JPH01152355A - Ph sensor - Google Patents
Ph sensorInfo
- Publication number
- JPH01152355A JPH01152355A JP62309740A JP30974087A JPH01152355A JP H01152355 A JPH01152355 A JP H01152355A JP 62309740 A JP62309740 A JP 62309740A JP 30974087 A JP30974087 A JP 30974087A JP H01152355 A JPH01152355 A JP H01152355A
- Authority
- JP
- Japan
- Prior art keywords
- sensor
- layer
- silicon
- film
- silicon oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 230000005669 field effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000001020 plasma etching Methods 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 3
- 238000009413 insulation Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thin Film Transistor (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、 ｐＨセンサに関する。更に詳しくは。[Detailed description of the invention] [Industrial application field] The present invention relates to a pH sensor. For more details.
電界効果型トランジスタのゲート絶縁層上にｐＨ感応層
を設けたｐＨセンサに関する。The present invention relates to a pH sensor in which a pH sensitive layer is provided on a gate insulating layer of a field effect transistor.
従来の電界効果型トランジスタのゲート絶縁層上にｐＨ
感応層を設けたｐＨセンサは、ｐＨ感応層として窒化け
い素（ｓｉｉＮ＊）層が形成されており、結晶性シリコ
ン基板から次のような工程によって製造されている。pH on the gate insulating layer of a conventional field effect transistor
A pH sensor provided with a sensitive layer has a silicon nitride (siiN*) layer formed as the pH sensitive layer, and is manufactured from a crystalline silicon substrate through the following process.
基板にＰ型ウェハを用い、シリコンアイランド作成−フ
イールド酸化−リン拡＠（ソース・ドレイン形成）−ゲ
ート酸化−窒化けい素の化学蒸着−プラズマエツチング
によるコンタクトホール穴あけ−アルミニウム蒸着によ
る電極形成−水素アニール−ワイヤーボンディングとい
う一連の工程を経てｌ５ＦＥＴ（ｉｏｎ ５ｅｎｓｉｔ
ｉｖｅ ＦＥＴ）が製作されており、この過程でソース
およびドレインとなる２つのｎ型領域を表面部分に形成
させたＰ型性シリコン基板上の二酸化けい素ゲート絶縁
層上に窒化けい素蒸着膜を形成せしめることが行われて
いる。Using a P-type wafer as the substrate, silicon island creation - field oxidation - phosphorus expansion @ (source/drain formation) - gate oxidation - chemical vapor deposition of silicon nitride - contact hole drilling by plasma etching - electrode formation by aluminum evaporation - hydrogen annealing - Through a series of wire bonding processes, the 15FET (ion 5ensit)
In this process, a silicon nitride vapor-deposited film is deposited on a silicon dioxide gate insulating layer on a P-type silicon substrate with two n-type regions forming the source and drain on the surface. Formation is underway.
かかる従来のｌ５ＦＥ！Ｔにおいて、イオン感応層とし
ての窒化けい素蒸着膜を形成させるためには。Such conventional l5FE! In order to form a silicon nitride vapor deposited film as an ion-sensitive layer at T.
高価なＬＰＧＶＤ装置（熱ＣＶＤ装置）を用い、ガスと
してアンモニア、シランおよび水素の３種のガスを使用
しなければならず、このため温度、時間、ガス流量など
の各要因について複雑な制御を必要とし、操作的に煩雑
であるという欠点がみられた。An expensive LPGVD device (thermal CVD device) must be used and three types of gases, ammonia, silane, and hydrogen, must be used, which requires complex control of various factors such as temperature, time, and gas flow rate. However, the drawback was that it was complicated to operate.
そこで、本発明者は、操作的に簡単な方法で同様の性能
を示すイオン感応層を求めて種々検討の結果、イオン感
応層を一酸化けい素の蒸着膜で形成させることにより、
かかる課題が効果的に解決されることを見出した。Therefore, the inventor of the present invention conducted various studies in search of an ion-sensitive layer that exhibits similar performance using a method that is easy to operate, and as a result, by forming the ion-sensitive layer with a vapor-deposited film of silicon monoxide,
It has been found that this problem can be effectively solved.
〔問題点を解決するための手段〕および〔作用〕従って
、本発明は電界効果型トランジスタｐＨセンサに係り、
このｐＨセンサは、ソース（電子供給口）およびドレイ
ン（電子排出口）となる２つのｎ型領域を表面部分に形
成させたＰ型性シリコン基板上の二酸化けい素ゲート絶
縁層上に一酸化けい素蒸着膜を形成せしめてなる。[Means for Solving the Problem] and [Operation] Therefore, the present invention relates to a field effect transistor pH sensor,
This pH sensor uses silicon monoxide on a silicon dioxide gate insulating layer on a P-type silicon substrate, which has two n-type regions formed on its surface to serve as a source (electron supply port) and a drain (electron discharge port). A bare vapor deposition film is formed.
一酸化けい素蒸着膜の形成は、基板温度約ｌＯ〜５０℃
、タングステンボード温度約１７００℃以上で、市販Ｓ
ｉＯを用い、蒸着時の真空度５ Ｘ １０−’〜５×１
Ｏ−４Ｔｏｒｒ程度で行われ、層の厚さが約５００−１
ｏｏｏ。The silicon monoxide vapor deposited film is formed at a substrate temperature of approximately lO to 50°C.
, at a tungsten board temperature of about 1700°C or higher, commercially available S
Using iO, the degree of vacuum during evaporation is 5 x 10-' to 5 x 1
It is carried out at about O-4 Torr, and the layer thickness is about 500-1
ooooo.
人の蒸着膜として形成させる。It is formed as a vapor-deposited film.
その後プラズマエツチングによるコンタクトホール穴あ
け以降ワイヤボンディング迄の各工程が適用され、 ｐ
Ｈセンサが製作されるが、製作されたｐＨセンサは、通
常の電界効果型トランジスタのゲート金属部分を除去し
、その代りにＰＨ感応層を形成させた構造を有している
。After that, each process from drilling contact holes by plasma etching to wire bonding is applied.
An H sensor is manufactured, but the manufactured pH sensor has a structure in which the gate metal part of a typical field effect transistor is removed and a PH sensitive layer is formed in its place.
このｐＨ感応性電界効果型トランジスタは、それを水溶
液中に浸漬した場合、ｐＨ感応層としてのＳｉＯの表面
層は、次のような電気化学的な解離平衡に支配されてい
るものと考えられる：
この場合の界面電位は、ネルンストの式で表わされる。When this pH-sensitive field effect transistor is immersed in an aqueous solution, the surface layer of SiO as the pH-sensitive layer is considered to be governed by the following electrochemical dissociation equilibrium: The interfacial potential in this case is expressed by the Nernst equation.
従って、電界効果型トランジスタのＳｉＯ層界面に発生
する界面電位を測定することにより、このＳｉＯ蒸着電
界効果型トランジスタはｐＨセンサとして使用し得るこ
とが確認される。Therefore, by measuring the interfacial potential generated at the SiO layer interface of the field effect transistor, it is confirmed that this SiO deposited field effect transistor can be used as a pH sensor.
電界効果型トランジスタのゲート絶縁層上にｐＨ感応層
を設けたｐＨセンサにおいて、ＰＨ感応層として一酸化
けい素蒸着膜を設けることにより、従来の窒化けい素蒸
着膜を設けたものと比較して製作がきわめて容易でしか
も同等のｐｉ（感応特性を示すｐｔｔセンサが得られる
゛。In a pH sensor in which a pH sensitive layer is provided on the gate insulating layer of a field effect transistor, by providing a silicon monoxide vapor deposited film as the pH sensitive layer, compared to a conventional silicon nitride vapor deposited film, It is possible to obtain a PTT sensor that is extremely easy to manufacture and exhibits equivalent pi (ptt) sensitivity characteristics.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例１
ｐ型シリコン基板を用い、常法により、ゲート金属部分
を除去した電界効果型トランジスタを製作し、その際Ｓ
ｉＯ２ゲート絶縁層（厚さ１０００人）の上に、基板温
度３０℃、蒸着時の真空度Ｉ Ｘ １０”’Ｔｏｒｒで
厚さ２０００人のＳｉＯ蒸着層を形成させ、以下所要の
各工程を施し、ｌ５ＦＥＴｔｉ−ｉ造した。Example 1 Using a p-type silicon substrate, a field effect transistor with the gate metal part removed was manufactured by a conventional method, and at that time S
An SiO vapor deposition layer with a thickness of 2000 layers was formed on the iO2 gate insulating layer (1000 layers thick) at a substrate temperature of 30°C and a vacuum level of I x 10'' Torr during deposition, and the following required steps were performed. , 15FETti-i was constructed.
このｐＨセンサを、第３図に示される測定装置を用い、
即ちエレクトロメータ１１およびレコーダ１２を含む測
定回路に接続されているＳｉＯ蒸着ｌ５ＦＥＴ １３お
よび銀／塩化銀参照電極１４をそれぞれ浸漬させた被測
定液（各ｐＨ値に調整された２０ｍＭＴｒｉｓ−ＨＣＱ
緩衝液）１５を恒温セル１６で一定温度（２５℃）に保
持した装置を用い、ソース−ドレイン間の電流（５００
μＡ）および電圧（４ｖ）をそれぞれ−定に保ちながら
、電位によりｐＨ特性を測定した。Using this pH sensor, the measuring device shown in Fig. 3,
That is, the SiO vapor-deposited 15FET 13 and the silver/silver chloride reference electrode 14 connected to the measurement circuit including the electrometer 11 and the recorder 12 were immersed in the measurement liquid (20mM Tris-HCQ adjusted to each pH value).
A source-drain current (500
The pH characteristics were measured by potential while keeping the μA) and voltage (4v) constant.
その結果は、第１図のグラフに示されるように、ｐ）１
１〜１２の範囲内でｌｐＨ当り約５７ｍＶの感度が直線
性をもって示され、ｐＨセンサとしての有効性が示され
た。The results are as shown in the graph of FIG.
A sensitivity of about 57 mV per lpH was demonstrated with linearity within the range of 1 to 12, demonstrating its effectiveness as a pH sensor.
比較例１
実施例１において、ＳｉＯ蒸着層の代りに、同じ厚さの
Ｓｉ、 Ｎ、蒸着層を形成させたものについて同様の測
定を行なうと、第１図のグラ“フに併記されるように、
１ｐＨ当り約５９ｍＶの感度を示した。Comparative Example 1 When similar measurements were made in Example 1 with Si, N, and evaporated layers of the same thickness formed instead of the SiO evaporated layer, the results were as shown in the graph of Figure 1. To,
It showed a sensitivity of about 59 mV per pH.
実施例２、比較例２
実施例１または比較例１のｐＨセンサについて、それら
の応答特性を調べるため、２５℃の蒸留水１００ｍＱ中
にｐＨセンサを浸漬させた後、ＩＮＨＣＱまたはＩＮ
ＮａＯＨを０．１ｍｆｌ宛加えたところ、それぞれ第２
図の実線（実施例２）または点線（比較例２）で示され
るような挙動を示し、いずれも３０秒間以内に定常値に
到達した。Example 2, Comparative Example 2 In order to investigate the response characteristics of the pH sensor of Example 1 or Comparative Example 1, the pH sensor was immersed in 100 mQ of distilled water at 25°C, and then INHCQ or IN
When 0.1 mfl of NaOH was added, the second
The behavior was as shown by the solid line (Example 2) or the dotted line (Comparative Example 2) in the figure, and both reached a steady value within 30 seconds.
第１〜２図は、それぞれ実施例１、比較例１および実施
例２．比較例２の測定結果を示すグラフである。また、
第３図は、ＰＨメータの電位測定装置の概要図である。
（符号の説明）
１３・・・・・ＳｉＯ蒸着ｌ５ＦＥＴ
１４・・・・・銀／塩化銀参照電極
１５・・・・・被測定液
代理人 区弁理士 吉
１）俊 夫 −
綜
− づ 張
第２図
時間（今）
第３図1 and 2 show Example 1, Comparative Example 1, and Example 2, respectively. 7 is a graph showing the measurement results of Comparative Example 2. Also,
FIG. 3 is a schematic diagram of a potential measuring device for a PH meter. (Explanation of symbols) 13...SiO vapor deposited 15FET 14...Silver/silver chloride reference electrode 15...Measured liquid representative Yoshichi, patent attorney
1) Toshio − 綜− zu Zhang Figure 2 Time (now) Figure 3
Claims (1)
部分に形成させたｐ型性シリコン基板上の二酸化けい素
ゲート絶縁層上に一酸化けい素蒸着膜を形成せしめてな
る電界効果型トランジスタｐＨセンサ。1. A field effect transistor pH in which a silicon monoxide vapor deposited film is formed on a silicon dioxide gate insulating layer on a p-type silicon substrate with two n-type regions forming a source and a drain formed on the surface portion. sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62309740A JPH01152355A (en) | 1987-12-09 | 1987-12-09 | Ph sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62309740A JPH01152355A (en) | 1987-12-09 | 1987-12-09 | Ph sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01152355A true JPH01152355A (en) | 1989-06-14 |
Family
ID=17996727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62309740A Pending JPH01152355A (en) | 1987-12-09 | 1987-12-09 | Ph sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01152355A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6464940B1 (en) | 1999-06-14 | 2002-10-15 | Sumitomo Metal Industries, Ltd. | pH sensor and pH measurement method employing the same |
| CN103282767A (en) * | 2011-01-07 | 2013-09-04 | 国立大学法人三重大学 | Ion-selective electrode |
-
1987
- 1987-12-09 JP JP62309740A patent/JPH01152355A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6464940B1 (en) | 1999-06-14 | 2002-10-15 | Sumitomo Metal Industries, Ltd. | pH sensor and pH measurement method employing the same |
| CN103282767A (en) * | 2011-01-07 | 2013-09-04 | 国立大学法人三重大学 | Ion-selective electrode |
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