JPS6151260B2 - - Google Patents
Info
- Publication number
- JPS6151260B2 JPS6151260B2 JP9708380A JP9708380A JPS6151260B2 JP S6151260 B2 JPS6151260 B2 JP S6151260B2 JP 9708380 A JP9708380 A JP 9708380A JP 9708380 A JP9708380 A JP 9708380A JP S6151260 B2 JPS6151260 B2 JP S6151260B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- present
- sensitivity
- palladium
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】
本発明はガス検知素子にかかわり、酸化物超微
粒子膜を感応部として有するガス検知素子の、メ
タンに対する感度を向上させ、さらに水素に対す
る低温で感度を向上させることを目的とする。Detailed Description of the Invention The present invention relates to a gas detection element, and an object of the present invention is to improve the sensitivity of a gas detection element having an oxide ultrafine particle film as a sensitive part to methane, and further to improve the sensitivity to hydrogen at low temperatures. shall be.
先に本出願人は、平均粒径が十数Åから千Å程
度の酸化物超微粒子で構成され、ガスや水蒸気に
対して抵抗値が敏感に変化する感応膜を有するガ
ス検知素子を提案した（特願昭53−100620号）。
このような感応膜を有するガス検知素子は感度の
点ですぐれているが、外的作用因子の種類によつ
ては、素子を動作させるのに加熱する必要があ
る。したがつてできる限り低温で動作することが
消費電力節減の面から求められている。 Previously, the applicant proposed a gas sensing element that is composed of ultrafine oxide particles with an average particle size of about 10-10 Å to about 1,000 Å and has a sensitive film whose resistance value changes sensitively to gas or water vapor. (Special Application No. 100620, Showa 53).
A gas sensing element having such a sensitive film has excellent sensitivity, but depending on the type of external agent, it may be necessary to heat the element to operate it. Therefore, in order to reduce power consumption, it is required to operate at as low a temperature as possible.
また、メタンガスに対しては、、プロパンガ
ス、イソブタンガス等に対するよりも感度が低
く、加熱温度も比較的高温を必要とするなど、実
用上の問題点があつた。 Furthermore, there are practical problems in that the sensitivity to methane gas is lower than that to propane gas, isobutane gas, etc., and a relatively high heating temperature is required.
本発明は、簡単な構造でメタンや水素に対する
感度を向上させ、しかも動作温度を低下させたガ
ス検知素子を提供しようとするものである。 The present invention aims to provide a gas detection element that has a simple structure, has improved sensitivity to methane and hydrogen, and has a lower operating temperature.
すなわち、本発明のガス検知素子は、少なくと
も表面の一部がパラジウムからなる一対の電極を
設置した絶縁性支持基体上に平均粒径が十数Åか
ら百数十Åの金属酸化物超微粒子膜を形成したこ
とを特徴とする。 That is, the gas sensing element of the present invention comprises a metal oxide ultrafine particle film with an average particle diameter of 10-odd Å to 100-odd angstroms on an insulating support substrate on which a pair of electrodes, at least a portion of which is made of palladium, is provided. It is characterized by the formation of
以下、図面を参照しながら本発明の一実施例を
説明する。第１図および第２図は本発明の一実施
例であるガス検知素子を示す。本発明によるガス
検知素子は、図に示すように、ガラスやセラミツ
クスなどよりなる絶縁基板１上に、表面部の一部
がパラジウムよりなる一対の電極２，３を設け、
かつ電極２，３のパラジウム部に接触するよう
に、錫、チタン、亜鉛あるいはニツケル等の金属
酸化物半導体の超微粒子膜４を形成してなるもの
である。 An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 and FIG. 2 show a gas sensing element which is an embodiment of the present invention. As shown in the figure, the gas detection element according to the present invention has a pair of electrodes 2 and 3 whose surface portions are partially made of palladium on an insulating substrate 1 made of glass, ceramics, etc.
Further, an ultrafine particle film 4 of a metal oxide semiconductor such as tin, titanium, zinc, or nickel is formed so as to be in contact with the palladium portions of the electrodes 2 and 3.
本発明によるガス検知素子は、一般に次のよう
にして製造される。たとえば、電極としてパラジ
ウム蒸着膜、金属酸化物として錫酸化物を用いた
ガス検知素子の製造例を第３図を用いて説明す
る。 The gas sensing element according to the present invention is generally manufactured as follows. For example, an example of manufacturing a gas sensing element using a palladium vapor deposited film as an electrode and a tin oxide as a metal oxide will be described with reference to FIG.
真空蒸着装置１１内の試料ホルダー１２に、第
１図で示したような絶縁基板１を取付け、電極形
成用マスク（図示省略）をセツトする。また蒸発
用ボート１３には蒸発材料１４としてパラジウム
をセツトし、もう一方の蒸発用ボート１５には蒸
発材料１６として錫もしくはその酸化物をセツト
する。しかるのち排気口１７に接続された真空ポ
ンプ（図示省略）を作動させて排気を行ない、装
置１１内の真空度を10-6Torr.のオーダにした
後、蒸発用電源１８によりボート１３に通電して
発熱させ、蒸発材料１４を数秒から数分間蒸発さ
せる。たとえば120〜160Wの電力をボート１３に
加えると、厚さ2000Åのパラジウム蒸着膜からな
る一対の電極２，３（第１図、第２図）が絶縁基
板１上に形成される。電極が形成された後、電極
形成用マスク（図示省略）を超微粒子膜形成用マ
スク（図示省略）に切り換え、酸素ガス導入口１
９のコツクを開いて装置１１内に酸素ガスを導入
し、その圧力をたとえば0.5Torr.程度に保つ。次
に蒸発用電源２０によりボート１５に通電して発
熱させ、酸素ガス0.5Torr.雰囲気のもとで蒸発用
材料１６を数秒から数分間蒸発させる。たとえ
ば、蒸発用材料１６として錫を選び120〜160Wの
電力をボート１５に加えると、平均粒径が約40Å
の超微粒子からなる約20μｍの厚さの錫酸化物の
超微粒子の膜４が、第１図、第２図に示すように
基板１上に形成された。 An insulating substrate 1 as shown in FIG. 1 is attached to a sample holder 12 in a vacuum evaporation apparatus 11, and an electrode forming mask (not shown) is set. Palladium is set in the evaporation boat 13 as an evaporation material 14, and tin or its oxide is set in the other evaporation boat 15 as an evaporation material 16. After that, a vacuum pump (not shown) connected to the exhaust port 17 is operated to perform exhaustion, and after the degree of vacuum in the device 11 is on the order of 10 -6 Torr., the boat 13 is energized by the evaporation power source 18. The evaporation material 14 is evaporated for several seconds to several minutes by generating heat. For example, when a power of 120 to 160 W is applied to the boat 13, a pair of electrodes 2 and 3 (FIGS. 1 and 2) made of a palladium vapor-deposited film with a thickness of 2000 Å is formed on the insulating substrate 1. After the electrodes are formed, the electrode formation mask (not shown) is switched to the ultrafine particle film formation mask (not shown), and the oxygen gas inlet 1
9 is opened to introduce oxygen gas into the device 11, and its pressure is maintained at, for example, about 0.5 Torr. Next, the boat 15 is energized by the evaporation power source 20 to generate heat, and the evaporation material 16 is evaporated for several seconds to several minutes in an oxygen gas atmosphere of 0.5 Torr. For example, if tin is selected as the evaporation material 16 and a power of 120 to 160 W is applied to the boat 15, the average particle size will be about 40 Å.
A film 4 of ultrafine tin oxide particles with a thickness of about 20 μm was formed on the substrate 1 as shown in FIGS. 1 and 2.
ここでは電極としてパラジウム蒸着膜を例にあ
げて述べたが、たとえば他の金属で電極下地を形
成しておきその上に重ねてパラジウムを蒸着して
も同様な効果が得られることはいうまでもなく、
また蒸発材料を蒸発させる方法として抵抗加熱法
を例にあげたが、他の方法でもよいことはいうま
でもない。 Here, we have used a palladium vapor-deposited film as an example of the electrode, but it goes without saying that the same effect can be obtained by forming an electrode base of another metal and then depositing palladium on top of it. Without,
Furthermore, although the resistance heating method has been given as an example of a method for evaporating the evaporation material, it goes without saying that other methods may also be used.
上述のように、酸化物超微粒子膜の電極として
酸化物超微粒子膜との接触面の少なくとも一部が
パラジウムであるような電極を用いることによ
り、酸化物超微粒子膜の電導度を損なうことなく
容易にガスが水蒸気などの外的作用因子に対する
感応性を高めることができる。 As mentioned above, by using an electrode for the ultrafine oxide particle film in which at least a portion of the contact surface with the ultrafine oxide particle film is made of palladium, it is possible to avoid impairing the conductivity of the ultrafine oxide particle film. Gases can easily increase sensitivity to external agents such as water vapor.
第４図ａ，ｂはそれぞれメタンガスおよび水素
ガスに対する感度を相対的に比較して示す図であ
る。図ａ，ｂのそれぞれにおける実線Ａは、酸素
ガス圧0.5Torr中で、厚さ20μｍの錫酸化物超微
粒子膜を金よりなる電極上に形成して作製した従
来のガス検知素子の場合を示し、破線Ｂは酸素ガ
ス圧0.5Torr中で、厚さ20μｍの錫酸化物超微粒
子膜をパラジウムよりなる電極上に形成した本発
明にかかるガス検知素子の場合を示す。 FIGS. 4a and 4b are diagrams showing a relative comparison of sensitivity to methane gas and hydrogen gas, respectively. The solid line A in each of Figures a and b indicates the case of a conventional gas sensing element manufactured by forming a tin oxide ultrafine particle film with a thickness of 20 μm on an electrode made of gold at an oxygen gas pressure of 0.5 Torr. , broken line B shows the case of a gas sensing element according to the present invention in which a tin oxide ultrafine particle film with a thickness of 20 μm is formed on an electrode made of palladium under an oxygen gas pressure of 0.5 Torr.
メタンガスに対しては、第４図ａに示すよう
に、何れの素子温度においても本発明にかかるガ
ス検知素子は従来の検知素子より感度が高い。そ
して感度を有する素子温度が従来よりも100数10
度低温側に移つている。 As for methane gas, as shown in FIG. 4a, the gas detection element according to the present invention has higher sensitivity than the conventional detection element at any element temperature. And the temperature of the sensitive element is 100 times higher than before.
The temperature is moving to the lower temperature side.
一方水素ガスに対しては、第４図ｂに示すよう
に、比較的高温域ではほとんど両者の感度差はな
いが、低温域では本発明にかかる素子の感度が従
来のそれに比べて著しく増大する。 On the other hand, for hydrogen gas, as shown in Figure 4b, there is almost no difference in sensitivity between the two in a relatively high temperature range, but in a low temperature range the sensitivity of the element according to the present invention increases significantly compared to the conventional one. .
なお本発明にかかる素子と従来の素子との間に
は電導度の差は全くなかつた。 Note that there was no difference in electrical conductivity between the element according to the present invention and the conventional element.
本発明においては、電極にパラジウムを用いて
いるだけであり、感応膜自身の構造は従来のもの
と少しも変わらずむろん膜の空孔性は損なわれな
い。また製造工程も従来と全く同じであり、した
がつて製造にあたつて特に新たな設備を要せず非
常に効率的である。 In the present invention, only palladium is used for the electrode, and the structure of the sensitive membrane itself is not different from the conventional one, and of course the porosity of the membrane is not impaired. Furthermore, the manufacturing process is exactly the same as the conventional one, so the manufacturing process is very efficient and does not require any new equipment.
本発明によれば以上のようにメタンに対する感
度を向上させるとともに動作温度を引き下げるこ
とができ、さらに水素に対しては低温での感度を
いちじるしく高めることができる。 According to the present invention, as described above, the sensitivity to methane can be improved and the operating temperature can be lowered, and furthermore, the sensitivity to hydrogen at low temperatures can be significantly increased.
第１図、第２図はそれぞれ本発明の一実施例で
あるガス検知素子を示す図で、このうち第１図は
平面図、第２図は第１図の破線XX′を含む断面
図、第３図は本発明にかかるガス検知素子を製造
するための装置の一例を示す図、第４図ａ，ｂは
それぞれ本発明にかかる検知素子の効果を説明す
るための図で、このうち第４図ａは素子温度と、
メタンガスに対する感度との関係を、また、第４
図ｂは素子温度と、水素ガスに対する感度との関
係をそれぞれ示す。
１……基板、２，３……電極、４……超微粒子
膜。
FIG. 1 and FIG. 2 are views showing a gas detection element which is an embodiment of the present invention, of which FIG. 1 is a plan view, FIG. 2 is a sectional view including the broken line XX' in FIG. FIG. 3 is a diagram showing an example of an apparatus for manufacturing a gas sensing element according to the present invention, and FIGS. 4a and 4b are diagrams for explaining the effects of the sensing element according to the present invention, respectively. Figure 4a shows the element temperature and
The relationship between the sensitivity to methane gas and the fourth
Figure b shows the relationship between element temperature and sensitivity to hydrogen gas. 1... Substrate, 2, 3... Electrode, 4... Ultrafine particle film.
Claims (1)
一対の電極を設置した絶縁性支持基体上に平均粒
径が十数Åから百数十Åの金属酸化物超微粒子膜
を形成してなることを特徴とするガス検知素子。 ２ 前記酸化物が錫酸化物である特許請求の範囲
第１項記載のガス検知素子。[Claims] 1. A metal oxide ultrafine particle film having an average particle size of 10-odd Å to 100-odd Å is formed on an insulating support substrate on which a pair of electrodes, at least a portion of which is made of palladium, is disposed. A gas detection element characterized by: 2. The gas sensing element according to claim 1, wherein the oxide is a tin oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9708380A JPS5722547A (en) | 1980-07-15 | 1980-07-15 | Gas sensing element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9708380A JPS5722547A (en) | 1980-07-15 | 1980-07-15 | Gas sensing element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5722547A JPS5722547A (en) | 1982-02-05 |
| JPS6151260B2 true JPS6151260B2 (en) | 1986-11-07 |
Family
ID=14182738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9708380A Granted JPS5722547A (en) | 1980-07-15 | 1980-07-15 | Gas sensing element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5722547A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02193051A (en) * | 1989-01-20 | 1990-07-30 | Stanley Electric Co Ltd | Gas sensor using organic semiconductor |
| JP4602000B2 (en) * | 2004-06-16 | 2010-12-22 | 株式会社鷺宮製作所 | Hydrogen gas detection element, hydrogen gas sensor, and hydrogen gas detection method |
-
1980
- 1980-07-15 JP JP9708380A patent/JPS5722547A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5722547A (en) | 1982-02-05 |
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