JP2019152566A - Gas sensor group and method for analyzing combustible gas - Google Patents
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Description
本発明は、ガスセンサ群及び可燃性ガスの分析方法に関する。 The present invention relates to a gas sensor group and a method for analyzing a combustible gas.
生活環境には、様々なニオイ成分が存在する。これらのニオイ成分の殆どは、極微量の有機分子であり、揮発性有機化合物（ＶＯＣ）と呼ばれる。ＶＯＣには、様々な性質を有する化合物が存在する。室内には、建材、内装、家具等からの放散、居住者による化粧品、芳香剤等の使用等により、合計で数十から百数十ｐｐｂに相当する様々な低濃度のＶＯＣが存在する。このため、特定のＶＯＣを検知する生活環境には、通常、一定濃度の水蒸気と、低濃度の揮発性不純物が存在する。 There are various odor components in the living environment. Most of these odor components are trace amounts of organic molecules and are called volatile organic compounds (VOC). In VOC, there are compounds having various properties. There are various low-concentration VOCs corresponding to tens to hundreds of ppb in total, due to the use of building materials, interiors, furniture, etc., the use of cosmetics, fragrances, and the like by residents. For this reason, a certain concentration of water vapor and a low concentration of volatile impurities usually exist in a living environment where a specific VOC is detected.
例えば、医療分野において、呼気中に含まれるＶＯＣは、口臭、代謝、疾患との関連性が指摘されており、呼気中のＶＯＣと、健康状態に相関があるとされている。また、食品分野において、食品から発するニオイに相当するＶＯＣと、鮮度や品質に相関があるとされている。このため、特定のＶＯＣのモニタリングは、健康状態や食品の管理に有効である。ただし、特定のＶＯＣは、室内で検知されることになり、室内には、揮発性不純物が存在するため、揮発性不純物に影響されずに、特定のＶＯＣを検知する必要がある。 For example, in the medical field, VOCs contained in exhaled breath have been pointed out to be associated with bad breath, metabolism, and disease, and it is said that there is a correlation between the exhaled VOC and the health condition. Further, in the food field, it is said that there is a correlation between VOC corresponding to odor generated from food, freshness and quality. For this reason, monitoring of a specific VOC is effective for health status and food management. However, a specific VOC is detected indoors, and since a volatile impurity exists in the room, it is necessary to detect the specific VOC without being affected by the volatile impurity.
その一方、ＶＯＣに代表される可燃性ガスを検知するため、金属酸化物ｎ型半導体による半導体式ガスセンサが従来から利用されている。半導体式センサは、価格やランニングコストが低い。代表的な半導体式ガスセンサは、酸化スズセンサであり、感応部を構成する酸化スズ粒子の表面に大気中の酸素が吸着し、キャリア電子が吸着酸素に補足されることで、粒界のポテンシャル障壁が増大し、粒界の電気抵抗が増大する。このため、酸化スズ粒子の表面に可燃性ガスが到達し、表面の吸着酸素を消費することで、粒界のポテンシャル障壁が減少し、電気抵抗が減少する。ここで、酸化スズセンサは、所謂、粒界応答型半導体式ガスセンサに分類される。 On the other hand, in order to detect a combustible gas represented by VOC, a semiconductor gas sensor using a metal oxide n-type semiconductor has been conventionally used. Semiconductor sensors are low in price and running cost. A typical semiconductor gas sensor is a tin oxide sensor, in which atmospheric oxygen is adsorbed on the surface of tin oxide particles constituting the sensitive part, and carrier electrons are captured by the adsorbed oxygen, thereby reducing the potential barrier at the grain boundary. And the electrical resistance of the grain boundary increases. For this reason, combustible gas reaches the surface of the tin oxide particles and consumes adsorbed oxygen on the surface, thereby reducing the potential barrier at the grain boundary and decreasing the electrical resistance. Here, the tin oxide sensor is classified as a so-called grain boundary response type semiconductor gas sensor.
しかしながら、粒界応答型半導体式ガスセンサは、その性質上、ガス選択性を発現するのが難しい。 However, it is difficult for the grain boundary responsive semiconductor gas sensor to exhibit gas selectivity due to its properties.
このような状況で、揮発性不純物を含む室内で、特定の可燃性ガスを検知することが可能なガスセンサ群を開発することが望まれている。 Under such circumstances, it is desired to develop a gas sensor group capable of detecting a specific combustible gas in a room containing volatile impurities.
そこで、半導体式ガスセンサを代表とするガスセンサを複数有するガスセンサ群から得られるシグナルの主成分分析等の統計解析を実施する方法が検討されている。 Therefore, a method of performing statistical analysis such as principal component analysis of a signal obtained from a gas sensor group having a plurality of gas sensors typified by a semiconductor gas sensor has been studied.
個々のガスセンサで、特定の可燃性ガスのみを検知するのは、その性質上、難しいが、複数のガスセンサから得られるシグナルの統計解析を実施すると、一定の傾向が得られる（例えば、特許文献１〜３参照）。 Although it is difficult to detect only a specific combustible gas with an individual gas sensor, a certain tendency is obtained when statistical analysis of signals obtained from a plurality of gas sensors is performed (for example, Patent Document 1). To 3).
しかしながら、揮発性不純物を含む加湿空気中の可燃性ガスを充分に分離検知することができない。 However, the combustible gas in the humidified air containing volatile impurities cannot be sufficiently separated and detected.
特許文献４には、複数種の粒界応答型の半導体式ガスセンサと、１種以上のバルク応答型の半導体式ガスセンサを有するガスセンサ群が開示されている。 Patent Document 4 discloses a gas sensor group having a plurality of types of grain boundary response type semiconductor gas sensors and one or more types of bulk response type semiconductor gas sensors.
一般に、ガスセンサ群を小型化することが望まれている。ここで、ガスセンサ群を小型化するためには、ガスセンサ群を構成する複数のガスセンサを同一の基板上に配置することが考えられるが、このためには、複数のガスセンサの駆動温度が近いことが好ましい。 In general, it is desired to downsize the gas sensor group. Here, in order to reduce the size of the gas sensor group, it is conceivable to arrange a plurality of gas sensors constituting the gas sensor group on the same substrate. For this purpose, the driving temperatures of the plurality of gas sensors are close. preferable.
しかしながら、バルク応答型の半導体式ガスセンサは、一般に、粒界応答型の半導体式ガスセンサよりも駆動温度が高いため、ガスセンサ群を小型化しにくい。 However, since the bulk response type semiconductor gas sensor generally has a higher driving temperature than the grain boundary response type semiconductor gas sensor, it is difficult to reduce the size of the gas sensor group.
本発明の一態様は、小型化しやすく、揮発性不純物を含む加湿空気中の可燃性ガスを充分に分離検知することが可能なガスセンサ群を提供することを目的とする。 An object of one embodiment of the present invention is to provide a gas sensor group that can be easily miniaturized and can sufficiently detect and detect combustible gas in humidified air containing volatile impurities.
本発明の一態様は、可燃性ガスの検知に用いられるガスセンサ群であって、複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子を有し、前記ｎ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種と、前記ｐ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種が同一の基板上に配置されているガスセンサを含む。 One embodiment of the present invention is a gas sensor group used for detection of combustible gas, and includes a plurality of types of n-type semiconductor type semiconductor gas sensor elements and one or more types of p-type semiconductor type semiconductor gas sensor elements. And a gas sensor in which at least one of the n-type semiconductor type semiconductor gas sensor elements and at least one of the p-type semiconductor type semiconductor gas sensor elements are arranged on the same substrate.
本発明の一態様により、小型化しやすく、揮発性不純物を含む加湿空気中の可燃性ガスを充分に分離検知することが可能なガスセンサ群を提供することができる。 According to one embodiment of the present invention, it is possible to provide a gas sensor group that can be easily downsized and can sufficiently detect and detect combustible gas in humidified air containing volatile impurities.
次に、本発明を実施するための形態を説明する。 Next, the form for implementing this invention is demonstrated.
［ガスセンサ群］
本実施形態のガスセンサ群は、可燃性ガスの検知に用いられ、複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子を有する。本実施形態のガスセンサ群は、検知原理の異なる粒界応答型の半導体式ガスセンサ素子を用いることで、後述する主成分分析の精度を向上させることができる。また、本実施形態のガスセンサ群は、ｎ型半導体型の半導体式ガスセンサ素子と、ｐ型半導体型の半導体式ガスセンサ素子の駆動温度の差が小さく、同一の基板上に配置することができる。
[Gas sensor group]
The gas sensor group of this embodiment is used for detection of combustible gas, and has a plurality of types of n-type semiconductor type semiconductor gas sensor elements and one or more types of p-type semiconductor type semiconductor gas sensor elements. The gas sensor group of this embodiment can improve the accuracy of principal component analysis described later by using a grain boundary response type semiconductor gas sensor element having a different detection principle. Further, the gas sensor group of the present embodiment has a small driving temperature difference between the n-type semiconductor type semiconductor gas sensor element and the p-type semiconductor type gas sensor element, and can be arranged on the same substrate.
本願明細書及び特許請求の範囲において、可燃性ガスを、気体として存在し得る物質であり、半導体式ガスセンサ素子で検知することが可能なガスと定義する。即ち、可燃性ガスは、後述する半導体式ガスセンサ素子を構成する金属酸化物（粒子）の表面で酸化することが可能な物質である。 In the present specification and claims, a combustible gas is a substance that can exist as a gas and is defined as a gas that can be detected by a semiconductor gas sensor element. That is, the combustible gas is a substance that can be oxidized on the surface of the metal oxide (particles) constituting the semiconductor gas sensor element described later.
可燃性ガスとしては、ＶＯＣ等の有機化合物、硫化水素、水素、一酸化炭素等の無機化合物が挙げられる。 Examples of the combustible gas include organic compounds such as VOC, and inorganic compounds such as hydrogen sulfide, hydrogen, and carbon monoxide.
ＶＯＣとしては、脂肪族炭化水素、芳香族炭化水素、エステル、アルコール、アルデヒド、ケトン、テルペン、ハロゲン化炭化水素等が挙げられる。中でも、ノナナール、デカン、アセトン、アセトイン等の患者の呼気に含まれる成分が好ましい。アセトイン、ノナナール、デカンは肺がん患者の呼気に、アセトンは糖尿病患者の呼気に相関があると報告されている。以下に報告例を示す：アセトイン（G. Songa, et al., Lung Cancer 67 (2010) 227-231）、ノナナール（P. Fuchs et al., Int. J. Cancer 126 (2010) 2663-2670.）、デカン（D. Poli et al., Respiratory Research 6 (2005) 71-80.）、アセトン（C. Wang, et al., IEEE Sens. J. 10 (2010) 54-63.）
本実施形態において、ｎ型半導体型の半導体式ガスセンサ素子は、ｎ型半導体の金属酸化物粒子で感応部が構成されている。金属酸化物粒子の表面に、大気中の酸素が吸着してキャリア電子を補足することで、金属酸化物粒子の粒界の自由電子濃度が減少し、電気抵抗が増大した状態になる。金属酸化物粒子の表面に可燃性ガスが到達して酸化すると、その過程で表面の吸着酸素を消費するため、粒界の自由電子濃度が増大し、電気抵抗が減少した状態になる。電気抵抗の減少量は、到達する可燃性ガスの種類や濃度に依存する。このため、金属酸化物粒子の表面は、酸素だけでなく水分子も吸着する。大気中の湿度が変化すると、金属酸化物粒子の表面に吸着する水分子の量が変化し、金属酸化物粒子の表面に吸着する酸素分子の量に影響を与える。その結果、ｎ型半導体型の半導体式ガスセンサ素子は、湿度の変化の影響を受けやすい。
Examples of VOC include aliphatic hydrocarbons, aromatic hydrocarbons, esters, alcohols, aldehydes, ketones, terpenes, halogenated hydrocarbons, and the like. Among these, components contained in the patient's breath such as nonanal, decane, acetone, and acetoin are preferable. Acetoin, nonanal, and decane have been reported to correlate with exhalation of lung cancer patients and acetone with exhalation of diabetic patients. Reported examples are: Acetoin (G. Songa, et al., Lung Cancer 67 (2010) 227-231), Nonanal (P. Fuchs et al., Int. J. Cancer 126 (2010) 2663-2670. ), Decane (D. Poli et al., Respiratory Research 6 (2005) 71-80.), Acetone (C. Wang, et al., IEEE Sens. J. 10 (2010) 54-63.)
In the present embodiment, the n-type semiconductor type semiconductor gas sensor element has a sensitive portion made of n-type semiconductor metal oxide particles. Oxygen in the atmosphere is adsorbed on the surface of the metal oxide particles and captures carrier electrons, so that the free electron concentration at the grain boundaries of the metal oxide particles decreases and the electric resistance increases. When the combustible gas reaches the surface of the metal oxide particles and oxidizes, the adsorbed oxygen on the surface is consumed in the process, so that the free electron concentration at the grain boundary increases and the electric resistance decreases. The amount of decrease in electrical resistance depends on the type and concentration of the combustible gas that is reached. For this reason, the surface of the metal oxide particles adsorbs not only oxygen but also water molecules. When the humidity in the atmosphere changes, the amount of water molecules adsorbed on the surface of the metal oxide particles changes, which affects the amount of oxygen molecules adsorbed on the surface of the metal oxide particles. As a result, the n-type semiconductor type semiconductor gas sensor element is susceptible to changes in humidity.
本実施形態において、ｐ型半導体型の半導体式ガスセンサ素子は、ｐ型半導体の金属酸化物粒子で感応部が構成されている。金属酸化物粒子の表面に、大気中の酸素が吸着してキャリア電子を補足することで、金属酸化物粒子の粒界の正孔濃度が増大し、電気抵抗が減少した状態になる。金属酸化物粒子の表面に可燃性ガスが到達して酸化すると、その過程で表面の吸着酸素を消費するため、粒界の正孔濃度が減少し、電気抵抗が増大した状態になる。電気抵抗の減少量は、到達する可燃性ガスの種類や濃度に依存する。金属酸化物粒子の表面における酸素のやりとりが電気抵抗に影響を与えることは、ｎ型半導体型の半導体式ガスセンサ素子と類似するが、ｐ型半導体型の半導体式ガスセンサ素子は、水分子よりも酸素分子の方が吸着されやすいので、ｐ型半導体型の半導体式ガスセンサ素子は、湿度の変化の影響を受けにくい。 In the present embodiment, the p-type semiconductor type semiconductor gas sensor element has a sensitive portion made of p-type semiconductor metal oxide particles. Oxygen in the atmosphere is adsorbed on the surface of the metal oxide particles and captures carrier electrons, whereby the hole concentration at the grain boundaries of the metal oxide particles increases and the electrical resistance decreases. When the combustible gas reaches the surface of the metal oxide particles and oxidizes, the adsorbed oxygen on the surface is consumed in the process, so that the hole concentration at the grain boundary decreases and the electrical resistance increases. The amount of decrease in electrical resistance depends on the type and concentration of the combustible gas that is reached. The fact that the exchange of oxygen on the surface of the metal oxide particles affects the electrical resistance is similar to that of an n-type semiconductor type semiconductor gas sensor element, but a p-type semiconductor type semiconductor gas sensor element is more oxygen than water molecules. Since molecules are more easily adsorbed, the p-type semiconductor type semiconductor gas sensor element is less susceptible to changes in humidity.
ｐ型半導体型の金属酸化物は、ランタン鉄酸化物（ＬａＦｅＯ３）であることが好ましい。これにより、ｐ型半導体型の半導体式ガスセンサ素子の駆動温度と、ｎ型半導体型の半導体式ガスセンサ素子の駆動温度の差を特に小さくすることができる。 The p-type semiconductor type metal oxide is preferably lanthanum iron oxide (LaFeO 3 ). Thereby, the difference between the driving temperature of the p-type semiconductor type semiconductor gas sensor element and the driving temperature of the n-type semiconductor type semiconductor gas sensor element can be particularly reduced.
なお、ｐ型半導体型の金属酸化物粒子に、貴金属触媒粒子が担持されることで、可燃性ガスに対する応答特性を制御することができる。 In addition, the response characteristic with respect to combustible gas is controllable by carrying | supporting a noble metal catalyst particle on the p-type semiconductor type metal oxide particle.
貴金属としては、特に限定されないが、白金、パラジウム、金、銀、ロジウム、ルテニウム等が挙げられ、２種以上併用してもよい。これらの中でも、白金、金、パラジウムの併用が好ましい。 Although it does not specifically limit as a noble metal, Platinum, palladium, gold | metal | money, silver, rhodium, ruthenium etc. are mentioned, You may use 2 or more types together. Among these, the combined use of platinum, gold, and palladium is preferable.
本実施形態のガスセンサ群は、ｎ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種と、ｐ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種が同一の基板上に配置されているガスセンサを含む。 In the gas sensor group of this embodiment, at least one of n-type semiconductor type semiconductor gas sensor elements and at least one of p-type semiconductor type semiconductor gas sensor elements are arranged on the same substrate. Includes gas sensor.
このとき、ガスセンサは、基板を直接加熱することが可能なヒータを有することが好ましい。これにより、同一の基板上に配置されている半導体式ガスセンサ素子を駆動することができる。 At this time, the gas sensor preferably has a heater capable of directly heating the substrate. Thereby, the semiconductor type gas sensor element arrange | positioned on the same board | substrate can be driven.
［可燃性ガスの分析方法］
本実施形態の可燃性ガスの分析方法は、本実施形態のガスセンサ群を用いて、可燃性ガスを分析する方法であり、複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子が１種以上の可燃性ガスを検知して応答した応答値を得る工程を含む。
[Flammable gas analysis method]
The method for analyzing flammable gas according to this embodiment is a method for analyzing flammable gas using the gas sensor group according to this embodiment, and includes a plurality of types of n-type semiconductor semiconductor gas sensor elements and one or more types of semiconductor gas sensor elements. The step includes a step of obtaining a response value in response to detection of one or more types of combustible gas by a p-type semiconductor type semiconductor gas sensor element.
本実施形態の可燃性ガスの分析方法は、複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子の応答値から成るデータを主成分分析する工程をさらに含むことが好ましい。これにより、加湿空気中の１種以上の可燃性ガスを充分に分離検知することができる。 The method for analyzing a combustible gas according to the present embodiment performs principal component analysis on data including response values of a plurality of types of n-type semiconductor type semiconductor gas sensor elements and one or more types of p-type semiconductor type semiconductor gas sensor elements. It is preferable to further include a step. Thereby, 1 or more types of combustible gas in humidified air can fully be separated and detected.
本実施形態の可燃性ガスの分析方法は、例えば、医療分野では、呼気を検知することにより、健康状態を管理するシステム、食品分野では、食品を管理するシステムに適用することができる。 The method for analyzing combustible gas according to the present embodiment can be applied to a system for managing health by detecting exhalation in the medical field, and a system for managing food in the food field, for example.
以下に、本発明の実施例を説明するが、本発明は、以下の実施例によって、何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
［実施例１］
実施例１では、６種のｎ型半導体型の半導体式ガスセンサ素子（２種のＳｎＯ２＋Ｍ（ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２））、ＺｎＯ、ＺｎＯ＋Ｍ、ＦｅＺｒＯ、ＦｅＺｒＯ＋Ｍ）と、２種のｐ型半導体型の半導体式ガスセンサ素子（ＬａＦｅＯ３、ＬａＦｅＯ３＋Ｍ）の合計８種のガスセンサ素子を用いた。具体的には、上面に櫛型電極を４個、下面にヒータパターンを有するガスセンサ用の基板（図１、２参照）２枚に、それぞれ異なる４個の半導体式ガスセンサ素子を搭載した小型のガスセンサ２個からなるガスセンサ群を作製した。
[Example 1]
In Example 1, six types of n-type semiconductor type semiconductor gas sensor elements (two types of SnO 2 + M (SnO 2 + M (1), SnO 2 + M (2)), ZnO, ZnO + M, FeZrO, FeZrO + M), A total of eight types of gas sensor elements of two types of p-type semiconductor type semiconductor gas sensor elements (LaFeO 3 , LaFeO 3 + M) were used. Specifically, a small gas sensor in which four different semiconductor gas sensor elements are mounted on two gas sensor substrates (see FIGS. 1 and 2) each having four comb-shaped electrodes on the upper surface and a heater pattern on the lower surface. A group of two gas sensors was produced.
以下、用いた８種のガスセンサ素子について説明する。 Hereinafter, the eight types of gas sensor elements used will be described.
ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）は、それぞれ産業技術総合研究所で作製した、Ｐｔ、Ｐｄ及びＡｕが各１質量％添加されているＳｎＯ２を感応部とするガスセンサ素子である（Sens. Actuators B 187(2013)135-141参照）。ここで、様々なＶＯＣに対して、一定の感度を示すようにするため、ＳｎＯ２にＰｔ、Ｐｄ及びＡｕを添加して高度化している。ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）は、製法を調整することにより、感応部の厚さが異なる。ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）の感応部の厚さを直接測定することはできないが、同様の製法で作製したＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）の厚さは、それぞれ４．６μｍ及び２．８μｍであった。このため、ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）は、応答特性が異なる。なお、ＳｎＯ２＋Ｍ（１）、ＳｎＯ２＋Ｍ（２）は、上記文献に記載されている方法に従って作製した。 SnO 2 + M (1) and SnO 2 + M (2) are gas sensor elements made by the National Institute of Advanced Industrial Science and Technology, each having SnO 2 added with 1% by mass of Pt, Pd, and Au as sensitive parts. (See Sens. Actuators B 187 (2013) 135-141). Here, in order to show a certain sensitivity to various VOCs, Pt, Pd, and Au are added to SnO 2 to make it more sophisticated. SnO 2 + M (1) and SnO 2 + M (2) differ in the thickness of the sensitive part by adjusting the production method. Although the thickness of the sensitive part of SnO 2 + M (1) and SnO 2 + M (2) cannot be directly measured, the thickness of SnO 2 + M (1) and SnO 2 + M (2) produced by the same manufacturing method Were 4.6 μm and 2.8 μm, respectively. For this reason, SnO 2 + M (1) and SnO 2 + M (2) have different response characteristics. SnO 2 + M (1) and SnO 2 + M (2) were prepared according to the method described in the above-mentioned document.
ＺｎＯ、ＺｎＯ＋Ｍは、それぞれ産業技術総合研究所で作製した、ＺｎＯを感応部とするガスセンサ素子、Ｐｔ、Ｐｄ及びＡｕが各１質量％添加されているＺｎＯを感応部とするガスセンサ素子である。ここで、ＺｎＯは、酸化セリウム粒子の製法（Sensors 2015, 15, 9427-9437参照）を参考にして、硝酸亜鉛水溶液に水酸化ナトリウム水溶液を滴下して水酸化亜鉛の沈殿物を得た後、カーボンパウダーと均一に混合し、焼成することで、作製した。ＺｎＯ＋Ｍは、ＳｎＯ２＋Ｍと同様にして、作製した。 ZnO and ZnO + M are gas sensor elements having ZnO as a sensitive part and gas sensor elements having ZnO added with 1% by mass of Pt, Pd, and Au, respectively, manufactured by AIST. Here, ZnO was obtained by dropping a sodium hydroxide aqueous solution into a zinc nitrate aqueous solution by referring to a method for producing cerium oxide particles (see Sensors 2015, 15, 9427-9437). It was produced by uniformly mixing with carbon powder and firing. ZnO + M was produced in the same manner as SnO 2 + M.
ＦｅＺｎＯ、ＦｅＺｎＯ＋Ｍは、それぞれ産業技術総合研究所で作製した、Ｆｅ２Ｏ３とＺｎＯの混合物を感応部とするガスセンサ素子、Ｐｔ、Ｐｄ及びＡｕが各１質量％添加されている、Ｆｅ２Ｏ３とＺｎＯの混合物を感応部とするガスセンサ素子である。ここで、ＦｅＺｎＯは、酸化セリウム粒子の製法（Sensors 2015, 15, 9427-9437参照）を参考にして、硝酸鉄と硝酸ジルコニルの混合水溶液にアンモニア水を滴下して混合水酸化物の沈殿物を得た後、カーボンパウダーを均一に混合し、焼成することで、作製した。ＦｅＺｎＯ＋Ｍは、ＳｎＯ２＋Ｍと同様にして、作製した。 FeZnO and FeZnO + M are each a gas sensor element produced by the National Institute of Advanced Industrial Science and Technology using a mixture of Fe 2 O 3 and ZnO as a sensitive part, and Pt, Pd, and Au are added in an amount of 1% by mass, Fe 2 O 3 Is a gas sensor element having a mixture of ZnO and ZnO as a sensitive part. Here, with regard to FeZnO, referring to the method for producing cerium oxide particles (Sensors 2015, 15, 9427-9437), ammonia water is dropped into a mixed aqueous solution of iron nitrate and zirconyl nitrate to form a mixed hydroxide precipitate. After being obtained, carbon powder was uniformly mixed and fired. FeZnO + M was produced in the same manner as SnO 2 + M.
ＬａＦｅＯ３、ＬａＦｅＯ３＋Ｍは、それぞれ産業技術総合研究所で作製した、ＬａＦｅＯ３を感応部とするガスセンサ素子、Ｐｔ、Ｐｄ及びＡｕが各１質量％添加されているＬａＦｅＯ３を感応部とするガスセンサ素子である。ここで、ＬａＦｅＯ３は、酸化セリウム粒子の製法（Sensors 2015, 15, 9427-9437参照）を参考にして、硝酸鉄と硝酸ランタンの混合水溶液にアンモニア水を滴下して混合水酸化物の沈殿物を得た後、カーボンパウダーを均一に混合し、焼成することで、作製した。ＬａＦｅＯ３＋Ｍは、ＳｎＯ２＋Ｍと同様にして、作製した。ＬａＦｅＯ３、ＬａＦｅＯ３＋Ｍは、可燃性ガスの存在下で電気抵抗が増大する応答を示すことから、ｐ型半導体型の半導体式センサに分類される。 LaFeO 3, LaFeO 3 + M was prepared in AIST each gas sensor for the gas sensor element to a LaFeO 3 and sensitive part, Pt, a LaFeO 3 of Pd and Au are added each 1 wt% and the sensitive part It is an element. Here, LaFeO 3 is a precipitate of mixed hydroxide by dropping ammonia water into a mixed aqueous solution of iron nitrate and lanthanum nitrate with reference to the production method of cerium oxide particles (see Sensors 2015, 15, 9427-9437). Then, carbon powder was uniformly mixed and fired. LaFeO 3 + M was produced in the same manner as SnO 2 + M. LaFeO 3 and LaFeO 3 + M are classified as p-type semiconductor type semiconductor sensors because they show a response in which electric resistance increases in the presence of a combustible gas.
以上の８種のガスセンサ素子は、基板の最高温度が概ね３００℃となるように駆動させた。図２に示す基板の下面のヒータパターンは、白金の厚膜であり、図中、左から３ｍｍ程度を境に、左側のパターンは、右側の２本の太い配線よりも配線が細くなっており、電流密度が増大するため、左のパターンは発熱する。なお、右側の２本の細い配線は、４端子法で電圧を制御する配線である。図１に示す基板の上面の４個の櫛型電極は、左側の２個の櫛型電極が発熱箇所の真上になり、右側の２個の櫛型電極が発熱箇所から外れた箇所にある。これにより、駆動温度に差をつけることができ、最適温度の高いガスセンサ素子を左側に、最適温度の低いガスセンサ素子を右側に配置することで、同一の基板に最適温度の異なるガスセンサ素子を配置することができる。 The above eight types of gas sensor elements were driven so that the maximum temperature of the substrate was approximately 300 ° C. The heater pattern on the lower surface of the substrate shown in FIG. 2 is a thick platinum film. In the drawing, the pattern on the left side is thinner than the two thick lines on the right side, about 3 mm from the left. Since the current density increases, the left pattern generates heat. Note that the two thin wires on the right are wires that control the voltage by the four-terminal method. The four comb-shaped electrodes on the upper surface of the substrate shown in FIG. 1 have the two left comb-shaped electrodes right above the heat generating portion and the two right comb-shaped electrodes are out of the heat generating portion. . Accordingly, it is possible to make a difference in driving temperature, and by arranging gas sensor elements having a high optimum temperature on the left side and gas sensor elements having a low optimum temperature on the right side, gas sensor elements having different optimum temperatures are arranged on the same substrate. be able to.
図３に、本実施例で使用した計測システムのガスフロー図を示す。 FIG. 3 shows a gas flow diagram of the measurement system used in this example.
２個のガスセンサは、ガス雰囲気の制御が可能なセンサ室１に入れて密閉した。 The two gas sensors were sealed in a sensor chamber 1 capable of controlling the gas atmosphere.
次に、センサ室１へ流すガスについて具体的に説明する。 Next, the gas flowing into the sensor chamber 1 will be specifically described.
まず、計測中のセンサ室１に流す窒素・酸素混合ガスの総流量は、常に５００ｍＬ／ｍｉｎとなるようにした。次に、計測中のセンサ室１に流す窒素と酸素の体積比は、常に４：１となるようにした。即ち、窒素の流量は、４００ｍＬ／ｍｉｎとなり、酸素の流量は１００ｍＬ／ｍｉｎとなる。このうち、窒素は、２００ｍＬ／ｍｉｎを蒸留水の入った水バブラー２に通じ、酸素は、全量の１００ｍＬ／ｍｉｎを蒸留水の入った水バブラー２に通じた。ここで、水バブラー２は、水温が常に２０℃となるように制御した。即ち、窒素２００ｍＬ／ｍｉｎ及び酸素１００ｍＬ／ｍｉｎは、水蒸気で飽和されており、乾燥状態の窒素２００ｍＬ／ｍｉｎと混合されて、センサ室１に到達するため、センサ室１に到達した時の窒素・酸素混合ガスの湿度は、２０℃換算で６０％ＲＨに相当する（以下、これを合成空気と表記する）。 First, the total flow rate of the nitrogen / oxygen mixed gas flowing into the sensor chamber 1 during measurement was always set to 500 mL / min. Next, the volume ratio of nitrogen and oxygen flowing into the sensor chamber 1 during measurement was always 4: 1. That is, the flow rate of nitrogen is 400 mL / min, and the flow rate of oxygen is 100 mL / min. Among these, nitrogen passed 200 mL / min to the water bubbler 2 containing distilled water, and oxygen passed 100 mL / min of the total amount to the water bubbler 2 containing distilled water. Here, the water bubbler 2 was controlled so that the water temperature was always 20 ° C. That is, nitrogen 200 mL / min and oxygen 100 mL / min are saturated with water vapor and mixed with dry nitrogen 200 mL / min to reach the sensor chamber 1. The humidity of the oxygen mixed gas corresponds to 60% RH in terms of 20 ° C. (hereinafter referred to as “synthetic air”).
本実施例で用いたターゲットＶＯＣは、アセトイン、ノナナール、デカン、アセトンの４種であり、センサ室１に到達した時の濃度が１ｐｐｍとなるように調整した。 The target VOCs used in this example were acetoin, nonanal, decane, and acetone, and the concentration when reaching the sensor chamber 1 was adjusted to 1 ppm.
これらのターゲットＶＯＣは、窒素ベースのガスボンベからのガス、又は、溶媒からガスを作製するガス発生器３としての、パーミエーター（ガステック社製）に窒素ガスを通じて作製した。具体的には、アセトンが前者に該当し、アセトイン、ノナナール、デカンが後者に該当する。これらのターゲットＶＯＣを流す際には、流したガスの流量に相当する分、乾燥状態の窒素の流量を減じることで、ガスの総流量５００ｍＬ／ｍｉｎ、窒素と酸素の体積比４：１を常に維持した。 These target VOCs were produced by passing nitrogen gas through a permeator (manufactured by Gastec) as a gas generator 3 for producing gas from a nitrogen-based gas cylinder or gas from a solvent. Specifically, acetone corresponds to the former, and acetoin, nonanal, and decane correspond to the latter. When flowing these target VOCs, the flow rate of dry nitrogen is reduced by an amount corresponding to the flow rate of the flowed gas, so that the total flow rate of gas is 500 mL / min and the volume ratio of nitrogen and oxygen is always 4: 1. Maintained.
主成分分析は、ガスセンサの応答値Ｓを用いた。なお、ｎ型半導体型の半導体式センサ素子の応答値Ｓは、式
Ｓ＝Ｒａ／Ｒｇ
（式中、Ｒａは、合成空気を流したときのガスセンサの電気抵抗であり、Ｒｇは、１ｐｐｍのターゲットＶＯＣを含む合成空気を流したときのガスセンサの電気抵抗である。）
により定義される。
In the principal component analysis, the response value S of the gas sensor was used. Note that the response value S of the n-type semiconductor type semiconductor sensor element is expressed by the equation S = Ra / Rg
(In the formula, Ra is the electric resistance of the gas sensor when synthetic air is flowed, and Rg is the electric resistance of the gas sensor when synthetic air containing 1 ppm of target VOC is flowed.)
Defined by
ｎ型半導体型の半導体式センサ素子は、ターゲットＶＯＣに対して、電気抵抗が減少する応答を示すのに対し、ｐ型半導体型の半導体式センサ素子は、ターゲットＶＯＣに対して、電気抵抗が増大する応答を示す。そのため、ｐ型半導体型の半導体式センサ素子の応答値Ｓは、式
Ｓ＝Ｒｇ／Ｒａ
により定義される。
An n-type semiconductor type semiconductor sensor element shows a response with a decrease in electrical resistance with respect to the target VOC, whereas a p-type semiconductor type semiconductor sensor element has an increase in electrical resistance with respect to the target VOC. Indicates a response to Therefore, the response value S of the p-type semiconductor type semiconductor sensor element is expressed by the formula S = Rg / Ra
Defined by
８種の半導体式ガスセンサ素子を用いて、４種のターゲットＶＯＣをそれぞれ２回計測した。得られた６４個の応答値Ｓを用いて主成分分析を実施した。 Each of four types of target VOCs was measured twice using eight types of semiconductor gas sensor elements. A principal component analysis was performed using the 64 response values S obtained.
図４に、第１主成分及び第２主成分による主成分得点と固有ベクトルを示す。各軸に各主成分の寄与率を示す。 FIG. 4 shows principal component scores and eigenvectors based on the first principal component and the second principal component. Each axis shows the contribution ratio of each main component.
図４から、第２主成分までの累積寄与率が８７．８％であることがわかる。これは、半導体式ガスセンサ素子８種のうち、７．０２４種分（＝８種×０．８７８）の価値が集約されていることを示す。図４に示す通り、アセトイン、ノナナール、デカン、アセトンの間の主成分得点が分離されており、充分に分離検知できることがわかる。 From FIG. 4, it can be seen that the cumulative contribution rate up to the second principal component is 87.8%. This shows that the value of 7.024 types (= 8 types × 0.878) is aggregated among the 8 types of semiconductor gas sensor elements. As shown in FIG. 4, the main component scores among acetoin, nonanal, decane, and acetone are separated, and it can be seen that sufficient separation detection is possible.
なお、図４中の矢印が示す各半導体式ガスセンサ素子の固有ベクトル（ただし、ＺｎＯとＳｎＯ２＋Ｍ（２）の矢印は重なっている）に着目すると、ｎ型半導体型の半導体式ガスセンサ素子に分類される６種の固有ベクトルは、概ね第１主成分の軸に平行方向か、やや右肩下がりの方向に平行である。これに対し、ｐ型半導体の半導体式センサ素子に分類される２種の固有ベクトルは、ｎ型半導体型の半導体式ガスセンサ素子の固有ベクトルに対し、概ね直交する方向で第２主成分の軸に概ね平行方向を示している。このことから、第２主成分の軸方向の分解能は、概ねｐ型半導体型の半導体式センサ素子が担っており、主成分得点の分離性の向上に寄与していると考えられる。 Note that the eigenvectors of the semiconductor gas sensor elements indicated by the arrows in FIG. 4 (however, the arrows of ZnO and SnO 2 + M (2) overlap) are classified as n-type semiconductor type semiconductor gas sensor elements. The six eigenvectors are generally parallel to the axis of the first principal component or slightly parallel to the downward direction. On the other hand, the two types of eigenvectors classified as p-type semiconductor semiconductor sensor elements are substantially parallel to the axis of the second principal component in a direction substantially perpendicular to the eigenvectors of the n-type semiconductor semiconductor gas sensor elements. Shows direction. From this, it can be considered that the axial resolution of the second principal component is generally borne by the p-type semiconductor type semiconductor sensor element and contributes to the improvement of the separation of the principal component score.
［比較例１］
比較例１では、６種のｎ型半導体型の半導体式ガスセンサ素子（ＳｎＯ２＋Ｍの２種、ＺｎＯ、ＺｎＯ＋Ｍ、ＦｅＺｒＯ、ＦｅＺｒＯ＋Ｍ）を用いた。なお、比較例１は、実施例１から、ｐ型半導体型の半導体式ガスセンサ素子を除去したものに相当する。
[Comparative Example 1]
In Comparative Example 1, six types of semiconductor gas sensor elements of n type semiconductor type (two types of SnO 2 + M, ZnO, ZnO + M, FeZrO, FeZrO + M) were used. In addition, the comparative example 1 is corresponded to what remove | excluded the p-type semiconductor type semiconductor type gas sensor element from Example 1. FIG.
図５に、第１主成分及び第２主成分による主成分得点と固有ベクトルを示す。各軸に各主成分の寄与率を示す。 FIG. 5 shows principal component scores and eigenvectors based on the first principal component and the second principal component. Each axis shows the contribution ratio of each main component.
図５から、第２主成分までの累積寄与率が９４．８％であることがわかる。これは、ガスセンサ６種のうち、５．６８８種分（＝６種×０．９４８）の価値が集約されていることを示す。また、図５から、実施例１（図４参照）と比較して、アセトンの主成分得点（▽）とノナナールの主成分得点（□）が近接していることがわかる。具体的には、アセトンとノナナールの主成分得点の第２主成分が、図４では正負に分かれていたが、図５では共に負であり、値もほぼ同一である。これは、実施例１で概ね第２主成分の軸方向の分解能を担っていたｐ型半導体型の半導体式ガスセンサの情報が失われたことに由来していると考えられる。 From FIG. 5, it can be seen that the cumulative contribution rate up to the second principal component is 94.8%. This indicates that the value of 5.688 types (= 6 types × 0.948) among the 6 types of gas sensors is aggregated. Moreover, it can be seen from FIG. 5 that the main component score (ア セ ト ン) of acetone and the main component score (□) of nonanal are close compared to Example 1 (see FIG. 4). Specifically, the second main component of the main component scores of acetone and nonanal is divided into positive and negative in FIG. 4, but in FIG. 5, both are negative and the values are almost the same. This is considered to be due to the loss of the information of the p-type semiconductor type semiconductor gas sensor that was responsible for the axial resolution of the second main component in Example 1.
１ センサ室
２ 水バブラー
３ ガス発生器
４ 弁
５ ニードル弁を有する流量計
６ 三方弁
７ クロスオーバー四方弁
DESCRIPTION OF SYMBOLS 1 Sensor chamber 2 Water bubbler 3 Gas generator 4 Valve 5 Flow meter with needle valve 6 Three-way valve 7 Crossover four-way valve
Claims (7)
複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子を有し、
前記ｎ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種と、前記ｐ型半導体型の半導体式ガスセンサ素子のうちの少なくとも１種が同一の基板上に配置されているガスセンサを含むことを特徴とするガスセンサ群。 A group of gas sensors used to detect flammable gases,
A plurality of types of n-type semiconductor type semiconductor gas sensor elements and one or more types of p-type semiconductor type semiconductor gas sensor elements;
It includes a gas sensor in which at least one of the n-type semiconductor type semiconductor gas sensor elements and at least one of the p-type semiconductor type gas sensor elements are arranged on the same substrate. Gas sensor group.
前記複数種のｎ型半導体型の半導体式ガスセンサ素子と、１種以上のｐ型半導体型の半導体式ガスセンサ素子が１種以上の可燃性ガスを検知して応答した応答値を得る工程を含むことを特徴とする可燃性ガスの分析方法。 A method for analyzing a combustible gas using the gas sensor group according to any one of claims 1 to 5,
Including a step of obtaining a response value by detecting the response of one or more types of combustible gas by the plurality of types of n-type semiconductor type semiconductor gas sensor elements and one or more types of p-type semiconductor type semiconductor gas sensor elements. A method for analyzing flammable gas.
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