JP2006084335A - Concentration cell type oxygen sensor - Google Patents

Concentration cell type oxygen sensor Download PDF

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JP2006084335A
JP2006084335A JP2004269761A JP2004269761A JP2006084335A JP 2006084335 A JP2006084335 A JP 2006084335A JP 2004269761 A JP2004269761 A JP 2004269761A JP 2004269761 A JP2004269761 A JP 2004269761A JP 2006084335 A JP2006084335 A JP 2006084335A
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oxygen sensor
solid electrolyte
cell type
concentration cell
electrolyte plate
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Yukio Matsuki
幸生 松木
Kiyoteru Kato
清輝 加藤
Teruyuki Takayama
輝之 高山
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Fujikura Ltd
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Fujikura Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a concentration cell type oxygen sensor, which can be made compact, has a high measurement precision, and has a high long-term stability. <P>SOLUTION: The concentration cell type oxygen sensor 10 is equipped with a solid electrolyte plate 11, a sealant 12 which is arranged opposite to the solid electrolyte plate 11 and has a recessed section 13 formed at its center section; an annular sealing member 14 which seals the space between the solid electrolyte plate 11 and the sealant 12, a reference electrode 15 made up of a metal-metallic oxide charged into a sealed space that is formed by sealing the recessed section 13 of the sealant 12 by using the solid electrolyte plate 11, a second lead wire 19 which extends from the reference electrode 15 to the outside of the sealed space, an electrode 16 which is disposed on a surface opposite to the surface being in contact with the reference electrode 15 of the solid electrolyte plate 11, and a heater 17 which is disposed on a surface opposite to the surface being in contact with the reference electrode 15 of the sealant 12. The recessed section 13 is formed such that its inner volume ranges from 1 mm<SP>3</SP>to 10 mm<SP>3</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、例えば、高純度の窒素雰囲気中の残存酸素濃度の監視用などに用いられる濃淡電池式酸素センサに関するものである。   The present invention relates to a concentration cell type oxygen sensor used, for example, for monitoring a residual oxygen concentration in a high purity nitrogen atmosphere.

従来、工業用窒素発生器から発生する高純度の窒素中に含まれる残存酸素濃度から窒素発生器の性能低下を常時監視する用途や、半導体露光装置で純窒素をパージした時の残存酸素濃度から露光性能の低下を常時監視する用途などに酸素センサが利用されている。高純度の窒素中の残存酸素濃度の監視用としては、大気を参照ガスとしたジルコニア濃淡電池式センサやジルコニア限界電流式酸素センサが用いられている。   Conventionally, from the residual oxygen concentration contained in the high-purity nitrogen generated from industrial nitrogen generators, the application of constantly monitoring the performance degradation of the nitrogen generator, and the residual oxygen concentration when purging pure nitrogen with a semiconductor exposure device Oxygen sensors are used for applications such as constantly monitoring for deterioration in exposure performance. For monitoring the residual oxygen concentration in high purity nitrogen, a zirconia concentration cell type sensor or a zirconia limit current type oxygen sensor using the atmosphere as a reference gas is used.

図２は、従来の濃淡電池式酸素センサを示す概略断面図である。
この濃淡電池式酸素センサ１００では、円板状の固体電解質板１０１と、中央部に凹部１０３が形成された円板状の封止体１０２とが対向配置されている。また、固体電解質板１０１と封止体１０２との間は、円環状の封止材１０４によって気密に封止されている。そして、固体電解質板１０１および封止体１０２で形成される密封空間内には、参照電極１０５をなす金属−金属酸化物（以下、「Ｍ−ＭＯ」と略記することもある。）が充填されている。 FIG. 2 is a schematic cross-sectional view showing a conventional concentration cell type oxygen sensor.
In this concentration cell type oxygen sensor 100, a disk-shaped solid electrolyte plate 101 and a disk-shaped sealing body 102 having a concave portion 103 formed in the central portion are disposed to face each other. Further, the solid electrolyte plate 101 and the sealing body 102 are hermetically sealed by an annular sealing material 104. The sealed space formed by the solid electrolyte plate 101 and the sealing body 102 is filled with a metal-metal oxide (hereinafter also abbreviated as “M-MO”) forming the reference electrode 105. ing.

固体電解質板１０１の参照電極１０５と接する面とは反対の面には、電極１０６が設けられている。また、電極１０６には、リード線１０８が接続されている。一方、固体電解質板１０１の参照電極１０５と接する面にも、リード線１０９が接続されている。このリード線１０９は、封止材１０４を気密に貫通して、濃淡電池式酸素センサ１００の内部から外部に引き出されている。また、封止体１０２の参照電極１０５と接する面とは反対の面には、ヒータ１０７がパターン形成されている。さらに、ヒータ１０７には、リード線１１０が接続されている（例えば、特許文献１参照。）。  An electrode 106 is provided on the surface of the solid electrolyte plate 101 opposite to the surface in contact with the reference electrode 105. A lead wire 108 is connected to the electrode 106. On the other hand, the lead wire 109 is also connected to the surface of the solid electrolyte plate 101 in contact with the reference electrode 105. This lead wire 109 penetrates the sealing material 104 in an airtight manner, and is led out from the inside of the concentration cell type oxygen sensor 100 to the outside. A heater 107 is patterned on the surface of the sealing body 102 opposite to the surface in contact with the reference electrode 105. Further, a lead wire 110 is connected to the heater 107 (see, for example, Patent Document 1).

この濃淡電池式酸素センサ１００では、封止体１０２の厚みが厚すぎるため、熱伝導性に劣るので、ヒータ１０７からの熱が伝わり難く、ヒータ１０７の消費電力が大きくなるという欠点がある。また、濃淡電池式酸素センサ１００全体の均熱性も悪く、参照電極１０５が均一に所定の温度にならないため、参照電極１０５の内部における標準酸素分圧を、精度良く所定の分圧に設定することができないので、酸素濃度を精度良く測定できないという欠点がある。   In this concentration cell type oxygen sensor 100, since the sealing body 102 is too thick, it is inferior in thermal conductivity, so that heat from the heater 107 is difficult to be transmitted and power consumption of the heater 107 is increased. In addition, since the temperature uniformity of the entire concentration cell oxygen sensor 100 is poor and the reference electrode 105 does not uniformly reach a predetermined temperature, the standard oxygen partial pressure inside the reference electrode 105 should be set to the predetermined partial pressure with high accuracy. However, the oxygen concentration cannot be measured accurately.

また、図３に示すように、封止体１０２の厚みが薄すぎると、凹部１０３も小さくなり、この凹部１０３内に充填されるＭ−ＭＯの量が少なくなるので、濃淡電池式センサ１００は早期に機能しなくなるおそれがある。なぜならば、Ｍ−ＭＯの充填量が少ないと、Ｍ−ＭＯのうちの金属の全てが早期に酸化して金属酸化物になってしまい、Ｍ−ＭＯの平衡状態が損なわれてしまうからである。   In addition, as shown in FIG. 3, when the thickness of the sealing body 102 is too thin, the concave portion 103 is also small, and the amount of M-MO filled in the concave portion 103 is reduced. There is a risk of not functioning early. This is because if the amount of M-MO filling is small, all of the metals in M-MO are oxidized early to become metal oxides, and the equilibrium state of M-MO is impaired. .

この濃淡電池式酸素センサ１００では、図４に示すように、封止体１０２に形成された凹部１０３の内容積が大きすぎると、この凹部１０３内に充填されたＭ−ＭＯからなる参照電極１０５の熱伝導性が悪くなり、参照電極１０５が均一に所定の温度にならない。よって、参照電極１０５の内部における標準酸素分圧を、精度良く所定の分圧に設定することができないので、酸素濃度を精度良く測定できないという欠点がある。   In this concentration cell type oxygen sensor 100, as shown in FIG. 4, if the inner volume of the recess 103 formed in the sealing body 102 is too large, the reference electrode 105 made of M-MO filled in the recess 103. Therefore, the reference electrode 105 does not reach a predetermined temperature uniformly. Therefore, the standard oxygen partial pressure inside the reference electrode 105 cannot be accurately set to a predetermined partial pressure, so that there is a drawback that the oxygen concentration cannot be measured with high accuracy.

さらに、図５に示すように、封止体１０２に形成された凹部１０３の内容積が小さすぎると、この凹部１０３内に充填されるＭ−ＭＯの量が少なくなるので、濃淡電池式センサ１００は早期に機能しなくなるおそれがある。なぜならば、Ｍ−ＭＯの充填量が少ないと、Ｍ−ＭＯのうちの金属の全てが早期に酸化して金属酸化物になってしまい、Ｍ−ＭＯの平衡状態が損なわれてしまうからである。
特開２００４−１７７３２２号公報 Further, as shown in FIG. 5, if the inner volume of the recess 103 formed in the sealing body 102 is too small, the amount of M-MO filled in the recess 103 is reduced. May fail early. This is because if the amount of M-MO filling is small, all of the metals in M-MO are oxidized early to become metal oxides, and the equilibrium state of M-MO is impaired. .
JP 2004-177322 A

本発明は、前記事情に鑑みてなされたもので、小型化が可能、かつ、測定精度および長期安定性に優れた濃淡電池式酸素センサを提供することを目的とする。   The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a concentration cell type oxygen sensor that can be miniaturized and has excellent measurement accuracy and long-term stability.

本発明は、上記課題を解決するために、固体電解質板と、該固体電解質板と対向するように配置され、中央部に凹部が形成された封止体と、前記固体電解質板と前記封止体との間を封止する環状の封止材と、前記固体電解質板により前記封止体の凹部が密封されてなる密封空間内に充填された金属−金属酸化物からなる参照電極と、該参照電極から前記密封空間の外部に延びるリード線と、前記固体電解質板の前記参照電極と接する面とは反対の面に設けられた電極と、前記封止体の前記参照電極と接する面とは反対の面に設けられたヒータと、を備えた濃淡電池式酸素センサであって、前記凹部の内容積は１ｍｍ３以上、１０ｍｍ３以下である濃淡電池式酸素センサを提供する。 In order to solve the above-described problems, the present invention provides a solid electrolyte plate, a sealing body that is disposed so as to face the solid electrolyte plate, and has a recess formed in the center, the solid electrolyte plate, and the sealing An annular sealing material that seals between the body, a reference electrode made of a metal-metal oxide filled in a sealed space formed by sealing a concave portion of the sealing body with the solid electrolyte plate, A lead wire extending from the reference electrode to the outside of the sealed space, an electrode provided on a surface opposite to the surface in contact with the reference electrode of the solid electrolyte plate, and a surface in contact with the reference electrode of the sealing body A concentration cell type oxygen sensor comprising a heater provided on the opposite surface, wherein the inner volume of the recess is 1 mm 3 or more and 10 mm 3 or less.

上記構成の濃淡電池式酸素センサにおいて、前記凹部の深さは０．２ｍｍ以上、１ｍｍ以下であることが好ましい。
また、前記凹部の深さは０．５ｍｍ以上、０．８ｍｍ以下であることがより好ましい。 In the concentration cell oxygen sensor having the above configuration, the depth of the recess is preferably 0.2 mm or more and 1 mm or less.
The depth of the recess is more preferably 0.5 mm or more and 0.8 mm or less.

本発明の濃淡電池式酸素センサによれば、封止体に形成された凹部の内容積が１ｍｍ３以上、１０ｍｍ３以下であるから、凹部内には適量の金属−金属酸化物が充填されるから、金属−金属酸化物の平衡状態が適正に保たれ、濃淡電池式センサは長期間安定に機能する。また、参照電極の均熱性が向上するから、参照電極の内部における標準酸素分圧を、精度良く所定の分圧に設定することができるようになり、酸素濃度の測定精度が向上する。
また、凹部の深さを０．２ｍｍ以上、１ｍｍ以下とすれば、凹部内に適量の金属−金属酸化物を充填することができるとともに、凹部内に充填された金属−金属酸化物からなる参照電極全体に熱が伝わり易くなるため、均熱性をより向上することができる。
したがって、本発明の濃淡電池式酸素センサによれば、酸素濃度の測定精度に優れ、長期安定性に優れるとともに、小型化、省電力化された濃淡電池式酸素センサを実現することができる。 According to the concentration cell type oxygen sensor of the present invention, since the internal volume of the recess formed in the sealing body is 1 mm 3 or more and 10 mm 3 or less, the recess is filled with an appropriate amount of metal-metal oxide. Therefore, the equilibrium state of the metal-metal oxide is maintained properly, and the concentration cell type sensor functions stably for a long time. In addition, since the temperature uniformity of the reference electrode is improved, the standard oxygen partial pressure inside the reference electrode can be accurately set to a predetermined partial pressure, and the measurement accuracy of the oxygen concentration is improved.
Further, when the depth of the recess is 0.2 mm or more and 1 mm or less, the recess can be filled with an appropriate amount of metal-metal oxide, and the reference is made of the metal-metal oxide filled in the recess. Since heat is easily transmitted to the entire electrode, the thermal uniformity can be further improved.
Therefore, according to the concentration cell type oxygen sensor of the present invention, it is possible to realize a concentration cell type oxygen sensor which is excellent in measuring accuracy of oxygen concentration, excellent in long-term stability, and reduced in size and power.

以下、本発明を実施した濃淡電池式酸素センサについて、図面を参照して説明する。   Hereinafter, a concentration cell type oxygen sensor embodying the present invention will be described with reference to the drawings.

図１は、本発明に係る濃淡電池式酸素センサの一実施形態を示す概略断面図である。
図１中、符号１０は濃淡電池式酸素センサ、１１は固体電解質板、１２は封止体、１３は凹部、１４は封止材、１５は参照電極、１６は電極、１７はヒータ、１８は第一のリード線、１９は第二のリード線、２０は第三のリード線をそれぞれ表している。 FIG. 1 is a schematic sectional view showing an embodiment of a concentration cell oxygen sensor according to the present invention.
In FIG. 1, reference numeral 10 is a concentration cell type oxygen sensor, 11 is a solid electrolyte plate, 12 is a sealing body, 13 is a recess, 14 is a sealing material, 15 is a reference electrode, 16 is an electrode, 17 is a heater, 18 is The first lead wire, 19 is the second lead wire, and 20 is the third lead wire.

この実施形態の濃淡電池式酸素センサ１０は、固体電解質板１１と、封止体１２と、封止材１４と、参照電極１５と、電極１６と、ヒータ１７と、第一のリード線１８と、第二のリード線１９と、第三のリード線２０とから概略構成されている。   The concentration cell type oxygen sensor 10 of this embodiment includes a solid electrolyte plate 11, a sealing body 12, a sealing material 14, a reference electrode 15, an electrode 16, a heater 17, and a first lead wire 18. The second lead wire 19 and the third lead wire 20 are schematically configured.

この濃淡電池式酸素センサ１０では、円板状の固体電解質板１１と、中央部に円形状の凹部１３が形成された円板状の封止体１２とが対向配置されている。また、固体電解質板１１と封止体１２との間は、円環状の封止材１４によって気密に封止されている。そして、固体電解質板１１および封止体１２で形成される密封空間（凹部１３）内には、参照電極１５をなす金属−金属酸化物が充填されている。  In this concentration cell type oxygen sensor 10, a disk-shaped solid electrolyte plate 11 and a disk-shaped sealing body 12 in which a circular recess 13 is formed in the central part are arranged to face each other. Further, the solid electrolyte plate 11 and the sealing body 12 are hermetically sealed with an annular sealing material 14. The sealed space (recessed portion 13) formed by the solid electrolyte plate 11 and the sealing body 12 is filled with a metal-metal oxide that forms the reference electrode 15.

固体電解質板１１の参照電極１５と接する面とは反対の面には、電極１６が設けられている。また、電極１６には、第一のリード線１８が接続されている。一方、固体電解質板１１の参照電極１５と接する面にも、第二のリード線１９が接続されている。この第二のリード線１９は、封止材１４を気密に貫通して、濃淡電池式酸素センサ１０の内部から外部に引き出されている。また、封止体１２の参照電極１５と接する面とは反対の面には、ヒータ１７がパターン形成されている。さらに、ヒータ１７には、第三のリード線２０が接続されている   An electrode 16 is provided on the surface of the solid electrolyte plate 11 opposite to the surface in contact with the reference electrode 15. A first lead wire 18 is connected to the electrode 16. On the other hand, the second lead wire 19 is also connected to the surface of the solid electrolyte plate 11 in contact with the reference electrode 15. The second lead wire 19 penetrates the sealing material 14 in an airtight manner and is drawn out from the inside of the concentration cell type oxygen sensor 10. A heater 17 is patterned on the surface of the sealing body 12 opposite to the surface in contact with the reference electrode 15. Furthermore, a third lead wire 20 is connected to the heater 17.

この濃淡電池式酸素センサ１０では、封止体１２に形成された凹部１３の内容積が１ｍｍ３以上、１０ｍｍ３以下となっている。
凹部１３の内容積が１ｍｍ３未満では、凹部１３内に充填されるＭ−ＭＯの量が少なくなり、Ｍ−ＭＯのうちの金属の全てが早期に酸化して金属酸化物になってしまい、Ｍ−ＭＯの平衡状態が損なわれてしまうので、濃淡電池式センサ１０は早期に機能しなくなるおそれがある。一方、凹部１３の内容積が１０ｍｍ３を超えると、この凹部１３内に充填されたＭ−ＭＯからなる参照電極１５が大きくなりすぎて、参照電極１５の熱伝導性が悪くなり、均一に所定の温度にならない。したがって、参照電極１５の内部における標準酸素分圧を、精度良く所定の分圧に設定することができないので、酸素濃度を精度良く測定することができないという欠点がある。また、参照電極１５が大きくなりすぎると、濃淡電池式酸素センサ１０を小型化することができない上に、省電力化することもできない。 In the concentration cell type oxygen sensor 10, the inner volume of the recess 13 formed in the sealing body 12 is 1 mm 3 or more and 10 mm 3 or less.
If the inner volume of the recess 13 is less than 1 mm 3 , the amount of M-MO filled in the recess 13 is reduced, and all of the metal in the M-MO is oxidized early to become a metal oxide, Since the equilibrium state of the M-MO is impaired, the concentration cell type sensor 10 may not function at an early stage. On the other hand, if the internal volume of the recess 13 exceeds 10 mm 3 , the reference electrode 15 made of M-MO filled in the recess 13 becomes too large, and the thermal conductivity of the reference electrode 15 is deteriorated and uniformly determined. Does not reach the temperature. Therefore, the standard oxygen partial pressure inside the reference electrode 15 cannot be accurately set to a predetermined partial pressure, so that there is a drawback that the oxygen concentration cannot be measured with high accuracy. Further, if the reference electrode 15 becomes too large, the concentration cell type oxygen sensor 10 cannot be reduced in size and power saving cannot be achieved.

また、凹部１３の深さは０．２ｍｍ以上、１ｍｍ以下が好ましく、０．５ｍｍ以上、０．８ｍｍ以下がより好ましい。
凹部１３の深さが０．２ｍｍ未満では、凹部１３内に充填されるＭ−ＭＯの量が少なくなり、Ｍ−ＭＯのうちの金属の全てが早期に酸化して金属酸化物になってしまい、Ｍ−ＭＯの平衡状態が損なわれてしまうので、濃淡電池式センサ１０は早期に機能しなくなるおそれがある。一方、凹部１３の深さが１ｍｍを超えると、この凹部１３内に充填されたＭ−ＭＯからなる参照電極１５が大きくなりすぎて、参照電極１５の熱伝導性が悪くなり、均一に所定の温度にならない。 The depth of the recess 13 is preferably 0.2 mm or more and 1 mm or less, and more preferably 0.5 mm or more and 0.8 mm or less.
If the depth of the recess 13 is less than 0.2 mm, the amount of M-MO filled in the recess 13 is reduced, and all of the metal in the M-MO is oxidized early to become a metal oxide. Since the equilibrium state of the M-MO is impaired, the concentration cell type sensor 10 may not function at an early stage. On the other hand, when the depth of the concave portion 13 exceeds 1 mm, the reference electrode 15 made of M-MO filled in the concave portion 13 becomes too large, the thermal conductivity of the reference electrode 15 is deteriorated, and a predetermined value is uniformly obtained. Does not reach temperature.

さらに、凹部１３の形状が固体電解質板１１と対向する面から見て円形状である場合、凹部１３の直径は２．５ｍｍ以上、５ｍｍ以下であることが好ましい。   Furthermore, when the shape of the recess 13 is circular as viewed from the surface facing the solid electrolyte plate 11, the diameter of the recess 13 is preferably 2.5 mm or more and 5 mm or less.

また、濃淡電池式酸素センサ１０を小型化、省電力化するためには、封止体１２を出来る限り小さくすることが望ましいが、濃淡電池式酸素センサ１０の均熱性を確保し、参照電極１５をなすＭ−ＭＯの凹部１３への充填量を十分なものとするためには、封止体１２の形状が円板状である場合、封止体１２の外径は５ｍｍ以上、１０ｍｍ以下が好ましく、封止体１２の厚みは０．５ｍｍ以上、１．５ｍｍ以下が好ましい。   In order to reduce the size and power consumption of the concentration cell type oxygen sensor 10, it is desirable to make the sealing body 12 as small as possible. However, the temperature uniformity of the concentration cell type oxygen sensor 10 is ensured and the reference electrode 15 is secured. In order to make the filling amount of the M-MO in the recess 13 sufficient, the outer diameter of the sealing body 12 is 5 mm or more and 10 mm or less when the shape of the sealing body 12 is a disk shape. Preferably, the thickness of the sealing body 12 is 0.5 mm or more and 1.5 mm or less.

固体電解質板１１としては、円板状のジルコニア板が挙げられる。
固体電解質板１１をなすジルコニアとしては、イオン伝導性に優れることから、イットリウム酸化物を８ｍｏｌ％含むジルコニア（ＺｒＯ２−８ｍｏｌ％Ｙ２Ｏ３）からなるものが望ましい。なお、固体電解質板１１としては、ジルコニアに酸化カルシウム（ＣａＯ）、酸化マグネシウム（ＭｇＯ）などの無機ドーパントを添加して、酸素イオン伝導のための空格子点を形成するようにしたものも用いることができる。 Examples of the solid electrolyte plate 11 include a disk-shaped zirconia plate.
The zirconia forming the solid electrolyte plate 11 is preferably made of zirconia (ZrO 2 -8 mol% Y 2 O 3 ) containing 8 mol% of yttrium oxide because of excellent ion conductivity. In addition, as the solid electrolyte plate 11, zirconia added with an inorganic dopant such as calcium oxide (CaO) or magnesium oxide (MgO) to form vacancies for oxygen ion conduction is also used. Can do.

封止体１２としては、円板状のジルコニア板が挙げられる。
封止体１２をなすジルコニアとしては、固体電解質板１１と耐熱性および線膨張特性が概略等しく、かつ加工性に富む、イットリウム酸化物を２ｍｏｌ％〜４ｍｏｌ％含むジルコニア（ＺｒＯ２−２〜４ｍｏｌ％Ｙ２Ｏ３）からなるものが望ましい。 Examples of the sealing body 12 include a disk-shaped zirconia plate.
The zirconia forming the sealing body 12 is zirconia (ZrO 2 -2 to 4 mol%) containing 2 mol% to 4 mol% of yttrium oxide, which has substantially the same heat resistance and linear expansion characteristics as those of the solid electrolyte plate 11 and excellent workability. Y 2 O 3 ) is desirable.

封止材１４をなす材質としては、密封性と接着性を兼ね備えたガラスなどが挙げられる。   Examples of the material forming the sealing material 14 include glass having both sealing performance and adhesiveness.

参照電極１５をなす材質としては、パラジウム（Ｐｄ）、銅（Ｃｕ）、鉛（Ｐｂ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）などの一部を酸化してなり、Ｐｄ−ＰｄＯ、Ｃｕ−Ｃｕ２Ｏ、Ｐｂ−ＰｂＯ、Ｎｉ−ＮｉＯ、Ｃｏ−ＣｏＯなどからなる金属−金属酸化物が挙げられる。 As a material forming the reference electrode 15, palladium (Pd), copper (Cu), lead (Pb), nickel (Ni), cobalt (Co), etc. are partially oxidized to form Pd—PdO, Cu—Cu. Examples of the metal-metal oxide include 2 O, Pb—PbO, Ni—NiO, and Co—CoO.

電極１６をなす材質としては、白金などの金属が挙げられる。
ヒータ１７をなす材質としては、白金などの金属が挙げられる。 Examples of the material forming the electrode 16 include metals such as platinum.
Examples of the material forming the heater 17 include metals such as platinum.

第一のリード線１８、第二のリード線１９および第三のリード線２０としては、白金からなるリード線が挙げられる。   Examples of the first lead wire 18, the second lead wire 19, and the third lead wire 20 include lead wires made of platinum.

次に、図１を参照して、この実施形態の濃淡電池式酸素センサの製造方法について説明する。
まず、ジルコニアからなる固体電解質板１１を作製する。
固体電解質板１１は、例えば、ジルコニアからなる直径１０ｍｍの棒状体を、厚み約０．２ｍｍに切断して円板状のジルコニア板とし、この円板状のジルコニア板を研磨によって厚みを調整することにより得られる。 Next, with reference to FIG. 1, the manufacturing method of the concentration cell type | mold oxygen sensor of this embodiment is demonstrated.
First, the solid electrolyte plate 11 made of zirconia is produced.
The solid electrolyte plate 11 is formed by, for example, cutting a rod-shaped body made of zirconia having a diameter of 10 mm into a thickness of about 0.2 mm to obtain a disk-shaped zirconia plate, and adjusting the thickness by polishing the disk-shaped zirconia plate. Is obtained.

次いで、作製された固体電解質板１１上に、例えば、白金ペーストを塗布し、この白金ペーストを所定の温度で焼成して、白金からなる電極１６を形成する。   Next, for example, a platinum paste is applied onto the produced solid electrolyte plate 11, and this platinum paste is baked at a predetermined temperature to form an electrode 16 made of platinum.

次いで、電極１６に白金などからなる第一のリード線１８を接続する。   Next, a first lead wire 18 made of platinum or the like is connected to the electrode 16.

次いで、固体電解質板１１の電極１６が形成された面とは反対の面に、第二のリード線１９を接続する。   Next, the second lead wire 19 is connected to the surface of the solid electrolyte plate 11 opposite to the surface on which the electrode 16 is formed.

また、上記一連の工程とは別に、円板状の封止体１２の一方の面の中央部に、通常のセラミックスのざぐり加工に用いられる加工冶具により、所定の内容積および深さの凹部１３を形成する。   In addition to the series of steps described above, a recess 13 having a predetermined internal volume and depth is formed at the center of one surface of the disk-shaped sealing body 12 by a processing jig used for ordinary spotting of ceramics. Form.

次いで、封止体１２の凹部１３が形成された面とは反対の面に、白金からなるヒータ１７をパターン形成する。ヒータ１７は、封止体１２の凹部１３が形成された面とは反対の面に絶縁用ガラス膜を積層した後、例えば、白金ペーストを所定のパターン状に塗布し、焼成して形成する。   Next, a heater 17 made of platinum is formed in a pattern on the surface opposite to the surface on which the recess 13 of the sealing body 12 is formed. The heater 17 is formed by, for example, applying a platinum paste in a predetermined pattern and baking it after laminating an insulating glass film on the surface opposite to the surface on which the recess 13 of the sealing body 12 is formed.

次いで、封止体１２の凹部１３内に、参照電極１５を形成するための金属粉末を充填する。金属粉末には、必要に応じて、安定化ジルコニアの粉末を配合してもよい。   Next, a metal powder for forming the reference electrode 15 is filled in the recess 13 of the sealing body 12. You may mix | blend the powder of stabilized zirconia with a metal powder as needed.

次いで、封止体１２の凹部１３が形成された面の周縁部に、ガラスからなる円環状の封止材１４を、約１０００℃の温度で融着することにより、封止体１２上に封止材１４を積層する。   Next, an annular sealing material 14 made of glass is fused to the peripheral edge of the surface of the sealing body 12 where the recess 13 is formed at a temperature of about 1000 ° C., so that the sealing body 12 is sealed. The stop material 14 is laminated.

なお、この時、封止体１２の側面または封止材１４の側面に第二のリード線１９を挿入することができる程度の溝を設けておき、第二のリード線１９をこの溝に挿通した状態で、封止体１２上に封止材１４を積層する。   At this time, a groove is provided on the side surface of the sealing body 12 or the side surface of the sealing material 14 so that the second lead wire 19 can be inserted, and the second lead wire 19 is inserted into the groove. In this state, the sealing material 14 is laminated on the sealing body 12.

次いで、固体電解質板１１を、この封止材１４が積層された封止体１２に重ね合わせて、凹部１３を封止して、金属粉末を密封することにより、固体電解質板１１、封止体１２、封止材１４および参照電極用の金属粉末からなる積層体が得られる。この金属粉末の封止処理では、封止材１４を約１０００℃に加熱して、固体電解質板１１を封止材１４に融着する。   Next, the solid electrolyte plate 11 and the sealing body are formed by superimposing the solid electrolyte plate 11 on the sealing body 12 on which the sealing material 14 is laminated, sealing the recess 13 and sealing the metal powder. 12, the laminated body which consists of the metal powder for the sealing material 14 and a reference electrode is obtained. In this metal powder sealing process, the sealing material 14 is heated to about 1000 ° C., and the solid electrolyte plate 11 is fused to the sealing material 14.

次いで、白金などからなる第三のリード線２１をヒータ１７に接続する。
最後に、上記の積層体を、濃淡電池式酸素センサの作動温度まで加熱することにより、この積層体内に密封された金属粉末は、その一部が酸化してＭ−ＭＯからなる参照電極１５となり、一定の酸素分圧で安定し、濃淡電池式酸素センサ１０が得られる。 Next, the third lead wire 21 made of platinum or the like is connected to the heater 17.
Finally, by heating the above laminate to the operating temperature of the concentration cell type oxygen sensor, the metal powder sealed in the laminate is partially oxidized to become the reference electrode 15 made of M-MO. The concentration sensor is stable at a constant oxygen partial pressure, and the concentration cell type oxygen sensor 10 is obtained.

なお、参照電極用の金属粉末を濃淡電池式酸素センサの作動温度まで加熱することにより、パラジウム（Ｐｄ）、銅（Ｃｕ）、鉛（Ｐｂ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）などの金属粉末の一部が酸化して、Ｐｄ−ＰｄＯ、Ｃｕ−Ｃｕ２Ｏ、Ｐｂ−ＰｂＯ、Ｎｉ−ＮｉＯ、Ｃｏ−ＣｏＯなどからなる参照電極１５が形成される。 In addition, metals such as palladium (Pd), copper (Cu), lead (Pb), nickel (Ni), cobalt (Co) are heated by heating the metal powder for the reference electrode to the operating temperature of the concentration cell type oxygen sensor. Part of the powder is oxidized to form a reference electrode 15 made of Pd—PdO, Cu—Cu 2 O, Pb—PbO, Ni—NiO, Co—CoO, or the like.

以下、実験例により本発明をさらに具体的に説明するが、本発明は以下の実験例に限定されるものではない。   Hereinafter, the present invention will be described more specifically with experimental examples, but the present invention is not limited to the following experimental examples.

（実験例１）
図１に示すような濃淡電池式酸素センサを作製した。
この濃淡電池式酸素センサでは、円板状の封止体の外径を６ｍｍ、厚みを１．５ｍｍとした。また、封止体に形成した凹部の直径を３ｍｍとし、深さを０．１ｍｍとした。
凹部内に充填した参照電極用の金属粉末をパラジウム粉末とした。
得られた濃淡電池式酸素センサにおいて、凹部の内容積を算出した。結果を表１に示す。
また、得られた濃淡電池式酸素センサを用いて、酸素濃度測定を１０００時間行い、この間に固体電解質板に発生する起電力を測定した。この酸素濃度測定において温度を４５０℃に設定し、測定する酸素濃度を３０ｐｐｍとした。結果を表１に示す。
さらに、酸素濃度測定において、濃淡電池式酸素センサの測定精度を評価した。酸素濃度３０ｐｐｍを検知した際に、固体電解質板に生じる起電力の理論値は４８．３ｍＶである。そこで、評価の基準を、起電力が４５ｍＶ以上、５１ｍＶ以下の場合に○、起電力が４２ｍＶ以上、５４ｍＶ以下の場合に△、起電力が４２ｍＶ未満、５４ｍＶを超える場合に×とした。結果を表１に示す。 (Experimental example 1)
A concentration cell type oxygen sensor as shown in FIG. 1 was produced.
In this concentration cell type oxygen sensor, the outer diameter of the disk-shaped sealing body was 6 mm and the thickness was 1.5 mm. Moreover, the diameter of the recessed part formed in the sealing body was 3 mm, and the depth was 0.1 mm.
The metal powder for the reference electrode filled in the recess was palladium powder.
In the obtained concentration cell type oxygen sensor, the internal volume of the recess was calculated. The results are shown in Table 1.
Moreover, using the obtained concentration cell type oxygen sensor, the oxygen concentration was measured for 1000 hours, and the electromotive force generated in the solid electrolyte plate during this time was measured. In this oxygen concentration measurement, the temperature was set to 450 ° C., and the measured oxygen concentration was 30 ppm. The results are shown in Table 1.
Furthermore, in the oxygen concentration measurement, the measurement accuracy of the concentration cell type oxygen sensor was evaluated. When an oxygen concentration of 30 ppm is detected, the theoretical value of the electromotive force generated in the solid electrolyte plate is 48.3 mV. Therefore, the evaluation criteria were “◯” when the electromotive force was 45 mV or more and 51 mV or less, “Δ” when the electromotive force was 42 mV or more and 54 mV or less, and “X” when the electromotive force was less than 42 mV or more than 54 mV. The results are shown in Table 1.

（実験例２）
封止体に形成した凹部の深さを０．２ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表１に示す。 (Experimental example 2)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1 except that the depth of the recess formed in the sealing body was 0.2 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 1.

（実験例３）
封止体に形成した凹部の深さを０．５ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表１に示す。 (Experimental example 3)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1 except that the depth of the recess formed in the sealing body was 0.5 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 1.

（実験例４）
封止体に形成した凹部の深さを１．０ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表１に示す。 (Experimental example 4)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1 except that the depth of the recess formed in the sealing body was 1.0 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 1.

（実験例５）
封止体に形成した凹部の深さを１．３ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表１に示す。 (Experimental example 5)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1, except that the depth of the recess formed in the sealing body was 1.3 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 1.

Figure 2006084335
Figure 2006084335

表１の結果から、凹部の深さを０．２ｍｍ〜１．０ｍｍとし、かつ、凹部の内容積を１．４ｍｍ３〜７ｍｍ３とした濃淡電池式酸素センサにおいて、実用可能な測定精度を示すことが確認された。 The results in Table 1, the depth of the recess and 0.2 mm to 1.0 mm, and, in the concentration cell type oxygen sensor in which the internal volume of the recess and 1.4mm 3 ~7mm 3, showing a practical measuring accuracy It was confirmed.

（実験例６）
封止体に形成した凹部の直径を４ｍｍとし、深さを０．５ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表２に示す。 (Experimental example 6)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1 except that the diameter of the recess formed in the sealing body was 4 mm and the depth was 0.5 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 2.

（実験例７）
封止体に形成した凹部の直径を４ｍｍとし、深さを０．８ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表２に示す。 (Experimental example 7)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1, except that the diameter of the recess formed in the sealing body was 4 mm and the depth was 0.8 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 2.

（実験例８）
封止体に形成した凹部の直径を４ｍｍとし、深さを１．０ｍｍとした以外は実験例１と同様にして、濃淡電池式酸素センサを作製した。
また、実験例１と同様にして、凹部の内容積を算出し、固体電解質板に発生する起電力を測定し、濃淡電池式酸素センサの測定精度を評価した。結果を表２に示す。 (Experimental example 8)
A concentration cell type oxygen sensor was produced in the same manner as in Experimental Example 1 except that the diameter of the recess formed in the sealing body was 4 mm and the depth was 1.0 mm.
Further, in the same manner as in Experimental Example 1, the inner volume of the recess was calculated, the electromotive force generated in the solid electrolyte plate was measured, and the measurement accuracy of the concentration cell type oxygen sensor was evaluated. The results are shown in Table 2.

Figure 2006084335
Figure 2006084335

表２の結果から、凹部の深さを０．５ｍｍ〜０．８ｍｍとし、かつ、凹部の内容積を６．３ｍｍ３〜１０ｍｍ３とした濃淡電池式酸素センサにおいて、実用可能な測定精度を示すことが確認された。 The results in Table 2, the depth of the recess and 0.5 mm to 0.8 mm, and, in the concentration cell type oxygen sensor the internal volume of the recess was 6.3 mm 3 to 10 mm 3, showing a practical measuring accuracy It was confirmed.

本発明の濃淡電池式酸素センサは、工業用窒素発生装置から発生する高純度窒素中の酸素濃度の測定や、半導体露光装置の純窒素パージ後の残存酸素濃度の測定だけでなく、自動車の排ガス中の酸素濃度の測定や、燃焼装置の排ガス中の酸素濃度の測定など、幅広い分野における酸素濃度の測定に供される濃淡電池式酸素センサとしても適用可能である。   The concentration cell type oxygen sensor of the present invention is not only used for measuring oxygen concentration in high-purity nitrogen generated from industrial nitrogen generators or measuring residual oxygen concentration after pure nitrogen purge of semiconductor exposure equipment, but also for exhaust gas from automobiles. It can also be applied as a concentration cell type oxygen sensor used for measuring oxygen concentration in a wide range of fields, such as measurement of oxygen concentration in the exhaust gas and measurement of oxygen concentration in the exhaust gas of the combustion apparatus.

本発明に係る濃淡電池式酸素センサの一実施形態を示す概略断面図である。It is a schematic sectional drawing which shows one Embodiment of the concentration cell type oxygen sensor which concerns on this invention. 従来の濃淡電池式酸素センサの一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the conventional concentration cell type | mold oxygen sensor. 従来の濃淡電池式酸素センサの他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the conventional concentration cell type oxygen sensor. 従来の濃淡電池式酸素センサの他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the conventional concentration cell type oxygen sensor. 従来の濃淡電池式酸素センサの他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the conventional concentration cell type oxygen sensor.

符号の説明Explanation of symbols

１０・・・濃淡電池式酸素センサ、１１・・・固体電解質板、１２・・・封止体、１３・・・凹部、１４・・・封止材、１５・・・参照電極、１６・・・電極、１７・・・ヒータ、１８・・・第一のリード線、１９・・・第二のリード線、２０・・・第三のリード線。
DESCRIPTION OF SYMBOLS 10 ... Concentration cell type oxygen sensor, 11 ... Solid electrolyte board, 12 ... Sealing body, 13 ... Recessed part, 14 ... Sealing material, 15 ... Reference electrode, 16 ... -Electrode, 17 ... heater, 18 ... first lead wire, 19 ... second lead wire, 20 ... third lead wire.

Claims (3)

固体電解質板と、該固体電解質板と対向するように配置され、中央部に凹部が形成された封止体と、前記固体電解質板と前記封止体との間を封止する環状の封止材と、前記固体電解質板により前記封止体の凹部が密封されてなる密封空間内に充填された金属−金属酸化物からなる参照電極と、該参照電極から前記密封空間の外部に延びるリード線と、前記固体電解質板の前記参照電極と接する面とは反対の面に設けられた電極と、前記封止体の前記参照電極と接する面とは反対の面に設けられたヒータと、を備えた濃淡電池式酸素センサであって、
前記凹部の内容積は１ｍｍ３以上、１０ｍｍ３以下であることを特徴とする濃淡電池式酸素センサ。 A solid electrolyte plate, a sealing body disposed so as to face the solid electrolyte plate and having a recess formed in the center thereof, and an annular seal that seals between the solid electrolyte plate and the sealing body A reference electrode made of a metal-metal oxide filled in a sealed space formed by sealing a recess of the sealing body with the solid electrolyte plate, and a lead wire extending from the reference electrode to the outside of the sealed space And an electrode provided on a surface opposite to the surface in contact with the reference electrode of the solid electrolyte plate, and a heater provided on a surface opposite to the surface in contact with the reference electrode of the sealing body. A concentration cell oxygen sensor,
The concentration cell-type oxygen sensor according to claim 1, wherein an inner volume of the recess is 1 mm 3 or more and 10 mm 3 or less. 前記凹部の深さは０．２ｍｍ以上、１ｍｍ以下であることを特徴とする請求項１に記載の濃淡電池式酸素センサ。   2. The concentration cell type oxygen sensor according to claim 1, wherein the depth of the concave portion is 0.2 mm or more and 1 mm or less. 前記凹部の深さは０．５ｍｍ以上、０．８ｍｍ以下であることを特徴とする請求項１に記載の濃淡電池式酸素センサ。

The concentration cell type oxygen sensor according to claim 1, wherein the depth of the recess is 0.5 mm or more and 0.8 mm or less.

JP2004269761A 2004-09-16 2004-09-16 Concentration cell type oxygen sensor Withdrawn JP2006084335A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054233A (en) * 2008-08-26 2010-03-11 Japan Atomic Energy Agency Oxygen concentration sensor, method for forming the same and method for measuring concentration of oxygen in high-temperature and high-pressure water
CN110088608A (en) * 2016-12-15 2019-08-02 松下知识产权经营株式会社 Hydrogen detection device, fuel cell car, hydrogen leakage monitoring self system, compound sensor module, hydrogen detection method and program

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010054233A (en) * 2008-08-26 2010-03-11 Japan Atomic Energy Agency Oxygen concentration sensor, method for forming the same and method for measuring concentration of oxygen in high-temperature and high-pressure water
CN110088608A (en) * 2016-12-15 2019-08-02 松下知识产权经营株式会社 Hydrogen detection device, fuel cell car, hydrogen leakage monitoring self system, compound sensor module, hydrogen detection method and program
CN110088608B (en) * 2016-12-15 2021-06-08 新唐科技日本株式会社 Hydrogen detection device, fuel cell vehicle, hydrogen leakage monitoring system, composite sensor module, hydrogen detection method, and program recording medium

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