WO2016066089A1 - 一种基于单个加热元件的甲烷传感器及制备方法和应用 - Google Patents

一种基于单个加热元件的甲烷传感器及制备方法和应用 Download PDF

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Publication number
WO2016066089A1
WO2016066089A1 PCT/CN2015/093007 CN2015093007W WO2016066089A1 WO 2016066089 A1 WO2016066089 A1 WO 2016066089A1 CN 2015093007 W CN2015093007 W CN 2015093007W WO 2016066089 A1 WO2016066089 A1 WO 2016066089A1
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layer
silicon
heating element
measuring element
ambient temperature
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French (fr)
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马洪宇
丁恩杰
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China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology CUMT
China University of Mining and Technology Beijing CUMTB
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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
    • G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
    • G01N27/16—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature caused by burning or catalytic oxidation of surrounding material to be tested, e.g. of gas

Definitions

  • the invention relates to a methane sensor and a preparation method and application thereof, in particular to a methane sensor based on a single heating element used in industrial mineral networking, and a preparation method and application thereof.
  • the low-concentration methane used in coal mines is still based on the traditional platinum wire-heated catalytic combustion methane sensor.
  • the principle is based on the catalytic combustion reaction of methane gas.
  • the catalytic combustion type methane sensor consumes a large amount of power. Due to the use of the catalyst, the methane sensor has the disadvantages of carbon deposition, poisoning, activation, etc., and the performance is unstable and the calibration time is short.
  • the existing catalytic combustion type methane sensor uses a manual or mechanically wound coil of a precious metal such as platinum wire as a heating element, which is difficult to mass-produce, and has poor consistency and interchangeability, and therefore cannot be satisfactorily satisfied.
  • An object of the present invention is to provide a simple heating element-based methane sensor capable of detecting low-concentration methane based on a single heating element, and a preparation method and application thereof, which are simple in structure and independent of a catalyst.
  • a single heating element-based methane sensor of the present invention includes a heating element, a measuring element and an ambient temperature measuring element; the ambient temperature measuring element is disposed on a support;
  • the heating element is composed of two fixed ends, two supporting arms A arranged side by side and a heater, and two ends of the two supporting arms A are respectively connected with the fixed end and the heater to form a two-terminal device;
  • the length of the support arm A is at least 300 um;
  • the measuring element is composed of two fixed ends, a measuring member and two supporting arms B, the two supporting arms B are respectively connected to both ends of the measuring member, and the other two supporting arms B are One end is respectively connected with two fixed ends to form a two-terminal device;
  • each of the supporting cantilevers B has a length of at least 100 ⁇ m;
  • the fixed end of the heating element and the fixed end of the measuring element are independently arranged on the support, and the rest Suspended in the air;
  • the heating element and the measuring element are structurally a cantilever structure;
  • the heater of the heating element is a ring structure, and the measuring member of the measuring element has a "one" structure or an arc-shaped structure. Heater and measuring element of
  • the support comprises a substrate and an isolating silicon oxide layer disposed on the substrate, and a top crystalline silicon layer disposed on the isolated silicon oxide; the heating element, the measuring component and the ambient temperature measuring component are disposed on the isolated silicon oxide
  • the top layer of the single crystal silicon layer is formed, and the silicon structures of the heating element, the measuring element and the ambient temperature measuring element are respectively disconnected from the other top silicon layer on the isolation silicon oxide;
  • the substrate is silicon or other a material that can be processed by a MEMS process;
  • the ambient temperature measuring component disposed on the support includes two electrode terminals, and a measuring resistor;
  • the fixed end of the heating element and the measuring element and the electrode terminal of the ambient temperature measuring element are processed by a top layer of single crystal silicon layer, a silicon oxide layer is formed outside the top layer of the single crystal silicon layer, and an electrical extraction pad is provided on the silicon oxide layer.
  • a metal; a doped silicon layer is disposed in the top single crystal silicon layer of the fixed end and the electrode lead end; the electric lead pad metal is in ohmic contact by a window of the silicon oxide layer and a doped silicon layer at the fixed end;
  • a support arm A of the heating element protruding from the air and a heater and a measuring member protruding from the measuring element and the outer surface of the support arm B are provided with a passivation protective layer; the ambient temperature measuring element
  • the outer surface of the silicon resistance is also provided with a passivation protective layer;
  • the passivation protective layer is silicon oxide, or yttrium oxide, or a silicon oxide/alumina composite layer, or a yttrium oxide/alumina composite layer, or yttrium oxide/ a silicon nitride composite layer, or an aluminum oxide/silicon nitride composite layer, or a silicon oxide/silicon nitride composite layer, or a composite layer formed by combining materials of silicon oxide, hafnium oxide, aluminum oxide, silicon nitride;
  • the thickness of the silicon is at least 10 nm
  • the thickness of the yttrium oxide is at least 5 um
  • the thickness of the aluminum oxide is at least 6 nm
  • a methane detection application method of a methane sensor based on a single heating element the heating element of a methane sensor based on a single heating element is passed through a large current or a large voltage is applied to a working area on the left side of the turning point in the current-resistance characteristic curve
  • the heating temperature of the heater is above 500 ° C.
  • the turning point is the maximum point of resistance that occurs when the resistance increases with current or voltage.
  • the ambient temperature measuring component is passed without generating a slight current which is significantly higher than the ambient air temperature; when there is no methane gas, the measuring component is affected by the heating high temperature of the heating element, and the temperature is increased, and the resistance is also increased; when methane gas is present and When the concentration is increased, the temperature of the heating element is lowered, and the temperature of the independent measuring element is also reduced by the influence of the measuring element, resulting in a decrease in the self-resistance, and the measurement of the methane concentration is performed by detecting the change of the electrical parameter (such as resistance) of the measuring element by an electrical measurement method;
  • the ambient temperature measuring component measures the ambient temperature to adjust the heating element State, data can also be used for measuring the obtained temperature compensation.
  • the preparation method of the methane sensor based on a single heating element includes the following three preparation methods:
  • the steps of the preparation method (1) are as follows:
  • the first step is to prepare oxygen on the front side of the SOI wafer, that is, on the top layer of the single crystal silicon layer, using the SOI wafer as the substrate.
  • Silicon layer
  • the silicon oxide layer on the top layer of the single crystal silicon layer is patterned to form a window required for doping or ion implantation;
  • doping or ion implantation forms a doped silicon layer
  • the fourth step is to form a metal layer on the front side of the SOI wafer by deposition or evaporation;
  • the metal layer formed in the fourth step is patterned to form an electrical extraction pad metal and annealed to form an ohmic contact;
  • lithography forms an etch window pattern required for preparing the structure of the heating element, the measuring element and the ambient temperature measuring element, and then the SiO method is used to dry etch the silicon oxide layer and the top silicon layer, and the etching stops. Isolating the silicon oxide layer to form a structure of the heating element, the measuring element and the ambient temperature measuring element on the insulating silicon oxide layer;
  • an etch protection layer is prepared on the front side of the SOI silicon wafer (top layer single crystal silicon layer), and the etch protection layer is a photoresist or PSG (phosphorus silicate glass), and the etch protection layer covers the entire SOI silicon wafer.
  • a pattern of a back silicon etch window is formed on the back side of the SOI wafer, and is etched by a dry etching method such as wet etching or ICP or DRIE to remove the silicon etch window pattern on the back side of the SOI wafer.
  • a dry etching method such as wet etching or ICP or DRIE to remove the silicon etch window pattern on the back side of the SOI wafer.
  • the underlying silicon, the substrate, is etched to stop the isolation of the silicon oxide layer;
  • the isolating silicon oxide layer exposed from the substrate is wet-etched by using a hydrofluoric acid solution or a hydrofluoric acid gas mist to release the heating element and the temperature measuring element;
  • the etching protection layer formed in the seventh step is removed;
  • the exposed silicon is oxidized to form a thin silicon oxide layer
  • the protective layer is used to cover the front surface of the SOI silicon wafer, and the protective layer is a photoresist.
  • the protective layer covers a front portion of the SOI wafer except the heating element, the measuring element floating structure and the measuring resistance of the ambient temperature measuring element; the photoresist can be used as a protective layer; and the micro-printing device can be used for precise positioning after preparation.
  • the photoresist used as a protective layer may also be prepared by spraying using a masking plate overlying the front side of the SOI wafer; the masking plate only exposes the heating element, the measuring element suspended structure, and the environment The measuring element of the temperature measuring component, while the remaining portion of the SOI substrate is blocked by the masking plate;
  • the ALD method is used to prepare cerium oxide on the outer surface of the heating element, the measuring element floating structure and the measuring resistance of the ambient temperature measuring element, or to prepare an aluminum oxide film, or to prepare a cerium oxide/alumina composite film, or to prepare oxidation a silicon/yttria/alumina composite film, together with a thin layer of silicon oxide layer formed in the eleventh step, constitutes a passivation protective layer;
  • the protective layer used in the twelfth step is removed and dried;
  • the SOI silicon wafer is diced and split, and a large number of heating elements, a methane sensor in which the measuring element is integrated with the ambient temperature measuring element;
  • a silicon oxide layer is prepared on the top layer single crystal silicon layer by using a SOI silicon wafer as a substrate;
  • the silicon oxide layer on the top layer of the single crystal silicon layer is patterned to form a window required for doping or ion implantation;
  • doping or ion implantation forms a doped silicon layer
  • lithography forms an etch window pattern required for preparing the heating element, the measuring element and the structural temperature measuring element; the RIE method is used to dry etch the silicon oxide layer and the top silicon layer, and the etching stops in isolation.
  • a silicon oxide layer forming a structure of a heating element, a measuring element, and an ambient temperature measuring element on the isolated silicon oxide layer;
  • an etch protection layer is prepared on the front side of the SOI silicon wafer (top layer single crystal silicon layer), and the etch protection layer is a photoresist or PSG (phosphorus silicate glass), and the etch protection layer covers the entire SOI silicon wafer.
  • the underlying silicon of the SOI wafer ie, the substrate, is etched by wet etching or dry etching such as ICP or DRIE, and the etching stops at the isolation silicon oxide layer;
  • the isolating silicon oxide layer exposed from the substrate is wet-etched by a hydrofluoric acid solution or an aerosol, and the heating element and the temperature measuring element are released;
  • the etch protection layer formed in the fifth step is removed
  • the exposed silicon is oxidized to form a thin layer of silicon oxide
  • the protective layer is used to cover the front surface of the SOI silicon wafer, and the protective layer is a photoresist, and the protective layer covers the front part of the SOI silicon wafer except the heating resistor, the measuring component floating structure and the measuring resistance of the ambient temperature measuring component;
  • the photoresist can be used as a protective layer;
  • the photoresist used as a protective layer can be prepared after precise positioning by using a micro-jet printing device; or can be prepared by spraying using a masking plate covering the front surface of the SOI silicon wafer. a layer of photoresist; the masking plate exposes only the heating element, the measuring element flying structure, and the measuring resistance of the ambient temperature measuring element, while the remaining SOI substrate front portion is blocked by the masking plate;
  • an ALD method is used to prepare an aluminum oxide or tantalum oxide film on the outer surface of the heating element, the measuring element suspended structure, and the measuring resistance of the ambient temperature measuring element;
  • silicon nitride is prepared by PECVD at 400-450 ° C; prepared into a silicon oxide/silicon nitride conforming film, or a silicon oxide/alumina/silicon nitride composite film, or a yttria/silicon nitride composite film. Or a silicon oxide/yttria/alumina/silicon nitride conforming film, which together with the thin layer of oxysilicon layer formed in the ninth step and the aluminum oxide or yttrium oxide layer formed in the eleventh step constitute a passivation protective layer.
  • the protective layer used in the tenth step is removed and dried;
  • a photoresist is prepared on the front side of the SOI silicon wafer, and after lithography, the heating element, the fixed end of the measuring component, and the electrode lead end of the ambient temperature measuring component are exposed;
  • the photoresist is removed, dried; and annealed to form an ohmic contact
  • the SOI silicon wafer is diced and split, and a plurality of methane sensors integrated by the heating element, the measuring component and the ambient temperature measuring component are obtained according to the invention;
  • the first step to the thirteenth step are the first step to the thirteenth step of the preparation method (2),
  • a masking plate is prepared, the pattern on the masking plate being the same as the heating element on the SOI silicon wafer, the fixed end of the measuring component, and the electrode terminal of the ambient temperature measuring component; the masking plate is placed on the front side of the SOI wafer
  • the metal layer is prepared by sputtering, deposition, etc., and the electrical extraction pad metal (22) is formed only on the heating element, the fixed end of the measuring element, and the electrode terminal of the ambient temperature measuring element; Forming an ohmic contact;
  • the SOI wafer is diced and lobed to obtain a plurality of methane sensors integrated by the heating element, the measuring element and the ambient temperature measuring element according to the present invention.
  • the present invention provides a novel methane sensor processed using silicon as a processing material and processed by a CMOS-compatible MEMS process based on a single heating element, a separate measuring element, and a catalyst-free low
  • concentration of methane is detected and a separate ambient temperature sensing element is provided to detect the on-chip temperature of the sensor. Since the above scheme is employed, the methane sensor of the present invention has the following effective effects:
  • the methane sensor of the present invention uses a separate heating element and measuring element to detect a low concentration (0 to 4%) of methane gas without using a catalyst; since the catalyst and the catalytic carrier are not used, the performance of the sensor is not affected by the catalyst. There is no problem of sensitivity reduction, poisoning, activation, etc. caused by a decrease in catalyst activity; and methane detection can be realized without catalytic combustion of methane, and thus oxygen participation is not required, so the methane sensor of the present invention does not detect methane. Affected by oxygen in the air;
  • the heater of the heating element of the methane sensor of the present invention is suspended in the air and away from the silicon substrate, and the distance is greater than 300 um, and the silicon heater can be heated to a high temperature of 500 ° C or higher with a lower power, and the corresponding work is performed.
  • the consumption is about 80-90 mW; the heating element and the measuring element are independent of each other, and there is no direct contact, that is, there is no solid medium connection, so there is no energy loss path in the form of heat conduction from the heating element to the temperature measuring element, and thus the effective loss is also effectively reduced.
  • the power consumption of the heating element during operation; and, the methane sensor of the present invention requires only the heating element Heating to high temperature; measuring components and ambient temperature measuring components can operate with very low current, without heating to high temperature, so the power consumption of measuring components and ambient temperature measuring components is extremely low; the above comprehensive measures are greatly reduced
  • the overall power consumption of the methane sensor of the present invention therefore has the advantage of low power consumption.
  • the heating element, the measuring component and the ambient temperature measuring component of the methane sensor of the invention are processed by using single crystal silicon as a raw material, so that the processing process is uniform and simple, and the process is compatible with CMOS, and mass production is carried out by using a CMOS process, and the cost is low. It also enables the processed methane sensor to have good consistency and interchangeability, and is easy to implement batch calibration, which can further improve sensor performance and reduce the cost of sensor calibration.
  • the heating element, the measuring element and the ambient temperature measuring element of the methane sensor of the invention are all processed by single crystal silicon, and the methane sensor of the invention is operated under high temperature due to the stable performance of the single crystal silicon at high temperature. Has good stability and long life.
  • Single crystal silicon does not have the disadvantages of metal, such as platinum and tungsten, which are easily volatilized, sublimated, and migrated at a high temperature of 500 degrees Celsius or higher, and there is no disadvantage that the grain boundary resistance of the polysilicon resistor is easily changed at high temperatures and cannot be controlled.
  • the passivation layer provided on the outer surface of the heating element, the measuring element and the ambient temperature measuring element of the present invention also reduces the influence of the external environment on the above components, thereby further improving the stability of the performance of the methane sensor of the present invention.
  • the heating element and the measuring component of the methane sensor of the invention are independent of the structure of the ambient temperature measuring component, and are convenient for separately regulating the heating component and simultaneously detecting the temperature measuring component separately, so that there is no coupling relationship between heating and temperature measurement. It is no longer limited by the traditional single element heating and temperature measurement function multiplexing, which makes the methane sensor of the invention have multiple working modes, and the control configuration is simple and flexible, and can further improve the intelligence level of the methane sensor of the invention. And sensing performance.
  • the ambient temperature measuring component of the methane sensor of the present invention is used for independently detecting the on-chip temperature of the methane sensor of the present invention, which provides the closest and most realistic temperature data to the heating element and the measuring component, and is advantageous for the most accurate measurement data.
  • the excellent temperature compensation also lays the foundation for the intelligentization of the methane sensor of the invention.
  • the methane sensor of the invention has small size, low power consumption and fast response speed of up to 40 ms; the independent structure of the heating element and the measuring component enables the measuring component to detect the methane concentration with a very low self-heating effect, itself The reduction in thermal noise further enhances the sensitivity of the sensor of the present invention.
  • the methane sensor process of the present invention is CMOS compatible, enabling monolithic integration of sensors and their signal processing circuits. 10.
  • the methane sensor of the present invention can meet the demand for a high performance methane sensor in a portable environment using a battery, a use environment such as a coal mine underground environment Internet of Things.
  • the methane sensor based on a single heating element uses a stable silicon as a heating material, and does not require a catalyst to achieve high sensitivity detection of low concentration methane; this makes the methane sensor have stable performance.
  • the advantages of stable and long-term stability are no disadvantages such as poisoning, carbon deposition, activation, etc.
  • the power consumption of the methane sensor of the present invention is mainly determined by the power consumption of a single heating element used, and the power consumption of the measuring component and the ambient temperature measuring component.
  • the methane sensor of the present invention facilitates the use of a computer to flexibly adjust the temperature of the heating element according to the ambient temperature obtained by the on-chip integrated ambient temperature measuring component, and directly performs temperature compensation, thereby improving the sensor performance.
  • the methane sensor of the invention has good anti-interference performance, high sensitivity, low mass production cost and good consistency, and is easy to be quickly and batch-calibrated.
  • FIG. 1 is a top plan view of a methane sensor based on a single heating element of the present invention.
  • FIG. 2 is a cross-sectional view showing a fixed end of a heating element and a measuring element of the present invention, that is, a cross-sectional view taken along line A-A in FIG. 1.
  • Fig. 3 is a top plan view showing the heating element and the measuring element of the present invention disposed on the same side.
  • Embodiment 1 As shown in FIG. 1 and FIG. 2, the methane sensor comprises a heating element 101, a measuring element 102 and an ambient temperature measuring element 103; the ambient temperature measuring element 103 is disposed on the support 100;
  • the heating element 101 is composed of two fixed ends 1001, two supporting arms A1012 arranged side by side and a heater 1011. Two ends of the two supporting arms A1012 are respectively connected with the fixed end 1001 and the heater 1011 to form a two-terminal device.
  • the length of each of the support arms A1012 is at least 300 um;
  • the measuring element 102 is composed of two fixed ends 1001, a measuring member 1021 and two supporting arms B 1022, and the two supporting arms B 1022 are respectively connected to the two ends of the measuring member 1021 Connecting, the other ends of the two support arms B 1022 are respectively connected to the two fixed ends 1001 to form a two-terminal device;
  • each of the support cantilevers B1022 has a length of at least 100 ⁇ m;
  • the fixed end 1001 of the heating element 101 and the measuring element 102 The fixed ends 1001 are disposed independently of each other on the support 100, and the remaining portions are suspended in the air;
  • the heating element 101 and the measuring element 102 are structurally cantilevered
  • the measuring member 1021 of the measuring element 102 has a "one" structure or an arc-like structure as shown in FIG. 3; as shown in FIG. 1, the heating element 101 and the measuring element 102 Provided on the left and right sides; the heater 1011 of the heating element 101 is not in contact with the measuring member 1021 of the measuring element 102, and the distance is 2 um to 200 um.
  • the holder 101 includes a substrate 11 and an isolating silicon oxide layer 12 disposed on the substrate 11, and a top crystalline silicon layer 13 disposed on the isolated silicon oxide 12; a heating element 101, a measuring element 102, and an ambient temperature measurement
  • the element 103 is formed by using a top-level single crystal silicon layer 13 provided on the isolation silicon oxide 12, and the silicon structure of the heating element 101, the measuring element 102 and the ambient temperature measuring element 103 are respectively separated from the other top single crystals on the isolation silicon oxide 12.
  • the silicon layer 13 is not connected to each other;
  • the substrate 11 is silicon or other material that can be processed by a MEMS process;
  • the ambient temperature measuring element 103 disposed on the holder 100 includes two electrode terminals 1031 and a measuring resistor. 1032;
  • the heating element 101 and the fixed end 1001 of the measuring element 102 and the electrode terminal 1031 of the ambient temperature measuring element 103 are formed by the top single crystal silicon layer 13 and a silicon oxide layer 23 is disposed outside the top single crystal silicon layer 13 in the silicon oxide layer.
  • the layer 23 is provided with an electric lead-out pad metal 22;
  • the top end single-crystal silicon layer 13 of the fixed end 1001 and the electrode lead-out end 1031 is provided with a doped silicon layer 24;
  • the electric lead-out pad metal 22 passes through a silicon oxide layer
  • the window of 23 is in contact with the doped silicon layer 24 of the fixed end 1001 to form an ohmic contact;
  • the support arm A1012 of the heating element 101 protruding from the air and the heater 1011 and the outer surface of the measuring member 1021 and the supporting arm B 1022 of the measuring element 102 protruding in the air are provided with a passivation protective layer 14;
  • the outer surface of the measured silicon resistor 1031 of the ambient temperature measuring element 103 is also provided with a passivation protective layer 14;
  • the passivation protective layer 14 is silicon oxide, or tantalum oxide, or a silicon oxide/alumina composite layer, or tantalum oxide/ Alumina composite layer, or yttria/silicon nitride composite layer, or alumina/silicon nitride composite layer, or silicon oxide/silicon nitride composite layer, or silicon oxide, yttrium oxide, aluminum oxide, silicon nitride A composite layer formed by combining materials; wherein the thickness of the silicon oxide is at least 10 nm, the thickness of the yttrium oxide is at least 5 um, the thickness of the aluminum oxide is
  • a methane detection application method of a methane sensor based on a single heating element the heating element 101 of a methane sensor based on a single heating element is operated with a larger current or a larger voltage to enter the left side of the turning point in the current-resistance characteristic curve
  • the heating temperature of the region and the heater 1011 is above 500 ° C.
  • the turning point is the maximum point of resistance that occurs when the resistance increases with current or voltage. When the current or voltage continues to increase, the resistance does not continue to increase but decreases.
  • the measuring element 102 and the ambient temperature measuring element 103 are both passed through without generating a minute current that is significantly higher than the ambient air temperature; when there is no methane gas, the measuring element 102 is affected by the heating high temperature of the heating element 101, and the temperature is increased, and the resistance is also increased.
  • the temperature of the heating element 101 decreases, the temperature of the independent measuring element 102 is also reduced, resulting in a decrease in the electrical resistance thereof, and the electrical parameters such as the resistance change of the measuring component 102 are detected by an electrical measurement method.
  • the measuring component 103 measures the ambient temperature to adjust the heating state of the heating element 101, and can also be used to temperature compensate the data obtained by the measurement.
  • the preparation method of the methane sensor based on a single heating element includes the following three preparation methods;
  • the steps of the preparation method (1) are as follows:
  • the first step using a SOI wafer as a substrate, on the front side of the SOI wafer, that is, on the top layer of single crystal silicon layer 13 to prepare a silicon oxide layer 23;
  • the silicon oxide layer 23 on the top layer of the single crystal silicon layer 13 is patterned to form a window required for doping or ion implantation;
  • the third step doping or ion implantation to form a doped silicon layer 24;
  • the fourth step is to form a metal layer on the front side of the SOI wafer by deposition or evaporation;
  • the metal layer formed in the fourth step is patterned to form an electrical extraction pad metal 22 and annealed to form an ohmic contact;
  • photolithography forms an etching window pattern required for preparing the structural shape of the heating element 101, the measuring element 102 and the ambient temperature measuring element 103, and then dry etching the silicon oxide layer by reactive ion etching using RIEReactive Ion Etching. And the top layer of the single crystal silicon layer 13, the etching stops on the isolating silicon oxide layer 12, and the structure of the heating element 101, the measuring element 102 and the ambient temperature measuring element 103 is formed on the isolating silicon oxide layer 12;
  • an etch protection layer is prepared on the front side of the SOI silicon wafer, and the etch protection layer is photoresist or PSG (phosphorus silicate glass), and the protection layer is photoresist or PSG (phosphorus silicon) Glass), the etch protection layer covers the front side of the entire SOI silicon wafer;
  • a pattern of the back silicon etch window is formed after pattern lithography on the back side of the SOI wafer, and the silicon etch window pattern on the back side of the SOI wafer is etched by wet etching or dry etching such as ICP or DRIE.
  • the underlying silicon that is, the substrate 11, the etching stops at the isolation silicon oxide layer 12;
  • the ninth step using a hydrofluoric acid solution or hydrofluoric acid aerosol wet etching of the isolated silicon oxide layer 12 exposed from the substrate 11, releasing the heating element 103 and the temperature measuring element 104;
  • the etching protection layer formed in the seventh step is removed;
  • the exposed silicon is oxidized to form a thin silicon oxide layer
  • the front surface of the SOI silicon wafer is covered with a protective layer which is a photoresist, and the protective layer covers the SOI except the heating element 101, the floating structure of the measuring element 102, and the measuring resistor 1032 of the ambient temperature measuring element 103.
  • the front part of the silicon wafer; the photoresist can be used as a protective layer; the photoresist used as the protective layer can be prepared by precise positioning after the micro-printing device; or the masking plate covering the front surface of the SOI silicon wafer can be sprayed.
  • the photoresist is used as a protective layer; the masking plate exposes only the heating element 101, the measuring element 102 suspended structure, and the measuring resistor 1032 of the ambient temperature measuring element 103, while the remaining SOI substrate front portion is masked Block
  • yttrium oxide is prepared on the outer surface of the heating element 101, the floating structure of the measuring element 102, and the measuring resistor 1032 of the ambient temperature measuring element 103 by using an ALD atomic layer deposition method, or an aluminum oxide film is prepared, or yttrium oxide/oxidation is prepared.
  • the protective layer used in the twelfth step is removed and dried;
  • the SOI silicon wafer is diced and split, and a plurality of methane sensors integrated by the heating element 101, the measuring component 102 and the ambient temperature measuring component 103 are obtained according to the present invention;
  • the first step using a SOI silicon wafer as a substrate, a silicon oxide layer 23 is prepared on the top layer single crystal silicon layer 13;
  • the silicon oxide layer 23 on the top layer of the single crystal silicon layer 13 is patterned to form a window required for doping or ion implantation;
  • the third step doping or ion implantation to form a doped silicon layer 24;
  • the fourth step photolithography forms an etching window pattern required for preparing the structural shape of the heating element 101, the measuring element 102 and the ambient temperature measuring element (103); the silicon oxide layer 23 and the top layer are etched by RIE dry etching The crystalline silicon layer 13 is etched to stop the silicon oxide layer 12, and the structure of the heating element 101, the measuring element 102 and the ambient temperature measuring element 103 is formed on the isolated silicon oxide layer 12;
  • an etch protection layer is prepared on the front side of the SOI silicon wafer, and the etch protection layer is a photoresist or a PSG (phosphorus silicate glass), and the etch protection layer covers the front surface of the entire SOI wafer. ;
  • a pattern of a back silicon etch window is formed after pattern lithography on the back side of the SOI wafer, and a silicon etch window pattern on the back side of the SOI wafer is etched by wet etching or dry etching such as ICP or DRIE.
  • the underlying silicon that is, the substrate 11, the etching stops at the isolation silicon oxide layer 12;
  • the seventh step using a hydrofluoric acid solution or aerosol wet etching of the isolated silicon oxide layer 12 exposed from the substrate 11, releasing the heating element 103 and the temperature measuring element 104;
  • the etch protection layer formed in the fifth step is removed
  • the exposed silicon is oxidized to form a thin layer of silicon oxide
  • the front surface of the SOI silicon wafer is covered with a protective layer, and the protective layer is a photoresist, and the protective layer covers the heating resistor 101, the floating structure of the measuring component 102, and the measuring resistor 1032 of the ambient temperature measuring component 103.
  • the front side of the SOI wafer; the photoresist can be used as a protective layer; the photoresist can be prepared as a protective layer after precise positioning by using a micro-printing device; or can be sprayed using a masking plate covering the front surface of the SOI wafer.
  • the method of preparing the photoresist used as a protective layer the masking plate exposes only the heating element 101, the measuring element 102 suspended structure, and the measuring resistor 1032 of the ambient temperature measuring element 103, while the remaining SOI substrate front portion is Masked version obscured;
  • an aluminum oxide or hafnium oxide film is prepared on the outer surface of the heating element 101, the measuring element 102 suspended structure, and the measuring resistor 1032 of the ambient temperature measuring element 103 by an ALD atomic layer deposition method;
  • silicon nitride is prepared by PECVD at 400-450 ° C; prepared into a silicon oxide/silicon nitride conforming film, or a silicon oxide/alumina/silicon nitride composite film, or a yttria/silicon nitride composite film. Or a silicon oxide/yttria/alumina/silicon nitride conforming film, forming a passivation protective layer 14 together with a thin layer of silicon oxide layer formed in the ninth step, and an aluminum oxide or tantalum oxide layer formed in the eleventh step;
  • the protective layer used in the tenth step is removed and dried;
  • the fourteenth step preparing a photoresist on the front side of the SOI silicon wafer, after lithography, exposing the heating element 101, the fixed end 1001 of the measuring element 102, and the electrode lead end 1031 of the ambient temperature measuring element 103;
  • the photoresist is removed, dried; and annealed to form an ohmic contact
  • the SOI silicon wafer is diced and split, and a plurality of methane sensors integrated by the heating element 101, the measuring component 102 and the ambient temperature measuring component 103 are obtained according to the present invention;
  • the first step to the thirteenth step are the first step to the thirteenth step of the second method of preparation
  • a masking plate is prepared, the pattern on the masking plate being the same as the heating element 101 on the SOI silicon wafer, the fixed end 1001 of the measuring element 102, and the electrode lead end 1031 of the ambient temperature measuring element 103;
  • the metal is prepared by sputtering, deposition, etc., and is formed only on the heating element 101, the fixed end 1001 of the measuring element 102, and the electrode terminal 1031 of the ambient temperature measuring element 103. Electrically extracting the pad metal (22); annealing to form an ohmic contact;
  • the SOI wafer is diced and split, and a plurality of methane sensors integrated by the heating element 101, the measuring element 102 and the ambient temperature measuring element 103 are obtained.
  • Embodiment 2 The heating element 101 and the measuring element 102 of the methane sensor based on a single heating element are disposed on the same side as shown in FIG. Others are the same as in the first embodiment.

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Abstract

一种基于单个加热元件的甲烷传感器及制备方法和应用，适用于工矿企业中使用。该甲烷传感器包括加热元件（101）、测量元件（102）、环境温度测量元件（103）。该甲烷传感器的加热元件（101）的加热器（1011）和测量元件（102）的测量构件（1021）通过支撑臂悬置于空气中，加热元件（101）单独加热到高温工作状态，测量元件（102）单独用于检测瓦斯气体浓度，环境温度测量元件（103）检测片上温度用于温度补偿。该甲烷传感器加工工艺与CMOS工艺兼容。该传感器的优点为：结构简单、功耗低、灵敏度高、抗干扰性好、成本低。

Description

一种基于单个加热元件的甲烷传感器及制备方法和应用 技术领域
本发明涉及一种甲烷传感器及制备方法和应用，特别是一种工矿物联网中使用的基于单个加热元件的甲烷传感器及制备方法和应用。
背景技术
随着物联网的发展，当前的甲烷传感器无法满足单兵装备等对低功耗、长寿命、低成本的检测低浓度甲烷的甲烷传感器的需求。
目前用于煤矿井下检测低浓度甲烷的仍多是基于传统铂丝加热的催化燃烧式甲烷传感器，其原理是基于甲烷气体的催化燃烧反应释热效应。催化燃烧式甲烷传感器功耗较大，由于催化剂的使用，该种甲烷传感器具有积碳、中毒、激活等缺点，且性能不稳定、校验时间短。除此之外，现有催化燃烧式甲烷传感器采用铂丝等贵金属手工或机械绕制的线圈作为加热元件，难以批量化生产、且一致性与互换性较差，因此，不能很好的满足物联网对低功耗高性能甲烷传感器的应用需求。而红外甲烷传感器价格高、传感元件受粉尘与水汽严重影响；这两种甲烷传感器都不能很好的满足物联网对低功耗甲烷传感器的应用需求。其它的甲烷传感器亦难以适应煤矿井下特殊的使用环境。
发明内容
技术问题：本发明的目的是提供一种结构简单，不依赖催化剂，基于单个加热元件的能够检测低浓度甲烷的基于单个加热元件的甲烷传感器及制备方法和应用。
技术方案：为实现上述目的，本发明的基于单个加热元件的甲烷传感器包括加热元件、测量元件与环境温度测量元件；所述环境温度测量元件设在支座上；
所述加热元件由两个固定端、两个并排设置的支撑臂A与加热器构成，两个支撑臂A的两端分别与固定端和加热器相连接，形成二端子器件；所述每个支撑臂A的长度至少300um；所述测量元件由两个固定端、测量构件和两个支撑臂B构成，两个支撑臂B分别与测量构件的两端相连接，两个支撑臂B的另一端分别与两个固定端相连，构成二端子器件；所述每个支撑悬臂B的长度至少100um；所述加热元件的固定端与测量元件的固定端相互独立的设在支座上，其余部分悬置在空气中；加热元件和测量元件在结构上都为悬臂梁结构；所述加热元件的加热器为环形结构，所述测量元件的测量构件为“一”字结构或圆弧状结构，所述加热元件的加热器与测量元 件的测量构件之间不接触，所述相隔距离为2um至200um。
所述支座包括衬底与设在衬底上的隔离氧化硅层，及设在隔离氧化硅上的顶层单晶硅层；加热元件、测量元件与环境温度测量元件采用设在隔离氧化硅上的顶层单晶硅层加工形成，加热元件、测量元件与环境温度测量元件的硅结构分别都与隔离氧化硅上的其它的顶层单晶硅层隔离不相连接；所述衬底为硅或其它可采用MEMS工艺加工的材料；所述设在支座上的环境温度测量元件包括两个电极引出端、及测量电阻；
加热元件与测量元件的固定端及环境温度测量元件的电极引出端由顶层单晶硅层形加工成，在顶层单晶硅层外有氧化硅层，在氧化硅层上设有电引出焊盘金属；所述固定端与电极引出端的顶层单晶硅层内设有掺杂硅层；所述电引出焊盘金属通过氧化硅层的窗口与固定端的掺杂硅层相接触构成欧姆接触；
所述加热元件的伸出在空气中的支撑臂A与加热器以及测量元件的伸出在空气中的测量构件、支撑臂B的外表面设有钝化保护层；所述环境温度测量元件的测量硅电阻的外表面同样设有钝化保护层；所述钝化保护层为氧化硅，或氧化铪，或氧化硅/氧化铝复合层，或氧化铪/氧化铝复合层，或氧化铪/氮化硅复合层，或氧化铝/氮化硅复合层，或氧化硅/氮化硅复合层，或氧化硅、氧化铪、氧化铝、氮化硅几种材料组合形成的复合层；其中氧化硅的厚度至少10nm，氧化铪的厚度至少为5um，氧化铝厚度至少6nm，氮化硅厚度至少10nm，整个钝化保护层的厚度不超过1um。
一种基于单个加热元件的甲烷传感器的甲烷检测应用方法，所述基于单个加热元件的甲烷传感器的加热元件通以较大电流或施加较大电压进入电流-电阻特性曲线中转折点左侧的工作区域、加热器的加热温度在500℃以上，所述转折点为电阻随电流或电压增大而出现的电阻最大点，当电流或电压继续增大时，电阻不再继续增大反而减小；测量元件与环境温度测量元件则都通以不产生明显高于环境空气温度的微小电流；当没有甲烷气体时，测量元件受加热元件的加热高温影响温度升高，电阻也增大；当甲烷气体出现及浓度增加时，加热元件的温度降低，独立的测量元件受其影响温度也降低，导致自身电阻的降低，通过电学测量方法检测测量元件的电学参数(如电阻)的变化实现甲烷浓度的测量；采用环境温度测量元件测量环境温度，用以调整加热元件的加热状态，还可用以对测量所获得的数据进行温度补偿。
基于单个加热元件的甲烷传感器的制备方法包括以下三种制备方法：
制备方法(一)的步骤为：
第一步，以SOI硅片为基片，在SOI硅片的正面，即在顶层单晶硅层上制备氧 化硅层；
第二步，图形化顶层单晶硅层上之上的氧化硅层，形成掺杂或离子注入所需的窗口；
第三步，掺杂或离子注入形成掺杂硅层；
第四步，在SOI硅片的正面通过淀积或蒸发形成金属层；
第五步，图形化第四步形成的金属层，形成电引出焊盘金属，退火形成欧姆接触；
第六步，光刻形成制备加热元件、测量元件与环境温度测量元件结构形状所需的刻蚀窗口图形，随后采用RIE方法干法刻蚀氧化硅层及顶层单晶硅层，刻蚀停止于隔离氧化硅层，在隔离氧化硅层上形成加热元件、测量元件与环境温度测量元件的结构；
第七步，在SOI硅片的正面(顶层单晶硅层面)制备刻蚀保护层，刻蚀保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
第八步，在SOI硅片背面图形光刻后形成背面硅刻蚀窗口的图形，采用湿法刻蚀或ICP或DRIE等干法刻蚀方法刻蚀去除SOI硅片背面硅刻蚀窗口图形内的底层硅，即衬底，刻蚀停止于隔离氧化硅层；
第九步，采用氢氟酸溶液或氢氟酸气雾湿法刻蚀从衬底露出的隔离氧化硅层，释放出加热元件与测温元件；
第十步，去除第七步所形成的刻蚀保护层；
第十一步，对暴露出的硅进行氧化，形成薄层氧化硅层；
第十二步，采用保护层覆盖SOI硅片的正面，保护层为光刻胶，
Figure PCTCN2015093007-appb-000001
所述保护层覆盖除加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻以外的SOI硅片正面部分；可以光刻胶作为保护层；可采用微喷印设备在精确定位后制备用作保护层的光刻胶；也可使用覆盖在SOI硅片正面的掩蔽版采用喷涂的方法制备所述用作保护层的光刻胶；所述掩蔽版仅露出加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻，而其余的SOI基片正面部分则被掩蔽版遮挡住；
第十三步，采用ALD方法在加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻的外表面制备氧化铪，或制备氧化铝薄膜，或制备氧化铪/氧化铝复合薄膜，或制备氧化硅/氧化铪/氧化铝复合薄膜，与第十一步形成的薄层氧硅层共同构成钝化保护层；
第十四步，去除第十二步使用的保护层，干燥；
第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件、 测量元件与环境温度测量元件集成在一起的甲烷传感器；
或制备方法(二)的步骤为：
第一步，以SOI硅片为基片，在顶层单晶硅层上制备氧化硅层；
第二步，图形化顶层单晶硅层上之上的氧化硅层，形成掺杂或离子注入所需的窗口；
第三步，掺杂或离子注入形成掺杂硅层；
第四步，光刻形成制备加热元件、测量元件与环境温度测量元件结构形状所需的刻蚀窗口图形；采用RIE方法干法刻蚀氧化硅层及顶层单晶硅层，刻蚀停止于隔离氧化硅层，在隔离氧化硅层上形成加热元件、测量元件与环境温度测量元件的结构；
第五步，在SOI硅片的正面(顶层单晶硅层面)制备刻蚀保护层，刻蚀保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
第六步，在SOI硅片背面光刻，采用湿法刻蚀或ICP或DRIE等干法刻蚀方法刻蚀SOI硅片的底层硅，即衬底，刻蚀停止于隔离氧化硅层；
第七步，采用氢氟酸溶液或气雾湿法刻蚀从衬底露出的隔离氧化硅层，释放出加热元件与测温元件；
第八步，去除第五步所形成的刻蚀保护层；
第九步，对暴露出的硅进行氧化，形成薄层氧化硅层；
第十步，采用保护层覆盖SOI硅片的正面，保护层为光刻胶，所述保护层覆盖除加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻以外的SOI硅片正面部分；可以光刻胶作为保护层；可采用微喷印设备在精确定位后制备用作保护层的光刻胶；也可使用覆盖在SOI硅片正面的掩蔽版采用喷涂的方法制备所述用作保护层的光刻胶；所述掩蔽版仅露出加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻，而其余的SOI基片正面部分则被掩蔽版遮挡住；
第十一步，采用ALD方法在加热元件、测量元件悬空结构以及环境温度测量元件的测量电阻的外表面制备氧化铝或氧化铪薄膜；
第十二步，采用PECVD在400～450℃制备氮化硅；制备成氧化硅/氮化硅符合薄膜，或氧化硅/氧化铝/氮化硅复合薄膜，或氧化铪/氮化硅复合薄膜，或氧化硅/氧化铪/氧化铝/氮化硅符合薄膜，与第九步形成的薄层氧硅层、第十一步形成的氧化铝或氧化铪层共同构成钝化保护层。
第十三步，去除第十步使用的保护层，干燥；
第十四步，在SOI硅片正面制备光刻胶，光刻后露出加热元件、测量元件的固定端、环境温度测量元件的电极引出端；
第十五步，通过淀积或蒸发在加热元件、测量元件的固定端、环境温度测量元件的电极引出端上形成电引出焊盘金属；
第十六步，去除光刻胶，干燥；退火形成欧姆接触；
第十七步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件、测量元件与环境温度测量元件集成在一起的甲烷传感器；
或制备方法(三)的步骤为：
第一步至第十三步同制备方法(二)的第一步至第十三步，
第十四步，制备掩蔽版，所述掩蔽版上的图形与SOI硅片上的加热元件、测量元件的固定端、环境温度测量元件的电极引出端的图形相同；掩蔽版置于SOI硅片正面之上并对准后，通过溅射、沉积等方法制备金属层，仅在加热元件、测量元件的固定端、环境温度测量元件的电极引出端之上形成电引出焊盘金属(22)；退火形成欧姆接触；
第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件、测量元件与环境温度测量元件集成在一起的甲烷传感器。
有益效果：本发明提供了一种新型的甲烷传感器，该甲烷传感器以硅为加工材料，采用CMOS兼容的MEMS工艺加工，该甲烷传感器基于单个加热元件、单独的测量元件而未采用催化剂实现对低浓度甲烷的检测，并设有单独的环境温度传感元件检测传感器的片上温度。由于采用了上述方案，本发明的甲烷传感器具有以下有效效果：
1、本发明的甲烷传感器使用独立的加热元件与测量元件检测低浓度(0～4％)甲烷气体，未使用催化剂；由于没使用催化剂与催化载体，因此，传感器的性能不受催化剂的影响，不存在催化剂活性降低导致的灵敏度降低、中毒、激活等问题；并且无需对甲烷进行催化燃式反即可实现甲烷检测，也就不需要氧气的参与，因此本发明的甲烷传感器对甲烷的检测不受空气中氧气的影响；
2、本发明的甲烷传感器的加热元件的加热器悬在空气中且远离硅衬底，距离大于300um以上，以较低的功率即可将硅加热器加热到500℃以上的高温，相应的功耗为80～90mW左右；加热元件与测量元件相互独立，没有直接接触，即不存在固态介质连接，因此不存在从加热元件到测温元件的热传导形式的能量损失路径，因此也有效的降低了加热元件工作时的功耗；并且，本发明的甲烷传感器只有加热元件需要 加热到高温；测量元件与环境温度测量元件都只需极低的电流即可工作，而无需加热至高温，因此测量元件与环境温度测量元件的功耗都极低；上述的综合措施大幅降低了本发明的甲烷传感器的总体功耗，因此具有低功耗的优势。
3、本发明的甲烷传感器的加热元件、测量元件与环境温度测量元件都以单晶硅为原材料加工获得，使得加工工艺统一、简单，且工艺与CMOS兼容，采用CMOS工艺批量生产，成本低廉、还可使加工的甲烷传感器具有良好的一致性、互换性，易于实现批量校准，能进一步提高传感器性能并降低传感器校准环节的成本。
4、本发明的甲烷传感器的加热元件、测量元件与环境温度测量元件都以单晶硅加工得到，由于单晶硅在高温下具有稳定的性能，这使本发明的甲烷传感器在高温工作状态下具有良好的稳定性与长的寿命。单晶硅不存在铂、钨等金属加热材料在500摄氏度以上的高温容易挥发、升华、迁移等缺点、也不存在多晶硅电阻在高温下晶界电阻易于变化、无法掌控的缺点。同时，在本发明的加热元件、测量元件与环境温度测量元件的外表面设置的钝化层也降低了外界环境对上述元器件的影响，从而进一步提高了本发明的甲烷传感器性能的稳定性。
5、本发明的甲烷传感器的加热元件、测量元件与环境温度测量元件结构上的独立，便于单独调控加热元件、同时单独对测温元件进行检测，使加热与测温之间不存在耦合关系，不再受传统的单一元件加热与测温功能复用的限制，这使本发明的甲烷传感器可具有多种工作模式，且使调控配置简单、灵活，能进一步提高本发明甲烷传感器的智能化水平及传感性能。
6、本发明的甲烷传感器的环境温度测量元件用于独立检测本发明的甲烷传感器的片上温度，这提供了与加热元件、测量元件距离最近、最真实的温度数据，有利于对测量数据进行最佳的温度补偿、同时也为本发明的甲烷传感器智能化奠定了基础。
7、本发明的甲烷传感器，尺寸小、功耗低，并且响应速度快、可达40ms左右；加热元件与测量元件结构上的独立可使测量元件以极低的自加热效应检测甲烷浓度，自身热噪声的降低使本发明的传感器的灵敏度进一步得到提升。
8、本发明的甲烷传感器工艺与CMOS兼容，可实现传感器及其信号处理电路的单片集成。10、本发明的甲烷传感器能够满足采用电池的便携装备、煤矿井下环境物联网等使用环境对高性能甲烷传感器的需求。
优点：本发明提供的基于单个加热元件的甲烷传感器，以性能稳定的硅为加热材料，无需采用催化剂实现低浓度甲烷的高灵敏度检测；这使该甲烷传感器具有性能稳 定、长期稳定性好的优点，无中毒、积碳、激活等缺点；本发明的甲烷传感器的功耗主要由采用的单个加热元件的功耗决定，测量元件及环境温度测量元件消耗的功耗极低，因此传感器的总体功耗低；本发明的甲烷传感器有利于采用计算机根据片上集成的环境温度测量元件获得的环境温度灵活的调节加热元件的温度、完成直接进行温度补偿，从而提高传感器的性能。本发明的甲烷传感器抗干扰性能好、灵敏度高，批量生产成本低且一致性好，易于批量快速校准。
附图说明
图1为本发明的基于单个加热元件的甲烷传感器的俯视示意图。
图2为本发明的加热元件和测量元件的固定端的剖视图，即图1中的A-A截面剖视图。
图3为本发明的加热元件、测量元件设置在同一侧时的俯视示意图。
图中：100-支座，101-加热元件，102-测量元件，103-环境温度测量元件，1001-固定端，1012-支撑臂A，1011-加热器，1021-测量构件，1022-支撑臂B，1031-电极引出端，1032-测量电阻，11-衬底，12-隔离氧化硅层，13-顶层单晶硅层，14-钝化保护层，22-电引出焊盘金属，23-氧化硅层，24-掺杂硅层。
具体实施方式
下面结合附图对本发明的实施例作进一步的描述：
实施例1：如在图1、图2中，该甲烷传感器包括加热元件101、测量元件102与环境温度测量元件103；所述环境温度测量元件103设在支座100上；
所述加热元件101由两个固定端1001、两个并排设置的支撑臂A1012与加热器1011构成，两个支撑臂A1012的两端分别与固定端1001和加热器1011相连接，形成二端子器件；所述每个支撑臂A1012的长度至少300um；所述测量元件102由两个固定端1001、测量构件1021和两个支撑臂B1022构成，两个支撑臂B1022分别与测量构件1021的两端相连接，两个支撑臂B1022的另一端分别与两个固定端1001相连，构成二端子器件；所述每个支撑悬臂B1022的长度至少100um；所述加热元件101的固定端1001与测量元件102的固定端1001相互独立的设在支座100上，其余部分悬置在空气中；加热元件101和测量元件102在结构上都为悬臂梁结构；所述加热元件101的加热器1011为环形结构，测量元件102的测量构件1021为“一”字结构或如图3中所示的圆弧状结构；如图1所示，所述加热元件101与测量元件102 设在左右两侧；所述加热元件101的加热器1011与测量元件102的测量构件1021之间不接触，所述相隔距离为2um至200um。所述支座101包括衬底11与设在衬底11上的隔离氧化硅层12，及设在隔离氧化硅12上的顶层单晶硅层13；加热元件101、测量元件102与环境温度测量元件103采用设在隔离氧化硅12上的顶层单晶硅层13加工形成，加热元件101、测量元件102与环境温度测量元件103的硅结构分别都与隔离氧化硅12上的其它的顶层单晶硅层13隔离不相连接；所述衬底11为硅或其它可采用MEMS工艺加工的材料；所述设在支座100上的环境温度测量元件103包括两个电极引出端1031、及测量电阻1032；
加热元件101与测量元件102的固定端1001及环境温度测量元件103的电极引出端1031由顶层单晶硅层13加工形成，在顶层单晶硅层13外设有氧化硅层23，在氧化硅层23上设有电引出焊盘金属22；所述固定端1001与电极引出端1031的顶层单晶硅层13内设有掺杂硅层24；所述电引出焊盘金属22通过氧化硅层23的窗口与固定端1001的掺杂硅层24相接触构成欧姆接触；
所述加热元件101的伸出在空气中的支撑臂A1012与加热器1011以及测量元件102的伸出在空气中的测量构件1021、支撑臂B1022的外表面设有钝化保护层14；所述环境温度测量元件103的测量硅电阻1031的外表面同样设有钝化保护层14；所述钝化保护层14为氧化硅，或氧化铪，或氧化硅/氧化铝复合层，或氧化铪/氧化铝复合层，或氧化铪/氮化硅复合层，或氧化铝/氮化硅复合层，或氧化硅/氮化硅复合层，或氧化硅、氧化铪、氧化铝、氮化硅几种材料组合形成的复合层；其中氧化硅的厚度至少10nm，氧化铪的厚度至少为5um，氧化铝厚度至少6nm，氮化硅厚度至少10nm，整个钝化保护层的厚度不超过1um。
一种基于单个加热元件的甲烷传感器的甲烷检测应用方法，所述基于单个加热元件的甲烷传感器的加热元件101通以较大电流或施加较大电压进入电流-电阻特性曲线中转折点左侧的工作区域、加热器1011的加热温度在500℃以上，所述转折点为电阻随电流或电压增大而出现的电阻最大点，当电流或电压继续增大时，电阻不再继续增大反而减小；测量元件102与环境温度测量元件103则都通以不产生明显高于环境空气温度的微小电流；当没有甲烷气体时，测量元件102受加热元件101的加热高温影响温度升高，电阻也增大；当甲烷气体出现及浓度增加时，加热元件101的温度降低，独立的测量元件102受其影响温度也降低，导致自身电阻的降低，通过电学测量方法检测测量元件102的电学参数如电阻的变化实现甲烷浓度的测量；采用环境温 度测量元件103测量环境温度，用以调整加热元件101的加热状态，还可用以对测量所获得的数据进行温度补偿。
基于单个加热元件的甲烷传感器的制备方法包括以下三种制备方法；
制备方法(一)的步骤为：
第一步，以SOI硅片为基片，在SOI硅片的正面，即在顶层单晶硅层13上制备氧化硅层23；
第二步，图形化顶层单晶硅层13上之上的氧化硅层23，形成掺杂或离子注入所需的窗口；
第三步，掺杂或离子注入形成掺杂硅层24；
第四步，在SOI硅片的正面通过淀积或蒸发形成金属层；
第五步，图形化第四步形成的金属层，形成电引出焊盘金属22，退火形成欧姆接触；
第六步，光刻形成制备加热元件101、测量元件102与环境温度测量元件103结构形状所需的刻蚀窗口图形，随后采用RIEReactive Ion Etching，反应离子刻蚀方法干法刻蚀氧化硅层23及顶层单晶硅层13，刻蚀停止于隔离氧化硅层12，在隔离氧化硅层12上形成加热元件101、测量元件102与环境温度测量元件103的结构；
第七步，在SOI硅片的正面顶层单晶硅层面制备刻蚀保护层，刻蚀保护层为光刻胶或PSG(磷硅玻璃)，所述保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
第八步，在SOI硅片背面图形光刻后形成背面硅刻蚀窗口的图形，采用湿法刻蚀或ICP或DRIE等干法刻蚀方法刻蚀去除SOI硅片背面的硅刻蚀窗口图形内的底层硅，即衬底11，刻蚀停止于隔离氧化硅层12；
第九步，采用氢氟酸溶液或氢氟酸气雾湿法刻蚀从衬底11露出的隔离氧化硅层12，释放出加热元件103与测温元件104；
第十步，去除第七步所形成的刻蚀保护层；
第十一步，对暴露出的硅进行氧化，形成薄层氧化硅层；
第十二步，采用保护层覆盖SOI硅片的正面，保护层为光刻胶，所述保护层覆盖除加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032以外的SOI硅片正面部分；可以光刻胶作为保护层；可采用微喷印设备在精确定位后制备用作保护层的光刻胶；也可使用覆盖在SOI硅片正面的掩蔽版采用喷涂的方法制 备所述用作保护层的光刻胶；所述掩蔽版仅露出加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032，而其余的SOI基片正面部分则被掩蔽版遮挡住；
第十三步，采用ALD原子层沉积方法在加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032的外表面制备氧化铪，或制备氧化铝薄膜，或制备氧化铪/氧化铝复合薄膜，或制备氧化硅/氧化铪/氧化铝复合薄膜，与第十一形成的薄层氧硅层共同构成钝化保护层14；
第十四步，去除第十二步使用的保护层，干燥；
第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件101、测量元件102与环境温度测量元件103集成在一起的甲烷传感器；
或制备方法(二)的步骤为：
第一步，以SOI硅片为基片，在顶层单晶硅层13上制备氧化硅层23；
第二步，图形化顶层单晶硅层13上之上的氧化硅层23，形成掺杂或离子注入所需的窗口；
第三步，掺杂或离子注入形成掺杂硅层24；
第四步，第四步，光刻形成制备加热元件101、测量元件102与环境温度测量元件(103)结构形状所需的刻蚀窗口图形；采用RIE干法刻蚀氧化硅层23及顶层单晶硅层13，刻蚀停止于隔离氧化硅层12，在隔离氧化硅层12上形成加热元件101、测量元件102与环境温度测量元件103的结构；
第五步，在SOI硅片的正面顶层单晶硅层面制备刻蚀保护层，刻蚀保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
第六步，在SOI硅片背面图形光刻后形成背面硅刻蚀窗口的图形，采用湿法刻蚀或ICP或DRIE等干法刻蚀方法刻蚀去除SOI硅片背面的硅刻蚀窗口图形内的底层硅，即衬底11，刻蚀停止于隔离氧化硅层12；
第七步，采用氢氟酸溶液或气雾湿法刻蚀从衬底11露出的隔离氧化硅层12，释放出加热元件103与测温元件104；
第八步，去除第五步所形成的刻蚀保护层；
第九步，对暴露出的硅进行氧化，形成薄层氧化硅层；
第十步，采用保护层覆盖SOI硅片的正面，保护层为光刻胶，所述保护层覆盖除加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032 以外的SOI硅片正面部分；可以光刻胶作为保护层；可采用微喷印设备在精确定位后制备用作保护层的光刻胶；也可使用覆盖在SOI硅片正面的掩蔽版采用喷涂的方法制备所述用作保护层的光刻胶；所述掩蔽版仅露出加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032，而其余的SOI基片正面部分则被掩蔽版遮挡住；
第十一步，采用ALD原子层沉积方法在加热元件101、测量元件102悬空结构以及环境温度测量元件103的测量电阻1032的外表面制备氧化铝或氧化铪薄膜；
第十二步，采用PECVD在400～450℃制备氮化硅；制备成氧化硅/氮化硅符合薄膜，或氧化硅/氧化铝/氮化硅复合薄膜，或氧化铪/氮化硅复合薄膜，或氧化硅/氧化铪/氧化铝/氮化硅符合薄膜，与第九步形成的薄层氧硅层、第十一步形成的氧化铝或氧化铪层共同构成钝化保护层14；
第十三步，去除第十步使用的保护层，干燥；
第十四步，在SOI硅片正面制备光刻胶，光刻后露出加热元件101、测量元件102的固定端1001、环境温度测量元件103的电极引出端1031；
第十五步，通过淀积或蒸发在加热元件101、测量元件102的固定端1001、环境温度测量元件103的电极引出端1031上形成电引出焊盘金属22；
第十六步，去除光刻胶，干燥；退火形成欧姆接触；
第十七步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件101、测量元件102与环境温度测量元件103集成在一起的甲烷传感器；
或制备方法(三)的步骤为：
第一步至第十三步同制备方法二的第一步至第十三步，
第十四步，制备掩蔽版，所述掩蔽版上的图形与SOI硅片上的加热元件101、测量元件102的固定端1001、环境温度测量元件103的电极引出端1031的图形相同；掩蔽版置于SOI硅片正面之上并对准后，通过溅射、沉积等方法制备金属，仅在加热元件101、测量元件102的固定端1001、环境温度测量元件103的电极引出端1031之上形成电引出焊盘金属(22)；退火形成欧姆接触；
第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件101、测量元件102与环境温度测量元件103集成在一起的甲烷传感器。
实施例2：所述基于单个加热元件的甲烷传感器的加热元件101、测量元件102设置在同一侧，如图3所示。其它与实施例1同。

Claims (3)

  1. 一种基于单个加热元件的甲烷传感器，其特征在于：它包括加热元件(101)、测量元件(102)与环境温度测量元件(103)；所述环境温度测量元件(103)设在支座(100)上；
    所述加热元件(101)由两个固定端(1001)、两个并排设置的支撑臂A(1012)与加热器(1011)构成，两个支撑臂A(1012)的两端分别与固定端(1001)和加热器(1011)相连接，形成二端子器件；所述每个支撑臂A(1012)的长度至少300um；所述测量元件(102)由两个固定端(1001)、测量构件(1021)和两个支撑臂B(1022)构成，两个支撑臂B(1022)分别与测量构件(1021)的两端相连接，两个支撑臂B(1022)的另一端分别与两个固定端(1001)相连，构成二端子器件；所述每个支撑臂B(1022)的长度至少100um；所述加热元件(101)的固定端(1001)与测量元件(102)的固定端(1001)相互独立的设在支座(100)上，其余部分悬置在空气中；加热元件(101)和测量元件(102)在结构上都为悬臂梁结构；所述加热元件(101)的加热器(1011)与测量元件(102)的测量构件(1021)不接触，相距2um至200um；
    所述支座(101)包括衬底(11)与设在衬底(11)上的隔离氧化硅层(12)，及设在隔离氧化硅(12)上的顶层单晶硅层(13)；加热元件(101)、测量元件(102)与环境温度测量元件(103)采用设在隔离氧化硅(12)上的顶层单晶硅层(13)加工形成，加热元件(101)、测量元件(102)与环境温度测量元件(103)的硅结构分别都与隔离氧化硅(12)上的其它的顶层单晶硅层(13)隔离不相连接；所述衬底(11)为硅或其它可采用MEMS工艺加工的材料；所述设在支座(100)上的环境温度测量元件(103)包括两个电极引出端(1031)、及测量电阻(1032)；
    加热元件(101)与测量元件(102)的固定端(1001)及环境温度测量元件(103)的电极引出端(1031)由顶层单晶硅层(13)加工形成，在顶层单晶硅层(13)外有氧化硅层(23)，在氧化硅层(23)上设有电引出焊盘金属(22)；所述固定端(1001)与电极引出端(1031)的顶层单晶硅层(13)内设有掺杂硅层(24)；所述电引出焊盘金属(22)通过氧化硅层(23)的窗口与固定端(1001)的掺杂硅层(24)相接触构成欧姆接触；
    所述加热元件(101)的伸出在空气中的支撑臂A(1012)与加热器(1011) 以及测量元件(102)的伸出在空气中的测量构件(1021)、支撑臂B(1022)的外表面设有钝化保护层(14)；所述环境温度测量元件(103)的测量硅电阻(1031)的外表面同样设有钝化保护层(14)；所述钝化保护层(14)为氧化硅，或氧化铪，或氧化硅/氧化铝复合层，或氧化铪/氧化铝复合层，或氧化铪/氮化硅复合层，或氧化铝/氮化硅复合层，或氧化硅/氮化硅复合层，或氧化硅、氧化铪、氧化铝、氮化硅几种材料组合形成的复合层；其中氧化硅的厚度至少10nm，氧化铪的厚度至少为5um，氧化铝厚度至少6nm，氮化硅厚度至少10nm，整个钝化保护层的厚度不超过1um。
  2. 一种基于单个加热元件的甲烷传感器的应用，其特征在于：所述基于单个加热元件的甲烷传感器的加热元件(101)通以较大电流或施加较大电压进入电流-电阻特性曲线中转折点左侧的工作区域、加热器(1011)的加热温度在500℃以上，所述转折点为电阻随电流或电压增大而出现的电阻最大点，当电流或电压继续增大时，电阻不再继续增大反而减小；测量元件(102)与环境温度测量元件(103)则都通以不产生明显高于环境空气温度的微小电流；当没有甲烷气体时，测量元件(102)受加热元件(101)的加热高温影响温度升高，电阻也增大；当甲烷气体出现及浓度增加时，加热元件(101)的温度降低，独立的测量元件(102)受其影响温度也降低，导致自身电阻的降低，通过电学测量方法检测测量元件(102)的电学参数(如电阻)的变化实现甲烷浓度的测量；采用环境温度测量元件(103)测量环境温度，用以调整加热元件(101)的加热状态，还可用以对测量所获得的数据进行温度补偿。
  3. 如权力要求1所述的基于单个加热元件的甲烷传感器的制备方法，其特征在于；
    制备方法(一)的步骤为：
    第一步，以SOI硅片为基片，在SOI硅片的正面，即在顶层单晶硅层(13)上制备氧化硅层(23)；
    第二步，图形化顶层单晶硅层(13)上之上的氧化硅层(23)，形成掺杂或离子注入所需的窗口；
    第三步，掺杂或离子注入形成掺杂硅层(24)；
    第四步，在SOI硅片的正面通过淀积或蒸发形成金属层；
    第五步，图形化第四步形成的金属层，形成电引出焊盘金属(22)，退火形成欧姆接触；
    第六步，光刻形成制备加热元件(101)、测量元件(102)与环境温度测量元件(103)结构形状所需的刻蚀窗口图形，随后采用RIE(Reactive Ion Etching，反应离子刻蚀)方法干法刻蚀氧化硅层(23)及顶层单晶硅层(13)，刻蚀停止于隔离氧化硅层(12)，在隔离氧化硅层(12)上形成加热元件(101)、测量元件(102)与环境温度测量元件(103)的结构；
    第七步，在SOI硅片的正面(顶层单晶硅层面)制备刻蚀保护层，保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
    第八步，在SOI硅片背面图形光刻后形成背面硅刻蚀窗口的图形，采用湿法刻蚀或ICP(Inductively Coupled Plasma，感应耦合等离子体刻蚀)或DRIE(Deep Reactive Ion Etching，深反应离子刻蚀)等干法刻蚀方法刻蚀去除SOI硅片背面硅刻蚀窗口图形内的底层硅，即衬底(11)，刻蚀停止于隔离氧化硅层(12)；
    第九步，采用氢氟酸溶液或氢氟酸气雾湿法刻蚀从衬底(11)露出的隔离氧化硅层(12)，释放出加热元件(103)与测温元件(104)；
    第十步，去除第七步所形成的刻蚀保护层；
    第十一步，对暴露出的硅进行氧化，形成薄层氧化硅层；
    第十二步，采用保护层覆盖SOI硅片的正面，所述保护层覆盖除加热元件(101)、测量元件(102)悬空结构以及环境温度测量元件(103)的测量电阻(1032)以外的SOI硅片正面部分；
    第十三步，采用ALD(原子层沉积)方法在加热元件(101)、测量元件(102)的悬空结构以及环境温度测量元件(103)的测量电阻(1032)的外表面制备氧化铪，或制备氧化铝薄膜，或制备氧化铪/氧化铝复合薄膜，或制备氧化硅/氧化铪/氧化铝复合薄膜，与第十一步形成的薄层氧硅层共同构成形成钝化保护层(14)；
    第十四步，去除第十二步使用的保护层，干燥；
    第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件(101)、测量元件(102)与环境温度测量元件(103)集成在一起的甲烷传感器；
    或制备方法(二)步骤为：
    第一步，以SOI硅片为基片，在顶层单晶硅层(13)上制备氧化硅层(23)；
    第二步，图形化顶层单晶硅层(13)上之上的氧化硅层(23)，形成掺杂或离子注入所需的窗口；
    第三步，掺杂或离子注入形成掺杂硅层(24)；
    第四步，光刻形成制备加热元件(101)、测量元件(102)与环境温度测量元件(103)结构形状所需的刻蚀窗口图形；采用RIE(Reactive Ion Etching，反应离子刻蚀)方法干法刻蚀氧化硅层(23)及顶层单晶硅层(13)，刻蚀停止于隔离氧化硅层(12)，在隔离氧化硅层(12)上形成加热元件(101)、测量元件(102)与环境温度测量元件(103)的结构；
    第五步，在SOI硅片的正面(顶层单晶硅层面)制备刻蚀保护层，刻蚀保护层为光刻胶或PSG(磷硅玻璃)，所述刻蚀保护层覆盖整个SOI硅片的正面；
    第六步，在SOI硅片背面图形光刻后形成背面硅刻蚀窗口的图形，采用湿法刻蚀或ICP(Inductively Coupled Plasma，感应耦合等离子体刻蚀)或DRIE(Deep Reactive Ion Etching，深反应离子刻蚀)等干法刻蚀方法刻蚀去除SOI硅片背面硅刻蚀窗口图形内的底层硅，即衬底(11)，刻蚀停止于隔离氧化硅层(12)；
    第七步，采用氢氟酸溶液或气雾湿法刻蚀从衬底(11)露出的隔离氧化硅层(12)，释放出加热元件(103)与测温元件(104)；
    第八步，去除第五步所形成的刻蚀保护层；
    第九步，对暴露出的硅进行氧化，形成薄层氧化硅层；
    第十步，采用保护层覆盖SOI硅片的正面，所述保护层覆盖除加热元件(101)、测量元件(102)悬空结构以及环境温度测量元件(103)的测量电阻(1032)以外的SOI硅片正面部分；
    第十一步，采用ALD(原子层沉积)方法在加热元件(101)、测量元件(102)悬空结构以及环境温度测量元件(103)的测量电阻(1032)的外表面制备氧化铝或氧化铪薄膜；
    第十二步，采用PECVD(Plasma Enhanced Chemical Vapor Deposition，等离子体增强化学气相沉积法)在在加热元件(101)、测量元件(102)悬空结构以及环境温度测量元件(103)的测量电阻(1032)的外表面制备氮化硅，制备温度400～450℃；制备成氧化硅/氮化硅复合薄膜，或氧化硅/氧化铝/氮化硅复合薄膜，或氧化铪/氮化硅复合薄膜，或氧化硅/氧化铪/氧化铝/氮化硅符合薄膜，与第九步形成的薄层氧硅层、第十一步形成的氧化铝或氧化铪层共同构成钝化保护层 (14)；
    第十三步，去除第十步使用的保护层，干燥；
    第十四步，在SOI硅片正面制备光刻胶，光刻后露出加热元件(101)、测量元件(102)的固定端(1001)、环境温度测量元件(103)的电极引出端(1031)；
    第十五步，通过淀积或蒸发在加热元件(101)、测量元件(102)的固定端(1001)、环境温度测量元件(103)的电极引出端(1031)上形成电引出焊盘金属(22)；
    第十六步，去除光刻胶，干燥；退火形成欧姆接触；
    第十七步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件(101)、测量元件(102)与环境温度测量元件(103)集成在一起的甲烷传感器；
    或制备方法(三)步骤为：
    第一步至第十三步同制备方法(二)的第一步至第十三步，
    第十四步，制备掩蔽版，所述掩蔽版上的图形与SOI硅片上的加热元件(101)、测量元件(102)的固定端(1001)、环境温度测量元件(103)的电极引出端(1031)的图形相同；掩蔽版置于SOI硅片正面之上并对准后，通过溅射、沉积等方法制备金属，仅在加热元件(101)、测量元件(102)的固定端(1001)、环境温度测量元件(103)的电极引出端(1031)之上形成电引出焊盘金属(22)；退火形成欧姆接触；
    第十五步，对SOI硅片进行划片与裂片，得到本发明所述的大量的由加热元件(101)、测量元件(102)与环境温度测量元件(103)集成在一起的甲烷传感器。
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CN103482562A (zh) * 2013-09-26 2014-01-01 中国矿业大学 一种叠层结构的微瓦斯传感器及其制备方法
CN103499617A (zh) * 2013-09-26 2014-01-08 中国矿业大学 一种单片微瓦斯传感器及其制备方法
CN203519541U (zh) * 2013-09-26 2014-04-02 中国矿业大学 一种可回收重复制备的微瓦斯传感器
CN203519540U (zh) * 2013-09-26 2014-04-02 中国矿业大学 一种单片微瓦斯传感器
CN104316574A (zh) * 2014-10-31 2015-01-28 中国矿业大学 一种基于单个加热元件的甲烷传感器及制备方法和应用
CN204154679U (zh) * 2014-10-31 2015-02-11 中国矿业大学 一种基于单个加热元件的甲烷传感器

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