JPH0882613A - Manufacture for electrode film for sensor - Google Patents
Manufacture for electrode film for sensorInfo
- Publication number
- JPH0882613A JPH0882613A JP24472794A JP24472794A JPH0882613A JP H0882613 A JPH0882613 A JP H0882613A JP 24472794 A JP24472794 A JP 24472794A JP 24472794 A JP24472794 A JP 24472794A JP H0882613 A JPH0882613 A JP H0882613A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- electrode film
- sensor
- insulating substrate
- film
- 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]
【産業上の利用分野】本発明は、センサ用電極膜の製造
法に関する。更に詳しくは、電極膜が形成される絶縁性
基板に対する付着力を向上せしめたセンサ用電極膜の製
造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an electrode film for a sensor. More specifically, the present invention relates to a method for manufacturing a sensor electrode film having improved adhesion to an insulating substrate on which an electrode film is formed.
【0002】[0002]
【従来の技術】従来から、各種センサに用いられる電極
には、大気中で酸化物を形成し難く、安定性の高い金、
白金、パラジウム等の貴金属が電極材料として用いられ
ている。これらの貴金属電極材料は、絶縁性基板、一般
にはSiO2、Al2O3等の酸化物基板上に薄膜状に堆積さ
れ、電極を形成するが、酸化物基板と貴金属薄膜とは付
着性に乏しく、加工途中あるいは経時的に剥がれるとい
う問題がある。その原因については、これらの酸化物と
貴金属との間で金属酸化物を形成し難いためであるとい
う説もあるが定かではない。2. Description of the Related Art Conventionally, electrodes used for various sensors are made of gold, which is highly stable because it is difficult to form an oxide in the atmosphere.
Noble metals such as platinum and palladium are used as electrode materials. These noble metal electrode materials are deposited on an insulating substrate, generally an oxide substrate such as SiO 2 or Al 2 O 3 in a thin film form to form an electrode. There is a problem that it is scarce and peels off during processing or over time. There is a theory that it is difficult to form a metal oxide between these oxides and a noble metal, but it is not clear.
【0003】これら両者間の付着性を改善する方法とし
ては、酸化物基板との付着力の強い金属層を設けること
が一般に行われている。このとき、それが電極として用
いられるセンサの作製段階あるいは使用段階において高
温に曝されることがなければそこに格別の配慮はいら
ず、付着力の強いクロムを利用することが多い。[0003] As a method of improving the adhesion between the two, a metal layer having a strong adhesion to an oxide substrate is generally provided. At this time, unless the sensor used as an electrode is exposed to a high temperature in a manufacturing stage or a use stage, no special consideration is given thereto, and chromium having a strong adhesive force is often used.
【0004】しかしながら、一部のセンサではセンサの
作製段階においてアニールが施され、また温度センサで
は高温で使用されることが多く、ガスセンサに至っては
高温動作しなければならないなど、電極部分を含めたセ
ンサが高温に曝される場合も非常に多い。[0004] However, some sensors are annealed at the stage of manufacturing the sensor, and temperature sensors are often used at a high temperature, and the gas sensor must operate at a high temperature. Very often, sensors are exposed to high temperatures.
【0005】ところで、付着力の強い金属層を介在させ
た貴金属薄膜電極が高温に曝されると、金属相互間の拡
散が顕著となり、抵抗率に変化を及ぼすようになる。更
に、雰囲気が大気などの酸化性雰囲気の場合には、貴金
属中に拡散した金属の酸化が起こり、これもまた抵抗率
に影響を及ぼすようになる。従って、付着力を改善する
ための層としては、貴金属と相互拡散を起こし難い材料
から形成させる必要がある。When a noble metal thin film electrode having a metal layer having strong adhesion is exposed to a high temperature, diffusion between the metals becomes remarkable and the resistivity changes. Further, when the atmosphere is an oxidizing atmosphere such as air, oxidation of the metal diffused in the noble metal occurs, which also affects the resistivity. Therefore, it is necessary to form the layer for improving the adhesive force from a material that hardly causes mutual diffusion with the noble metal.
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、酸化
物基板等の絶縁性基板上に貴金属薄膜を電極膜として形
成させるに際し、その間に貴金属と相互拡散し難い材料
からなる付着力の強い層を積層させたセンサ用電極膜の
製造法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to form a noble metal thin film as an electrode film on an insulating substrate such as an oxide substrate, in which the noble metal is made of a material that is hard to interdiffuse and has strong adhesion. It is to provide a method of manufacturing an electrode film for a sensor in which layers are laminated.
【0007】[0007]
【課題を解決するための手段】かかる本発明の目的は、
絶縁性基板上にけい素および貴金属を順次堆積させた
後、約500〜900℃の大気中に保持してセンサ用電極膜を
製造することによって達成される。SUMMARY OF THE INVENTION The object of the present invention is as follows.
This is achieved by sequentially depositing silicon and a noble metal on an insulating substrate, and then maintaining the atmosphere in the atmosphere at about 500 to 900 ° C. to manufacture an electrode film for a sensor.
【0008】絶縁性基板としては、前述のSiO2、Al2O3
等の酸化物基板以外にもガラス基板等も用いられる。け
い素および貴金属の堆積は、真空蒸着法、スパッタリン
グ法、イオンプレーティング法など、一般に薄膜形成に
用いられている任意の方法で行うことができ、それの段
階的な堆積は、同一の反応装置を用いて段階的に行うこ
とができる。その際、Si層は一般に約0.5〜100nm、好ま
しくは約5〜50nmの膜厚で、また貴金属層は一般に約50
〜500nm、好ましくは約100〜300nmの膜厚で形成せしめ
る。As the insulating substrate, the above-mentioned SiO 2 , Al 2 O 3 are used.
In addition to oxide substrates such as glass substrates, glass substrates and the like can be used. The silicon and the noble metal can be deposited by any method generally used for forming a thin film such as a vacuum vapor deposition method, a sputtering method, an ion plating method, and the stepwise deposition thereof can be performed by the same reaction apparatus. Can be performed stepwise. The Si layer generally has a thickness of about 0.5-100 nm, preferably about 5-50 nm, and the noble metal layer generally has a thickness of about 50 nm.
It is formed with a film thickness of ~ 500 nm, preferably about 100-300 nm.
【0009】このようにして絶縁性基板上に形成せしめ
た貴金属/Si積層膜は、絶縁性基板との付着力を高める
ために、約500〜900℃、好ましくは約600〜800℃の大気
中に約0.5〜10時間程度保持される。これ以下の保持温
度では、付着力の改善効果が十分ではなく、一方これ以
上の温度に保持されると、貴金属薄膜自身の粒成長が著
しくなる。また、このような高温保持を適用することに
より、センサ用電極膜として一定の抵抗率を示すように
なる。The noble metal / Si laminated film thus formed on the insulating substrate is exposed to the atmosphere of about 500 to 900 ° C., preferably about 600 to 800 ° C., in order to enhance the adhesive force with the insulating substrate. Hold for about 0.5-10 hours. At a holding temperature lower than this, the effect of improving the adhesive force is not sufficient, while at a temperature higher than this, grain growth of the noble metal thin film itself becomes remarkable. Moreover, by applying such high temperature holding, the sensor electrode film exhibits a constant resistivity.
【0010】[0010]
【発明の効果】酸化物基板等の絶縁性基板上に貴金属薄
膜を電極膜として形成させるに際し、その間に付着力の
強いけい素薄膜を積層して形成させた上、これを高温の
大気中に保持することにより、絶縁性基板と貴金属電極
膜との間の付着力を高め、また抵抗率を一定のものとす
ることができるので、これを温度センサ、ガスセンサを
始めとする各種センサのセンサ用電極として有効に使用
することができる。EFFECTS OF THE INVENTION When a noble metal thin film is formed as an electrode film on an insulating substrate such as an oxide substrate, a silicon thin film having a strong adhesive force is laminated between them, and the thin film is exposed to a high temperature atmosphere. By holding it, the adhesive force between the insulating substrate and the noble metal electrode film can be increased and the resistivity can be made constant, so this can be used for temperature sensors, gas sensors and other sensors. It can be effectively used as an electrode.
【0011】[0011]
【実施例】次に、実施例について本発明を説明する。Next, the present invention will be described by way of examples.
【0012】実施例 基板ホルダーにアルミナ平板を設置した真空蒸着装置内
に、真空蒸着用のSiるつぼとPtるつぼとを入れ、装置内
を5×10-6Torr以下に排気した。その後、電子ビームでS
iを加熱し、アルミナ平板上にSiを50nm堆積させ、その
真空状態を保持したまま、続けてPtを電子ビームで加熱
し、Ptを300nm堆積させて、Pt/Si積層膜をアルミナ平板
上に形成させた。EXAMPLE A Si crucible and a Pt crucible for vacuum deposition were placed in a vacuum deposition apparatus in which an alumina flat plate was placed on a substrate holder, and the apparatus was evacuated to 5 × 10 -6 Torr or less. Then S with electron beam
i is heated to deposit 50 nm of Si on the alumina flat plate, and while maintaining the vacuum state, Pt is continuously heated by an electron beam to deposit Pt of 300 nm to deposit the Pt / Si laminated film on the alumina flat plate. Formed.
【0013】このPt/Si積層膜形成アルミナ平板を、500
℃、600℃、700℃または800℃の大気中にそれぞれ5時間
保持し、Pt/Si積層膜のアルミナ平板に対する付着力
を、引張試験法により測定した。その保持温度と付着力
との関係は、図1のグラフに示される。また、保持温度
と抵抗率との関係は、図2のグラフに示される。This Pt / Si laminated film forming alumina flat plate was
The adhesive force of the Pt / Si laminated film to the alumina flat plate was measured by a tensile test method by holding each in the atmosphere of ℃, 600 ℃, 700 ℃ or 800 ℃ for 5 hours. The relationship between the holding temperature and the adhesive force is shown in the graph of FIG. The relationship between the holding temperature and the resistivity is shown in the graph of FIG.
【0014】比較例 実施例において、Siを堆積させることなく、Pt膜(膜厚3
00nm)のみをアルミナ平板上に形成させた。Pt膜のアル
ミナ平板に対する付着力および抵抗率は、図1および図
2のグラフ中に併記されている。Comparative Example In the example, the Pt film (thickness 3
Only 00 nm) was formed on an alumina plate. The adhesion and resistivity of the Pt film to the alumina plate are also shown in the graphs of FIGS. 1 and 2.
【0015】以上の結果から、次のようなことがいえ
る。 (1)Pt/Si積層膜は、600℃以上の高温保持が適用されな
い場合でも、Pt膜の2.7倍程度付着力が大きいが、600℃
以上の高温保持を適用することにより、600kgf/cm2以上
という十分なる付着力を示すようになる。 (2)500℃以上の高温保持が適用されない場合、Pt膜の抵
抗率1.5×10-5Ω・cmに対し、Pt/Si積層膜は2.9×10-5
Ω・cmであったが、500℃以上の高温保持を適用するこ
とにより、2×10-5Ω・cm程度のほぼ一定の抵抗率を示
すようになる。From the above results, the following can be said. (1) Pt / Si laminated film has 2.7 times more adhesive force than Pt film, even if high temperature holding of 600 ° C or higher is not applied.
By applying the above high temperature holding, sufficient adhesive force of 600 kgf / cm 2 or more is exhibited. (2) When the high temperature holding of 500 ℃ or more is not applied, the resistivity of Pt film is 1.5 × 10 -5 Ωcm, whereas the Pt / Si laminated film is 2.9 × 10 -5.
Although it was Ω · cm, by applying a high temperature holding of 500 ° C. or more, it becomes to show an almost constant resistivity of about 2 × 10 −5 Ω · cm.
【図1】実施例における保持温度と付着力との関係を示
すグラフである。FIG. 1 is a graph showing the relationship between holding temperature and adhesive force in an example.
【図2】実施例における保持温度と抵抗率との関係を示
すグラフである。FIG. 2 is a graph showing the relationship between the holding temperature and the resistivity in the example.
Claims (1)
次堆積せしめた後、約500〜900℃の大気中に保持するこ
とを特徴とするセンサ用電極膜の製造法。1. A method for producing an electrode film for a sensor, which comprises sequentially depositing silicon and a noble metal on an insulating substrate and then holding the same in the atmosphere at about 500 to 900 ° C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24472794A JPH0882613A (en) | 1994-09-13 | 1994-09-13 | Manufacture for electrode film for sensor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24472794A JPH0882613A (en) | 1994-09-13 | 1994-09-13 | Manufacture for electrode film for sensor |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0882613A true JPH0882613A (en) | 1996-03-26 |
Family
ID=17123005
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24472794A Pending JPH0882613A (en) | 1994-09-13 | 1994-09-13 | Manufacture for electrode film for sensor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0882613A (en) |
-
1994
- 1994-09-13 JP JP24472794A patent/JPH0882613A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH09145489A (en) | Resistance thermometer | |
JPH01118760A (en) | Sensor | |
JPH0359450A (en) | Gas sensitive element | |
Wang et al. | Sputter deposition of yttria-stabilized zirconia and silver cermet electrodes for SOFC applications | |
JP4137254B2 (en) | Method for producing transparent conductive laminate | |
JP2002042582A (en) | Manufacturing method of substrate with transparent conductive film, and the substrate manufactured by the method, and touch panel using the substrate | |
JP3304541B2 (en) | Method of forming ohmic electrode | |
US6217722B1 (en) | Process for producing Ti-Cr-Al-O thin film resistors | |
JP2001189114A (en) | Manufacturing method of transparent electrode | |
JPS62222616A (en) | Heat-resistant electrode thin film | |
GB2081517A (en) | Method for making electrically conductive penetrations into thin films | |
JP2001135149A (en) | Zinc oxide-based transparent electrode | |
JP2000108244A (en) | Transparent conductive film, its manufacture, and base having transparent conductive film | |
JP3542012B2 (en) | Thin film gas sensor | |
JPH0882613A (en) | Manufacture for electrode film for sensor | |
JPH0933470A (en) | Gas sensor | |
JPH04230906A (en) | Transparent conductive laminated body | |
US6059937A (en) | Sensor having tin oxide thin film for detecting methane gas and propane gas, and process for manufacturing thereof | |
JPH03262101A (en) | Platinum temperature sensor | |
JP3489844B2 (en) | Transparent conductive film and method for producing the same | |
JP3654841B2 (en) | Transparent conductive film and method for producing the same | |
JPH07122724A (en) | Ohmic electrode of n-type cubic boron nitride semiconductor and its formation | |
JP2996922B2 (en) | Tin oxide thin film sensor for sensing hydrogen and method of manufacturing the same | |
US6420826B1 (en) | Flat panel display using Ti-Cr-Al-O thin film | |
JPH05263219A (en) | Production of copper indium selenide thin film |