JPS6116018B2 - - Google Patents
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- Publication number
- JPS6116018B2 JPS6116018B2 JP7347079A JP7347079A JPS6116018B2 JP S6116018 B2 JPS6116018 B2 JP S6116018B2 JP 7347079 A JP7347079 A JP 7347079A JP 7347079 A JP7347079 A JP 7347079A JP S6116018 B2 JPS6116018 B2 JP S6116018B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- gas
- gas detection
- temperature compensation
- stannic 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.)
- Expired
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 46
- 238000001514 detection method Methods 0.000 claims description 39
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- 229910052701 rubidium Inorganic materials 0.000 claims description 9
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 150000002504 iridium compounds Chemical class 0.000 claims description 5
- 150000002908 osmium compounds Chemical class 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 73
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000035945 sensitivity Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 239000001294 propane Substances 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229940102127 rubidium chloride Drugs 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】
この発明は、新規な温度補償素子を備えた金属
酸化物半導体ガス検知装置に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal oxide semiconductor gas detection device equipped with a novel temperature compensation element.
一般に従来より知られているガス検知素子は酸
化第二スズまたは酸化亜鉛、酸化第二鉄などの金
属酸化物にＰd，Ｐtなどの白金系触媒の他にＳ
b，Ａl，Ｆe，Ｎi，Ｚo，Ｓi，Ｔi，Ｚrなどを添加
してガス感度を向上させる研究が行われてきた
が、温度特性については顧みられず、事実従来よ
りガス感度の優れたガス検知素子は多く知られて
いるが、温度特性の優れたガス検知素子は皆無に
等しい。 Generally, conventionally known gas detection elements contain metal oxides such as stannic oxide, zinc oxide, or ferric oxide, as well as platinum-based catalysts such as P d and P t .
Research has been conducted to improve gas sensitivity by adding b , A l , F e , N i , Zo, S i , T i , Z r, etc., but the temperature characteristics have not been considered, and in fact, conventional Although many gas detection elements with better gas sensitivity are known, there are almost no gas detection elements with excellent temperature characteristics.
そこで、従来より知られたガス検知素子を使用
してガス検知を行う場合には、最高のガス感度を
確保するような特定温度に素子温度を維持する
か、或はガス検知素子の温度特性を補償しながら
測定を行うことがなされてきた。 Therefore, when performing gas detection using a conventionally known gas detection element, it is necessary to maintain the element temperature at a specific temperature that ensures the highest gas sensitivity, or to adjust the temperature characteristics of the gas detection element. Measurements have been made with compensation.
しかし、素子温度を特定温度に維持する方法に
おいては、加熱用電源電圧変動が環境温度変化の
影響を受けて素子温度が変化するため実際上、ガ
ス感度特性を一定に保持することは困難である。 However, in the method of maintaining the element temperature at a specific temperature, it is difficult to maintain the gas sensitivity characteristics constant because the element temperature changes due to fluctuations in the heating power supply voltage being affected by changes in the environmental temperature. .
またガス検知素子の温度特性を補償する方法に
ついては、従来より使用電源電圧変動に対しては
安定化電源、チエナーダイオードを、環境温度変
化に対してはバイメタル、サーミスタを使用して
きたが、これらの補償法は必然的に複雑な電気回
路になりがちで高価なわりに補償範囲が狭いもの
になつている。 In addition, conventional methods for compensating the temperature characteristics of gas detection elements have been to use stabilized power supplies and Chener diodes to deal with fluctuations in the power supply voltage, and to use bimetals and thermistors to deal with environmental temperature changes. Compensation methods tend to require complicated electrical circuits, are expensive, and have a narrow compensation range.
この発明は、上記実情に鑑みガス検知素子のガ
ス感度を確実に、且つ高度に維持することができ
るような温度補償素子を備えたガス検知装置を開
発する目的で研究した結果、ガス検知素子と同じ
抵抗温度係数をもちながらガス感度の殆んどない
新規な金属酸化物半導体を温度補償素子として使
用することにより所期の目的とする補償効果が得
られることを見出して完成したものである。 In view of the above circumstances, this invention was developed as a result of research aimed at developing a gas detection device equipped with a temperature compensation element that can reliably and highly maintain the gas sensitivity of the gas detection element. This method was completed after discovering that the desired compensation effect can be obtained by using a new metal oxide semiconductor, which has the same resistance temperature coefficient but has almost no gas sensitivity, as a temperature compensation element.
この発明に使用する温度補償素子は、酸化第二
スズ、酸化亜鉛を主成分とし、これにルビジウ
ム、イリジウム化合物の一種又は二種以上を
0.1wt％から3wt％の範囲で添加し、焼成してな
る焼結体から構成される。 The temperature compensation element used in this invention has stannic oxide and zinc oxide as main components, and one or more of rubidium and iridium compounds.
It is composed of a sintered body that is added in a range of 0.1wt% to 3wt% and fired.
ここで、ルビジウム、イリジウム化合物の添加
範囲を0.1wt％から3wt％としたのは、0.1wt％以
下或は3wt％以上では十分な温度補償効果が得ら
れないためである。 Here, the reason why the addition range of rubidium and iridium compounds is set from 0.1 wt% to 3 wt% is because a sufficient temperature compensation effect cannot be obtained if the amount is less than 0.1 wt% or more than 3 wt%.
例えば酸化第二スズに塩化パラジウムを添加し
た場合にはプロパンガス感度は向上するのである
が、酸化第二スズにルビジウム、イリジウム化合
物を添加すると、酸化第二スズのプロパンガス感
度は完全に失われる。 For example, when palladium chloride is added to stannic oxide, the propane gas sensitivity improves, but when rubidium or iridium compounds are added to stannic oxide, the propane gas sensitivity of stannic oxide is completely lost. .
第１図は、種々の触媒を酸化第二スズに添加し
た素子のプロパンガス検知特性を示すものであ
る。これによれば、添加によつて無添加の酸化第
二スズ素子より高い感度を示したが、オスミウ
ム、ロジウムについては無添加の酸化第二スズ素
子と同程度の感度を示し、ルビジウムについては
プロパンガスに対する検出能力を失わせる効果を
もつており、またイリジウムについてはこれより
低温度焼成して素子を製造した場合にプロパンガ
ス検出能力を失わせる。この効果はｎ型半導体を
原子価制御することによりｐ型半導体化した結果
得られたものである。 FIG. 1 shows the propane gas detection characteristics of devices in which various catalysts are added to stannic oxide. According to this, the dopant showed higher sensitivity than the undoped stannic oxide element, but it showed the same sensitivity for osmium and rhodium as the undoped stannic oxide element, and for rubidium it showed the same sensitivity as the unadded stannic oxide element. It has the effect of causing a loss of gas detection ability, and when an element is manufactured by firing iridium at a lower temperature than this, it causes a loss of propane gas detection ability. This effect was obtained as a result of converting an n-type semiconductor into a p-type semiconductor by controlling the valence.
また、ガス検知素子とこの発明に係る温度補償
素子の抵抗温度特性の比較は第２図に示す。ここ
でガス検知素子は93wt％酸化第二スズ、1wt％塩
化パラジウム、1wt％焼結助剤、5wt％ガラス成
分を主成分とするものを使用した。Ａは、検知素
子の空気中における抵抗温度曲線、Ｃは、検知素
子のプロパンガス0.1v％含む空気中における抵抗
温度曲線を示す。また温度補償素子は92wt％酸
化第二スズ、1wt％塩化パラジウム、1wt％塩化
ルビジウム、1wt％焼結助剤、5wt％ガラス成分
を主成分とするものを使用した。Ｂは、温度補償
素子の空気中における抵抗温度曲線、Ｄは、温度
補償素子のプロパンガス0.1v％含む空気中におけ
る抵抗温度曲線を示す。 Further, a comparison of the resistance temperature characteristics of the gas detection element and the temperature compensation element according to the present invention is shown in FIG. Here, the gas sensing element used was one whose main components were 93 wt% stannic oxide, 1 wt% palladium chloride, 1 wt% sintering aid, and 5 wt% glass. A shows the resistance temperature curve of the sensing element in air, and C shows the resistance temperature curve of the sensing element in air containing 0.1v% propane gas. Moreover, the temperature compensation element used was one whose main components were 92wt% stannic oxide, 1wt% palladium chloride, 1wt% rubidium chloride, 1wt% sintering aid, and 5wt% glass component. B shows the resistance temperature curve of the temperature compensation element in air, and D shows the resistance temperature curve of the temperature compensation element in air containing 0.1 v% of propane gas.
第２図によれば、検知素子はガス検知前後でＡ
とＣの電気抵抗比率が最大を示すときの素子温
度、即ち250℃から450℃の間のある特定温度で測
定を行うのであるが、ＡとＣの電気抵抗比率が素
子温度で変わるため、温度補償する必要がある。
この場合ＣとＤの電気抵抗比率は、第２図より明
らかなように素子温度に関係なく常に一定である
から検知素子の温度補償素子として利用すること
ができるのである。 According to Figure 2, the detection element is A before and after gas detection.
Measurements are made at the element temperature when the electrical resistance ratio of It is necessary to compensate.
In this case, the electric resistance ratio between C and D is always constant regardless of the element temperature, as is clear from FIG. 2, so it can be used as a temperature compensating element for the sensing element.
尚、第２図にはＣとＤの電気抵抗比率が素子温
度に関係なく常に一定である場合を示したが、検
知ガスの種類或は検知素子の成分が異なる場合に
は、この比率が一定でなくなることもある。 Note that although Figure 2 shows the case where the electrical resistance ratio of C and D is always constant regardless of the element temperature, if the type of sensing gas or the component of the sensing element is different, this ratio will be constant. Sometimes it disappears.
このような場合には、素子の抵抗温度係数の低
下に寄与するオスミウム化合物、ロジウムの１種
又は２種以上を素子中に加えて検知素子と温度補
償素子の電気抵抗比率を一定にしてもよい。 In such cases, one or more types of osmium compounds and rhodium, which contribute to lowering the temperature coefficient of resistance of the element, may be added to the element to keep the electrical resistance ratio between the sensing element and the temperature compensation element constant. .
第３図は、オスミウム化合物、ロジウムが素子
の抵抗温度係数の低下に寄与することを示す素子
の抵抗温度特性曲線である。ここで(イ)は塩化ルビ
ジウム0.7wt％添加した酸化第二スズ素子の抵抗
温度曲線、(ロ)は塩化イリジウム1.7wt％添加した
酸化第二スズ素子の抵抗温度曲線、(ハ)は酸化オス
ミウム1.4wt％添加した酸化第二スズ素子の抵抗
温度曲線、(ニ)はロジウム粉末0.6wt％添加した酸
化第二スズ素子の抵抗温度曲線、(ホ)は塩化パラジ
ウム1wt％添加した酸化第二スズ素子の抵抗温度
曲線を示す。 FIG. 3 is a resistance-temperature characteristic curve of the device showing that the osmium compound and rhodium contribute to lowering the temperature coefficient of resistance of the device. Here, (a) is the resistance temperature curve of the stannic oxide element doped with 0.7wt% rubidium chloride, (b) is the resistance temperature curve of the stannic oxide element doped with 1.7wt% iridium chloride, and (c) is the resistance temperature curve of the stannic oxide element doped with 1.7wt% iridium chloride. Resistance temperature curve of stannic oxide element doped with 1.4 wt%, (d) is resistance temperature curve of stannic oxide element doped with 0.6 wt% rhodium powder, (e) shows resistance temperature curve of stannic oxide element doped with 1 wt% palladium chloride. The resistance temperature curve of the element is shown.
これより明らかな如く、ルビジウム、イリジウ
ム、パラジウムについては抵抗温度係数の低下が
全く認められなかつたが、酸化オスミウムとロジ
ウムについては抵抗温度係数の低下に寄与する。
したがつてオスミウム化合物、ロジウムの１種又
は２種以上を、ガス検知素子の特性に合致するよ
うに0.1wt％から3wt％の範囲内で素子中に配合
すれば、検知素子と温度補償素子の電気抵抗比率
を一定にすることができる。 As is clear from this, no reduction in the temperature coefficient of resistance was observed for rubidium, iridium, and palladium, but osmium oxide and rhodium contributed to a reduction in the temperature coefficient of resistance.
Therefore, if one or more types of osmium compounds and rhodium are mixed into the element in a range of 0.1wt% to 3wt% to match the characteristics of the gas sensing element, the sensing element and temperature compensation element can be combined. The electrical resistance ratio can be kept constant.
なお、オスミウム化合物、ロジウムの配合量が
0.1wt％以下では周囲温度による素子特性の変動
を補償する効果が低下し、また3wt％以上では配
合物によるガス感度選択能力の変化を考慮する必
要が生じてくる。 In addition, the amount of osmium compound and rhodium is
Below 0.1 wt%, the effect of compensating for fluctuations in device characteristics due to ambient temperature decreases, and above 3 wt%, it becomes necessary to consider changes in the ability to select gas sensitivity due to the composition.
尚、オスミウム、ロジウムは第１図にも示した
ようにガス感度については無添加の酸化第二スズ
素子と同程度の感度を示すため、ガスによる影響
がなく、したがつて検知素子、温度補償素子のい
ずれに配合してもよい。 As shown in Figure 1, osmium and rhodium exhibit gas sensitivity comparable to that of an additive-free stannic oxide element, so they are not affected by gas, and therefore the sensing element and temperature compensation It may be added to any of the elements.
次に、この発明に係る温度補償素子を利用した
補償法について説明すると、この補償は検知素子
を組み込んだ検知回路に、温度補償素子を組み込
んだ温度補償回路を併設した装置を利用すること
により行うことができる。 Next, a compensation method using a temperature compensation element according to the present invention will be explained. This compensation is performed by using a device in which a temperature compensation circuit incorporating a temperature compensation element is attached to a detection circuit incorporating a detection element. be able to.
例えば、ブリツジ回路の一辺に検知素子を組み
込み、他の一辺に温度補償素子を組み込んだ回路
装置を利用することができる。即ち、被検知ガス
を含むガスが検知素子を通過する際の電気抵抗値
を温度補償素子によつて補償して測定し、該測定
値よりガス中の被検知ガス量を測定するのであ
る。 For example, a circuit device can be used in which a sensing element is built into one side of the bridge circuit and a temperature compensation element is built into the other side. That is, the electrical resistance value of the gas containing the gas to be detected passes through the sensing element is compensated and measured by the temperature compensating element, and the amount of the gas to be detected in the gas is determined from the measured value.
この場合検知素子と温度補償素子の温度が同一
でないこと、検知素子と温度補償素子の電気抵抗
比率が一定になり得ず、補償効果が発揮できな
い。しかし、検知素子と温度補償素子の温度は、
電源電圧変動や環境温度変化の影響を受けるとこ
ろからこれを同一にすることは困難である。 In this case, the temperatures of the sensing element and the temperature compensating element are not the same, and the electric resistance ratio of the sensing element and the temperature compensating element cannot be constant, so that no compensation effect can be achieved. However, the temperature of the sensing element and temperature compensation element is
It is difficult to make them the same because they are affected by power supply voltage fluctuations and environmental temperature changes.
この発明では、電源電圧変動や環境温度変化の
影響を受けないようにするために、第４図に示す
ように加熱可能な電気絶縁体基板１の一面には両
端に電極２ａ，２ｂを有する加熱抵抗体３を設
け、電極２ａ，２ｂには加熱用電源４を接続する
とともに、基板１の他面には両端に電極５ａ，５
ｂを有するガス検知素子６と両端に電極７ａ，７
ｂを有する温度補償素子８を設け、更にガス検知
素子６、温度補償素子８及び固定抵抗Ｒ、可変抵
抗R′でガス検知用ブリツヂ回路を構成する。 In this invention, in order to avoid the influence of power supply voltage fluctuations and environmental temperature changes, as shown in FIG. A resistor 3 is provided, a heating power source 4 is connected to the electrodes 2a and 2b, and electrodes 5a and 5 are connected to the other side of the substrate 1 at both ends.
gas sensing element 6 having a
A temperature compensating element 8 having a temperature compensation element 8 is provided, and a bridge circuit for gas detection is further comprised of the gas detecting element 6, the temperature compensating element 8, a fixed resistor R, and a variable resistor R'.
そしてガス検知測定に際しては加熱用電源４に
よつて加熱抵抗体３を加熱し、ガス検知素子６と
温度補償素子８を同一の加熱条件下において温度
補償しながらガス検知を行うのである。 During gas detection and measurement, the heating resistor 3 is heated by the heating power source 4, and the gas detection is performed while compensating the temperature of the gas detection element 6 and temperature compensation element 8 under the same heating conditions.
この場合ガス検知素子６と温度補償素子８は同
一の加熱条件下に置かれているため、電源電圧変
動や環境温度変化の影響を受けることなく測定す
ることができ、したがつて出力端子Ｏからは正確
に温度補償された測定値を取出すことができる。 In this case, since the gas detection element 6 and the temperature compensation element 8 are placed under the same heating conditions, measurement can be performed without being affected by power supply voltage fluctuations or environmental temperature changes. can take accurate temperature compensated measurements.
尚、第４図の実施例では、加熱可能な電気絶縁
体基板１の裏面に加熱抵抗体４を設け、該加熱抵
抗体３を加熱する例について述べたが、加熱抵抗
体３を設けなくても電源電圧変動や環境温度変化
の影響を受けないような場合には、同一基板上に
検知素子と温度補償素子を設ければよい。 In the embodiment shown in FIG. 4, the heating resistor 4 is provided on the back surface of the heatable electrical insulating substrate 1, and the heating resistor 3 is heated. However, the heating resistor 3 may not be provided. If the sensor is not affected by power supply voltage fluctuations or environmental temperature changes, the sensing element and the temperature compensation element may be provided on the same substrate.
一方、上記実施例では温度補償素子を用いてガ
ス検知素子の温度補償を行う例について述べた
が、ガス検知素子にオスミウム化合物、ロジウム
の１種又は２種以上を配合して温度特性のないよ
うな検知素子を形成し、これを用いてガス検知を
行えば、特別に温度補償素子を用いなくても温度
補償された検知を行うことができる。 On the other hand, in the above embodiment, an example was described in which the temperature compensation element is used to compensate for the temperature of the gas detection element. By forming a sensing element and performing gas detection using this, temperature-compensated sensing can be performed without using a special temperature-compensating element.
また、この実施例ではプロパンガスについて述
べたが、金属酸化物中に配合するパラジウム、ル
ビジウム、イリジウム、オスミウム、ロジウムの
種類を選択し、また添加量を選択することにより
一酸化炭素ガス、都市ガス等のガス検知の温度補
償も行うことができる。 In this example, propane gas was described, but by selecting the types of palladium, rubidium, iridium, osmium, and rhodium mixed in the metal oxide, and by selecting the amount added, carbon monoxide gas, city gas, etc. Temperature compensation for gas detection can also be performed.
第５図は、パラジウム、ルビジウムを酸化第二
スズに添加した場合のプロパンガス（実線）、一
酸化炭素ガス（破線）の選択特性を示すものであ
り、このようにガス選択性の異なる素子を使用す
ることにより２種以上のガスを含む場合のガス検
知を行うことができる。 Figure 5 shows the selectivity characteristics of propane gas (solid line) and carbon monoxide gas (dashed line) when palladium and rubidium are added to stannic oxide. By using this, it is possible to detect gases containing two or more types of gases.
第６図は、２種以上のガスを含む場合のガス検
知の実施態様を示すものであり、電気絶縁体基板
１の一面にはガス検知素子６と温度補償素子８の
他にガス検知素子６′、温度補償素子８′を設け、
第４図に示すようにガス検知素子６、温度補償素
子８を組込んだブリツヂ回路を構成するとともに
ガス検知素子６′、温度補償素子８′を組込んだブ
リツヂ回路を構成する。 FIG. 6 shows an embodiment of gas detection when two or more types of gases are included. ', a temperature compensation element 8' is provided,
As shown in FIG. 4, a bridge circuit incorporating a gas sensing element 6 and a temperature compensating element 8 is constructed, and a bridge circuit incorporating a gas sensing element 6' and a temperature compensating element 8' is constructed.
そしてガス検知測定に際しては加熱用電源４に
よつて加熱抵抗体３を加熱し、ガス検知素子６，
６′、温度補償素子８，８′を同一の加熱条件下に
おいて温度補償しながらガス検知を行うのであ
る。 When performing gas detection measurement, the heating resistor 3 is heated by the heating power source 4, and the gas detection element 6,
Gas detection is performed while temperature compensating the temperature compensating elements 6' and 8' under the same heating condition.
この場合ガス検知素子６，６′にガス選択性あ
るいは素子を使用すれば、２種のガス、例えばプ
ロパンと一酸化炭素が別々の素子に検知される。
そこで多種類のガスを同時に、しかも温度補償さ
れて正確に測定することができるのである。 In this case, if gas selectivity or elements are used for the gas detection elements 6, 6', two types of gases, for example propane and carbon monoxide, are detected by separate elements.
Therefore, it is possible to measure many types of gases simultaneously and accurately with temperature compensation.
更に、この発明で製造されたガス検知素子は故
障がなく、微弱素子温度変化も瞬時に確実に補償
でき、かつ安価で小型化したものを得ることがで
きる。 Furthermore, the gas detection element manufactured according to the present invention has no failures, can instantaneously and reliably compensate for slight changes in element temperature, and can be made inexpensive and compact.
次に、この発明を実施例によつて具体的に説明
するが、この発明はこの要旨を超えない限り、以
下の実施例に限定されるものでない。 Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例
93wt％酸化第二スズ、1wt％塩化パラジウム、
1wt％焼結助剤、5wt％ガラス成分を主成分とす
るガス検知素子６は素子温度300℃のとき最大プ
ロパンガス感度を示した。Example 93wt% stannic oxide, 1wt% palladium chloride,
Gas sensing element 6, whose main components were 1wt% sintering aid and 5wt% glass, exhibited maximum propane gas sensitivity when the element temperature was 300°C.
一方、92wt％酸化第二スズ、1wt％塩化パラジ
ウム、1wt％塩化ルビジウム、1wt％焼結助剤、
5wt％ガラス成分を主成分とする温度補償素子８
は、ガス検知素子６と同じ抵抗温度特性をもちな
がらガスに極めて感応しにくい特性をもつもので
あつた。 Meanwhile, 92wt% stannic oxide, 1wt% palladium chloride, 1wt% rubidium chloride, 1wt% sintering aid,
Temperature compensation element 8 whose main component is 5wt% glass component
Although it had the same resistance-temperature characteristics as gas detection element 6, it was extremely insensitive to gas.
この両素子を電気絶縁体基板１上に印刷し、
650℃から800℃の電気炉中で焼成し、第４図に示
した電気回路に組み込むことにより、ガス感度は
電源電圧変動や環境温度変化の影響を受けること
なく測定することができた。 Both elements are printed on an electrical insulator substrate 1,
By firing in an electric furnace at 650°C to 800°C and incorporating it into the electrical circuit shown in Figure 4, gas sensitivity could be measured without being affected by power supply voltage fluctuations or environmental temperature changes.
第１図は、種々の触媒を添加した素子のガス検
出特性を示す図、第２図は、素子の表面温度に対
しての電気抵抗特性を示す図、第３図は、種々の
触媒を添加した場合の抵抗温度特性を示す図、第
４図は、この発明の一実施態様を示す回路装置の
概略図、第５図は、種々の触媒を添加した場合の
ガス選択特性を示す図、第６図は、２種以上のガ
スを同時に検知する場合の実施態様を示す図。
Figure 1 shows the gas detection characteristics of the element with various catalysts added. Figure 2 shows the electrical resistance characteristics with respect to the surface temperature of the element. Figure 3 shows the gas detection characteristics of the element with various catalysts added. 4 is a schematic diagram of a circuit device showing an embodiment of the present invention. FIG. 5 is a diagram showing gas selection characteristics when various catalysts are added. FIG. 6 is a diagram showing an embodiment in which two or more types of gas are detected simultaneously.
Claims (1)
検知装置において、該温度補償素子として酸化第
二スズ、酸化亜鉛を主成分とし、これにルビジウ
ム、イリジウム化合物の１種又は２種以上を
0.1wt％から3wt％添加して焼成してなる焼結体
を使用することを特徴とするガス検知装置。 ２ 温度補償素子を備えた金属酸化物半導体ガス
検知装置において、該温度補償素子として酸化第
二スズ、酸化亜鉛を主成分とし、これにルビジウ
ム、イリジウム化合物の１種又は２種以上を
0.1wt％から3wt％添加し、更にオスミウム化合
物、ロジウムの１種又は２種以上を0.1wt％から
3wt％添加して焼成してなる焼結体を使用するこ
とを特徴とするガス検知装置。[Scope of Claims] 1. A metal oxide semiconductor gas detection device equipped with a temperature compensation element, which contains stannic oxide and zinc oxide as main components, and one or two of rubidium and iridium compounds. more than seeds
A gas detection device characterized by using a sintered body formed by adding 0.1wt% to 3wt% and firing. 2. In a metal oxide semiconductor gas detection device equipped with a temperature compensation element, the temperature compensation element contains stannic oxide and zinc oxide as main components, and one or more of rubidium and iridium compounds.
Add from 0.1wt% to 3wt%, and further add one or more of osmium compounds and rhodium from 0.1wt%.
A gas detection device characterized by using a sintered body made by adding 3wt% and firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7347079A JPS55166032A (en) | 1979-06-13 | 1979-06-13 | Gas detecting element and gas detecting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7347079A JPS55166032A (en) | 1979-06-13 | 1979-06-13 | Gas detecting element and gas detecting method |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25509885A Division JPS61221638A (en) | 1985-11-15 | 1985-11-15 | Gas detecting element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55166032A JPS55166032A (en) | 1980-12-24 |
| JPS6116018B2 true JPS6116018B2 (en) | 1986-04-26 |
Family
ID=13519184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7347079A Granted JPS55166032A (en) | 1979-06-13 | 1979-06-13 | Gas detecting element and gas detecting method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55166032A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59188549A (en) * | 1983-04-11 | 1984-10-25 | Shinkosumosu Denki Kk | Two-terminal type semiconductor gas detecting element |
| JPS6244252U (en) * | 1985-09-04 | 1987-03-17 | ||
| US5012671A (en) * | 1988-11-15 | 1991-05-07 | Ricoh Company, Ltd. | Gas detecting device |
| CN104040347B (en) * | 2012-04-30 | 2016-06-15 | 科学与工业研究会 | For the sensor combinations thing that the acetone in breathing detects |
-
1979
- 1979-06-13 JP JP7347079A patent/JPS55166032A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55166032A (en) | 1980-12-24 |
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