JP5724005B2 - Contact combustion type gas sensor - Google Patents

Contact combustion type gas sensor Download PDF

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JP5724005B2
JP5724005B2 JP2014019975A JP2014019975A JP5724005B2 JP 5724005 B2 JP5724005 B2 JP 5724005B2 JP 2014019975 A JP2014019975 A JP 2014019975A JP 2014019975 A JP2014019975 A JP 2014019975A JP 5724005 B2 JP5724005 B2 JP 5724005B2
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insulating film
opening
detection resistor
supporting insulating
resistor
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JP2014077809A (en
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奥野　辰行
辰行 奥野
敦子 住廣
敦子 住廣
江頭　誠
誠 江頭
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Yazaki Energy System Corp
Tokyo Gas Co Ltd
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Tokyo Gas Co Ltd
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Description

本発明は接触燃焼式ガスセンサに関し、更に詳しくは、可燃性ガスを検知するのに適した接触燃焼式ガスセンサに関する。   The present invention relates to a catalytic combustion type gas sensor, and more particularly to a catalytic combustion type gas sensor suitable for detecting a combustible gas.

接触燃焼式ガスセンサとしては、ガス検知素子と参照素子とで構成されたものがある。そのガス検知原理は、検知抵抗体（発熱体）により加熱されたガス検知素子上の貴金属触媒等に被検知ガスが接触すると、この被検知ガスが燃焼して検知抵抗体を温度上昇させて抵抗上昇を起こすことを領している。この検知抵抗体の抵抗上昇をブリッジ回路で電圧差として捉えることにより、被検知ガス濃度を検知することができる。   As a contact combustion type gas sensor, there is one composed of a gas detection element and a reference element. The gas detection principle is that when the gas to be detected comes into contact with a noble metal catalyst or the like on the gas detection element heated by the detection resistor (heating element), the gas to be detected is burned and the temperature of the detection resistor is increased to increase resistance. It is responsible for causing the rise. By detecting the increase in resistance of the detection resistor as a voltage difference by the bridge circuit, the concentration of the gas to be detected can be detected.

通常、ガス検知素子と参照素子は、例えば白金等の貴金属細線をコイル状に巻いた検知抵抗体を一対備える。ガス検知素子の検知抵抗体には貴金属触媒を担持したセラミック粉体のペーストを、参照素子の検知抵抗体には貴金属触媒を担持しないセラミック粉体のペーストを塗布して、それぞれペーストを加熱焼結して作製されている。このようにして得られた一対のセンサ素子を、ブリッジ回路に構成してガス濃度に応じた電圧信号を捉えるのが一般である。   In general, the gas detection element and the reference element include a pair of detection resistors in which a noble metal thin wire such as platinum is wound in a coil shape. Apply a ceramic powder paste carrying a noble metal catalyst to the sensing resistor of the gas sensing element, and apply a ceramic powder paste that does not carry a noble metal catalyst to the sensing resistor of the reference element. It is made. In general, the pair of sensor elements thus obtained is configured as a bridge circuit to capture a voltage signal corresponding to the gas concentration.

近年、このような接触燃焼式ガスセンサでは、検知抵抗体に断続的に通電しても必要な加熱温度が得られるように、検知抵抗体を通電するとき熱時定数をできるだけ小さくして省電力化したり、小型化の要望を満足するように、検知抵抗体支持部を基板に形成した凹部空間から浮かせた構造のマイクロセンサが開発されている（例えば、特許文献１および２参照）。   In recent years, in such a contact combustion type gas sensor, when the sensing resistor is energized, the thermal time constant is made as small as possible to save power so that the required heating temperature can be obtained even if the sensing resistor is energized intermittently. In order to satisfy the demand for miniaturization, a microsensor having a structure in which a detection resistor support portion is floated from a recessed space formed on a substrate has been developed (see, for example, Patent Documents 1 and 2).

図１５および図１６に示すように、このような接触燃焼式ガスセンサにおけるガス検知素子１００は、基板１０１の表面側に白金（Ｐｔ）でなる検知抵抗体１０３をパルス波形状に形成し、検知抵抗体１０３の両端部を延在してそれぞれパッド部１０３Ａ、１０３Ｂとしている。そして、検知抵抗体１０３が形成された島状の検知抵抗体支持部１１１が基板１０１から浮き上がるように、検知抵抗体１０３の下方の基板１０１に空洞１１０を形成している。この検知抵抗体支持部１１１の四隅には、空洞１１０を跨いで基板１０１と一体的に設けられたアーム部１０６、１０７、１０８、１０９が延在されている。このように検知部１１１が空洞１１０を介して基板１０１から浮いた構造としたことにより、検知抵抗体１０３が形成された面の熱容量を小さくしている。   As shown in FIGS. 15 and 16, the gas detection element 100 in such a catalytic combustion type gas sensor forms a detection resistor 103 made of platinum (Pt) in a pulse wave shape on the surface side of the substrate 101, thereby detecting the detection resistor. Both ends of the body 103 are extended to form pad portions 103A and 103B, respectively. A cavity 110 is formed in the substrate 101 below the detection resistor 103 so that the island-shaped detection resistor support 111 on which the detection resistor 103 is formed floats from the substrate 101. Arm portions 106, 107, 108, and 109 that are provided integrally with the substrate 101 are extended across the cavity 110 at the four corners of the detection resistor support portion 111. As described above, the detection unit 111 is structured so as to float from the substrate 101 through the cavity 110, thereby reducing the heat capacity of the surface on which the detection resistor 103 is formed.

図１６に示すように、検知抵抗体支持部１１１は、絶縁膜１０２の上に検知抵抗体１０３が形成され、検知抵抗体１０３の上に保護膜１０４が形成され、検知抵抗体支持部１１１の表面から裏面に亘って触媒層１０５が被覆されている。なお、ガス検知素子は、貴金属触媒が担持されたセラミック焼結体でなる触媒層１０５で覆われ、他方の参照素子は貴金属触媒を担持しないセラミック焼結体で覆われている。   As shown in FIG. 16, the detection resistor support 111 has a detection resistor 103 formed on the insulating film 102, a protective film 104 formed on the detection resistor 103, and the detection resistor support 111. A catalyst layer 105 is coated from the front surface to the back surface. The gas detection element is covered with a catalyst layer 105 made of a ceramic sintered body carrying a noble metal catalyst, and the other reference element is covered with a ceramic sintered body not carrying a noble metal catalyst.

特開２００８−２９８６１７号公報JP 2008-298617 A 特開２００７−２７８９９６号公報JP 2007-278996 A

検知抵抗体の上部を覆う触媒層は、検知対象ガスが触媒層に接触して触媒燃焼した場合、燃焼熱はほとんどが放熱によりロスが大きく、効率よく検知抵抗体へ熱伝達されず、ガス感度が小さいものであった。触媒量を増加して検知対象ガスが触媒層に接触したときの燃焼熱を増加させるために抵抗体支持部１１１の裏面（空洞側の面）に触媒層１０５を形成する接触燃焼式ガスセンサが上述の特許文献１および２に開示されている。このような形態のガスセンサでは、セラミック粉体のペーストが、平面構造の検知抵抗体１０３が形成された抵抗体支持部１１１の上に厚膜印刷や、定量吐出装置（ディスペンサ）などを用いて塗布されるが、抵抗体支持部１１１の裏面側に触媒を担持したセラミック焼結体を形成する工法が繊細かつ複雑で、また、抵抗体支持部１１１の裏面側にセラミック焼結体が正しく形成されているかを確認することが困難であった。したがって、接触燃焼式ガスセンサのガス感度の向上を確実に図ることが困難であった。   The catalyst layer that covers the upper part of the sensing resistor, when the gas to be detected comes into contact with the catalyst layer and undergoes catalytic combustion, most of the combustion heat is lost due to heat dissipation, and heat is not efficiently transferred to the sensing resistor. Was small. The contact combustion type gas sensor which forms the catalyst layer 105 on the back surface (surface on the cavity side) of the resistor support portion 111 in order to increase the heat of combustion when the amount of catalyst increases and the detection target gas contacts the catalyst layer is described above. Patent Documents 1 and 2 of the present application are disclosed. In such a gas sensor, the ceramic powder paste is applied onto the resistor support portion 111 on which the planar detection resistor 103 is formed by using thick film printing or a quantitative discharge device (dispenser). However, the method of forming the ceramic sintered body carrying the catalyst on the back side of the resistor support 111 is delicate and complex, and the ceramic sintered body is correctly formed on the back side of the resistor support 111. It was difficult to check if Therefore, it has been difficult to reliably improve the gas sensitivity of the catalytic combustion type gas sensor.

そこで、本発明の目的は、ガス感度が高く、長期にわたって安定な感度特性を維持する接触燃焼式ガスセンサを提供することにある。   Therefore, an object of the present invention is to provide a catalytic combustion type gas sensor that has high gas sensitivity and maintains stable sensitivity characteristics over a long period of time.

本発明の特徴は、接触燃焼式ガスセンサであって、基板と、この基板上に形成した凹部空間を跨ぐように形成された支持用絶縁膜と、この支持用絶縁膜における凹部空間と反対側の面に配設され且つ通電から生じる熱によって燃焼する検知対象ガスの燃焼熱に応じて電気抵抗値が変化する検知抵抗体と、この検知抵抗体の近傍の少なくとも支持用絶縁膜を貫通する開口部と、この開口部を通して支持用絶縁膜の両面側に一体的に設けられ、支持用絶縁膜の凹部空間と反対側の面で検知抵抗体を覆い、支持用絶縁膜の凹部空間側の面で開口部の開口領域よりも広く膨出した構造に形成された触媒層と、検知抵抗体上に形成された保護膜と、を備え、保護膜は、検知抵抗体の側壁まで覆うことを要旨とする。なお、本発明では、このような構成のもの（ガス検知素子）と同様の構成で触媒層のみが触媒を担持しない材料層で構成されたもの（参照素子）を備えることが好ましい。
A feature of the present invention is a catalytic combustion type gas sensor, which is a substrate, a supporting insulating film formed so as to straddle a recessed space formed on the substrate, and a recessed space in the supporting insulating film opposite to the recessed space. A detection resistor whose electrical resistance value is changed according to the combustion heat of the detection target gas disposed on the surface and combusted by heat generated by energization, and an opening that penetrates at least the supporting insulating film in the vicinity of the detection resistor And provided integrally on both sides of the supporting insulating film through the opening, covering the detection resistor with the surface of the supporting insulating film opposite to the recessed space, and on the surface of the supporting insulating film on the recessed space side. A catalyst layer formed in a structure that bulges wider than the opening region of the opening, and a protective film formed on the detection resistor, and the protective film covers the side wall of the detection resistor To do . In addition, in this invention, it is preferable to provide the thing (reference element) comprised by the material layer which does not carry | support a catalyst only in a catalyst layer by the structure similar to the thing of such a structure (gas detection element).

本発明では、支持用絶縁膜の凹部空間と反対側で検知対象ガスが触媒層に接触して生じた燃焼熱に加えて、支持用絶縁膜の裏面側の凹部空間を通過した検知対象ガスが開口部を介して触媒層に接触した燃焼熱も検知抵抗体に伝導するため、電気抵抗値の変化を大きくすることができ、接触燃焼式ガスセンサ全体として感度を向上させることができる。また、触媒層は、支持用絶縁膜の凹部空間側の開口部の開口領域よりも広く膨出した構造に形成されているため所謂アンカー効果を有し、支持用絶縁膜の凹部空間と反対側へ触媒層が剥がれることを抑制する作用がある。   In the present invention, in addition to the combustion heat generated when the detection target gas contacts the catalyst layer on the side opposite to the concave space of the support insulating film, the detection target gas that has passed through the concave space on the back side of the support insulating film is Since the combustion heat that has contacted the catalyst layer via the opening is also conducted to the detection resistor, the change in the electric resistance value can be increased, and the sensitivity of the contact combustion gas sensor as a whole can be improved. In addition, the catalyst layer has a so-called anchor effect because it is formed in a structure that swells wider than the opening region of the opening on the recessed space side of the supporting insulating film, and is opposite to the recessed space of the supporting insulating film. This has the effect of inhibiting the catalyst layer from peeling off.

ここで、開口部は、検知抵抗体の長手方向に沿って配置された複数の矩形の穴や、検知抵抗体の長手方向に沿って形成されたスリットである。開口部が多数の矩形の穴の場合、穴が間欠的に開けられているため、支持用絶縁膜の剛性の低下を抑制することができる。開口部がスリットである場合は、検知対象ガスが開口部を介して触媒層に接触する面積もしくは、開口部から膨出する触媒量が増大し、凹部空間を通過した検知対象ガスが触媒層と接触する面積が大きくなり、センサ感度をさらに向上できる。 Here, the opening, a plurality of or rectangular holes arranged along the longitudinal direction of the sensing resistor, Ru slit der formed along the longitudinal direction of the sensing resistor. In the case where the opening is a large number of rectangular holes, since the holes are opened intermittently, a decrease in rigidity of the supporting insulating film can be suppressed. When the opening is a slit, the area where the detection target gas contacts the catalyst layer through the opening or the amount of catalyst that swells from the opening increases, and the detection target gas that has passed through the recess space is separated from the catalyst layer. The contact area is increased, and the sensor sensitivity can be further improved.

また、触媒層は、支持用絶縁膜の凹部空間と反対側の面からセラミック粉体のペーストが塗布されて、このペーストが焼結されてなるようにすると、支持用絶縁膜の凹部空間と反対側から塗布された触媒層が開口部を通して支持用絶縁膜の凹部空間側に膨出するように形成することが容易且つ確実となる。   Further, the catalyst layer is coated with a ceramic powder paste from the surface opposite to the recessed space of the supporting insulating film, and the paste is sintered, so that it is opposite to the recessed space of the supporting insulating film. It is easy and reliable to form the catalyst layer applied from the side so as to bulge through the opening to the concave space side of the supporting insulating film.

本発明によれば、ガス感度が高く、長期にわたって安定な感度特性を維持できる接触燃焼式ガスセンサを実現できる。   According to the present invention, it is possible to realize a catalytic combustion type gas sensor that has high gas sensitivity and can maintain stable sensitivity characteristics over a long period of time.

本発明の第１の実施の形態に係る接触燃焼式ガスセンサのガス検知素子の触媒層を形成する前の状態を示す平面図である。It is a top view which shows the state before forming the catalyst layer of the gas detection element of the catalytic combustion type gas sensor which concerns on the 1st Embodiment of this invention. 図１のII-II断面図である。It is II-II sectional drawing of FIG. 本発明の第１の実施の形態に係る接触燃焼式ガスセンサのガス検知素子の平面図である。It is a top view of the gas detection element of the catalytic combustion type gas sensor which concerns on the 1st Embodiment of this invention. 図３のIV-IV断面図である。FIG. 4 is a sectional view taken along line IV-IV in FIG. 3. 第１の実施の形態に係る接触燃焼式ガスセンサのガス検知素子の要部拡大断面図である。It is a principal part expanded sectional view of the gas detection element of the catalytic combustion type gas sensor which concerns on 1st Embodiment. 本発明の第１の実施の形態の変形例に係る接触燃焼式ガスセンサのガス検知素子の平面図である。It is a top view of the gas detection element of the contact combustion type gas sensor which concerns on the modification of the 1st Embodiment of this invention. 図６VII-VII断面図である。FIG. 6 is a sectional view taken along line VII-VII. 本発明の第２の実施の形態に係る接触燃焼式ガスセンサのガス検知素子の平面図である。It is a top view of the gas detection element of the catalytic combustion type gas sensor which concerns on the 2nd Embodiment of this invention. 図８のIX-IX断面図である。It is IX-IX sectional drawing of FIG. 本発明の第２の実施の形態の変形例に係る接触燃焼式ガスセンサのガス検知素子の平面図である。It is a top view of the gas detection element of the contact combustion type gas sensor which concerns on the modification of the 2nd Embodiment of this invention. 図９のXI-XI断面図である。It is XI-XI sectional drawing of FIG. 本発明の第１の実施の形態に係る接触燃焼式ガスセンサの平面図である。It is a top view of the contact combustion type gas sensor concerning a 1st embodiment of the present invention. 第１の実施の形態に係る接触燃焼式ガスセンサを用いたブリッジ回路である。It is a bridge circuit using the contact combustion type gas sensor concerning a 1st embodiment. 比較例、第１実施例および第２実施例におけるメタン濃度と１Ｖ当たりの出力電圧の実験結果を示す図である。It is a figure which shows the experimental result of the methane density | concentration and the output voltage per 1V in a comparative example, 1st Example, and 2nd Example. 従来の接触燃焼式ガスセンサのガス検知素子の平面図である。It is a top view of the gas detection element of the conventional catalytic combustion type gas sensor. 従来の接触燃焼式ガスセンサのガス検知素子の断面図である。It is sectional drawing of the gas detection element of the conventional catalytic combustion type gas sensor.

以下、本発明の各実施の形態に係る接触燃焼式ガスセンサの詳細を図面に基づいて説明する。但し、図面は模式的なものであり、各層の厚みや厚みの比率などは現実のものとは異なることに留意すべきである。また、図面相互間においても互いの寸法の関係や比率が異なる部分が含まれている。   Hereinafter, the details of the catalytic combustion type gas sensor according to each embodiment of the present invention will be described with reference to the drawings. However, it should be noted that the drawings are schematic, and the thicknesses and ratios of the layers are different from actual ones. Moreover, the part from which the relationship and ratio of a mutual dimension differ also in between drawings is contained.

（第１の実施の形態）
図１〜図５、図１２および図１３は、本発明の第１の実施の形態に係る接触燃焼式ガスセンサについて示している。図１および図２は触媒層１２を形成する前の状態を示し、図３および図４は触媒層１２を形成した後の状態を示している。本実施の形態に係る接触燃焼式ガスセンサは、図１２に示すように、同一の基板にガス検知素子２０と参照素子２１とを備えて構成されている。なお、ガス検知素子２０と参照素子２１とは、ガス検知素子２０が触媒を担持したセラミック焼結体でなる触媒層１２を有し、参照素子２１が触媒を担持しないセラミック焼結体層１２Ａでなる点が異なるだけである。したがって、ガス検知素子２０の構成を詳細に説明し、参照素子２１の構成の説明は省略する。 (First embodiment)
1 to 5, 12, and 13 show a catalytic combustion type gas sensor according to a first embodiment of the present invention. 1 and 2 show a state before the catalyst layer 12 is formed, and FIGS. 3 and 4 show a state after the catalyst layer 12 is formed. As shown in FIG. 12, the catalytic combustion type gas sensor according to the present embodiment includes a gas detection element 20 and a reference element 21 on the same substrate. The gas detection element 20 and the reference element 21 include a catalyst layer 12 made of a ceramic sintered body in which the gas detection element 20 supports a catalyst, and the reference element 21 is a ceramic sintered body layer 12A that does not support a catalyst. The only difference is. Therefore, the configuration of the gas detection element 20 will be described in detail, and the description of the configuration of the reference element 21 will be omitted.

図３および図４に示すように、ガス検知素子２０は、基板１と、この基板１上に形成した凹部（凹部空間）１０を跨ぐように形成された絶縁膜（以下、支持用絶縁膜という。）２と、支持用絶縁膜２における凹部１０と反対側の面に配設され且つ通電から生じる熱によって燃焼する検知対象ガスの燃焼熱に応じて電気抵抗値が変化する検知抵抗体３Ａと、この検知抵抗体３Ａの近傍の少なくとも支持用絶縁膜２を貫通する開口部１１と、この開口部１１を通して支持用絶縁膜２の両面側に一体的に設けられ、支持用絶縁膜２の凹部１０と反対側の面で検知抵抗体３Ａを覆い、支持用絶縁膜２の凹部１０側の開口部１１の開口領域よりも広く膨出した膨出部１２Ａが形成された触媒層１２と、備えて構成されている。   As shown in FIG. 3 and FIG. 4, the gas detection element 20 includes an insulating film (hereinafter referred to as a supporting insulating film) formed so as to straddle the substrate 1 and a recess (recessed space) 10 formed on the substrate 1. 2) and a detection resistor 3A that is disposed on the surface of the supporting insulating film 2 opposite to the recess 10 and has an electric resistance value that changes according to the combustion heat of the detection target gas that is burned by the heat generated by energization. An opening 11 penetrating at least the support insulating film 2 in the vicinity of the detection resistor 3A and a concave portion of the support insulating film 2 provided integrally on both sides of the support insulating film 2 through the opening 11 And a catalyst layer 12 having a bulging portion 12A that covers the detection resistor 3A on the surface opposite to the surface 10 and bulges wider than the opening region of the opening 11 on the concave portion 10 side of the supporting insulating film 2. Configured.

基板１は、所定の結晶方位を有するシリコン単結晶からなり、その上面に平面形状が矩形の凹部１０が設けられている。この凹部１０は、基板１をエッチングすることにより形成されている。基板１の表面には、絶縁膜（支持用絶縁膜を含む）２が形成されている。この絶縁膜２は、基板１の上面に対し物理蒸着により形成された酸化アルミニウム膜である。   The substrate 1 is made of a silicon single crystal having a predetermined crystal orientation, and a concave portion 10 having a rectangular planar shape is provided on the upper surface thereof. The recess 10 is formed by etching the substrate 1. An insulating film (including a supporting insulating film) 2 is formed on the surface of the substrate 1. This insulating film 2 is an aluminum oxide film formed by physical vapor deposition on the upper surface of the substrate 1.

絶縁膜２は、基板１の上面に対し物理蒸着（ＰＶＤ）により形成された酸化アルミニウム膜でなる。酸化アルミニウムは、電気的絶縁性を有するとともに、高い熱伝導率を有している。なお、酸化アルミニウム膜以外にも、酸化シリコンや窒化シリコン等の絶縁性を有し且つ熱伝導率の良い物質を用いてもよい。また、物理蒸着以外にも、例えば化学蒸着処理や他の方法を用いて絶縁膜２を形成してもよい。   The insulating film 2 is an aluminum oxide film formed on the upper surface of the substrate 1 by physical vapor deposition (PVD). Aluminum oxide has electrical insulation and high thermal conductivity. In addition to the aluminum oxide film, a substance having an insulating property and high thermal conductivity such as silicon oxide or silicon nitride may be used. In addition to physical vapor deposition, the insulating film 2 may be formed using, for example, chemical vapor deposition or other methods.

図１および図２に示すように、この絶縁膜２におけるガス検知素子形成領域には、白金（Ｐｔ）でなる検知抵抗体３Ａがパルス波形状（ジグザグ状）に形成され、検知抵抗体３Ａの両端部分３Ｂを延在してそれぞれの最端部をパッド部３Ｃ、３Ｄとしている。そして、支持用絶縁膜２の上に検知抵抗体３Ａが形成された島状の検知抵抗体支持部５が基板１から浮き上がるように、検知抵抗体３Ａの下方に上記凹部１０をエッチングにより加工、形成している。この検知抵抗体支持部５の四隅には、この凹部（凹部空間）１０を跨いで基板１と一体的に設けられたアーム部６、７、８、９を架け渡すように一体に形成している。このように検知抵抗体支持部５が凹部１０を介して基板１から浮いた構造としたことにより、検知抵抗体３Ａが形成された面の熱容量を小さくしている。   As shown in FIGS. 1 and 2, a detection resistor 3A made of platinum (Pt) is formed in a pulse wave shape (zigzag shape) in the gas detection element formation region of the insulating film 2, and the detection resistor 3A Both end portions 3B are extended to form pad portions 3C and 3D at the extreme ends. Then, the recess 10 is processed by etching below the detection resistor 3A so that the island-shaped detection resistor support portion 5 in which the detection resistor 3A is formed on the support insulating film 2 is lifted from the substrate 1. Forming. At the four corners of the detection resistor support portion 5, the arm portions 6, 7, 8, 9 provided integrally with the substrate 1 are formed so as to cross over the recess (recess space) 10. Yes. As described above, the detection resistor support portion 5 is structured so as to float from the substrate 1 through the recess 10, thereby reducing the heat capacity of the surface on which the detection resistor 3 </ b> A is formed.

図２に示すように、検知抵抗体支持部５は、支持用絶縁膜２の上に検知抵抗体３Ａが形成され、検知抵抗体３Ａの上に保護膜４が形成されている。そして、図１および図２に示すように、検知抵抗体３Ａの近傍には、検知抵抗体３Ａの長手方向に沿って、複数の矩形状の開口部１１が間欠的に形成されている。この開口部１１は、保護膜４および絶縁膜２を貫通している。図３および図４に示すように、検知抵抗体支持部５の表面全体に亘って触媒層１２が形成されている。この触媒層１２は、開口部１１にも充填され、開口部１１における凹部１０側の開口から開口領域よりも外側へ膨出する膨出部１２Ａを有している。   As shown in FIG. 2, in the detection resistor support portion 5, a detection resistor 3A is formed on the supporting insulating film 2, and a protective film 4 is formed on the detection resistor 3A. As shown in FIGS. 1 and 2, a plurality of rectangular openings 11 are intermittently formed in the vicinity of the detection resistor 3A along the longitudinal direction of the detection resistor 3A. The opening 11 penetrates the protective film 4 and the insulating film 2. As shown in FIGS. 3 and 4, a catalyst layer 12 is formed over the entire surface of the detection resistor support 5. This catalyst layer 12 is also filled in the opening 11 and has a bulging portion 12A that bulges outward from the opening region from the opening on the concave portion 10 side in the opening 11.

本実施の形態に係る接触燃焼式ガスセンサにおけるガス検知素子２０は、検知抵抗体支持部５とアーム部６、７、８、９を残して、基板１に凹部１０が形成されているため、抵抗体支持部５の下面側にも検知対象ガスが回り込むことができる。図５に示すように、抵抗体支持部５の表面側の触媒層１２に検知対象ガスが接触すると、その燃焼熱は、検知抵抗体３Ａに伝達されるとともに、開口部１１内の触媒層１２と保護膜４を介して検知抵抗体３Ａの側壁部へ伝達される。また、抵抗体支持部５の下面側に回りこんだ検知対象ガスは触媒槽１２の膨出部１２Ａに接触して検知対象ガスが燃焼し燃焼量が増加する。さらに、膨出部１２Ａは検知抵抗体近傍に存在するため、膨出部１２Ａに接触したガスの燃焼熱は、図中膨出部１２Ａ内に矢印で示すように、開口部１１内に充填された触媒層１２と検知抵抗体３Ａの側壁に存在する保護膜４とを介して伝達されやすくなる。このため、検知抵抗体３Ａへ伝導される燃焼熱は、従来の構造に比較して大幅に増加するため（燃焼熱量と熱伝達効率が向上するため）、センサ感度を向上させることができる。   Since the gas detection element 20 in the catalytic combustion type gas sensor according to the present embodiment has the recess 10 formed in the substrate 1 except for the detection resistor support 5 and the arms 6, 7, 8, 9, the resistance The detection target gas can also enter the lower surface side of the body support portion 5. As shown in FIG. 5, when the detection target gas comes into contact with the catalyst layer 12 on the surface side of the resistor support portion 5, the combustion heat is transmitted to the detection resistor 3 </ b> A and the catalyst layer 12 in the opening 11. And transmitted through the protective film 4 to the side wall portion of the detection resistor 3A. Further, the detection target gas that has come to the lower surface side of the resistor support portion 5 comes into contact with the bulging portion 12A of the catalyst tank 12, and the detection target gas burns to increase the amount of combustion. Furthermore, since the bulging portion 12A exists in the vicinity of the detection resistor, the combustion heat of the gas that has contacted the bulging portion 12A is filled in the opening portion 11 as indicated by an arrow in the bulging portion 12A in the figure. It becomes easy to transmit through the catalyst layer 12 and the protective film 4 existing on the side wall of the detection resistor 3A. For this reason, since the combustion heat conducted to the detection resistor 3A is significantly increased as compared with the conventional structure (because the amount of combustion heat and heat transfer efficiency are improved), the sensor sensitivity can be improved.

また、本実施の形態では、触媒層１２において凹部１０側に形成された膨出部１２Ａが、触媒層１２が剥離することを防止する所謂アンカー効果を奏するため、耐久性の高い接触燃焼式ガスセンサを得ることができる。   In the present embodiment, the bulging portion 12A formed on the concave portion 10 side in the catalyst layer 12 has a so-called anchor effect that prevents the catalyst layer 12 from being peeled off. Therefore, a highly durable catalytic combustion gas sensor Can be obtained.

（第１の実施の形態の変形例）
図６および図７は、上記第１の実施の形態の変形例に係るガス検知素子２０Ａを示している。この変形例は、図６の平面図から判るように、屈曲して互いに平行をなす検知抵抗体３Ａ同士の間だけではなく、抵抗体支持部５の周縁部に沿う検知抵抗体３Ａの外側にも開口部１１Ａを付加したものである。この変形例における他の構成は、上記第１の実施の形態の構成と同様である。 (Modification of the first embodiment)
6 and 7 show a gas detection element 20A according to a modification of the first embodiment. As can be seen from the plan view of FIG. 6, this modification is not only between the detection resistors 3 </ b> A bent and parallel to each other, but also on the outside of the detection resistors 3 </ b> A along the peripheral edge of the resistor support portion 5. Is also provided with an opening 11A. Other configurations in this modification are the same as those in the first embodiment.

この変形例では、上記第１の実施の形態における検知抵抗体３Ａに沿って形成される開口部１１に加えて、外側の開口部１１Ａも存在するため、検知抵抗体３Ａの側壁に開口部１１、１１Ａ内に充填された触媒層１２を介して伝達される燃焼熱を増やすため、さらにセンサ感度を向上させる効果がある。   In this modification, in addition to the opening 11 formed along the sensing resistor 3A in the first embodiment, an outer opening 11A is also present, so the opening 11 is formed on the side wall of the sensing resistor 3A. In order to increase the combustion heat transmitted through the catalyst layer 12 filled in 11A, the sensor sensitivity is further improved.

（第２の実施の形態）
図８および図９は、本発明の第２の実施の形態に係る接触燃焼式ガスセンサにおけるガス検知素子２０Ｂを示している。このガス検知素子２０Ｂは、上記した第１の実施の形態に係るガス検知素子２０における開口部１１をスリット１１Ｂとしたものであり、他の構成は上記第１の実施の形態と同様である。 (Second Embodiment)
8 and 9 show a gas detection element 20B in the catalytic combustion type gas sensor according to the second embodiment of the present invention. In this gas detection element 20B, the opening 11 in the gas detection element 20 according to the first embodiment described above is formed as a slit 11B, and other configurations are the same as those in the first embodiment.

スリット１１Ｂは、屈曲して互いに平行をなす検知抵抗体３Ａ同士の間に長手方向に沿って形成されている。このように開口部をスリット１１Ｂとすることにより開口部から膨出する触媒層が増加する。これにより、抵抗体支持部５の下面に回り込んだ検知対象ガスと触媒層との接触面積が増加し、検知抵抗体３Ａに伝達される燃焼熱が大幅に増加する。このスリット１１Ｂ内の触媒層１２は検知抵抗体３Ａの側壁に沿って長手方向に形成されるため、抵抗体支持部５の上側および下側（凹部１０側）からの燃焼熱が触媒層１２を介して効率よく伝達される。したがって、本実施の形態に係る接触燃焼式ガスセンサは、そのセンサ感度がさらに向上するという効果を奏する。   The slit 11B is formed along the longitudinal direction between the sensing resistors 3A that are bent and parallel to each other. Thus, the catalyst layer which swells from an opening part increases by making an opening part into the slit 11B. As a result, the contact area between the gas to be detected that has entered the lower surface of the resistor support 5 and the catalyst layer is increased, and the combustion heat transferred to the detection resistor 3A is significantly increased. Since the catalyst layer 12 in the slit 11B is formed in the longitudinal direction along the side wall of the detection resistor 3A, the heat of combustion from the upper side and the lower side (the concave portion 10 side) of the resistor support portion 5 causes the catalyst layer 12 to flow. Is transmitted efficiently. Therefore, the catalytic combustion type gas sensor according to the present embodiment has an effect that the sensor sensitivity is further improved.

また、本実施の形態では、開口部がスリット１１Ｂであるため、触媒層１２を製造する過程で触媒を担持させたセラミック粉体のペーストを塗布したときに、スリット１１Ｂの凹部１０側の開口から膨出するペースト量が大きくなり、図９に示すように、表面張力により絶縁膜２の下側面全体を覆うように形成することができる。なお、このセラミック粉体のペーストを焼結した場合も同様の形状を維持する。したがって、製造された接触燃焼式ガスセンサでは、触媒層１２の剥がれを防止する構造を有し、接触燃焼式ガスセンサの耐久性を高め、長期にわたって安定なガス感度特性を得られるという効果がある。   In this embodiment, since the opening is the slit 11B, when the ceramic powder paste carrying the catalyst is applied in the process of manufacturing the catalyst layer 12, the opening from the recess 10 side of the slit 11B is applied. As shown in FIG. 9, the amount of paste that bulges out can be formed so as to cover the entire lower surface of the insulating film 2 by surface tension. The same shape is maintained when the ceramic powder paste is sintered. Therefore, the manufactured catalytic combustion type gas sensor has a structure that prevents the catalyst layer 12 from peeling off, and has an effect of improving the durability of the catalytic combustion type gas sensor and obtaining stable gas sensitivity characteristics over a long period of time.

（第２の実施の形態の変形例）
図１０および図１１は、上記第２の実施の形態の変形例に係るガス検知素子２０Ｃを示している。この変形例は、上記第２の実施の形態に係るガス検知素子２０Ｂにおいて抵抗体支持部５の周縁部に検知抵抗体３Ａを囲むスリット１１Ｃを加えたものであり、他の構成は上記第２の実施の形態と同様である。 (Modification of the second embodiment)
10 and 11 show a gas detection element 20C according to a modification of the second embodiment. This modification is obtained by adding a slit 11C surrounding the detection resistor 3A to the periphery of the resistor support 5 in the gas detection element 20B according to the second embodiment, and the other configuration is the second configuration. This is the same as the embodiment.

この変形例では、検知抵抗体３Ａを囲むようにスリット１１Ｃが形成されているため、このスリット１１Ｂ内の触媒層１２を介して検知抵抗体３Ａの側壁へ伝達される燃焼熱はさらに大きくなる。このため、この変形例では、上記第２の実施の形態よりも燃焼熱を効率よく伝達することができ、センサ感度を向上させることができる。   In this modification, since the slit 11C is formed so as to surround the detection resistor 3A, the combustion heat transmitted to the side wall of the detection resistor 3A via the catalyst layer 12 in the slit 11B is further increased. For this reason, in this modified example, combustion heat can be transmitted more efficiently than in the second embodiment, and the sensor sensitivity can be improved.

（実験例）
次に、第１実施例、第２実施例および比較例についての実験例について説明する。第１実施例、第２実施例および比較例の接触燃焼式ガスセンサは、凹部の構造、寸法、各材料膜の膜厚、抵抗長さ、構成材料などは、同一の規格で作製した。図１２に示すように、上記した第１の実施の形態に係る接触燃焼式ガスセンサを第１実施例とし、図８および図９に示した第２の実施の形態に係る接触燃焼式ガスセンサを図１２に示すように同一基板に参照素子を作り込んだものを第２実施例とし、図１５および図１６に示した従来のガス検知素子をそなえた接触燃焼式ガスセンサを比較例とした。そして、これら接触燃焼式ガスセンサを用いて、図１３に示すように、パルス電圧電源３０、電圧計３１、固定抵抗器Ｒ１、Ｒ２、可変抵抗器Ｒｖを用いて、ブリッジ回路を組んでメタン（ＣＨ４）を検知対象ガスとして用いてガス感度を測定し、図１４に示すような結果が得られた。なお、符号３、３Ｃ、３Ｅは、パッド部３を示す。 (Experimental example)
Next, experimental examples of the first example, the second example, and the comparative example will be described. The contact combustion type gas sensors of the first example, the second example, and the comparative example were manufactured according to the same standards for the structure and dimensions of the recesses, the film thickness of each material film, the resistance length, the constituent materials, and the like. As shown in FIG. 12, the catalytic combustion type gas sensor according to the first embodiment described above is the first example, and the catalytic combustion type gas sensor according to the second embodiment shown in FIGS. As shown in FIG. 12, the reference substrate is formed on the same substrate as the second embodiment, and the contact combustion type gas sensor having the conventional gas detection element shown in FIGS. 15 and 16 is used as a comparative example. Then, using these catalytic combustion type gas sensors, as shown in FIG. 13, a bridge circuit is assembled using a pulse voltage power source 30, a voltmeter 31, fixed resistors R1, R2, and a variable resistor Rv to form methane (CH The gas sensitivity was measured using 4 ) as the detection target gas, and the results shown in FIG. 14 were obtained. Reference numerals 3, 3 </ b> C, and 3 </ b> E denote pad portions 3.

なお、接触燃焼式ガスセンサへの印加電圧は、各センサ素子温度を約４００℃に統一するために、検知抵抗体の抵抗値に従って個別調整をした。一方、ブリッジ回路検出の場合、ガスの接触燃焼による温度変化で検知抵抗体の抵抗変化が生じ、ブリッジバランスが崩れることによって、電圧出力を得ることができるが、検知抵抗体の抵抗変化によるブリッジ電圧の変化は、ブリッジ回路に印加する電圧に依存してしまうため、図１４では検出回路への印加電圧１Ｖ当たりのメタン感度特性として示している。   The applied voltage to the contact combustion type gas sensor was individually adjusted according to the resistance value of the detection resistor in order to unify the temperature of each sensor element to about 400 ° C. On the other hand, in the case of the bridge circuit detection, the resistance change of the detection resistor occurs due to the temperature change due to the contact combustion of the gas, and the voltage output can be obtained by breaking the bridge balance, but the bridge voltage due to the resistance change of the detection resistor Since this change depends on the voltage applied to the bridge circuit, FIG. 14 shows the methane sensitivity characteristic per 1 V applied voltage to the detection circuit.

図１４に示すように、いずれの接触燃焼式ガスセンサも、ガス濃度に対して直線的な出力を示したが、第１実施例および第２実施例では、開口部１１Ａもしくはスリット１１Ｂ内の触媒層１２が燃焼熱の伝達に寄与するため、抵抗体支持部５の裏面側（凹部１０側）での接触燃焼反応も触媒層１２を介して検知抵抗体３Ａの側壁へ速やかに伝達されるため、比較例に比べて第１実施例で約２０％、第２実施例で約４０％の感度向上効果が確認された。   As shown in FIG. 14, all the catalytic combustion type gas sensors showed a linear output with respect to the gas concentration, but in the first and second embodiments, the catalyst layer in the opening 11A or the slit 11B. 12 contributes to the transmission of combustion heat, so that the catalytic combustion reaction on the back surface side (recess 10 side) of the resistor support 5 is also quickly transmitted to the side wall of the detection resistor 3A via the catalyst layer 12. The sensitivity improvement effect of about 20% was confirmed in the first example and about 40% in the second example as compared with the comparative example.

（その他の実施の形態）
上述した実施の形態の開示の一部をなす論述および図面はこの発明を限定するものであると理解すべきではない。この開示から当業者には様々な代替実施の形態、実施例および運用技術が明らかとなろう。 (Other embodiments)
It should not be understood that the descriptions and drawings which form part of the disclosure of the above-described embodiments limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

例えば、上記各実施の形態では、凹部１０の平面形状を矩形としたが、これに限定されるものではない。   For example, in each of the above embodiments, the planar shape of the recess 10 is rectangular, but the present invention is not limited to this.

また、上記各実施の形態では、アーム部６、７、８、９を抵抗体支持部５の四隅から延在する形態としたが、アーム部の本数や形態はこれに限定されるものではない。   In each of the above embodiments, the arm portions 6, 7, 8, and 9 are extended from the four corners of the resistor support portion 5. However, the number and form of the arm portions are not limited thereto. .

さらに、上記各実施の形態では、検知抵抗体３Ａを覆うように保護膜４を形成したが、この保護膜４を省略する構成としても勿論よい。   Further, in each of the above-described embodiments, the protective film 4 is formed so as to cover the detection resistor 3A. However, the protective film 4 may be omitted.

また、上記各実施の形態では、検知抵抗体３Ａが１本を屈曲形状に形成したものであるが、複数本の検知抵抗体３Ａを備える構成としても構わない。   Further, in each of the above embodiments, one detection resistor 3A is formed in a bent shape, but a configuration including a plurality of detection resistors 3A may be employed.

さらに、上記各実施の形態では、凹部１０が基板１の表面側に形成された態様について説明したが、検知抵抗体支持部の下側に検知対象ガスが回りこむ構造を有していれば、凹部が基板１の裏面側に形成された態様のガス検知素子に適用して勿論よい。   Further, in each of the above-described embodiments, the aspect in which the recess 10 is formed on the surface side of the substrate 1 has been described. However, if the detection target gas has a structure around which the detection target gas flows around, Of course, the present invention may be applied to a gas detection element having a recess formed on the back side of the substrate 1.

１…基板
２…絶縁膜
３Ａ…検知抵抗体
１０…凹部
１１…開口部
１２…触媒層
１２Ａ…膨出部
２０，２０Ａ，２０Ｂ，２０Ｃ…ガス検知素子 DESCRIPTION OF SYMBOLS 1 ... Board | substrate 2 ... Insulating film 3A ... Detection resistor 10 ... Recessed part 11 ... Opening part 12 ... Catalyst layer 12A ... Swelling part 20, 20A, 20B, 20C ... Gas detection element

Claims (3)

基板と、
前記基板上に形成した凹部空間を跨ぐように形成された支持用絶縁膜と、
前記支持用絶縁膜における前記凹部空間と反対側の面に配設され且つ通電から生じる熱によって燃焼する検知対象ガスの燃焼熱に応じて電気抵抗値が変化する検知抵抗体と、
前記検知抵抗体の近傍の少なくとも前記支持用絶縁膜を貫通する開口部と、
前記開口部を通して前記支持用絶縁膜の両面側に一体的に設けられ、前記支持用絶縁膜の前記凹部空間と反対側の面で前記検知抵抗体を覆い、前記支持用絶縁膜の前記凹部空間側の前記開口部の開口領域よりも広く膨出した構造に形成された触媒層と、
前記検知抵抗体上に形成された保護膜と、を備え、
前記保護膜は、前記検知抵抗体の側壁まで覆い、
前記開口部は、前記検知抵抗体の長手方向に沿って配置された複数の矩形の穴である
ことを特徴とする接触燃焼式ガスセンサ。 A substrate,
A supporting insulating film formed so as to straddle the recessed space formed on the substrate;
A detection resistor that is disposed on a surface of the supporting insulating film opposite to the recessed space and has an electrical resistance value that changes in accordance with the combustion heat of the detection target gas that is burned by heat generated by energization;
An opening that penetrates at least the supporting insulating film in the vicinity of the sensing resistor;
It is provided integrally on both sides of the supporting insulating film through the opening, covers the detection resistor with the surface of the supporting insulating film opposite to the recessed space, and the recessed space of the supporting insulating film. A catalyst layer formed in a structure bulging wider than the opening region of the opening on the side,
A protective film formed on the detection resistor,
The protective film is not covered to the sidewall of the sense resistor,
The contact combustion type gas sensor , wherein the opening is a plurality of rectangular holes arranged along a longitudinal direction of the detection resistor . 基板と、
前記基板上に形成した凹部空間を跨ぐように形成された支持用絶縁膜と、
前記支持用絶縁膜における前記凹部空間と反対側の面に配設され且つ通電から生じる熱によって燃焼する検知対象ガスの燃焼熱に応じて電気抵抗値が変化する検知抵抗体と、
前記検知抵抗体の近傍の少なくとも前記支持用絶縁膜を貫通する開口部と、
前記開口部を通して前記支持用絶縁膜の両面側に一体的に設けられ、前記支持用絶縁膜の前記凹部空間と反対側の面で前記検知抵抗体を覆い、前記支持用絶縁膜の前記凹部空間側の前記開口部の開口領域よりも広く膨出した構造に形成された触媒層と、
前記検知抵抗体上に形成された保護膜と、を備え、
前記保護膜は、前記検知抵抗体の側壁まで覆い、
前記開口部は、前記検知抵抗体の長手方向に沿って形成されたスリットである
ことを特徴とする接触燃焼式ガスセンサ。 A substrate,
A supporting insulating film formed so as to straddle the recessed space formed on the substrate;
A detection resistor that is disposed on a surface of the supporting insulating film opposite to the recessed space and has an electrical resistance value that changes in accordance with the combustion heat of the detection target gas that is burned by heat generated by energization;
An opening that penetrates at least the supporting insulating film in the vicinity of the sensing resistor;
It is provided integrally on both sides of the supporting insulating film through the opening, covers the detection resistor with the surface of the supporting insulating film opposite to the recessed space, and the recessed space of the supporting insulating film. A catalyst layer formed in a structure bulging wider than the opening region of the opening on the side,
A protective film formed on the detection resistor,
The protective film covers up to the side wall of the detection resistor,
The opening is a slit formed along the longitudinal direction of the detection resistor.
The contact combustion type gas sensor characterized by the above-mentioned . 前記触媒層は、前記支持用絶縁膜の前記凹部空間と反対側の面から触媒金属を担持したセラミック粉体のペーストが塗布、焼結されてなる
ことを特徴とする請求項１又は請求項２のいずれかに記載の接触燃焼式ガスセンサ。
3. The catalyst layer is formed by applying and sintering a ceramic powder paste carrying a catalyst metal from a surface opposite to the recessed space of the supporting insulating film. The contact combustion type gas sensor according to any one of the above.
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