JPS58221156A - Correction electrode for measuring ph and ph measuring method - Google Patents
Correction electrode for measuring ph and ph measuring methodInfo
- Publication number
- JPS58221156A JPS58221156A JP57104631A JP10463182A JPS58221156A JP S58221156 A JPS58221156 A JP S58221156A JP 57104631 A JP57104631 A JP 57104631A JP 10463182 A JP10463182 A JP 10463182A JP S58221156 A JPS58221156 A JP S58221156A
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- JP
- Japan
- Prior art keywords
- electrode
- measurement
- film
- measuring
- correction
- Prior art date
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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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Photovoltaic Devices (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は半導体基板を有するｐＨ測定用補正電極に関
し、ｐ Ｈ測定電極に発生する光起電力を補正するＰＨ
測定用補正電極及びその装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pH measurement correction electrode having a semiconductor substrate.
This invention relates to a measurement correction electrode and its device.
従来、電極な用い″ＣＰＨｍ＆測定する装置はを
その電極としてガラス電極が使用している。このガラス
電極は水嵩イオンに感応する感応性ガラスで作った薄い
ガラス電極球を有し、この内部には既知のｐＨ値をもっ
た内部液と不分極電極としての銀−塩化銀電極を入れた
ものである。Conventionally, devices that measure CPHm& have used glass electrodes as electrodes.This glass electrode has a thin glass electrode bulb made of sensitive glass that is sensitive to water bulk ions, and inside this It contains an internal solution with a known pH value and a silver-silver chloride electrode as a non-polarized electrode.
しかし、この電極はガラス製であるため、容易に破損す
る欠点がある。また、ガラス電極球の部分の厚さを一定
にすることがむずかしいので、製品ととＫばらつきがあ
る。しかも、ガラス膜の厚さがあまり厚（なると−所定
の電位が実際のＦ” ｌ（［Ｋ対応しないことも起って
いる。However, since this electrode is made of glass, it has the disadvantage of being easily damaged. Furthermore, since it is difficult to make the thickness of the glass electrode bulb constant, there are variations in K between products. Moreover, if the thickness of the glass film is too thick, the predetermined potential may not correspond to the actual F''l([K).
さらに、内部液な必要とするため、製品の小形化が困離
であり、液の補給も必要となることがあり、保守管理が
面倒であった。上記電極な微小化した場合、イオン感応
部の有効面積が減少し、インピーダンスが非常に増加す
る。従って雑音が入り易く応答もおそ（なり、さらに高
インピーダンスの増巾器が必要となり、精度的にもわる
（、また装置自身が階価になる等の欠点を有していた。Furthermore, since an internal liquid is required, it is difficult to miniaturize the product, and it is sometimes necessary to replenish the liquid, making maintenance management troublesome. When the electrodes are miniaturized, the effective area of the ion-sensing portion decreases, and the impedance increases significantly. Therefore, noise easily enters, the response is slow (and a high-impedance amplifier is required, which impairs accuracy (and the device itself becomes expensive).
そこで本出願人は、上記の欠点を除去するため、特願昭
５６−８８８０２号に示すようにＰＨＭを薄膜にし、低
いイオン感応層を提供した。しかしながら上記Ｓｉ基板
上にＴａ２０ａ膜を形成したｐＨ感応層を有するｐ Ｈ
電極は光に対しても感応し、測定室が暗室のような暗い
所でないと正確な測定が行なわれないといへ欠点を有し
ていた。Therefore, in order to eliminate the above-mentioned drawbacks, the present applicant made PHM into a thin film to provide a low ion sensitivity layer as shown in Japanese Patent Application No. 56-88802. However, the pH sensitive layer having a Ta20a film formed on the Si substrate is
The electrodes were sensitive to light and had the disadvantage that accurate measurements could only be made in a dark room.
この発明の目的は上記の欠点に録み光が入射しても正確
な測定が行えるようにしたｐＨ測定用補正電極および測
定力法な提供することＫある。SUMMARY OF THE INVENTION An object of the present invention is to provide a correction electrode for pH measurement and a measuring force method that can overcome the above-mentioned drawbacks and allow accurate measurement even when light is incident.
以下この発明の一実施例な説明する。An embodiment of this invention will be described below.
第１図はｐＨ測定用補正電極２２の補正電極基板１で、
半導体基板としてのｐｍ’ｔｖコン基板２にＴＩＬ２０
１ ｇ ３ ｋ形成する。このＴａ２０５膜３は真空Ｍ
＃ スパッタリング法、 ＣＶ Ｄ （Ｃｈａｍｌｅ
ａｌＶａｐｏｕｒ Ｄｅｐｏｓｉｔｉｏｎ ３などの方
法で１００ＯＡ８度の厚さに形成する。さらに’ｒａ２
０ｇ膜３の上Ｋ例えばＩｎ２０Ｂ−５ｎ０２混甘物など
からなる透明電極４が付けられている。この透明電極４
はたとえばスパッタリング法、真空蒸ｆｆ１ｆｆｉなど
で形成する。この透明電極４には外部に出力するための
導線６が半田付けなどの方法で接続されている。またシ
リコン基板２の裏面にはＡｌ。FIG. 1 shows the correction electrode substrate 1 of the correction electrode 22 for pH measurement.
TIL20 on pm'tv controller board 2 as a semiconductor board
Forms 1 g 3 k. This Ta205 film 3 is in vacuum M
# Sputtering method, CV D (Chamle
It is formed to a thickness of 100OA8 degrees using a method such as alVapour Deposition 3. Furthermore, 'ra2
A transparent electrode 4 made of, for example, In20B-5n02 mixed sweetener is attached on top of the 0g film 3. This transparent electrode 4
is formed by, for example, a sputtering method, vacuum evaporationff1ffi, or the like. A conducting wire 6 for outputting to the outside is connected to the transparent electrode 4 by a method such as soldering. Further, the back surface of the silicon substrate 2 is made of Al.
Ｃｒ 、 ＮＩ 、 Ａｕ−Ａｇ合金などからなる電極
８が蒸着等の方法で形成されており、この電極８には導
線７が接続されている。なお、電極基板ｌの全面もしく
は透明電極の表面を例えばポリエチレン、ポリエステル
等の合成樹脂の透明被膜５で被覆し、防水と絶縁作用を
なしている。An electrode 8 made of Cr, NI, Au-Ag alloy, etc. is formed by a method such as vapor deposition, and a conductive wire 7 is connected to this electrode 8. The entire surface of the electrode substrate 1 or the surface of the transparent electrode is coated with a transparent coating 5 made of synthetic resin such as polyethylene or polyester to provide waterproof and insulating properties.
このように形成された補正電極基板１を第２図に示すよ
うに透明電極４側を外側に向けて筒体平の開口端に固着
し−Ｃｐ）Ｉ測定用補正電極２２を形成する。上記ｐＨ
測定用補正電極２２な第３図に示すように測定用セル１
５内に配設し。As shown in FIG. 2, the correction electrode substrate 1 thus formed is fixed to the open end of the cylindrical body with the transparent electrode 4 side facing outward to form the -Cp)I measurement correction electrode 22. Above pH
As shown in FIG. 3, the measurement correction electrode 22 has a measurement cell 1.
Placed within 5.
夫々の導線６，７を第１の増巾器１８に接続する。The respective conductors 6, 7 are connected to a first amplifier 18.
一方本件出願人がすでに出願している例えば第４図に示
すシリコノ基板１０上に五酸化タンタル（Ｔａ２ｅｓ）
を有するｐＨ感応基板９を先端に有したｐＨ測定用電極
２１を上記測定用セル１５内に配設し、そのｐ Ｈ測定
用電極２１の導線１３を＠２の増巾器１９の一端に接続
する。On the other hand, the present applicant has already applied, for example, on the silicone substrate 10 shown in FIG.
A pH measuring electrode 21 having a pH sensitive substrate 9 at its tip is arranged in the measuring cell 15, and the conductor 13 of the pH measuring electrode 21 is connected to one end of the amplifier 19 of @2. do.
第２の増巾器１９の他端には測定用セル１５内に設けら
れた比較電極１７を接続している。なお、１２はＡｕ、
ＡＩなどの金屑電極である。第１、第２の増巾器１８，
１９の出力端を差動増巾器２０に接続している。A comparison electrode 17 provided within the measurement cell 15 is connected to the other end of the second amplifier 19. In addition, 12 is Au,
It is a gold scrap electrode such as AI. first and second amplifiers 18,
The output end of 19 is connected to a differential amplifier 20.
次にこのように配設した夫々の電極１７，２１゜２２の
作用を説明する。Next, the functions of the electrodes 17, 21 and 22 arranged in this manner will be explained.
先ず、測定用セル１５に被検液１６を供給し、夫々の電
極１７，２１．２２に被検液を接触させる。上記電極の
中、ｐＨ測定用電極２１のＴａ２ｅｓ膜と比較電極１７
との間には第５図に示すような、被検液１６のｐＨ値に
応じた電位が発生する。このときｐＨ＃１定用補圧用補
正電極２２基板ｌの全面もしくは表面を透明被ｊＪｉ５
で覆われているので被検液１６に接触しても、被検液１
６のｐＨにより感応した電位は発生しない。そこでｐＨ
測定用電極２１及びｐＨ測定用補正電極２２に光が入射
すると、第６図のように光の強度によって光起電力が生
じ電位が発生する。従って比較電極１７とｐＨ測定用電
極２１との間に生じる電位Ｅｔは
Ｅｔ−Ｅｔ ＋ Ｅｐ
となる。ここで、 ＥＩは被検液１６における水素イオ
ンによる比較電極１７とｐＨ測定用電極２１との間の電
位差であり、Ｅｐは光起電力によるｐｆ（測定用電極２
１のＴ”ｘＯｉ Ｍｌ １とシリフッ基板１０との間の
電位差である。つまり、比較電極１７とｐＨ測定用電極
２１とは閣の電位Ｅｔには光起電力による電位差Ｅｐが
誤差分として含まれている。First, the test liquid 16 is supplied to the measurement cell 15, and the test liquid is brought into contact with each electrode 17, 21, 22. Among the above electrodes, the Ta2es film of the pH measurement electrode 21 and the comparison electrode 17
A potential corresponding to the pH value of the test liquid 16 is generated as shown in FIG. At this time, the entire surface or surface of the pH #1 constant pressure compensation correction electrode 22 substrate l is covered with a transparent coating.
Even if it comes into contact with the test liquid 16, the test liquid 1
With a pH of 6, no sensitive potential is generated. So the pH
When light enters the measuring electrode 21 and the pH measuring correction electrode 22, a photovoltaic force is generated due to the intensity of the light, and a potential is generated, as shown in FIG. Therefore, the potential Et generated between the comparison electrode 17 and the pH measurement electrode 21 becomes Et-Et + Ep. Here, EI is the potential difference between the reference electrode 17 and the pH measurement electrode 21 due to hydrogen ions in the test liquid 16, and Ep is the pf (measurement electrode 21) due to photovoltaic force.
This is the potential difference between the reference electrode 17 and the pH measurement electrode 21.The potential Et between the comparison electrode 17 and the pH measurement electrode 21 includes the potential difference Ep due to the photovoltaic force as an error. ing.
また、ｐＨ測定用補正電極２２のＴａｊＯｓ膜３は被検
液１６に接触しないので、このＴａ２Ｑ５膜３とシリコ
ン基８２２との間には光起電力による電位差ＥＰ’だけ
現われる。この電位差ＥＰ’は前記−差分の電位Ｅ、
Ｋはぼ等しい値である。そこで、上式で示すようにこの
電位差Ｅｐ′と前記電位差Ｅ、ｌとの差をとれば、求め
たい電位差Ｅ】が得られる。Furthermore, since the TajOs film 3 of the pH measurement correction electrode 22 does not come into contact with the test liquid 16, a potential difference EP' due to photovoltaic force appears between the Ta2Q5 film 3 and the silicon base 822. This potential difference EP' is the -difference potential E,
K has approximately the same value. Therefore, as shown in the above equation, by taking the difference between this potential difference Ep' and the potential differences E and l, the desired potential difference E] can be obtained.
ｇ、 ＝ ［ｉ４− Ｅｐ
−８：ｇｔ−ｇｐ＋
これは第３図の差動増巾器２ｏの出力として求めること
かできる。なお、増幅器１８は電位差Ｅｐ′、増幅器１
９は電位差Ｅｔをそれぞれ増幅するものであるが、ｌ
Ｅｐ Ｅｐ’ Ｉ ＝ｍｉｎ トなるようにそれぞ
れのゲインを調整しておく。g, = [i4-Ep-8:gt-gp+ This can be obtained as the output of the differential amplifier 2o in FIG. Note that the amplifier 18 has a potential difference Ep', and the amplifier 1
9 amplifies the potential difference Et, but l
Each gain is adjusted so that Ep Ep' I =min.
ところで、被検液中のＨ＋イオンによる電位差Ｅ１が得
られたなら、さらに既知Ｈ＋イオン濃度Ｃ２の試液によ
る電位差Ｅ２ を求めるとＮｅｒｎｓｔ の式
Ｒ：気体定数、Ｔ：絶対温度、Ｆ：）７ラデ一定数
より被検ｇＨ＋イオン濃度Ｃ＋は
となりｐＨは
ｐＨ＝−１ｏｇｃｌ
となる。By the way, once the potential difference E1 due to H+ ions in the test solution is obtained, the potential difference E2 due to the test solution with the known H+ ion concentration C2 can be found using the Nernst equation R: gas constant, T: absolute temperature, F:)7 rad. From the constant number, the test gH+ ion concentration C+ becomes, and the pH becomes pH=-1ogcl.
第７図は、第１図で示［、たＰｌ（測定用補正電極２２
と、第４図で示したｐＨ測定電極２１’に一体化したｐ
Ｈ測定用複合電極装置３０である。FIG. 7 shows the graph shown in FIG.
and p integrated into the pH measurement electrode 21' shown in FIG.
This is a composite electrode device 30 for H measurement.
即ち、シリ：１〕基板３１の中央部に全幅に亘って横切
る例えばボｐノ＋Ｂ）％Ｆ：拡散させたチャンネルスト
ッパー３２に形成し、このチャンネルストッパー３２を
間に介してＰＨ感応部（ｐＨ釧定電極）３３および光起
電力補正部（ｐＨ測定用補正電極）３４が形成され℃い
る。That is, silicon: 1] A channel stopper 32 is formed across the entire width of the central part of the substrate 31, e.g. A photovoltaic force correction section (correction electrode for pH measurement) 34 is formed.
このように一体化した複合電極装置３０は第８図に示１
ように比較電極１７と共に測定セル１５に配設し所定の
測定方法で測定すると、補 ７−
正された正確な電位を求める事ができる。The composite electrode device 30 integrated in this way is shown in FIG.
If the reference electrode 17 and the reference electrode 17 are placed in the measurement cell 15 and measured using a predetermined measurement method, a corrected and accurate potential can be obtained.
以上詳述したようＫ、この発明によると明るい場所でも
正確な測定ができ−Ｑ！ｉＫ：、”）コン基板にＴＩＬ
２０１１ ＮＫを形成したｐＨ電極と組合せて使用する
事により著しい効果Ｙ奏し得る。構造簡単Ｋ Ｌ ”Ｃ
取扱い操作も容易なｐＨ測定用補正電極およびｐＨ測定
方法を提供できる。As detailed above, according to this invention, accurate measurements can be made even in bright places. iK:,”) TIL on the control board
By using it in combination with a pH electrode formed with 2011 NK, remarkable effects can be achieved. Simple structure K L “C
It is possible to provide a correction electrode for pH measurement and a pH measurement method that are easy to handle.
第１図はこの発明の一実施例な示すための説明図−第２
図は同側構造図、第３図は回倒の測定方法説明図、第４
図はｐＨ電極説明図、Ｉ！５図及び第６図は回倒の特性
曲線図、第７図はこの発明の他の実施例を示す説明図、
第８図は回倒の測定方法を説明するための図である。
２・・・−・シリコン基数
３・−・・・ＴＩＬ２０１１膜
４・・・・・・透明電極
５・・・・・・透明被膜
１５・・・測定セル
２０・・・差動増巾器
８−
３５・・・チャンネルス１ツパ−
第５図
第６図
！！ｉｉ ／Ｉ （ｆｔ）
第７図
第８図Fig. 1 is an explanatory diagram for showing one embodiment of the present invention - Fig. 2
The figure is a diagram of the ipsilateral structure, Figure 3 is an explanatory diagram of the method for measuring rotation, and Figure 4 is an illustration of the method for measuring rotation.
The figure is a pH electrode explanatory diagram, I! 5 and 6 are characteristic curve diagrams of rotation, and FIG. 7 is an explanatory diagram showing another embodiment of the present invention.
FIG. 8 is a diagram for explaining a method for measuring rotation. 2...-Silicon base number 3--TIL2011 film 4...Transparent electrode 5...Transparent coating 15...Measuring cell 20...Differential amplifier 8 - 35... Channels 1 Tupah - Figure 5 Figure 6! ! ii /I (ft) Figure 7 Figure 8
Claims (1)
応（２）半導体基板にＴａｘｅｓ膜を形成したｐＨ感応
基板上に設けた透明電極層を覆うように透明被膜を施し
たＰ′Ｈ渕定周定用補正電極導体基板にチャンネルスト
ッパーを介して接続した半導体基板１ｃＴａｔｏｓ膜を
形成したＰＨ感応電極を一体に設けた事を特徴とするｐ
Ｈ測定用電極装置。 （３）半導体基板にＴａ＊Ｏｉ膜を形成したｐＨ感応基
板上に設けた透明電極層を覆うように透明被膜を施した
ｐＨ測定用補正電極を測定セル内に配設すると共に半導
体基板上にＴａ１ｓ ＩＩＩ ％：影形成たｐＨ測定用
電極を測定セル内に配設し、光起電力による電位差を差
動増巾器により補正するよ５Ｋした事を４Ｉ黴とするｐ
Ｈ測定方法。[Scope of Claims] +1) PH-sensitive with a Ta20B film formed on a semiconductor substrate (2) P' with a transparent coating applied to cover a transparent electrode layer provided on a pH-sensitive substrate with a Taxes film formed on a semiconductor substrate A semiconductor substrate 1c connected to a conductor substrate of a correction electrode for fixing the circumference of H-buchi through a channel stopper.P characterized in that a PH sensitive electrode formed with a Tatos film is integrally provided.
Electrode device for H measurement. (3) A correction electrode for pH measurement with a transparent coating applied to cover a transparent electrode layer provided on a pH-sensitive substrate with a Ta*Oi film formed on the semiconductor substrate is disposed inside the measurement cell, and a correction electrode is provided on the semiconductor substrate. Ta1s III %: A shaded pH measurement electrode is placed in the measurement cell, and the potential difference due to photovoltaic force is corrected by a differential amplifier.
H measurement method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57104631A JPS58221156A (en) | 1982-06-17 | 1982-06-17 | Correction electrode for measuring ph and ph measuring method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57104631A JPS58221156A (en) | 1982-06-17 | 1982-06-17 | Correction electrode for measuring ph and ph measuring method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58221156A true JPS58221156A (en) | 1983-12-22 |
Family
ID=14385788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57104631A Pending JPS58221156A (en) | 1982-06-17 | 1982-06-17 | Correction electrode for measuring ph and ph measuring method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58221156A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172892A1 (en) * | 1984-03-01 | 1986-03-05 | Molecular Devices Corp | Method and device employing photoresponsive semiconductor electrode for determining analyte. |
| KR100441662B1 (en) * | 2001-08-11 | 2004-07-27 | 재단법인 포항산업과학연구원 | Micro pH sensor with auto-calibration function |
| JP2007171119A (en) * | 2005-12-26 | 2007-07-05 | Nikka Micron Kk | Sensor for detecting concentration of aqueous ozone solution |
-
1982
- 1982-06-17 JP JP57104631A patent/JPS58221156A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172892A1 (en) * | 1984-03-01 | 1986-03-05 | Molecular Devices Corp | Method and device employing photoresponsive semiconductor electrode for determining analyte. |
| KR100441662B1 (en) * | 2001-08-11 | 2004-07-27 | 재단법인 포항산업과학연구원 | Micro pH sensor with auto-calibration function |
| JP2007171119A (en) * | 2005-12-26 | 2007-07-05 | Nikka Micron Kk | Sensor for detecting concentration of aqueous ozone solution |
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