１５，１６に対応する一辺200μｍの矩形状
開口パターンを５ケ有するステンレス網製スクリ
ーンを治具として、先にイオン感応ペーストをシ
リコンチツプ１上ゲート絶縁領域上に印刷、塗布
乾燥してイオン感応膜１２，１３，１４，１５，
１６を分離形成した。本実施例では乳剤厚20μ
ｍ、メツシユ数165のスクリーンを使用した。こ
のためゲート絶縁領域上に形成されたK+イオン
感応膜の厚みは約1μｍ程度である。K+イオン感
応膜の厚みとしては5μｍ〜200μｍの範囲であれ
ば良い。5μｍ未満の場合にはイオン感応膜の劣
化が短期間におこる。また200μｍを越えるイオ
ン感応膜の劣化に関しては問題が無いが、応答速
度が長くなるという欠点がある。まあ本実施例で
はイオン関応膜中超微粒子状無水シリカ（商品名
アエロジル）濃度が23％になるように添加した
が、添加量としてはイオン感応膜中濃度で５％〜
50％の範囲であれば問題はない。５％未満の添加
量ではイオン感応ペーストの粘度が低く印刷後ペ
ーストが流延し、イオン感応膜の分離形成が困難
となる。また50％を越える添加量では塗布膜中で
イオンチヤネルが有効に形成されずイオン応答を
示さないという問題が生じる。さて、本実施例に
よるマルチISFETはK+感応性であるため、標準
KCl溶液並びにダブルジヤンクシヨン型参照電極
を用いてイオン応答性を調べた。KCl濃度範囲
10-1mol／〜10-5mol／で、夫々のISFETに
対してスロープ感度59ｍＶ／decadeが得られた。
このスロープ感度はネルンストの理論感度の一致
しており、イオン感応膜に超微粒子状無水シリカ
を混合しても適正な濃度範囲にあればイオン応答
に全く支障を生じないことがわかつた。
Next, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a plan view of an embodiment of a multi-ISFET in which ion-sensitive membranes are separately formed according to the present invention.
Using a 2 mm square silicon chip 1, source regions 7, 8, 9, 10, 11 and drain regions 7',
Five ion-sensitive films 1 of the same type are placed on the five gate insulating regions sandwiched between 8', 9', 10', and 11'.
2, 13, 14, 15, and 16 are formed separately. In this embodiment, ion-sensitive membranes 12, 13, 1
A K + ion-sensitive film having the same composition was applied to samples 4, 15, and 16 at the same time. The coating process will be described below. First, an ion-sensitive membrane composition was prepared by dissolving 240 mg of polyvinyl chloride as a membrane base material, 540 mg of dioctyl adipate as a plasticizer, and 50 mg of a neutral carrier antibiotic valinomycin as an ion-sensitive substance in 2 ml of cyclohexanone solvent. Next, 250 mg of ultrafine anhydrous silica (trade name: Aerosil) as an inorganic material for adjusting viscosity was added to the previously prepared ion-sensitive membrane composition and mixed to prepare an ion-sensitive paste. Next, FIG. 1 shows ion-sensitive membranes 12, 13, 1.
Using a stainless steel mesh screen having 5 rectangular opening patterns of 200 μm on each side corresponding to numbers 4, 15, and 16 as a jig, first print an ion-sensitive paste on the gate insulating region of the silicon chip 1, apply it, and dry it to remove the ions. Sensitive film 12, 13, 14, 15,
16 was separated and formed. In this example, the emulsion thickness is 20μ.
A screen with 165 meshes was used. Therefore, the thickness of the K + ion sensitive film formed on the gate insulating region is about 1 μm. The thickness of the K + ion-sensitive membrane may range from 5 μm to 200 μm. If it is less than 5 μm, the ion-sensitive membrane will deteriorate in a short period of time. Further, although there is no problem with deterioration of the ion-sensitive membrane exceeding 200 μm, there is a drawback that the response speed becomes longer. Well, in this example, it was added so that the concentration of ultrafine anhydrous silica (trade name Aerosil) in the ion-sensitive membrane was 23%, but the amount added was 5% to 5% in terms of the concentration in the ion-sensitive membrane.
There is no problem if it is within 50%. If the amount added is less than 5%, the viscosity of the ion-sensitive paste will be low and the paste will flow after printing, making it difficult to separate and form an ion-sensitive membrane. Further, if the amount added exceeds 50%, a problem arises in that ion channels are not effectively formed in the coating film and no ion response is exhibited. Now, since the multi-ISFET according to this example is K + sensitive, the standard
Ion responsiveness was investigated using a KCl solution and a double junction reference electrode. KCl concentration range
10 -1 mol/~10 -5 mol/, a slope sensitivity of 59 mV/decade was obtained for each ISFET.
This slope sensitivity coincides with Nernst's theoretical sensitivity, and it was found that even if ultrafine anhydrous silica particles are mixed into the ion-sensitive membrane, as long as the concentration is within the appropriate range, there will be no problem at all with the ion response.
次にイオン交換体をイオン感応物質とするCl-
感応性マルチISFETを第１図の構成に従つて形
成した。膜母材ポリ塩化ビニル240mg、可塑剤ノ
ルマルテトラデシルアルコール70mg、イオン感応
物質としてイオン交換形の４級アンモニウム塩メ
チルトリドデシルアンモニウムクロライド120mg、
溶媒シクロヘキサノン２mlよりなるイオン感応膜
組成物に超微粒子状無水シリカ（商品名アエロジ
ル）100mgを添加、混合したイオン感応ペースト
を用いてCl-感応マルチISFETを前記K+感応マル
チISFETと同様な方法により形成した。本実施
例によるCl-感応マルチISFETはCl-イオン濃度
範囲10-1mol／〜10-4mol／で夫々のISFET
に対して52ｍＶ／decadeのスロープ感度が得ら
れた。本実施例ではイオン感応膜中超粒子状無水
シリカ（商品名アエロジル）濃度が19％になるよ
うに添加したが、添加量としては前記K+感応マ
ルチISFETと同様に５％〜50％の範囲であれば
問題はない。その理由も前記K+感応マルチ
ISFETの場合と同様である。本実施例のCl-イオ
ン感応膜の厚みは前記実施例でのK+イオン感応
膜と同時に10μｍ程度である。Cl-イオン感応膜
の厚みとしては5μｍ〜200μｍの範囲であれば良
い。この理由は前記K+イオン感応膜の場合と同
一である。 Next, Cl - using an ion exchanger as an ion-sensitive substance
A sensitive multi-ISFET was formed according to the configuration shown in FIG. Membrane base material polyvinyl chloride 240mg, plasticizer n-tetradecyl alcohol 70mg, ion exchange type quaternary ammonium salt methyl tridodecyl ammonium chloride 120mg as ion sensitive substance,
Using an ion-sensitive paste prepared by adding and mixing 100 mg of ultrafine anhydrous silica (trade name: Aerosil) to an ion-sensitive membrane composition consisting of 2 ml of cyclohexanone as a solvent, a Cl - sensitive multi-ISFET was fabricated in the same manner as the K + -sensitive multi-ISFET. Formed. The Cl - sensitive multi-ISFET according to this example has a Cl - ion concentration range of 10 -1 mol/~10 -4 mol/ of each ISFET.
A slope sensitivity of 52 mV/decade was obtained. In this example, the concentration of ultraparticulate anhydrous silica (trade name Aerosil) in the ion-sensitive membrane was 19%, but the amount added was in the range of 5% to 50% as in the K + sensitive multi-ISFET. There is no problem if there is. The reason is also the K + sensitive multi
The same is true for ISFET. The thickness of the Cl - ion-sensitive membrane in this example is about 10 μm, which is the same as that of the K + ion-sensitive membrane in the previous example. The thickness of the Cl - ion sensitive membrane may be in the range of 5 μm to 200 μm. The reason for this is the same as in the case of the K + ion-sensitive membrane.
以上２つの実施例においては膜母材にポリ塩化
ビニル、粘度調整用不活性無機材料に超微粒子状
無水シリカを使用したが、これに代わり、膜母材
としてポリビニルブチラール等のビニル系樹脂や
ポリシロキサンを、粘度調整用不活性無機材料に
超微粒子状無水酸化アルミニウムや超微粒子状無
水酸化チタンを用いても何んら支障ははい。 In the above two examples, polyvinyl chloride was used as the membrane base material and ultrafine anhydrous silica was used as the inert inorganic material for viscosity adjustment. There is no problem in using siloxane with ultrafine anhydrous aluminum oxide or ultrafine anhydrous titanium oxide as an inert inorganic material for viscosity adjustment.
第２図は本発明によるイオン感応膜が分離形成
されたマルチISFETの他の一実施例の平面図で
ある。２mm×1.6mm角のシリコチツプ２０を用い、
ソース領域２５，２６，２７とドレイン領域２
５′，２６′，２７′ではさみ込まれる３ケのゲー
ト絶縁領域上に３ケの異種のイオン感応膜２９，
３０，３１を分離形成している。本実施例ではゲ
ート絶縁膜にSi3N4を使用しているため、ソース
領域２８とドレイン領域２８′で形成される
ISFETはPH感応性ISFETとして利用できる。 FIG. 2 is a plan view of another embodiment of a multi-ISFET in which ion-sensitive membranes are separately formed according to the present invention. Using 20 mm x 1.6 mm square silicon chips,
Source regions 25, 26, 27 and drain region 2
Three different types of ion sensitive films 29,
30 and 31 are formed separately. In this example, since Si 3 N 4 is used for the gate insulating film, the gate insulating film is formed by the source region 28 and drain region 28'.
ISFET can be used as PH sensitive ISFET.
イオン感応膜２９，３０，３１はそれぞれ
Na+、K+、Cl-感応膜である。K+、Cl-各イオン
感応膜は前記実施例で使用したK+、Cl-各イオン
感応ペーストを使用し形成した。一方、Na+イオ
ン感応膜は膜母材ポリ塩化ビニル240mg、可塑剤
ジオクチルアジペート540mg、Na+イオン感応物
としてニユートラルキヤリヤ型天然化合物モニン
シン60mgを溶媒シクロヘシサノン２mlに容解した
イオン感応膜組成物に超微粒子状無水シリカ（商
品名アエロジル）250mgを添加、混合したNa+イ
オン感応ペースト用いて形成した。次に具体的な
感応膜形成法について述べる。第２図イオン感応
膜２９に対応する一辺200μｍの矩形状開口パタ
ーンを１ケ有する同一ステンレススクリーンを３
枚準備し、まずその１枚を用いてイオン感応膜２
９位置にNa+イオン感応ペーストを塗布乾燥して
Na+イオン感応膜２９を形成した。次に他の１枚
のスクリーンを用いて感応膜３０位置にK+イオ
ン感応ペーストを塗布乾燥してK+イオン感応膜
３０を形成した。最後に、残り１枚のスクリーン
を用いて感応膜３１位置にCl-イオン感応ペース
トを塗布乾燥してCl-イオン感応膜３１を形成し
た。以上の工程では３枚の同一スクリーンを用意
し、感応ペースト種類毎に使い分けたが、これは
感応ペーストの混合汚染を防止するためである。
以上の工程によりワンチツプ内にNa+、K+、
Cl-、PH各イオン感応ISFETを形成すことが出来
た。次にこれらのISFETのイオン応答性につい
て調べた。K+、Cl-用ISFETについては前記実施
例と同様なイオン応答性が得られた。一方、
Na+、PH各ISFETについてはそれぞれ52ｍＶ／
pNa+、54ｍＶ／PHのスロープ感度が得られた。 The ion sensitive membranes 29, 30, 31 are respectively
It is a Na + , K + , and Cl - sensitive membrane. The K + and Cl - ion-sensitive films were formed using the K + and Cl - ion-sensitive pastes used in the above examples. On the other hand, the Na + ion-sensitive membrane is an ion-sensitive membrane composition containing 240 mg of polyvinyl chloride as a membrane base material, 540 mg of dioctyl adipate as a plasticizer, and 60 mg of a neutral carrier type natural compound moninsin as a Na + ion sensitizer dissolved in 2 ml of cyclohesisanone solvent. 250 mg of ultrafine anhydrous silica (trade name: Aerosil) was added and mixed to form a Na + ion sensitive paste. Next, a specific method for forming a sensitive film will be described. Three identical stainless steel screens each having one rectangular opening pattern of 200 μm on each side corresponding to the ion-sensitive membrane 29 in FIG.
First, use one of the ion-sensitive membranes to
Apply Na + ion sensitive paste to position 9 and dry.
A Na + ion sensitive membrane 29 was formed. Next, using another screen, a K + ion sensitive paste was applied to the sensitive film 30 position and dried to form a K + ion sensitive film 30. Finally, using the remaining screen, a Cl - ion sensitive paste was applied to the sensitive film 31 position and dried to form a Cl - ion sensitive film 31. In the above process, three identical screens were prepared and used separately for each type of sensitive paste, in order to prevent mixing and contamination of the sensitive pastes.
Through the above process, Na + , K + ,
We were able to form ISFETs sensitive to Cl - and PH ions. Next, we investigated the ion responsiveness of these ISFETs. Regarding the ISFET for K + and Cl -, the same ion responsiveness as in the above example was obtained. on the other hand,
52mV/each for Na + and PH ISFETs
A slope sensitivity of 54 mV/PH was obtained for pNa + .
次に前記実施例によるワンチツプ内にPH、
Na+、K+、Cl-各イオン感応ISFETが形成された
マルチISFETチツプのPH感応ISFETゲート絶縁
領域上にイオン不感応性ポリパラキシリレン薄膜
を形成したマルチISFETを構成した。ポリパラ
キシリレン薄膜の分離形成は、一辺200μｍの矩
形状開口パターンを１ケ有するメタルマスクを用
い、ポリパラキシリレンの熱分解再重合反応によ
り行つた。すなわち、PH感応ISFETゲート絶縁
領域上に先のメタルマスク開口部を重ね合わせ、
高真空中でポリパラキシリレンを熱分解し、PH感
応ISFETゲート上で再重合させることによりポ
リパラキシリレン薄膜を形成した。膜厚が10μｍ
になるように熱分解再重合反応の時間を制御し
た。ポリパラキシリレンが最表面に形成された
ISFETはイオン不感応性であるため参照電極と
して利用できる。本実施例で形成したポリパラキ
シリレン被覆ISFETを参照電極として他のNa+、
K+、Cl-各イオン感応ISFETのイオン応答を調べ
ると、前記実施例と同様なスロープ感度が得られ
た。 Next, in the one chip according to the above embodiment, PH,
A multi-ISFET was constructed by forming an ion-insensitive polyparaxylylene thin film on the PH-sensitive ISFET gate insulating region of a multi-ISFET chip in which Na + , K + , and Cl - ion-sensitive ISFETs were formed. The polyparaxylylene thin film was separated and formed by thermal decomposition and repolymerization reaction of polyparaxylylene using a metal mask having one rectangular opening pattern of 200 μm on each side. That is, the previous metal mask opening is superimposed on the PH-sensitive ISFET gate insulation region,
Polyparaxylylene thin films were formed by thermally decomposing polyparaxylylene in high vacuum and repolymerizing it on the PH-sensitive ISFET gate. Film thickness is 10μm
The time of the pyrolysis repolymerization reaction was controlled so that Polyparaxylylene was formed on the top surface
Since ISFET is ion-insensitive, it can be used as a reference electrode. Using the polyparaxylylene coated ISFET formed in this example as a reference electrode, other Na + ,
When the ion responses of the K + and Cl - ion sensitive ISFETs were investigated, slope sensitivities similar to those of the previous example were obtained.
以上述べた４つの実施例でのマルチISFETで
は、第１図または第２図にあるように、棒状下地
FETゲート絶縁膜上に矩形状イオン感応膜また
はイオン不感応膜を形成したが、各ゲート絶縁膜
上をイオン感応膜またはイオン不感応膜が完全に
被い、かつ分離しているならばその形状はいかな
るものでもよい。またイオン感応膜の塗布に際し
ては所定開口パターンが形成されたステンレス製
スクリーンを治具として使用したが、これに代わ
り開口パターンが形成されたメタルマスクなどの
治具を用いても何んら支障はない。またワンチツ
プ内に形成されるISFETの個数も、以上述べた
４つの実施例にある５ケあるいは４ケに限らず任
意の個数であつてもよいことは言うまでもない。 In the multi-ISFET in the four embodiments described above, as shown in Fig. 1 or 2, the rod-shaped base
A rectangular ion-sensitive film or ion-insensitive film is formed on the FET gate insulating film, but if the ion-sensitive film or ion-insensitive film completely covers each gate insulating film and is separated, then the shape can be anything. In addition, when applying the ion-sensitive film, a stainless steel screen with a predetermined opening pattern was used as a jig, but there is no problem with using a metal mask or other jig with an opening pattern instead. do not have. Further, it goes without saying that the number of ISFETs formed in one chip is not limited to the five or four in the four embodiments described above, but may be any number.
また、不活性無機材料は粘度調整用であるか
ら、２種以上のものを混合して用いてもなんらさ
しつかえない。 Further, since the inert inorganic material is used for adjusting viscosity, there is no problem even if two or more kinds of inorganic materials are used in combination.
上記のように本発明によるマルチISFETは、
膜母材、イオン感応物質、溶媒および粘度調整用
不活性無機材料よりなるイオン感応ペーストを、
所定のパターンが形成されたスクリーンを介して
ゲート絶縁領域上に印刷塗布することにより、即
ちスクリーン印刷により、複数のゲート絶縁膜上
イオン感応膜が分離形成されるため、特定のイオ
ン感応膜の劣化が他のISFETの性能に影響を与
えない効果がある。
As mentioned above, the multi-ISFET according to the present invention is
An ion-sensitive paste consisting of a membrane base material, an ion-sensitive substance, a solvent, and an inert inorganic material for viscosity adjustment,
By printing and coating on the gate insulating region through a screen on which a predetermined pattern is formed, that is, by screen printing, multiple ion-sensitive films on the gate insulating film are formed separately, so that deterioration of a specific ion-sensitive film is prevented. has the effect of not affecting the performance of other ISFETs.
第１図は同種のイオン感応膜が分離形成された
マルチISFETの一実施例の平面図、第２図は異
種のイオン感応膜が分離形成されたマルチ
ISFETの一実施例の平面図である。
１……シリコンチツプ、２，３，４，５，６…
…ソース電極、７，８，９，１０，１１……ソー
ス領域、２′，３′，４′，５′，６′……ドレイン
電極、７′，８′，９′，１０′，１１′……ドレイ
ン領域、１２，１３，１４，１５，１６……イオ
ン感応膜、２０……シリコンチツプ、２１，２
２，２３，２４……ソース電極、２５，２６，２
７，２８……ソース領域、２１′，２２′，２３′，
２４′……ドレイン電極、２５′，２６′，２７′，
２８′……ドレイン領域、２９，３０，３１……
イオン感応膜。
Figure 1 is a plan view of an example of a multi-ISFET in which ion-sensitive membranes of the same type are formed separately, and Figure 2 is a plan view of an example of a multi-ISFET in which ion-sensitive membranes of different types are formed separately.
FIG. 2 is a plan view of one embodiment of an ISFET. 1... Silicon chip, 2, 3, 4, 5, 6...
... Source electrode, 7, 8, 9, 10, 11... Source region, 2', 3', 4', 5', 6'... Drain electrode, 7', 8', 9', 10', 11 '...Drain region, 12, 13, 14, 15, 16... Ion sensitive film, 20... Silicon chip, 21, 2
2, 23, 24...source electrode, 25, 26, 2
7, 28...source region, 21', 22', 23',
24'...Drain electrode, 25', 26', 27',
28'...Drain region, 29, 30, 31...
Ion sensitive membrane.
Claims (1)
該ゲート絶縁領域上にイオン感応膜を有するマル
チイオン感応性電界効果型トランジスタの製造方
法において、膜母材およびイオン感応物質を有機
溶媒に溶解したイオン感応膜組成物に粘度調整用
不活性無機材料を添加混合し、イオン感応ペース
トを調整し、このイオン感応ペーストを上記ゲー
ト絶縁領域上にスクリーン印刷により塗布し、乾
燥し、各イオン感応膜を互いに分離して形成する
ことを特徴とするマルチイオン感応性電界効果型
トランジスタの製造方法。 ２ 上記ゲート絶縁領域の少なくとも１つの領域
上に、イオンに感応しない膜を設ける工程を有す
ることを特徴とする特許請求の範囲第１項記載の
マルチイオン感応性電界効果型トランジスタの製
造方法。 ３ 上記膜母材がビニル系樹脂であることを特徴
とする特許請求の範囲第１項記載のマルチイオン
感応性電界効果型トランジスタの製造方法。 ４ 上記イオン感応膜がニユートラルキヤリヤ型
感応物質であることを特徴とする特許請求の範囲
第１項記載のマルチイオン感応性電界効果型トラ
ンジスタの製造方法。 ５ 上記粘度調整用不活性無機材料が、無水シリ
カ、無水酸化アルミニウム及び無水酸化チタンか
らなる群から選ばれた少なくとも１種の材料の超
微粒子であることを特徴とする特許請求の範囲第
１項記載のマルチイオン感応性電界効果型トラン
ジスタの製造方法。 ６ 上記イオン感応膜の厚みが５〜200μｍの範
囲であることを特徴とする特許請求の範囲第１項
記載のマルチイオン感応性電界効果型トランジス
タの製造方法。 ７ 上記粘度調整用不活性無機材料が、イオン感
応膜の５〜50重量％であることを特徴とする特許
請求の範囲第１項又は第５項記載のマルチイオン
感応性電界効果型トランジスタの製造方法。[Claims] 1. Having a plurality of gate insulating regions on the same substrate,
In the method for manufacturing a multi-ion sensitive field effect transistor having an ion sensitive film on the gate insulating region, an inert inorganic material for viscosity adjustment is added to an ion sensitive film composition in which a film base material and an ion sensitive substance are dissolved in an organic solvent. is added and mixed to prepare an ion-sensitive paste, this ion-sensitive paste is applied onto the gate insulating region by screen printing, and dried to form each ion-sensitive film separately from each other. A method for manufacturing a sensitive field effect transistor. 2. The method of manufacturing a multi-ion sensitive field effect transistor according to claim 1, further comprising the step of providing a film not sensitive to ions on at least one region of the gate insulating region. 3. The method for manufacturing a multi-ion sensitive field effect transistor according to claim 1, wherein the membrane base material is a vinyl resin. 4. The method of manufacturing a multi-ion sensitive field effect transistor according to claim 1, wherein the ion sensitive film is a neutral carrier sensitive material. 5. Claim 1, wherein the viscosity-adjusting inert inorganic material is ultrafine particles of at least one material selected from the group consisting of anhydrous silica, anhydrous aluminum oxide, and anhydrous titanium oxide. A method of manufacturing the multi-ion sensitive field effect transistor described. 6. The method for manufacturing a multi-ion sensitive field effect transistor according to claim 1, wherein the ion sensitive film has a thickness in the range of 5 to 200 μm. 7. Production of a multi-ion sensitive field effect transistor according to claim 1 or 5, wherein the viscosity-adjusting inert inorganic material accounts for 5 to 50% by weight of the ion-sensitive membrane. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60021749A JPS61181956A (en) | 1985-02-08 | 1985-02-08 | Multi-ion responsive fe type transistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60021749A JPS61181956A (en) | 1985-02-08 | 1985-02-08 | Multi-ion responsive fe type transistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61181956A JPS61181956A (en) | 1986-08-14 |
| JPH0544986B2 true JPH0544986B2 (en) | 1993-07-07 |
Family
ID=12063711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60021749A Granted JPS61181956A (en) | 1985-02-08 | 1985-02-08 | Multi-ion responsive fe type transistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61181956A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5421983A (en) * | 1993-11-12 | 1995-06-06 | E. I. Du Pont De Nemours And Company | Anion selective electrodes containing fumed silica |
| DE10163557B4 (en) * | 2001-12-21 | 2007-12-06 | Forschungszentrum Jülich GmbH | Transistor-based sensor with specially designed gate electrode for high-sensitivity detection of analytes |
| JP4843077B2 (en) * | 2008-12-03 | 2011-12-21 | 韓國電子通信研究院 | Biosensor with transistor structure and manufacturing method thereof |
| LU101020B1 (en) * | 2018-11-28 | 2020-05-28 | Luxembourg Inst Science & Tech List | Ion-sensitive field effect transistor |
| WO2024181340A1 (en) * | 2023-03-02 | 2024-09-06 | 株式会社村田製作所 | Sensor and detection method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219478A (en) * | 1975-08-04 | 1977-02-14 | Nippon Kokan Kk <Nkk> | Apparatus for cooling waste gas from dust incinerating furnaces |
| JPS5730603U (en) * | 1980-07-25 | 1982-02-18 |
-
1985
- 1985-02-08 JP JP60021749A patent/JPS61181956A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219478A (en) * | 1975-08-04 | 1977-02-14 | Nippon Kokan Kk <Nkk> | Apparatus for cooling waste gas from dust incinerating furnaces |
| JPS5730603U (en) * | 1980-07-25 | 1982-02-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61181956A (en) | 1986-08-14 |
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