JP2001235442A - Gas sensor - Google Patents
Gas sensorInfo
- Publication number
- JP2001235442A JP2001235442A JP2000048816A JP2000048816A JP2001235442A JP 2001235442 A JP2001235442 A JP 2001235442A JP 2000048816 A JP2000048816 A JP 2000048816A JP 2000048816 A JP2000048816 A JP 2000048816A JP 2001235442 A JP2001235442 A JP 2001235442A
- Authority
- JP
- Japan
- Prior art keywords
- film
- heater
- platinum
- glass
- gas
- 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
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、家庭用ガス漏れ警
報器などに用いられるガスセンサに関し、特に消費電力
を少なくしたガスセンサ実現のためのヒータ膜を、簡単
な製法と品質管理で提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas sensor used for a gas leak alarm device for home use, and more particularly to a heater film for realizing a gas sensor with reduced power consumption by a simple manufacturing method and quality control. is there.
【０００２】[0002]
【従来の技術】ガスセンサは、例えば、一酸化炭素やメ
タンガス、プロパンガスに選択的に感応し、家庭用ガス
漏れ警報器などに用いられる。この種のガス漏れ警報器
は、商用電源の１００Ｖを用いて作動するが、設置性を
改善するために乾電池で駆動するなどの低消費電力タイ
プが最近提案されている。図３は、特開平１１−８３７
７７号公報に記載された従来のガスセンサの構造であ
る。このガスセンサは、酸化錫などの金属酸化物薄膜か
らなるガス検知部１を、電機絶縁層２を介して動作温度
保持用のヒータ３の上面に形成した構成としている。ヒ
ータ３は、スパッタ法により形成された薄膜であり、そ
の材質はＮｉ−Ｃｒ系合金、Ｆｅ−Ｃｒ系合金、Ｓｉ
Ｃ、ＲｕＯ2、ＭｏＳｉＯ2、ＷＳｉ2、ＴａＳｉ2、のう
ちのいずれかである。そして、その比抵抗は、これら材
料固有の比抵抗０．４〜１．４×１０-6Ωmを組み合わ
せた０．４０×１０-6Ωm以上が良いとしている。ま
た、ヒータ３は、熱絶縁層４を介在させて支持基板５の
上部に積層されている。2. Description of the Related Art A gas sensor selectively responds to, for example, carbon monoxide, methane gas, and propane gas, and is used for a household gas leak alarm. This type of gas leak alarm operates using a commercial power supply of 100 V, but a low power consumption type such as driving with a dry battery has been recently proposed to improve installation. FIG.
It is a structure of a conventional gas sensor described in JP-A-77-77. This gas sensor has a configuration in which a gas detection unit 1 made of a thin film of a metal oxide such as tin oxide is formed on an upper surface of a heater 3 for maintaining an operating temperature via an electric insulating layer 2. The heater 3 is a thin film formed by a sputtering method, and is made of a Ni—Cr alloy, a Fe—Cr alloy, Si
C, RuO 2, MoSiO 2, WSi 2, TaSi 2, is one of. The specific resistance is preferably 0.40 × 10 −6 Ωm or more obtained by combining the specific resistances of these materials of 0.4 to 1.4 × 10 −6 Ωm. Further, the heater 3 is stacked on the support substrate 5 with the heat insulating layer 4 interposed therebetween.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来例
で使用される材料のヒータは、下記の３つの問題点があ
った。第１の問題点は、消費電力を小さくする目的でヒ
ータの抵抗を大きくするための、ヒータ膜厚の薄膜化お
よび線幅の極細化に関して高度で複雑な製造技術と精度
の高い品質管理を必要とする問題である。第２の問題点
は、ヒータの耐久酸化劣化を防止するためにその上部に
形成される、電気絶縁層の気密性に関して高度で複雑な
製造技術と精度の高い品質管理を必要とする問題であ
る。第３の問題点は、センサ動作温度を長期間にわたり
同一に維持するための制御回路が複雑になる問題であ
る。However, the heater made of the material used in the conventional example has the following three problems. The first problem is that, in order to increase the resistance of the heater in order to reduce the power consumption, it is necessary to use a sophisticated and complicated manufacturing technique and highly accurate quality control for thinning the heater film thickness and making the line width extremely thin. It is a problem. The second problem is a problem that requires a sophisticated and complicated manufacturing technique and high-precision quality control regarding the airtightness of the electric insulating layer formed on the heater in order to prevent the durable oxidation deterioration of the heater. . A third problem is that a control circuit for maintaining the same sensor operating temperature for a long period of time becomes complicated.
【０００４】第１の問題点について説明する。ヒータ
は、材料固有の比抵抗０．４〜１．４×１０-6Ωmを組
み合わせた０．４０×１０-6Ωm以上が良いとしている
訳だが、その組み合わせでは特開平１１−８３７７７号
公報の明細書本文に記載された２×１０-6Ωmが実用レ
ベルにおいて上限であり、それ以上の比抵抗値の実現は
高度で複雑な技術を必要とする。一方、この小さい比抵
抗の材料を用いてヒータの消費電力を小さくするために
は、ヒータ膜厚を薄膜化および線幅を極細化してヒータ
抵抗を大きくすればよい。しかしながら、このヒータ膜
厚の薄膜化および線幅の極細化は、高度で複雑な製造技
術と精度の高い品質管理を必要とする。[0004] The first problem will be described. The heater preferably has a specific resistance of 0.40 × 10 −6 Ωm or more obtained by combining the specific resistances of the materials of 0.4 to 1.4 × 10 −6 Ωm. The upper limit of the practical level is 2 × 10 −6 Ωm described in the text of the specification, and realization of a higher specific resistance value requires a sophisticated and complicated technique. On the other hand, in order to reduce the power consumption of the heater by using the material having the small specific resistance, the heater thickness may be reduced and the line width may be reduced to increase the heater resistance. However, the thinning of the heater film thickness and the thinning of the line width require advanced and complicated manufacturing techniques and high-quality control.
【０００５】第２の問題点について説明する。ヒータの
材質は、Ｎｉ−Ｃｒ系合金、Ｆｅ−Ｃｒ系合金、Ｓｉ
Ｃ、ＲｕＯ2、ＭｏＳｉＯ2、ＷＳｉ2、ＴａＳｉ2、であ
るが、これらを発熱材としてそのまま空気中で長期間使
用すると酸化されて抵抗値が著しく増大する。このヒー
タの耐久酸化劣化を防止するため、その上部に気密性の
電気絶縁層を形成する訳であるが、この気密性の高い電
気絶縁層の形成には、高度で複雑な製造技術と精度の高
い品質管理とを必要とする。The second problem will be described. The material of the heater is Ni-Cr alloy, Fe-Cr alloy, Si
C, RuO 2, MoSiO 2, WSi 2, TaSi 2, a but, the resistance value is oxidized with these is used directly for a long time in the air as a heating member is increased remarkably. In order to prevent the durable oxidation and deterioration of the heater, an airtight electric insulating layer is formed on the heater. However, the formation of this highly airtight electric insulating layer requires sophisticated and complicated manufacturing technology and precision. Requires high quality control.
【０００６】第３の問題点について説明する。ヒータ
は、その上部に気密性の高い電気絶縁層を形成して酸化
劣化が起こりにくくしているが、ヒータ膜の膜厚が薄い
ためここを流れる電流の電流密度が高い。そのため、長
期間使用すると熱劣化して抵抗値が僅かに増大する。こ
の抵抗変化が起った場合に、例えば、直流電圧を印加し
て発熱させる方式では流れる電流が変化し、これにとも
ないセンサ動作温度が変化してセンサ出力が変化する問
題が起る。これを防ぐため、定電力を印加してセンサ動
作温度を長期間にわたり同一に維持する訳だが、この定
電力印加方式は制御回路が複雑になる問題がある。The third problem will be described. The heater has a highly airtight electrical insulating layer formed thereon to prevent oxidation deterioration. However, since the heater film is thin, the current density of the current flowing therethrough is high. Therefore, when used for a long period of time, the resistance is slightly increased due to thermal deterioration. When this resistance change occurs, for example, in a method in which a DC voltage is applied to generate heat, the flowing current changes, and the sensor operating temperature changes with this, causing a problem that the sensor output changes. In order to prevent this, a constant power is applied to keep the sensor operating temperature the same for a long period of time. However, this constant power application method has a problem that a control circuit becomes complicated.
【０００７】本発明は、前記する従来の課題を解決し、
消費電力を少なくしたガスセンサ実現のためのヒータ膜
を簡単な製法と品質管理で提供することを目的とするも
のである。[0007] The present invention solves the above-mentioned conventional problems,
It is an object of the present invention to provide a heater film for realizing a gas sensor with reduced power consumption by a simple manufacturing method and quality control.
【０００８】[0008]
【課題を解決するための手段】本発明は上記課題を解決
するために、絶縁性支持基板と、絶縁性支持基板の一方
の面に順に積層させたヒータ膜と、気密性を有する絶縁
膜と、ガス感応膜とから構成され、ヒータ膜は、主成分
の耐酸化性発熱材料と副成分の耐熱性金属酸化物と結合
材のガラスとからなる印刷焼成膜であり、比抵抗が２３
〜２２８６×１０-6Ωmであるとした。In order to solve the above-mentioned problems, the present invention provides an insulating support substrate, a heater film sequentially laminated on one surface of the insulating support substrate, and an airtight insulating film. , A gas-sensitive film, and the heater film is a printed and fired film made of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and glass as a binder, and has a specific resistance of 23.
２２2286 × 10 −6 Ωm.
【０００９】ヒータ膜は、主成分の耐酸化性発熱材料に
副成分の耐熱性金属酸化物を混ぜ、これらをガラスで結
合させた印刷焼成膜である。そのため、その比抵抗は、
一般的な耐酸化性発熱材料である白金の０．１０×１０
-6Ωm（２５℃の値）よりはるか大きく、その値は２３
〜２２８６×１０-6Ωmに調整されている。そのため、
ヒータ膜は、単純な小面積形状に厚膜印刷するだけで、
膜厚が厚く線幅が太くても大きな抵抗が簡単に得られ、
複雑な製造技術と品質管理技術を必要としない。また、
ヒータ膜の長さが短くできるので、ガスセンサが小型化
して熱容量が低減し、消費電力が少さくできる。The heater film is a printing and firing film in which a heat-resistant metal oxide as a main component is mixed with an oxidation-resistant heat-generating material as a main component, and these are combined with glass. Therefore, its specific resistance is
0.10 × 10 of platinum, a general oxidation resistant heat generating material
-6 Ωm (at 25 ° C), which is 23
It is adjusted to ８６2286 × 10 −6 Ωm. for that reason,
The heater film is simply printed on a thick film in a simple small area shape.
Even if the film thickness is large and the line width is large, a large resistance can be easily obtained.
No complicated manufacturing and quality control techniques are required. Also,
Since the length of the heater film can be shortened, the gas sensor can be downsized, the heat capacity can be reduced, and the power consumption can be reduced.
【００１０】また、ヒータ膜は耐酸化性発熱材料を使用
しているため、空気酸化に強く抵抗値の増大が小さい。
従って、その上部に形成する電気絶縁層は一般的な気密
性でよく、その形成は簡単な製造技術と品質管理で対応
できる。しかも、ヒータ膜は厚膜化しているため、電流
密度が低減しヒータ膜の抵抗変化は極めて小さくなる。
このため、直流電圧を印加して発熱させる方式でセンサ
動作温度を長期間一定にすることができて、制御回路が
簡単になる。Further, since the heater film uses an oxidation-resistant heat-generating material, it is resistant to air oxidation and has a small increase in resistance value.
Therefore, the electrical insulating layer formed thereon may be of a general hermeticity, and the formation can be handled by a simple manufacturing technique and quality control. In addition, since the heater film is thickened, the current density is reduced, and the change in resistance of the heater film is extremely small.
Therefore, the operating temperature of the sensor can be kept constant for a long time by applying a DC voltage to generate heat, and the control circuit is simplified.
【００１１】[0011]
【発明の実施の形態】本発明は、各請求項に記載した発
明の形態で実施することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention can be embodied in the embodiments described in the claims.
【００１２】すなわち、請求項１に記載の発明は、絶縁
性支持基板と、前記絶縁性支持基板の一方の面に順に積
層させたヒータ膜と、気密性を有する絶縁膜と、ガス感
応膜とから構成され、前記ヒータ膜は、主成分の耐酸化
性発熱材料と副成分の耐熱性金属酸化物と結合材のガラ
スとからなる印刷焼成膜であり、比抵抗が２３〜２２８
６×１０-6Ωmであるガスセンサとすることで実施でき
る。That is, the invention according to claim 1 includes an insulating supporting substrate, a heater film sequentially laminated on one surface of the insulating supporting substrate, an airtight insulating film, and a gas-sensitive film. The heater film is a printed and fired film made of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and glass as a binder, and has a specific resistance of 23 to 228.
This can be implemented by using a gas sensor of 6 × 10 −6 Ωm.
【００１３】ヒータ膜は、主成分の耐酸化性発熱材料に
副成分の耐熱性金属酸化物を混ぜ、これらをガラスで結
合させた印刷焼成膜であり、その比抵抗が２３〜２２８
６×１０-6Ωmに調整されている。そのため、ヒータ膜
は膜厚が厚くしかも線幅も太くても大きな抵抗が得ら
れ、単純形状に厚膜印刷するだけで高抵抗のヒータ膜が
簡単に製造できる。しかも、ヒータ膜は、空気酸化に強
い材料を使用しているため抵抗値の増大が小さく、その
上部に形成する電気絶縁層は、一般的な気密性でよくそ
の形成は簡単な製造技術と品質管理で対応できる。ま
た、ヒータ膜を厚膜化しているため電流密度が低減し、
ヒータ膜の抵抗変化は極めて小さくなる。このため、直
流電圧を印加して発熱させる方式でセンサ動作温度を長
期間一定にすることができ、制御回路が簡単になる。The heater film is a printed baked film in which a heat-resistant metal oxide as a main component is mixed with a heat-resistant metal oxide as a main component and these are combined with glass, and has a specific resistance of 23 to 228.
It is adjusted to 6 × 10 −6 Ωm. Therefore, even if the heater film has a large thickness and a large line width, a large resistance can be obtained, and a high-resistance heater film can be easily manufactured only by printing a thick film in a simple shape. In addition, since the heater film uses a material that is resistant to air oxidation, the increase in resistance value is small, and the electric insulating layer formed on the heater film is generally airtight and the formation is easy with a simple manufacturing technique and quality. Can be managed by management. In addition, the current density is reduced due to the thicker heater film,
The resistance change of the heater film becomes extremely small. For this reason, the sensor operating temperature can be kept constant for a long period of time by applying a DC voltage to generate heat, and the control circuit is simplified.
【００１４】請求項２に記載の発明は、絶縁性支持基板
と、前記絶縁性支持基板の一方の面に形成されたヒータ
膜と、前記絶縁性支持基板の他面に形成されたガス感応
膜とから構成され、前記ヒータ膜は、主成分の耐酸化性
発熱材料と副成分の耐熱性金属酸化物と結合材のガラス
とからなる印刷焼成膜であり、比抵抗が２３〜２２８６
×１０-6Ωmであるガスセンサとすることで実施でき
る。According to a second aspect of the present invention, there is provided an insulating support substrate, a heater film formed on one surface of the insulating support substrate, and a gas-sensitive film formed on the other surface of the insulating support substrate. The heater film is a printed and fired film made of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and glass as a binder, and has a specific resistance of 23 to 2286.
It can be implemented by using a gas sensor of × 10 −6 Ωm.
【００１５】ヒータ膜は、主成分の耐酸化性発熱材料に
副成分の耐熱性金属酸化物を混ぜ、これらをガラスで結
合させた印刷焼成膜であり、その比抵抗が２３〜２２８
６×１０-6Ωmに調整されている。そのため、ヒータは
膜厚が厚くしかも線幅も太くても大きな抵抗が得られ、
単純形状に厚膜印刷するだけで高抵抗のヒータ膜が簡単
に製造できる。しかも、ヒータ膜は、空気酸化に強い材
料を使用しているため抵抗値の増大が小さく、さらにヒ
ータ膜を厚膜化しているため電流密度が低減し、ヒータ
膜の抵抗変化は極めて小さくなる。このため、直流電圧
を印加して発熱させる方式でセンサ動作温度を長期間一
定にすることができ、制御回路が簡単になる。The heater film is a printed and fired film obtained by mixing a heat-resistant metal oxide as a main component with a heat-resistant metal oxide as a sub-component and bonding them with glass, and has a specific resistance of 23 to 228.
It is adjusted to 6 × 10 −6 Ωm. Therefore, even if the heater has a large thickness and a large line width, a large resistance can be obtained.
A high-resistance heater film can be easily manufactured simply by printing a thick film in a simple shape. Moreover, since the heater film uses a material that is resistant to air oxidation, the increase in resistance value is small, and since the heater film is made thicker, the current density is reduced and the change in resistance of the heater film is extremely small. For this reason, the sensor operating temperature can be kept constant for a long period of time by applying a DC voltage to generate heat, and the control circuit is simplified.
【００１６】請求項３に記載の発明は、ヒータ膜が主成
分の白金と副成分のアルミナと結合材のガラスからなる
請求項１または２に記載のガスセンサとすることで実施
できる。According to a third aspect of the present invention, the gas sensor according to the first or second aspect can be implemented in which the heater film is made of platinum as a main component, alumina as a subcomponent, and glass as a binder.
【００１７】耐酸化性発熱材料として白金を使用してい
るため、空気酸化に強く抵抗値の増大が小さい。また、
高表面積と高融点のアルミナと、ガラスを副成分として
使用しているため、アルミナ粒子の表面に無数存在する
凹部に白金粒子がくいこみ、白金粒子が移動し難くなっ
ている。そのため、比抵抗の変化がない優れたヒータ膜
が得られる。Since platinum is used as the oxidation-resistant heat generating material, it is resistant to air oxidation and has a small increase in resistance. Also,
Since alumina having a high surface area and a high melting point and glass are used as subcomponents, platinum particles are entrapped in innumerable concave portions on the surface of the alumina particles, and the platinum particles are hard to move. Therefore, an excellent heater film having no change in specific resistance can be obtained.
【００１８】請求項４に記載の発明は、絶縁膜が、主成
分の硝子と、前記硝子の軟化温度より高い溶融温度を持
つ耐熱高表面積性金属酸化物の副成分からなる請求項１
記載のガスセンサとすることで実施できる。According to a fourth aspect of the present invention, the insulating film comprises glass as a main component and a sub-component of a heat-resistant high surface area metal oxide having a melting temperature higher than the softening temperature of the glass.
This can be implemented by using the gas sensor described above.
【００１９】耐熱高表面積性金属酸化物の表面に無数存
在する凹部に硝子が侵入して、硝子と耐熱高表面積性金
属酸化物が強固に固着し、絶縁膜の組成物がヒータ膜に
流れ込むことを抑制する。その結果、ヒータ膜や絶縁膜
は良好な電気特性および絶縁性を示し、これらの積層膜
の耐熱衝撃性も向上する。Glass penetrates into a myriad of concave portions present on the surface of the heat-resistant high-surface-area metal oxide, and the glass and the heat-resistant high-surface-area metal oxide are firmly fixed, and the composition of the insulating film flows into the heater film. Suppress. As a result, the heater film and the insulating film exhibit good electrical characteristics and insulating properties, and the thermal shock resistance of these laminated films is also improved.
【００２０】請求項５に記載の発明は、ガス感応膜が、
気密性の安定化ジルコニアスパッタ膜と、前記安定化ジ
ルコニアスパッタ膜の上部に形成した通気性の有る一対
の白金薄膜と、前記白金薄膜の片面上部に配置させた酸
化触媒層とからなり、前記安定化ジルコニアスパッタ膜
は、主成分のアルゴンに副成分の酸素を混合させたガス
雰囲気中で安定化ジルコニアをスパッタして得た品を８
００〜１３００℃で加熱焼成して得る請求項１または２
に記載のガスセンサとすることで実施できる。According to a fifth aspect of the present invention, the gas-sensitive film comprises:
An airtight hermetic zirconia sputtered film, a pair of air-permeable platinum thin films formed on the stabilized zirconia sputtered film, and an oxidation catalyst layer disposed on one side of the platinum thin film, The sputtered zirconia film was prepared by sputtering stabilized zirconia in a gas atmosphere in which oxygen as a main component was mixed with argon as a main component.
3. The composition according to claim 1, which is obtained by heating and baking at 00 to 1300 ° C.
It can be implemented by using the gas sensor described in (1).
【００２１】主成分のアルゴンに副成分の酸素を混合さ
せたガス雰囲気中でスパッタを行い、その後に８００〜
１３００℃の加熱エイジング処理を施した安定化ジルコ
ニアスパッタ膜であるため、結晶性や電導性に優れた安
定化ジルコニアの膜が得られて、大きなセンサ出力を有
するガスセンサとなる。Sputtering is carried out in a gas atmosphere in which oxygen as a main component is mixed with argon as a main component, and then 800 to
Since this is a stabilized zirconia sputtered film subjected to a heat aging treatment at 1300 ° C., a stabilized zirconia film excellent in crystallinity and electrical conductivity is obtained, and the gas sensor has a large sensor output.
【００２２】請求項６に記載の発明は、フッ素樹脂を主
成分とする被膜を、一対の白金薄膜の間に貼付して、白
金分子もしくは原子を真空中で蒸発させて白金薄膜を形
成する請求項５記載のガスセンサとすることで実施でき
る。According to a sixth aspect of the present invention, there is provided a method of forming a platinum thin film by adhering a coating mainly composed of a fluororesin between a pair of platinum thin films and evaporating platinum molecules or atoms in a vacuum. Item 5 can be implemented by using the gas sensor.
【００２３】フッ素樹脂を主成分とする被膜を、一対の
白金薄膜の間に貼付して、白金分子もしくは原子を真空
中で蒸発させて白金薄膜を形成しているため、白金薄膜
の間に付着する白金量が減少し、ガスセンサの出力が増
大する。A film mainly composed of a fluororesin is adhered between a pair of platinum thin films, and platinum molecules or atoms are evaporated in vacuum to form a platinum thin film. The amount of platinum generated decreases, and the output of the gas sensor increases.
【００２４】[0024]
【実施例】以下、本発明の実施例を添付図面に基づいて
説明する。Embodiments of the present invention will be described below with reference to the accompanying drawings.
【００２５】（実施例１）図１は本発明の第１の実施例
であるガスセンサの断面図である。ガスセンサは、絶縁
性支持基板６と、絶縁性支持基板６の一方の面に順に積
層させたヒータ膜７と、気密性を有する絶縁膜８と、ガ
ス感応膜９とから構成される。ヒータ膜７は、主成分の
耐酸化性発熱材料と副成分の耐熱性金属酸化物と結合材
のガラスとからなる印刷焼成膜であり、比抵抗が２３〜
２２８６×１０-6Ωmに調整されている。Embodiment 1 FIG. 1 is a sectional view of a gas sensor according to a first embodiment of the present invention. The gas sensor includes an insulating support substrate 6, a heater film 7 sequentially laminated on one surface of the insulating support substrate 6, an airtight insulating film 8, and a gas sensitive film 9. The heater film 7 is a printed and fired film made of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and glass as a binder, and has a specific resistance of 23 to
It is adjusted to 2286 × 10 −6 Ωm.
【００２６】ガス感応膜９は、安定化ジルコニアスパッ
タ膜１０と、安定化ジルコニアスパッタ膜１０の上部に
形成した通気性を有する一対の白金薄膜１１，１２と、
片面の白金薄膜１１の上部に配置させた通気性と耐熱性
を有する酸化触媒層１３とからなる。安定化ジルコニア
スパッタ膜１０は、主成分のアルゴンに副成分の酸素を
混合させたガス雰囲気中で安定化ジルコニアをスパッタ
して得た０．５〜５μm膜厚品を８００〜１３００℃で
加熱焼成して得る。白金薄膜１１，１２は、アルゴンガ
ス雰囲気中で白金をスパッタして得た０．１〜０．５μ
m膜厚品である。The gas-sensitive film 9 includes a stabilized zirconia sputtered film 10, a pair of air-permeable platinum thin films 11 and 12 formed on the stabilized zirconia sputtered film 10,
An oxidation catalyst layer 13 having air permeability and heat resistance is disposed on the platinum thin film 11 on one side. The stabilized zirconia sputtered film 10 is prepared by sputtering stabilized zirconia in a gas atmosphere in which oxygen as a main component is mixed with argon as a main component, and is heated and fired at 800 to 1300 ° C. at a thickness of 0.5 to 5 μm. Get it. Platinum thin films 11 and 12 were formed by sputtering platinum in an argon gas atmosphere.
m film thickness product.
【００２７】以下、ガスセンサを試作し、その効果判定
を行った。構成材料とその製造方法について記す。Hereinafter, a gas sensor was prototyped, and its effect was determined. The constituent materials and the manufacturing method are described.
【００２８】絶縁性支持基板６は、アルミナを主成分と
した基板であり、寸法２．５mm×２．５mm、膜厚０．２
mmである。The insulating support substrate 6 is a substrate mainly composed of alumina and has a size of 2.5 mm × 2.5 mm and a thickness of 0.2 mm.
mm.
【００２９】ヒータ膜７は、耐酸化性発熱材料である白
金粉末８５部とアルミナ粉末１０部とガラス粉末５部の
印刷焼成膜であり、絶縁性支持基板６に前述組成のペー
ストを厚膜印刷し乾燥後に１０００℃１時間焼成して得
ている。その寸法は２mm×２mmで膜厚は１０μmであ
る。The heater film 7 is a printed and baked film of 85 parts of platinum powder, which is an oxidation-resistant heat-generating material, 10 parts of alumina powder, and 5 parts of glass powder. After drying, firing is performed at 1000 ° C. for 1 hour. Its dimensions are 2 mm × 2 mm and the film thickness is 10 μm.
【００３０】絶縁膜８は、アルミナのスパッタ膜であ
り、ヒータ膜７のリード線取り出し部以外の部分を覆う
様にして形成した膜である。The insulating film 8 is a sputtered film of alumina, and is a film formed so as to cover a portion of the heater film 7 other than the lead wire take-out portion.
【００３１】ガス感応膜９の製法を述べる。まず、絶縁
膜８の上部に、アルゴン８０％と酸素２０％の混合ガス
雰囲気中で安定化ジルコニアをスパッタして、膜厚１μ
mの安定化ジルコニアスパッタ膜１０を形成した。この
安定化ジルコニアスパッタ膜１０を１０００℃で１時間
熱処理して結晶性を高めたのち、この上部に白金をスパ
ッタして通気性を有する一対の白金薄膜１１、１２を膜
厚０．３μm形成した。そして、片面の白金薄膜１１の
上部に、白金粒子を無機接着剤に混合させて通気性と耐
熱性を付与した酸化触媒層１３を塗布した。A method for manufacturing the gas sensitive film 9 will be described. First, stabilized zirconia is sputtered on the insulating film 8 in a mixed gas atmosphere of 80% argon and 20% oxygen to form a film having a thickness of 1 μm.
Thus, a stabilized zirconia sputtered film 10 was formed. The stabilized zirconia sputtered film 10 was heat-treated at 1000 ° C. for 1 hour to enhance the crystallinity, and then platinum was sputtered on the film to form a pair of breathable platinum thin films 11 and 12 having a thickness of 0.3 μm. . Then, an oxidation catalyst layer 13 in which platinum particles were mixed with an inorganic adhesive to impart air permeability and heat resistance was applied to the upper part of the platinum thin film 11 on one side.
【００３２】最後に、ヒータ膜７と白金薄膜１１、１２
に白金リード線を接続して、ガスセンサが完成である。
このガスセンサを通気性ステンレス製ケースに断熱材を
介して収納し、そのガス検知特性を評価した。ヒータ膜
７への直流電圧付与と白金薄膜１１、１２の起電力検知
は、ガスセンサのリード線を接続した通気性ステンレス
製ケースの外部端子で行った。Finally, the heater film 7 and the platinum thin films 11, 12
Then, a platinum lead wire is connected, and the gas sensor is completed.
This gas sensor was housed in a breathable stainless steel case via a heat insulating material, and its gas detection characteristics were evaluated. The application of the DC voltage to the heater film 7 and the detection of the electromotive force of the platinum thin films 11 and 12 were performed at external terminals of a gas-permeable stainless steel case to which a lead wire of a gas sensor was connected.
【００３３】ガスセンサを加熱するために付与されるヒ
ータ膜７の電圧電流特性の解析を行った。その結果、最
適動作温度４５０℃に加熱するには、３．０Ｖで２１０
mＡの電流（電力０．６３Ｗ）が必要であり、その際の
４５０℃到達時間（暖気時間と称する）は２分であっ
た。ヒータ膜７は、電圧３．０Ｖ印加で電流２１０mＡ
が流れて４５０℃になるので、その時の抵抗は１４．３
Ωであり、その寸法２mm×２mmと膜厚１０μmから比抵
抗を算出すると、比抵抗は１４３×１０-6Ωmとなる。
一方、ヒータ膜７はその両端に白金リード線が接続され
ており、白金リード線を介して、発熱のための電圧３．
２７Ｖが印加されている。そこで、白金リード線を介し
ての電圧値３．２７Ｖから、ヒータ膜への印加電圧値
３．０Ｖを差し引いて、白金リード線の電圧０．２７Ｖ
を求めた。この白金リード線の電圧０．２７Ｖは、白金
リード線の持つ抵抗値により電圧０．２７Ｖがここで消
費されていることを意味する。The voltage-current characteristics of the heater film 7 provided for heating the gas sensor were analyzed. As a result, to heat to the optimum operating temperature of 450 ° C.,
A current of mA (power of 0.63 W) was required, and the time required to reach 450 ° C. (referred to as warm-up time) was 2 minutes. The heater film 7 has a current of 210 mA when a voltage of 3.0 V is applied.
Flows to 450 ° C., and the resistance at that time is 14.3.
When the specific resistance is calculated from the dimensions 2 mm × 2 mm and the film thickness of 10 μm, the specific resistance is 143 × 10 −6 Ωm.
On the other hand, a platinum lead wire is connected to both ends of the heater film 7, and a voltage for heat generation is increased via the platinum lead wire.
27V is applied. Therefore, the voltage of 3.07 V applied to the heater film is subtracted from the voltage of 3.27 V via the platinum lead to obtain a voltage of 0.27 V for the platinum lead.
I asked. The voltage of 0.27 V of the platinum lead means that the voltage of 0.27 V is consumed by the resistance of the platinum lead.
【００３４】また、ガスセンサを４５０℃に加熱し、一
酸化酸素１０００ppmを含む空気に曝したところ、２０m
vの出力電圧が検知された。なお、空気だけだと１mvの
出力電圧mが検知される。When the gas sensor was heated to 450 ° C. and exposed to air containing 1000 ppm of oxygen monoxide,
Output voltage of v is detected. If only air is used, an output voltage m of 1 mv is detected.
【００３５】次に、比抵抗が異なるヒータ膜７を試作
し、動作温度４５０℃における抵抗とその時の電流電圧
そして４５０℃到達暖気時間、白金リード線に付与され
た電圧、センサ出力を測定した。その結果を（表１）に
示す。実験は、ヒータ膜７の比抵抗および抵抗が異なる
以外は、前述と同じである。ヒータ膜７の比抵抗は、主
成分の耐酸化性発熱材料（白金もしくは酸化ルテニウム
を使用）と、副成分の耐熱性金属酸化物（アルミナもし
くは酸化ジルコニアもしくは酸化マグネシウムを使用）
と、結合材であるガラスの材料組成を変化させて、調整
した。Next, heater films 7 having different specific resistances were experimentally manufactured, and the resistance at the operating temperature of 450 ° C., the current voltage at that time, the warm-up time to 450 ° C., the voltage applied to the platinum lead wire, and the sensor output were measured. The results are shown in (Table 1). The experiment is the same as described above except that the specific resistance and the resistance of the heater film 7 are different. The specific resistance of the heater film 7 is determined by using an oxidation-resistant heat-generating material (using platinum or ruthenium oxide) as a main component and a heat-resistant metal oxide (using alumina, zirconia or magnesium oxide) as a sub-component.
And by changing the material composition of the glass as the binder.
【００３６】[0036]
【表１】 [Table 1]
【００３７】比抵抗が２３〜２２８６×１０-6Ωmであ
る試作番号３〜１０のヒータ膜は、暖気時間３分弱以内
と短時間で４５０℃に到達している。また、白金リード
線電圧は０．６８Ｖ以下と、ヒータ膜電圧１．２Ｖ以上
と比較してその値が小さく、熱損失が小さい。そのた
め、ヒータ膜として良好な特性を示した。The heater films of Prototype Nos. 3 to 10 having specific resistances of 23 to 2286 × 10 −6 Ωm reach 450 ° C. in a short time within a warm-up time of less than 3 minutes. The platinum lead wire voltage is 0.68 V or less, which is smaller than the heater film voltage of 1.2 V or more, and the heat loss is small. Therefore, good characteristics were exhibited as a heater film.
【００３８】その中で特に、比抵抗が２３〜１２９０×
１０-6Ωmである試作番号３〜８のヒータ膜は、暖気時
間２分と極めて短時間に４５０℃に到達し、しかも、白
金リード線電圧はヒータ膜電圧の半分強以下と、優れた
特性を示した。Among them, particularly, the specific resistance is 23 to 1290 ×
The heater films of prototype numbers 3 to 8 of 10 -6 Ωm reach 450 ° C. in a very short time of 2 minutes, and the platinum lead wire voltage is less than half of the heater film voltage and excellent characteristics. showed that.
【００３９】一方、比抵抗が２３×１０-6Ωm未満であ
る試作番号１および２のヒータ膜は、白金リード線電圧
が１．１８Ｖ以上でヒータ膜電圧が０．６８Ｖ以下と、
白金リード線電圧がこの比抵抗値を境に大きく上昇し、
熱損失が極めて大きくなるため不適格であった。また、
比抵抗が１７５０×１０-6Ωmを超えた試作番号１０の
ヒータ膜は、暖気時間８分とその時間がこの比抵抗値を
境に極めて長くなり、４５０℃になかなか到達しないた
め不適格であった。これは、比抵抗が大きいためにその
電気容量が大きくなり、その電気的充填に長時間を要す
るためである。On the other hand, the heater films of prototype numbers 1 and 2 having a specific resistance of less than 23 × 10 −6 Ωm have a platinum lead wire voltage of 1.18 V or more and a heater film voltage of 0.68 V or less.
The platinum lead wire voltage rises significantly after this specific resistance,
It was ineligible due to the extremely high heat loss. Also,
The heater film of prototype No. 10 having a specific resistance exceeding 1750 × 10 −6 Ωm was not suitable because the warm-up time was 8 minutes and the time became extremely long at the boundary of the specific resistance value and did not easily reach 450 ° C. Was. This is because the electric resistance is large because the specific resistance is large, and it takes a long time for the electric filling.
【００４０】ヒータ膜の比抵抗は、その抵抗値と面積寸
法と膜厚を測定し、これらの関係式から算出した。比抵
抗および抵抗は、ヒータ膜の温度が４５０℃の時の値で
あるが、室温の時の比抵抗および抵抗は、４５０℃の値
に約０．３を乗ずることで求められた。The specific resistance of the heater film was calculated by measuring the resistance value, the area dimension, and the film thickness, and calculating from these relational expressions. The specific resistance and the resistance are values when the temperature of the heater film is 450 ° C., and the specific resistance and the resistance at room temperature are obtained by multiplying the value at 450 ° C. by about 0.3.
【００４１】耐酸化性発熱材料は、白金もしくは酸化ル
テニウムが最適である。白金は比抵抗が０．１０６×１
０-6Ωm（室温）、酸化ルテニウムは比抵抗が０．４０
×１０-6Ωm（室温）であり、いずれも耐酸化性発熱材
料として一般的に用いられる材料である。As the oxidation-resistant heat generating material, platinum or ruthenium oxide is most suitable. Platinum has a specific resistance of 0.106 × 1
0 -6 Ωm (room temperature), specific resistance of ruthenium oxide is 0.40
× 10 -6 Ωm (room temperature), all of which are generally used as oxidation-resistant heat-generating materials.
【００４２】ガス感応膜９は、酸化スズ、白金などの貴
金属を担持した酸化スズ、酸化インジウム、パラジウム
などの貴金属を担持した酸化インジウム、酸化亜鉛、酸
化鉄、などの半導体型が使用可能である。これら半導体
型ガス感応膜は、厚膜印刷法やスパッタ法を用いてその
酸化物を膜化し、用途に応じて貴金属が担持される構成
である。例えば、酸化スズの場合、塩化スズなどの加水
分解物であるスズ酸を熱分解して酸化スズを製造し、そ
のペーストを絶縁性支持基板に厚膜印刷し７００℃で焼
成することでガス感応膜を得る。また、必要に応じて酸
化スズの表面に塩化白金酸を滴下し熱などで還元して、
白金を担持させた酸化スズとし、感度を高めたガス感応
膜を得る。As the gas-sensitive film 9, a semiconductor type such as tin oxide, indium oxide, zinc oxide, iron oxide, or the like, which supports a noble metal such as tin oxide, indium oxide, or palladium, which can support a noble metal such as tin oxide or platinum, can be used. . These semiconductor-type gas-sensitive films have a structure in which an oxide thereof is formed into a film using a thick-film printing method or a sputtering method, and a noble metal is supported according to a use. For example, in the case of tin oxide, stannic acid, which is a hydrolyzate such as tin chloride, is pyrolyzed to produce tin oxide, and the paste is thick-film-printed on an insulating support substrate and baked at 700 ° C. to be gas-sensitive. Obtain a membrane. Also, if necessary, chloroplatinic acid is dropped on the surface of tin oxide and reduced by heat or the like,
Platinum-supported tin oxide is used to obtain a gas-sensitive film with increased sensitivity.
【００４３】（実施例２）図２は本発明の第２の実施例
であるガスセンサの断面図である。実施例１との相違点
は、絶縁性支持基板６の一方の面にヒータ膜７を、他面
にガス感応膜９を形成した点である。なお、実施例１と
同一符号のものは同一構造を有し、説明は省略する。(Embodiment 2) FIG. 2 is a sectional view of a gas sensor according to a second embodiment of the present invention. The difference from the first embodiment is that the heater film 7 is formed on one surface of the insulating support substrate 6 and the gas-sensitive film 9 is formed on the other surface. The components having the same reference numerals as those in the first embodiment have the same structure, and a description thereof will be omitted.
【００４４】比抵抗が異なるヒータ膜７を試作し、動作
温度４５０℃における抵抗とその時の電流電圧そして４
５０℃到達暖気時間、白金リード線に付与された電圧、
センサ出力を測定した。その結果を（表２）に示す。実
験は、ヒータ膜７の上部に絶縁膜がない以外は、前述の
実施例１と同じであり、最適動作温度４５０℃に加熱す
るには電力０．７４Ｗが必要であった。ヒータ膜７の比
抵抗は、主成分の耐酸化性発熱材料（白金もしくは酸化
ルテニウムを使用）と、副成分の耐熱性金属酸化物（ア
ルミナもしくは酸化ジルコニアもしくは酸化マグネシウ
ムを使用）と、結合材であるガラスの材料組成を変化さ
せて、調整した。A heater film 7 having a different specific resistance was manufactured on a trial basis.
50 ° C warm-up time, voltage applied to platinum lead wire,
The sensor output was measured. The results are shown in (Table 2). The experiment was performed in the same manner as in Example 1 except that the insulating film was not provided on the heater film 7. The heating operation required an electric power of 0.74 W to be heated to the optimum operating temperature of 450 ° C. The specific resistance of the heater film 7 is determined by an oxidation-resistant heat-generating material (using platinum or ruthenium oxide) as a main component, a heat-resistant metal oxide as an auxiliary component (using alumina, zirconia or magnesium oxide), and a binder. It was adjusted by changing the material composition of a certain glass.
【００４５】[0045]
【表２】 [Table 2]
【００４６】比抵抗が２３〜２２８６×１０-6Ωmであ
る試作番号３〜１０のヒータ膜は、暖気時間３分弱以内
と短時間で４５０℃に到達している。また、白金リード
線電圧は０．７２Ｖ以下と、ヒータ膜電圧１．３１Ｖ以
上と比較してその値が小さく、熱損失が小さい。そのた
め、ヒータ膜として良好な特性を示した。The heater films of prototype numbers 3 to 10 having a specific resistance of 23 to 2286 × 10 −6 Ωm reach 450 ° C. in a short time within a warm-up time of less than 3 minutes. The platinum lead wire voltage is 0.72 V or less, which is smaller than the heater film voltage of 1.31 V or more, and the heat loss is small. Therefore, good characteristics were exhibited as a heater film.
【００４７】その中で特に、比抵抗が２３〜１２９０×
１０-6Ωmである試作番号３〜８のヒータ膜は、暖気時
間２分と極めて短時間に４５０℃に到達し、しかも、白
金リード線電圧はヒータ膜電圧の半分強以下と、優れた
特性を示した。Among them, the specific resistance is 23 to 1290 ×
The heater films of prototype numbers 3 to 8 of 10 -6 Ωm reach 450 ° C. in a very short time of 2 minutes, and the platinum lead wire voltage is less than half of the heater film voltage and excellent characteristics. showed that.
【００４８】一方、比抵抗が２３×１０-6Ωm未満であ
る試作番号１および２のヒータ膜は、白金リード線電圧
が１．２８Ｖ以上でヒータ膜電圧が０．７４Ｖ以下と、
白金リード線電圧がこの比抵抗値を境に大きく上昇し、
熱損失が極めて大きくなるため不適格であった。また、
比抵抗が１７５０×１０-6Ωmを超えた試作番号１０の
ヒータ膜は、暖気時間９分とその時間がこの比抵抗値を
境に極めて長くなり、４５０℃になかなか到達しないた
め不適格であった。これは、比抵抗が大きいためにその
電気容量が大きくなり、その電気的充填に長時間を要す
るためである。On the other hand, heater films of prototypes Nos. 1 and 2 having a specific resistance of less than 23 × 10 −6 Ωm have a platinum lead wire voltage of 1.28 V or more and a heater film voltage of 0.74 V or less.
The platinum lead wire voltage rises significantly after this specific resistance,
It was ineligible due to the extremely high heat loss. Also,
The heater film of Prototype No. 10 having a specific resistance exceeding 1750 × 10 −6 Ωm was ineligible because the warm-up time was 9 minutes and the time became extremely long at the boundary of the specific resistance value and did not easily reach 450 ° C. Was. This is because the electric resistance is large because the specific resistance is large, and it takes a long time for the electric filling.
【００４９】比抵抗および抵抗は、ヒータ膜の温度が４
５０℃の時の値であるが、室温の時の比抵抗および抵抗
は、４５０℃の値に約０．３を乗ずることで求められ
た。The specific resistance and the resistance were determined when the temperature of the heater film was 4
The specific resistance and the resistance at room temperature were obtained by multiplying the value at 450 ° C. by about 0.3.
【００５０】ガス感応膜９は、酸化スズ、白金などの貴
金属を担持した酸化スズ、酸化インジウム、パラジウム
などの貴金属を担持した酸化インジウム、酸化亜鉛、酸
化鉄、などの半導体型が使用可能である。これら半導体
型ガス感応膜は、厚膜印刷法やスパッタ法を用いてその
酸化物を膜化し、用途に応じて貴金属が担持される構成
である。As the gas-sensitive film 9, a semiconductor type such as tin oxide, indium oxide, indium oxide, zinc oxide, iron oxide, or the like carrying a noble metal such as tin oxide, indium oxide, or palladium can be used. . These semiconductor-type gas-sensitive films have a structure in which an oxide thereof is formed into a film using a thick-film printing method or a sputtering method, and a noble metal is supported according to a use.
【００５１】（実施例３）実施例３は、ヒータ膜７の材
質・組成について検討した。Example 3 In Example 3, the material and composition of the heater film 7 were studied.
【００５２】耐酸化性発熱材料として、比抵抗０．１０
６×１０-6Ωm（室温）の白金、比抵抗０．４×１０-6
Ωm（室温）の酸化ルテニウムを用い、これら発熱材料
に各種の耐熱性金属酸化物の粉末とガラス粉末を混合し
て、ヒータ膜を試作した。使用したガラスは、熱膨張係
数が６．６×１０-6（１/geg）、転移温度が６６０℃、
軟化開始温度が８５０℃、の物性を有する、酸化カルシ
ウムー酸化バリウムー二酸化珪素の組成系粉末である。
ヒータ膜は、アルミナ製の絶縁性支持基板にそのペース
ト（粉末を有機溶剤と混合したもの）を印刷し乾燥後
に、１０００℃で１時間焼成して得ている。このヒータ
膜を４５０℃で５００時間作動させ、比抵抗値の変化を
測定した結果を（表３）に示す。As an oxidation-resistant heat generating material, a specific resistance of 0.10
6 × 10 -6 Ωm (room temperature) platinum, specific resistance 0.4 × 10 -6
Heater films were prototyped by using Ωm (room temperature) ruthenium oxide, mixing these heat-generating materials with various heat-resistant metal oxide powders and glass powders. The glass used had a coefficient of thermal expansion of 6.6 × 10 −6 (1 / geg), a transition temperature of 660 ° C.,
It is a calcium oxide-barium oxide-silicon dioxide composition-based powder having physical properties of a softening start temperature of 850 ° C.
The heater film is obtained by printing and drying the paste (a mixture of powder and an organic solvent) on an insulating support substrate made of alumina, and then baking it at 1000 ° C. for 1 hour. This heater film was operated at 450 ° C. for 500 hours, and the result of measuring the change in the specific resistance value is shown in (Table 3).
【００５３】[0053]
【表３】 [Table 3]
【００５４】白金にアルミナとガラスを混合した試作番
号１のヒータ膜は、比抵抗の変化がない優れたヒータ膜
であった。その理由は、アルミナの高表面積と融点にあ
り、以下詳細に説明する。アルミナは１００〜２００m2
/gの表面積を有する材料であり、白金の表面積２〜３m2
/gと比較してその値が１００倍弱大きい。そのため、重
量割合にしてアルミナを白金の１割弱混合したとして
も、アルミナの表面積の方が白金の表面積より１０倍弱
大きい。そのため、アルミナ粒子の表面に無数存在する
凹部に白金粒子がくいこみ、ガラスとの相乗効果で白金
粒子が移動し難くなっている。また、アルミナは融点約
２０００℃で白金は融点１７７℃と耐熱に優れているた
め、ヒータ膜形成時の１０００℃焼成やヒータ動作の４
５０℃によって熱分解が起こらない。以上の２つの理由
により、白金にアルミナとガラスを混合したヒータ膜
は、比抵抗の変化がない優れたヒータ膜になっている。The heater film of prototype No. 1 in which alumina and glass were mixed with platinum was an excellent heater film having no change in specific resistance. The reason lies in the high surface area and melting point of alumina, which will be described in detail below. Alumina is 100 to 200 m 2
/ g surface area, platinum surface area 2-3 m 2
The value is slightly less than 100 times larger than / g. Therefore, even if alumina is mixed in a weight ratio of less than 10% of platinum, the surface area of alumina is slightly less than 10 times larger than the surface area of platinum. For this reason, the platinum particles are entrapped in innumerable concave portions on the surface of the alumina particles, and the platinum particles hardly move due to a synergistic effect with glass. Alumina has a melting point of about 2000 ° C. and platinum has a melting point of 177 ° C., which is excellent in heat resistance.
No thermal decomposition occurs at 50 ° C. For the above two reasons, a heater film obtained by mixing alumina and glass with platinum is an excellent heater film having no change in specific resistance.
【００５５】また、比抵抗を２３〜１２９０×１０-6Ω
mに調整するためにヒータ膜は、白金が８０〜９０wt
％、硝子が３〜７wt％、アルミナが残部の配合割合を必
要とした。そしてこの組成配合において、ヒータ膜は比
抵抗の変化がない優れた膜になっていた。The specific resistance is 23 to 1290 × 10 −6 Ω.
In order to adjust the temperature to m, the heater film is made of 80 to 90 wt% platinum.
%, 3 to 7% by weight of glass, and the balance of alumina required the balance. With this composition, the heater film was an excellent film having no change in specific resistance.
【００５６】一方、酸化マグネシウムおよびジルコニア
は、融点約２８００℃であり耐熱に優れるが、表面積は
数十m2/gと白金より一桁大きい。このため、白金に酸化
マグネシウムを混合した試作番号２のヒータ膜や、白金
にジルコニアを混合した試作番号３のヒータ膜は、ヒー
タ膜形成時の焼成により両者が固着せず、白金粒子が一
層移動し易くなって比抵抗の変化が僅かにある。なお、
実験は、酸化マグネシウムやジルコニアを用いたが、他
の低表面積の耐熱性金属酸化物を用いたヒータ膜も同様
に比抵抗の変化が僅かにあり、その理由は表面積が小さ
いため白金粒子が移動し易くなっている。On the other hand, magnesium oxide and zirconia have melting points of about 2800 ° C. and are excellent in heat resistance, but have a surface area of several tens m 2 / g, which is one digit larger than that of platinum. Therefore, the heater film of prototype No. 2 in which magnesium oxide was mixed with platinum and the heater film of prototype No. 3 in which zirconia was mixed with platinum did not adhere to each other due to firing during the formation of the heater film, and the platinum particles moved further. And the change in specific resistance is slight. In addition,
In the experiment, magnesium oxide and zirconia were used, but the resistivity of the heater film using other low-surface-area heat-resistant metal oxides also changed slightly, because platinum particles migrated because the surface area was small. It is easy to do.
【００５７】最後に、酸化ルテニウムにアルミナとガラ
スを混合した試作番号４のヒータ膜の場合について説明
する。酸化ルテニウムは、８５０℃以上に曝されると熱
分解して酸素が解離し金属ルテニウムに解離しやすくな
る。この特性のため、試作番号４のヒータ膜は、ヒータ
膜形成の１０００℃１時間焼成によって酸化ルテニウム
の熱分解が起って、耐酸化性が僅かながら失われてしま
い、比抵抗の変化が僅かにあるヒータ膜になっている。Finally, a description will be given of a case of a heater film of prototype No. 4 in which alumina and glass are mixed with ruthenium oxide. When exposed to 850 ° C. or higher, ruthenium oxide is thermally decomposed, oxygen is dissociated, and is easily dissociated into ruthenium metal. Due to this characteristic, the heater film of prototype No. 4 suffers thermal decomposition of ruthenium oxide by baking at 1000 ° C. for 1 hour for the formation of the heater film, so that the oxidation resistance is slightly lost, and the change in specific resistance is slight. Heater film.
【００５８】（実施例４）実施例４は、絶縁膜８の材質
・組成について検討した。Example 4 In Example 4, the material and composition of the insulating film 8 were studied.
【００５９】絶縁膜は、硝子を主成分としており、ヒー
タ膜の上部にその厚膜印刷膜を積層して焼成することで
得られる。そのため、絶縁膜で使用される硝子の軟化温
度すなわち焼成温度が最適でないと、絶縁膜の焼成によ
ってヒータ膜の特性が変化する。焼成温度の異なる硝子
を用いその厚膜印刷膜で、ヒータ膜と絶縁膜の積層膜を
試作した。そして、これら膜のヒータ特性、絶縁特性、
積層膜を得るための焼成回数、耐熱衝撃特性、を評価し
た。The insulating film is mainly composed of glass, and is obtained by laminating a thick print film on the heater film and firing it. Therefore, if the softening temperature of the glass used for the insulating film, that is, the firing temperature is not optimal, the characteristics of the heater film change due to the firing of the insulating film. A prototype of a laminated film of a heater film and an insulating film was manufactured using a thick printed film using glass having different firing temperatures. And the heater characteristics, insulation characteristics,
The number of firings and the thermal shock resistance for obtaining the laminated film were evaluated.
【００６０】試作番号１は、ヒータ膜に焼成温度１２０
０℃の硝子を用い、絶縁膜に焼成温度１２００℃の硝子
を用いたものである。１２００℃焼成してヒータ膜を予
め形成したのち、その上部に厚膜印刷し１０００℃焼成
して絶縁膜を形成しているため、２回の焼成を経てい
る。Prototype No. 1 shows that the heater film had a firing temperature of 120.
In this example, glass of 0 ° C. is used, and glass of 1200 ° C. is used for the insulating film. After baking at 1200 ° C. to form a heater film in advance, thick film printing is performed on the heater film, and baking is performed at 1000 ° C. to form an insulating film. Therefore, baking is performed twice.
【００６１】試作番号２は、ヒータ膜も絶縁膜も焼成温
度１０００℃の硝子を用いたものであり、両者の厚膜印
刷の積層膜を１０００℃同時焼成して、ヒータ膜と絶縁
膜を形成しているため、焼成回数は１回である。Prototype No. 2 uses a glass having a firing temperature of 1000 ° C. for both the heater film and the insulating film, and simultaneously forms a thick film printed laminated film at 1000 ° C. to form a heater film and an insulating film. Therefore, the number of firing is one.
【００６２】試作番号３は、ヒータ膜に焼成温度８００
℃の硝子を用い、絶縁膜に焼成温度１０００℃の硝子を
用いたものである。８００℃焼成してヒータ膜を予め形
成したのち、その上部に厚膜印刷し１０００℃焼成して
絶縁膜を形成しているため、２回の焼成を経ている。The prototype No. 3 shows that the heater film has a sintering temperature of 800.
A glass having a firing temperature of 1000 ° C. was used for the insulating film. After baking at 800 ° C. to form a heater film in advance, a thick film is printed on the heater film, and baking is performed at 1000 ° C. to form an insulating film.
【００６３】これら試作品において、ヒータ膜は白金８
８部とアルミナ７部と硝子５部の混合品、絶縁膜は硝子
１００wt％品、を使用している。硝子は両方とも、絶縁
性支持基板として用いるアルミナと熱膨張係数が±１０
％以内で同じ材料を使用した。In these prototypes, the heater film was made of platinum 8
A mixture of 8 parts, 7 parts of alumina and 5 parts of glass is used, and the insulation film is made of 100% by weight of glass. Both glass and alumina used as an insulating support substrate have a thermal expansion coefficient of ± 10.
The same material was used within%.
【００６４】ヒータ膜の特性は、その上部に絶縁膜を形
成することでヒータ膜の抵抗がどの様に変化するかを測
定し、絶縁膜の形成前後で抵抗変化が、±５％以内なら
良好、±５〜２０％なら比較的良好、±２０％以上なら
悪い、と判断した。なお、試作番号２のサンプルは、同
時焼成しているため絶縁膜の形成前後の抵抗変化を測定
できない。そこで、絶縁膜の断面を観察してヒータ膜を
構成する白金の絶縁膜への混入度合いを測定し、その混
入度合いから抵抗変化を推定した。抵抗変化の推定は、
試作番号１および３のサンプルの、ヒータ膜を構成する
白金の絶縁膜への混入度合いを参考にしている。The characteristics of the heater film are determined by measuring how the resistance of the heater film changes by forming an insulating film on the heater film. If the resistance change before and after the formation of the insulating film is within ± 5%, it is good. , ± 5% to 20%, and ± 20% or more, poor. Note that the sample of prototype No. 2 cannot be measured for resistance change before and after the formation of the insulating film because the sample is fired simultaneously. Therefore, the cross section of the insulating film was observed to measure the degree of mixing of platinum constituting the heater film into the insulating film, and the resistance change was estimated from the degree of mixing. The estimation of the resistance change is
Reference is made to the degree of mixing of the samples of prototype numbers 1 and 3 into the insulating film of platinum constituting the heater film.
【００６５】絶縁膜の特性は、絶縁膜の両端に直流５０
０Ｖ印加した際の絶縁抵抗を測定し、絶縁抵抗値が５Ｍ
Ω以上なら良好、１〜５ＭΩなら比較的良好、１ＭΩ以
下なら絶縁膜として使用できないため不適格、と判断し
た。The characteristics of the insulating film are as follows.
Measure the insulation resistance when 0V is applied.
It was judged as good if it was Ω or more, relatively good if it was 1 to 5 MΩ, and unsuitable because it could not be used as an insulating film if it was 1 MΩ or less.
【００６６】積層膜の耐熱衝撃特性は、ヒータ膜を間欠
通電して急激な温度上昇を５０回付与した際に、ヒータ
膜の抵抗がどの様に変化するかを測定し、間欠通電の前
後で抵抗変化が、±５％以内なら良好、±５〜１０％な
ら比較的良好、±１０％以上なら使用できないため不適
格、と判断した。The thermal shock resistance of the laminated film is measured by measuring how the resistance of the heater film changes when the heater film is intermittently energized and a rapid temperature rise is applied 50 times, and before and after the intermittent energization. If the resistance change was within ± 5%, it was judged to be good, if ± 5 to 10%, it was judged to be relatively good, and if it was more than ± 10%, it was judged unsuitable because it could not be used.
【００６７】試作したヒータ膜と絶縁膜の焼成条件およ
び特性を（表４）に示す。Table 4 shows the firing conditions and characteristics of the prototype heater film and insulating film.
【００６８】[0068]
【表４】 [Table 4]
【００６９】絶縁膜の焼成温度がヒータ膜焼成温度より
低いか同等である試作番号１と２は、ヒータ膜や絶縁膜
さらに積層膜は比較的良好な特性を示すことがわかる。
一方、絶縁膜の焼成温度がヒータ膜焼成温度より高い試
作番号３のサンプルは、絶縁膜の焼成時に絶縁膜の組成
物がヒータ膜に流れ込んで絶縁膜とヒータ膜が融合して
各々の物性が変化して、ヒータ膜および絶縁膜はその特
性が悪化して使用できない。It is understood that the prototypes Nos. 1 and 2 in which the baking temperature of the insulating film is lower than or equal to the baking temperature of the heater film show relatively good characteristics of the heater film, the insulating film, and the laminated film.
On the other hand, in the sample of Prototype No. 3 in which the sintering temperature of the insulating film is higher than the sintering temperature of the heater film, the composition of the insulating film flows into the heater film during the sintering of the insulating film, and the insulating film and the heater film fuse to form a physical property. As a result, the characteristics of the heater film and the insulating film deteriorate so that they cannot be used.
【００７０】さて、いずれの試作番号品も、絶縁膜がガ
ラスであるため、積層膜の耐熱衝撃性は充分でなく、熱
衝撃性により微細なクラックが発生してヒータ膜の抵抗
が僅かに変化している。そこで、積層膜の耐熱衝撃性の
向上を試みた。In each of the prototypes, since the insulating film is glass, the thermal shock resistance of the laminated film is not sufficient, and fine cracks occur due to the thermal shock and the resistance of the heater film slightly changes. are doing. Therefore, an attempt was made to improve the thermal shock resistance of the laminated film.
【００７１】硝子の中に、硝子の軟化温度より高い溶融
温度を持つ耐熱高表面積性金属酸化物を少量混合した絶
縁膜を試作し、その特性を評価した結果を（表５）に示
す。An insulating film in which a small amount of a heat-resistant and high-surface-area metal oxide having a melting temperature higher than the softening temperature of the glass was mixed was manufactured on a trial basis, and the characteristics were evaluated. The results are shown in Table 5.
【００７２】実験は、ヒータ膜および絶縁膜も焼成温度
１０００℃の硝子を用い、両者の厚膜印刷の積層膜を１
０００℃同時焼成してヒータ膜と絶縁膜を形成してお
り、これ以外は前述と同じ方法で膜を形成し、同じ評価
手法で評価を行った。In the experiment, the heater film and the insulating film were also made of glass having a firing temperature of 1000 ° C.
A heater film and an insulating film were formed by simultaneous baking at 000 ° C. Except for this, a film was formed by the same method as described above, and evaluation was performed by the same evaluation method.
【００７３】[0073]
【表５】 [Table 5]
【００７４】アルミナや酸化マグネシウムそしてジルコ
ニアなどの耐熱高表面積性金属酸化物を硝子に混合した
試作番号２〜４は、良好な特性のヒータ膜と絶縁膜と積
層膜であった。その理由は、これら耐熱高表面積性金属
酸化物の融点と高表面積にあり、詳細に以下説明する。
例えば、アルミナは融点約２０００℃であり、硝子の軟
化温度１０００℃より耐熱に優れている。この高融点の
ため、アルミナ粒子は、硝子の焼成時に溶解することな
く硝子の中に粒子として分散している。一方、アルミナ
は１００〜２００m2/gの表面積を有する材料であり、硝
子の表面積の数m2/gと比較してその値が１００倍弱大き
い。そのため、重量割合にしてアルミナを硝子の１割強
混合したとしても、アルミナの表面積の方が硝子の表面
積より約１０倍大きい。そのため、アルミナ粒子の表面
に無数存在する凹部に硝子が侵入して硝子とアルミナ粒
子が強固に固着し、絶縁膜の組成物がヒータ膜に流れ込
むことを抑制する。この硝子とアルミナ粒子の強固な固
着により、ヒータ膜ち絶縁膜は良好な電気特性を示し、
積層膜の耐熱衝撃性も向上する。酸化マグネシウムやジ
ルコニアの場合も同じであり、両者とも融点約２８００
℃で、表面積は数十m2/gであるため、アルミナ粒子の表
面に無数存在する凹部に硝子が侵入して硝子とアルミナ
粒子が強固に固着し、絶縁膜の組成物がヒータ膜に流れ
込むことを抑制する。したがって、ヒータ膜と絶縁膜は
良好な電気特性および絶縁特性を示し、積層膜の耐熱衝
撃性も向上する。また、試作番号２〜４は、充分なる気
密性も得られた。Prototypes Nos. 2 to 4 in which a heat-resistant and high-surface-area metal oxide such as alumina, magnesium oxide, and zirconia were mixed with glass were heater films, insulating films, and laminated films having good characteristics. The reason lies in the melting point and high surface area of these heat-resistant and high-surface area metal oxides, which will be described in detail below.
For example, alumina has a melting point of about 2000 ° C., and is superior in heat resistance to glass softening temperature of 1000 ° C. Due to this high melting point, the alumina particles are dispersed as particles in the glass without being dissolved during firing of the glass. Meanwhile, the alumina is a material having a surface area of 100 to 200 m 2 / g, the value is a little less than a large 100-fold compared to the number m 2 / g of surface area of the glass. Therefore, even if alumina is mixed in a weight ratio of more than 10% of glass, the surface area of alumina is about 10 times larger than the surface area of glass. For this reason, the glass penetrates into countless concave portions existing on the surface of the alumina particles, the glass and the alumina particles are firmly fixed, and the composition of the insulating film is prevented from flowing into the heater film. Due to the strong adhesion between the glass and the alumina particles, the heater film or the insulating film shows good electric characteristics,
The thermal shock resistance of the laminated film is also improved. The same is true for magnesium oxide and zirconia, both of which have a melting point of about 2800.
At ℃, the surface area is several tens of m 2 / g, so that the glass penetrates into the myriad of concave parts on the surface of the alumina particles, the glass and the alumina particles are firmly fixed, and the composition of the insulating film flows into the heater film Restrain that. Therefore, the heater film and the insulating film exhibit good electric and insulating characteristics, and the thermal shock resistance of the laminated film is also improved. Prototype Nos. 2 to 4 also exhibited sufficient airtightness.
【００７５】また、絶縁膜は、硝子とアルミナ粉末の配
合割合の変更（アルミナ粉末を２〜３０部配合）および
アルミナ粉末以外の材料使用（酸化マグネシウムやジル
コニアを２〜２０部配合）しても、良好な絶縁特性と充
分なる気密性を示し、ヒータ膜との積層膜の耐熱衝撃性
も向上した。The insulating film can be formed by changing the mixing ratio of glass and alumina powder (mixing 2 to 30 parts of alumina powder) and using a material other than alumina powder (mixing 2 to 20 parts of magnesium oxide or zirconia). In addition, good insulation properties and sufficient airtightness were exhibited, and the thermal shock resistance of the laminated film with the heater film was also improved.
【００７６】（実施例５）実施例５は、ガス感応膜の製
法について検討した。Example 5 In Example 5, a method for producing a gas-sensitive film was examined.
【００７７】ガス感応膜は、センサ出力が空気中の湿度
の影響を受け難い、固体電解質型センサのガス感応膜を
使用した。固体電解質型センサは、酸素イオン導電性の
安定化ジルコニアと、この安定化ジルコニアの上部に形
成した一対の白金電極と、白金電極の片面上部に配置さ
せた酸化触媒膜とから構成させる。この構成において、
安定化ジルコニアは、薄膜化することでヒータ膜の消費
電力低減ができ、気密性の膜にすることで高いセンサ出
力を得ることができるスパッタ法を採用した。スパッタ
法で形成した安定化ジルコニアスパッタ膜は、その物性
（結晶性、酸素イオン導電性）とセンサ出力が、スパッ
タを行うガス雰囲気とスパッタ膜形成用材質体の材質、
さらに形成したスパッタ膜のエイジング温度の影響を大
きく受け、これらが最適でないと良好な物性とセンサ出
力特性が得られない。また、スパッタ膜をエイジングす
る際にその温度が高いと、絶縁膜の特性が変化し、その
下に存在するヒータ膜が良好な特性を示さない。そこ
で、その影響を解析した。その結果を（表６）に示す。As the gas-sensitive film, a gas-sensitive film of a solid electrolyte type sensor whose sensor output is hardly affected by humidity in the air was used. The solid electrolyte sensor is composed of stabilized zirconia having oxygen ion conductivity, a pair of platinum electrodes formed on the stabilized zirconia, and an oxidation catalyst film disposed on one surface of the platinum electrode. In this configuration,
For the stabilized zirconia, a sputtering method capable of reducing the power consumption of the heater film by making the film thinner and obtaining a high sensor output by making the film airtight is adopted. The physical properties (crystallinity, oxygen ion conductivity) and sensor output of the stabilized zirconia sputtered film formed by the sputtering method depend on the gas atmosphere in which the sputtering is performed, the material of the sputtered film forming material,
Further, it is greatly affected by the aging temperature of the formed sputtered film. If these are not optimal, good physical properties and sensor output characteristics cannot be obtained. If the temperature is high when aging the sputtered film, the characteristics of the insulating film change, and the heater film underneath does not show good characteristics. Therefore, the effect was analyzed. The results are shown in (Table 6).
【００７８】[0078]
【表６】 [Table 6]
【００７９】安定化ジルコニアスパッタ膜は、安定化ジ
ルコニアをターゲットとして用いそのスパッタ膜１μm
を、アルゴンを主成分とするガス雰囲気（圧力０．０６
ｔｏｒｒ）で形成用材質体に形成し、その後に高温で１
時間の加熱エイジング処理を施して製作している。製作
は、スパッタ時のガス雰囲気組成、形成用材質体の材料
種別、エイジング温度を変化させて行った。The stabilized zirconia sputtered film was formed by using stabilized zirconia as a target and forming a sputtered film having a thickness of 1 μm.
In a gas atmosphere containing argon as a main component (pressure 0.06).
(torr) to form a forming material body,
It is manufactured by subjecting it to heat aging for a long time. The fabrication was performed by changing the composition of the gas atmosphere at the time of sputtering, the material type of the forming material, and the aging temperature.
【００８０】物性は、製作膜の物性である。結晶性は、
Ｘ線回折装置による測定と断面の光学顕微鏡観察で判断
し、結晶性に優れしかも気密性のある緻密膜なら優れる
と判断し、結晶性が悪くしかも通気性のある多孔質膜な
ら悪いと判断した。電導性は複素インピーダンス法で測
定した酸素イオン電導性であり、酸素イオン電導性に優
れた膜なら優れると判断し、酸素イオン電導性が悪い膜
なら悪いと判断した。The physical properties are the physical properties of the produced film. Crystallinity is
Judgment was made by measurement with an X-ray diffractometer and observation of the cross section with an optical microscope, and it was judged that a dense film with excellent crystallinity and airtightness was excellent, and a porous film with poor crystallinity and air permeability was bad. . The conductivity was oxygen ion conductivity measured by the complex impedance method. A film having excellent oxygen ion conductivity was judged to be excellent, and a film having poor oxygen ion conductivity was judged to be bad.
【００８１】絶縁膜は、安定化ジルコニアスパッタ膜を
製作する前に予め形成したものである。絶縁膜の特性
は、絶縁膜の両端に直流５００Ｖ印加した際の絶縁抵抗
を測定し、絶縁抵抗値が５ＭΩ以上なら良好、１〜５Ｍ
Ωなら比較的良好、１ＭΩ以下なら絶縁膜として使用で
きないため不適格、と判断した。The insulating film is formed before forming a stabilized zirconia sputtered film. The characteristics of the insulating film were measured by measuring the insulation resistance when a DC voltage of 500 V was applied to both ends of the insulation film.
Ω was relatively good, and 1 MΩ or less was judged as unsuitable because it could not be used as an insulating film.
【００８２】センサ出力は、製作した安定化ジルコニア
スパッタ膜の上部に、通気性の有る一対の白金薄膜をス
パッタ法で形成して電極とし、この白金薄膜の片面上部
に白金溶液を滴下して酸化触媒層を形成した、固体電解
質型センサの出力である。ヒータ膜を通電して４５０℃
に温度調整し、一酸化炭素１０００ppmを含む空気に曝
した際に測定したセンサ出力である。The sensor output was obtained by forming a pair of air permeable platinum thin films by sputtering on the manufactured stabilized zirconia sputtered film to form electrodes, and oxidizing a platinum solution by dropping a platinum solution on one upper surface of the platinum thin film. It is the output of the solid electrolyte type sensor which formed the catalyst layer. 450 ° C by energizing the heater film
Is the sensor output measured when the temperature was adjusted to and the air was exposed to air containing 1000 ppm of carbon monoxide.
【００８３】試作番号１は、アルゴンのガス雰囲気中で
アルミナ絶縁性支持基板にスパッタを行い、その後に１
０００℃でエイジング処理を施こす安定化ジルコニアス
パッタ膜の特性である。Prototype No. 1 was obtained by sputtering an alumina insulating support substrate in an argon gas atmosphere,
This is a characteristic of a stabilized zirconia sputtered film subjected to an aging treatment at 000 ° C.
【００８４】試作番号２は、アルゴン８０％と酸素２０
％の混合ガスのガス雰囲気中でスパッタを行い、他条件
は試作番号１と同一の安定化ジルコニアスパッタ膜の特
性である。The prototype No. 2 is composed of 80% argon and 20% oxygen.
%, And the other conditions are the same characteristics of the stabilized zirconia sputtered film as in Prototype No. 1.
【００８５】試作番号３は、軟化温度１２００℃の硝子
からなる絶縁膜（硝子絶縁膜と記す）にスパッタを行
い、他条件は試作番号２と同一の安定化ジルコニアスパ
ッタ膜の特性である。Prototype No. 3 is obtained by sputtering a glass insulating film having a softening temperature of 1200 ° C. (hereinafter referred to as “glass insulating film”). Other conditions are the same characteristics of the stabilized zirconia sputtered film as Prototype No. 2.
【００８６】試作番号４は、硝子（軟化温度１２００
℃）９０部とアルミナ粉末１０部からなる絶縁膜（硝子
系絶縁膜と記す）にスパッタを行い、他条件は試作番号
２と同一の安定化ジルコニアスパッタ膜の特性である。The prototype No. 4 is made of glass (softening temperature 1200
(° C.) Sputtering was performed on an insulating film (hereinafter, referred to as a glass-based insulating film) consisting of 90 parts of alumina powder and 10 parts of alumina powder.
【００８７】試作番号５は、アルミナをスパッタした絶
縁膜（アルミナ系絶縁膜と記す）にスパッタを行い、他
条件は試作番号２と同一の安定化ジルコニアスパッタ膜
の特性である。The prototype No. 5 performs sputtering on an insulating film obtained by sputtering alumina (referred to as an alumina-based insulating film). Other conditions are the same characteristics of the stabilized zirconia sputtered film as the prototype No. 2.
【００８８】試作番号６〜１０は、エイジング処理の温
度を異ならせ、他条件は試作番号２と同一の安定化ジル
コニアスパッタ膜の特性である。The prototype Nos. 6 to 10 differ in the temperature of the aging treatment, and the other conditions are the same characteristics of the stabilized zirconia sputtered film as the prototype No. 2.
【００８９】試作番号２〜５および７〜９は、主成分の
アルゴンに副成分の酸素を混合させたガス雰囲気中でス
パッタを行い、その後に８００〜１３００℃の加熱エイ
ジング処理を施した安定化ジルコニアスパッタ膜である
ため、優れたセンサ出力を有することがわかる。以下、
詳細に説明する。The prototypes Nos. 2 to 5 and 7 to 9 are made by performing sputtering in a gas atmosphere in which oxygen as a main component is mixed with argon as a main component, and then performing heat aging treatment at 800 to 1300 ° C. It can be seen that the sputtered zirconia film has an excellent sensor output. Less than,
This will be described in detail.
【００９０】まず、スパッタを行うガス雰囲気につい
て、試作番号１と２の例で説明する。試作番号１は、安
定化ジルコニアのスパッタをアルゴンだけのガス雰囲気
中で行っているため、安定化ジルコニア中の酸素が選択
的に抜けて結晶性や電導性に劣る膜ができ、センサ出力
が小さくなっている。また、酸素が選択的に抜けるため
組成変化が起り、安定化ジルコニアのスパッタターゲッ
トが白色から黒色に変化した。一方、試作番号２は、ア
ルゴンに酸素を混合したガス雰囲気中でスパッタを行っ
ているため、結晶性や電導性に優れた安定化ジルコニア
の膜が得られ、センサ出力が大きくなっている。安定化
ジルコニアのスパッタターゲットは、白色そのままであ
り組成変化はなかった。酸素の混合量は５〜５０％が最
適であった。そこで以後は、アルゴンに酸素を混合した
ガス雰囲気中でスパッタを行うこととした。First, the gas atmosphere in which sputtering is performed will be described with reference to examples of prototype numbers 1 and 2. In Prototype No. 1, since the stabilized zirconia was sputtered in a gas atmosphere containing only argon, oxygen in the stabilized zirconia was selectively released to form a film having poor crystallinity and electrical conductivity, and the sensor output was small. Has become. Further, a composition change occurred because oxygen was selectively released, and the sputter target of stabilized zirconia changed from white to black. On the other hand, in Prototype No. 2, since sputtering is performed in a gas atmosphere in which oxygen is mixed with argon, a stabilized zirconia film having excellent crystallinity and conductivity is obtained, and the sensor output is large. The stabilized zirconia sputter target was white as it was and there was no change in composition. The optimal amount of oxygen was 5 to 50%. Therefore, thereafter, sputtering is performed in a gas atmosphere in which oxygen is mixed with argon.
【００９１】次に、加熱エイジング処理の温度につい
て、試作番号２と６〜１０の例で説明する。試作番号６
は、８００℃未満でエイジングを行っているため、結晶
性や電導性に劣る膜ができ、センサ出力が小さくなって
いる。これは、スパッタ直後の安定化ジルコニアスパッ
タ膜は、結晶性や電導性に劣る膜であり、８００℃未満
のエイジングでは結晶性や電導性の向上が図れないため
である。一方、試作番号２と７〜９は、８００〜１３０
０℃の加熱エイジング処理を施しているため、結晶性や
電導性に優れた安定化ジルコニアの膜が得られ、優れた
センサ出力を有する。また、試作番号１０は、１３００
℃を超える加熱エイジング処理を施しているため、電導
性は問題ないがスパッタ膜形成用材質（この場合はアル
ミナ絶縁性支持基板）との熱反応物生成により結晶性が
劣る膜ができ、センサ出力が小さくなっている。以上の
ことより以後は、８００〜１３００℃の加熱エイジング
処理を施こすこととした。Next, the temperature of the heat aging treatment will be described with reference to prototypes 2 and 6 to 10. Prototype number 6
Since aging is performed at a temperature lower than 800 ° C., a film having poor crystallinity and conductivity is formed, and the sensor output is small. This is because the stabilized zirconia sputtered film immediately after sputtering is a film having poor crystallinity and conductivity, and cannot be improved in aging at a temperature of less than 800 ° C. On the other hand, the prototype numbers 2 and 7 to 9 are 800 to 130
Due to the heat aging treatment at 0 ° C., a stabilized zirconia film having excellent crystallinity and electrical conductivity is obtained, and has an excellent sensor output. Prototype number 10 is 1300
Heat aging treatment over 100 ° C has been performed, so there is no problem in conductivity, but a film with poor crystallinity is formed due to the generation of a thermal reaction product with the material for forming a sputtered film (in this case, an alumina insulating support substrate). Is getting smaller. From the above, the heat aging treatment at 800 to 1300 ° C. is performed thereafter.
【００９２】一方、センサ出力は、スパッタ膜形成用材
質の影響を受ける。そこで、その影響を試作番号２〜５
で検討した。その結果、アルミナ系絶縁膜、ガラス系絶
縁膜、アルミナ絶縁性支持基板、ガラス絶縁膜の順にセ
ンサ出力が小さくなっている。この理由は、アルゴンに
酸素を混合したガス雰囲気でスパッタを行っているた
め、安定化ジルコニアスパッタ分子と酸素分子の挙動が
スパッタ膜形成用材質とその表面粗さによって変化し、
スパッタ膜形成用材質とその表面粗さによって多種の配
行性のスパッタ膜ができるためである。そのため、最適
な配行性のスパッタ膜が出来たときに、大きなセンサ出
力が得られることとなる。特に、スパッタ膜形成用材質
の表面粗さは重要である。アルミナをスパッタしたアル
ミナ系絶縁膜（試作番号５）と、硝子９０部とアルミナ
粉末１０部からなるガラス系絶縁膜（試作番号４）は、
表面が粗いため大きなセンサ出力が得られ、スパッタ膜
形成用材質として最適であった。なお、ガラス系絶縁膜
は、硝子とアルミナ粉末の配合割合の変更（アルミナ粉
末を２〜３０部配合）およびアルミナ粉末以外の材料使
用（酸化マグネシウムやジルコニアを２〜２０部配合）
しても、大きなセンサ出力が得られた。On the other hand, the sensor output is affected by the material for forming the sputtered film. Therefore, the influence of the prototype numbers 2-5
Was considered. As a result, the sensor output decreases in the order of the alumina-based insulating film, the glass-based insulating film, the alumina-insulating support substrate, and the glass insulating film. The reason is that, because sputtering is performed in a gas atmosphere in which oxygen is mixed with argon, the behavior of stabilized zirconia sputtered molecules and oxygen molecules changes depending on the sputtered film forming material and its surface roughness,
This is because various types of sputtered films can be formed depending on the material for forming the sputtered film and its surface roughness. Therefore, when a sputtered film having an optimal arrangement is formed, a large sensor output is obtained. In particular, the surface roughness of the material for forming a sputtered film is important. An alumina-based insulating film obtained by sputtering alumina (prototype number 5) and a glass-based insulating film composed of 90 parts of glass and 10 parts of alumina powder (prototype number 4)
Because the surface was rough, a large sensor output was obtained, and it was optimal as a material for forming a sputtered film. For the glass-based insulating film, the mixing ratio of glass and alumina powder was changed (2 to 30 parts of alumina powder was mixed) and a material other than alumina powder was used (2 to 20 parts of magnesium oxide and zirconia were mixed).
Even so, a large sensor output was obtained.
【００９３】（実施例６）実施例６は、安定化ジルコニ
アスパッタ膜の上部に、通気性の有る一対の白金薄膜を
形成する方法について検討した。Example 6 In Example 6, a method of forming a pair of air permeable platinum thin films on the stabilized zirconia sputtered film was studied.
【００９４】絶縁性支持基板に安定化ジルコニアスパッ
タ膜を形成し、このスパッタ膜の上部に、通気性の有る
一対の白金薄膜を大きな面積で形成しようとすると、絶
縁性支持基板が小型になる程、白金薄膜間の距離が短く
なる。一方、白金薄膜は、スパッタ法もしくは電子ビー
ム法さらには蒸着法で形成され、いずれの方法も白金を
蒸発させて形成させる方法である。白金を蒸発させて同
一面に形成した白金薄膜２個を電極として使用する場合
に、２個の白金薄膜の間に蒸発白金が多量に付着する
と、センサ出力が小さくなる問題が起る。そこで、その
低減方法を検討した。When a stabilized zirconia sputtered film is formed on an insulating support substrate, and a pair of air-permeable platinum thin films are formed on the sputtered film with a large area, the smaller the insulating support substrate becomes, the smaller the size of the insulating support substrate becomes. Therefore, the distance between the platinum thin films becomes shorter. On the other hand, a platinum thin film is formed by a sputtering method, an electron beam method, or a vapor deposition method, and each method is a method of evaporating platinum to form the platinum thin film. When two platinum thin films formed on the same surface by evaporating platinum are used as electrodes, a large amount of evaporated platinum adheres between the two platinum thin films, causing a problem that the sensor output becomes small. Then, the reduction method was examined.
【００９５】まず、２．５×２．５mmの絶縁性支持基板
（材質アルミナ）の表面に、ヒータ膜と絶縁膜を積層し
て形成し、この絶縁層の表面に安定化ジルコニアスパッ
タ膜を２×２mmの大きさで形成したものを試作した。そ
して、この安定化ジルコニアスパッタ膜の上部に、０．
４mmの距離を離して通気性の有る一対の白金薄膜（０．
７×０．７mm）を、スパッタ法で形成した。最後に、こ
の白金薄膜の片面上部に白金溶液を滴下して酸化触媒層
を形成し、リード線を取り付けて固体電解質型センサの
完成である。ヒータ膜で４５０℃に温度調整し、一酸化
炭素１０００ppmを含む空気に曝した際に測定したセン
サ出力を測定した。First, a heater film and an insulating film are laminated on the surface of an insulating support substrate (alumina) of 2.5 × 2.5 mm, and a stabilized zirconia sputtering film is formed on the surface of the insulating layer. A prototype formed with a size of 2 mm was prototyped. Then, on top of the stabilized zirconia sputtered film, 0.1.
A pair of breathable platinum thin films (0.
7 × 0.7 mm) was formed by a sputtering method. Finally, a platinum solution is dropped on the upper surface of one side of the platinum thin film to form an oxidation catalyst layer, and a lead wire is attached to complete the solid electrolyte sensor. The temperature was adjusted to 450 ° C. by a heater film, and the sensor output measured when exposed to air containing 1000 ppm of carbon monoxide was measured.
【００９６】白金薄膜を形成する際に、フッ素樹脂のシ
ートを一対の白金薄膜の間に貼付した製法のセンサは、
２０mvのセンサ出力が得られ、白金薄膜の間に付着した
白金量も極めて少なかった。一方、フッ素樹脂のシート
を使用しない製法のセンサは、１mvのセンサ出力が得ら
れ、白金薄膜の間に付着した白金量が多かった。When a platinum thin film is formed, a sensor of a manufacturing method in which a sheet of fluororesin is stuck between a pair of platinum thin films,
A sensor output of 20 mv was obtained, and the amount of platinum adhering between the platinum thin films was extremely small. On the other hand, a sensor manufactured using no fluororesin sheet produced a sensor output of 1 mv, and the amount of platinum adhering between the platinum thin films was large.
【００９７】次に、フッ素樹脂シートの材料組成を検討
した。その結果、フッ素樹脂が６０％以上含有する非粘
着耐熱性シート（１５０℃１時間放置でも変形なし）で
あれば、蒸発する白金の温度１５０℃に耐えることがで
きた。また特に、フッ素樹脂が８０％以上含有する非粘
着耐熱性シートであれば、蒸発する白金の温度２００℃
に耐えることができた。その結果、白金薄膜の間に付着
した白金量が低減して、大きなセンサ出力が得られた。Next, the material composition of the fluororesin sheet was examined. As a result, the non-adhesive heat-resistant sheet containing 60% or more of the fluororesin (having no deformation even when left at 150 ° C. for 1 hour) was able to withstand the evaporating platinum temperature of 150 ° C. In particular, in the case of a non-adhesive heat resistant sheet containing 80% or more of a fluororesin, the temperature of evaporated platinum is 200 ° C
Was able to endure. As a result, the amount of platinum adhered between the platinum thin films was reduced, and a large sensor output was obtained.
【００９８】白金薄膜は、スパッタ法以外に、電子ビー
ム法さらには蒸着法で形成することも可能であり、いず
れの方法も白金を蒸発させて安定化ジルコニアスパッタ
膜の表面に白金薄膜を形成させている。この際、蒸発す
る白金の最高温度（１５０℃最悪でも２００℃）以下の
場所に、安定化ジルコニアスパッタ膜を配置して膜形成
を行うことで、フッ素樹脂シートの耐熱性が確保でき、
大きなセンサ出力を得ることができた。また、フッ素樹
脂のシートは、冶具を用いて一対の白金薄膜の間にその
シートを介在させ、貼付することも可能でありこの場合
も、大きなセンサ出力を得ることができた。The platinum thin film can be formed by an electron beam method or a vapor deposition method other than the sputtering method. In each case, platinum is evaporated to form a platinum thin film on the surface of the stabilized zirconia sputtered film. ing. At this time, the heat resistance of the fluororesin sheet can be secured by arranging the stabilized zirconia sputtered film in a place at or below the maximum temperature of the evaporating platinum (150 ° C. or worse, 200 ° C.).
A large sensor output could be obtained. Further, the sheet of fluororesin can be adhered by interposing the sheet between a pair of platinum thin films using a jig, and in this case also, a large sensor output could be obtained.
【００９９】[0099]
【発明の効果】以上の説明から明らかなように、本発明
のガスセンサによれば、次の効果が得られる。As is apparent from the above description, the following effects can be obtained according to the gas sensor of the present invention.
【０１００】請求項１記載の発明によれば、絶縁性支持
基板に形成されておりその上部に絶縁層が積層されるヒ
ータ膜は、主成分の耐酸化性発熱材料と副成分の耐熱性
金属酸化物と結合材のガラスとからなる印刷焼成膜であ
り、比抵抗が２３〜２２８６×１０-6Ωmとしている。
そのため、ヒータ膜は、単純な小面積形状に厚膜印刷す
るだけで、膜厚が厚く線幅が太くても大きな抵抗が簡単
に得られ、複雑な製造技術と品質管理技術を必要としな
い。また、ヒータ膜の長さが短くできるので、ガスセン
サが小型化して熱容量が低減し、消費電力が少さくな
る。しかも、ヒータ膜は、空気酸化に強い材料を使用し
ているため抵抗値の増大が小さく、その上部に形成する
絶縁層は、一般的な気密性でよくその形成は簡単な製造
技術と品質管理で対応できる。また、ヒータ膜を厚膜化
しているため電流密度が低減し、ヒータ膜の抵抗変化は
極めて小さくなる。このため、直流電圧を印加して発熱
させる方式でセンサ動作温度を長期間一定にすることが
でき、制御回路が簡単になる。According to the first aspect of the present invention, the heater film formed on the insulating support substrate, on which the insulating layer is laminated, is composed of the oxidation-resistant heat-generating material of the main component and the heat-resistant metal of the sub-component. It is a printed fired film made of an oxide and a binder glass, and has a specific resistance of 23 to 2286 × 10 −6 Ωm.
Therefore, the heater film can easily obtain a large resistance even when the film thickness is large and the line width is large simply by printing a thick film in a simple small area shape, and does not require complicated manufacturing technology and quality control technology. Further, since the length of the heater film can be shortened, the gas sensor is downsized, the heat capacity is reduced, and the power consumption is reduced. In addition, since the heater film uses a material that is resistant to air oxidation, the increase in resistance is small, and the insulating layer formed on the heater film has general airtightness, and its formation is simple with manufacturing technology and quality control. Can respond. Further, since the heater film is made thicker, the current density is reduced, and the resistance change of the heater film becomes extremely small. For this reason, the sensor operating temperature can be kept constant for a long period of time by applying a DC voltage to generate heat, and the control circuit is simplified.
【０１０１】請求項２記載の発明によれば、絶縁性支持
基板の一方の面に形成されたヒータ膜は、主成分の耐酸
化性発熱材料と副成分の耐熱性金属酸化物と結合材のガ
ラスとからなる印刷焼成膜であり、比抵抗が２３〜２２
８６×１０-6Ωmとしている。そのため、ヒータ膜は、
単純な小面積形状に厚膜印刷するだけで、膜厚が厚く線
幅が太くても大きな抵抗が簡単に得られ、複雑な製造技
術と品質管理技術を必要としない。また、ヒータ膜の長
さが短くできるので、ガスセンサが小型化して熱容量が
低減し、消費電力が少さくなる。しかも、ヒータ膜は、
空気酸化に強い材料を使用しているため抵抗値の増大が
小さく、さらにヒータ膜を厚膜化しているため電流密度
が低減し、ヒータ膜の抵抗変化は極めて小さくなる。こ
のため、直流電圧を印加して発熱させる方式でセンサ動
作温度を長期間一定にすることができ、制御回路が簡単
になる。According to the second aspect of the present invention, the heater film formed on one surface of the insulating support substrate is composed of the oxidation-resistant heat-generating material of the main component, the heat-resistant metal oxide of the sub-component, and the binder. It is a printed and fired film made of glass and has a specific resistance of 23 to 22.
86 × 10 −6 Ωm. Therefore, the heater film
By simply printing a thick film in a simple small area shape, a large resistance can be easily obtained even if the film thickness is large and the line width is large, and complicated manufacturing technology and quality control technology are not required. Further, since the length of the heater film can be shortened, the gas sensor is downsized, the heat capacity is reduced, and the power consumption is reduced. Moreover, the heater film is
Since a material resistant to air oxidation is used, the increase in resistance value is small, and since the heater film is thickened, the current density is reduced and the change in resistance of the heater film is extremely small. For this reason, the sensor operating temperature can be kept constant for a long period of time by applying a DC voltage to generate heat, and the control circuit is simplified.
【０１０２】請求項３記載の発明によれば、ヒータ膜
は、主成分の白金と副成分のアルミナと結合材のガラス
からなるため、空気酸化に強く抵抗値の増大が小さい。
また、高表面積と高融点のアルミナと、ガラスを副成分
として使用しているため、白金粒子が強固に固着して移
動し難くなり、抵抗の変化がない優れた耐久性を有する
ヒータ膜が得られる。According to the third aspect of the present invention, since the heater film is made of platinum as the main component, alumina as the sub component, and glass as the binder, it is resistant to air oxidation and has a small increase in resistance.
In addition, since alumina and glass having a high surface area and a high melting point and glass are used as sub-components, platinum particles are firmly fixed and hard to move, and a heater film having excellent durability without change in resistance is obtained. Can be
【０１０３】請求項４記載の発明によれば、絶縁膜は、
主成分の硝子と、前記硝子の軟化温度より高い溶融温度
を持つ耐熱高表面積性金属酸化物の副成分からなるた
め、硝子と耐熱高表面積性金属酸化物が強固に固着し、
絶縁膜の組成物がヒータ膜に流れ込むことを抑制する。
その結果、ヒータ膜や絶縁膜は良好な電気特性および絶
縁性を示し、しかもこれらの積層膜の耐熱衝撃性も向上
する。According to the fourth aspect of the present invention, the insulating film is
Since the main component glass and the heat-resistant high-surface-area metal oxide having a melting temperature higher than the softening temperature of the glass are composed of sub-components, the glass and the heat-resistant high-surface-area metal oxide are firmly fixed,
The composition of the insulating film is prevented from flowing into the heater film.
As a result, the heater film and the insulating film exhibit good electric characteristics and insulating properties, and the thermal shock resistance of these laminated films is also improved.
【０１０４】請求項５記載の発明によれば、ガス感応膜
は、気密性の安定化ジルコニアスパッタ膜と、その上部
に形成した通気性の有る一対の白金薄膜と、白金薄膜の
片面上部に配置させた酸化触媒層とから構成される。そ
して、安定化ジルコニアスパッタ膜は、主成分のアルゴ
ンに副成分の酸素を混合させたガス雰囲気中でスパッタ
を行い、その後に８００〜１３００℃の加熱エイジング
処理を施している。このため、結晶性や電導性に優れた
安定化ジルコニアの膜となり、大きなセンサ出力が得ら
れる。According to the fifth aspect of the present invention, the gas-sensitive film is a gas-tight stabilized zirconia sputtered film, a pair of air-permeable platinum thin films formed on the film, and an upper portion of one side of the platinum thin film. And an oxidation catalyst layer. The stabilized zirconia sputtered film is sputtered in a gas atmosphere in which oxygen as a main component is mixed with argon as a main component, and then subjected to a heat aging treatment at 800 to 1300 ° C. For this reason, a stabilized zirconia film having excellent crystallinity and conductivity is obtained, and a large sensor output is obtained.
【０１０５】請求項６記載の発明によれば、白金薄膜
は、フッ素樹脂を主成分とする被膜を一対の白金薄膜の
間に貼付し、白金分子もしくは原子を真空中で蒸発させ
て形成される。フッ素樹脂を主成分とする被膜により、
白金薄膜の間に付着する白金量が減少するため、大きな
センサ出力が得られる。According to the sixth aspect of the present invention, the platinum thin film is formed by adhering a coating mainly composed of a fluororesin between a pair of platinum thin films and evaporating platinum molecules or atoms in a vacuum. . With a coating mainly composed of fluororesin,
Since the amount of platinum adhering between the platinum thin films is reduced, a large sensor output can be obtained.
【図１】本発明の実施例１におけるガスセンサの断面図FIG. 1 is a cross-sectional view of a gas sensor according to a first embodiment of the present invention.
【図２】本発明の実施例２におけるガスセンサの断面図FIG. 2 is a sectional view of a gas sensor according to a second embodiment of the present invention.
【図３】従来のガスセンサの断面図FIG. 3 is a cross-sectional view of a conventional gas sensor.
６ 絶縁性支持基板 ７ ヒータ膜 ８ 絶縁膜 ９ ガス感応膜 １０ 安定化ジルコニアスパッタ膜 １１、１２ 一対の白金薄膜 １３ 酸化触媒層 Reference Signs List 6 Insulating support substrate 7 Heater film 8 Insulating film 9 Gas sensitive film 10 Stabilized zirconia sputtered film 11, 12 A pair of platinum thin films 13 Oxidation catalyst layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宇野 克彦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 丹羽 孝 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 梅田 孝裕 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 2G046 AA01 BA01 BA04 BA08 BA09 BB02 BE03 BE07 BE08 BF04 EA02 EA04 EA08 EA11 EA18 FA05 FB02 FE03 FE31 FE49 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Katsuhiko Uno 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Takahiro Umeda 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture F-term in Matsushita Electric Industrial Co., Ltd. (reference)
Claims (6)
一方の面に順に積層させたヒータ膜と、気密性を有する
絶縁膜と、ガス感応膜とから構成され、前記ヒータ膜
は、主成分の耐酸化性発熱材料と副成分の耐熱性金属酸
化物と結合材のガラスとからなる印刷焼成膜であり、比
抵抗が２３〜２２８６×１０-6Ωmであるガスセンサ。An insulating support substrate, a heater film sequentially laminated on one surface of the insulating support substrate, an air-tight insulating film, and a gas-sensitive film, wherein the heater film comprises: A gas sensor which is a printed baked film composed of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and glass as a binder, and has a specific resistance of 23 to 2286 × 10 −6 Ωm.
一方の面に形成されたヒータ膜と、前記絶縁性支持基板
の他面に形成されたガス感応膜とから構成され、前記ヒ
ータ膜は、主成分の耐酸化性発熱材料と副成分の耐熱性
金属酸化物と結合材のガラスとからなる印刷焼成膜であ
り、比抵抗が２３〜２２８６×１０-6Ωmであるガスセ
ンサ。2. The heater according to claim 1, further comprising an insulating support substrate, a heater film formed on one surface of the insulating support substrate, and a gas-sensitive film formed on the other surface of the insulating support substrate. The film is a printed and baked film composed of an oxidation-resistant heat-generating material as a main component, a heat-resistant metal oxide as a sub-component, and a glass as a binder, and has a specific resistance of 23 to 2286 × 10 −6 Ωm.
ミナと結合材のガラスからなる請求項１または２に記載
のガスセンサ。3. The gas sensor according to claim 1, wherein the heater film is made of platinum as a main component, alumina as a sub component, and glass as a binder.
化温度より高い溶融温度を持つ耐熱高表面積性金属酸化
物の副成分からなる請求項１に記載のガスセンサ。4. The gas sensor according to claim 1, wherein the insulating film comprises glass as a main component and a sub-component of a heat-resistant and high-surface-area metal oxide having a melting temperature higher than the softening temperature of the glass.
スパッタ膜と、前記安定化ジルコニアスパッタ膜の上部
に形成した通気性の有る一対の白金薄膜と、前記白金薄
膜の片面上部に配置させた酸化触媒層とからなり、前記
安定化ジルコニアスパッタ膜は、主成分のアルゴンに副
成分の酸素を混合させたガス雰囲気中での安定化ジルコ
ニアのスパッタ膜を８００〜１３００℃で加熱焼成した
膜である請求項１または２に記載のガスセンサ。5. A gas-sensitive film comprising: a gas-tight stabilized zirconia sputtered film; a pair of air-permeable platinum thin films formed on the stabilized zirconia sputtered film; The stabilized zirconia sputtered film is a film obtained by heating and sintering a sputtered film of stabilized zirconia in a gas atmosphere in which oxygen as a main component is mixed with argon as a main component at 800 to 1300 ° C. The gas sensor according to claim 1, wherein:
ッタ膜の表面に貼付させたフッ素樹脂を主成分とする被
膜の両側部に、白金分子もしくは原子を減圧中で蒸発さ
せて形成した膜である請求項５記載のガスセンサ。6. A pair of platinum thin films are formed by evaporating platinum molecules or atoms under reduced pressure on both sides of a film mainly composed of a fluororesin adhered to the surface of a stabilized zirconia sputtered film. The gas sensor according to claim 5, wherein
Priority Applications (1)
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|---|---|---|---|
| JP2000048816A JP2001235442A (en) | 2000-02-25 | 2000-02-25 | Gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000048816A JP2001235442A (en) | 2000-02-25 | 2000-02-25 | Gas sensor |
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| Publication Number | Publication Date |
|---|---|
| JP2001235442A true JP2001235442A (en) | 2001-08-31 |
Family
ID=18570849
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000048816A Pending JP2001235442A (en) | 2000-02-25 | 2000-02-25 | Gas sensor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014505881A (en) * | 2011-02-02 | 2014-03-06 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Electronic components including ceramic supports and use of ceramic supports |
| JP5524234B2 (en) * | 2009-11-06 | 2014-06-18 | 株式会社日立製作所 | Gas sensor |
| WO2020079966A1 (en) * | 2018-10-15 | 2020-04-23 | Ｎｉｓｓｈａ株式会社 | Mems gas sensor and mems gas sensor manufacturing method |
| JP2022526947A (en) * | 2019-03-26 | 2022-05-27 | セルモビリティ・インコーポレイテッド | Gas sensor device based on metal oxide foam |
-
2000
- 2000-02-25 JP JP2000048816A patent/JP2001235442A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5524234B2 (en) * | 2009-11-06 | 2014-06-18 | 株式会社日立製作所 | Gas sensor |
| US9228973B2 (en) | 2009-11-06 | 2016-01-05 | Hitachi, Ltd. | Gas sensor |
| JP2014505881A (en) * | 2011-02-02 | 2014-03-06 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Electronic components including ceramic supports and use of ceramic supports |
| WO2020079966A1 (en) * | 2018-10-15 | 2020-04-23 | Ｎｉｓｓｈａ株式会社 | Mems gas sensor and mems gas sensor manufacturing method |
| JP2020063914A (en) * | 2018-10-15 | 2020-04-23 | Ｎｉｓｓｈａ株式会社 | MEMS gas sensor and method for manufacturing MEMS gas sensor |
| CN112805557A (en) * | 2018-10-15 | 2021-05-14 | Ｎｉｓｓｈａ株式会社 | MEMS gas sensor and method for manufacturing MEMS gas sensor |
| TWI818072B (en) * | 2018-10-15 | 2023-10-11 | 日商日寫股份有限公司 | Microelectromechanical system gas sensor and method of manufacturing microelectromechanical system gas sensor |
| US12055507B2 (en) | 2018-10-15 | 2024-08-06 | Nissha Co., Ltd. | MEMS gas sensor and method for manufacturing MEMS gas sensor |
| JP2022526947A (en) * | 2019-03-26 | 2022-05-27 | セルモビリティ・インコーポレイテッド | Gas sensor device based on metal oxide foam |
| JP7655856B2 (en) | 2019-03-26 | 2025-04-02 | セルモビリティ・インコーポレイテッド | Gas sensor devices based on metal oxide foams |
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