JPS6152934B2 - - Google Patents
Info
- Publication number
- JPS6152934B2 JPS6152934B2 JP9924580A JP9924580A JPS6152934B2 JP S6152934 B2 JPS6152934 B2 JP S6152934B2 JP 9924580 A JP9924580 A JP 9924580A JP 9924580 A JP9924580 A JP 9924580A JP S6152934 B2 JPS6152934 B2 JP S6152934B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- oxide
- sensitive
- ultrafine particle
- 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.)
- Expired
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- 239000011882 ultra-fine particle Substances 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 6
- 239000007789 gas Substances 0.000 claims 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910020941 Sn-Mn Inorganic materials 0.000 description 1
- 229910008953 Sn—Mn Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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】
本発明は金属酸化物超微粒子膜よりなりガス検
出に用いるガス感応膜およびその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas sensitive membrane made of a metal oxide ultrafine particle membrane and used for gas detection, and a method for manufacturing the same.
金属酸化物のなかでもとりわけ錫（Sn）酸化
物の超微粒子よりなるガス感応膜はガス検出感応
度が非常にすぐれることからガスセンサ用材料と
してきわめて有望視されている。 Among metal oxides, gas-sensitive films made of ultrafine particles of tin (Sn) oxide have excellent gas detection sensitivity, and are therefore considered to be extremely promising as materials for gas sensors.
ここで従来のガス感応膜について説明する。 Here, a conventional gas sensitive membrane will be explained.
まず第１図を用いた従来のガス感応膜の製造方
法を説明する。 First, a conventional method for manufacturing a gas-sensitive membrane will be explained using FIG.
図に示すように、通常の真空蒸着装置１中の試
料ホルダー２に、超微粒子材料を付着させるべき
基板（たとえばガラス基板）３を保持する。蒸着
用ボート４中にSn、もしくはSnO、またはSnO2
などの蒸発材料５をセツトしたのち、排気口６に
接続した真空ポンプ（図示せず）を作動させて、
装置１内を５×10-6Torr程度の真空度にする。
それから、O2ガス導入口７のコツクを開き、装
置１内にO2ガスを導入し、その圧力をO.1Torrか
ら10Torr程度に保つ。次に、蒸発用電源８によ
りボート４に通電して発熱させ、O2ガス雰囲気
のもとで蒸発材料５を十数秒から数分間蒸発させ
る。 As shown in the figure, a substrate (for example, a glass substrate) 3 to which ultrafine particle material is to be attached is held in a sample holder 2 in an ordinary vacuum evaporation apparatus 1 . Sn, SnO, or SnO 2 in vapor deposition boat 4
After setting the evaporation material 5 such as, a vacuum pump (not shown) connected to the exhaust port 6 is operated,
The inside of the device 1 is made to have a degree of vacuum of about 5×10 -6 Torr.
Then, open the O 2 gas inlet 7 to introduce O 2 gas into the apparatus 1, and maintain the pressure at about 0.1 Torr to 10 Torr. Next, the boat 4 is energized by the evaporation power source 8 to generate heat, and the evaporation material 5 is evaporated for a few seconds to several minutes in an O 2 gas atmosphere.
それにより、粒径が数10Åの錫酸化物の膜が形
成される。 As a result, a tin oxide film with a grain size of several tens of angstroms is formed.
超微粒子の大きさについては、一義的な定義は
困難であるが、応用物理（第44巻７号P795）に
も述べられているように、注目する事象におい
て、その物性値がバルクの状態と著しく異なる値
を示す領域の粒子が超微粒子と定義される。 It is difficult to unambiguously define the size of ultrafine particles, but as stated in Applied Physics (Vol. 44, No. 7, p. 795), in the event of interest, the physical properties of the particles are similar to the bulk state. Particles in the region showing significantly different values are defined as ultrafine particles.
本発明においては、対象としているセンサの同
一のセンサ動作温度における感度がバルク（蒸着
膜や焼結体）で作製したものよりも大幅に増加す
る数10Å程度の粒径を持つ粒子を超微粒子と考え
る。すなわち、0.1Torrから10Torr程度の範囲の
O2ガス雰囲気中で蒸着を行うことにより得られ
る粒子である。 In the present invention, ultrafine particles are used as particles with a particle size of several tens of angstroms, which significantly increases the sensitivity of the target sensor at the same sensor operating temperature compared to that produced in bulk (deposited film or sintered body). think. That is, in the range of about 0.1 Torr to 10 Torr.
These particles are obtained by vapor deposition in an O 2 gas atmosphere.
たとえばO2ガス圧力を0.5Torrにして蒸発材料
５をSnに選び、70〜80A、4Vの電力を１分間ボ
ート４に印加すると、約１μｍの厚さのSn酸化
物の超微粒子が基板３の表面に付着形成された。
ここでは蒸発材料を蒸発させるのに抵抗加熱によ
る方法を例にあげて述べたが、他の方法、たとえ
ば誘導加熱、あるいは赤体線加熱による方法でも
よいことは言うまでもない。 For example, when the O 2 gas pressure is set to 0.5 Torr, the evaporation material 5 is selected as Sn, and a power of 70 to 80 A and 4 V is applied to the boat 4 for 1 minute, ultrafine particles of Sn oxide with a thickness of about 1 μm are deposited on the substrate 3. Adhesion formed on the surface.
Here, a method using resistance heating has been described as an example for evaporating the evaporation material, but it goes without saying that other methods such as induction heating or red body heating may also be used.
次に上述のようにして作られたガスセンサの一
例を第２図に示す。このガスセンサは、図に示す
ように、基板３上にあらかじめ一対の電極９，１
０が真空蒸着などの周知の方法によつて設けられ
ており、さらに、その上に超微粒子膜１１が形成
されているものである。検出対象となる雰囲気中
に入れると、ガス、アルコールの濃度に応じて、
電極９，１０間の抵抗値が変化する。 Next, FIG. 2 shows an example of a gas sensor made as described above. As shown in the figure, this gas sensor has a pair of electrodes 9 and 1 placed on a substrate 3 in advance.
0 is provided by a well-known method such as vacuum evaporation, and an ultrafine particle film 11 is further formed thereon. When placed in the atmosphere to be detected, depending on the concentration of gas and alcohol,
The resistance value between electrodes 9 and 10 changes.
このようにして作成したガスセンサーのアルコ
ール雰囲気中でのセンサ抵抗値の動作温度依存性
を第３図の曲線Ａ群で示す。 The operating temperature dependence of the sensor resistance value of the gas sensor thus prepared in an alcohol atmosphere is shown by group A of curves in FIG.
ここでＲOは空気中（アルコール濃度0ppm）
でのセンサ抵抗値、ＲGはアルコール濃度50ppm
雰囲気中でのセンサ抵抗値である。第４図中の曲
線ＡによりSn酸化物超微粒子ガス感応膜のＲO／
ＲGの動作温度依存性を示す。約170℃以上の動作
温度で感度を有しはじめ300℃付近で最大の感度
を有している。このように従来のガス感応膜では
ガスの検知の動作温度が比較的高い温度領域にあ
り、このため使用に際しては感応膜加熱用に多く
の電力を要していた。 Here R O is in the air (alcohol concentration 0 ppm)
Sensor resistance value at , R G is alcohol concentration 50ppm
This is the sensor resistance value in the atmosphere. According to the curve A in Fig. 4, R O / of the Sn oxide ultrafine particle gas-sensitive film
The operating temperature dependence of R G is shown. It begins to be sensitive at operating temperatures of approximately 170°C or higher, and has maximum sensitivity at around 300°C. As described above, in the conventional gas sensitive membrane, the operating temperature for gas detection is in a relatively high temperature range, and therefore, when used, a large amount of electric power is required to heat the sensitive membrane.
本発明は上記Sn酸化物単一超微粒子膜形成時
に適当な触媒作用を有する超微粒子材料を混合し
て、混合酸化物超微粒子膜にすることにより素子
の感度を低下させることなく、素子の動作温度を
低下できることを見出したことに基ずいてなされ
たもので、以下に図面を用いその実施例を説明す
る。 In the present invention, when forming the Sn oxide single ultrafine particle film, an ultrafine particle material having an appropriate catalytic action is mixed to form a mixed oxide ultrafine particle film, thereby allowing the device to operate without reducing the sensitivity of the device. This was made based on the discovery that the temperature could be lowered, and examples thereof will be described below with reference to the drawings.
本発明によるガス感応膜の製造方法は先に第１
図を用いて述べた錫酸化物超微粒子ガス感応膜の
製造方法とほとんど同じである。ただ異なるの
は、O2ガス雰囲気中でSnを蒸発させる時に、同
時に、触媒材料であるマンガン（Mn）を蒸発さ
せて、基板上にSn酸化物とMn醸化物とが適当な
割合で混合した混合酸化物超微粒子ガス感応膜を
作成する点である。例えばO2ガス雰囲気を
1Torr、蒸発ボート温度を1100℃にしてSn及び
Mnを同時に蒸発させると平均粒径が45Å程度の
SnO2超微粒子と平均粒径が80Å程度のMnO超微
粒子とが混合した混合酸化物超微粒子膜が基板上
に形成される。ここで、MnO超微粒子の粒経及
びSnO2超微粒子に対する混合割合の制御は所望
の比率のSn―Mn合金を蒸発源として用いてもよ
いが蒸発ボート温度、蒸発ボートと基板との距離
などの蒸発条件を制御することによりSnとMnと
を独立に蒸発させても容易におこなうことができ
る。なお蒸発材料としては上記SnおよびMnの他
に、それぞれの酸化物を用いてもよい。このよう
にして作成した混合酸化物超微粒子ガス感応膜の
抵抗値と動作温度との関係を第３図中の曲線Ｂ群
で示す。抵抗値はSn酸化物単一超微粒子ガス感
応膜に比べて高くなつている。また混合酸化物超
微粒子ガス感応膜のＲO／ＲGの動作温度依存性を
第４図中の曲線Ｂに示す。図に示すように約50℃
以上の動作温度が感度を有し始め150℃付近で最
大の感度を有する。 The method for manufacturing a gas-sensitive membrane according to the present invention first begins with the first step.
This method is almost the same as the manufacturing method of the tin oxide ultrafine particle gas-sensitive membrane described using the figures. The only difference is that when Sn is evaporated in an O 2 gas atmosphere, manganese (Mn), which is a catalyst material, is evaporated at the same time, and Sn oxide and Mn brewer are mixed on the substrate in an appropriate ratio. The point is to create a mixed oxide ultrafine particle gas-sensitive membrane. For example, O 2 gas atmosphere
Sn and
When Mn is evaporated at the same time, the average particle size is about 45 Å.
A mixed oxide ultrafine particle film containing a mixture of SnO 2 ultrafine particles and MnO ultrafine particles having an average particle size of about 80 Å is formed on the substrate. Here, the grain size of the MnO ultrafine particles and the mixing ratio with respect to the SnO 2 ultrafine particles may be controlled by using a Sn-Mn alloy of a desired ratio as an evaporation source, but the evaporation boat temperature, the distance between the evaporation boat and the substrate, etc. By controlling the evaporation conditions, Sn and Mn can be easily evaporated independently. In addition to the Sn and Mn described above, oxides of each may be used as the evaporation material. The relationship between the resistance value and the operating temperature of the mixed oxide ultrafine particle gas-sensitive membrane thus prepared is shown by group B of curves in FIG. The resistance value is higher than that of a Sn oxide single ultrafine particle gas-sensitive film. Curve B in FIG. 4 shows the operating temperature dependence of R O /R G of the mixed oxide ultrafine particle gas-sensitive membrane. Approximately 50℃ as shown in the figure
Sensitivity begins to develop at operating temperatures above 150°C, and maximum sensitivity is reached at around 150°C.
第４図の曲線ＡとＢとを比較すると明らかなよ
うに、混合酸化物超微粒子ガス感応膜の場合Ｂの
方がSn酸化物単一超微粒子ガス感応膜の場合Ａ
よりも約150℃低い動作温度で同等の感度を有し
ていることがわかる。 As is clear from comparing curves A and B in Figure 4, B is better for the mixed oxide ultrafine particle gas-sensitive film than A is for the Sn oxide single ultrafine particle gas-sensitive film.
It can be seen that it has the same sensitivity at an operating temperature approximately 150°C lower than that of the previous model.
第５図に混合酸化物超微粒子ガス感応膜中の
Mn酸化物とSn酸化物とのモル比と最大感度を与
える動作温度との関係を示す。Mn酸化物の割合
が0.5〜10％の範囲で動作温度を低下させる効果
が現われ、１〜５％程度でこの効果は最大にな
る。 Figure 5 shows the mixed oxide ultrafine particles in the gas-sensitive film.
The relationship between the molar ratio of Mn oxide and Sn oxide and the operating temperature that provides maximum sensitivity is shown. An effect of lowering the operating temperature appears when the proportion of Mn oxide is in the range of 0.5 to 10%, and this effect is maximum when the proportion of Mn oxide is about 1 to 5%.
以上に述べたように、本発明によれば感度を何
ら低下させることなくしてガス検出動作温度を容
易に引き下げることができ、したがつて感応膜加
熱用の電力消費を低く押えることができる。 As described above, according to the present invention, the gas detection operating temperature can be easily lowered without any reduction in sensitivity, and therefore the power consumption for heating the sensitive membrane can be kept low.
第１図は従来のガス感応膜の製造方法を説明す
るための図で真空蒸着装置中においてガス感応膜
が形成されている様子を示す。第２図は従来のガ
ス感応膜を用いたガスセンサの平面図、第３図な
らびに第４図はガス感応膜の動作温度に対する抵
抗値依存性および感度依存性をそれぞれ示す図
で、何れの図においても従来のガス感応膜におけ
る場合と本発明によるガス感応膜における場合と
を対比して示す。第５図は本発明によるガス感応
膜中におけるMn酸化物とSn酸化物との混合比と
最大感度温度との関係を示す図である。
１……真空蒸着装置、３……基板、５……蒸発
材料、１１……超微粒子膜。
FIG. 1 is a diagram for explaining a conventional method for manufacturing a gas-sensitive film, and shows how a gas-sensitive film is formed in a vacuum evaporation apparatus. Figure 2 is a plan view of a gas sensor using a conventional gas-sensitive membrane, and Figures 3 and 4 are diagrams showing the resistance value dependence and sensitivity dependence of the gas-sensitive membrane on operating temperature, respectively. Also, the case of a conventional gas-sensitive membrane and the case of a gas-sensitive membrane according to the present invention are shown in comparison. FIG. 5 is a diagram showing the relationship between the mixing ratio of Mn oxide and Sn oxide in the gas-sensitive film according to the present invention and the maximum sensitivity temperature. DESCRIPTION OF SYMBOLS 1... Vacuum evaporation device, 3... Substrate, 5... Evaporation material, 11... Ultrafine particle film.
Claims (1)
化物の超微粒子膜からなることを特徴とするガス
感応膜。 ２ マンガン酸化物の錫酸化物に対する割合が
0.5mol％〜10mol％の範囲にあることを特徴とす
る特許請求の範囲第１項記載のガス感応膜。 ３ 錫もしくはその酸化物と、マンガンもしくは
その酸化物とを酸素ガス雰囲気中で同時に蒸発さ
せて錫酸化物およびマンガン酸化物を含む金属酸
化物の超微粒子膜を支持基板上に形成することを
特徴とするガス感応膜の製造方法。[Scope of Claims] 1. A gas-sensitive film comprising an ultrafine particle film of a metal oxide containing tin oxide and manganese oxide. 2 The ratio of manganese oxide to tin oxide is
The gas-sensitive membrane according to claim 1, characterized in that the content is in the range of 0.5 mol% to 10 mol%. 3. Tin or its oxide and manganese or its oxide are simultaneously evaporated in an oxygen gas atmosphere to form an ultrafine particle film of metal oxide containing tin oxide and manganese oxide on the supporting substrate. A method for producing a gas-sensitive membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9924580A JPS5723850A (en) | 1980-07-18 | 1980-07-18 | Gas sensitive film and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9924580A JPS5723850A (en) | 1980-07-18 | 1980-07-18 | Gas sensitive film and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5723850A JPS5723850A (en) | 1982-02-08 |
| JPS6152934B2 true JPS6152934B2 (en) | 1986-11-15 |
Family
ID=14242306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9924580A Granted JPS5723850A (en) | 1980-07-18 | 1980-07-18 | Gas sensitive film and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5723850A (en) |
-
1980
- 1980-07-18 JP JP9924580A patent/JPS5723850A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5723850A (en) | 1982-02-08 |
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