JPH053540B2 - - Google Patents
Info
- Publication number
- JPH053540B2 JPH053540B2 JP59069336A JP6933684A JPH053540B2 JP H053540 B2 JPH053540 B2 JP H053540B2 JP 59069336 A JP59069336 A JP 59069336A JP 6933684 A JP6933684 A JP 6933684A JP H053540 B2 JPH053540 B2 JP H053540B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- sensor
- film
- platinum
- gas sensor
- 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 - Lifetime
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)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、水素ガスの気体中に含有される量を
電気的信号として検出する水素ガスセンサーに関
する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a hydrogen gas sensor that detects the amount of hydrogen gas contained in the gas as an electrical signal.
従来例の構成とその問題点
最近、エネルギー需要の増大、環境汚染による
クリーンエネルギーの要望から、水素ガスをエネ
ルギー源に使用しようとする要求が高まつてい
る。一方、水素ガスは、引火点が低く危険性の高
いガスであることから水素ガスのガス漏れを検出
する優れたガスセンサーの要求も高まりつつあ
る。Conventional configurations and their problems Recently, due to the increase in energy demand and the desire for clean energy due to environmental pollution, there has been an increasing demand for using hydrogen gas as an energy source. On the other hand, since hydrogen gas is a highly dangerous gas with a low flash point, there is an increasing demand for excellent gas sensors that can detect hydrogen gas leaks.
従来、一般に使用されている水素ガスセンサー
は、加熱白金線において水素ガスを燃焼させるこ
とによる白金線の電気抵抗値変化を利用したもの
である。このようなセンサーにおいては、次の欠
点を有していた。すなわち、水素ガス以外のイソ
ブタン、プロパン等の可燃性のガスが共存する場
合にも、水素ガスと同様に感知してしまい誤動作
する。そのため水素ガスだけを感知できる信頼性
の高いセンサーが望まれていた。 Conventionally, commonly used hydrogen gas sensors utilize changes in the electrical resistance of a platinum wire caused by burning hydrogen gas in a heated platinum wire. Such a sensor had the following drawbacks. That is, even if a flammable gas other than hydrogen gas, such as isobutane or propane, coexists, it will be detected in the same way as hydrogen gas, resulting in malfunction. Therefore, there was a need for a highly reliable sensor that could only detect hydrogen gas.
従来より、酸化タングステン（WO3）が白金
等の触媒により水素と反応することが知られてい
た。その反応機構は、酸化タングステンと白金も
しくはパラジウム等の接触界面において、水素ガ
スが酸化タングステン中にInter calationするこ
とであり、その結果、生成したタングステンブロ
ンズの電気抵抗が極端に低くなる。 It has been known that tungsten oxide (WO 3 ) reacts with hydrogen using a catalyst such as platinum. The reaction mechanism is that hydrogen gas intercalates into tungsten oxide at the contact interface between tungsten oxide and platinum, palladium, etc., and as a result, the electrical resistance of the produced tungsten bronze becomes extremely low.
このような現象を利用したものとして、例え
ば、特開昭57−74648号公報には、スパツタ蒸着
によるWO3膜を利用したガスセンサーが記載さ
れている。しかし、これらのWO3膜は多結晶体
であり、水素ガスに対して感度の低いものであつ
た。 As a device that utilizes such a phenomenon, for example, Japanese Patent Application Laid-open No. 74648/1983 describes a gas sensor that utilizes a WO 3 film formed by sputter deposition. However, these WO 3 films were polycrystalline and had low sensitivity to hydrogen gas.
発明の目的
本発明は、このWO3膜を利用する水素ガスセ
ンサーを改良して、より高感度で、信頼性の高い
水素ガスセンサーを提供することを目的とする。Purpose of the Invention The purpose of the present invention is to improve the hydrogen gas sensor using this WO 3 membrane and provide a hydrogen gas sensor with higher sensitivity and reliability.
発明の構成
本発明の水素ガスセンサーは、基板上に互いに
独立した２つの電極を設け、これらの電極上にま
たがつて真空蒸着法によつてアモルフアスWO3
膜を設け、その上に白金またはパラジウム層を設
けたものである。Structure of the Invention The hydrogen gas sensor of the present invention has two mutually independent electrodes provided on a substrate, and amorphous WO 3 is deposited over these electrodes by vacuum evaporation.
A membrane is provided on which a platinum or palladium layer is provided.
実施例の説明
実施例 １
セラミツク、ガラス等の絶縁性基板上に、Pt、
Pd、Ni、Ti、Al、Au、Ag、Ta、ITOなどから
なる２つの電極を独立して設け、それらの上にま
たがつてアモルフアスWO3膜を真空蒸着法の１
つである抵抗加熱法によつて形成し、さらにその
上に蒸着法によつて白金層を設けた。Description of Examples Example 1 Pt,
A vacuum evaporation method where two electrodes made of Pd, Ni, Ti, Al, Au, Ag, Ta, ITO, etc. are provided independently, and an amorphous WO 3 film is straddled over them.
It was formed by a resistance heating method, and a platinum layer was further provided thereon by a vapor deposition method.
第１図は上記のようにして構成した水素ガスセ
ンサーを示す。１は基板、２，３は電極、４は
WO3膜、５は白金層である。WO3は、その充填
密度が5.4／cm3、膜厚3000Å、電極間の寸法は0.5
mm×0.5mmである。また白金層の膜厚は10〜100Å
程度で、アイランド状に蒸着されている。６，７
はそれぞれ電極２，３のリードであり、両者は電
気抵抗検出器に接続される。 FIG. 1 shows a hydrogen gas sensor constructed as described above. 1 is the substrate, 2 and 3 are electrodes, 4 is
WO 3 film, 5 is a platinum layer. WO 3 has a packing density of 5.4/cm 3 , a film thickness of 3000 Å, and a dimension between electrodes of 0.5
It is mm×0.5mm. Also, the thickness of the platinum layer is 10 to 100 Å.
It is deposited in the form of islands. 6,7
are the leads of electrodes 2 and 3, respectively, and both are connected to an electrical resistance detector.
上記のセンサー部に一定濃度の水素ガスを吹き
つけると、電極２，３間の抵抗が大きく変化す
る。水素ガス濃度と電極間の抵抗値の関係は第２
図のようになつた。同図より、H2濃度1000ppm
に対する100ppmの電気抵抗値の比は9.3倍であ
る。これに対してスパツタリング法で形成し、熱
処理した結晶状態のセンサーの比は２倍で感度が
低かつた。 When a certain concentration of hydrogen gas is blown onto the sensor section, the resistance between the electrodes 2 and 3 changes significantly. The relationship between the hydrogen gas concentration and the resistance value between the electrodes is the second
It turned out like the picture. From the same figure, H2 concentration 1000ppm
The ratio of the electrical resistance value of 100ppm to that of 100ppm is 9.3 times. On the other hand, a crystalline sensor formed by a sputtering method and heat-treated had twice the sensitivity, resulting in lower sensitivity.
なお、電気抵抗値の測定は、±50mV、60Hzで
行なつた。測定値は、水素ガス吹きつけ後２秒後
の値である。この後センサー部に空気を吹きつけ
ると、３〜５秒以内に元の状態に回復した。 Note that the electrical resistance value was measured at ±50 mV and 60 Hz. The measured value is the value 2 seconds after spraying hydrogen gas. After this, when air was blown onto the sensor part, it returned to its original state within 3 to 5 seconds.
実施例 ２
実施例１においてアモルフアスWO3膜の蒸着
時の真空度をかえて異なつた充填密度の膜を3000
Åの厚みに蒸着し、実施例１と同様のセンサーを
作成して試験した。その結果、充填密度が低くな
る膜ほど水素ガスに対する感度が高くなつた。し
かし、充填密度が低くなるとWO3膜自身が脆く
なり安定性に欠けることが判つた。安定で、かつ
高感度のWO3膜は、充填密度4.0〜6.0g／cm3のも
のが好ましかつた。Example 2 In Example 1, the degree of vacuum during vapor deposition of the amorphous WO 3 film was changed to produce films with different packing densities.
A sensor similar to that of Example 1 was prepared and tested. As a result, the lower the packing density of the membrane, the higher the sensitivity to hydrogen gas. However, it was found that when the packing density became low, the WO 3 film itself became brittle and lacked stability. The stable and highly sensitive WO 3 membrane preferably has a packing density of 4.0 to 6.0 g/cm 3 .
さらに、WO3膜の充填密度を5.4g／cm3と一定に
して膜厚を変化させて検討した結果、薄い状態の
膜ほど高い感度を示した。好ましい膜厚は100〜
10000Åの範囲であつた。 Furthermore, when the packing density of the WO 3 film was kept constant at 5.4 g/cm 3 and the film thickness was varied, the results showed that the thinner the film, the higher the sensitivity. The preferred film thickness is 100~
It was in the range of 10,000 Å.
実施例 ３
実施例１において、Ptを蒸着法で析出させる
代わりにWO3膜が蒸着された基板をアルコール
を30％含む塩化白金酸水溶液に浸漬し、太陽光も
しくはキセノンランプにより光照射してWO3膜
上へPtを光電気化学的に析出させた。他は同様
にして実施例１と同様のセンサーを作成した。こ
のセンサーの水素ガスに対する感度は実施例１の
センサーより約２倍ほど高感度であつた。Example 3 In Example 1, instead of depositing Pt by the vapor deposition method, the substrate on which the WO 3 film was deposited was immersed in a chloroplatinic acid aqueous solution containing 30% alcohol, and irradiated with sunlight or a xenon lamp to deposit the WO 3 film. Pt was photoelectrochemically deposited onto the 3 films. A sensor similar to Example 1 was produced in the same manner as in other respects. The sensitivity of this sensor to hydrogen gas was about twice as high as that of the sensor of Example 1.
実施例 ４
実施例３における光電気化学的にPtを析出さ
せる条件を変化させて、WO3膜上にPtを析出さ
せてセンサーを作成し、水素ガスに対する感度を
測定した。その結果、Ptを析出させる条件とし
て、塩化白金酸濃度が１×10-2〜１×10-5モル／
の範囲が好ましく、又、添加するアルコールと
して、エタノール、メタノール、プロパノールの
他種々のアルコールが使用でき、その濃度は10〜
80％の範囲で効果があつた。Example 4 A sensor was prepared by depositing Pt on a WO 3 film by changing the conditions for photoelectrochemically depositing Pt in Example 3, and its sensitivity to hydrogen gas was measured. As a result, the conditions for precipitating Pt were such that the concentration of chloroplatinic acid was 1 x 10 -2 to 1 x 10 -5 mol/
A range of 10 to 10 is preferable, and various alcohols other than ethanol, methanol, and propanol can be used as the alcohol to be added, and the concentration thereof is 10 to 10.
It was effective within 80%.
塩化白金酸の他、塩化白金酸カリウムも使用で
きる。又、照射する光は、2.7eV以上のエネルギ
ーの光においてPtの析出が可能であつた。 In addition to chloroplatinic acid, potassium chloroplatinate can also be used. In addition, Pt could be precipitated when the irradiated light had an energy of 2.7 eV or more.
なお、以上の実施例は、触媒としてPtを使用
した例を示したが、Ptに代えてPdを使用した場
合も全く同様の効果が確認できた。 In addition, although the above example showed an example in which Pt was used as a catalyst, exactly the same effect was confirmed when Pd was used instead of Pt.
なお、実施例においては真空蒸着法として抵抗
加熱法について説明したが、これに代えてEB（電
子線）加熱法を用いても同様の効果が得られた。 In addition, in the examples, a resistance heating method was explained as a vacuum evaporation method, but the same effect was obtained even if an EB (electron beam) heating method was used instead.
発明の効果
以上のように、本発明によれば、高感度の水素
ガスセンサーが得られる。Effects of the Invention As described above, according to the present invention, a highly sensitive hydrogen gas sensor can be obtained.
第１図は本発明の実施例の水素ガスセンサーの
縦断面図、第２図は水素ガス濃度とセンサーの電
気抵抗値の関係を示す図である。
１……基板、２，３……電極、４……WO3膜、
５……白金層。
FIG. 1 is a longitudinal sectional view of a hydrogen gas sensor according to an embodiment of the present invention, and FIG. 2 is a diagram showing the relationship between the hydrogen gas concentration and the electrical resistance value of the sensor. 1... Substrate, 2, 3... Electrode, 4... WO 3 film,
5...Platinum layer.
Claims (1)
がつて真空蒸着法によつてアモルフアス酸化タン
グステン層を設け、さらにその上に白金またはパ
ラジウムを析出させたことを特徴とする水素ガス
センサー。 ２ アモルフアス酸化タングステン層が、充填密
度4.0〜6.0g／cm3である特許請求の範囲第１項記
載の水素ガスセンサー。 ３ 白金またはパラジウムが光電気化学的に析出
させたものである特許請求の範囲第１項記載の水
素ガスセンサー。[Claims] 1. An amorphous tungsten oxide layer is provided by a vacuum evaporation method over two electrodes provided on the same substrate, and platinum or palladium is further deposited on the amorphous tungsten oxide layer. hydrogen gas sensor. 2. The hydrogen gas sensor according to claim 1, wherein the amorphous tungsten oxide layer has a packing density of 4.0 to 6.0 g/cm 3 . 3. The hydrogen gas sensor according to claim 1, wherein platinum or palladium is deposited photoelectrochemically.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59069336A JPS60211348A (en) | 1984-04-06 | 1984-04-06 | Gaseous hydrogen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59069336A JPS60211348A (en) | 1984-04-06 | 1984-04-06 | Gaseous hydrogen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60211348A JPS60211348A (en) | 1985-10-23 |
| JPH053540B2 true JPH053540B2 (en) | 1993-01-18 |
Family
ID=13399604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59069336A Granted JPS60211348A (en) | 1984-04-06 | 1984-04-06 | Gaseous hydrogen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60211348A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007279061A (en) * | 2007-06-19 | 2007-10-25 | Osaka Gas Co Ltd | Pulse-driven thin film gas sensor and manufacturing method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4440572C2 (en) * | 1994-11-14 | 1997-05-07 | Fraunhofer Ges Forschung | Glazing element with variable transmission |
| AU2001259459A1 (en) * | 2000-05-05 | 2001-11-20 | Midwest Research Institute | Pd/ni-wo3 anodic double layer gasochromic device |
| JP4056987B2 (en) * | 2004-04-28 | 2008-03-05 | アルプス電気株式会社 | Hydrogen sensor and hydrogen detection method |
| JP2007071866A (en) * | 2005-08-10 | 2007-03-22 | Tokyo Univ Of Science | Thin film for gas sensor, element body for gas sensor, and method for manufacturing element body for gas sensor |
| JP4775708B2 (en) * | 2006-04-04 | 2011-09-21 | 独立行政法人日本原子力研究開発機構 | Hydrogen gas detection material and coating method thereof |
| JP5422281B2 (en) * | 2009-07-13 | 2014-02-19 | 株式会社アルバック | Hydrogen gas sensor and method for manufacturing hydrogen gas sensor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013142B2 (en) * | 1977-05-16 | 1985-04-05 | 株式会社東芝 | gas sensing element |
| JPS53141098A (en) * | 1977-05-16 | 1978-12-08 | Toshiba Corp | Gas sensing element |
| JPS53141097A (en) * | 1977-05-16 | 1978-12-08 | Toshiba Corp | Gas sensing element |
| US4249156A (en) * | 1979-03-09 | 1981-02-03 | General Motors Corporation | Uncompensated low temperature stoichiometric air/fuel ratio exhaust gas sensor |
| JPS5938541B2 (en) * | 1979-12-22 | 1984-09-18 | 松下電工株式会社 | Flammable gas detection element |
| DE3032476A1 (en) * | 1980-08-28 | 1982-04-01 | Siemens AG, 1000 Berlin und 8000 München | SELECTIVE THICK-LAYER GAS SENSOR HIGH SENSITIVITY AND STABILITY FOR DETECTING AND MEASURING GASEOUS HYDROCARBON IMPURITIES IN THE AIR BASED ON TOLFRAMOXIDE (WHERE (DOWN ARROW)) X (POSTED), HOWEVER |
| JPS5857702A (en) * | 1981-09-30 | 1983-04-06 | 三洋電機株式会社 | Moisture sensor |
| JPS58182545A (en) * | 1982-04-21 | 1983-10-25 | Hitachi Ltd | Carbon monoxide gas detection element |
-
1984
- 1984-04-06 JP JP59069336A patent/JPS60211348A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007279061A (en) * | 2007-06-19 | 2007-10-25 | Osaka Gas Co Ltd | Pulse-driven thin film gas sensor and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60211348A (en) | 1985-10-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |