WO2022052392A1 - 一种旁热式硅基薄膜催化氢气传感器及其加工方法 - Google Patents

一种旁热式硅基薄膜催化氢气传感器及其加工方法 Download PDF

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WO2022052392A1
WO2022052392A1 PCT/CN2021/070618 CN2021070618W WO2022052392A1 WO 2022052392 A1 WO2022052392 A1 WO 2022052392A1 CN 2021070618 W CN2021070618 W CN 2021070618W WO 2022052392 A1 WO2022052392 A1 WO 2022052392A1
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layer
heating coil
thin film
film catalytic
silicon
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沈方平
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苏州芯镁信电子科技有限公司
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/22—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures
    • G01N25/28—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures the rise in temperature of the gases resulting from combustion being measured directly
    • G01N25/30—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures the rise in temperature of the gases resulting from combustion being measured directly using electric temperature-responsive elements
    • G01N25/32—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures the rise in temperature of the gases resulting from combustion being measured directly using electric temperature-responsive elements using thermoelectric elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

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  • the invention belongs to the technical field of hydrogen sensors, in particular to a side-heated silicon-based thin film catalytic hydrogen sensor and a processing method thereof.
  • Catalytic combustion gas sensor utilizes the thermal effect principle of catalytic combustion, and is composed of a detection element and a compensation element to form a measurement bridge. When it rises, the resistance of the platinum wire inside it also rises accordingly, so that the balance bridge is out of balance, and an electrical signal proportional to the concentration of combustible gas is output.
  • the catalysts are usually made of noble metal catalysts supported by porous alumina ceramics, which are usually olive-shaped or spherical, so they are called bead-type elements.
  • the catalyst consists of a very fine platinum wire, typically only 25-50 microns. The diameter of the catalyst is about 0.5-1mm, and the platinum wire is easily broken under strong vibration; the noble metal catalyst supported by porous ceramics has a high response to all combustible gases, so it can only be used as a combustible gas sensor. Not a single hydrogen sensor.
  • the porous ceramics of the catalyst are very easy to adsorb fine particles in the air, resulting in a great decrease in the specific surface area of the porous ceramics, and the catalytic activity is also greatly reduced, which means that the sensor needs to be calibrated regularly to correct errors, and the service life is also greatly improved. reduce.
  • the purpose of the present invention is to address the above shortcomings, to provide a side-heated silicon-based thin film catalytic hydrogen sensor, which has a reasonable structure and layout, can greatly reduce cross-interference, has high stability and reliability, and thus prolongs the service life. Not only the sensor has low power consumption and high sensitivity, but also has a simple production process and low production cost.
  • the invention also provides a processing method of a side-heated silicon-based thin film catalytic hydrogen sensor.
  • a side-heated silicon-based thin-film catalytic hydrogen sensor comprising a silicon substrate, a heat insulating layer, a heating coil, a thin-film catalytic layer and a thin-film resistance layer;
  • the upper surface of the silicon substrate is provided with a thermal insulation layer, and the lower surface of the silicon substrate is processed with thermal insulation grooves extending to the thermal insulation layer;
  • the upper surface of the heat insulating layer is provided with a patterned first heating coil and a second heating coil, and the first heating coil and the second heating coil are connected in series to draw out electrical signals from the lead pads;
  • a first thin film catalytic layer and a second thin film catalytic layer are respectively disposed on the heat insulating layer adjacent to the first heating coil and the second heating coil, the surface of the first thin film catalytic layer is left empty, and the second thin film catalytic layer The surface of the layer is covered with a high temperature resistant dielectric layer;
  • the edge of the upper surface of the heat insulating layer is provided with a thin film resistance layer.
  • the first heating coil and the second heating coil are one or more of platinum, platinum-series metal alloys, iron, iron-series metal alloys, titanium, tungsten, titanium-tungsten alloys, and conductive metal nitrides and the difference between the temperature coefficients of resistance of the first heating coil and the second heating coil is 0-100ppm/°C.
  • the thin film catalytic layer is located inside, or outside, or above, or below the heating coil.
  • the first heating coil and the second heating coil are both closed shapes with a hollowed-out center, and the first thin film catalytic layer and the second thin film catalytic layer are located on the inner side of the heating coil, respectively. inside the hollow parts of the first heating coil and the second heating coil.
  • the first heating coil and the second heating coil are both continuously bent serpentine structures, and the first thin film catalytic layer is arranged on the left and right of the first heating coil.
  • the second thin film catalytic layer is arranged on the left and right sides of the second heating coil.
  • the first thin film catalytic layer is arranged above or below the first heating coil and the surface is left empty, and the second thin film catalytic layer is arranged on the second
  • the upper or lower surface of the heating coil is covered with a high temperature resistant medium layer, and an insulating layer is arranged between the thin film catalytic layer and the heating coil.
  • the distance between the thin film catalytic layer and the heating coil is 5nm-100um.
  • the material of the thin film catalytic layer is one or more of platinum group metals and their alloys, tin oxide, nickel oxide, cerium oxide, tungsten oxide, and titanium oxide.
  • the material of the high temperature resistant dielectric layer is one or more of aluminum oxide, silicon oxide, silicon nitride, hafnium oxide, and zirconium oxide.
  • the void area of the thin film catalytic layer overlaps with the thin film catalytic layer, and the void area can also be set to be larger or smaller than the area of the thin film catalytic layer.
  • a processing method of a side-heated silicon-based thin film catalytic hydrogen sensor comprising the following steps:
  • S2 depositing a silicon nitride layer on the cleaned silicon substrate by a low pressure chemical vapor deposition method, and then depositing a silicon dioxide layer on the surface of the silicon nitride layer by a plasma enhanced chemical vapor deposition method to obtain a heat insulating layer;
  • step S3 on the substrate obtained in step S2, deposit a high temperature buffer layer on the surface of the heat insulating layer obtained in step S2 by magnetron sputtering method, thermal evaporation deposition method or plasma enhanced chemical deposition method;
  • step S4 on the substrate obtained in S3, carry out glue, photolithography, and development treatment, and use magnetron sputtering or the deposition method in step S3 to deposit a material layer with a high temperature coefficient of resistance, and use a peeling process to obtain Graphical heating coil;
  • step S5 deposit a layer of thin film catalytic material on the inside or outside of the heating coil obtained in step S4 by the method described in step S4;
  • step S6 using the process described in S2, deposit silicon nitride and silicon dioxide on the surface of the substrate obtained in step S4;
  • S9 Perform glue leveling, photolithography, and development processing on the back of the substrate obtained in S8. First, deep reactive ion etching is used to remove most of the silicon, and then wet etching is used to remove the remaining silicon to prepare an adiabatic groove.
  • the first thin film catalytic layer and the second thin film catalytic layer are respectively arranged near the first heating coil and the second heating coil, and the first thin film catalytic layer and the second thin film catalytic layer are used to catalyze the combustion of hydrogen to the first heating coil respectively.
  • the heating coil and the second heating coil are bypassed to replace the original direct heating and heating method of the first noble metal catalytic layer and the second noble metal catalytic layer, which can greatly reduce cross-interference, reduce the thermal shock of the heating coil, and make the sensor more stable. And reliability is improved, extending the service life.
  • the thin film catalytic layer when located inside or outside the heating coil, a planarized MEMS processing structure is formed, the thickness of the hydrogen sensor is not increased, and the overall volume of the hydrogen sensor is not affected.
  • Both the first heating coil and the second heating coil are closed shapes with a hollow in the middle.
  • the first thin film catalytic layer and the second thin film catalytic layer are located in the corresponding hollow parts respectively.
  • the hydrogen heat of the catalytic combustion of the first thin film catalytic layer affects the A heating coil forms a balanced side heating effect, and the side heating area is larger, and the heat utilization rate is high, so the detection result is sensitive.
  • the first heating coil and the second heating coil are both bent serpentine structures, the first thin film catalytic layer and the second thin film catalytic layer are located on both sides of the corresponding heating coil, and the hydrogen heat of the catalytic combustion of the first thin film catalytic layer
  • the first heating coil forms a surrounding heating effect, and the heating efficiency is high, so the detection result is sensitive.
  • the silicon-based thin film catalytic hydrogen sensor provided by the present invention uses a precious metal thin film layer as the catalytic layer. Compared with the traditional bead type catalytic sensor, it avoids the rupture of the catalytic beads under strong vibration and improves its shock resistance.
  • Fig. 1 is the top-view structure schematic diagram of the present invention's thin-film catalytic layer in the form inside the heating coil;
  • Fig. 2 is the front structure schematic diagram of Fig. 1 of the present invention.
  • Fig. 3 is the top view structure schematic diagram of the present invention's thin-film catalytic layer in the form of the side of the heating coil;
  • FIG. 4 is a schematic top view of the structure of the present invention in the form of the thin film catalytic layer located above the heating coil.
  • a side-heated silicon-based thin-film catalytic hydrogen sensor includes a silicon substrate, a heat insulating layer, a heating coil, a thin-film catalytic layer and a thin-film resistance layer.
  • the heating coil includes a first heating coil 3 and a second heating coil 4
  • the thin-film catalytic layer includes a first thin-film catalytic layer 5 and a second thin-film catalytic layer 6 .
  • a heat insulating layer 2 is provided on the upper surface of the silicon substrate 1 , and a heat insulating groove 7 extending to the heat insulating layer 2 is processed on the lower surface of the silicon substrate 1 .
  • the heat insulating groove 7 prevents the heat on the surface of the heat insulating layer 2 from being transferred downward through the silicon substrate 1, thereby improving the heat utilization rate of the heating coil and the detection sensitivity of the sensor.
  • the first heating coil 3 and the second heating coil 4 which are patterned are arranged on the heat insulating layer 2.
  • the heat insulating layer 2 is also etched with lead wires and a plurality of lead pads 8.
  • a first thin film catalytic layer 5 and a second thin film catalytic layer 6 are respectively disposed on the heat insulating layer 2 adjacent to the first heating coil 3 and the second heating coil 4, the surface of the first thin film catalytic layer 5 is left empty, and the second thin film catalytic layer 6 The surface is covered with a high temperature resistant dielectric layer 9 .
  • the first thin film catalytic layer 5 left on the surface can catalyze the combustion of hydrogen, and the heat generated by the combustion makes the temperature of the first heating coil 3 higher than the temperature of the second heating coil 4, so that its resistance value rises, destroying the balance of the bridge and generating Since the hydrogen concentration has a linear relationship with the voltage, the hydrogen concentration value can be obtained according to the voltage signal.
  • the surface of the second thin film catalytic layer 6 is covered with a high temperature resistant dielectric layer 9, which can prevent the resistance of the second heating coil from fluctuating with changes in the environment.
  • a ring of thin film resistance layer 10 is arranged on the edge of the heat insulating layer 2, and both ends of the thin film resistance layer 10 are also connected with lead pads 8.
  • the thin film resistance layer 10 is used to measure the ambient temperature or provide temperature to the sensor.
  • the first heating coil 3 and the second heating coil 4 are one or more of platinum, platinum-series metal alloys, iron, iron-series metal alloys, titanium, tungsten, titanium-tungsten alloys, and conductive metal nitrides; and the first The difference between the temperature coefficients of resistance of the heating coil 3 and the second heating coil 4 is 0-100 ppm/°C.
  • the thin film catalytic layer is located inside, or outside, or above, or below the heating coil.
  • the first heating coil 3 and the second heating coil 4 are closed shapes with a hollow in the middle, such as rectangles, diamonds or other closed structures, and the first thin film catalytic layer 5 and the The second thin film catalytic layer 6 is located in the hollow parts of the first heating coil 3 and the second heating coil 4 respectively.
  • the first heating coil 3 and the second heating coil 4 are both continuously bent serpentine structures, and the first thin film catalytic layer 5 is arranged on the left and right sides of the first heating coil 3 , the second thin film catalytic layer 6 is arranged on the left and right sides of the second heating coil 4 .
  • the first thin film catalytic layer 5 is arranged above or below the first heating coil 3 and the surface is left blank, and the second thin film catalytic layer 6 is arranged in the second heating coil 4.
  • the upper or lower surface of the film is covered with a high temperature resistant medium layer, and an insulating layer is arranged between the thin film catalytic layer and the heating coil.
  • the distance between the thin film catalytic layer and the heating coil is 5nm-100um to reduce the cross-interference between the two and the thermal shock of the heat to the heating coil and prolong its service life.
  • the material of the thin film catalytic layer is one or more of platinum group metals and their alloys, tin oxide, nickel oxide, cerium oxide, tungsten oxide, and titanium oxide.
  • the material of the high temperature resistant dielectric layer is one or more of aluminum oxide, silicon oxide, silicon nitride, hafnium oxide and zirconium oxide.
  • the area of the blank area of the thin film catalytic layer may be greater than, less than or equal to the area of the thin film catalytic layer.
  • a processing method of a side-heated silicon-based thin film catalytic hydrogen sensor comprising the following steps:
  • step S3 on the substrate obtained in S2, deposit a layer of high temperature buffer layer 11 on the surface of the heat insulating layer 2 obtained in step S2 by magnetron sputtering;
  • step S5 by the method described in step S4, deposit a layer of thin film catalytic material inside the two heating coils obtained in step S4;
  • step S6 using the process described in S2, deposit silicon nitride and silicon dioxide on the surface of the substrate obtained in step S4;
  • S9 perform glue leveling, photolithography, and development on the back of the substrate obtained in S8. First, deep reactive ion etching is used to remove most of the silicon, and then wet etching is used to remove the remaining silicon to prepare an adiabatic groove 7.
  • a processing method of a side-heated silicon-based thin film catalytic hydrogen sensor comprising the following steps:
  • the silicon substrate 1 is cleaned by a standard RCA process and dried with nitrogen gas;
  • step S3 on the substrate obtained in S2, deposit a layer of high temperature buffer layer 11 on the surface of the heat insulating layer 2 obtained in step S2 by thermal evaporation deposition method;
  • step S4 On the substrate obtained in S3, carry out glue, photolithography, and development processing, and use the deposition method in step S3 to deposit a material layer with a high temperature coefficient of resistance, and use a lift-off process to obtain two patterned heating A coil, the heating coil is a continuously bent serpentine structure;
  • step S5 using the method described in step S4, deposit a layer of thin-film catalytic material on the left and right sides of the heating coil obtained in step S4, respectively, and the thin-film catalytic layer can be in a linear shape;
  • step S6 using the process described in S2, deposit silicon nitride and silicon dioxide on the surface of the substrate obtained in step S4;
  • S9 perform glue leveling, photolithography, and development on the back of the substrate obtained in S8. First, deep reactive ion etching is used to remove most of the silicon, and then wet etching is used to remove the remaining silicon to prepare an adiabatic groove 7.
  • the side-heated silicon-based thin-film catalytic hydrogen sensor is shown in Figure 3.
  • the present invention is placed in a hydrogen environment, and the hydrogen undergoes flameless combustion under the action of the first thin film catalytic layer 5 with a hollow surface. Therefore, the heat generated by the combustion makes the temperature of the first heating coil 3 higher than that of the second heating coil 4, and the resistance of the precious metal inside the first heating coil 3 also increases accordingly, so that the balance bridge is unbalanced, A voltage signal proportional to the concentration of combustible gas is output, so the hydrogen concentration value can be obtained according to the voltage signal.

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Abstract

一种旁热式硅基薄膜催化氢气传感器，通过MEMS加工工艺获得，该传感器包括硅基底（1），硅基底（1）上表面设有绝热层（2），硅基底（1）下表面开有一个或一对延伸至绝热层（2）的绝热槽（7），绝热层（2）表面设有高电阻温度系数材料组成的第一加热线圈（4）和第二加热线圈（5），两加热线圈的内侧、外侧或上方分别配置第一催化薄膜层（5）和第二催化薄膜层（6），第一催化薄膜层（5）表面覆盖有一层耐高温介质层（9），第二催化薄膜层（6）表面留空，绝热层（2）外圈设有贵金属薄膜电阻（10）。该氢气传感器可以同时在催化燃烧和热导两种模式下工作，体积小，功耗低，响应快，使用寿命长。

Description

一种旁热式硅基薄膜催化氢气传感器及其加工方法 技术领域
本发明属于氢气传感器技术领域，具体涉及一种旁热式硅基薄膜催化氢气传感器及其加工方法。
背景技术
催化燃烧式气体传感器是利用催化燃烧的热效应原理，由检测元件和补偿元件配对构成测量电桥，在一定温度条件下，可燃气体在检测元件载体表面及催化剂的作用下发生无焰燃烧，载体温度就升高，通过它内部的铂丝电阻也相应升高，从而使平衡电桥失去平衡，输出一个与可燃气体浓度成正比的电信号。
为提高催化效率，催化剂通常为多孔氧化铝陶瓷负载的贵金属催化剂制成，通常为橄榄型或球形，因此被称为珠式元件。催化剂包括的铂丝十分纤细，通常只有25-50微米。而催化剂的直径大约为0.5-1mm，在较强的震动下，铂丝极易断裂；多孔陶瓷负载的贵金属催化剂对于所有的可燃气体均具有很高的响应，因此，只能作为可燃气体传感器而非单一的氢气传感器。
同时，催化剂的多孔陶瓷极易吸附空气中的细小颗粒，导致多孔陶瓷的比表面积极大的下降，催化活性也大大降低，这意味着，传感器需定期进行校准以修正误差，并且使用寿命也大大降低。
我公司申请号为201810220141.2的中国专利文件《一种氢气传感器及其加工方法》，公开了一种微型氢气传感器，能够测量任何氢气浓度，弥补了现有技术的缺点；使得氢气传感器的选择性、安全性、稳定性、灵敏度以及输出信号弱等问题已经得到不同程度 的解决。但该装置稳定性和使用寿命仍有待进一步改善。
发明内容
本发明的目的是针对上述不足，提供一种旁热式硅基薄膜催化氢气传感器，其构造布局合理，可大大减少交叉干扰，稳定性和可靠性高，进而延长了使用寿命，再者本装置不仅传感器功耗低、灵敏度高，且生产工艺简单、生产成本低。本发明还提供一种旁热式硅基薄膜催化氢气传感器的加工方法。
本发明提供了如下的技术方案：
一种旁热式硅基薄膜催化氢气传感器，包括硅基底、绝热层、加热线圈、薄膜催化层和薄膜电阻层；
所述硅基底的上表面设有绝热层，所述硅基底的下表面加工有延伸至所述绝热层的绝热槽；
所述绝热层的上表面设有图形化处理的第一加热线圈与第二加热线圈，所述第一加热线圈与第二加热线圈串联后由引线焊盘引出电信号；
所述绝热层上临近所述第一加热线圈与第二加热线圈处分别配置第一薄膜催化层与第二薄膜催化层，所述第一薄膜催化层的表面留空，所述第二薄膜催化层的表面覆盖耐高温介质层；
所述绝热层上表面的边缘设有薄膜电阻层。
优选的，所述第一加热线圈与所述第二加热线圈为铂、铂系金属合金、铁、铁系金属合金、钛、钨、钛钨合金、导电性金属氮化物中的一种或者几种；且所述第一加热线圈与第二加热线圈的电阻温度系数的差值在0-100ppm/℃。
进一步的，所述薄膜催化层位于加热线圈的内侧、或者外侧、或者上方、或者下方。
其中，当薄膜催化层位于加热线圈的内侧时，所述第一加热线圈与第二加热线圈均为中部镂空的封闭状图形，所述第一薄膜催化层与所述第二薄膜催化层分别位于所述第一加热线圈与第二加热线圈的镂空部内。
当薄膜催化层位于加热线圈的外侧时，所述第一加热线圈与第二加热线圈均为连续弯折的蛇形结构，所述第一薄膜催化层分列于所述第一加热线圈的左右两侧，所述第二薄膜催化层分列于第二加热线圈的左右两侧。
当薄膜催化层位于加热线圈的上方或者下方时，所述第一薄膜催化层分列于所述第一加热线圈的上方或者下方且表面留空，所述第二薄膜催化层分列于第二加热线圈的上方或者下方且表面覆盖一层耐高温介质层，所述薄膜催化层与加热线圈之间设置有绝缘层。
优选的，所述薄膜催化层与所述加热线圈的间距为5nm-100um。
优选的，所述薄膜催化层的材质为铂系金属及其合金、氧化锡、氧化镍、氧化铈、氧化钨、氧化钛其中的一种或几种。
优选的，所述耐高温介质层的材质为氧化铝、氧化硅、氮化硅、氧化铪、氧化锆中的一种或者几种。
所述薄膜催化层的留空区域与所述薄膜催化层重叠，也可以将留空区域设置成大于或者小于薄膜催化层的面积。
一种旁热式硅基薄膜催化氢气传感器的加工方法，包括以下步骤：
S1：采用标准RCA制程对硅基底进行清洗，并使用氮气吹干；
S2：以低压化学气相沉积法在洗净的硅基底上沉积氮化硅层，然后以等离子体增强化学气相沉积法在氮化硅层表面沉积二氧化硅层，获得绝热层；
S3：在S2获得的衬底上，以磁控溅射法或者热蒸发沉积法或者等离子体增强化学沉积法在步骤S2中获得的绝热层表面沉积一层高温缓冲层；
S4：在S3获得的衬底上，进行匀胶、光刻、显影处理，并采用磁控溅射法或S3步骤中的沉积方法沉积一层高电阻温度系数的材料层，使用剥离工艺，得到图形化的加热线圈；
S5：以S4步骤中所述方法，在S4步骤中获得的加热线圈内侧或外侧沉积一层薄膜催化材料；
S6：利用S2中所述工艺，在S4步骤中获得的衬底表面沉积氮化硅和二氧化硅；
S7：在S6获得的衬底上，进行匀胶、光刻、显影处理，采用等离子体刻蚀工艺，去除第一薄膜催化层上方的氮化硅和二氧化硅；
S8：利用S4所述工艺，在S7获得的衬底表面沉积外圈薄膜电阻层；
S9：在S8获得的衬底背面进行匀胶、光刻、显影处理，先使用深反应离子刻蚀去除绝大多数的硅，再使用湿法腐蚀去除残余的硅，制备出绝热槽。
本发明的有益效果是：
1.本发明将第一薄膜催化层与第二薄膜催化层分别配置于临近第一加热线圈与第二加热线圈处，利用第一薄膜催化层与第二薄膜催化层催化氢气燃烧分别对第一加热线圈与第二加热线圈进行旁热，取代原来的第一贵金属催化层与第二贵金属催化层直接加热升温的方式，可大大减少交叉干扰，减小加热线圈的受热冲击，使传感器的稳定性和可靠性得到提高，延长了使用寿命。
2.本发明当薄膜催化层位于加热线圈的内侧或者外侧时，形成平面化MEMS加工结构，没有增加氢气传感器的厚度，不影响氢气传感器的整体体积。
3.第一加热线圈与第二加热线圈均为中部镂空的封闭状图形，第一薄膜催化层与第二薄膜催化层分别位于相应的镂空部内，第一薄膜催化层催化燃烧的氢气热量对第一加热线圈形成均衡的旁热效果，且旁热面积更大，热量利用率高，因此检测结果灵敏。
4.第一加热线圈与第二加热线圈均为弯折的蛇形结构，第一薄膜催化层、第二薄膜催化层位于相应的加热线圈两侧，第一薄膜催化层催化燃烧的氢气热量对第一加热线圈形成包围式的旁热效果，旁热效率高，因此检测结果灵敏。
5.本发明提供的硅基薄膜催化氢气传感器，采用贵金属薄膜层作为催化层，相比传统珠式催化传感器，避免了在强震动下催化珠破裂的情况，提升了其抗震性。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。在附图中：
图1是本发明薄膜催化层位于加热线圈内部形式的俯视结构示意图；
图2是本发明的图1的主视结构示意图；
图3是本发明薄膜催化层位于加热线圈旁侧形式的俯视结构示意图；
图4是本发明薄膜催化层位于加热线圈上方形式的俯视结构示意图。
图中标记为：1.硅基底；2.绝热层；3.第一加热线圈；4.第二加热线圈；5.第一薄膜催化层；6.第二薄膜催化层；7.绝热槽；8.引线焊盘；9.耐高温介质层；10.薄膜电阻层；11.高温缓冲层。
具体实施方式
如图1至图4所示，一种旁热式硅基薄膜催化氢气传感器，包括硅基底、绝热层、 加热线圈、薄膜催化层和薄膜电阻层。其中，加热线圈包括第一加热线圈3和第二加热线圈4，薄膜催化层包括第一薄膜催化层5和第二薄膜催化层6。
如图1所示，硅基底1的上表面设有绝热层2，硅基底1的下表面加工有延伸至绝热层2的绝热槽7。绝热槽7阻止绝热层2表面的热量通过硅基底1向下传递，提高了加热线圈的热量利用率和传感器的检测灵敏度。
如图2所示，绝热层2上面设有图形化处理的第一加热线圈3与第二加热线圈4，绝热层2上还蚀刻有引线和多个引线焊盘8，第一加热线圈3、第二加热线圈4通过引线串联后由引线焊盘8引出电信号。
绝热层2上临近第一加热线圈3与第二加热线圈4处分别配置第一薄膜催化层5与第二薄膜催化层6，第一薄膜催化层5的表面留空，第二薄膜催化层6的表面覆盖耐高温介质层9。表面留空的第一薄膜催化层5可催化氢气燃烧，燃烧产生的热量使第一加热线圈3的温度高于第二加热线圈4的温度，从而其阻值上升，破坏了电桥平衡而产生电势，因为氢气浓度与电压成线性关系，因此根据该电压信号可得到氢气浓度值。第二薄膜催化层6的表面覆盖耐高温介质层9，可避免第二加热线圈的电阻随环境变化而波动。
绝热层2上的边缘设有一圈薄膜电阻层10，薄膜电阻层10的两端也连接有引线焊盘8，薄膜电阻层10用于测量环境温度或者给传感器提供温度。
第一加热线圈3与第二加热线圈4为铂、铂系金属合金、铁、铁系金属合金、钛、钨、钛钨合金、导电性金属氮化物中的一种或者几种；且第一加热线圈3与第二加热线圈4的电阻温度系数的差值在0-100ppm/℃。
薄膜催化层位于加热线圈的内侧、或者外侧、或者上方、或者下方。
其中，当薄膜催化层位于加热线圈的内侧时，第一加热线圈3与第二加热线圈4均为中部镂空的封闭状图形，例如矩形、菱形或者其他封闭状结构，第一薄膜催化层5与第二薄膜催化层6分别位于第一加热线圈3与第二加热线圈4的镂空部内。
当薄膜催化层位于加热线圈的外侧时，第一加热线圈3与第二加热线圈4均为连续弯折的蛇形结构，第一薄膜催化层5分列于第一加热线圈3的左右两侧，第二薄膜催化层6分列于第二加热线圈4的左右两侧。
当薄膜催化层位于加热线圈的上方或者下方时，第一薄膜催化层5分列于第一加热线圈3的上方或者下方且表面留空，第二薄膜催化层6分列于第二加热线圈4的上方或者下方且表面覆盖一层耐高温介质层，薄膜催化层与加热线圈之间设置有绝缘层。
薄膜催化层与加热线圈的间距为5nm-100um，以减少二者之间的交叉干扰和热量对加热线圈的热冲击，延长其使用寿命。
其中，薄膜催化层的材质为铂系金属及其合金、氧化锡、氧化镍、氧化铈、氧化钨、氧化钛其中的一种或几种。耐高温介质层的材质为氧化铝、氧化硅、氮化硅、氧化铪、氧化锆中的一种或者几种。
需要说明的是，薄膜催化层的留空区域面积可以大于、小于或者等于薄膜催化层的面积。
下面例举旁热式硅基薄膜催化氢气传感器的加工方法：
实施例1
一种旁热式硅基薄膜催化氢气传感器的加工方法，包括以下步骤：
S1：采用标准RCA制程对硅基底进行清洗，并使用氮气吹干；
S2：以低压化学气相沉积法在洗净的硅基底1上沉积氮化硅层，然后以等离子体增 强化学气相沉积法在氮化硅层表面沉积二氧化硅层，获得绝热层2；
S3：在S2获得的衬底上，以磁控溅射法在步骤S2中获得的绝热层2表面沉积一层高温缓冲层11；
S4：在S3获得的衬底上，进行匀胶、光刻、显影处理，并采用磁控溅射法或沉积方法沉积一层高电阻温度系数的材料层，使用剥离工艺，得到两个图形化的加热线圈，该加热线圈为中部镂空的封闭状图形；
S5：以S4步骤中所述方法，在S4步骤中获得的两个加热线圈内侧沉积一层薄膜催化材料；
S6：利用S2中所述工艺，在S4步骤中获得的衬底表面沉积氮化硅和二氧化硅；
S7：在S6获得的衬底上，进行匀胶、光刻、显影处理，采用等离子体刻蚀工艺，去除第一薄膜催化层5上方的氮化硅和二氧化硅而形成表面留空；
S8：利用S4所述工艺，在S7获得的衬底表面沉积外圈的薄膜电阻层10；
S9：在S8获得的衬底背面进行匀胶、光刻、显影处理，先使用深反应离子刻蚀去除绝大多数的硅，再使用湿法腐蚀去除残余的硅，制备出绝热槽7，形成如图1和图2所示的旁热式硅基薄膜催化氢气传感器。
实施例2
一种旁热式硅基薄膜催化氢气传感器的加工方法，包括以下步骤：
S1：采用标准RCA制程对硅基底1进行清洗，并使用氮气吹干；
S2：以低压化学气相沉积法在洗净的硅基底1上沉积氮化硅层，然后以等离子体增强化学气相沉积法在氮化硅层表面沉积二氧化硅层，获得绝热层2；
S3：在S2获得的衬底上，以热蒸发沉积法在步骤S2中获得的绝热层2表面沉积一层高温缓冲层11；
S4：在S3获得的衬底上，进行匀胶、光刻、显影处理，并采用S3步骤中的沉积方法沉积一层高电阻温度系数的材料层，使用剥离工艺，得到两个图形化的加热线圈，该加热线圈为连续弯折的蛇形结构；
S5：以S4步骤中所述方法，在S4步骤中获得的加热线圈的左右两侧分别沉积一层薄膜催化材料，该层薄膜催化层可以为直线形状；
S6：利用S2中所述工艺，在S4步骤中获得的衬底表面沉积氮化硅和二氧化硅；
S7：在S6获得的衬底上，进行匀胶、光刻、显影处理，采用等离子体刻蚀工艺，去除第一薄膜催化层5上方的氮化硅和二氧化硅而形成表面留空；
S8：利用S4所述工艺，在S7获得的衬底表面沉积外圈的薄膜电阻层10；
S9：在S8获得的衬底背面进行匀胶、光刻、显影处理，先使用深反应离子刻蚀去除绝大多数的硅，再使用湿法腐蚀去除残余的硅，制备出绝热槽7，形成如图3所示的旁热式硅基薄膜催化氢气传感器。
工作原理：
本发明置于氢气环境中，氢气在表面留空的第一薄膜催化层5的作用下发生无焰燃烧，由于第一薄膜催化层5表面留空，第二薄膜催化层6表面覆有耐高温介质层9，因此燃烧产生的热量使第一加热线圈3的温度高于第二加热线圈4的温度，通过第一加热线圈3内部贵金属的电阻也相应升高，从而使平衡电桥失去平衡，输出一个与可燃气体浓度成正比的电压信号，因此根据该电压信号可得到氢气浓度值。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施 例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种旁热式硅基薄膜催化氢气传感器，其特征在于，包括硅基底、绝热层、加热线圈、薄膜催化层和薄膜电阻层；
    所述硅基底的上表面设有绝热层，所述硅基底的下表面加工有延伸至所述绝热层的绝热槽；
    所述绝热层的上表面设有图形化处理的第一加热线圈与第二加热线圈，所述第一加热线圈与第二加热线圈串联后由引线焊盘引出电信号；
    所述绝热层上临近所述第一加热线圈与第二加热线圈处分别配置第一薄膜催化层与第二薄膜催化层，所述第一薄膜催化层的表面留空，所述第二薄膜催化层的表面覆盖耐高温介质层；
    所述绝热层上表面的边缘设有薄膜电阻层。
  2. 根据权利要求1所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述第一加热线圈与所述第二加热线圈为铂、铂系金属合金、铁、铁系金属合金、钛、钨、钛钨合金、导电性金属氮化物中的一种或者几种；且所述第一加热线圈与第二加热线圈的电阻温度系数的差值在0-100ppm/℃。
  3. 根据权利要求2所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述薄膜催化层位于加热线圈的内侧、或者外侧、或者上方、或者下方。
  4. 根据权利要求3所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述第一加热线圈与第二加热线圈均为中部镂空的封闭状图形，所述第一薄膜催化层与所述第二薄膜催化层分别位于所述第一加热线圈与第二加热线圈的镂空部内。
  5. 根据权利要求3所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述第 一加热线圈与第二加热线圈均为连续弯折的蛇形结构，所述第一薄膜催化层分列于所述第一加热线圈的左右两侧，所述第二薄膜催化层分列于第二加热线圈的左右两侧。
  6. 根据权利要求3所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述第一薄膜催化层分列于所述第一加热线圈的上方或者下方且表面留空，所述第二薄膜催化层分列于第二加热线圈的上方或者下方且表面覆盖一层耐高温介质层，所述薄膜催化层与加热线圈之间设置有绝缘层。
  7. 根据权利要求4或5所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述薄膜催化层与所述加热线圈的间距为5nm-100um。
  8. 根据权利要求1所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述薄膜催化层的材质为铂系金属及其合金、氧化锡、氧化镍、氧化铈、氧化钨、氧化钛其中的一种或几种；所述耐高温介质层的材质为氧化铝、氧化硅、氮化硅、氧化铪、氧化锆中的一种或者几种。
  9. 根据权利要求1所述的旁热式硅基薄膜催化氢气传感器，其特征在于，所述薄膜催化层的留空区域与所述薄膜催化层重叠，或者留空区域面积大于或者小于薄膜催化层的面积。
  10. 一种旁热式硅基薄膜催化氢气传感器的加工方法，包括以下步骤：
    S1：采用标准RCA制程对硅基底进行清洗，并使用氮气吹干；
    S2：以低压化学气相沉积法在洗净的硅基底上沉积氮化硅层，然后以等离子体增强化学气相沉积法在氮化硅层表面沉积二氧化硅层，获得绝热层；
    S3：在S2获得的衬底上，以磁控溅射法或者热蒸发沉积法或者等离子体增强化学沉积法在步骤S2中获得的绝热层表面沉积一层高温缓冲层；
    S4：在S3获得的衬底上，进行匀胶、光刻、显影处理，并采用磁控溅射法或S3步骤中的沉积方法沉积一层高电阻温度系数的材料层，使用剥离工艺，得到图形化的加热线圈；
    S5：以S4所述方法，在S4步骤中获得的加热线圈内侧或外侧沉积一层薄膜催化材料；
    S6：利用S2中所述工艺，在S4中获得的衬底表面沉积氮化硅和二氧化硅；
    S7：在S6获得的衬底上，进行匀胶、光刻、显影处理，采用等离子体刻蚀工艺，去除第一薄膜催化层上方的氮化硅和二氧化硅；
    S8：利用S4所述工艺，在S7获得的衬底表面沉积外圈薄膜电阻层；
    S9：在S8获得的衬底背面进行匀胶、光刻、显影处理，先使用深反应离子刻蚀去除绝大多数的硅，再使用湿法腐蚀去除残余的硅，制备出绝热槽。
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