TW201250239A - Gas detection device and gas detection method - Google Patents

Gas detection device and gas detection method Download PDF

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TW201250239A
TW201250239A TW101103511A TW101103511A TW201250239A TW 201250239 A TW201250239 A TW 201250239A TW 101103511 A TW101103511 A TW 101103511A TW 101103511 A TW101103511 A TW 101103511A TW 201250239 A TW201250239 A TW 201250239A
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layer
heater layer
temperature
gas
gas detecting
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TW101103511A
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TWI445953B (en
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Makoto Okamura
Takuya Suzuki
Takahiko Maeda
Hisao Ohnishi
Toshiro Nakayama
Atsushi Nonaka
Takashi Nakajima
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Fuji Electric Co Ltd
Osaka Gas Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid

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Abstract

Provided are a gas detection device and a gas detection method which are capable of detecting gas with high accuracy while preventing an error detection by making it possible to sufficiently remove condensation water while maintaining a compact structure which allows easy installation and attaining low power consumption. The gas detection method for detecting gas on the basis of electric characteristics of a gas detection layer (6) by using a sensor element (1) having the gas detection layer (6), the electric characteristics of which change by being in contact with gas, and a heater layer (4) which is capable of heating the gas detection layer (6), in the state in which a voltage is intermittently applied to the heater layer (4) at a predetermined period t1 and is energized for a predetermined energizing time t2, thereby heating the gas detection layer (6). In the gas detection method, the condensation or extra water on the gas detection layer (6) is detected for, and if the condensation or extra water on the gas detection layer (6) is detected, an energizing time t2' with respect to the heater layer (4) is set to be longer than the predetermined energizing time t2, or the period t1 during which the heater layer (4) is energized is set to be shorter than a predetermined period t1'.

Description

201250239 六、發明說明： 【發明所屬之技術領域】 本發明是有關利用感測器元件來檢測氣體的氣體檢測 裝置及氣體檢測方法，該感測器元件係具有藉由與氣體的 接觸而電氣特性變化之氣體檢測層、及可加熱前述氣體檢 測層的加熱器層。 【先前技術】 一般，氣體感測器是使用在氣體檢測裝置等，構成對 於特定的氣體、例如CO (—氧化碳素）、CH4 (甲烷氣體 )、C3H8 (丙烷氣體）、CH3OH (甲醇蒸氣）等選擇性地 感應。有關如此的氣體感測器是其特性上被要求高感度、 高選擇性、高回應性、高可靠度、及低耗費電力。 並且，在使用氣體感測器的氣體檢測裝置之中，家庭 用的氣體洩漏警報器是以都市瓦斯（Town gas)用或丙烷 氣體用的可燃性氣體的檢測作爲目的者，以燃燒機器的不 完全燃燒氣體的檢測作爲目的者、或合倂該等雙方的機能 者等存在。然而，無論是那個的氣體洩漏警報器皆因爲高 成本或設置的難易性的問題而未廣泛普及。爲了廣泛普及 氣體洩漏警報器，特別要求改善設置性。爲了因應如此的 要求，驅動源使用電池的同時謀求無線化，藉此提供小型 的氣體感測器。驅動源使用電池時，使氣體感測器低耗費 電力化特別重要。然而，接觸燃燒式或半導體式的氣體感 測器是在被加熱至400 °C~5 00 °C的高溫的狀態下檢測氣體 201250239 。因此，爲了維持高溫狀態，需要耗費更多的電力，此在 使氣體感測器低耗費電力化上會成爲問題。 於是，在專利文獻1揭示間歇驅動的薄膜氣體感測器 1。如圖1所示，在此薄膜氣體感測器1中設有Si基板2 ，在Si基板2設有貫通孔2a。以能夠覆蓋此貫通孔2a的 開口之方式，在Si基板2上全體配設有熱絕緣支持層3。 有關熱絕緣支持層3的構成是在Si基板2上全體配設有 熱氧化Si02層3a，在熱氧化Si02層3a上全體配設有 CVD-Si3N4層3b，在CVD-Si3N4層3b上全體配設有CVD-Si02 層 3c。 而且，在熱絕緣支持層3上的中央部配設有加熱器層 4，以能夠覆蓋熱絕緣支持層3全體及加熱器層4的方式 配設有電氣絕緣層5。在電氣絕緣層5上的中央部配設有 氣體檢測層6。有關氣體檢測層6的構成是在電氣絕緣層 5上的中央部配設一對的接合層6a，在一對的接合層6a 上分別配設有感知層電極6b，且以能夠連結一對的感知層 電極6b之間的方式在電氣絕緣層5上配設有感知層6c。 更在電氣絕緣層5上以能夠覆蓋感知層電極6b及感知層 6c的方式配設有選擇燃燒層6d。因此，專利文獻1的薄 膜氣體感測器，藉由使用微細加工製程的隔膜構造等’高 絕熱性•低熱容量性佳。 有關在此薄膜氣體感測器1中進行的加熱器層4的間 歇驅動，是例如在檢測出CH4、C3H8等的可燃性氣體時’ 以50ms〜500ms的一定時間對加熱器層4施加電壓而通電 201250239 (High狀態），使加熱器層4的溫度能夠成爲4〇0°C〜 5 00 °C的高溫，藉由感知層電極6b來測定感知層6c的電 阻値，由該電阻値的變化來檢測出CH4、C3H8等的可燃性 氣體濃度。在處於高溫下的選擇燃燒層6d中，藉由使CO 、H2 (氫）等的還元性氣體及其他的雜氣燃燒，不活性的 CH4、C3H8等的可燃性氣體會透過選擇燃燒層6d而擴散 ，且到達感知層6c而與感知層6c的Sn〇2反應的結果， Sn02的電阻値會變化，所以利用此來檢測出氣體機器等的 氣體洩漏時所發生的CH4、C3H8等的可燃性氣體的濃度。 而且，一定時間設定不對加熱器層4施加電壓，不通電的 狀態（Off狀態）。如此的間歇驅動是被稱爲High· Off驅 動，以預定的週期（例如60秒週期）重複High狀態及 Off狀態。 並且，在檢測不完全燃燒時所發生的C0時，以50ms 〜5 00ms的一定時間對加熱器層4施加電壓而通電（High 狀態），使加熱器層4的溫度能夠一旦成爲400°C〜500°C 的高溫狀態，在進行薄膜氣體感測器1的洗滌之後，施加 電壓而通電（Low狀態），使加熱器層4的溫度能夠降溫 成約1 00°C的低溫狀態，在此低溫狀態下檢測C0。此時， 可知C0感度及選擇性會變高。而且，一定時間設定不對 加熱器層4施加電壓，不通電的狀態（〇ff狀態）。如此 的間歇驅動是被稱爲High-Low-Off驅動，以預定的週期 (例如150秒週期）來重複High狀態、Low狀態、及 狀態。 -5- 201250239 而且，在Low狀態中進行CO檢測，且在High狀態 中除了薄膜氣體感測器1的洗滌以外也進行甲烷檢測，藉 此可在1個的薄膜氣體感測器1中檢測甲烷及CO的雙方 [先行技術文獻] [專利文獻] [專利文獻1]特開2005-164566號公報 【發明內容】 (發明所欲解決的課題） 然而，在上述的間歇驅動中加熱器層4爲Off狀態的 期間，加熱器層4的溫度會降低至周圍的溫度。因此，薄 膜氣體感測器1容易受到周圍溫溼度的影響。特別是在接 受急劇的周圍溫溼度變化的影響時，包含氣體檢測層6的 薄膜氣體感測器1全體恐有結露之虞。當薄膜氣體感測器 1結露時，薄膜氣體感測器1的各要素的電阻會大幅度降 低，恐有錯誤發出氣體洩漏普報之虞。 本發明是有鑑於如此的實情而硏發者，其目的是在於 提供一種維持設置容易小型的構造，且謀求低耗費電力化 的同時，可充分地除去結露的水分，藉此防止誤檢測，而 可成爲精度高的氣體檢測之氣體檢測裝置及氣體檢測方法 -6- 201250239 (用以解決課題的手段） 爲了解決課題，本發明的氣體檢測裝置之一形態，係 具備= 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 暦， 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間；及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲： 設有用以檢測前述氣體檢測層的結露之結露檢測部， 當前述結露檢測部檢測到前述氣體檢測層的結露時， 將往前述加熱器層的通電時間控制成比前述預定的通電時 間長，或將通電至前述加熱器層的週期控制成比前述預定 的週期短。 此情況，本發明的氣體檢測裝置之一形態是如以下那 樣構成爲理想。 (1 )前述結露檢測部係構成測定前述預定的通電時 間內形成一定的前述加熱器層的溫度，當前述測定的加熱 器層的溫度爲預定的溫度以下時，檢測前述氣體檢測層的 結露，或 (2 )前述結露檢測部係構成在前述預定的通電時間 201250239 內的預定的時間測定前述加熱器層的溫度，當前述測定的 加熱器層的溫度與前述加熱器層的加熱目標溫度的比之溫 度回應性爲預定的比例以下時，檢測前述氣體檢測層的結 露。 而且，前述結露檢測部係構成測定前述加熱器層的電 阻値，由前述預定的時間內測定的前述加熱器層的電阻値 、及預先求取的前述加熱器層的電阻溫度係數、基準溫度 、及前述基準溫度的前述加熱器層的電阻値來算出前述加 熱器層的溫度，藉此構成測定前述加熱器層的溫度。 又，爲了解決課題，本發明的氣體檢測裝置之另一形 態，係具備： 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 層； 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間；及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲： 設有水分檢測部，其係檢測利用前述加熱器層之前述 氣體檢測層的加熱後留在前述氣體檢測層的水分， 當前述水分檢測部檢測到留在前述氣體檢測層的水分 時，將往前述加熱器層的通電時間控制成比前述預定的通 -8- 201250239 電時間長，或將通電至前述加熱器層的週期控制成比前述 預定的週期短。 此情況，本發明的氣體檢測裝置之另一形態是如以下 那樣構成爲理想。 前述水分檢測部係構成在前述預定的通電時間內的預 定的時間測定前述加熱器層的溫度，當前述測定的加熱器 層的溫度與前述加熱器層的加熱目標溫度的比之溫度回應 性爲預定的比例以下時，檢測留在前述氣體檢測層的水分 而且，前述水分檢測部係構成測定前述加熱器層的電 阻値，由前述預定的時間內測定的前述加熱器層的電阻値 、及預先求取的前述加熱器層的電阻溫度係數、基準溫度 、以及前述基準溫度的前述加熱器層的電阻値來算出前述 加熱器層的溫度，藉此測定前述加熱器層的溫度。 爲了解決課題，本發明的氣體檢測方法之一形態，係 利用具有藉由與氣體的接觸而電氣特性變化的氣體檢測層 及可加熱前述氣體檢測層的加熱器層之感測器元件，在以 預定的週期來間歇性地對前述加熱器層施加電壓而通電預 定的通電時間，藉此在加熱氣體檢測層的狀態下，根據前 述氣體檢測層的電氣特性來檢測氣體之氣體檢測方法，其 特徵係包含： 檢測前述氣體檢測層的結露之步驟；及 當檢測到前述氣體檢測層的結露時，使往前述加熱器 層的通電時間比前述預定的通電時間長，或使通電至前述 201250239 加熱器層的週期比前述預定的週期短之步驟。 此情況，本發明的氣體檢測方法之一形態是如以下那 樣構成爲理想。 (1 )檢測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內形成一定的前述加熱器層 的溫度之步驟；及 當前述測定的加熱器層的溫度爲預定的溫度以下時， 檢測前述氣體檢測層的結露之步驟。 (2)檢測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫度在 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的加熱 目標溫度的比之溫度回應性爲預定的比例以下時，檢測前 述氣體檢測層的結露之步驟。 而且，測定前述加熱器層的溫度之步驟包含： 測定通電狀態的前述加熱器層的電阻値之步驟；及 由前述測定的前述加熱器層的電阻値、及預先求取的 前述加熱器層的電阻溫度係數、基準溫度、以及前述基準 溫度的前述加熱器層的電阻値來算出前述加熱器層的溫度 之步驟。 又，爲了解決課題，本發明的氣體檢測方法之另一形 態，係利用具有藉由與氣體的接觸而電氣特性變化的氣體 -10- 201250239 檢測層及可加熱前述氣體檢測層的加熱器層之感測器 ，在以預定的週期來間歇性地對前述加熱器層施加電 通電預定的通電時間，藉此在加熱前述氣體檢測層的 下，根據前述氣體檢測層的電氣特性來檢測氣體之氣 測方法，其特徵係包含： 檢測利用前述加熱器層之前述氣體檢測層的加熱 在前述氣體檢測層的水分之步驟：及 當檢測到留在前述氣體檢測層的水分時，使往前 熱器層的通電時間比前述預定的通電時間長，或使通 前述加熱器層的週期比前述預定的週期短之步驟。 此情況，本發明的氣體檢測方法之另一形態是如 那樣構成爲理想。 檢測留在前述氣體檢測層的水分之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的 目標溫度的比之溫度回應性爲預定的比例以下時，檢 在前述氣體檢測層的水分之步驟。 而且，測定前述加熱器層的溫度之步驟包含： 在前述預定的時間內測定前述加熱器層的電阻値 驟；及 由測定的前述加熱器層的電阻値、及預先求取的 加熱器層的電阻溫度係數、基準溫度、以及前述基準 的前述加熱器層的電阻値來算出前述加熱器層的溫度 元件 壓而 狀態 體檢 後留 述加 電至 以下 度在 加熱 測留 之步 前述 溫度 之步 -11 - 201250239201250239 VI. Description of the Invention: [Technical Field] The present invention relates to a gas detecting device and a gas detecting method for detecting a gas using a sensor element having electrical characteristics by contact with a gas A gas detecting layer that changes and a heater layer that can heat the gas detecting layer. [Prior Art] Generally, a gas sensor is used in a gas detecting device or the like to constitute a specific gas such as CO (carbon monoxide), CH4 (methane gas), C3H8 (propane gas), and CH3OH (methanol vapor). Equally induced. Such gas sensors are required to be characterized by high sensitivity, high selectivity, high responsiveness, high reliability, and low power consumption. Further, among the gas detecting devices using the gas sensors, the gas leaking alarms for household use are aimed at detecting the flammable gas for urban gas or propane gas, and the burning device does not The detection of the complete combustion gas exists as a target person, or a function of both of them. However, no matter which gas leakage alarm is used, it is not widely used because of the high cost or the difficulty of setting. In order to widely popularize gas leak alarms, it is particularly required to improve the setness. In response to such a request, the drive source uses a battery while being wireless, thereby providing a small gas sensor. When the drive source uses a battery, it is particularly important to make the gas sensor low in power consumption. However, the contact gas or semiconductor type gas sensor detects gas at a high temperature of 400 ° C to 500 ° C. 201250239 . Therefore, in order to maintain a high temperature state, more power is required, which is a problem in that the gas sensor is low in power consumption. Thus, Patent Document 1 discloses an intermittently driven thin film gas sensor 1. As shown in FIG. 1, the thin film gas sensor 1 is provided with a Si substrate 2, and the Si substrate 2 is provided with a through hole 2a. The thermal insulating support layer 3 is entirely provided on the Si substrate 2 so as to cover the opening of the through hole 2a. The thermal insulation support layer 3 has a structure in which a thermal oxidation SiO 2 layer 3a is disposed on the Si substrate 2, and a CVD-Si3N4 layer 3b is disposed on the thermal oxidation SiO 2 layer 3a, and is entirely provided on the CVD-Si3N4 layer 3b. A CVD-SiO 2 layer 3c is provided. Further, a heater layer 4 is disposed at a central portion of the heat insulating support layer 3, and an electrically insulating layer 5 is disposed so as to cover the entire heat insulating support layer 3 and the heater layer 4. A gas detecting layer 6 is disposed at a central portion of the electrically insulating layer 5. The gas detecting layer 6 is configured such that a pair of bonding layers 6a are disposed at a central portion of the electrically insulating layer 5, and a sensing layer electrode 6b is disposed on each of the pair of bonding layers 6a, and a pair of the electrodes can be connected. A sensing layer 6c is disposed on the electrically insulating layer 5 in such a manner as to be between the sensing layer electrodes 6b. Further, the selective combustion layer 6d is disposed on the electrically insulating layer 5 so as to cover the sensing layer electrode 6b and the sensing layer 6c. Therefore, the film gas sensor of Patent Document 1 has a high heat insulating property and a low heat capacity by using a separator structure of a microfabrication process. In the intermittent driving of the heater layer 4 performed in the thin film gas sensor 1, for example, when a combustible gas such as CH4 or C3H8 is detected, a voltage is applied to the heater layer 4 for a certain period of time from 50 ms to 500 ms. When the current is applied to 201250239 (High state), the temperature of the heater layer 4 can be set to a high temperature of 4 〇 0 ° C to 500 ° C, and the resistance 値 of the sensing layer 6 c is measured by the sensing layer electrode 6 b. The concentration of flammable gas such as CH4, C3H8, etc. is detected. In the selective combustion layer 6d at a high temperature, by burning a regenerative gas such as CO or H2 (hydrogen) and other miscellaneous gases, inactive flammable gases such as CH4 and C3H8 pass through the selective combustion layer 6d. As a result of the diffusion and reaching the sensing layer 6c and reacting with the Sn2 of the sensing layer 6c, the resistance Sn of Sn02 changes. Therefore, the flammability of CH4, C3H8, etc. generated when a gas leaking in a gas device or the like is detected is detected. The concentration of the gas. Further, a state in which no voltage is applied to the heater layer 4 and no power is applied (off state) is set for a certain period of time. Such intermittent driving is called High·Off driving, and the High state and the Off state are repeated in a predetermined cycle (for example, a 60 second cycle). Further, when detecting C0 generated when incomplete combustion is performed, a voltage is applied to the heater layer 4 at a constant time of 50 ms to 500 ms to be energized (High state), and the temperature of the heater layer 4 can be 400 ° C. In the high temperature state of 500 ° C, after the washing of the thin film gas sensor 1 , a voltage is applied and energized (Low state), and the temperature of the heater layer 4 can be lowered to a low temperature state of about 100 ° C. C0 is detected below. At this time, it is understood that the C0 sensitivity and selectivity become high. Further, a state in which no voltage is applied to the heater layer 4 and no power is supplied (〇 ff state) is set for a certain period of time. Such an intermittent drive is called a High-Low-Off drive, and the High state, the Low state, and the state are repeated at a predetermined cycle (e.g., a 150 second cycle). -5- 201250239 Moreover, CO detection is performed in the Low state, and methane detection is performed in addition to the washing of the thin film gas sensor 1 in the High state, whereby methane can be detected in one thin film gas sensor 1 In the intermittent driving, the heater layer 4 is in the intermittent driving described above. [Patent Document 1] JP-A-2005-164566 (Patent Document 1) During the off state, the temperature of the heater layer 4 is lowered to the surrounding temperature. Therefore, the membrane gas sensor 1 is susceptible to the influence of ambient temperature and humidity. In particular, when the influence of a sudden change in ambient temperature and humidity is received, the entire film gas sensor 1 including the gas detecting layer 6 may be dew condensation. When the thin film gas sensor 1 is dew condensation, the resistance of each element of the thin film gas sensor 1 is drastically lowered, and there is a fear that a gas leak will be erroneously reported. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a structure that is easy to maintain and small in size, and that is capable of reducing power consumption while sufficiently reducing power of dew condensation, thereby preventing erroneous detection. Gas detection device and gas detection method capable of high-precision gas detection -6-201250239 (Means for Solving the Problem) In order to solve the problem, one aspect of the gas detection device of the present invention includes a sensor element. A gas detecting layer that changes electrical characteristics by contact with a gas, and a heater 可 that can heat the gas detecting layer, and a heater control unit that heats the gas detecting layer at a predetermined cycle a voltage is applied to the heater layer intermittently, and a predetermined energization time is applied; and a gas detecting unit detects the gas based on electrical characteristics of the gas detecting layer heated by the heater layer, and is characterized in that: a condensation detecting portion for detecting condensation of the gas detecting layer, wherein the condensation detecting portion detects the gas When condensation layer is measured, the time to the energization of the heater layer is controlled to a predetermined time than the energization time period, or the period of energization to the heater layer is controlled to be shorter than the predetermined period. In this case, one aspect of the gas detecting device of the present invention is preferably constructed as follows. (1) The condensation detecting unit is configured to detect a temperature at which the heater layer is formed to be constant in the predetermined energization time period, and to detect dew condensation of the gas detection layer when the temperature of the heater layer measured is equal to or lower than a predetermined temperature. Or (2) the condensation detecting unit configured to measure the temperature of the heater layer at a predetermined time within the predetermined energization time 201250239, and compare the temperature of the heater layer measured to the heating target temperature of the heater layer. When the temperature response is less than or equal to a predetermined ratio, the condensation of the gas detecting layer is detected. Further, the condensation detecting unit is configured to measure a resistance 値 of the heater layer, a resistance 値 of the heater layer measured in the predetermined time period, and a temperature coefficient of resistance and a reference temperature of the heater layer obtained in advance. The temperature of the heater layer is calculated by calculating the resistance 値 of the heater layer at the reference temperature, thereby constituting the temperature of the heater layer. Moreover, in another aspect of the gas detecting device of the present invention, the sensor device includes: a gas detecting layer that changes in electrical characteristics by contact with a gas, and a gas detecting element that can heat the gas a heater layer of a layer, wherein a heater control unit intermittently applies a voltage to the heater layer at a predetermined cycle to energize the gas detection layer, and energizes a predetermined energization time; and a gas detection unit The gas is detected based on the electrical characteristics of the gas detecting layer heated by the heater layer, and is characterized in that a moisture detecting unit is provided to detect the heating of the gas detecting layer by the heater layer and to remain in the foregoing In the moisture of the gas detecting layer, when the moisture detecting unit detects the moisture remaining in the gas detecting layer, the energization time to the heater layer is controlled to be longer than the predetermined time of the current period of -8 - 201250239, or the power is turned on. The period to the aforementioned heater layer is controlled to be shorter than the aforementioned predetermined period. In this case, another aspect of the gas detecting device of the present invention is preferably constructed as follows. The moisture detecting unit is configured to measure a temperature of the heater layer at a predetermined time during the predetermined energization time, and a temperature response ratio of a temperature of the heater layer measured to a heating target temperature of the heater layer is When the predetermined ratio is less than or equal to a predetermined ratio, the moisture remaining in the gas detecting layer is detected, and the moisture detecting unit is configured to measure the electric resistance of the heater layer, and the electric resistance of the heater layer measured in the predetermined time period and a predetermined The temperature of the heater layer is calculated by calculating the temperature coefficient of resistance of the heater layer, the reference temperature, and the resistance 値 of the heater layer of the reference temperature, thereby measuring the temperature of the heater layer. In order to solve the problem, one aspect of the gas detecting method of the present invention is a sensor element having a gas detecting layer that changes electrical characteristics by contact with a gas and a heater layer that can heat the gas detecting layer. A gas detection method for detecting a gas according to an electrical characteristic of the gas detection layer in a state where the gas detection layer is heated, by applying a voltage to the heater layer intermittently and discharging a predetermined energization time, in a predetermined cycle. The method includes: detecting a condensation of the gas detection layer; and detecting a condensation time of the gas detection layer, causing an energization time to the heater layer to be longer than the predetermined energization time, or energizing to the aforementioned 201250239 heater The step of the layer is shorter than the aforementioned predetermined period. In this case, one aspect of the gas detecting method of the present invention is preferably constructed as follows. (1) The step of detecting condensation of the gas detecting layer includes: measuring a temperature at which a predetermined temperature of the heater layer is formed in the predetermined energization time; and when the temperature of the heater layer measured as described above is a predetermined temperature or lower, The step of detecting condensation of the aforementioned gas detecting layer. (2) the step of detecting the condensation of the gas detecting layer comprises: measuring a temperature of the heater layer in the predetermined energization time for a predetermined time of the heater layer; and when the heater layer is determined as described above The step of detecting condensation of the gas detecting layer when the temperature response ratio of the temperature to the heating target temperature of the heater layer is less than a predetermined ratio. Further, the step of measuring the temperature of the heater layer includes: a step of measuring a resistance 値 of the heater layer in an energized state; and a resistance 値 of the heater layer measured as described above, and a predetermined heater layer of the heater layer The step of calculating the temperature of the heater layer by the resistance temperature coefficient, the reference temperature, and the resistance 値 of the heater layer of the reference temperature. Further, in order to solve the problem, another aspect of the gas detecting method of the present invention uses a gas having a change in electrical characteristics by contact with a gas -10-201250239 and a heater layer capable of heating the gas detecting layer. The sensor intermittently applies electric current to the heater layer for a predetermined energization time at a predetermined cycle, thereby detecting the gas gas according to the electrical characteristics of the gas detecting layer under heating of the gas detecting layer. The measuring method includes: detecting a step of heating the gas detecting layer in the gas detecting layer by using the gas detecting layer of the heater layer: and when detecting moisture remaining in the gas detecting layer, causing a forward heat device The energization time of the layer is longer than the predetermined energization time, or the step of passing the heater layer is shorter than the predetermined period. In this case, another aspect of the gas detecting method of the present invention is preferably configured as described above. The step of detecting the moisture remaining in the gas detecting layer includes: a step of measuring the temperature of the heater layer in the predetermined energization time for the predetermined time of the heater layer; and the temperature of the heater layer measured as described above When the ratio of the target temperature of the heater layer is lower than a predetermined ratio, the step of detecting the moisture of the gas detecting layer is performed. Further, the step of measuring the temperature of the heater layer includes: measuring a resistance of the heater layer in the predetermined time period; and measuring a resistance 値 of the heater layer and a heater layer obtained in advance The temperature coefficient of resistance, the reference temperature, and the resistance 値 of the heater layer of the above-mentioned reference are used to calculate the temperature element pressure of the heater layer, and the state is checked after the physical examination to the following step in the temperature of the heating measurement step - 11 - 201250239

[發明的效果] 若根據本發明的氣體檢測裝置之一形態，則可取得以 下的效果。 本發明的氣體檢測裝置，係具備： 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 層； 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間：及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲： 設有用以檢測前述氣體檢測層的結露之結露檢測部， 當前述結露檢測部檢測到前述氣體檢測層的結露時， 將往前述加熱器層的通電時間控制成比前述預定的通電時 間長，或將通電至前述加熱器層的週期控制成比前述預定 的週期短。 爲此，在一定時間內，往前述加熱器層的通電時間會 比結露檢測前更增加，藉此加熱前述氣體檢測層的時間會 增加。因此，藉由結露而附著於前述感測器元件的水分會 提前充分蒸發，前述感測器元件會從結露的狀態提前'陕復 -12- 201250239 至正常的狀態。所以，可將往前述加熱器層的電壓施加設 爲間歇性者，一面謀求低耗費電力化，一面防止誤檢測， 而來提高氣體檢測的精度。 又，若根據本發明的氣體檢測裝置之一形態，則可取 得以下的效果。 (1 )前述結露檢測部係構成測定前述預定的通電時 間內形成一定的前述加熱器層的溫度，當前述測定的加熱 器層的溫度爲預定的溫度以下時，檢測前述氣體檢測層的 結露，或 (2 )前述結露檢測部係構成在前述預定的通電時間 內的預定的時間測定前述加熱器層的溫度，當前述測定的 加熱器層的溫度與前述加熱器層的加熱目標溫度的比之溫 度回應性爲預定的比例以下時，檢測前述氣體檢測層的結 露。 而且，前述結露檢測部係構成測定前述加熱器層的電 阻値，由前述預定的時間內測定的前述加熱器層的電阻値 、及預先求取的前述加熱器層的電阻溫度係數、基準溫度 、以及前述基準溫度的前述加熱器層的電阻値來算出前述 加熱器層的溫度’藉此構成測定前述加熱器層的溫度。 爲此，不需要用以檢測結露的結露感測器或溫度感測 器等，前述感測器元件及氣體檢測裝置不會有因零件數量 增加而大型化的情況，可一面維持設置容易且小型的構造 ，一面將往前述加熱器層的電壓施加設爲間歇性者，謀求 低耗費電力化，且防止誤檢測，而來提高氣體檢測的精度 -13- 201250239 又，若根據本發明的氣體檢測裝置之另一形態，則可 取得以下的效果。 本發明的氣體檢測裝置，係具備： 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 層； 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間；及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲= 設有水分檢測部，其係檢測利用前述加熱器層之前述 氣體檢測層的加熱後留在前述氣體檢測層的水分， 當前述水分檢測部檢測到留在前述氣體檢測層的水分 時，將往前述加熱器層的通電時間控制成比前述預定的通 電時間長，或將通電至前述加熱器層的週期控制成比前述 預定的週期短。 爲此，在一定時間內，往前述加熱器層的通電時間會 比剩餘水分檢測前更增加，藉此加熱前述氣體檢測層的時 間會增加。因此，附著於前述感測器元件的剩餘水分會提 前充分蒸發，前述感測器元件可對應於剩餘水分附著那樣 的高溼度環境來提前恢復至正常的狀態。所以，可將往前 -14- 201250239 述加熱器層的電壓施加設爲間歇性者，一面謀求低耗費電 力化，一面防止誤檢測，而來提高氣體檢測的精度。 又，若根據本發明的氣體檢測裝置之另一形態，則可 取得以下的效果。 前述水分檢測部係構成在前述預定的通電時間內的預 定的時間測定前述加熱器層的溫度，當前述測定的加熱器 層的溫度與前述加熱器層的加熱目標溫度的比之溫度回應 性爲預定的比例以下時，檢測留在前述氣體檢測層的水分 〇 而且，前述水分檢測部係構成測定前述加熱器層的電 阻値，由前述預定的時間內測定的前述加熱器層的電阻値 、及預先求取的前述加熱器層的電阻溫度係數、基準溫度 、以及前述基準溫度的前述加熱器層的電阻値來算出前述 加熱器層的溫度，藉此測定前述加熱器層的溫度。 爲此，因爲藉由測定前述加熱器層的電阻値且檢測前 述加熱器層的溫度來進行剩餘水分的檢測，所以不需要用 以檢測剩餘水分的水分感測器或溫度感測器等，前述感測 器元件及前述氣體檢測裝置不會有因零件數量增加而大型 化的情況，可一面維持設置容易且小型的構造，一面將往 前述加熱器層的電壓施加設爲間歇性者，謀求低耗費電力 化，且防止誤檢測，而來提高氣體檢測的精度。 若根據本發明的氣體檢測方法之一形態，則可取得以 下的效果。 本發明的氣體檢測方法，係利用具有藉由與氣體的接 -15- 201250239 觸而電氣特性變化的氣體檢測層及可加熱前述氣體檢測層 的加熱器層之感測器元件，在以預定的週期來間歇性地對 前述加熱器層施加電壓而通電預定的通電時間，藉此在加 熱氣體檢測層的狀態下，根據前述氣體檢測層的電氣特性 來檢測氣體之氣體檢測方法，其特徵係包含： 檢測前述氣體檢測層的結露之步驟；及 當檢測到前述氣體檢測層的結露時，使往前述加熱器 層的通電時間比前述預定的通電時間長，或使通電至前述 加熱器層的週期比前述預定的週期短之步驟。 爲此，在一定時間內，往前述加熱器層的通電時間會 比結露檢測前更增加，藉此加熱前述氣體檢測層的時間會 增加。因此，藉由結露而附著於前述感測器元件的水分會 提前充分蒸發，前述感測器元件會從結露的狀態提前恢復 至正常的狀態。所以，可將往前述加熱器層的電壓施加設 爲間歇性者，一面謀求低耗費電力化，一面防止誤檢測， 而來提高氣體檢測的精度。 又，若根據本發明的氣體檢測方法之一形態，則可取 得以下的效果。 (η檢測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內形成一定的前述加熱器層 的溫度之步驟；及 當前述測定的加熱器層的溫度爲預定的溫度以下時， 檢測前述氣體檢測層的結露之步驟，或 -16- 201250239 (2 )檢測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫度在 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的加熱 目標溫度的比之溫度回應性爲預定的比例以下時，檢測前 述氣體檢測層的結露之步驟。 而且，測定前述加熱器層的溫度之步驟包含： 在前述預定的時間內測定前述加熱器層的電阻値之步 驟；及 由測定的前述加熱器層的電阻値、及預先求取的前述 加熱器層的電阻溫度係數、基準溫度、以及前述基準溫度 的前述加熱器層的電阻値來算出前述加熱器層的溫度之步 驟。 爲此，前述感測器元件可藉由測定前述加熱器層的溫 度或電阻値之簡單的方法來提前且確實地檢測結露而除去 結露，且可將往加熱器層的電壓施加設爲間歇性者，一面 謀求低耗費電力化，一面防止誤檢測，而來提高氣體檢測 的精度。 又，若根據本發明的氣體檢測方法之另一形態，則可 取得以下的效果。 本發明的氣體檢測方法，係利用具有藉由與氣體的接 觸而電氣特性變化的氣體檢測層及可加熱前述氣體檢測層 的加熱器層之感測器元件，在以預定的週期來間歇性地對 -17- 201250239 前述加熱器層施加電壓而通電預定的通電時間，藉此在前 述加熱氣體檢測層的狀態下，根據前述氣體檢測層的電氣 特性來檢測氣體之氣體檢測方法，其特徵係包含： 檢測利用前述加熱器層之前述氣體檢測層的加熱後留 在前述氣體檢測層的水分之步驟；及 當檢測到留在前述氣體檢測層的水分時，使往前述加 熱器層的通電時間比前述預定的通電時間長，或使通電至 前述加熱器層的週期比前述預定的週期短之步驟。 爲此，在一定時間內，往前述加熱器層的通電時間會 比剩餘水分檢測前更增加，藉此加熱前述氣體檢測層的時 間會增加。因此，附著於前述感測器元件的剩餘水分會提 前充分蒸發，前述感測器元件可對應於剩餘水分附著那樣 的高溼度環境來提前恢復至正常的狀態。所以，可將往前 述加熱器層的電壓施加設爲間歇性者，一面謀求低耗費電 力化，一面防止誤檢測，而來提高氣體檢測的精度。 又，若根據本發明的氣體檢測方法之另一形態，則可 取得以下的效果。 檢測留在前述氣體檢測層的水分之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫度在 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的加熱 目標溫度的比之溫度回應性爲預定的比例以下時，檢測留 在前述氣體檢測層的水分之步驟。 而且，測定前述加熱器層的溫度之步驟包含： -18- 201250239 在前述預定的時間內測定前述加熱器層的電阻値之步 驟；及 由測定的前述加熱器層的電阻値、及預先求取的前述 加熱器層的電阻溫度係數、基準溫度、以及前述基準溫度 的前述加熱器層的電阻値來算出前述加熱器層的溫度之步 驟。 爲此，前述感測器元件可藉由測定加熱器層的溫度或 電阻値之簡單的方法來提前且確實地檢測剩餘水分而除去 剩餘水分，且可將往前述加熱器層的電壓施加設爲間歇性 者，一面謀求低耗費電力化，一面防止誤檢測，而來提高 氣體檢測的精度。 【實施方式】 [第1實施形態] 以下說明有關本發明的第1實施形態的氣體檢測裝置 及氣體檢測方法。圖1是表示在本發明的第1實施形態的 氣體檢測裝置及氣體檢測方法中所使用的感測器元件的薄 膜氣體感測器1的槪略剖面圖。如圖1所示般、薄膜氣體 感測器1是具備Si基板2、熱絕緣支持層3、加熱器層4 、電氣絕緣層5、及氣體檢測層6。在S i基板2是設有貫 通孔2a。熱絕緣支持層3是具備熱氧化Si02層3a、CVD-Si3N4層3b、及CVD-Si02層3c。氣體檢測層6是具備接 合層6a、感知層電極6b、感知層6c、及選擇燃燒層6d。 另外，Si基板2是由矽晶圓所構成，加熱器層4是構成可 -19- 201250239 加熱氣體檢測層6，氣體檢測層6是構成例如對C0、CH4 、C3H8、CH3OH等選擇性地感應時電氣特性會變化。 說明如此的薄膜氣體感測器1的製造方法的一例。在 Si基板2的表面及背面形成熱氧化Si02層3a。其次，在 熱氧化Si02層3a上，藉由電漿CVD法來依序形成CVD-Si3N4 層 3b、及 CVD-Si〇2 層 3c。 而且，藉由濺射法來依序形成加熱器層4、及由Si02 所構成的電氣絕緣層5。其次，爲了形成氣體檢測層6， 在電氣絕緣層5上，藉由濺射法來依序形成接合層6a、感 知層電極6b、及摻雜Sb之Sn02所構成的感知層6c。在 第1實施形態中，利用濺射法的成膜是例如使用RF磁控 管濺射裝置爲理想。成膜條件是例如由Ta或Ti所構成的 接合層6a、及由Pt或Au所構成的感知層電極6b時，將 Ar氣體壓力設爲IPa，將基板溫度設爲300°C，將RF功率 設爲2W/cm2，將接合層6a及感知層電極6b的厚度分別 設爲500A及2000A爲理想。 以能夠充分地覆蓋感知層6c的方式，藉由網版印刷 法來塗佈選擇燃燒層6d，然後，在500°C的溫度下進行！ 小時以上燒結。選擇燃燒層6d是由在Al2〇3載持Pd作爲 觸媒的燒結材所構成。其次，藉由蝕刻來從Si基板2的 背面除去矽，形成貫通孔2a。另外，在此說明的薄膜氣體 感測器1的製造方法爲其一例，亦可使用其他的製造方法 〇 說明具備薄膜氣體感測器1的氣體檢測裝置的構成。 -20- 201250239 圖2是表示本發明的第1實施形態的氣體檢測裝置的構成 的槪略的方塊圖。若參照圖2，則在氣體檢測裝置是設有 微電腦控制電路7，微電腦控制電路7是構成控制氣體檢 測裝置的全體。在氣體檢測裝置是設有被連接至薄膜氣體 感測器1的加熱器層4的加熱器控制電路8，此加熱器控 制電路8是被連接至微電腦控制電路7。在氣體檢測裝置 是設有被連接至微電腦控制電路7及加熱器控制電路8的 電源電路9，氣體檢測裝置是構成藉由電源電路9來動作 。電源電路9的一例是可使用乾電池或充電池等的消耗電 池。電源電路9的其他例是亦可藉由商用電源及定電壓電 路來構成。 加熱器控制電路8是構成從電源電路9所供給的電壓 可變換成用以驅動薄膜氣體感測器1全體的感測器電壓及 用以加熱加熱器層4的加熱器電壓。如圖3所示般，有關 時間t與施加於加熱器層4的電壓V的關係，微電腦控制 電路7中所含的加熱器控制部7a是構成以時間t!的週期 ，重複在時間t2的期間對加熱器層4施加電壓V ,通電， 而使能夠提高加熱器層4的溫度來加熱氣體檢測層6，在 加熱器層4是被間歇性地通電。其一例可將時間t i設爲 60s〜150s，將時間t2設爲50ms〜500ms。 若再度參照圖2，則在氣體檢測裝置是設有被連接至 薄膜氣體感測器1的加熱器層4的結露檢測電路1 〇，此結 露檢測電路10是被連接至微電腦控制電路7，當薄膜氣體 感測器1尤其是氣體檢測層6結露時，結露會藉由微電腦 -21 - 201250239 控制電路7中所含的結露檢測部7b來檢測。在此其一例 爲具備結露檢測電路10被連接至加熱器層4的分流電阻 (未圖示），構成結露檢測部7b會測定分流電阻的兩端 電壓。在結露檢測電路1 0中，爲了將有關分流電阻的兩 端電壓的類比訊號變換成數位訊號來送至結露檢測部7b， 而設有A/D變換電路（未圖示）。在微電腦控制電路7中 ，構成可從結露檢測部7b傳達測得結露的訊息給加熱器 控制部7a。 在此，將藉由結露檢測電路1 〇所測定的加熱器電阻 的電阻値設爲R時，有關加熱器層4，若將形成基準的溫 度設爲基準溫度Tq ( °C )，將基準溫度T。的加熱器電阻 的基準電阻値設爲R〇(Q)，且將加熱器層4的電阻溫度 係數設爲a ( 1 /°C )，則加熱器層4的溫度T ( °C )是藉由 式（1 )來算出。 T= ( R/R〇-l ) /α + Τ〇 ...(1) 電阻溫度係數α，基準溫度TG的基準電阻値RG是預 先求取的數値》 預先求取電阻溫度係數α的方法，是將薄膜氣體感測 器1放入高溫爐，使高溫爐的溫度上昇，而來測定加熱器 層4的電阻値的變化。此時，將測定的電阻値與溫度的關 係顯示於圖4的圖表。如圖4所示般，有關複數的加熱器 層4的樣本，在約〇°C〜約50(TC的溫度範圍，加熱器層4 的電阻値是分別線形性地變化。將該等複數的加熱器層4 的樣本的傾斜度的平均設爲電阻溫度係數α»並且，基準 -22- 201250239 溫度To的基準電阻値RQ是從圖4的圖表預先讀取。 例如，電阻溫度係數α及基準電阻値R〇，在利用1片 的矽晶圓來製作的複數個薄膜感測器1中，因爲各薄膜感 測器1間的偏差少，所以亦可使用同樣的數値。而且，電 阻溫度係數α及基準電阻値Ro亦可按每批製造的薄膜感 測器1，使用同樣的數値。 結露檢測部7b是構成在通電至加熱器層4的時間 內測定形成一定的溫度T，當此溫度T形成結露檢測溫度 Ή以下時，檢測氣體檢測層6的結露，可將測得結露的訊 息傳達給加熱器控制部7a。其一例可想像，當結露檢測溫 度ΊΊ是將加熱加熱器層4的目標溫度之加熱目標溫度T2 設爲400°C~500°C的範圍時，考慮誤差等來對Τ2設爲-5°C ~〇°C的範圍。 若再度參照圖2，則在氣體檢測裝置設有被連接至薄 膜氣體感測器1的氣體檢測層6的氣體檢測電路1 1。氣體 檢測電路1 1是分別被連接至微電腦控制電路7所含的都 市瓦斯檢測部7c及CO氣體檢測部7d。都市瓦斯檢測部 7c是構成可根據氣體檢測層6的電氣特性來檢測例如都市 瓦斯中所含的CH4 (甲烷氣體）等。CO氣體檢測部7d也 是構成可根據氣體檢測層6的電氣特性來檢測CO (—氧 化碳素）。藉由氣體檢測層6來檢測氣體時，從氣體檢測 層6所發出的訊號是形成類比訊號。因此，在氣體檢測電 路1 1設有A/D變換電路（未圖示），用以將此類比訊號 變換成數位訊號’送至都市瓦斯檢測部7 c及C Ο氣體檢測 -23- 201250239 部7d。 在氣體檢測裝置設有啓報顯示電路12，用以在檢測氣 體時視覺性地顯示啓報，啓報顯示電路1 2是具備燈等的 啓報顯示部（未圖示）。此瞀報顯示電路12是被連接至 微電腦控制電路7中所含的顯示控制部7e。在氣體檢測裝 置設有笤報音輸出電路1 3，用以在檢測氣體時聽覺性地輸 出啓報，笤報音輸出電路1 3是具備喇叭等輸出警報作爲 聲音的啓報音輸出部（未圖示）。此普報音輸出電路13 是被連接至微電腦控制電路7中所含的瞢報音控制部7f。 在氣體檢測裝置設有外部輸出電路1 4，用以在檢測氣 體時進行電性的外部輸出，外部輸出電路14是構成可對 外部的機器傳送訊號等的電性的外部輸出。此外部輸出電 路14是被連接至微電腦控制電路7中所含的外部輸出控 制部7g。而且，在氣體檢測裝置設有被連接至微電腦控制 電路7的外部記憶電路15。此外部記憶電路15是構成可 記憶被使用在結露的水分除去及氣體檢測之臨界値及設定 値、以及檢測氣體而發出瞀報時之資料等的履歴。 另外，微電腦控制電路7是藉由微電腦等的CPU及 其周邊電路所構成》加熱器控制部7a、結露檢測部7b、 都市瓦斯檢測手段7c、CO氣體檢測部7d、顯示控制部7e 、曾報音控制部7f、及外部輸出控制部7g是藉由硬體或 軟體所構成。 參照圖5來說明本發明的第1實施形態的氣體檢測方 法。 -24- 201250239 如圖5所示的流程圖，以能夠加熱氣體檢測層6的方 式，在時間t2的期間對加熱器層4施加電壓而通電（S 1 ) ，在如此的通電狀態下，測定加熱器層4的電阻値R，根 據式（1 )藉由計算來測定加熱器層4的溫度T ( S2 ) ^ 其次，判斷加熱器層4的溫度T是否爲結露檢測溫度 以下（S3 )。當溫度T比結露檢測溫度Τι大時，判斷爲 無異常（S4 )，再度於時間t2的期間對加熱器層4施加電 壓而通電（S1)。另一方面，當加熱器層4溫度T爲結露 檢測溫度ΤΊ以下時，判斷成氣體檢測層6結露（S5 )， 而拉長對加熱器層4通電的時間，設爲時間t2 ’（ >t2 )( S6 )，在時間t2’的期間通電至加熱器層4的狀態下，測 定加熱器層4的電阻値R，而藉由計算來測定加熱器層4 的溫度T ( S2 )。 若如以上那樣根據本發明的第1實施形態，則在檢測 到結露時，拉長對加熱器層4施加電壓而通電的通電時間 t2，因此在一定時間內，往加熱器層4的通電時間會比結 露檢測前更增加，藉此加熱氣體檢測層6的時間會增加。 因此，藉由結露而附著於薄膜氣體感測器1的水分會提前 充分蒸發，薄膜氣體感測器1會從結露的狀態提前恢復至 正常的狀態。所以，可將往加熱器層4的電壓施加設爲間 歇性者’一面謀求低耗費電力化，一面防止誤檢測，而來 提高氣體檢測的精度。 若根據本發明的第1實施形態，則可藉由測定加熱器 層4的電阻値R且測定加熱器層4的溫度T來進行結露的 -25- 201250239 檢測，因此不需要用以檢測結露的結露感測器或溫度感測 器等，薄膜氣體感測器1及氣體檢測裝置不會有因零件數 量增加而大型化的情況，可一面維持設置容易且小型的構 造，一面將往加熱器層4的電壓施加設爲間歇性者，謀求 低耗費電力化，且防止誤檢測，而來提高氣體檢測的精度 〇 若根據本發明的第1實施形態，則薄膜氣體感測器1 可藉由測定加熱器層4的溫度或電阻値之簡單的方法來提 前且確實地檢測結露而除去結露，且可將往加熱器層4的 電壓施加設爲間歇性者，一面謀求低耗費電力化，一面防 止誤檢測，而來提高氣體檢測的精度。 [第2實施形態] 以下說明有關本發明的第2實施形態的氣體檢測裝置 及氣體檢測方法。第2實施形態的氣體檢測裝置及氣體檢 測方法的基本的構成是形成與第1實施形態的氣體檢測裝 置的構成同樣。與第1實施形態同樣的要素是利用與第1 實施形態问樣的符號及名稱來說明。在此是針對跑第1實 施形態不同的構成來進行說明。 若再度參照圖2 ’則結露檢測部7 b是在通電至加熱器 層4的時間tl內’測定預定的時間h ( 〇<t3<ti )的加熱器 層4的溫度T。g此加熱器層4的溫度τ與加熱器層4的 加熱目標溫度Τ'2的比之溫度回應性a ( =τ/Τ2 )爲結露檢 測溫度回應性A，以下時’檢測氣體檢測層6的結露，而 -26- 201250239 將檢測結露的情形傳達給加熱器控制部7 a。其一例可想像 將通電至加熱器層4的週期的時間tl設爲60s〜150s ,通 電至加熱器層4的時間t2設爲50ms~500ms時，將測定溫 度回應性A的時間t3設爲時間t2的中間的値，測定處於 加熱器層4的溫度上昇中的過渡狀態的加熱器層4的溫度 回應性 A，而且，可想像將加熱目標溫度 T2設爲 400°C〜500t：的範圍，有關結露檢測溫度回應性Α,是考慮 誤差等設爲9 5 % ~ 1 0 0 %。 參照圖6來說明本發明的第2實施形態的氣體檢測方 法。 如圖6所示的流程圖，以能夠加熱氣體檢測層6的方 式，在時間t2的期間對加熱器層4施加電壓而通電（S 1 1 )，在如此的通電狀態下，測定加熱器層4的電阻値R， 根據式（1)藉由計算來測定加熱器層4的溫度T，藉由 計算來測定此溫度T與加熱目標溫度T2的比之溫度回應 性A ( S 1 2 )。其次，判斷此溫度回應性Α是否爲結露檢 測溫度回應性A,以下（S 1 3 )。當溫度回應性A比結露檢 測溫度回應性Αι大時，判斷成無異常（S 14)，再度於時 間t2的期間對加熱器層4施加電壓而通電（S 1 1 )。另一 方面，當溫度回應性A爲結露檢測溫度回應性A!以下時 ，判斷成氣體檢測層6結露（S 1 5 )，而拉長對加熱器層 4通電的時間，設爲時間t2’（ >t2 ) ( S16 )，在時間t2’ 的期間通電至加熱器層4的狀態下，測定加熱器層4的電 阻値R，而藉由計算來測定加熱器層4的溫度T ’且藉由 -27- 201250239 計算來測定此溫度τ與加熱目標溫度Tz的比之溫度回應 性 A ( S 1 2 )。 如以上那樣根據本發明的第2實施形態’可取得與第 1實施形態同樣的效果。 [第3實施形態] 以下說明有關本發明的第3實施形態的氣體檢測裝置 及氣體檢測方法。第3實施形態的氣體檢測裝置及氣體檢 測方法的基本的構成是形成與第1實施形態的氣體檢測裝 置的構成同樣。與第1實施形態同樣的要素是利用與第1 實施形態同樣的符號及名稱來說明。在此是針對與第1實 施形態不同的構成來進行說明。 圖1所示的感知層6c爲構成多孔質構造或柱狀構造 ，感知層6c的比表面積會增加，感知層6c與檢測對象的 氣體的接觸面積會增加。並且，在選擇燃燒層6d，貴金屬 觸媒（例如Pd )爲了有效地燃燒除去非檢測對象的氣體 ，而使用多孔質體的γ-Α1203等作爲載體載持，在此多孔 質體中設置具有數nm〜數μιη直徑的多數個細孔。在如此 的細孔是藉由根據下記的式（2)的毛管凝縮來吸附水。 另外’式（2 )是「Kelvin的式」，在式（2)是將毛管的 半徑設爲]^(11〇 ，表面張力設爲γ( N/m )，液體（吸附 的水）的分子量設爲M( mol)，毛管壁與液體的接觸角 度設爲Θ (度），液體的比重設爲p( kg/m3 )，氣體定數 設爲Rgas ( J/mol · κ)，絶對溫度設爲Ta(K)，蒸氣壓 -28 - 201250239 與飽和蒸氣壓的相對壓設爲P/P0。 [數1] ^__2^cos^ …⑵ PRgjAj[Effects of the Invention] According to one aspect of the gas detecting device of the present invention, the following effects can be obtained. A gas detecting device according to the present invention includes: a sensor element having a gas detecting layer that changes in electrical characteristics by contact with a gas, and a heater layer that can heat the gas detecting layer; and a heater control unit In order to heat the gas detecting layer, a voltage is intermittently applied to the heater layer at a predetermined cycle, and a predetermined energization time is energized: and a gas detecting portion is heated according to the heater layer. The gas detecting layer is configured to detect a gas, and is characterized in that: a dew condensation detecting unit for detecting condensation of the gas detecting layer is provided, and when the dew condensation detecting unit detects dew condensation of the gas detecting layer, the heater is turned on The energization time of the layer is controlled to be longer than the aforementioned predetermined energization time, or the period of energization to the heater layer is controlled to be shorter than the predetermined period. For this reason, the energization time to the heater layer is increased more than before the condensation detection for a certain period of time, whereby the time for heating the gas detection layer is increased. Therefore, the moisture attached to the sensor element by condensation can be sufficiently evaporated in advance, and the sensor element is advanced from the state of condensation to the state of 'Shaanfu -12-201250239 to the normal state. Therefore, the application of the voltage to the heater layer can be intermittent, and the power consumption can be reduced, and erroneous detection can be prevented, thereby improving the accuracy of gas detection. Further, according to one aspect of the gas detecting device of the present invention, the following effects can be obtained. (1) The condensation detecting unit is configured to detect a temperature at which the heater layer is formed to be constant in the predetermined energization time period, and to detect dew condensation of the gas detection layer when the temperature of the heater layer measured is equal to or lower than a predetermined temperature. Or (2) the condensation detecting unit is configured to measure the temperature of the heater layer at a predetermined time during the predetermined energization time, and compare the temperature of the heater layer measured and the heating target temperature of the heater layer. When the temperature response is below a predetermined ratio, the condensation of the gas detecting layer is detected. Further, the condensation detecting unit is configured to measure a resistance 値 of the heater layer, a resistance 値 of the heater layer measured in the predetermined time period, and a temperature coefficient of resistance and a reference temperature of the heater layer obtained in advance. And calculating the temperature of the heater layer by the resistance 値 of the heater layer at the reference temperature, thereby constituting the temperature of the heater layer. Therefore, there is no need for a dew condensation sensor or a temperature sensor for detecting dew condensation, and the sensor element and the gas detecting device are not enlarged due to an increase in the number of parts, and the setting can be easily and small. In the structure, the application of the voltage to the heater layer is intermittent, and the power consumption is reduced, and the erroneous detection is prevented, thereby improving the accuracy of the gas detection. 13-201250239 Further, the gas detection according to the present invention In another aspect of the device, the following effects can be obtained. A gas detecting device according to the present invention includes: a sensor element having a gas detecting layer that changes in electrical characteristics by contact with a gas, and a heater layer that can heat the gas detecting layer; and a heater control unit In order to heat the gas detecting layer, a voltage is intermittently applied to the heater layer at a predetermined cycle, and a predetermined energization time is applied; and a gas detecting portion is heated according to the heater layer. The gas detecting layer is configured to detect a gas, and is characterized in that: a moisture detecting unit that detects moisture remaining in the gas detecting layer after heating of the gas detecting layer of the heater layer is used, and the moisture detecting is performed. When detecting the moisture remaining in the gas detecting layer, controlling the energization time to the heater layer to be longer than the predetermined energization time, or controlling the period of energization to the heater layer to be shorter than the predetermined period . For this reason, the energization time to the heater layer is increased more than before the residual moisture detection for a certain period of time, whereby the time for heating the gas detecting layer is increased. Therefore, the remaining moisture adhering to the aforementioned sensor element is sufficiently evaporated in advance, and the aforementioned sensor element can be restored to a normal state in advance in response to a high-humidity environment such as residual moisture adhesion. Therefore, it is possible to increase the voltage detection by applying the voltage of the heater layer to the previous -14-201250239, and to prevent the erroneous detection while improving the accuracy of the gas detection while reducing the power consumption. Further, according to another aspect of the gas detecting device of the present invention, the following effects can be obtained. The moisture detecting unit is configured to measure a temperature of the heater layer at a predetermined time during the predetermined energization time, and a temperature response ratio of a temperature of the heater layer measured to a heating target temperature of the heater layer is When the predetermined ratio is equal to or lower than the predetermined ratio, the moisture detecting unit is configured to detect the moisture remaining in the gas detecting layer, and the moisture detecting unit is configured to measure the electric resistance 値 of the heater layer, and the electric resistance of the heater layer measured in the predetermined time period, and The temperature of the heater layer is calculated by calculating the temperature coefficient of the heater layer of the heater layer, the reference temperature, and the resistance 値 of the heater layer in the reference temperature, thereby measuring the temperature of the heater layer. Therefore, since the residual moisture is detected by measuring the resistance 値 of the heater layer and detecting the temperature of the heater layer, a moisture sensor or a temperature sensor or the like for detecting residual moisture is not required. The sensor element and the gas detecting device are not increased in size due to an increase in the number of components, and the voltage applied to the heater layer can be intermittently maintained while maintaining a small and easy-to-install structure. It is electrically powered and prevents false detection, which improves the accuracy of gas detection. According to one aspect of the gas detecting method of the present invention, the following effects can be obtained. The gas detecting method of the present invention utilizes a gas detecting layer having a change in electrical characteristics by a contact with a gas -15 - 201250239 and a sensor element capable of heating the heater layer of the gas detecting layer, at a predetermined A gas detecting method for detecting a gas according to an electrical characteristic of the gas detecting layer in a state where the gas detecting layer is heated, by applying a voltage to the heater layer intermittently and periodically energizing a predetermined energization time. : a step of detecting condensation of the gas detecting layer; and when detecting condensation of the gas detecting layer, making an energization time to the heater layer longer than the predetermined energization time, or a period of energizing to the heater layer A step shorter than the aforementioned predetermined period. For this reason, the energization time to the heater layer is increased more than before the condensation detection for a certain period of time, whereby the time for heating the gas detection layer is increased. Therefore, moisture adhering to the aforementioned sensor element by condensation can be sufficiently evaporated in advance, and the aforementioned sensor element can be restored to a normal state from the state of dew condensation. Therefore, the application of the voltage to the heater layer can be intermittent, and the power consumption can be reduced, and erroneous detection can be prevented, thereby improving the accuracy of gas detection. Further, according to one aspect of the gas detecting method of the present invention, the following effects can be obtained. (n) the step of detecting the condensation of the gas detecting layer includes: measuring a temperature of forming a predetermined heater layer in the predetermined energization time; and detecting when the temperature of the heater layer measured is less than a predetermined temperature The step of dew condensation of the gas detecting layer, or -16-201250239 (2), the step of detecting the condensation of the gas detecting layer comprises: determining the temperature of the heater layer in the predetermined energization time for the predetermined time And a step of detecting the condensation of the gas detecting layer when the temperature response ratio of the temperature of the heater layer and the heating target temperature of the heater layer is less than a predetermined ratio. The step of the temperature of the heater layer includes: a step of measuring a resistance 値 of the heater layer within the predetermined time; and a resistance 値 of the heater layer measured and a resistance of the heater layer determined in advance The temperature coefficient, the reference temperature, and the resistance 値 of the heater layer of the reference temperature to calculate the foregoing The step of the temperature of the heater layer. For this reason, the sensor element can detect dew condensation in advance and surely by the simple method of measuring the temperature or resistance of the heater layer, and can remove the condensation. When the voltage application of the layer is intermittent, the accuracy of the gas detection can be improved while preventing the erroneous detection while reducing the power consumption. Further, according to another aspect of the gas detecting method of the present invention, the following can be obtained. The gas detecting method of the present invention uses a sensor element having a gas detecting layer that changes in electrical characteristics by contact with a gas and a heater layer that can heat the gas detecting layer, and is intermittent at a predetermined cycle. A gas detection method for detecting a gas according to the electrical characteristics of the gas detecting layer in a state in which the heating gas detecting layer is applied, by applying a voltage to the heater layer of -17 to 201250239, and energizing a predetermined energization time. The method includes: detecting moisture remaining in the gas detecting layer after heating of the gas detecting layer using the heater layer And when the moisture remaining in the gas detecting layer is detected, the energization time to the heater layer is longer than the predetermined energization time, or the period of energization to the heater layer is shorter than the predetermined period Therefore, for a certain period of time, the energization time to the heater layer is increased more than before the residual moisture detection, whereby the time for heating the gas detection layer is increased. Therefore, the remaining attached to the aforementioned sensor element The water is sufficiently evaporated in advance, and the sensor element can be restored to a normal state in advance in response to a high-humidity environment in which residual moisture adheres. Therefore, it is possible to apply the voltage to the heater layer intermittently. The power consumption is reduced, and the accuracy of gas detection is improved while preventing erroneous detection. Further, according to another aspect of the gas detecting method of the present invention, the following effects can be obtained. The step of detecting moisture remaining in the gas detecting layer includes: a step of measuring a temperature of the heater layer in the predetermined energization time for the predetermined time in the heater layer; and a temperature of the heater layer measured as described above The step of detecting the moisture remaining in the gas detecting layer when the temperature response ratio to the heating target temperature of the heater layer is less than a predetermined ratio. Further, the step of measuring the temperature of the heater layer includes: -18 - 201250239, the step of measuring the resistance 値 of the heater layer in the predetermined time period; and the resistance 値 of the heater layer measured, and predetermining The temperature coefficient of the heater layer, the reference temperature, and the resistance 値 of the heater layer of the reference temperature are used to calculate the temperature of the heater layer. Therefore, the sensor element can detect the remaining moisture in advance and surely by the simple method of measuring the temperature or resistance of the heater layer to remove the remaining moisture, and can apply the voltage to the heater layer. Intermittently, while reducing power consumption and reducing erroneous detection, the accuracy of gas detection is improved. [Embodiment] [First Embodiment] A gas detecting device and a gas detecting method according to a first embodiment of the present invention will be described below. Fig. 1 is a schematic cross-sectional view showing a membrane gas sensor 1 of a sensor element used in a gas detecting device and a gas detecting method according to a first embodiment of the present invention. As shown in Fig. 1, the thin film gas sensor 1 includes a Si substrate 2, a thermal insulating support layer 3, a heater layer 4, an electrically insulating layer 5, and a gas detecting layer 6. The S i substrate 2 is provided with a through hole 2a. The thermal insulation support layer 3 is provided with a thermally oxidized SiO 2 layer 3a, a CVD-Si 3 N 4 layer 3 b, and a CVD-SiO 2 layer 3 c. The gas detecting layer 6 includes a bonding layer 6a, a sensing layer electrode 6b, a sensing layer 6c, and a selective combustion layer 6d. Further, the Si substrate 2 is composed of a germanium wafer, and the heater layer 4 constitutes a heating gas detecting layer 6 of -19-201250239, and the gas detecting layer 6 is configured to selectively induce, for example, C0, CH4, C3H8, CH3OH, and the like. The electrical characteristics will change. An example of a method of manufacturing such a thin film gas sensor 1 will be described. A thermally oxidized SiO 2 layer 3a is formed on the front and back surfaces of the Si substrate 2. Next, on the thermally oxidized SiO 2 layer 3a, the CVD-Si3N4 layer 3b and the CVD-Si〇2 layer 3c are sequentially formed by a plasma CVD method. Further, the heater layer 4 and the electrically insulating layer 5 made of SiO 2 are sequentially formed by a sputtering method. Next, in order to form the gas detecting layer 6, a sensing layer 6c composed of a bonding layer 6a, a sensing layer electrode 6b, and a Sn doped Sb is sequentially formed on the electrically insulating layer 5 by a sputtering method. In the first embodiment, the film formation by the sputtering method is preferably an RF magnetron sputtering apparatus, for example. When the film formation conditions are, for example, the bonding layer 6a composed of Ta or Ti and the sensing layer electrode 6b composed of Pt or Au, the Ar gas pressure is IPa, the substrate temperature is 300 ° C, and the RF power is obtained. It is preferable that the thickness of the bonding layer 6a and the sensing layer electrode 6b is 500 A and 2000 A, respectively, in the case of 2 W/cm 2 . The selective combustion layer 6d is applied by a screen printing method in such a manner that the sensing layer 6c can be sufficiently covered, and then carried out at a temperature of 500 °C! Sintered over hours. The combustion layer 6d is selected to be composed of a sintered material in which Pd is supported as a catalyst in Al2〇3. Next, ruthenium is removed from the back surface of the Si substrate 2 by etching to form a through hole 2a. Further, the method of manufacturing the thin film gas sensor 1 described herein is an example thereof, and another manufacturing method may be used. 的 The configuration of the gas detecting device including the thin film gas sensor 1 will be described. -20-201250239 Fig. 2 is a schematic block diagram showing a configuration of a gas detecting device according to a first embodiment of the present invention. Referring to Fig. 2, the gas detecting means is provided with a microcomputer control circuit 7, and the microcomputer control circuit 7 is the entirety of the control gas detecting means. The gas detecting means is provided with a heater control circuit 8 connected to the heater layer 4 of the thin film gas sensor 1, and this heater control circuit 8 is connected to the microcomputer control circuit 7. The gas detecting device is provided with a power supply circuit 9 connected to the microcomputer control circuit 7 and the heater control circuit 8, and the gas detecting device is configured to operate by the power supply circuit 9. An example of the power supply circuit 9 is a battery that can use a dry battery or a rechargeable battery. Other examples of the power supply circuit 9 can also be constructed by a commercial power supply and a constant voltage circuit. The heater control circuit 8 is configured to convert the voltage supplied from the power supply circuit 9 into a sensor voltage for driving the entire thin film gas sensor 1 and a heater voltage for heating the heater layer 4. As shown in FIG. 3, the heater control unit 7a included in the microcomputer control circuit 7 is configured to repeat the period at time t2 with respect to the relationship between the time t and the voltage V applied to the heater layer 4. During the period, the voltage V is applied to the heater layer 4 and energized, so that the temperature of the heater layer 4 can be increased to heat the gas detecting layer 6, and the heater layer 4 is intermittently energized. For example, the time t i can be set to 60 s to 150 s, and the time t 2 can be set to 50 ms to 500 ms. Referring again to FIG. 2, the gas detecting device is provided with a condensation detecting circuit 1 被 connected to the heater layer 4 of the thin film gas sensor 1, and the condensation detecting circuit 10 is connected to the microcomputer control circuit 7, when When the thin film gas sensor 1 is in particular dew condensation of the gas detecting layer 6, the condensation is detected by the condensation detecting portion 7b included in the control circuit 7 of the microcomputer-21 - 201250239. Here, as an example, a shunt resistor (not shown) having the dew condensation detecting circuit 10 connected to the heater layer 4 is provided, and the dew condensation detecting unit 7b measures the voltage across the shunt resistor. In the condensation detecting circuit 10, an analog/digital conversion circuit (not shown) is provided in order to convert the analog signal of the voltages of the two terminals of the shunt resistor into a digital signal and send it to the condensation detecting unit 7b. In the microcomputer control circuit 7, a message for transmitting the measured condensation from the condensation detecting unit 7b is configured to the heater control unit 7a. Here, when the resistance 値 of the heater resistor measured by the condensation detecting circuit 1 値 is R, the reference temperature is set as the reference temperature Tq ( ° C ) with respect to the heater layer 4 . T. The reference resistance 値 of the heater resistor is set to R 〇 (Q), and the temperature coefficient of resistance of the heater layer 4 is set to a ( 1 /° C.), and the temperature T ( ° C ) of the heater layer 4 is borrowed. Calculated by the formula (1). T = ( R / R 〇 - l ) / α + Τ〇 (1) The temperature coefficient of resistance α, the reference resistance 値 RG of the reference temperature TG is a predetermined number 値 Predetermined by the temperature coefficient of resistance α The method is to measure the change in the resistance 値 of the heater layer 4 by placing the thin film gas sensor 1 in a high temperature furnace to raise the temperature of the high temperature furnace. At this time, the relationship between the measured resistance 値 and temperature is shown in the graph of Fig. 4 . As shown in FIG. 4, with respect to the sample of the plurality of heater layers 4, the resistance 値 of the heater layer 4 varies linearly in a temperature range of about 〇 ° C to about 50 (TC). The average of the inclination of the sample of the heater layer 4 is set to the temperature coefficient of resistance α», and the reference resistance 値RQ of the reference -22-201250239 temperature To is read in advance from the graph of Fig. 4. For example, the temperature coefficient of resistance α and the reference In the plurality of thin film sensors 1 fabricated by using one wafer of tantalum wafers, the same number of turns can be used because the variation between the thin film sensors 1 is small. Moreover, the resistance temperature is also used. The coefficient α and the reference resistance 値Ro can also be used in the same manner for the thin film sensor 1 manufactured in each batch. The condensation detecting portion 7b is configured to form a certain temperature T during the time of energization to the heater layer 4, when When the temperature T forms the condensation detection temperature Ή or less, the condensation of the gas detection layer 6 is detected, and the detected condensation information can be transmitted to the heater control unit 7a. For example, it is conceivable that when the condensation detection temperature ΊΊ is to heat the heater layer 4 target temperature heating When the target temperature T2 is in the range of 400 ° C to 500 ° C, the range of -5 ° C to 〇 ° C is considered for the Τ 2 in consideration of an error, etc. If the reference is made again to Fig. 2, the gas detecting device is connected. The gas detecting circuit 1 to the gas detecting layer 6 of the thin film gas sensor 1. The gas detecting circuit 11 is connected to the urban gas detecting unit 7c and the CO gas detecting unit 7d included in the microcomputer control circuit 7, respectively. The detecting unit 7c is configured to detect, for example, CH4 (methane gas) contained in the urban gas according to the electrical characteristics of the gas detecting layer 6. The CO gas detecting unit 7d is also configured to detect CO according to the electrical characteristics of the gas detecting layer 6 ( - oxidized carbon. When the gas is detected by the gas detecting layer 6, the signal emitted from the gas detecting layer 6 forms an analog signal. Therefore, the gas detecting circuit 1 1 is provided with an A/D converting circuit (not shown). ), for converting such a specific signal into a digital signal 'to the urban gas detecting unit 7 c and C Ο gas detecting -23- 201250239 part 7d. The gas detecting device is provided with a reporting display circuit 12 for detecting gas Visually visible The report display circuit 12 is a report display unit (not shown) including a lamp, etc. The report display circuit 12 is connected to the display control unit 7e included in the microcomputer control circuit 7. The device is provided with a chirping sound output circuit 13 for audibly outputting a report when the gas is detected, and the 笤 sound output circuit 13 is an audible sound output unit (not shown) having an output alarm such as a horn as a sound. The general sound output circuit 13 is connected to the cymbal sound control unit 7f included in the microcomputer control circuit 7. The gas detecting device is provided with an external output circuit 14 for performing electrical externality when detecting gas. The output, external output circuit 14 is an external external output that constitutes an electrical signal that can be transmitted to an external device. The external output circuit 14 is connected to an external output control unit 7g included in the microcomputer control circuit 7. Further, the gas detecting means is provided with an external memory circuit 15 connected to the microcomputer control circuit 7. The external memory circuit 15 is configured to store information such as thresholds and settings for moisture removal and gas detection for dew condensation, and information for detecting gas and reporting. Further, the microcomputer control circuit 7 is constituted by a CPU such as a microcomputer and its peripheral circuits, a heater control unit 7a, a condensation detecting unit 7b, a city gas detecting means 7c, a CO gas detecting unit 7d, a display control unit 7e, and a report. The sound control unit 7f and the external output control unit 7g are configured by hardware or software. A gas detecting method according to a first embodiment of the present invention will be described with reference to Fig. 5 . -24-201250239 In the flowchart shown in FIG. 5, a voltage is applied to the heater layer 4 during the period of time t2 so that the gas detecting layer 6 can be heated (S1), and in the energized state, the measurement is performed. The resistance 値R of the heater layer 4 is measured by the equation (1) to measure the temperature T (S2) of the heater layer 4. Next, it is judged whether or not the temperature T of the heater layer 4 is equal to or lower than the condensation detection temperature (S3). When the temperature T is larger than the condensation detection temperature Τ, it is judged that there is no abnormality (S4), and the voltage is applied to the heater layer 4 during the period of time t2 to be energized (S1). On the other hand, when the temperature T of the heater layer 4 is equal to or lower than the condensation detection temperature ,, it is judged that the gas detecting layer 6 is dew condensation (S5), and the time for energizing the heater layer 4 is elapsed, and the time t2 ' is > T2) (S6), in a state where the heater layer 4 is energized during the period of time t2', the resistance 値R of the heater layer 4 is measured, and the temperature T (S2) of the heater layer 4 is measured by calculation. According to the first embodiment of the present invention, when the dew condensation is detected, the energization time t2 at which the voltage is applied to the heater layer 4 and the energization is applied, the energization time to the heater layer 4 is fixed for a certain period of time. It will increase more than before the condensation detection, whereby the time for heating the gas detecting layer 6 will increase. Therefore, the moisture adhering to the thin film gas sensor 1 by condensation is sufficiently evaporated in advance, and the thin film gas sensor 1 is restored from the state of dew condensation to the normal state in advance. Therefore, it is possible to reduce the power consumption while applying the voltage to the heater layer 4, and to prevent erroneous detection, thereby improving the accuracy of gas detection. According to the first embodiment of the present invention, since the resistance 値R of the heater layer 4 is measured and the temperature T of the heater layer 4 is measured to detect the dew condensation -25-201250239, it is not necessary to detect condensation. In the case of a dew condensation sensor, a temperature sensor, or the like, the thin film gas sensor 1 and the gas detecting device are not enlarged due to an increase in the number of parts, and the heater layer can be maintained while maintaining an easy-to-set structure. When the voltage application of 4 is intermittent, the power consumption is reduced and the erroneous detection is prevented, and the accuracy of the gas detection is improved. According to the first embodiment of the present invention, the thin film gas sensor 1 can be measured. A simple method of temperature or resistance of the heater layer 4 detects dew condensation in advance and reliably, and removes dew condensation, and can apply voltage to the heater layer 4 intermittently, thereby preventing low power consumption and preventing False detection to improve the accuracy of gas detection. [Second Embodiment] A gas detecting device and a gas detecting method according to a second embodiment of the present invention will be described below. The basic configuration of the gas detecting device and the gas detecting method of the second embodiment is the same as that of the gas detecting device of the first embodiment. The same elements as those of the first embodiment are described using the symbols and names in the first embodiment. Here, the configuration in which the first embodiment is different will be described. Referring again to Fig. 2', the condensation detecting unit 7b measures the temperature T of the heater layer 4 for a predetermined time h (? < t3 < ti ) within the time t1 when the heater layer 4 is energized. g, the temperature τ of the heater layer 4 and the heating target temperature Τ'2 of the heater layer 4 are temperature responsiveness a (=τ/Τ2) as the condensation detection temperature responsiveness A, and below the 'detection gas detection layer 6 Condensation, and -26-201250239 communicates the detection of condensation to the heater control unit 7a. In one example, it is conceivable that the time t1 for the period of energization to the heater layer 4 is 60 s to 150 s, and the time t2 for energizing the heater layer 4 is 50 ms to 500 ms, and the time t3 for measuring the temperature responsiveness A is set as time. In the middle of t2, the temperature response A of the heater layer 4 in the transient state in which the temperature of the heater layer 4 rises is measured, and it is conceivable that the heating target temperature T2 is set to a range of 400 ° C to 500 t : Regarding the condensation response temperature response, it is considered that the error is set to 9 5 % ~ 1 0 0 %. A gas detecting method according to a second embodiment of the present invention will be described with reference to Fig. 6 . As shown in the flowchart of FIG. 6, the heater layer 4 is energized by applying a voltage to the heater layer 4 during the period of time t2 so that the gas detecting layer 6 can be heated (S 1 1 ), and the heater layer is measured in such an energized state. The resistance 値R of 4 is measured by the equation (1) to determine the temperature T of the heater layer 4, and the temperature responsiveness A (S 1 2 ) of the ratio of the temperature T to the heating target temperature T2 is determined by calculation. Next, it is judged whether or not the temperature responsiveness 为 is the condensation detection temperature responsiveness A, below (S 1 3 ). When the temperature responsiveness A is greater than the condensation detection temperature responsiveness, it is judged that there is no abnormality (S 14), and a voltage is applied to the heater layer 4 during the period t2 to be energized (S 1 1 ). On the other hand, when the temperature responsiveness A is below the condensation detection temperature responsiveness A!, it is judged that the gas detecting layer 6 is dew condensation (S 15), and the time for energizing the heater layer 4 is set to be time t2'. (>t2) (S16), in a state where the heater layer 4 is energized during the period of time t2', the resistance 値R of the heater layer 4 is measured, and the temperature T' of the heater layer 4 is measured by calculation. The temperature response A (S 1 2 ) of this temperature τ to the heating target temperature Tz is determined by calculation from -27 to 201250239. As described above, according to the second embodiment of the present invention, the same effects as those of the first embodiment can be obtained. [Third Embodiment] A gas detecting device and a gas detecting method according to a third embodiment of the present invention will be described below. The basic configuration of the gas detecting device and the gas detecting method of the third embodiment is the same as that of the gas detecting device of the first embodiment. The same elements as those of the first embodiment are denoted by the same reference numerals and names as those of the first embodiment. Here, the configuration different from the first embodiment will be described. The sensing layer 6c shown in Fig. 1 has a porous structure or a columnar structure, and the specific surface area of the sensing layer 6c increases, and the contact area of the sensing layer 6c with the gas to be detected increases. Further, in the selection of the combustion layer 6d, the noble metal catalyst (for example, Pd) is used as a carrier for carrying out the gas of the non-detection target, and the porous body is used as a carrier, and the porous body is provided with a number. Nm ~ number μιη diameter of a number of pores. In such a pore, water is adsorbed by condensation of a capillary according to the following formula (2). Further, 'Formula (2) is "Kelvin's formula", and in Formula (2), the radius of the capillary is set to ^^(11〇, the surface tension is γ(N/m), and the molecular weight of the liquid (adsorbed water) Set to M (mol), the contact angle of the capillary wall with the liquid is set to Θ (degrees), the specific gravity of the liquid is set to p (kg/m3), and the gas constant is set to Rgas (J/mol · κ), absolute temperature Set to Ta (K), the relative pressure of vapor pressure -28 - 201250239 and saturated vapor pressure is set to P/P0. [Number 1] ^__2^cos^ (2) PRgjAj

、尸〇 J 並且’取代圖2所示的結露檢測部7b而設有水分檢 測部。水分檢測部是測定通電至加熱器層4的時間h內形 成一定的溫度T ’當此溫度T爲高溼度檢測溫度T3以下 時’氣體檢測層6會檢測處於比通常的驅動狀態更高溼度 的環境’而將檢測到高溼度環境的情形傳達給加熱器控制 部7a。其一例可想像，當高溼度檢測溫度τ3是將加熱加 熱器層4的目標溫度之加熱目標溫度Τ4設爲400艽〜500 °C 的範圍時’考慮誤差等來對T4設爲-15。(：~〇。(：的範圍。 而且，取代結露檢測電路1 〇，設有水分檢測電路。此 水分檢測電路的基本構成是與結露檢測電路1 〇同樣，水 分檢測電路之加熱器層4的溫度T ( °C )的算出方法也形 成與結露檢測電路1 0同樣。水分檢測電路是在微電腦控 制電路7中構成可從水分檢測部傳達檢測到高溼度環境的 情形給加熱器控制部7a。 在此’在通常的驅動環境中，在未通電至加熱器層4 時（以下稱爲「加熱器· Off時」）是在選擇燃燒層6d的 細孔吸附水’在通電至加熱器層4時（以下稱爲「加熱器 •On時」）是吸附於選擇燃燒層6d的細孔的水會脫離， 此脫離後的水是藉由蒸發來除去。因此，如此吸附後的水 不會影響薄膜氣體感測器1的特性。然而，在高溼度環境 -29- 201250239 中，加熱器· Off時吸附於選擇燃燒層6d的細孔的水的量 會增加，在加熱器· On時從選擇燃燒層6d的細孔脫離的 水不會藉由蒸發來充分地除去而留下，藉由如此的加熱器 •Off時的動作及加熱器· On時的動作的重複，此留下的 水分（以下稱爲「剩餘水分」）會蓄積。 參照圖1 2來說明本發明的第3實施形態的氣體檢測 方法。 如圖1 2所示的流程圖那樣，以能夠加熱氣體檢測層6 的方式，在時間t2的期間對加熱器層4施加電壓而通電（ S2 1 )，在如此的通電狀態下，測定加熱器層4的電阻値 R，根據式（1)藉由計算來測定加熱器層4的溫度T，藉 由計算來測定此溫度T與加熱目標溫度T4的比之溫度回 應性A ( S22 )。其次，判斷此溫度回應性Α是否爲高溼 度檢測溫度回應性A2以下（S23 )。當溫度回應性A比高 溼度檢測溫度回應性A2大時，在選擇燃燒層6d的細孔吸 附的水會藉由蒸發來除去，判斷成無異常（通常的驅動環 境）（S24 )，再度於時間t2的期間對加熱器層4施加電 壓而通電（S21)。另一方面，當溫度回應性A爲高溼度 檢測溫度回應性A2以下時，在選擇燃燒層6d的細孔吸附 的水不會藉由蒸發來充分地除去，存在剩餘水分，判斷成 高溼度環境（S25 )，而拉長對加熱器層4通電的時間， 設爲時間t2’（>t2) (S26)，在時間t2’的期間對加熱器 層4通電的狀態下，測定加熱器層4的電阻値R，而藉由 計算來測定加熱器層4的溫度T，且藉由計算來測定此溫 -30- 201250239 度τ與加熱目標溫度τ4的比之溫度回應性A ( S22 )。 若如以上那樣根據本發明的第3實施形態’則如在高 溼度環境下那樣在利用加熱器層4的加熱後檢測氣體檢測 層6的剩餘水分時，拉長對加熱器層4施加電壓而通電的 通電時間t2，因此在一定時間內，往加熱器層4的通電時 間會比剩餘水分檢測前更增加，藉此加熱氣體檢測層6的 時間會增加。因此，附著於薄膜氣體感測器1的剩餘水分 會提前充分蒸發，薄膜氣體感測器1可對應於剩餘水分附 著那樣的高溼度環境來提前恢復至正常的狀態。所以，可 將往加熱器層4的電壓施加設爲間歇性者，一面謀求低耗 費電力化，一面防止誤檢測，而來提高氣體檢測的精度。 若根據本發明的第3實施形態，則藉由測定加熱器層 4的電阻値R且測定加熱器層4的溫度T來進行剩餘水分 的檢測，因此不需要用以檢測剩餘水分的水分感測器或溫 度感測器等，薄膜氣體感測器1及氣體檢測裝置不會有因 零件數量增加而大型化的情況，可一面維持設置容易且小 型的構造，一面將往加熱器層4的電壓施加設爲間歇性者 ，謀求低耗費電力化，且防止誤檢測，而來提高氣體檢測 的精度。 若根據本發明的第3實施形態，則薄膜氣體感測器1 可藉由測定加熱器層4的溫度或電阻値之簡單的方法來提 前且確實地檢測剩餘水分而除去剩餘水分，且可將往加熱 器層4的電壓施加設爲間歇性者，一面謀求低耗費電力化 ，一面防止誤檢測，而來提高氣體檢測的精度。 -31 - 201250239 到目前爲止敘述有關本發明的實施形態，但本發明並 非限於已述的實施形態，可根據本發明的技術思想來實施 各種的變形及變更。 例如，作爲本發明的實施形態的變形例，亦可在第1 實施形態及第2實施形態中檢測結露時，縮短通電至加熱 器層4的週期的時間，設爲時間t" ( <tl )，而取代將 通電至加熱器層4的時間t2拉長成時間t2 ’。可取得與本 發明的第1實施形態及第2實施形態同樣的效果。 [實施例1] 針對本發明的第1實施形態及第2實施形態的氣體檢 測裝置及氣體檢測方法來說明實施例1。 在檢測結露前的狀態，將通電至加熱器層4的週期的 時間h設爲60s (秒），將通電至薄膜氣體感測器1的加 熱器層4的時間t2設爲100ms，將結露檢測溫度T,設爲 395°C，將加熱目標溫度T2設爲400°C。在檢測結露時， 將通電至加熱器層4的時間t2’設爲10s。另外，檢測結露 的手段及方法是第1實施形態及第2實施形態的手段及方 法的其中任一個皆可。 一邊參照圖7 —邊說明通電至實施例1的加熱器層4 的時間與加熱器層4的溫度之關係。剛發生結露後的加熱 器層4的溫度T是如以一點虛線B!所示般，在發生結露 狀態下開始通電之後20ms以後在100°C附近形成一定。然 而’剛對加熱器層4通電時間t2，之後的加熱器層4的溫 -32- 201250239 度T是如以點線c!所示般恢復至400°c，形成與以實線 D t所示之未發生結露的通常狀態同樣。這可想像是因爲結 露的水分蒸發。 —邊參照圖8 —邊說明通電至實施例1的加熱器層4 的時間與薄膜氣體感測器1的電阻値W之關係。剛發生 結露之後的薄膜氣體感測器1的電阻値W是如以一點虛 線B2所示般，在發生結露狀態下開始通電之後20ms以後 在1Ε + 3Ω ( 1 χ103Ω )附近形成一定。然而，剛對加熱器層 4通電時間t2 ’之後的薄膜氣體感測器1的電阻値W是如 以點線C2所示般恢復至1Ε + 5Ω~1Ε + 6Ω(1χ105Ω〜1χ106Ω )之間的値，形成與以實線D2所示之未發生結露的通常 狀態同樣。 [實施例2] 說明本發明的第1實施形態及第2實施形態的氣體檢 測裝置及氣體檢測方法的實施例2。 在檢測結露前的狀態，將通電至加熱器層4的週期的 時間h設爲60s (秒），將通電至薄膜氣體感測器1的加 熱器層4的時間t2設爲10〇ms，將結露檢測溫度Tl設爲 395°C，將加熱目標溫度τ2設爲400T：。在檢測結露時， 將通電至加熱器層4的週期的時間tr設爲Is。另外，檢 測結露的手段及方法可爲第1實施形態及第2實施形態的 手段及方法的其中任一個。在如此的氣體檢測裝置及氣體 檢測方法中’將時間t i，設爲1 s的週期之通電予以重複 -33- 201250239 40s後，可取得與實施例1同樣的結果。 [比較例] 說明氣體檢測裝置及氣體檢測方法的比較例。 在比較例中，經常將通電至薄膜氣體感測器1的加熱 器層4的時間t2設爲10 0ms，將驅動週期t!設爲60s。 一邊參照圖9 一邊說明通電至比較例的加熱器層4的 時間與加熱器層4的溫度的關係。剛發生結露之後的加熱 器層4的溫度T是如以一點虛線E!所示般，在發生結露 狀態下開始通電之後20ms以後在1 00°C附近形成一定。結 露發生後30min (分）經過時的加熱器層4的溫度T是如 以虛線F1所示般，形成與剛發生結露之後同樣。此主要 原因可想像是加熱器層4的熱被耗費在結露後的水分的蒸 發。結露發生後35min經過時的加熱器層4的溫度T是如 以二點虛線Gi所示般，即使開始通電之後50ms，也會像 未發生結露的通常狀態那樣未上昇至400°C附近。結露發 生後40min經過時的加熱器層4的溫度T是如以點線Η, 所示般，開始通電之後50ms，恢復至400°C附近，形成與 以實線I i所示之未發生結露的通常狀態同樣。這可想像是 因爲結露的水分蒸發。 通電至比較例的加熱器層4的時間與加熱器層4的溫 度回應性A的關係也是如圖1 0所示般，形成和通電至加 熱器層4的時間與加熱器層4的溫度的關係同樣。在圖1〇 中，以一點虛線E2來表示剛發生結露之後的狀態，以虛 -34- 201250239 線F2來表示結露發生後3 Omin經過時的狀態，以二點虛 線G2來表示結露發生後3 5min經過時的狀態，以二點虛 線G2來表示結露發生後40min經過時的狀態，以實線12 來表示未發生結露的通常狀態。 一邊參照圖11 一邊說明通電至比較例的加熱器層4 的時間與薄膜氣體感測器1的電阻値W的關係'。 剛發生結露之後的薄膜氣體感測器1的電阻値W是 如以一點虛線e3所示般，在結露發生狀態下開始通電之 後2 0ms以後，在氣體檢測電阻値W,以下的範圍，在 1Ε + 3Ω ( 1χ103Ω)附近形成一定。結露發生後30min經過 時的薄膜氣體感測器1的電阻値W是如以虛線F3所示般 ，形成與剛發生結露之後同樣。結露發生後3 5min經過時 的薄膜氣體感測器1的電阻値W是如以二點虛線G3所示 般，形成1Ε + 4Ω-1Ε + 5Ω ( 1χ104Ω〜1χ105Ω )，形成接近氣 體洩漏警報的臨界値之氣體檢測電阻値W!的値。結露發 生後40min經過時的薄膜氣體感測器1的電阻値W是如 以點線H3所示般，恢復至1Ε + 5Ω~1Ε + 6Ω ( 1 X 105Ω〜1 X 1 06Ω )之間的値，形成與以實線13所示之未發生結露的通 常狀態同樣。 如以上般，若對比實施例1、實施例2及比較例，則 在實施例1及實施例2中，因爲結露短時間蒸發，所以氣 體檢測層6的電阻値W難被檢測出像比較例那樣接近氣 體洩漏的警報的臨界値之氣體檢測電阻値Wi的値。因此 ，難發生氣體洩漏的誤警報。 -35- 201250239 【圖式簡單說明】 圖1是表示本發明的第1實施形態的薄膜氣體感測器 的槪略剖面圖。 圖2是本發明的第1實施形態的氣體檢測裝置的方塊 圖。 圖3是表示在本發明的第1實施形態中，間歇性地施 加於加熱器層的電壓的圖表。 圖4是表示從外部加熱薄膜氣體感測器的溫度與加熱 器層的電阻値的關係的圖表。 圖5是表示本發明的第1實施形態的氣體檢測的流程 圖。 圖6是表示本發明的第2實施形態的氣體檢測的流程 圖。 圖7是表示在實施例1中，通電至加熱器層的時間與 加熱器層的溫度的關係的圖表。 圖8是表示在實施例1中，通電至加熱器層的時間與 薄膜氣體感測器的電阻値的關係的圖表。 圖9是表示在比較例中，通電至加熱器層的時間與加 熱器層的溫度的關係的圖表。 圖1 0表示在比較例中，通電至加熱器層的時間與加 熱器層的溫度回應性的關係的圖表。 圖1 1是表示在比較例中，通電至加熱器層的時間與 薄膜氣體感測器的電阻値的關係的圖表。 -36- 201250239 圖1 2是表示本發明的第3實施形態的氣體檢測的流 程圖。 【主要元件符號說明】 1 :薄膜氣體感測器 4 :加熱器層 6 :氣體檢測層 7a :加熱器控制部 7b :結露檢測部 7c :都市瓦斯檢測部 7d : CO氣體檢測部 t， ti， ti’， t2， t2’， t3:時間 V，Vi :電壓 T :溫度The body J and the water detecting unit are provided instead of the condensation detecting unit 7b shown in Fig. 2 . The moisture detecting unit measures a certain temperature T′ during the time h of energization to the heater layer 4. When the temperature T is equal to or lower than the high humidity detecting temperature T3, the gas detecting layer 6 detects that the humidity is higher than the normal driving state. The environment 'transfers the situation in which the high humidity environment is detected to the heater control unit 7a. As an example, when the high humidity detection temperature τ3 is a range in which the heating target temperature Τ4 of the target temperature of the heating heater layer 4 is set to 400 艽 to 500 °C, T4 is set to -15 in consideration of an error or the like. (:~〇. (: range. Further, in place of the condensation detection circuit 1 〇, a moisture detecting circuit is provided. The basic configuration of the moisture detecting circuit is the same as that of the condensation detecting circuit 1 ,, and the heater layer 4 of the moisture detecting circuit The method of calculating the temperature T (°C) is also the same as that of the condensation detecting circuit 10. The moisture detecting circuit is configured in the microcomputer control circuit 7 to transmit a high-humidity environment from the moisture detecting unit to the heater control unit 7a. Here, in the normal driving environment, when the heater layer 4 is not energized (hereinafter referred to as "heater·off"), the pores of the combustion layer 6d are selected to adsorb water 'on the heater layer 4 At the time (hereinafter referred to as "heater/on"), the water adsorbed to the pores of the selected combustion layer 6d is detached, and the water after the detachment is removed by evaporation. Therefore, the water thus adsorbed does not affect The characteristics of the membrane gas sensor 1. However, in the high humidity environment -29-201250239, the amount of water adsorbed to the pores of the selected combustion layer 6d increases when the heater is off, and is selected when the heater is on. Combustion layer 6d The water from which the pores are detached is not sufficiently removed by evaporation, and the water remaining after the operation of the heater and the operation of the heater and the On is repeated (hereinafter referred to as The gas detection method according to the third embodiment of the present invention will be described with reference to Fig. 12. The flow detection layer 6 can be heated at time t2 as shown in the flowchart of Fig. 12 . During the period, a voltage is applied to the heater layer 4 to be energized (S2 1 ). In such an energized state, the resistance 値R of the heater layer 4 is measured, and the temperature T of the heater layer 4 is measured by calculation according to the formula (1). The temperature response responsiveness A (S22) of the temperature T to the heating target temperature T4 is determined by calculation. Secondly, it is judged whether the temperature responsiveness Α is below the high humidity detection temperature responsiveness A2 (S23). When the temperature is responsive When the sexual A is larger than the high humidity detection temperature responsiveness A2, the water adsorbed by the pores of the selected combustion layer 6d is removed by evaporation, and it is judged that there is no abnormality (normal driving environment) (S24), and again at time t2. Applying to the heater layer 4 during On the other hand, when the temperature responsiveness A is lower than the high humidity detection temperature responsiveness A2, the water adsorbed in the pores of the selected combustion layer 6d is not sufficiently removed by evaporation, and there is a surplus. The moisture is judged to be in a high humidity environment (S25), and the time for energizing the heater layer 4 is set to time t2' (>t2) (S26), and the heater layer 4 is energized during the time t2'. In the state, the resistance 値R of the heater layer 4 is measured, and the temperature T of the heater layer 4 is measured by calculation, and the temperature ratio of the temperature -30-201250239 degree τ to the heating target temperature τ4 is determined by calculation. Responsiveness A (S22). According to the third embodiment of the present invention as described above, when the remaining moisture of the gas detecting layer 6 is detected after heating by the heater layer 4 as in the high humidity environment, the voltage is applied to the heater layer 4 by elongating. Since the energization time t2 is energized, the energization time to the heater layer 4 is increased more than before the residual moisture detection for a certain period of time, whereby the time for heating the gas detection layer 6 is increased. Therefore, the remaining moisture attached to the membrane gas sensor 1 is sufficiently evaporated in advance, and the membrane gas sensor 1 can be restored to a normal state in advance in response to a high humidity environment such as residual moisture. Therefore, if the voltage applied to the heater layer 4 is intermittent, the power consumption can be reduced and the erroneous detection can be prevented, and the accuracy of the gas detection can be improved. According to the third embodiment of the present invention, since the resistance 値R of the heater layer 4 is measured and the temperature T of the heater layer 4 is measured to detect residual moisture, moisture sensing for detecting residual moisture is not required. The membrane gas sensor 1 and the gas detecting device do not increase in size due to an increase in the number of components, and the voltage to the heater layer 4 can be maintained while maintaining an easy-to-set structure. When the application is intermittent, the power consumption is reduced, and erroneous detection is prevented, and the accuracy of gas detection is improved. According to the third embodiment of the present invention, the thin film gas sensor 1 can detect the remaining moisture in advance and surely by the simple method of measuring the temperature or the resistance 値 of the heater layer 4, and remove the remaining moisture, and can When the voltage applied to the heater layer 4 is intermittent, the erroneous detection is prevented while the power consumption is reduced, and the accuracy of gas detection is improved. The present invention has been described so far, but the present invention is not limited to the embodiments described above, and various modifications and changes can be made without departing from the spirit and scope of the invention. For example, in the modification of the embodiment of the present invention, when the dew condensation is detected in the first embodiment and the second embodiment, the period of time during which the heater layer 4 is energized can be shortened, and the time t"(<tl Instead of the time t2 at which the heater layer 4 is energized, the time t2' is elongated. The same effects as those of the first embodiment and the second embodiment of the present invention can be obtained. [Embodiment 1] Embodiment 1 will be described with respect to a gas detecting device and a gas detecting method according to the first embodiment and the second embodiment of the present invention. In the state before the detection of the condensation, the time h of the period of energization to the heater layer 4 is set to 60 s (seconds), and the time t2 of the heater layer 4 energized to the thin film gas sensor 1 is set to 100 ms, and the condensation detection is performed. The temperature T was set to 395 ° C, and the heating target temperature T2 was set to 400 ° C. When the condensation is detected, the time t2' at which the heater layer 4 is energized is set to 10 s. Further, the means and method for detecting condensation may be any of the means and methods of the first embodiment and the second embodiment. The relationship between the time of energization to the heater layer 4 of the first embodiment and the temperature of the heater layer 4 will be described with reference to Fig. 7 . The temperature T of the heater layer 4 immediately after the condensation has occurred is as shown by a dotted line B!, and is formed at a temperature of about 100 ° C after 20 ms after the start of energization in the dew condensation state. However, 'the heater layer 4 is energized for the time t2, and the subsequent heater layer 4's temperature -32 - 201250239 degrees T is restored to 400 ° C as indicated by the dotted line c!, and is formed by the solid line D t The normal state in which condensation does not occur is the same. This is imaginable because the condensation of water evaporates. The relationship between the time of energization to the heater layer 4 of the first embodiment and the resistance 値W of the thin film gas sensor 1 will be described with reference to FIG. The resistance 値W of the thin film gas sensor 1 immediately after the condensation has occurred is as shown by a dotted line B2, and is formed in the vicinity of 1 Ε + 3 Ω (1 χ 103 Ω) 20 ms after the start of energization in the dew condensation state. However, the resistance 値W of the thin film gas sensor 1 immediately after the energization time t2' of the heater layer 4 is restored to between 1 Ε + 5 Ω to 1 Ε + 6 Ω (1 χ 105 Ω to 1 χ 106 Ω) as indicated by the dotted line C2. That is, the formation is the same as the normal state in which no condensation occurs as indicated by the solid line D2. [Embodiment 2] A second embodiment of the gas detecting device and the gas detecting method according to the first embodiment and the second embodiment of the present invention will be described. In the state before the detection of dew condensation, the time h of the period of energization to the heater layer 4 is set to 60 s (seconds), and the time t2 of energization to the heater layer 4 of the thin film gas sensor 1 is set to 10 〇ms, The condensation detection temperature T1 was set to 395 ° C, and the heating target temperature τ 2 was set to 400 T:. When the condensation is detected, the time tr of the period of energization to the heater layer 4 is set to Is. Further, the means and method for detecting condensation may be any one of the means and methods of the first embodiment and the second embodiment. In such a gas detecting device and a gas detecting method, the energization of the period t i for 1 s is repeated -33 - 201250239 40s, and the same results as in the first embodiment can be obtained. [Comparative Example] A comparative example of a gas detecting device and a gas detecting method will be described. In the comparative example, the time t2 at which the heater layer 4 of the thin film gas sensor 1 is energized is often set to 10 0 ms, and the drive period t! is set to 60 s. The relationship between the time of energization to the heater layer 4 of the comparative example and the temperature of the heater layer 4 will be described with reference to Fig. 9 . The temperature T of the heater layer 4 immediately after the condensation has occurred is as shown by a dotted line E!, and is formed at about 100 ° C after 20 ms after the start of energization in the dew condensation state. The temperature T of the heater layer 4 at the time of 30 minutes (minutes) after the occurrence of the condensation is as shown by the broken line F1, and is formed in the same manner as immediately after the condensation occurs. The main reason for this is that the heat of the heater layer 4 is consumed by the evaporation of moisture after condensation. The temperature T of the heater layer 4 at the time of 35 minutes after the occurrence of dew condensation is as shown by the two-dotted line Gi, and even if it is 50 ms after the start of energization, it does not rise to the vicinity of 400 °C as in the normal state in which dew condensation does not occur. The temperature T of the heater layer 4 when 40 minutes after the occurrence of dew condensation is as shown by the dotted line, 50 ms after the start of energization, and returns to the vicinity of 400 ° C, forming no condensation as indicated by the solid line I i The usual state is the same. This is imaginable because the condensation of water evaporates. The relationship between the time of energization to the heater layer 4 of the comparative example and the temperature responsiveness A of the heater layer 4 is also as shown in FIG. 10, the time of forming and energizing to the heater layer 4 and the temperature of the heater layer 4. The relationship is the same. In Fig. 1A, the state after the condensation has just occurred is indicated by a dotted line E2, and the state at the time of 3 Omin after the occurrence of condensation is indicated by the virtual line 34-201250239 line F2, and the occurrence of condensation after the dotted line G2 is shown. The state at the time of the passage of 5 minutes indicates the state when the elapse of 40 minutes after the occurrence of dew condensation by the two-dotted line G2, and the normal state in which dew condensation does not occur is indicated by the solid line 12. The relationship between the time when the heater layer 4 of the comparative example is energized and the resistance 値W of the thin film gas sensor 1 will be described with reference to FIG. 11 . The resistance 値W of the thin-film gas sensor 1 immediately after the condensation has occurred is as shown by a dotted line e3, and after 20 ms after the start of energization in the dew condensation state, the gas detection resistance 値W, the following range is 1 Ε + 3Ω (1χ103Ω) forms a certain vicinity. The resistance 値W of the thin film gas sensor 1 after 30 minutes after the occurrence of dew condensation is formed as shown by the broken line F3, and is formed just after the condensation has just occurred. The resistance 値W of the thin film gas sensor 1 after the elapse of 35 minutes after the condensation occurs is 1 Ε + 4 Ω - 1 Ε + 5 Ω (1 χ 104 Ω ~ 1 χ 105 Ω) as indicated by the two-dotted line G3, forming a critical value close to the gas leakage alarm.値 The gas detection resistor 値W! The resistance 値W of the thin film gas sensor 1 after 40 minutes after the occurrence of condensation is restored to 1 Ε + 5 Ω to 1 Ε + 6 Ω (1 X 105 Ω to 1 X 1 06 Ω) as indicated by the dotted line H3. The formation is the same as the normal state in which no condensation occurs as indicated by the solid line 13. As described above, in Comparative Example 1, Example 2, and Comparative Example, in Example 1 and Example 2, since the condensation was evaporated for a short time, the resistance 値W of the gas detecting layer 6 was hardly detected as a comparative example. That is close to the threshold of the gas detection resistor 値Wi of the alarm of the gas leakage. Therefore, it is difficult to cause a false alarm of gas leakage. [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing a thin film gas sensor according to a first embodiment of the present invention. Fig. 2 is a block diagram of a gas detecting device according to a first embodiment of the present invention. Fig. 3 is a graph showing voltages intermittently applied to the heater layer in the first embodiment of the present invention. Fig. 4 is a graph showing the relationship between the temperature of the film gas sensor heated from the outside and the resistance 値 of the heater layer. Fig. 5 is a flow chart showing gas detection in the first embodiment of the present invention. Fig. 6 is a flow chart showing gas detection in a second embodiment of the present invention. Fig. 7 is a graph showing the relationship between the time of energization to the heater layer and the temperature of the heater layer in the first embodiment. Fig. 8 is a graph showing the relationship between the time of energization to the heater layer and the resistance 値 of the thin film gas sensor in the first embodiment. Fig. 9 is a graph showing the relationship between the time of energization to the heater layer and the temperature of the heater layer in the comparative example. Fig. 10 is a graph showing the relationship between the time of energization to the heater layer and the temperature response of the heater layer in the comparative example. Fig. 11 is a graph showing the relationship between the time of energization to the heater layer and the resistance 値 of the thin film gas sensor in the comparative example. -36-201250239 Fig. 1 is a flow chart showing gas detection in the third embodiment of the present invention. [Description of main component symbols] 1 : Thin film gas sensor 4 : Heater layer 6 : Gas detecting layer 7 a : Heater control unit 7 b : Dew condensation detecting unit 7 c : Urban gas detecting unit 7 d : CO gas detecting unit t, ti, Ti', t2, t2', t3: time V, Vi: voltage T: temperature

To :基準溫度 T !:結露檢測溫度 T2，τ4 :加熱目標溫度 τ3 :高溼度檢測溫度 R :電阻値To : Reference temperature T !: Condensation detection temperature T2, τ4 : Heating target temperature τ3 : High humidity detection temperature R : Resistance 値

Ro :基準電阻値 W :電阻値 W!:氣體檢測電阻値 A :溫度回應性 A!:結露檢測溫度回應性 -37- 201250239 A2 :高溼度檢測溫度回應性 α :電阻溫度係數 rk :毛管的半徑 γ :表面張力 Μ :液體（吸附的水）的分子量 0:毛管壁與液體的接觸角度 Ρ :液體（吸附的水）的比重 Rgas :氣體定數 Ta :絶對溫度 P/Ρο :蒸氣壓與飽和蒸氣壓的相對壓 Bi，B2 :—點虛線 C!，C2 :點線 D,，D2 :實線 e,~e3 :—點虛線 F 1〜F 3 :虛線 G,~G3 :二點虛線 :點線 Ii-h :實線 -38-Ro : Reference resistance 値 W : Resistance 値 W!: Gas detection resistance 値 A : Temperature responsiveness A!: Condensation detection temperature responsiveness - 37 - 201250239 A2 : High humidity detection Temperature responsiveness α : Resistance temperature coefficient rk : capillary tube Radius γ : Surface tension Μ : Molecular weight of liquid (adsorbed water) 0: Contact angle of capillary wall with liquid Ρ : Specific gravity of liquid (adsorbed water) Rgas : Gas constant Ta : Absolute temperature P / Ρο : Vapor pressure Relative pressure to saturated vapor pressure Bi, B2: - dotted line C!, C2: dotted line D,, D2: solid line e, ~e3: - dotted line F 1~F 3 : dotted line G, ~G3: two points Dotted line: dotted line Ii-h: solid line -38-

Claims (1)

201250239 七、申請專利範圍： 1 ·一種氣體檢測裝置，係具備： 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 層； 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間；及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲： 設有用以檢測前述氣體檢測層的結露之結露檢測部， 當前述結露檢測部檢測到前述氣體檢測層的結露時， 將往前述加熱器層的通電時間控制成比前述預定的通電時 間長，或將通電至前述加熱器層的週期控制成比前述預定 的週期短。 2 ·如申請專利範圍第1項之氣體檢測裝置，其中，前 述結露檢測部係構成測定前述預定的通電時間內形成一定 的前述加熱器層的溫度，當前述測定的加熱器層的溫度爲 預定的溫度以下時，檢測前述氣體檢測層的結露。 3 .如申請專利範圍第1項之氣體檢測裝置，其中，前 述結露檢測部係構成在前述預定的通電時間內的預定的時 間測定前述加熱器層的溫度，當前述測定的加熱器層的溫 度與前述加熱器層的加熱目標溫度的比之溫度回應性爲預 -39- 201250239 定的比例以下時，檢測前述氣體檢測層的結露。 4 ·如申請專利範圍第2或3項之氣體檢測裝置，其中 ，前述結露檢測部係構成測定前述加熱器層的電阻値，由 前述預定的時間內測定的前述加熱器層的電阻値、及預先 求取的前述加熱器層的電阻溫度係數、基準溫度、以及前 述基準溫度的前述加熱器層的電阻値來算出前述加熱器層 的溫度，藉此構成測定前述加熱器層的溫度。 5. —種氣體檢測裝置，係具備： 感測器元件，其係具有：藉由與氣體的接觸而電氣特 性變化的氣體檢測層、及可加熱前述氣體檢測層的加熱器 層； 加熱器控制部，其係爲了加熱前述氣體檢測層，而以 預定的週期來間歇性地對前述加熱器層施加電壓，通電預 定的通電時間；及 氣體檢測部，其係根據藉由前述加熱器層所加熱的前 述氣體檢測層的電氣特性來檢測氣體， 其特徵爲： 設有水分檢測部，其係檢測利用前述加熱器層之前述 氣體檢測層的加熱後留在前述氣體檢測層的水分· 當前述水分檢測部檢測到留在前述氣體檢測層的水分 時，將往前述加熱器層的通電時間控制成比前述預定的通 電時間長，或將通電至前述加熱器層的週期控制成比前述 預定的週期短。 6. 如申請專利範圍第5項之氣體檢測裝置，其中，前 -40- 201250239 述水分檢測部係構成在前述預定的通電時間內的預定的時 間測定前述加熱器層的溫度，當前述測定的加熱器層的溫 度與前述加熱器層的加熱目標溫度的比之溫度回應性爲預 定的比例以下時，檢測留在前述氣體檢測層的水分。 7.如申請專利範圍第6項之氣體檢測裝置，其中，前 述水分檢測部係構成測定前述加熱器層的電阻値，由前述 預定的時間內測定的前述加熱器層的電阻値、及預先求取 的前述加熱器層的電阻溫度係數、基準溫度、以及前述基 準溫度的前述加熱器層的電阻値來算出前述加熱器層的溫 度，藉此測定前述加熱器層的溫度。 8 · —種氣體檢測方法，係利用具有藉由與氣體的接觸 而電氣特性變化的氣體檢測層及可加熱前述氣體檢測層的 加熱器層之感測器元件，在以預定的週期來間歇性地對前 述加熱器層施加電壓而通電預定的通電時間，藉此在加熱 前述氣體檢測層的狀態下，根據前述氣體檢測層的電氣特 性來檢測氣體之氣體檢測方法，其特徵係包含： 檢測前述氣體檢測層的結露之步驟；及 當檢測到前述氣體檢測層的結露時，使往前述加熱器 層的通電時間比前述預定的通電時間長，或使通電至前述 加熱器層的週期比前述預定的週期短之步驟。 9.如申請專利範圍第8項之氣體檢測方法，其中，檢 測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內形成一定的前述加熱器層 的溫度之步驟；及 -41 - 201250239 當前述測定的加熱器層的溫度爲預定的溫度以下時， 檢測前述氣體檢測層的結露之步驟。 10.如申請專利範圍第8項之氣體檢測方法，其中， 檢測前述氣體檢測層的結露之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫度在 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的加熱 目標溫度的比之溫度回應性爲預定的比例以下時，檢測前 述氣體檢測層的結露之步驟。 1 1.如申請專利範圍第9或1 0項之氣體檢測方法，其 中，測定前述加熱器層的溫度之步驟包含： 在前述預定的時間內測定前述加熱器層的電阻値之步 驟；及 由測定的前述加熱器層的電阻値、及預先求取的前述 加熱器層的電阻溫度係數、基準溫度、以及前述基準溫度 的前述加熱器層的電阻値來算出前述加熱器層的溫度之步 驟。 12· —種氣體檢測方法，係利用具有藉由與氣體的接 觸而電氣特性變化的氣體檢測層及可加熱前述氣體檢測層 的加熱器層之感測器元件，在以預定的週期來間歇性地對 前述加熱器層施加電壓而通電預定的通電時間，藉此在加 熱前述氣體檢測層的狀態下，根據前述氣體檢測層的電氣 特性來檢測氣體之氣體檢測方法，其特徵係包含： 檢測利用前述加熱器層之前述氣體檢測層的加熱後留 -42- 201250239 在前述氣體檢測層的水分之步驟；及 當檢測到留在前述氣體檢測層的水分時，使往前述加 熱器層的通電時間比前述預定的通電時間長，或使通電至 前述加熱器層的週期比前述預定的週期短之步驟。 1 3 .如申請專利範圍第1 2項之氣體檢測方法，其中， 檢測留在前述氣體檢測層的水分之步驟包含： 測定前述預定的通電時間內的前述加熱器層的溫度在 預定的時間前述加熱器層的溫度之步驟；及 當前述測定的加熱器層的溫度與前述加熱器層的加熱 目標溫度的比之溫度回應性爲預定的比例以下時，檢測留 在前述氣體檢測層的水分之步驟。 1 4 .如申請專利範圍第1 3項之氣體檢測方法，其中， 測定前述加熱器層的溫度之步驟包含： 在前述預定的時間內測定前述加熱器層的電阻値之步 驟；及 由測定的前述加熱器層的電阻値、及預先求取的前述 加熱器層的電阻溫度係數、基準溫度、以及前述基準溫度 的前述加熱器層的電阻値來算出前述加熱器層的溫度之步 -43-201250239 VII. Patent application scope: 1 . A gas detecting device comprising: a sensor element having a gas detecting layer whose electrical characteristics are changed by contact with a gas, and heating capable of heating the gas detecting layer a heater control unit that intermittently applies a voltage to the heater layer at a predetermined cycle to heat the gas detecting layer, and energizes a predetermined energization time; and the gas detecting unit is configured to The gas detecting layer of the gas detecting layer heated by the heater layer detects gas, and is characterized in that: a dew condensation detecting portion for detecting condensation of the gas detecting layer is provided, and the condensation detecting portion detects condensation of the gas detecting layer At this time, the energization time to the heater layer is controlled to be longer than the predetermined energization time, or the period of energization to the heater layer is controlled to be shorter than the predetermined period. The gas detecting device according to the first aspect of the invention, wherein the condensation detecting unit is configured to measure a temperature at which the predetermined heater layer is formed in the predetermined energization time, and the temperature of the heater layer measured is predetermined. When the temperature is below the temperature, the condensation of the gas detecting layer is detected. 3. The gas detecting device according to claim 1, wherein the condensation detecting unit is configured to measure a temperature of the heater layer at a predetermined time during the predetermined energization time, and to measure a temperature of the heater layer. When the temperature response ratio to the heating target temperature of the heater layer is less than or equal to a predetermined ratio of -39 to 201250239, dew condensation of the gas detecting layer is detected. The gas detecting device according to the second or third aspect of the invention, wherein the condensation detecting unit is configured to measure a resistance 値 of the heater layer, and a resistance 値 of the heater layer measured by the predetermined time period, The temperature of the heater layer is calculated by calculating the temperature coefficient of the heater layer in the heater layer, the reference temperature, and the resistance 値 of the heater layer in the reference temperature, and the temperature of the heater layer is measured. 5. A gas detecting device comprising: a sensor element having: a gas detecting layer whose electrical characteristics change by contact with a gas; and a heater layer capable of heating the gas detecting layer; heater control a portion for intermittently applying a voltage to the heater layer at a predetermined cycle to heat the gas detecting layer, and energizing a predetermined energization time; and a gas detecting portion that is heated by the heater layer The gas detecting layer is configured to detect a gas, and is characterized in that: a moisture detecting unit that detects moisture remaining in the gas detecting layer after heating of the gas detecting layer in the heater layer is used; When detecting the moisture remaining in the gas detecting layer, the detecting unit controls the energization time to the heater layer to be longer than the predetermined energization time, or controls the period of energization to the heater layer to be longer than the predetermined period. short. 6. The gas detecting device according to claim 5, wherein the moisture detecting unit of the first-40-201250239 is configured to measure the temperature of the heater layer at a predetermined time during the predetermined energization time, when the measured When the ratio of the temperature of the heater layer to the heating target temperature of the heater layer is less than or equal to a predetermined ratio, the moisture remaining in the gas detecting layer is detected. 7. The gas detecting device according to claim 6, wherein the moisture detecting unit is configured to measure a resistance 値 of the heater layer, and a resistance 値 of the heater layer measured in the predetermined time period and a predetermined The temperature of the heater layer is obtained by calculating the temperature of the heater layer by the temperature coefficient of resistance of the heater layer, the reference temperature, and the resistance 値 of the heater layer of the reference temperature. 8 a method for detecting a gas by using a gas detecting layer having a change in electrical characteristics by contact with a gas and a sensor element capable of heating the heater layer of the gas detecting layer, intermittently at a predetermined cycle A gas detecting method for detecting a gas based on electrical characteristics of the gas detecting layer while applying a voltage to the heater layer to apply a predetermined energization time, thereby heating the gas detecting layer, wherein the method includes: detecting the foregoing a step of dew condensation of the gas detecting layer; and when the condensation of the gas detecting layer is detected, the energization time to the heater layer is longer than the predetermined energization time, or the period of energization to the heater layer is longer than the predetermined period The short steps of the cycle. 9. The gas detecting method according to claim 8, wherein the detecting the condensation of the gas detecting layer comprises: measuring a temperature of forming a certain temperature of the heater layer in the predetermined energization time; and -41 201250239 When the temperature of the heater layer measured as described above is equal to or lower than a predetermined temperature, the step of dew condensation of the gas detecting layer is detected. 10. The gas detecting method according to claim 8, wherein the detecting the condensation of the gas detecting layer comprises: determining the temperature of the heater layer in the predetermined energization time for a predetermined time of the heater layer a step of detecting a condensation of the gas detecting layer when the temperature response of the temperature of the heater layer and the heating target temperature of the heater layer is less than a predetermined ratio. 1 1. The gas detecting method according to claim 9 or 10, wherein the step of measuring the temperature of the heater layer comprises: measuring a resistance 値 of the heater layer within the predetermined time; and The step of calculating the temperature of the heater layer by measuring the resistance 値 of the heater layer, the temperature coefficient of resistance of the heater layer obtained in advance, the reference temperature, and the resistance 値 of the heater layer at the reference temperature. 12. A gas detecting method using a gas detecting layer having a change in electrical characteristics by contact with a gas and a sensor element capable of heating the heater layer of the gas detecting layer, intermittently at a predetermined cycle A gas detecting method for detecting a gas based on electrical characteristics of the gas detecting layer while applying a voltage to the heater layer to apply a predetermined energization time to the gas detecting layer, wherein the gas detecting method includes: detecting and utilizing a step of retaining moisture of the gas detecting layer of the gas detecting layer of the heater layer after the heating of the gas detecting layer; and energizing time of the heater layer when the moisture remaining in the gas detecting layer is detected The step of lengthening the predetermined energization time or making the period of energization to the heater layer shorter than the predetermined period. The gas detecting method of claim 12, wherein the detecting the moisture remaining in the gas detecting layer comprises: measuring the temperature of the heater layer in the predetermined energization time at a predetermined time a step of temperature of the heater layer; and detecting a moisture remaining in the gas detecting layer when the ratio of the temperature of the heater layer measured to the heating target temperature of the heater layer is less than a predetermined ratio step. 1 . The gas detecting method according to claim 13 , wherein the step of measuring the temperature of the heater layer comprises: measuring a resistance 値 of the heater layer within the predetermined time; and determining The resistance 値 of the heater layer, the temperature coefficient of resistance of the heater layer obtained in advance, the reference temperature, and the resistance 値 of the heater layer of the reference temperature to calculate the temperature of the heater layer-43-
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