JPS63231254A - Gas sensor - Google Patents
Gas sensorInfo
- Publication number
- JPS63231254A JPS63231254A JP6420487A JP6420487A JPS63231254A JP S63231254 A JPS63231254 A JP S63231254A JP 6420487 A JP6420487 A JP 6420487A JP 6420487 A JP6420487 A JP 6420487A JP S63231254 A JPS63231254 A JP S63231254A
- Authority
- JP
- Japan
- Prior art keywords
- metal oxide
- film
- paste
- counter electrode
- printing
- 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.)
- Granted
Links
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229920000896 Ethulose Polymers 0.000 abstract description 4
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 abstract description 4
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010937 tungsten Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 229910001111 Fine metal Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 28
- 239000010409 thin film Substances 0.000 description 14
- 150000002902 organometallic compounds Chemical group 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000001293 FEMA 3089 Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明はガスセンサに関する。[Detailed description of the invention] [Purpose of the invention] (Industrial application field) The present invention relates to gas sensors.
（従来の技術）
従来から感ガス体として金属酸化物半導体を用いたガス
センサの例が数多く提案されている。(Prior Art) Many examples of gas sensors using metal oxide semiconductors as gas-sensitive bodies have been proposed.
例えば、酸化亜鉛、酸化スズ、酸化インジウム等のｎ型
半導体を用いた場合は、還元性ガスとの接触によりその
抵抗が減少することを利用してガスを検知する。逆に、
ｎ型半導体を用いた場合には、還元性ガスとの接触によ
り抵抗が増加することを利用する。しかし、半導体のみ
てはこの抵抗の減少または増加は起りに＜＜、たとえば
貴金属や金属酸化物を担持した多孔質の金属酸化物から
なる触媒層を半導体の上に重ねたりして用いられる。For example, when an n-type semiconductor such as zinc oxide, tin oxide, or indium oxide is used, the gas is detected by utilizing the fact that its resistance decreases upon contact with a reducing gas. vice versa,
When an n-type semiconductor is used, the increase in resistance due to contact with a reducing gas is utilized. However, this reduction or increase in resistance does not occur with semiconductors alone. For example, a catalyst layer made of a porous metal oxide supporting a noble metal or a metal oxide is used by overlaying the semiconductor.
この場合、例えば金属酸化物を担持させたアルミナ微粉
体と塩基性塩化アルミニウム水溶液とからペーストを調
製し、これを塗布、焼成するといった方法がとられてい
る。In this case, for example, a method is used in which a paste is prepared from alumina fine powder supporting a metal oxide and a basic aluminum chloride aqueous solution, and the paste is applied and fired.
最近、ガスセンサの小形化や、選択性向上と多機能化の
ための集積化、製造工程の自動化、バラツキの低減など
を目的として、厚膜技術を利用した平板形のガスセンサ
が注目されている。ガスセンサの平板化のための要素技
術としては、たとえば下記のような技術が提案されてい
る。Recently, flat gas sensors using thick film technology have been attracting attention for the purpose of downsizing gas sensors, integrating them to improve selectivity and multifunctionality, automating manufacturing processes, and reducing variations. For example, the following technologies have been proposed as elemental technologies for flattening gas sensors.
（１） 厚膜印刷によりヒータと絶ｄ膜を形成した発
熱体内蔵セラミック多層基板、
還元性ガスとの接触による半導体の抵抗変化は前記のよ
うな触媒層や、増感剤を用いたとしても、常温では小さ
く、しかも緩慢であるので、発熱体により素子を加熱す
ることが不可欠である。平板形の場合、発熱体を基板の
裏面に膜状に形成して一体化することが多いが、熱効率
を高め、量産性を向上させるために、基板表面状に発熱
体、絶縁膜、対向電極、ガス感応膜を積層した構造が提
案されている。(1) Ceramic multilayer substrate with a built-in heating element on which a heater and insulation film are formed by thick film printing.The resistance change of the semiconductor due to contact with reducing gas will not occur even if a catalyst layer or sensitizer is used as mentioned above. , is small and slow at room temperature, so it is essential to heat the element with a heating element. In the case of a flat plate type, the heating element is often formed as a film on the back side of the substrate and integrated, but in order to increase thermal efficiency and improve mass production, the heating element, insulating film, and counter electrode are formed on the surface of the substrate. , a structure in which gas-sensitive membranes are stacked has been proposed.
（２）還元性ガスに感応する金属酸化物半導体薄膜のス
クリーン印刷による形成。(2) Formation of a metal oxide semiconductor thin film sensitive to reducing gas by screen printing.
ガス感応性金属酸化物半導体の薄膜（膜厚１μｍ以下）
を有機金属化合物の熱分解により形成したガスセンサが
広く実用に供されている。これは、リフトオフ法により
有機金属化合物の薄膜が形成され、しかるのちに熱分解
により金属酸化物薄膜を得たものである。Gas-sensitive metal oxide semiconductor thin film (thickness 1 μm or less)
Gas sensors formed by thermal decomposition of organometallic compounds have been widely put into practical use. In this method, a thin film of an organometallic compound is formed by a lift-off method, and then a thin film of a metal oxide is obtained by thermal decomposition.
このような薄膜のパターン形成を容易にするために、ス
クリーン印刷可能なペーストが考案され、スクリーン印
刷による金属酸化物薄膜の形成が可能になった。To facilitate patterning of such thin films, screen printable pastes have been devised, making it possible to form metal oxide thin films by screen printing.
上記の技術を利用した平板形のガスセンサでは、前記の
触媒層もスクリーン印刷などによってパターン形成グす
ることが求められる。しかし、前記のごとくアルミナ微
粉体と塩基性塩化アルミニウム水溶液からなる系は、水
の揮発性が高いためにスクリーン印刷用のペーストとす
るのは適当ではない。また、有機溶剤などを含む有機系
を考えた場合、ペーストの粘度、チキソトロピーや、焼
成後の膜強度、ガス感応性などに難点があった。In a flat gas sensor using the above technology, the catalyst layer is also required to be patterned by screen printing or the like. However, as mentioned above, a system consisting of alumina fine powder and a basic aluminum chloride aqueous solution is not suitable for use as a paste for screen printing because of the high volatility of water. Furthermore, when considering organic systems containing organic solvents, there are problems with paste viscosity, thixotropy, film strength after firing, gas sensitivity, etc.
（発明が解決しようとする問題点）
本発明は、従来技術では多孔質の金属酸化物からなる触
媒層の印刷形成が困難な点に鑑みてなされたもので、粘
度、チキソトロピーなどのレオロジー特性や、溶剤の揮
発性などの適当なスクリーン印刷可能なペーストを用い
て、多孔質の金属酸化物からなる特性良好な触媒層を印
刷形成したガスセンサを得ることを目的とするものであ
る。(Problems to be Solved by the Invention) The present invention was made in view of the difficulty in printing and forming a catalyst layer made of porous metal oxide using conventional techniques. The purpose of this invention is to obtain a gas sensor in which a catalyst layer made of a porous metal oxide and having good characteristics is printed using a suitable screen-printable paste such as a volatile solvent.
［発明の構成］
（問題を解決するための手段）
本発明に係るガスセンサは、一対の電極が設けられた絶
縁基板と、この絶縁基板上で前記電極間に膜状に形成さ
れた金属酸化物半導体と、この金属酸化物半導体上にア
ルミニウム、ケイ素、ジルコニウムの群から選ばれる少
なくとも１種類の元素の酸化物微粉体と前記の群から選
ばれる少なくとも１種類の元素の有機化合物とを含む被
膜を印刷、熱分解して形成された多孔質の金属酸化物と
を具備したことを特徴とするものである。[Structure of the Invention] (Means for Solving the Problem) A gas sensor according to the present invention includes an insulating substrate provided with a pair of electrodes, and a metal oxide film formed between the electrodes on the insulating substrate. A semiconductor, and a coating containing, on the metal oxide semiconductor, an oxide fine powder of at least one element selected from the group of aluminum, silicon, and zirconium, and an organic compound of at least one element selected from the above group. It is characterized by comprising a porous metal oxide formed by printing and thermal decomposition.
（作用）
本６発明は、前記のごとき手段により、印刷性の良好な
ペーストを用いて、多孔質の金属酸化物からなる膜を印
刷形成でき、したがって小形化された高感度・高選択性
のガスセンサを高い量産性のもとに提供しうるちのであ
る。すなわち、前記のごとき手段によれば、粘度、チキ
ソトロピーなどのレオロジー特性や溶剤の揮発性の適度
な印刷可能なペーストを得ることができ、この金属酸化
物微粉体と有機金属化合物を含むペーストを用いて有機
被膜を印刷し、乾燥ののちに焼成すれば、有機金属化合
物が熱分解して酸化物に変化する。(Function) The present invention is capable of printing a film made of a porous metal oxide by using a paste with good printability by the above-described means, and is therefore capable of forming a highly sensitive and highly selective film with a small size. Uruchino provides gas sensors with high mass productivity. That is, according to the above-mentioned means, it is possible to obtain a printable paste with appropriate rheological properties such as viscosity and thixotropy, and appropriate solvent volatility, and using this paste containing metal oxide fine powder and an organometallic compound. When an organic film is printed, dried, and fired, the organometallic compound thermally decomposes and turns into an oxide.
このとき、前記金属酸化物微粉体と結合をつくってバイ
ンダとしてはたらき、強固な多孔質金属酸化物膜を形成
する。この多孔質金属酸化物膜は、その下層の半導体膜
との界面でガスの吸着・離脱を触媒するとともに、半導
体膜へのガスの透過に選択性をもたせることにより、こ
のガスセンサをして高感度、高選択性にせしめるもので
ある。At this time, it forms a bond with the metal oxide fine powder and acts as a binder, forming a strong porous metal oxide film. This porous metal oxide film catalyzes gas adsorption and desorption at the interface with the underlying semiconductor film, and also provides selectivity to gas permeation through the semiconductor film, making this gas sensor highly sensitive. , which gives high selectivity.
（実施例）
以下、図面を参照して本発明の実施例を詳細に説明する
。(Example) Hereinafter, an example of the present invention will be described in detail with reference to the drawings.
第１図は、本発明の一実施例の構造の説明図である。例
えば、アルミナ基板等の絶縁基板１の表面には対向電極
６および対向電極用コンタクトパッド９、ならびに発熱
体用コンタクトパッド４が設けられ、前記対向電極６の
上層には例えば酸化スズ系半導体膜等の金属酸化物半導
体薄膜７が形成され、この半導体薄膜７の上層には多孔
質金寓酸化物膜８が設けられている。そして、前記発熱
体用コンタクトパッド４には発熱体用リード線１０か取
り付けられ、前記対向電極用コンタクトパッド９には対
向電極用リード線１１が取り付けられている。FIG. 1 is an explanatory diagram of the structure of an embodiment of the present invention. For example, a counter electrode 6, a contact pad 9 for the counter electrode, and a contact pad 4 for a heating element are provided on the surface of an insulating substrate 1 such as an alumina substrate, and the upper layer of the counter electrode 6 is formed of, for example, a tin oxide semiconductor film or the like. A metal oxide semiconductor thin film 7 is formed, and a porous metal oxide film 8 is provided on the upper layer of this semiconductor thin film 7. A heating element lead wire 10 is attached to the heating element contact pad 4, and a counter electrode lead wire 11 is attached to the counter electrode contact pad 9.
つぎに、第２図および第３図を参照しながら前記ガスセ
ンサの製造方法を説明する。第２図は製造工程のフロー
チャート、第３図は、第１図のＩ−■断面から見た製造
工程の説明図である。Next, a method for manufacturing the gas sensor will be explained with reference to FIGS. 2 and 3. FIG. 2 is a flowchart of the manufacturing process, and FIG. 3 is an explanatory diagram of the manufacturing process as seen from the I-■ cross section of FIG. 1.
まず、ステップ２０１で、絶縁基板１の表面に７０重量
％の白金および３０重量％のタングステンからなる厚膜
の発熱体２を設ける（第３図（ａ）参照）。First, in step 201, a thick film heating element 2 made of 70% by weight platinum and 30% by weight tungsten is provided on the surface of an insulating substrate 1 (see FIG. 3(a)).
つぎにステップ２０２で、その上にはアルミナの絶縁体
３を膜状に設ける。その際に、発熱体の両端上にコンタ
クトパッド４を形成するために、絶縁体３の当該箇所に
はスルーホール５を設ける（第３図（ｂ）参照）。Next, in step 202, an alumina insulator 3 is provided thereon in the form of a film. At this time, in order to form contact pads 4 on both ends of the heating element, through holes 5 are provided at the corresponding locations of the insulator 3 (see FIG. 3(b)).
ステップ２０３で、膜状絶縁体３の上に金の厚膜により
一対の対向電極６を設ける（第３図（Ｃ）参照）。In step 203, a pair of opposing electrodes 6 are provided on the film-like insulator 3 using a thick gold film (see FIG. 3(C)).
つづいてステップ２０４では、前記対向電極６の上に例
えば酸化スズ系半導体薄膜等の金属酸化物半導体薄膜７
を重ねて形成する（第３図（ｄ ）参照）。Subsequently, in step 204, a metal oxide semiconductor thin film 7 such as a tin oxide semiconductor thin film is formed on the counter electrode 6.
(see Figure 3(d)).
前記半導体薄膜７は、以下のようにしてスクリーン印刷
により作成される。ヘキソエートスズとニオブレジネー
トの有機金属化合物の混合物（原子数比で１００ ：
１）を含み、エチルヒドロキシエチルセルロースとテレ
ピン油を含有する均一な溶液系ペーストを調製し、これ
を所定のパターンに印刷し、１２０°Ｃで１５分間乾燥
したのち、６００℃の電気炉で１０分間焼成する。上記
ペースト中の有機金属化合物が熱分解して、金属酸化物
半導体薄膜７が得られる。The semiconductor thin film 7 is created by screen printing as follows. A mixture of organometallic compounds of hexoate tin and niobreinate (atomic ratio: 100:
1), prepare a homogeneous solution-based paste containing ethyl hydroxyethyl cellulose and turpentine oil, print this into a predetermined pattern, dry it at 120°C for 15 minutes, and then dry it in an electric furnace at 600°C for 10 minutes. Fire. The organometallic compound in the paste is thermally decomposed and a metal oxide semiconductor thin film 7 is obtained.
ステップ２０５では前記半導体薄膜７の上に多孔質金属
酸化物膜を形成する（第３図（ｅ）参照）。In step 205, a porous metal oxide film is formed on the semiconductor thin film 7 (see FIG. 3(e)).
この多孔質金属酸化物膜８は以下のようにして作成され
る。まず、アルミナの微粉体を所定量はかりとり、これ
に例えばタングステン酸アンモニウム水溶液を加えベー
スト状とし、一定時間かくはんする。こののち乾燥し、
焼成する。つぎに、これに硫酸銅水溶液を加え、上記と
同様の操作を繰り返す。これでタングステンおよび銅の
酸化物を担持した触媒が得られる（以下これを触媒と称
する）。This porous metal oxide film 8 is created as follows. First, a predetermined amount of fine alumina powder is weighed out, and an aqueous solution of ammonium tungstate, for example, is added thereto to form a base and stirred for a predetermined period of time. After this, it dries,
Fire. Next, an aqueous copper sulfate solution is added to this, and the same operation as above is repeated. In this way, a catalyst supporting tungsten and copper oxides is obtained (hereinafter referred to as a catalyst).
金属酸化物微粉体を含む前記有機被膜の印刷用のペース
トは、以下のようにして調製される。まず、ペーストの
ベースポリマーであるエチルヒドロキシエチルセルロー
スを、６０〜８０℃に加熱したテレピン油に加えてかく
はんする。これが十分に溶解したら、アルミニウムレジ
ネートを加えて十分に混合し、さらに乳鉢上で前記触媒
と混合してペーストを得る。このペーストの組成は触媒
３０重量％アルミニウムレ
ジネート ２０重量％テレピン油
４７瓜量％エチルヒドロキシ
エチルセルロース ３重量％
である。これを所定のパターンに印刷し、１２０°Ｃで
１５分間乾燥したのち、５００℃で焼成する。The paste for printing the organic film containing metal oxide fine powder is prepared as follows. First, ethylhydroxyethylcellulose, which is the base polymer of the paste, is added to turpentine oil heated to 60 to 80°C and stirred. Once this is sufficiently dissolved, aluminum resinate is added and mixed thoroughly, and further mixed with the catalyst on a mortar to obtain a paste. The composition of this paste is catalyst: 30% by weight aluminum resinate 20% by weight turpentine oil
47% by weight of ethyl hydroxyethylcellulose 3% by weight. This is printed in a predetermined pattern, dried at 120°C for 15 minutes, and then fired at 500°C.
以上のごとく多孔質金属酸化物膜８を形成したのち、ス
テップ２０６では、多数個どりの基板の場合には各チッ
プに分割したのち、発熱体用コンタクトパッド４および
対向電極用コンタクトパッド９にそれぞれリード線１０
および１１をとりつけ、チップを実装する（第３図（ｆ
）参照）。After forming the porous metal oxide film 8 as described above, in step 206, in the case of a large number of substrates, the substrate is divided into each chip, and then the contact pads 4 for the heating element and the contact pads 9 for the counter electrode are respectively attached. Lead wire 10
and 11 and mount the chip (Fig. 3(f)
)reference).
上記のごとく製造したガスセンサの、各種ガス５００
ｐｐｍに対する感度（空気中の抵抗値をガス中の抵抗値
で除した値）を第１表に示す。なお、発熱体に印加する
電圧を調節して、素子温度は４００℃に設定しである。Various gases 500% of the gas sensor manufactured as above
Sensitivity to ppm (value obtained by dividing the resistance value in air by the resistance value in gas) is shown in Table 1. Note that the element temperature was set at 400° C. by adjusting the voltage applied to the heating element.
また、従来例として、前記と同じ触媒を塩基性塩化アル
ミニウム水溶液と混合してなるペーストを用いて製造し
たセンサのデータを示す。Furthermore, as a conventional example, data of a sensor manufactured using a paste made by mixing the same catalyst as described above with a basic aluminum chloride aqueous solution is shown.
第１表 ガス５００ｐｐｍに対する感度第１表から、上
記本発明の実施例によるセンサは、従来例のセンサとほ
ぼ同等の感度を有していることが明らかである。Table 1 Sensitivity to 500 ppm of gas From Table 1, it is clear that the sensor according to the embodiment of the present invention has almost the same sensitivity as the conventional sensor.
なお、リード線をボンディングしたのちに、触媒を含む
低粘度のペーストを塗布するという従来例によれば、例
えば多孔質アルミナと前記リード線とが接触するために
、高湿雰囲気中では酸性のアルミナがリード線の腐食を
促進する恐れがある。In addition, according to the conventional method of applying a low-viscosity paste containing a catalyst after bonding the lead wires, for example, because porous alumina and the lead wires come into contact, acidic alumina may accelerate lead wire corrosion.
印刷により、当該多孔質金属酸化物膜をパターン形成す
れば、この恐れが軽減される。Patterning the porous metal oxide film by printing alleviates this fear.
また、多孔質金属酸化物膜を形成する際の有機金属化合
物の量に関して、例えばアルミニウムレジネートの量が
少なすぎると（０，５重量％未満の場合）、多孔質アル
ミナの膜強度が小さすぎて実用に耐えず、逆に多すぎる
と（１５重量％以上の場合）、当該アルミナがち密にな
ってしまうために、センサとしての感度および応答性が
低すぎるので、いずれの場合も適当ではない。Regarding the amount of organometallic compound when forming a porous metal oxide film, for example, if the amount of aluminum resinate is too small (less than 0.5% by weight), the strength of the porous alumina film will be too low. If it is not practical, and if it is too large (15% by weight or more), the alumina will become dense and the sensitivity and response as a sensor will be too low, so either case is not suitable.
［発明の効果］
以上述べたように本発明によれば、多孔質金属酸化膜を
形成するに際し、印刷に用いるペーストのポリマーおよ
び溶剤の選択により、粘度、チキソトロピーなどのレオ
ロジー特性が良好で、溶剤の揮発性が小さい、印刷可能
なペーストを得ることができ、また前記ペーストが有機
金属化合物を含むことから、強固な多孔質の金属酸化物
膜を形成することができる。さらに、前記のごとく形成
された多孔質金属酸化物膜は、このガスセンサをして高
感度、高選択性にせしめている。さらに、それだけでは
なく、印刷によって膜厚や細孔分布などの制御が可能で
あることから、特性のバラツキが軽減できる。そのほか
、すべての成膜工程が印刷となりうろことから、量産性
の著しい向上が可能となる。[Effects of the Invention] As described above, according to the present invention, when forming a porous metal oxide film, by selecting the polymer and solvent of the paste used for printing, the rheological properties such as viscosity and thixotropy are good, and the solvent A printable paste with low volatility can be obtained, and since the paste contains an organometallic compound, a strong porous metal oxide film can be formed. Furthermore, the porous metal oxide film formed as described above makes this gas sensor highly sensitive and highly selective. Furthermore, since it is possible to control the film thickness, pore distribution, etc. by printing, variations in properties can be reduced. In addition, since all film formation steps are likely to be performed by printing, mass productivity can be significantly improved.
第１図は本発明の一実施例を示す平面図、第２図は本発
明の一実施例の製造工程のフローチャート、第３図は第
１図のＩ−Ｉ断面から見た各製造工程の断面図である。
１・・・絶縁基板、２・・・発熱体、３・・・絶縁体、
４・・・発熱体用コンタクトパッド、５・・・スルーホ
ール、６・・・対向電極、７・・・金属酸化物半導体薄
膜、８・・・多孔質金属酸化物膜、９・・・対向電極用
コンタクトパッド、１０・・・発熱体用リード線、１１
・・・対向電極用リード線。
出願人代理人 弁理士 鈴江武彦
第１ 図Fig. 1 is a plan view showing an embodiment of the present invention, Fig. 2 is a flowchart of the manufacturing process of an embodiment of the invention, and Fig. 3 is a diagram showing each manufacturing process as seen from the II cross section in Fig. FIG. 1... Insulating substrate, 2... Heating element, 3... Insulator,
4... Contact pad for heating element, 5... Through hole, 6... Counter electrode, 7... Metal oxide semiconductor thin film, 8... Porous metal oxide film, 9... Opposing Contact pad for electrode, 10... Lead wire for heating element, 11
...Lead wire for counter electrode. Applicant's agent Patent attorney Takehiko Suzue Figure 1
Claims (1)
前記電極間に膜状に形成された金属酸化物半導体と、こ
の金属酸化物半導体上にアルミニウム、ケイ素、ジルコ
ニウムの群から選ばれる少なくとも１種の元素の酸化物
微粉体と前記の群から選ばれる少なくとも一種の元素の
有機化合物とを含む被膜を印刷、熱分解して形成された
多孔質の金属酸化物とを具備したことを特徴とするガス
センサ。an insulating substrate provided with a pair of electrodes; a metal oxide semiconductor formed in the form of a film between the electrodes on the insulating substrate; and at least one selected from the group of aluminum, silicon, and zirconium formed on the metal oxide semiconductor. A porous metal oxide formed by printing and thermally decomposing a film containing fine oxide powder of one element and an organic compound of at least one element selected from the above group. gas sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62064204A JPH07104309B2 (en) | 1987-03-20 | 1987-03-20 | Gas sensor manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62064204A JPH07104309B2 (en) | 1987-03-20 | 1987-03-20 | Gas sensor manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63231254A true JPS63231254A (en) | 1988-09-27 |
| JPH07104309B2 JPH07104309B2 (en) | 1995-11-13 |
Family
ID=13251304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62064204A Expired - Lifetime JPH07104309B2 (en) | 1987-03-20 | 1987-03-20 | Gas sensor manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07104309B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2692047A1 (en) * | 1992-06-04 | 1993-12-10 | Gaz De France | Selective gas detection sensor and device for its implementation. |
| US7441440B2 (en) * | 2003-04-24 | 2008-10-28 | Sacmi Cooperativa Meccanici Imola Soc. Coop. A.R.L. | Thin semiconductor film gas sensor device |
| GB2520251A (en) * | 2013-11-12 | 2015-05-20 | Emma Newton | Hand held device for the detection of trace gases |
| CN105445420A (en) * | 2014-09-24 | 2016-03-30 | 普因特工程有限公司 | Micro Heater and Micro Sensor and Manufacturing Methods Thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5999244A (en) * | 1982-11-30 | 1984-06-07 | Toshiba Corp | Detector for gaseous co |
| JPS60149957A (en) * | 1984-01-17 | 1985-08-07 | Toshiba Corp | Gas sensor |
| JPS6151259A (en) * | 1984-08-20 | 1986-03-13 | Nissin Electric Co Ltd | Synchronizing method of multi cpu system |
| JPS6152423A (en) * | 1984-08-21 | 1986-03-15 | Aisin Seiki Co Ltd | Torque variation absorbing apparatus |
-
1987
- 1987-03-20 JP JP62064204A patent/JPH07104309B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5999244A (en) * | 1982-11-30 | 1984-06-07 | Toshiba Corp | Detector for gaseous co |
| JPS60149957A (en) * | 1984-01-17 | 1985-08-07 | Toshiba Corp | Gas sensor |
| JPS6151259A (en) * | 1984-08-20 | 1986-03-13 | Nissin Electric Co Ltd | Synchronizing method of multi cpu system |
| JPS6152423A (en) * | 1984-08-21 | 1986-03-15 | Aisin Seiki Co Ltd | Torque variation absorbing apparatus |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2692047A1 (en) * | 1992-06-04 | 1993-12-10 | Gaz De France | Selective gas detection sensor and device for its implementation. |
| US7441440B2 (en) * | 2003-04-24 | 2008-10-28 | Sacmi Cooperativa Meccanici Imola Soc. Coop. A.R.L. | Thin semiconductor film gas sensor device |
| GB2520251A (en) * | 2013-11-12 | 2015-05-20 | Emma Newton | Hand held device for the detection of trace gases |
| CN105445420A (en) * | 2014-09-24 | 2016-03-30 | 普因特工程有限公司 | Micro Heater and Micro Sensor and Manufacturing Methods Thereof |
| CN105445420B (en) * | 2014-09-24 | 2019-12-06 | 普因特工程有限公司 | Micro-heater and micro-sensor and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07104309B2 (en) | 1995-11-13 |
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