JP2648341B2 - Manufacturing method of thin film oxygen sensor - Google Patents
Manufacturing method of thin film oxygen sensorInfo
- Publication number
- JP2648341B2 JP2648341B2 JP63189890A JP18989088A JP2648341B2 JP 2648341 B2 JP2648341 B2 JP 2648341B2 JP 63189890 A JP63189890 A JP 63189890A JP 18989088 A JP18989088 A JP 18989088A JP 2648341 B2 JP2648341 B2 JP 2648341B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- weight
- resinate
- platinum
- oxygen 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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、固体電解質型薄膜酸素センサの多孔質薄膜
白金電極と薄膜ジルコニア固体電解質を製造する方法に
関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a porous thin-film platinum electrode and a thin-film zirconia solid electrolyte of a solid-electrolyte thin-film oxygen sensor.
（従来技術とその問題点） 従来、固体電解質型薄膜酸素センサの白金薄膜電極は
真空蒸着法で３μｍ程度の膜厚を形成し、固体電解質と
してのジルコニア薄膜はスパッタリングでやはり３μｍ
程度の膜厚を長時間かけて形成させている。この方法で
は特殊な製造装置が必要でその形成原理上歩留りが悪
く、高価な貴金属を有効に利用出来ない点や工業生産性
に欠けるなどの問題がある。(Prior art and its problems) Conventionally, a platinum thin film electrode of a solid electrolyte type thin film oxygen sensor has a thickness of about 3 μm by a vacuum evaporation method, and a zirconia thin film as a solid electrolyte has a thickness of 3 μm by sputtering.
A film having a thickness of about 30 minutes is formed over a long period of time. This method requires a special manufacturing apparatus, has a low yield due to its formation principle, and has problems such as the inability to effectively use expensive precious metals and the lack of industrial productivity.
他にペーストを用いる方法もあるが、膜厚10μｍ以上
で酸素センサとしての性能とくに応答性が悪い問題があ
る。There is another method using a paste, but there is a problem that the performance as an oxygen sensor, particularly the responsiveness, is poor when the film thickness is 10 μm or more.
（発明の目的） 本発明は、固体電解質型薄膜酸素センサの多孔質薄膜
白金電極と薄膜ジルコニア固体電解質形成における上記
従来の諸問題を解決するためになされたもので、有機白
金インクと有機ジルコニウムインクを用い簡便な方法で
薄膜を形成でき、省貴金属化を計りしかも応答性を高め
るための薄膜形成方法で0.1〜５μｍの薄膜を形成する
方法を提供することを目的とする。(Object of the Invention) The present invention has been made to solve the above-mentioned conventional problems in forming a porous thin film platinum electrode and a thin film zirconia solid electrolyte of a solid electrolyte type thin film oxygen sensor. It is an object of the present invention to provide a method for forming a thin film having a thickness of 0.1 to 5 [mu] m by a thin film forming method capable of forming a thin film by a simple method using a thin film, measuring a noble metal, and improving response.
（問題点を解決するための手段） 本発明は、固体電解質型薄膜酸素センサの多孔質薄膜
白金電極を、樹脂酸白金10〜30重量％、樹脂酸ビスマ
ス、樹脂酸ケイ素及び樹脂酸アンチモンをそれぞれ0.3
〜３重量％、ロジン誘導体樹脂１〜53重量％並びに残部
溶剤より成る有機白金インクを用いて形成し、薄膜ジル
コニア固体電解質を、樹脂酸ジルコニウム５〜20重量
％、樹脂酸イットリウム0.3〜10重量％、樹脂酸ケイ素
及び樹脂酸ビスマスをそれぞれ0.3〜３重量％、樹脂酸
ホウ素0.3〜５重量％、ロジン誘導体樹脂１〜49.7重量
％並びに残部溶剤より成る有機ジルコニウムインクを用
いて形成することを特徴とする酸素センサの製造方法で
ある。(Means for Solving the Problems) The present invention relates to a method for forming a porous thin film platinum electrode of a solid electrolyte type thin film oxygen sensor by using 10 to 30% by weight of platinum resinate, bismuth resinate, silicon resinate and antimony resinate, respectively. 0.3
-3% by weight, 1-53% by weight of a rosin derivative resin and the balance of a solvent are used to form a thin-film zirconia solid electrolyte, 5-20% by weight of zirconium resinate, 0.3-10% by weight of yttrium resinate , Silicon oxide resin and bismuth resin acid are each formed using an organic zirconium ink comprising 0.3 to 3% by weight of a resinate, 0.3 to 5% by weight of a boronate resin, 1 to 49.7% by weight of a rosin derivative resin, and the balance of a solvent. This is a method for manufacturing an oxygen sensor.
以下本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
（１）多孔質アルミナ基板または多孔質ガラス基板上に
有機白金インクをスクリーン印刷、筆塗り、ディッピン
グ、スプレー、スピンコーティング、スタンプ法等の各
種の一般的方法で塗布し、室温で10〜15分間乾燥した
後、100〜200℃で10〜15分間加熱乾燥する。次に700〜1
000℃で10〜15分間焼成して白金の多孔質薄膜を形成さ
せることできる。(1) An organic platinum ink is applied on a porous alumina substrate or a porous glass substrate by various general methods such as screen printing, brush coating, dipping, spraying, spin coating, stamping, and the like, and is then room temperature for 10 to 15 minutes. After drying, heat and dry at 100-200 ° C for 10-15 minutes. Then 700-1
By baking at 000 ° C. for 10 to 15 minutes, a porous thin film of platinum can be formed.
該多孔質アルミナ基板及び多孔質ガラス基板は酸素セ
ンサ用として一般的に用いられているもので問題はな
い。The porous alumina substrate and the porous glass substrate are generally used for an oxygen sensor and have no problem.
白金の多孔質薄膜を形成するために塗布する有機白金
インクは、樹脂酸の白金塩と他の樹脂酸の金属塩とバイ
ンダとしてのロジン誘導体樹脂及び溶剤で合成されたも
ので、その合成割合は、樹脂酸の白金塩を10〜30重量
％、他の樹脂酸の塩として樹脂酸鉛、樹脂酸ビスマス、
樹脂酸ケイ素及び樹脂酸アンチモンで0.3〜３重量％、
ロジン誘導体樹脂には例えばロジンのグリセリンエステ
ル、ロジンのペンタエリストール、エステル等で１〜53
重量％及び溶剤（残部）は例えばテルペンアルコール等
各成分に共通した有機溶媒を用い混合し溶解して合成す
る。Organic platinum ink applied to form a porous thin film of platinum is synthesized with a platinum salt of resin acid, a metal salt of another resin acid, a rosin derivative resin as a binder, and a solvent, and the synthesis ratio thereof is as follows. , 10-30% by weight of platinum salt of resin acid, lead resin, bismuth resin as salt of other resin acid,
0.3 to 3% by weight of silicon resinate and antimony resinate,
Rosin derivative resins include, for example, glycerin esters of rosin, pentaerythroles of rosin, esters, etc.
The weight% and the solvent (remainder) are synthesized by mixing and dissolving using an organic solvent common to each component such as terpene alcohol.
上記の割合で合成された有機白金インクを用いてスク
リーン印刷により塗布し、乾燥、焼成したときの白金薄
膜の厚さは0.05〜0.3μｍであり、任意の膜厚を得るに
は膜形成工程を繰り返せば簡単にでき、合成された有機
白金インクは液体であり、あらゆる形状の基体上に塗布
することができ、膜厚も安定したものが得られる。The thickness of the platinum thin film when applied by screen printing using the organic platinum ink synthesized in the above ratio, dried and baked is 0.05 to 0.3 μm, and a film forming step is required to obtain an arbitrary film thickness. It is easy to repeat, and the synthesized organoplatinum ink is a liquid, can be applied on substrates of any shape, and has a stable film thickness.
また１回の膜形成工程で膜厚を厚くしたい場合は、樹
脂酸の白金塩の割合を高めれば可能である。該白金の多
孔質薄膜としては0.1〜１μｍが好ましいとされてお
り、上記に示した合成割合の有機白金インクで数回、膜
形成工程を繰り返せば十分目的とする膜厚を得られる。
しかも繰り返し塗布、乾燥、焼成工程を行っても薄膜に
ヒビ割れを生ずることはなく、この方法で得られた薄膜
を拡大して観察すると均一な多孔質のものであった。When it is desired to increase the film thickness in one film forming step, it is possible to increase the ratio of the platinum salt of the resin acid. It is considered that the platinum thin film is preferably 0.1 to 1 μm, and the desired film thickness can be obtained sufficiently by repeating the film forming process several times with the organic platinum ink having the above-mentioned composition ratio.
In addition, no cracking occurred in the thin film even when the coating, drying and firing steps were repeated, and the thin film obtained by this method was observed to be uniform and porous when observed in an enlarged manner.
尚、該有機白金インクに合成されている白金以外の樹
脂酸の金属塩は基板の成分により割合及び金属成分を変
えることも密着性を高める場合等で可能である。Incidentally, the metal salt of a resin acid other than platinum synthesized in the organic platinum ink can be changed in proportion and metal component depending on the components of the substrate, for example, in the case of enhancing the adhesion.
（２）多孔質アルミナ基板または多孔質ガラス基板上に
白金の多孔質薄膜を形成させた後、有機ジルコニウムイ
ンクを上記有機白金インクを塗布する方法と同様に塗布
し、室温で10〜15分間乾燥し、100〜220℃で10〜15分間
加熱乾燥する。次に700〜1100℃で10〜15分間焼成して
固体電解質薄膜を形成する。(2) After forming a porous thin film of platinum on a porous alumina substrate or a porous glass substrate, an organic zirconium ink is applied in the same manner as the method of applying the organic platinum ink, and dried at room temperature for 10 to 15 minutes. Then, heat and dry at 100-220 ° C for 10-15 minutes. Next, baking is performed at 700 to 1100 ° C. for 10 to 15 minutes to form a solid electrolyte thin film.
ここで用いる有機ジルコニウムインクは、樹脂酸のジ
ルコニウム塩５〜20重量％、樹脂酸のイットリウム塩0.
3〜10重量％、他の樹脂酸の塩は樹脂ホウ素0.3〜５重量
％、樹脂酸ケイ素及び樹脂酸ビスマスをそれぞれ0.3〜
３重量％、ロジン誘導体樹脂にはガムロジン等で１〜4
9.7重量％及び溶剤（残部）はグリセリンエステル等で
各成分の共通した有機溶媒を用い混合し溶解して合成す
る。The organic zirconium ink used here is 5 to 20% by weight of a resin acid zirconium salt and a resin acid yttrium salt.
3 to 10% by weight, other resin acid salt is resin boron 0.3 to 5% by weight, silicon acid resin and bismuth resin acid are each 0.3 to 0.3%
3% by weight, rosin derivative resin with gum rosin etc.
9.7% by weight and the solvent (the remainder) are synthesized by mixing and dissolving glycerin ester or the like using an organic solvent having the same components.
上記の割合で合成された有機ジルコニウムインクを用
いてスクリーン印刷により塗布し、乾燥、焼成したとき
の酸化ジルコニウム（酸化イットリウムを含む）薄膜の
厚さは0.05〜0.1μｍであり、任意の膜厚を得るために
は膜形成工程を繰り返せば簡単にでき、合成された有機
ジルコニウムインクは液体であり、上記有機白金インク
同様、あらゆる形状の基体上に塗布することができ、膜
厚も安定したものが得られる。The thickness of the zirconium oxide (including yttrium oxide) thin film when applied by screen printing using the organic zirconium ink synthesized in the above ratio, dried, and baked is 0.05 to 0.1 μm. In order to obtain it, it is easy to repeat the film forming process, and the synthesized organic zirconium ink is a liquid, which can be applied on a substrate of any shape, like the above-mentioned organic platinum ink, and has a stable film thickness. can get.
該酸化ジルコニウム固体電解質薄膜は、固体電解質と
しての酸化ジルコニウムに安定剤として酸化イットリウ
ムを３〜８％モル加えたものが一般的であるが酸化イッ
トリウムを均一に分散させることが従来の方法ではむず
かしく、よって膜厚を数μｍ以上していたが、経済的に
不満な面があり、本法による薄膜は酸化ジルコニウム中
に酸化イットリウムが均一分散されており、0.5〜１μ
ｍで十分固体電解質として安定したものが得られる。The zirconium oxide solid electrolyte thin film is generally obtained by adding 3 to 8% by mole of yttrium oxide as a stabilizer to zirconium oxide as a solid electrolyte, but it is difficult to uniformly disperse yttrium oxide by a conventional method. Therefore, although the film thickness was several μm or more, there were economically unsatisfactory aspects, and the thin film obtained by this method had a uniform dispersion of yttrium oxide in zirconium oxide and a thickness of 0.5 to 1 μm.
With m, a sufficiently stable solid electrolyte can be obtained.
（３）多孔質アルミナ基板、または多孔質ガラス基板上
に多孔質白金薄膜を形成し、その上に酸化ジルコニウム
の固体電解質薄膜を形成した後、再度多孔質白金薄膜を
（１）とまったく同様に行い、形成することにより固体
電解質薄膜酸素センサを製造することができる。(3) A porous platinum thin film is formed on a porous alumina substrate or a porous glass substrate, a zirconium oxide solid electrolyte thin film is formed thereon, and the porous platinum thin film is formed again in exactly the same manner as (1). By performing and forming, a solid electrolyte thin film oxygen sensor can be manufactured.
以下本発明に係わる固体電解質薄膜酸素センサの多孔
質白金薄膜および酸化ジルコニウム固体電解質薄膜製造
方法実施例を記載するが、該実施例は本発明を限定する
ものではない。Hereinafter, an example of a method for producing a porous platinum thin film and a zirconium oxide solid electrolyte thin film of a solid electrolyte thin film oxygen sensor according to the present invention will be described, but the present invention is not limited thereto.
（実施例） 図は固体電解質型薄膜酸素センサの部分拡大断面図で
ある。(Example) The figure is a partially enlarged sectional view of a solid electrolyte type thin film oxygen sensor.
アルミナ平板状多孔質基板１の表面に有機白金インク
をスクリーン印刷により塗布し、室温で10分間乾燥し、
次に200℃で10分間加熱乾燥した後、1000℃で10分間焼
成し、塗布、乾燥、焼成工程を５回繰り返し行って0.5
μｍの多孔質白金薄膜２を形成した。An organic platinum ink is applied to the surface of the alumina flat porous substrate 1 by screen printing, and dried at room temperature for 10 minutes.
Next, after heating and drying at 200 ° C. for 10 minutes, baking is performed at 1000 ° C. for 10 minutes.
A μm porous platinum thin film 2 was formed.
次に有機ジルコニウムインクを用いてスクリーン印刷
により塗布し、室温で10分間乾燥し、次に200℃で10分
間加熱乾燥した後、1000℃で10分間焼成し、塗布、乾
燥、焼成工程を５回繰り返し行って0.5μｍの酸化ジル
コニウムの固体電解質薄膜３を形成した。さらにこの上
に多孔質白金薄膜を同じ有機白金インクを用いて同様に
塗布、乾燥、焼成工程を５回繰り返して0.5μｍの多孔
質白金薄膜２′を形成し、固体電解質薄膜酸素センサを
製造した。Next, it is applied by screen printing using an organic zirconium ink, dried at room temperature for 10 minutes, then heated and dried at 200 ° C. for 10 minutes, and then baked at 1000 ° C. for 10 minutes. This was repeated to form a 0.5 μm zirconium oxide solid electrolyte thin film 3. Further, a porous platinum thin film 2 ′ having a thickness of 0.5 μm was formed by repeating the coating, drying and baking steps 5 times with the same organic platinum ink using the same organic platinum ink to form a solid electrolyte thin film oxygen sensor. .
ここで用いた有機白金インクと有機ジルコニウムイン
クは表−１の成分と割合で合成した。The organic platinum ink and the organic zirconium ink used here were synthesized with the components and ratios shown in Table 1.
作製した酸素センサの応答性を、比較例として白金無
電解メッキ法で作製したものと比べたところ、下記の表
−２のような結果を得た。 When the responsiveness of the manufactured oxygen sensor was compared with that of a sensor manufactured by a platinum electroless plating method as a comparative example, the results shown in Table 2 below were obtained.
（発明の効果） 本発明は、固体電解質薄膜酸素センサの製造方法で多
孔質白金薄膜と薄膜ジルコニア固体電解質を、従来問題
とされていた欠点を解決するために有機白金インクと有
機ジルコニアインクを合成し、その塗布、乾燥、焼成の
薄膜形成方法により高価な貴金属を約1/10に省貴金属化
でき、小型で経済的でしかも応答性の良い酸素センサを
製造することが可能となったことは利用価値を大いに高
めることができよう。 (Effect of the Invention) The present invention synthesizes a porous platinum thin film and a thin film zirconia solid electrolyte in a method for manufacturing a solid electrolyte thin film oxygen sensor, and synthesizes an organic platinum ink and an organic zirconia ink in order to solve the drawbacks which have been conventionally regarded as problems. However, the thin film forming method of coating, drying and firing can reduce expensive noble metal to about 1/10 and reduce the cost of producing a small, economical and responsive oxygen sensor. The value of use could be greatly increased.
図は固体電解質型薄膜酸素センサの部分拡大断面図であ
る。 １……アルミナ平板状多孔質基板、２、２′……多孔質
白金薄膜、３……酸化ジルコニウムの固体電解質薄膜。The figure is a partially enlarged sectional view of the solid electrolyte type thin film oxygen sensor. 1 ... alumina plate-like porous substrate, 2,2 '... porous platinum thin film, 3 ... zirconium oxide solid electrolyte thin film.
Claims (1)
白金電極を、樹脂酸白金10〜30重量％、樹脂酸ビスマ
ス、樹脂酸ケイ素及び樹脂酸アンチモンをそれぞれ0.3
〜３重量％、ロジン誘導体樹脂１〜53重量％並びに残部
溶剤より成る有機白金インクを用いて形成し、薄膜ジル
コニア固体電解質を、樹脂酸ジルコニウム５〜20重量
％、樹脂酸イットリウム0.3〜10重量％、樹脂酸ケイ素
及び樹脂酸ビスマスをそれぞれ0.3〜３重量％、樹脂酸
ホウ素0.3〜５重量％、ロジン誘導体樹脂１〜49.7重量
％並びに残部溶剤より成る有機ジルコニウムインクを用
いて形成することを特徴とする酸素センサの製造方法。A porous thin-film platinum electrode of a solid-electrolyte thin-film oxygen sensor is prepared by mixing 10 to 30% by weight of platinum resinate, bismuth resinate, silicon resinate and antimony resinate with 0.3% each.
-3% by weight, 1-53% by weight of a rosin derivative resin and the balance of a solvent are used to form a thin-film zirconia solid electrolyte, 5-20% by weight of zirconium resinate, 0.3-10% by weight of yttrium resinate , Silicon oxide resin and bismuth resin acid are each formed using an organic zirconium ink comprising 0.3 to 3% by weight of a resinate, 0.3 to 5% by weight of a boronate resin, 1 to 49.7% by weight of a rosin derivative resin, and the balance of a solvent. Of manufacturing oxygen sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189890A JP2648341B2 (en) | 1988-07-29 | 1988-07-29 | Manufacturing method of thin film oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63189890A JP2648341B2 (en) | 1988-07-29 | 1988-07-29 | Manufacturing method of thin film oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0238964A JPH0238964A (en) | 1990-02-08 |
| JP2648341B2 true JP2648341B2 (en) | 1997-08-27 |
Family
ID=16248893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63189890A Expired - Lifetime JP2648341B2 (en) | 1988-07-29 | 1988-07-29 | Manufacturing method of thin film oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2648341B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03165253A (en) * | 1989-11-24 | 1991-07-17 | Matsushita Electric Ind Co Ltd | Oxygen sensor |
| KR100900092B1 (en) * | 2007-06-29 | 2009-05-28 | 서울산업대학교 산학협력단 | Preparation method of oxygen sensor |
| JP2009125256A (en) * | 2007-11-22 | 2009-06-11 | Kandado:Kk | Quiet sleep pillow |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2913633C2 (en) * | 1979-04-05 | 1986-01-23 | Robert Bosch Gmbh, 7000 Stuttgart | Electrochemical measuring sensor for the determination of the oxygen content in gases, in particular in exhaust gases from internal combustion engines, as well as a method for producing the same |
| JPS5614149A (en) * | 1979-07-16 | 1981-02-10 | Nissan Motor Co Ltd | Forming method for solid-state electrolyte thin film for oxygen sensor |
| JPS62227477A (en) * | 1986-03-31 | 1987-10-06 | Kawai Musical Instr Mfg Co Ltd | Production of zirconia membrane |
-
1988
- 1988-07-29 JP JP63189890A patent/JP2648341B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0238964A (en) | 1990-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2999854B2 (en) | Method for producing metal thin film for hydrogen sensor, gas sensor or pH response | |
| JP2648341B2 (en) | Manufacturing method of thin film oxygen sensor | |
| CN108922702A (en) | A kind of electrode production process of zinc oxide varistor | |
| JPS639327B2 (en) | ||
| JPH03115966A (en) | Production of solid electrolyte type oxygen sensor | |
| JP2555536B2 (en) | Method for manufacturing platinum temperature sensor | |
| JPH0554716A (en) | Silver paste for forming conductive thin film | |
| JPS6063174A (en) | Manufacture of thermal head | |
| JP2885886B2 (en) | Method for forming metal thin film on heat-resistant substrate | |
| JP2507102B2 (en) | Manufacturing method of temperature sensitive element | |
| JP3161477B2 (en) | Method of forming manganese cobalt oxide thin film | |
| JPH06347440A (en) | Manufacture of electrode for oxygen sensor | |
| JPH07104309B2 (en) | Gas sensor manufacturing method | |
| JPH03285091A (en) | Production of electrode | |
| JPH0227832B2 (en) | SERAMITSUKUSUKIBAN | |
| JPS5899143A (en) | Paste for forming transparent film | |
| JPH0256807A (en) | Organo-group metal sol ink | |
| JP3000454B1 (en) | Paste composition for undercoat of frit layer in transfer paper for precious metal painting and transfer paper for precious metal painting using the paste composition for undercoat | |
| JPS6454711A (en) | Manufacture of ruthenium oxide group thin-film | |
| JPS63139756A (en) | Manufacture of thermal head | |
| JPH05270838A (en) | Formation of manganese-cobalt oxide thin film | |
| JPH0466670A (en) | Production of thin noble metal film laminated material | |
| JPS60102702A (en) | Thick film resistance layer forming paste | |
| JPS61132578A (en) | Metallization of ceramic | |
| JPS6034096B2 (en) | Manufacturing method of liquid crystal cell |