WO2017206447A1 - Porous metal surface-modified interdigitated electrodes, manufacturing method thereof, and application - Google Patents

Porous metal surface-modified interdigitated electrodes, manufacturing method thereof, and application Download PDF

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WO2017206447A1
WO2017206447A1 PCT/CN2016/105881 CN2016105881W WO2017206447A1 WO 2017206447 A1 WO2017206447 A1 WO 2017206447A1 CN 2016105881 W CN2016105881 W CN 2016105881W WO 2017206447 A1 WO2017206447 A1 WO 2017206447A1
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layer
porous metal
electrode
metal
metal layer
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PCT/CN2016/105881
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French (fr)
Chinese (zh)
Inventor
黄兴桥
崔皓博
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惠州市力道电子材料有限公司
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Publication of WO2017206447A1 publication Critical patent/WO2017206447A1/en

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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

Definitions

  • the present invention relates to the field of sensor technologies, and in particular, to an interdigitated electrode of a porous metal-modified surface, a preparation method thereof, and an application thereof.
  • the interdigital electrode is a commonly used sensor-sensitive component.
  • a sensitive layer membrane sensitive to a certain gas component needs to be loaded on the surface of the interdigital electrode to generate a gas concentration change ⁇ on the interdigital electrode.
  • the loading of sensitive components is positively correlated with the sensitivity of the sensor to the target gas.
  • a sufficient amount of sensitive components are required to be applied to the interdigital electrodes.
  • the sensitive component of the load is difficult to fully contact with the gas due to the limitation of the specific surface area of the sensitive layer, and it is substantially difficult to significantly improve the sensitivity of the sensor.
  • Increasing the area of the interdigital electrode can increase the load of the sensitive layer and the contact area with the gas to some extent, but this method will increase the volume of the sensor on the one hand, and the sensitivity of the sensor is not obvious on the other hand, and it is difficult to invest. Application in industrial production.
  • An interdigitated electrode of a porous metal-modified surface comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and a reaction hole is disposed in the porous metal layer
  • the reaction wells are in communication with each other.
  • a surface of the electrode layer is modified with a porous metal layer, and the reaction in the porous metal layer is performed.
  • the pores increase the specific surface area of the interdigital electrodes, and provide more attachment sites for sensitive components without increasing the volume of the interdigital electrodes, thereby increasing the loading of sensitive components on the interdigital electrodes and the contact area of sensitive components with gases.
  • the sensitivity of the sensor produced can be greatly improved.
  • the insulating substrate may be made of any insulating material, such as ceramics, glass, prepreg, polymer resin, etc.; the electrode layer is made of a metal conductive material, and may be formed by a prior art such as pattern transfer or etching.
  • the electrode layer and the porous metal layer are generally made of a metal material having high electrical conductivity and chemical stability, such as gold, silver, copper, and the like.
  • the diameter of the reaction pore is 60-100 nm; the surface porosity of the porous metal layer is 20 ⁇ 3 ⁇ 4-5 0 ⁇ 3 ⁇ 4.
  • the prepared interdigital electrode can carry a sufficient amount of sensitive components on its surface, and the same can be avoided. Excessive porosity results in a decrease in the electrical conductivity of the porous metal layer and a decrease in the signal.
  • the porous metal layer has a thickness of 5 to 50 ⁇ m.
  • the porous metal layer is composed of a metal formed of one of Ag, Cu, Au, Al, Ni, Fe or an alloy formed of at least two of them.
  • the reaction pore diameter is 60-80 nm; the surface porosity of the porous metal layer is 30 ⁇ 3 ⁇ 4-40
  • a transition metal layer having a thickness of 50-800 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is an alloy layer formed of at least two of Ti, Mo, and W.
  • the transition metal layer may be attached to the insulating substrate by physical vapor deposition.
  • the presence of the transition metal layer can increase the bonding strength between the electrode layer and the insulating substrate, so that the interdigitated electrode can be formed on any of the insulating substrates.
  • the present invention also provides a method of preparing an interdigital electrode of the porous metal-modified surface, comprising the following steps:
  • S2 attaching an alloy layer on the electrode layer;
  • the alloy layer includes at least one stabilizing metal and at least one active metal;
  • S1 can be implemented by any of the prior art, the purpose of which is to form an interdigital electrode on an insulating substrate.
  • S2 is mainly coated with an alloy layer on the surface of the electrode layer by electroplating or electroless plating; the active metal in the alloy layer should be a metal having strong reducibility with respect to the stable metal, and is easily oxidized to metal ions to be removed. , such as zinc, tin, zirconium, etc.
  • the stabilizing metal can be selected from metals having high electrical conductivity and chemical stability, such as gold, silver, copper, and the like. In the present invention, the reducibility of the active metal is stronger than the stable metal.
  • the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 20-50, and the alloy layer is removed from the s3
  • the active metal means that the active metal in the alloy layer is removed by an alkaline agent having a pH of 8 - 10 and an oxidizing agent.
  • step S1 is specifically
  • the physical vapor deposition is magnetron sputtering
  • the magnetron sputtering method is specifically: sputtering
  • the target is metal, the diameter of the metal is 20-35mm, the thickness is 2-5mm; the distance between the target and the substrate is 15-20cm, the working gas is nitrogen and argon, respectively controlled by mass flow meter;
  • the vacuum chamber pressure Before entering the vacuum chamber, ultrasonically clean with acetone, alcohol, deionized water, pump the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputter 3-5 minutes with argon gas to clean the target surface;
  • the total sputtering pressure is controlled at 3-4 Pa, and the volume ratio of nitrogen to argon is controlled to be 2:1.
  • the sputtering power is controlled at 105-125w, and the sputtering time is 0.5-1.5h.
  • the magnetron sputtering method can form a transition metal layer on any insulating base layer (including but not limited to ceramics, glass, polymer), and further adhere the metal and etch the electrode layer.
  • the invention optimizes the parameters of the magnetron sputtering, improves the stability of the electrode layer and the insulating base layer, and avoids the problem that the electrode layer is easily separated from the insulating substrate due to the uneven force on both sides of the electrode layer due to the existence of the porous metal layer.
  • the present invention also provides an application of the interdigitated electrode of the porous metal-modified surface in the preparation of a gas sensor, the surface of the porous metal layer and the reaction well being loaded with a sensitive layer.
  • the sensitive layer is a tin dioxide layer having a thickness of 0.1-2 nm.
  • the present invention defines the thickness of the sensitive layer, at which the sensitive layer can provide sufficient sensitive components to sense the target gas, ⁇ also quickly transmits signals to the porous metal layer to avoid signal decay.
  • the present invention has the following beneficial effects compared with the prior art:
  • the present invention modifies a porous metal layer having a nano-scale pore structure on the surface of the electrode layer of the interdigital electrode, which can effectively increase the load of the sensitive component of the interdigital electrode and improve The detection sensitivity of the sensor;
  • the invention also adopts the de-alloying method to prepare the porous metal layer on the surface of the interdigital electrode, the obtained porous metal layer has high bonding strength with the electrode layer, and the signal transmission between the layers has no problems such as delay and attenuation, and the reaction pore distribution Evenly.
  • Figure 2 is a cross-sectional view of the present invention
  • 3 is one of the states of the interdigitated electrode of the porous metal-modified surface of the present invention in the preparation process
  • FIG. 5 is a third state of the interdigital electrode of the porous metal modified surface of the present invention in the preparation process
  • FIG. 6 is a fourth state of the interdigital electrode of the porous metal modified surface of the present invention in the preparation process
  • This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode 2 layer disposed on the surface of the insulating substrate; and a reaction surface of the electrode layer is porous In the metal layer 3, the porous metal layer 3 is provided with reaction holes 4; the reaction holes are in communication with each other.
  • the insulating substrate is made of a prepreg.
  • the diameter of the above reaction pores is 70-80 nm; and the surface porosity of the porous metal layer is 35 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 30 ⁇ m.
  • a transition metal layer 5 having a thickness of 100 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a W layer.
  • the electrode layer is composed of a copper layer and a gold layer wrapped around the copper layer.
  • the porous metal layer is made of Ag metal.
  • This embodiment provides an interdigital finger of a porous metal-modified surface, as shown in FIG. 1 and FIG. 2, comprising an insulating substrate 1, an electrode layer 2 disposed on the surface of the insulating substrate 1, and a reaction surface of the electrode layer 2;
  • the reaction holes 4 are provided in the porous metal layer; the reaction holes are in communication with each other.
  • a transition metal layer 5 having a thickness of 60 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
  • the insulating base layer is ceramic.
  • the diameter of the reaction well is 60-70 nm; and the surface porosity of the porous metal layer is 20 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 25 ⁇ m.
  • the above electrode layer is composed of an elemental substance of Ag.
  • the porous metal layer is made of Ag metal.
  • the porous metal layer is more likely to adhere to an electrode layer composed of a material having a similar property.
  • This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode 2 layer disposed on the surface of the insulating substrate; the reaction surface of the electrode layer is porous In the metal layer 3, the porous metal layer 3 is provided with reaction holes 4; the reaction holes are in communication with each other.
  • the insulating substrate is made of a prepreg.
  • the diameter of the above reaction pores is 70-80 nm; and the surface porosity of the porous metal layer is 35 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 30 ⁇ m.
  • a transition metal layer 5 having a thickness of 100 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a W layer.
  • the electrode layer is composed of a copper layer and a gold layer wrapped around the copper layer.
  • the porous metal layer is made of Ag metal.
  • This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode layer 2 disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous In the metal layer 3, four holes of the reaction are provided in the porous metal layer; and the reaction holes are in communication with each other.
  • the insulating base body is made of glass.
  • the diameter of the reaction well is 70-90 nm; and the surface porosity of the porous metal layer is 20 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 50 ⁇ m.
  • the porous metal layer is made of Cu metal.
  • the electrode layer may be made of copper.
  • a transition metal layer 5 having a thickness of 50 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo layer.
  • the embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, wherein the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
  • the diameter of the reaction pores is 85-100 nm; and the surface porosity of the porous metal layer is 40 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 15 ⁇ m.
  • the porous metal layer is an Ag metal.
  • the electrode layer is formed of copper metal.
  • a transition metal layer having a thickness of 500 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
  • the present embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
  • the insulating substrate is made of an epoxy resin.
  • the diameter of the reaction pore is 90-100 nm; the surface pore of the porous metal layer The rate is 45 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 35 ⁇ m.
  • the porous metal layer is a gold-silver alloy.
  • the electrode layer is composed of gold metal.
  • a transition metal layer having a thickness of 800 ⁇ is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo layer.
  • the embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate and an electrode layer disposed on a surface of the insulating substrate; the reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
  • the diameter of the reaction well is 60-70 nm; and the surface porosity of the porous metal layer is 20 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 50 ⁇ m.
  • the porous metal layer is formed of Au metal.
  • the electrode layer is formed of Au metal.
  • a transition metal layer having a thickness of 50-800 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo and W alloy layer.
  • the embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
  • the diameter of the reaction well is 70-75 nm; and the surface porosity of the porous metal layer is 25 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 35 ⁇ m.
  • the porous metal layer is made of Cu metal.
  • the electrode layer is composed of cu metal.
  • a transition metal layer having a thickness of 300 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
  • This embodiment provides a method for preparing the interdigitated electrode of the porous metal modified surface of Embodiment 1, which comprises the following steps: [0091] SI. Forming an electrode layer 2 on the insulating substrate 1 (as shown in FIG. 5);
  • the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 45 vol. ⁇ 3 ⁇ 4.
  • step SI is specifically
  • the physical vapor deposition is magnetron sputtering
  • the magnetron sputtering method is specifically: sputtering
  • the target is metal, the diameter of the metal is 25mm, the thickness is 4mm; the distance between the target and the substrate is 18cm, the working gas is nitrogen and argon, respectively controlled by mass flow meter; the substrate is placed in the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputtering for 4 minutes with argon gas to clean the target surface; then introducing nitrogen gas to control the total sputtering pressure At 3-4 Pa, the volume ratio of nitrogen to argon is controlled to be 2: 1, the sputtering power is controlled at 120 W, and the sputtering time is 1 h.
  • the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-tin alloy layer.
  • a gold-tin alloy plating solution to plate a gold-tin alloy layer.
  • the removal of the active metal in the alloy layer means that tin in the gold-tin alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M hydrogen peroxide to obtain a porous metal layer.
  • the porous gold layer prepared by the above method can ensure that the reaction pores in the porous gold layer are electrically connected to each other, and the diffusion speed of the gas in the porous gold layer is improved; and one of the alloys is removed by etching to effectively increase the porosity.
  • the uniformity of the reaction holes in the metal layer thereby effectively increasing the specific surface area of the porous metal layer.
  • This embodiment provides a method for preparing an interdigital electrode of a porous metal-modified surface according to Embodiment 2, which comprises the following steps:
  • the alloy layer includes at least one stable metal and at least one Lively metal
  • the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 50 vol. ⁇ 3 ⁇ 4.
  • step SI is specifically
  • the physical vapor deposition is magnetron sputtering, and the magnetron sputtering method is specifically: sputtering
  • the target is metal, the diameter of the metal is 35mm, the thickness is 2mm; the distance between the target and the substrate is 20cm, the working gas is nitrogen and argon, respectively controlled by the mass flow meter; the substrate is placed in the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputtering with argon for 3min to clean the target surface; then introducing nitrogen gas to control the total sputtering pressure At 4 Pa, the volume ratio of nitrogen to argon was controlled to 2: 1, the sputtering power was controlled at 105 W, and the sputtering time was 1.5 h.
  • the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-zinc alloy layer.
  • a gold-tin alloy plating solution to plate a gold-zinc alloy layer.
  • the removal of the active metal in the alloy layer means that zinc in the gold-zinc alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M of hydrogen peroxide to obtain a porous metal layer.
  • This embodiment provides a gas sensor prepared by interdigitated electrodes of a porous metal-modified surface as described in Example 1, wherein the porous metal layer and the surface of the reaction well are loaded with the sensitive layer 6.
  • the sensitive layer is a tin dioxide layer having a thickness of 0.9 nm.
  • This embodiment provides the use of an interdigitated electrode of a porous metal-modified surface as described in Embodiment 1 in the preparation of a gas sensor, wherein the surface of the porous metal layer and the reaction well is loaded with a sensitive layer.
  • the sensitive layer is a tin dioxide layer having a thickness of 3 nm.
  • the present comparative example provides an interdigitated electrode of a porous metal-modified surface, including an insulating substrate, disposed in insulation An electrode layer on the surface of the substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and a reaction hole is provided in the porous metal layer; and the reaction holes are in communication with each other.
  • a transition metal layer having a thickness of 60 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
  • the insulating base layer is a ceramic.
  • the diameter of the above reaction well is 10-40 nm; and the surface porosity of the porous metal layer is 60 ⁇ 3 ⁇ 4.
  • the thickness of the above porous metal layer is 50 ⁇ m.
  • the above electrode layer is composed of an elemental substance of Ag.
  • This embodiment provides a method for preparing the interdigitated electrode of the porous metal-modified surface of Example 2, which comprises the following steps:
  • the alloy layer includes at least one stabilizing metal and at least one active metal;
  • the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 20-50.
  • the removal of the active metal in the alloy layer in s3 means removal of the active metal in the alloy layer with an alkaline agent having a pH of 8-10 and an oxidizing agent.
  • step S1 is specifically
  • the physical vapor deposition is magnetron sputtering, and the magnetron sputtering method is specifically: sputtering
  • the target is metal, the diameter of the metal is 40mm, the thickness is 6mm; the distance between the target and the substrate is 10cm, the working gas is nitrogen and argon, respectively controlled by the mass flow meter; the substrate is placed before the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and filling with argon pre-splashing Shoot for 3-5min to clean the target surface; then pass nitrogen, control the total sputtering pressure at 3-4Pa, control the volume ratio of nitrogen to argon to 2:1, and the sputtering power is controlled at 105-125w, sputtering It is 0.5-1.5h
  • the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-zinc alloy layer.
  • a gold-tin alloy plating solution to plate a gold-zinc alloy layer.
  • the removal of the active metal in the alloy layer means that zinc in the gold-zinc alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M of hydrogen peroxide to obtain a porous metal layer.
  • the present invention provides an interdigitated electrode in which a porous metal-modified surface can increase the loading of sensitive components and increase the sensitivity of the sensor.

Abstract

Porous metal surface-modified interdigitated electrodes, a manufacturing method thereof, and application. The surfaces of electrode layers of the interdigitated electrodes are modified with a porous metal layer having a nano-scale porous structure, thus effectively increasing the amount of a sensitive material carried by the interdigitated electrodes, and enhancing detection sensitivity of a sensor. By employing a dealloying method to fabricate a porous metal layer on the surfaces of the interdigitated electrodes, the present invention acquires a porous metal layer having high bonding strength to an electrode layer, thus eliminating problems of delay, attenuation, etc. of inter-layer signal transmission, and providing a uniform distribution of reactive pores.

Description

一种多孔金属修饰表面的叉指电极、 其制备方法和应用 技术领域  Interdigitated electrode with porous metal modified surface, preparation method and application thereof
[0001] 本发明涉及传感器技术领域， 具体涉及一种多孔金属修饰表面的叉指电极、 其制备方法和应用。  [0001] The present invention relates to the field of sensor technologies, and in particular, to an interdigitated electrode of a porous metal-modified surface, a preparation method thereof, and an application thereof.
背景技术  Background technique
[0002] 叉指电极是常用的传感器敏感部件， 制备气体传感器吋， 需要在叉指电极表 面负载对某种气体成分敏感的敏感层 （膜） ， 以在气体浓度变化吋在叉指电极 上产生电势变化。 一般而言， 敏感成分的负载量与传感器对目标气体的灵敏度 呈正相关， 为保证传感器的灵敏度， 需要在叉指电极上负载足量的敏感成分。 但仅仅增加叉指电极上敏感成分的负载量， 由于敏感层比表面积的限定， 负载 的敏感成分难以与气体充分接触， 实质上难以显著提高传感器的灵敏度。 而增 加叉指电极的面积虽然可以一定程度上增加敏感层的负载量及与气体的接触面 积， 但该做法一方面将增加传感器的体积， 另一方面对传感器的灵敏度提升并 不明显， 难以投入工业化生产中应用。  [0002] The interdigital electrode is a commonly used sensor-sensitive component. To prepare a gas sensor, a sensitive layer (membrane) sensitive to a certain gas component needs to be loaded on the surface of the interdigital electrode to generate a gas concentration change 吋 on the interdigital electrode. The potential changes. In general, the loading of sensitive components is positively correlated with the sensitivity of the sensor to the target gas. To ensure the sensitivity of the sensor, a sufficient amount of sensitive components are required to be applied to the interdigital electrodes. However, merely increasing the loading amount of the sensitive component on the interdigital electrode, the sensitive component of the load is difficult to fully contact with the gas due to the limitation of the specific surface area of the sensitive layer, and it is substantially difficult to significantly improve the sensitivity of the sensor. Increasing the area of the interdigital electrode can increase the load of the sensitive layer and the contact area with the gas to some extent, but this method will increase the volume of the sensor on the one hand, and the sensitivity of the sensor is not obvious on the other hand, and it is difficult to invest. Application in industrial production.
技术问题  technical problem
[0003] 仅增加叉指电极上敏感成分的负载量， 由于敏感层比表面积的限定， 负载的 敏感成分难以与气体充分接触， 实质上难以显著提高传感器的灵敏度。 而增加 叉指电极的面积虽然可以一定程度上增加敏感层的负载量及与气体的接触面积 ， 但该做法一方面将增加传感器的体积， 另一方面对传感器的灵敏度提升并不 明显， 难以投入工业化生产中应用。  [0003] Increasing the loading amount of the sensitive component on the interdigital electrode only makes it difficult to sufficiently contact the sensitive component of the load due to the limitation of the specific surface area of the sensitive layer, and it is substantially difficult to significantly improve the sensitivity of the sensor. Increasing the area of the interdigital electrode can increase the load of the sensitive layer and the contact area with the gas to some extent, but this method will increase the volume of the sensor on the one hand, and the sensitivity of the sensor is not obvious on the other hand, and it is difficult to invest. Application in industrial production.
问题的解决方案  Problem solution
技术解决方案  Technical solution
[0004] 一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘基体表面的电 极层； 所述电极层的反应面设有多孔金属层， 所述多孔金属层中设有反应孔； 所述反应孔相互连通。  [0004] An interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and a reaction hole is disposed in the porous metal layer The reaction wells are in communication with each other.
[0005] 本发明中， 特别在电极层的表面修饰有多孔金属层， 通过多孔金属层中的反应 孔来增加叉指电极的比表面积， 在不增加叉指电极体积的前提下为敏感成分提 供更多的附着位点， 提高叉指电极上敏感成分的负载量以及敏感成分与气体的 接触面积， 最终可以大幅提升所制得的传感器的灵敏度。 所述绝缘基体可选用 任意一种绝缘材料制成， 如陶瓷、 玻璃、 半固化片、 高分子树脂等； 所述电极 层采用金属导电材料制成， 可以利用图形转移、 蚀刻等现有技术成型。 电极层 和多孔金属层一般选用高电导率且化学性质稳定的金属材料制成， 如金、 银、 铜等。 [0005] In the present invention, a surface of the electrode layer is modified with a porous metal layer, and the reaction in the porous metal layer is performed. The pores increase the specific surface area of the interdigital electrodes, and provide more attachment sites for sensitive components without increasing the volume of the interdigital electrodes, thereby increasing the loading of sensitive components on the interdigital electrodes and the contact area of sensitive components with gases. In the end, the sensitivity of the sensor produced can be greatly improved. The insulating substrate may be made of any insulating material, such as ceramics, glass, prepreg, polymer resin, etc.; the electrode layer is made of a metal conductive material, and may be formed by a prior art such as pattern transfer or etching. The electrode layer and the porous metal layer are generally made of a metal material having high electrical conductivity and chemical stability, such as gold, silver, copper, and the like.
[0006] 进一步的， 所述反应孔的直径为 60-lOOnm; 多孔金属层的表面孔隙率为 20<¾-5 0<¾。  [0006] Further, the diameter of the reaction pore is 60-100 nm; the surface porosity of the porous metal layer is 20<3⁄4-5 0<3⁄4.
[0007] 当多孔金属层的反应孔直径为 60-100nm、 表面孔隙率为 20<¾-50<¾， 所制得的叉 指电极其表面可以负载足够多的敏感成分， 同吋还可以避免孔隙率过高导致多 孔金属层的导电性能下降而弓 I发信号衰减。  [0007] When the porous metal layer has a reaction pore diameter of 60-100 nm and a surface porosity of 20<3⁄4-50<3⁄4, the prepared interdigital electrode can carry a sufficient amount of sensitive components on its surface, and the same can be avoided. Excessive porosity results in a decrease in the electrical conductivity of the porous metal layer and a decrease in the signal.
[0008] 更进一步的， 所述多孔金属层的厚度为的厚度为 5_50μηι。  Further, the porous metal layer has a thickness of 5 to 50 μm.
[0009] 优选的， 所述多孔金属层为 Ag、 Cu、 Au、 Al、 Ni、 Fe中的一种形成的金属或 其中至少两种形成的合金构成。  [0009] Preferably, the porous metal layer is composed of a metal formed of one of Ag, Cu, Au, Al, Ni, Fe or an alloy formed of at least two of them.
[0010] 优选的， 所述反应孔直径为 60-80nm; 所述多孔金属层的表面孔隙率为 30<¾-40[0010] Preferably, the reaction pore diameter is 60-80 nm; the surface porosity of the porous metal layer is 30<3⁄4-40
%; 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 50-800A; 所述过渡 金属层为 Ti、 Mo、 W中的至少两种形成的合金层。 A transition metal layer having a thickness of 50-800 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is an alloy layer formed of at least two of Ti, Mo, and W.
[0011] 过渡金属层可以选用物理气相沉积法附着在绝缘基体上。 过渡金属层的存在， 可以提高电极层与绝缘基体的结合强度， 使在任意一种绝缘基体上均可形成叉 指电极。 [0011] The transition metal layer may be attached to the insulating substrate by physical vapor deposition. The presence of the transition metal layer can increase the bonding strength between the electrode layer and the insulating substrate, so that the interdigitated electrode can be formed on any of the insulating substrates.
[0012] 本发明还提供一种制备所述多孔金属修饰表面的叉指电极的方法， 包括如下工 序：  The present invention also provides a method of preparing an interdigital electrode of the porous metal-modified surface, comprising the following steps:
[0013] S1.在绝缘基体上形成电极层；  [0013] S1 forming an electrode layer on the insulating substrate;
[0014] S2.在电极层上附着合金层； 所述合金层中包括至少一种稳定金属和至少一种 活泼金属；  [0014] S2 attaching an alloy layer on the electrode layer; the alloy layer includes at least one stabilizing metal and at least one active metal;
[0015] S3.除去所述合金层中的活泼金属， 残留部分即所述多孔金属层。  [0015] S3. Removing the active metal in the alloy layer, the residual portion is the porous metal layer.
[0016] S1可选用任意一种现有技术实现， 其目的是在绝缘基体上成型叉指电极。 [0017] S2主要是采用电镀或者化学镀的方法在电极层表面镀上合金层； 合金层中的活 泼金属应当是相对于稳定金属具有较强还原性的金属， 容易被氧化为金属离子 而除去， 如锌、 锡、 锆等。 所述稳定金属可选用电导率高而化学性质稳定的金 属实现， 如金、 银、 铜等。 本发明中， 活泼金属的还原性强于所述稳定金属。 [0016] S1 can be implemented by any of the prior art, the purpose of which is to form an interdigital electrode on an insulating substrate. [0017] S2 is mainly coated with an alloy layer on the surface of the electrode layer by electroplating or electroless plating; the active metal in the alloy layer should be a metal having strong reducibility with respect to the stable metal, and is easily oxidized to metal ions to be removed. , such as zinc, tin, zirconium, etc. The stabilizing metal can be selected from metals having high electrical conductivity and chemical stability, such as gold, silver, copper, and the like. In the present invention, the reducibility of the active metal is stronger than the stable metal.
[0018] 进一步的， 在上述方法中， 所述合金层为金锡合金层或金锌合金层或金锆合金 层， 其中活泼金属的含量为 20-50 所述 s3中除去所述合金层中的活泼金属 是指用 pH为 8- 10的碱性试剂和氧化试剂除去所述合金层中的活泼金属。  [0018] Further, in the above method, the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 20-50, and the alloy layer is removed from the s3 The active metal means that the active metal in the alloy layer is removed by an alkaline agent having a pH of 8 - 10 and an oxidizing agent.
[0019] 进一步的， 所述步骤 S1具体为  [0019] Further, the step S1 is specifically
[0020] sl. l.对绝缘基层进行物理气相沉积， 在其表面形成过渡金属层；  [0020] sl. l. Physical vapor deposition of the insulating substrate, forming a transition metal layer on the surface;
[0021] sl.2.在所述过渡金属层表面通过电化学沉积法形成金属层； [0021] sl. 2. forming a metal layer on the surface of the transition metal layer by electrochemical deposition;
[0022] sl.3在所述金属层表面通过曝光显影、 图形转移、 蚀刻形成所述电极层； [0023] 所述物理气相沉积为磁控溅射， 磁控溅射方法具体为： 溅射的靶材为金属， 金 属的直径为 20-35mm、 厚度为 2-5mm; 靶和基板之间的距离为 15-20cm， 工作气 体为氮气和氩气， 分别使用质量流量计控制； 基板在放入真空室之前， 分别用 丙酮、 酒精、 去离子水超声清洗， 溅射前将真空室气压抽到 1x10 - 4-Pa， 并充入 氩气预溅射 3-5min以清洗靶面； 随后通入氮气， 控制总溅射气压在 3-4Pa， 控制 氮气与氩气的体积比例为 2: 1， 溅射功率控制在 105-125w， 溅射吋间为 0.5-1.5h。 [0022] sl. 3 on the surface of the metal layer by exposure development, pattern transfer, etching to form the electrode layer; [0023] the physical vapor deposition is magnetron sputtering, the magnetron sputtering method is specifically: sputtering The target is metal, the diameter of the metal is 20-35mm, the thickness is 2-5mm; the distance between the target and the substrate is 15-20cm, the working gas is nitrogen and argon, respectively controlled by mass flow meter; Before entering the vacuum chamber, ultrasonically clean with acetone, alcohol, deionized water, pump the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputter 3-5 minutes with argon gas to clean the target surface; Into nitrogen, the total sputtering pressure is controlled at 3-4 Pa, and the volume ratio of nitrogen to argon is controlled to be 2:1. The sputtering power is controlled at 105-125w, and the sputtering time is 0.5-1.5h.
[0024] 采用磁控溅射法， 可以在任意的绝缘基层 （包括但不限于陶瓷、 玻璃、 高分子 聚合物） 上形成过渡金属层， 并进一步的附着上金属、 蚀刻出电极层。 本发明 对磁控溅射的参数进行优化， 提高电极层与绝缘基层的稳定性， 避免由于多孔 金属层的存在导致电极层两侧受力不均而容易与绝缘基体分离的问题。 [0024] The magnetron sputtering method can form a transition metal layer on any insulating base layer (including but not limited to ceramics, glass, polymer), and further adhere the metal and etch the electrode layer. The invention optimizes the parameters of the magnetron sputtering, improves the stability of the electrode layer and the insulating base layer, and avoids the problem that the electrode layer is easily separated from the insulating substrate due to the uneven force on both sides of the electrode layer due to the existence of the porous metal layer.
[0025] 本发明还提供一种所述多孔金属修饰表面的叉指电极在制备气体传感器中的应 用， 所述多孔金属层及反应孔的表面负载有敏感层。 [0025] The present invention also provides an application of the interdigitated electrode of the porous metal-modified surface in the preparation of a gas sensor, the surface of the porous metal layer and the reaction well being loaded with a sensitive layer.
[0026] 进一步的， 所述敏感层为二氧化锡层， 其厚度为 0.1-2nm。 Further, the sensitive layer is a tin dioxide layer having a thickness of 0.1-2 nm.
[0027] 为避免因敏感成分本身导电性能不佳而导致信号在敏感层传递吋产生衰变， 本 发明限定敏感层的厚度， 在该厚度下， 敏感层可提供足够的敏感成分感应目标 气体， 同吋还可快速将信号传递至多孔金属层， 避免发生信号衰变。  [0027] In order to avoid the decay of the signal transmitted by the sensitive layer due to the poor conductivity of the sensitive component itself, the present invention defines the thickness of the sensitive layer, at which the sensitive layer can provide sufficient sensitive components to sense the target gas,吋 also quickly transmits signals to the porous metal layer to avoid signal decay.
发明的有益效果 有益效果 Advantageous effects of the invention Beneficial effect
[0028] 本发明相对于现有技术具有如下的有益效果： 本发明在叉指电极的电极层表面 修饰具有纳米级孔结构的多孔金属层， 可有效增加叉指电极的敏感成分负载量 ， 提高传感器的检测灵敏度； 本发明还采用去合金法制备叉指电极表面的多孔 金属层， 所获得的多孔金属层与电极层结合强度高， 层间信号传递无延吋、 衰 减等问题， 反应孔分布均匀。  [0028] The present invention has the following beneficial effects compared with the prior art: The present invention modifies a porous metal layer having a nano-scale pore structure on the surface of the electrode layer of the interdigital electrode, which can effectively increase the load of the sensitive component of the interdigital electrode and improve The detection sensitivity of the sensor; the invention also adopts the de-alloying method to prepare the porous metal layer on the surface of the interdigital electrode, the obtained porous metal layer has high bonding strength with the electrode layer, and the signal transmission between the layers has no problems such as delay and attenuation, and the reaction pore distribution Evenly.
对附图的简要说明  Brief description of the drawing
附图说明  DRAWINGS
[0029] 图 1是本发明的结构示意图； 1 is a schematic structural view of the present invention;
[0030] 图 2是本发明的断面图； Figure 2 is a cross-sectional view of the present invention;
[0031] 图 3是本发明多孔金属修饰表面的叉指电极在制备过程中的状态之一；  3 is one of the states of the interdigitated electrode of the porous metal-modified surface of the present invention in the preparation process;
[0032] 图 4是本发明多孔金属修饰表面的叉指电极在制备过程中的状态之二； 4 is a second state of the interdigitated electrode of the porous metal modified surface of the present invention in the preparation process;
[0033] 图 5是本发明多孔金属修饰表面的叉指电极在制备过程中的状态之三； [0033] FIG. 5 is a third state of the interdigital electrode of the porous metal modified surface of the present invention in the preparation process;
[0034] 图 6是本发明多孔金属修饰表面的叉指电极在制备过程中的状态之四； 6 is a fourth state of the interdigital electrode of the porous metal modified surface of the present invention in the preparation process; [0034] FIG.
[0035] 图 7是本发明反应孔的局部放大图。 7 is a partial enlarged view of a reaction well of the present invention.
实施该发明的最佳实施例  BEST MODE FOR CARRYING OUT THE INVENTION
本发明的最佳实施方式  BEST MODE FOR CARRYING OUT THE INVENTION
[0036] 本实施例提供一种多孔金属修饰表面的叉指电极， 如图 1和图 2， 包括绝缘基, 1 、 设置在绝缘基体表面的电极 2层； 上述电极层的反应面设有多孔金属层 3， 上 述多孔金属层 3中设有反应孔 4; 所述反应孔相互连通。 本实施例中， 绝缘基体 采用半固化片制成。 [0036] This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode 2 layer disposed on the surface of the insulating substrate; and a reaction surface of the electrode layer is porous In the metal layer 3, the porous metal layer 3 is provided with reaction holes 4; the reaction holes are in communication with each other. In this embodiment, the insulating substrate is made of a prepreg.
[0037] 进一步的， 本实施例中上述反应孔的直径为 70-80nm; 多孔金属层的表面孔隙 率为 35<¾。  Further, in the present embodiment, the diameter of the above reaction pores is 70-80 nm; and the surface porosity of the porous metal layer is 35 < 3⁄4.
[0038] 更进一步的， 上述多孔金属层的厚度为的厚度为 30μηι。  Further, the thickness of the above porous metal layer is 30 μm.
[0039] 所述电极层与绝缘基层间还设有过渡金属层 5， 其厚度为 100A; 所述过渡金属 层为 W层。  [0039] A transition metal layer 5 having a thickness of 100 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a W layer.
[0040] 上述电极层由铜层以及包裹在铜层外的金层构成。  [0040] The electrode layer is composed of a copper layer and a gold layer wrapped around the copper layer.
[0041] 优选的， 上述多孔金属层为 Ag金属构成。 本发明的实施方式 [0041] Preferably, the porous metal layer is made of Ag metal. Embodiments of the invention
[0042] 为了便于本领域技术人员理解， 下面将结合附图以及实施例对本发明作进一步 详细描述：  [0042] In order to facilitate the understanding of those skilled in the art, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
[0043] 实施例 1 Embodiment 1
[0044] 本实施例提供一种多孔金属修饰表面的叉指电极， 如图 1和图 2， 包括绝缘基体 1、 设置在绝缘基体 1表面的电极层 2; 上述电极层 2的反应面设有多孔金属层 3， 上述多孔金属层中设有反应孔 4; 所述反应孔相互连通。  [0044] This embodiment provides an interdigital finger of a porous metal-modified surface, as shown in FIG. 1 and FIG. 2, comprising an insulating substrate 1, an electrode layer 2 disposed on the surface of the insulating substrate 1, and a reaction surface of the electrode layer 2; In the porous metal layer 3, the reaction holes 4 are provided in the porous metal layer; the reaction holes are in communication with each other.
[0045] 所述电极层与绝缘基层间还设有过渡金属层 5， 其厚度为 60A; 所述过渡金属层 为 Ti层。  [0045] A transition metal layer 5 having a thickness of 60 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
[0046] 本实施例中， 所述绝缘基层为陶瓷。  [0046] In this embodiment, the insulating base layer is ceramic.
[0047] 进一步的， 本实施例中上述反应孔的直径为 60-70nm; 多孔金属层的表面孔隙 率为 20<¾。  Further, in the present embodiment, the diameter of the reaction well is 60-70 nm; and the surface porosity of the porous metal layer is 20 < 3⁄4.
[0048] 更进一步的， 上述多孔金属层的厚度为的厚度为 25μηι。  Further, the thickness of the above porous metal layer is 25 μm.
[0049] 上述电极层由 Ag单质构成。 [0049] The above electrode layer is composed of an elemental substance of Ag.
[0050] 优选的， 上述多孔金属层为 Ag金属构成。 多孔金属层更容易附着在与其性质相 近的材料构成的电极层上。  [0050] Preferably, the porous metal layer is made of Ag metal. The porous metal layer is more likely to adhere to an electrode layer composed of a material having a similar property.
[0051] 实施例 2 Embodiment 2
[0052] 本实施例提供一种多孔金属修饰表面的叉指电极， 如图 1和图 2， 包括绝缘基, 1 、 设置在绝缘基体表面的电极 2层； 上述电极层的反应面设有多孔金属层 3， 上 述多孔金属层 3中设有反应孔 4; 所述反应孔相互连通。 本实施例中， 绝缘基体 采用半固化片制成。  [0052] This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode 2 layer disposed on the surface of the insulating substrate; the reaction surface of the electrode layer is porous In the metal layer 3, the porous metal layer 3 is provided with reaction holes 4; the reaction holes are in communication with each other. In this embodiment, the insulating substrate is made of a prepreg.
[0053] 进一步的， 本实施例中上述反应孔的直径为 70-80nm; 多孔金属层的表面孔隙 率为 35<¾。  Further, in the present embodiment, the diameter of the above reaction pores is 70-80 nm; and the surface porosity of the porous metal layer is 35 < 3⁄4.
[0054] 更进一步的， 上述多孔金属层的厚度为的厚度为 30μηι。  Further, the thickness of the above porous metal layer is 30 μm.
[0055] 所述电极层与绝缘基层间还设有过渡金属层 5， 其厚度为 100A; 所述过渡金属 层为 W层。  [0055] A transition metal layer 5 having a thickness of 100 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a W layer.
[0056] 上述电极层由铜层以及包裹在铜层外的金层构成。 [0057] 优选的， 上述多孔金属层为 Ag金属构成。 [0056] The electrode layer is composed of a copper layer and a gold layer wrapped around the copper layer. [0057] Preferably, the porous metal layer is made of Ag metal.
[0058] 实施例 3 Embodiment 3
[0059] 本实施例提供一种多孔金属修饰表面的叉指电极， 如图 1和图 2， 包括绝缘基, 1 、 设置在绝缘基体表面的电极层 2; 上述电极层的反应面设有多孔金属层 3， 上 述多孔金属层中设有反应 4孔； 所述反应孔相互连通。  [0059] This embodiment provides an interdigitated electrode of a porous metal-modified surface, as shown in FIGS. 1 and 2, including an insulating layer, 1 , an electrode layer 2 disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous In the metal layer 3, four holes of the reaction are provided in the porous metal layer; and the reaction holes are in communication with each other.
[0060] 本实施例中， 上述绝缘基体采用玻璃制成。  [0060] In this embodiment, the insulating base body is made of glass.
[0061] 进一步的， 本实施例中上述反应孔的直径为 70-90nm; 多孔金属层的表面孔隙 率为 20<¾。  Further, in the present embodiment, the diameter of the reaction well is 70-90 nm; and the surface porosity of the porous metal layer is 20<3⁄4.
[0062] 更进一步的， 上述多孔金属层的厚度为的厚度为 50μηι。  Further, the thickness of the above porous metal layer is 50 μm.
[0063] 优选的， 上述多孔金属层为 Cu金属构成。 本实施例中， 上述电极层可采用铜构 成。  Preferably, the porous metal layer is made of Cu metal. In this embodiment, the electrode layer may be made of copper.
[0064] 所述电极层与绝缘基层间还设有过渡金属层 5， 其厚度为 50A; 所述过渡金属层 为 Mo层。  [0064] A transition metal layer 5 having a thickness of 50 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo layer.
[0065] 实施例 4 Example 4
[0066] 本实施例提供一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘 基体表面的电极层； 上述电极层的反应面设有多孔金属层， 上述多孔金属层中 设有反应孔； 所述反应孔相互连通。  [0066] The embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, wherein the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
[0067] 进一步的， 本实施例中上述反应孔的直径为 85-lOOnm; 多孔金属层的表面孔隙 率为 40<¾。  Further, in the present embodiment, the diameter of the reaction pores is 85-100 nm; and the surface porosity of the porous metal layer is 40<3⁄4.
[0068] 更进一步的， 上述多孔金属层的厚度为的厚度为 15μηι。  Further, the thickness of the above porous metal layer is 15 μm.
[0069] 优选的， 上述多孔金属层为 Ag金属。 所述电极层由铜金属形成。  [0069] Preferably, the porous metal layer is an Ag metal. The electrode layer is formed of copper metal.
[0070] 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 500A; 所述过渡金属层 为 Ti层。  [0070] A transition metal layer having a thickness of 500 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
[0071] 实施例 5 Example 5
[0072] 本实施例提供一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘 基体表面的电极层； 上述电极层的反应面设有多孔金属层， 上述多孔金属层中 设有反应孔； 所述反应孔相互连通。 所述绝缘基体为环氧树脂构成。  [0072] The present embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other. The insulating substrate is made of an epoxy resin.
[0073] 进一步的， 本实施例中上述反应孔的直径为 90-lOOnm; 多孔金属层的表面孔隙 率为 45<¾。 [0073] Further, in the embodiment, the diameter of the reaction pore is 90-100 nm; the surface pore of the porous metal layer The rate is 45<3⁄4.
[0074] 更进一步的， 上述多孔金属层的厚度为的厚度为 35μηι。  Further, the thickness of the above porous metal layer is 35 μm.
[0075] 优选的， 上述多孔金属层为金银合金。 所述电极层由金金属构成。  [0075] Preferably, the porous metal layer is a gold-silver alloy. The electrode layer is composed of gold metal.
[0076] 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 800Α; 所述过渡金属层 为 Mo层。  [0076] A transition metal layer having a thickness of 800 Å is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo layer.
[0077] 实施例 6 Example 6
[0078] 本实施例提供一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘 基体表面的电极层； 上述电极层的反应面设有多孔金属层， 上述多孔金属层中 设有反应孔； 所述反应孔相互连通。  [0078] The embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate and an electrode layer disposed on a surface of the insulating substrate; the reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
[0079] 进一步的， 本实施例中上述反应孔的直径为 60-70nm; 多孔金属层的表面孔隙 率为 20<¾。  Further, in the present embodiment, the diameter of the reaction well is 60-70 nm; and the surface porosity of the porous metal layer is 20<3⁄4.
[0080] 更进一步的， 上述多孔金属层的厚度为的厚度为 50μηι。  Further, the thickness of the above porous metal layer is 50 μm.
[0081] 优选的， 上述多孔金属层为 Au金属形成。 所述电极层由 Au金属形成。  Preferably, the porous metal layer is formed of Au metal. The electrode layer is formed of Au metal.
[0082] 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 50-800A; 所述过渡金 属层为 Mo、 W合金层。  [0082] A transition metal layer having a thickness of 50-800 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Mo and W alloy layer.
[0083] 实施例 7 Example 7
[0084] 本实施例提供一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘 基体表面的电极层； 上述电极层的反应面设有多孔金属层， 上述多孔金属层中 设有反应孔； 所述反应孔相互连通。  [0084] The embodiment provides an interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and the porous metal layer is disposed Reaction well; the reaction wells are in communication with each other.
[0085] 进一步的， 本实施例中上述反应孔的直径为 70-75nm; 多孔金属层的表面孔隙 率为 25<¾。  Further, in the present embodiment, the diameter of the reaction well is 70-75 nm; and the surface porosity of the porous metal layer is 25 < 3⁄4.
[0086] 更进一步的， 上述多孔金属层的厚度为的厚度为 35μηι。  Further, the thickness of the above porous metal layer is 35 μm.
[0087] 优选的， 上述多孔金属层为 Cu金属构成。 所述电极层由 cu金属构成。  Preferably, the porous metal layer is made of Cu metal. The electrode layer is composed of cu metal.
[0088] 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 300A; 所述过渡金属层 为 Ti层。  [0088] A transition metal layer having a thickness of 300 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
[0089] 实施例 8 Example 8
[0090] 本实施例提供一种制备实施例 1所述多孔金属修饰表面的叉指电极的方法， 包 括如下工序： [0091] SI.在绝缘基体 1上形成电极层 2 (如图 5) ； [0090] This embodiment provides a method for preparing the interdigitated electrode of the porous metal modified surface of Embodiment 1, which comprises the following steps: [0091] SI. Forming an electrode layer 2 on the insulating substrate 1 (as shown in FIG. 5);
[0092] S2.在电极层上附着合金层 7 (如图 6) ； 所述合金层中包括至少一种稳定金属 和至少一种活泼金属；  [0092] S2. Attaching an alloy layer 7 on the electrode layer (as shown in FIG. 6); the alloy layer includes at least one stabilizing metal and at least one active metal;
[0093] S3.除去所述合金层中的活泼金属， 残留部分即所述多孔金属层。 [0093] S3. The active metal in the alloy layer is removed, and the remaining portion is the porous metal layer.
[0094] 本实施例优选的， 所述合金层为金锡合金层或金锌合金层或金锆合金层， 其中 活泼金属的含量为 45 vol.<¾。 [0094] Preferably, the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 45 vol.<3⁄4.
[0095] 所述步骤 SI具体为 [0095] the step SI is specifically
[0096] sl. l.对绝缘基层进行物理气相沉积， 在其表面形成过渡金属层 5 (如图 3) ； [0097] sl.2.在所述过渡金属层表面通过电化学沉积法形成金属层 （如图 4) ；  [0096] sl. l. Physical vapor deposition of the insulating base layer, forming a transition metal layer 5 on the surface thereof (Fig. 3); [0097] sl. 2. forming a metal by electrochemical deposition on the surface of the transition metal layer Layer (Figure 4);
[0098] sl.3在所述金属层表面通过曝光显影、 图形转移、 蚀刻形成所述电极层； [0099] 所述物理气相沉积为磁控溅射， 磁控溅射方法具体为： 溅射的靶材为金属， 金 属的直径为 25mm、 厚度为 4mm; 靶和基板之间的距离为 18cm， 工作气体为氮 气和氩气， 分别使用质量流量计控制； 基板在放入真空室之前， 分别用丙酮、 酒精、 去离子水超声清洗， 溅射前将真空室气压抽到 1x10 - 4-Pa， 并充入氩气预 溅射 4min以清洗靶面； 随后通入氮气， 控制总溅射气压在 3-4Pa， 控制氮气与氩 气的体积比例为 2: 1， 溅射功率控制在 120w， 溅射吋间为 lh。 [0098] sl. 3 on the surface of the metal layer by exposure development, pattern transfer, etching to form the electrode layer; [0099] the physical vapor deposition is magnetron sputtering, the magnetron sputtering method is specifically: sputtering The target is metal, the diameter of the metal is 25mm, the thickness is 4mm; the distance between the target and the substrate is 18cm, the working gas is nitrogen and argon, respectively controlled by mass flow meter; the substrate is placed in the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputtering for 4 minutes with argon gas to clean the target surface; then introducing nitrogen gas to control the total sputtering pressure At 3-4 Pa, the volume ratio of nitrogen to argon is controlled to be 2: 1, the sputtering power is controlled at 120 W, and the sputtering time is 1 h.
[0100] S2中， 具体为将电极层浸泡在金锡合金镀液中电镀上金锡合金层。 所述金锡合 金镀液、 电镀的具体操作为现有技术， 不在赘述。  [0100] In S2, specifically, the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-tin alloy layer. The specific operation of the gold-tin alloy plating solution and electroplating is prior art and will not be described again.
[0101] S3中， 除去所述合金层中的活泼金属是指将采用 5M的氢氧化钾溶液和 3M的双 氧水蚀刻除去金锡合金层中的锡， 获得多孔金属层。  In S3, the removal of the active metal in the alloy layer means that tin in the gold-tin alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M hydrogen peroxide to obtain a porous metal layer.
[0102] 采用上述方法制备多孔金层， 可以确保多孔金层中的反应孔相互导通， 提高气 体在多孔金层的扩散速度； 采用蚀刻的方法去除合金中的一种， 更可有效提高 多孔金属层中反应孔的均匀度， 从而有效增加多孔金属层的比表面积。  [0102] The porous gold layer prepared by the above method can ensure that the reaction pores in the porous gold layer are electrically connected to each other, and the diffusion speed of the gas in the porous gold layer is improved; and one of the alloys is removed by etching to effectively increase the porosity. The uniformity of the reaction holes in the metal layer, thereby effectively increasing the specific surface area of the porous metal layer.
[0103] 实施例 9  Example 9
[0104] 本实施例提供一种制备实施例 2所述多孔金属修饰表面的叉指电极的方法， 包 括如下工序：  [0104] This embodiment provides a method for preparing an interdigital electrode of a porous metal-modified surface according to Embodiment 2, which comprises the following steps:
[0105] S1.在绝缘基体上形成电极层； [0105] S1. forming an electrode layer on the insulating substrate;
[0106] S2.在电极层上附着合金层； 所述合金层中包括至少一种稳定金属和至少一种 活泼金属； [0106] S2. attaching an alloy layer on the electrode layer; the alloy layer includes at least one stable metal and at least one Lively metal
[0107] S3.除去所述合金层中的活泼金属， 残留部分即所述多孔金属层。  [0107] S3. The active metal in the alloy layer is removed, and the remaining portion is the porous metal layer.
[0108] 本实施例优选的， 所述合金层为金锡合金层或金锌合金层或金锆合金层， 其中 活泼金属的含量为 50 vol.<¾。  [0108] Preferably, in the embodiment, the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 50 vol.<3⁄4.
[0109] 所述步骤 SI具体为 [0109] the step SI is specifically
[0110] sl. l.对绝缘基层进行物理气相沉积， 在其表面形成过渡金属层；  [0110] sl. l. Physical vapor deposition of the insulating substrate, forming a transition metal layer on the surface;
[0111] sl.2.在所述过渡金属层表面通过电化学沉积法形成金属层； [0111] sl. 2. forming a metal layer on the surface of the transition metal layer by electrochemical deposition;
[0112] sl.3在所述金属层表面通过曝光显影、 图形转移、 蚀刻形成所述电极层； [0113] 所述物理气相沉积为磁控溅射， 磁控溅射方法具体为： 溅射的靶材为金属， 金 属的直径为 35mm、 厚度为 2mm; 靶和基板之间的距离为 20cm， 工作气体为氮 气和氩气， 分别使用质量流量计控制； 基板在放入真空室之前， 分别用丙酮、 酒精、 去离子水超声清洗， 溅射前将真空室气压抽到 1x10 - 4-Pa， 并充入氩气预 溅射 3min以清洗靶面； 随后通入氮气， 控制总溅射气压在 4Pa， 控制氮气与氩气 的体积比例为 2: 1， 溅射功率控制在 105w， 溅射吋间为 1.5h。 [0112] sl. 3 forming the electrode layer by exposure development, pattern transfer, etching on the surface of the metal layer; [0113] the physical vapor deposition is magnetron sputtering, and the magnetron sputtering method is specifically: sputtering The target is metal, the diameter of the metal is 35mm, the thickness is 2mm; the distance between the target and the substrate is 20cm, the working gas is nitrogen and argon, respectively controlled by the mass flow meter; the substrate is placed in the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and pre-sputtering with argon for 3min to clean the target surface; then introducing nitrogen gas to control the total sputtering pressure At 4 Pa, the volume ratio of nitrogen to argon was controlled to 2: 1, the sputtering power was controlled at 105 W, and the sputtering time was 1.5 h.
[0114] S2中， 具体为将电极层浸泡在金锡合金镀液中电镀上金锌合金层。 所述金锌合 金镀液、 电镀的具体操作为现有技术， 不在赘述。 [0114] In S2, specifically, the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-zinc alloy layer. The specific operation of the gold-zinc alloy plating solution and electroplating is prior art and will not be described again.
[0115] S3中， 除去所述合金层中的活泼金属是指将采用 5M的氢氧化钾溶液和 3M的双 氧水蚀刻除去金锌合金层中的锌， 获得多孔金属层。 In S3, the removal of the active metal in the alloy layer means that zinc in the gold-zinc alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M of hydrogen peroxide to obtain a porous metal layer.
[0116] 实施例 10 Example 10
[0117] 本实施例提供一种如实施例 1所述多孔金属修饰表面的叉指电极制备的气体传 感器， 如图 7， 其中所述多孔金属层及反应孔的表面负载有敏感层 6。  [0117] This embodiment provides a gas sensor prepared by interdigitated electrodes of a porous metal-modified surface as described in Example 1, wherein the porous metal layer and the surface of the reaction well are loaded with the sensitive layer 6.
[0118] 进一步的， 所述敏感层为二氧化锡层， 其厚度为 0.9nm。 [0118] Further, the sensitive layer is a tin dioxide layer having a thickness of 0.9 nm.
[0119] 实施例 11 Example 11
[0120] 本实施例提供一种如实施例 1所述多孔金属修饰表面的叉指电极的在制备气体 传感器中的应用， 其中所述多孔金属层及反应孔的表面负载有敏感层。  [0120] This embodiment provides the use of an interdigitated electrode of a porous metal-modified surface as described in Embodiment 1 in the preparation of a gas sensor, wherein the surface of the porous metal layer and the reaction well is loaded with a sensitive layer.
[0121] 进一步的， 所述敏感层为二氧化锡层， 其厚度为 3nm。 [0121] Further, the sensitive layer is a tin dioxide layer having a thickness of 3 nm.
[0122] 对比例 1 Comparative Example 1
[0123] 本对比例提供一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘 基体表面的电极层； 上述电极层的反应面设有多孔金属层， 上述多孔金属层中 设有反应孔； 所述反应孔相互连通。 [0123] The present comparative example provides an interdigitated electrode of a porous metal-modified surface, including an insulating substrate, disposed in insulation An electrode layer on the surface of the substrate; a reaction surface of the electrode layer is provided with a porous metal layer, and a reaction hole is provided in the porous metal layer; and the reaction holes are in communication with each other.
[0124] 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 60A; 所述过渡金属层 为 Ti层。 [0124] A transition metal layer having a thickness of 60 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is a Ti layer.
[0125] 本对比例中， 所述绝缘基层为陶瓷。  [0125] In the present comparative example, the insulating base layer is a ceramic.
[0126] 进一步的， 本对比例中上述反应孔的直径为 10-40nm; 多孔金属层的表面孔隙 率为 60<¾。  Further, in the present comparative example, the diameter of the above reaction well is 10-40 nm; and the surface porosity of the porous metal layer is 60 < 3⁄4.
[0127] 更进一步的， 上述多孔金属层的厚度为的厚度为 50μηι。  Further, the thickness of the above porous metal layer is 50 μm.
[0128] 上述电极层由 Ag单质构成。 [0128] The above electrode layer is composed of an elemental substance of Ag.
[0129] 对比例 2 Comparative Example 2
[0130] 本实施例提供一种制备实施例 2所述多孔金属修饰表面的叉指电极的方法， 包 括如下工序：  [0130] This embodiment provides a method for preparing the interdigitated electrode of the porous metal-modified surface of Example 2, which comprises the following steps:
[0131] S1.在绝缘基体上形成电极层； [0131] S1. forming an electrode layer on the insulating substrate;
[0132] S2.在电极层上附着合金层； 所述合金层中包括至少一种稳定金属和至少一种 活泼金属；  [0132] S2. attaching an alloy layer on the electrode layer; the alloy layer includes at least one stabilizing metal and at least one active metal;
[0133] S3.除去所述合金层中的活泼金属， 残留部分即所述多孔金属层。  [0133] S3. The active metal in the alloy layer is removed, and the remaining portion is the porous metal layer.
[0134] 本实施例优选的， 所述合金层为金锡合金层或金锌合金层或金锆合金层， 其中 活泼金属的含量为 20-50 [0134] In this embodiment, the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 20-50.
vol.%; 所述 s3中除去所述合金层中的活泼金属是指用 pH为 8-10的碱性试剂和氧 化试剂除去所述合金层中的活泼金属。  Vol.%; the removal of the active metal in the alloy layer in s3 means removal of the active metal in the alloy layer with an alkaline agent having a pH of 8-10 and an oxidizing agent.
[0135] 所述步骤 S1具体为 [0135] the step S1 is specifically
[0136] sl. l.对绝缘基层进行物理气相沉积， 在其表面形成过渡金属层；  [0136] sl. l. physical vapor deposition of the insulating substrate, forming a transition metal layer on the surface;
[0137] sl.2.在所述过渡金属层表面通过电化学沉积法形成金属层； [0137] sl. 2. forming a metal layer on the surface of the transition metal layer by electrochemical deposition;
[0138] sl.3在所述金属层表面通过曝光显影、 图形转移、 蚀刻形成所述电极层； [0139] 所述物理气相沉积为磁控溅射， 磁控溅射方法具体为： 溅射的靶材为金属， 金 属的直径为 40mm、 厚度为 6mm; 靶和基板之间的距离为 10cm， 工作气体为氮气 和氩气， 分别使用质量流量计控制； 基板在放入真空室之前， 分别用丙酮、 酒 精、 去离子水超声清洗， 溅射前将真空室气压抽到 1x10 - 4-Pa， 并充入氩气预溅 射 3-5min以清洗靶面； 随后通入氮气， 控制总溅射气压在 3-4Pa， 控制氮气与氩 气的体积比例为 2:1， 溅射功率控制在 105-125w， 溅射吋间为 0.5-1.5h。 [0138] sl. 3 forming the electrode layer by exposure development, pattern transfer, etching on the surface of the metal layer; [0139] the physical vapor deposition is magnetron sputtering, and the magnetron sputtering method is specifically: sputtering The target is metal, the diameter of the metal is 40mm, the thickness is 6mm; the distance between the target and the substrate is 10cm, the working gas is nitrogen and argon, respectively controlled by the mass flow meter; the substrate is placed before the vacuum chamber, respectively Ultrasonic cleaning with acetone, alcohol, deionized water, pumping the vacuum chamber pressure to 1x10 - 4- Pa before sputtering, and filling with argon pre-splashing Shoot for 3-5min to clean the target surface; then pass nitrogen, control the total sputtering pressure at 3-4Pa, control the volume ratio of nitrogen to argon to 2:1, and the sputtering power is controlled at 105-125w, sputtering It is 0.5-1.5h.
[0140] S2中， 具体为将电极层浸泡在金锡合金镀液中电镀上金锌合金层。 所述金锌合 金镀液、 电镀的具体操作为现有技术， 不在赘述。 [0140] In S2, specifically, the electrode layer is immersed in a gold-tin alloy plating solution to plate a gold-zinc alloy layer. The specific operation of the gold-zinc alloy plating solution and electroplating is prior art and will not be described again.
[0141] S3中， 除去所述合金层中的活泼金属是指将采用 5M的氢氧化钾溶液和 3M的双 氧水蚀刻除去金锌合金层中的锌， 获得多孔金属层。 In S3, the removal of the active metal in the alloy layer means that zinc in the gold-zinc alloy layer is removed by etching with a 5 M potassium hydroxide solution and 3 M of hydrogen peroxide to obtain a porous metal layer.
[0142] 实验例 1 Experimental Example 1
[0143] 1.1在实施例 1-7中和对比例附着上二氧化硫敏感材料 （可选用公告号为 1021758 1.1 In the examples 1-7 and the comparative examples attached to the sulfur dioxide sensitive material (optional bulletin number 1021758)
15B的中国发明专利所记载的敏感材料） ， 用于制成传感器。 测定传感器对二氧 化硫气体的检出限。 其结果如表 1所示。 The sensitive material described in the Chinese invention patent of 15B) is used to make a sensor. The detection limit of the sensor for sulfur dioxide gas was measured. The results are shown in Table 1.
[0144] 表 1.二氧化硫浓度检出限。 Table 1. Limit of detection of sulfur dioxide concentration.
[0145] 1.2在实施例 1-7中和对比例附着上对二氧化氮的敏感材料 （可选用公幵号为 102 608183A的中国发明专利所记载的敏感材料） ， 用于制成传感器。 测定传感器对 二氧化氮气体的检出限。 其结果如表 2所示。  [0145] 1.2 Sensitive materials for nitrogen dioxide in the examples 1-7 and the comparative examples (sensitive materials described in Chinese Patent Publication No. 102 608 183 A) were used to fabricate the sensor. The detection limit of the sensor for the nitrogen dioxide gas was measured. The results are shown in Table 2.
[0146] 表 2.二氧化氮浓度检出限。  Table 2. Detection limits for nitrogen dioxide concentration.
Figure imgf000013_0002
Figure imgf000013_0002
[0147] 1.3在实施例 10、 11制成的传感器。 测定传感器对一氧化碳气体的检出限。 其 果如表 3所示。  [0147] 1.3 Sensors made in Examples 10, 11. The detection limit of the sensor for carbon monoxide gas is measured. The result is shown in Table 3.
[0148] 表 3.—氧化碳浓度检出限。 [] Table 3. - Detection limit of carbon oxide concentration. []
实验 实施 实施 实施 实施 实施 实施 实施  Experiment implementation implementation implementation implementation implementation implementation
组 例 1^ 例 ^ 例 3 -' 例 4、 例 例 6^ 例  Group example 1^ Example ^ Example 3 - ' Example 4, Example 6^ Example
检出  Check out
限 0. 16 0. 05 0. 0 0. 1 : 0. 1 2、<： 0. 05 0. 03 39 Limits 0. 16 0. 05 0. 0 0. 1 : 0. 1 2, <: 0. 05 0. 03 39
C rag/ C rag/
™  TM
[0149] 实验例 2.层间结合强度测试。 Experimental Example 2. Interlayer bonding strength test.
[0150] 采用 GB/T 5270-2005对过渡金属层与绝缘基体间的结合强度进行测试。  [0150] The bonding strength between the transition metal layer and the insulating substrate was tested using GB/T 5270-2005.
[0151] 对实施例热震实验 （300°C) ， 观察表面形态， 其结果如表 4所示。  For the thermal shock test (300 ° C) of the examples, the surface morphology was observed, and the results are shown in Table 4.
[0152] 表 4.  Table 4
[]
Figure imgf000014_0001
[]
Figure imgf000014_0001
[0153] 以上为本发明的其中具体实现方式， 其描述较为具体和详细， 但并不能因此而 理解为对本发明专利范围的限制。 应当指出的是， 对于本领域的普通技术人员 来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和改进， 这些显而 易见的替换形式均属于本发明的保护范围。  The above is a specific implementation of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It is to be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
工业实用性  Industrial applicability
¾ 3⁄4
[0154] 本发明提供一种多孔金属修饰表面可增加敏感成分负载量、 提高传感器灵敏度 的叉指电极。 The present invention provides an interdigitated electrode in which a porous metal-modified surface can increase the loading of sensitive components and increase the sensitivity of the sensor.

Claims

权利要求书 Claim
[权利要求 1] 一种多孔金属修饰表面的叉指电极， 包括绝缘基体、 设置在绝缘基体 表面的电极层； 其特征在于： 所述电极层的反应面设有多孔金属层， 所述多孔金属层中设有反应孔； 所述反应孔相互连通。  [Claim 1] An interdigitated electrode of a porous metal-modified surface, comprising an insulating substrate, an electrode layer disposed on a surface of the insulating substrate; wherein: a reaction surface of the electrode layer is provided with a porous metal layer, the porous metal Reaction holes are provided in the layer; the reaction holes are in communication with each other.
[权利要求 2] 根据权利要求 1所述的多孔金属修饰表面的叉指电极， 其特征在于： 所述反应孔的直径为 60-lOOnm; 多孔金属层的表面孔隙率为 20<¾-50 。  [Claim 2] The interdigitated electrode of the porous metal-modified surface according to claim 1, wherein: the diameter of the reaction pore is 60-100 nm; and the surface porosity of the porous metal layer is 20 < 3⁄4-50.
[权利要求 3] 根据权利要求 1所述的多孔金属修饰表面的叉指电极， 其特征在于： 所述多孔金属层的厚度为的厚度为 5_50μηι。  The interdigitated electrode of the porous metal-modified surface according to claim 1, wherein the porous metal layer has a thickness of 5 to 50 μm.
[权利要求 4] 根据权利要求 1-3任一项所述的多孔金属修饰表面的叉指电极， 其特 征在于： 所述多孔金属层为 Ag、 Cu、 Au、 Al、 Ni、 Fe中的一种形成 的金属或其中至少两种形成的合金构成。  [Claim 4] The interdigitated electrode of the porous metal-modified surface according to any one of claims 1 to 3, wherein the porous metal layer is one of Ag, Cu, Au, Al, Ni, Fe The formed metal or an alloy formed of at least two of them.
[权利要求 5] 根据权利要求 4所述的多孔金属修饰表面的叉指电极， 其特征在于： 所述反应孔直径为 60-80nm; 所述多孔金属层的表面孔隙率为 30<¾-40 %; 所述电极层与绝缘基层间还设有过渡金属层， 其厚度为 50-800A ； 所述过渡金属层为 Ti、 Mo、 W中的至少两种形成的合金层。  [Claim 5] The interdigitated electrode of the porous metal-modified surface according to claim 4, wherein: the reaction pore diameter is 60-80 nm; and the porous metal layer has a surface porosity of 30<3⁄4-40 A transition metal layer having a thickness of 50-800 A is further disposed between the electrode layer and the insulating base layer; and the transition metal layer is an alloy layer formed of at least two of Ti, Mo, and W.
[权利要求 6] —种制备所述多孔金属修饰表面的叉指电极的方法， 包括如下工序：  [Claim 6] A method of preparing an interdigital electrode of the porous metal-modified surface, comprising the steps of:
51.在绝缘基体上形成电极层；  51. forming an electrode layer on the insulating substrate;
52.在电极层上附着合金层； 所述合金层中包括至少一种稳定金属和 至少一种活泼金属；  52. attaching an alloy layer on the electrode layer; the alloy layer comprising at least one stabilizing metal and at least one active metal;
53.除去所述合金层中的活泼金属， 残留部分即所述多孔金属层。 53. The active metal in the alloy layer is removed, and the remaining portion is the porous metal layer.
[权利要求 7] 根据权利要求 6所述的方法， 其特征在于： 所述合金层为金锡合金层 或金锌合金层或金锆合金层， 其中活泼金属的含量为 20-50 vol.%; 所 述 s3中除去所述合金层中的活泼金属是指用 pH为 8-10的碱性试剂和氧 化试剂除去所述合金层中的活泼金属。  [Claim 7] The method according to claim 6, wherein: the alloy layer is a gold-tin alloy layer or a gold-zinc alloy layer or a gold-zirconium alloy layer, wherein the content of the active metal is 20-50 vol.% Removal of the active metal in the alloy layer in the s3 means removal of the active metal in the alloy layer with an alkaline agent having a pH of 8-10 and an oxidizing agent.
[权利要求 8] 根据权利要求 6或 7所述的方法， 其特征在于： 所述步骤 S1具体为 sl.l.对绝缘基层进行物理气相沉积， 在其表面形成过渡金属层； sl.2.在所述过渡金属层表面通过电化学沉积法形成金属层； sl.3在所述金属层表面通过曝光显影、 图形转移、 蚀刻形成所述电极 层； [Claim 8] The method according to claim 6 or 7, wherein: the step S1 is specifically sl.l. Physical vapor deposition of the insulating base layer, forming a transition metal layer on the surface thereof; sl. Forming a metal layer on the surface of the transition metal layer by electrochemical deposition; Sl. 3 forming the electrode layer on the surface of the metal layer by exposure development, pattern transfer, etching;
所述物理气相沉积为磁控溅射， 磁控溅射方法具体为： 溅射的靶材为 金属， 金属的直径为 20-35mm、 厚度为 2-5mm; 靶和基板之间的距离 为 15-20cm， 工作气体为氮气和氩气， 分别使用质量流量计控制； 基 板在放入真空室之前， 分别用丙酮、 酒精、 去离子水超声清洗， 溅射 前将真空室气压抽到 1x10 4-Pa, 并充入氩气预溅射 3-5min以清洗靶面 ； 随后通入氮气， 控制总溅射气压在 3-4Pa， 控制氮气与氩气的体积 比例为 2: 1， 溅射功率控制在 105-125w， 溅射吋间为 0.5-1.5h。 The physical vapor deposition is magnetron sputtering, and the magnetron sputtering method is specifically: the sputtering target is metal, the diameter of the metal is 20-35 mm, the thickness is 2-5 mm; the distance between the target and the substrate is 15 -20cm, the working gas is nitrogen and argon, respectively controlled by mass flow meter; the substrate is ultrasonically cleaned with acetone, alcohol and deionized water before being placed in the vacuum chamber, and the vacuum chamber pressure is pumped to 1x10 4 before sputtering - Pa, and pre-sputtered with argon for 3-5min to clean the target surface; then pass nitrogen, control the total sputtering pressure at 3-4Pa, control the volume ratio of nitrogen to argon to 2: 1, sputtering power control At 105-125w, the sputtering time is 0.5-1.5h.
[权利要求 9] 一种如权利要求 1-5所述多孔金属修饰表面的叉指电极的在制备气体 传感器中的应用， 其特征在于： 所述多孔金属层及反应孔的表面负载 有敏感层。 [Claim 9] The use of an interdigitated electrode of a porous metal-modified surface according to any of claims 1 to 5 in the preparation of a gas sensor, characterized in that: the porous metal layer and the surface of the reaction well are loaded with a sensitive layer .
[权利要求 10] 根据权利要求 8所述的应用， 其特征在于： 所述敏感层为二氧化锡层 ， 其厚度为 0.1-2nm。  [Application 10] The application according to claim 8, wherein the sensitive layer is a tin dioxide layer having a thickness of 0.1 to 2 nm.
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Publication number Priority date Publication date Assignee Title
CN106053538A (en) * 2016-05-28 2016-10-26 惠州市力道电子材料有限公司 Interdigital electrode with porous metal modified surface and preparation method and application thereof
CN107447235A (en) * 2017-06-20 2017-12-08 广东工业大学 A kind of ordered porous nickel composite materials of nano-porous gold@and its preparation method and application
CN108802140A (en) * 2018-08-13 2018-11-13 广州钰芯传感科技有限公司 A kind of interdigital electrode and its preparation method and application of porous gold modification
CN109632909A (en) * 2018-12-14 2019-04-16 惠州市金百泽电路科技有限公司 A kind of production method of ceramic base sensing electrode surface fine-line
CN112285182A (en) * 2020-12-25 2021-01-29 广州钰芯智能科技研究院有限公司 High-precision interdigital electrode and preparation method and application thereof
CN115007861B (en) * 2022-06-10 2023-10-17 山东大学 Method for preparing porous tin and application of porous tin in sodium ion battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100595578C (en) * 2008-06-25 2010-03-24 华东师范大学 Method for preparing platinum nano-perforated electrode by evaporation deposition
US20120077057A1 (en) * 2010-09-27 2012-03-29 Kysar Jeffrey W Galvanostatic Dealloying for Fabrication of Constrained Blanket Nanoporous Gold Films
CN102766893A (en) * 2012-07-24 2012-11-07 上海交通大学 Preparation method of nano porous copper capable of being patterned
US20130321983A1 (en) * 2011-01-06 2013-12-05 Sungkyunkwan University Foundation For Corporate Collaboration Nano-porous electrode for super capacitor and manufacturing method thereof
CN106053538A (en) * 2016-05-28 2016-10-26 惠州市力道电子材料有限公司 Interdigital electrode with porous metal modified surface and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006126056A (en) * 2004-10-29 2006-05-18 Tdk Corp Carbon dioxide sensor
US8052854B1 (en) * 2007-05-25 2011-11-08 The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration Carbon dioxide gas sensors and method of manufacturing and using same
CN105112958B (en) * 2015-08-25 2017-09-26 中山大学 A kind of method for going alloyage to obtain nano-porous silver loaded on base material
CN205826581U (en) * 2016-05-28 2016-12-21 惠州市力道电子材料有限公司 Interdigital electrode, gas sensor and the gas detection equipment of a kind of porous metals modification of surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100595578C (en) * 2008-06-25 2010-03-24 华东师范大学 Method for preparing platinum nano-perforated electrode by evaporation deposition
US20120077057A1 (en) * 2010-09-27 2012-03-29 Kysar Jeffrey W Galvanostatic Dealloying for Fabrication of Constrained Blanket Nanoporous Gold Films
US20130321983A1 (en) * 2011-01-06 2013-12-05 Sungkyunkwan University Foundation For Corporate Collaboration Nano-porous electrode for super capacitor and manufacturing method thereof
CN102766893A (en) * 2012-07-24 2012-11-07 上海交通大学 Preparation method of nano porous copper capable of being patterned
CN106053538A (en) * 2016-05-28 2016-10-26 惠州市力道电子材料有限公司 Interdigital electrode with porous metal modified surface and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZENG, ZHIGANG ET AL.: "Fabrication of Microelectrode with Nanoporous Gold Thin Film", CHINESE JOURNAL OF VACUUM SCIENCE AND TECHNOLOGY, vol. 35, no. 10, 31 October 2015 (2015-10-31), pages 1185 - 1190, XP055585753 *

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