WO2015058495A1 - 一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法 - Google Patents

一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法 Download PDF

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WO2015058495A1
WO2015058495A1 PCT/CN2014/074881 CN2014074881W WO2015058495A1 WO 2015058495 A1 WO2015058495 A1 WO 2015058495A1 CN 2014074881 W CN2014074881 W CN 2014074881W WO 2015058495 A1 WO2015058495 A1 WO 2015058495A1
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metal oxide
template
microsphere
gas
porous film
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孙旭辉
张平平
张书敏
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Suzhou University
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/087—Oxides of copper or solid solutions thereof
    • 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

Definitions

  • the invention relates to the field of gas sensing materials for gas sensors, in particular to a method for preparing a multi-layer metal oxide porous film nano gas sensing material.
  • the metal oxide porous film material has a larger specific surface area than the bulk film material, and its sensitivity to gas is greatly improved. Therefore, in recent years, the metal oxide film has been made into a porous structure to improve the gas-sensitive response of the gas-sensitive material, and it has gradually become a trend, and it has also received more and more attention from researchers.
  • Ordered porous array film materials can be well applied to gas sensors because of their high specific surface area and perfect, regular hole-like array structure, and their application in gas sensors is becoming more and more A trend.
  • metal oxide microporous materials as gas sensing materials to improve the selectivity, repeatability and stability of gas sensors, which is also a challenge for polluting gas detection.
  • this perfect strategy requires the synthesis of such a perfect microporous structure material, so the synthesis of such microporous materials has become a very important factor restricting its wide application in high efficiency gas sensing devices.
  • metal oxide porous materials have also been prepared by hydrothermal method, template method, etc.
  • metal oxide porous materials, metal-doped metal oxide porous materials and mixed metal oxide porous materials have also been reported.
  • the co-assisted effect of two different metal oxides makes the gas-sensitive response of the combination of two different metal oxide gas-sensitive materials higher than that of a single gas-sensitive material.
  • the gas sensitivity parameter has been improved. So two or more are prepared Multi-layer porous films with different materials have gradually become a focus in the research of gas-sensitive materials, and have great application prospects in the field of gas sensors in the future.
  • the object of the present invention is to overcome the above problems existing in the prior art, and to provide a method for preparing a multilayer metal oxide porous film nano gas sensing material, which can prepare a regular porous array film gas sensing material and combine the materials by different materials. Improve the gas sensitivity of the material.
  • a method for preparing a multilayer metal oxide porous film nano gas sensing material comprising the following steps:
  • Step 1) self-assembling the microsphere template through a LB film method, a solution evaporation method, a spin coating method or a dip coating method on a substrate covered with an insulating layer to form a dense single-layer array 1 template;
  • Step 2 reducing the pitch of the microspheres by etching, and the pitch ranges from 1 nm to 1 ⁇ m;
  • Step 3) physically depositing a metal oxide film; Step 4) removing the template, preparing a porous array metal oxide film, and annealing to obtain a metal oxide porous film gas sensing material.
  • the insulating layer in the step 1 is preferably SiO x , 1 ⁇ x ⁇ 2, the insulating layer has a thickness of between 100 nm and 10 ⁇ m, and the substrate is Si, SiC s Si 3 N 4 , ceramic. one kind of sheet, preferably a Si substrate 2 Si ⁇ .
  • the microsphere template in the step 1 is one of an aqueous solution of polystyrene microspheres or an aqueous solution of silica microspheres, preferably an aqueous solution of polystyrene microspheres, and a volume of the aqueous solution of the polystyrene microspheres.
  • the mass concentration is from 0.5% to 3% mg/ml, preferably 1% mg/ml
  • the microsphere template has a diameter of from 100 nm to 5 ⁇ m, preferably 500 nm.
  • the method of etching in the step 2 includes plasma dry etching or
  • the microsphere template is an aqueous solution of polystyrene microspheres, and plasma dry etching is used, and the microsphere template is a wet aqueous solution of an aqueous solution of silica microspheres using HF solution or Plasma dry etching, the plasma dry etching plasma is from a plasma etching machine or a reactive ion etching machine.
  • the physical deposition in the step 3 is physical deposition by magnetron sputtering or physical deposition by electron beam evaporation.
  • the microsphere template is an aqueous solution of polystyrene microspheres, and the template is removed by ultrasonic treatment using an organic solvent, and the microsphere template is an aqueous solution of silica microspheres.
  • the HF solution is sonicated, and the annealing temperature in the step 4 is 200 ° C - 1000 ° C for 0.5 h - 10 h.
  • the gas-sensing response of the metal oxide porous film gas sensing material prepared by the method of the present invention depends on the combination of the materials, and the diameter of the pores in the L-shaped film.
  • the diameter of the ⁇ L hole depends on the characteristics of the plasma etching time. For example, if a 500 nm PS ball is used, the power is excited by a 90 W ⁇ 2 plasma. After etching for 1 min, the diameter of the PS becomes 450 nm. After 2 min of etching, the diameter of the PS microsphere is 400 nm.
  • the porous film is a simple metal oxide, the larger the pore diameter of the porous film, the higher the gas sensitivity response obtained.
  • the gas-sensitive response of the prepared two-layer porous film of different metal oxides is higher than that of a single metal oxide, and three different layers of metal are prepared.
  • the gas-sensitive response of the oxide multilayer film is improved compared to the two-layer metal oxide.
  • the invention can prepare high-quality single-layer or multi-layer metal oxide porous film gas sensing material, and the prepared metal oxide porous film gas sensing material has good integrity, uniform pore diameter structure and superior gas sensing performance.
  • Figure 1 is a schematic view showing the steps of preparing a single-layer metal oxide porous film gas sensing material
  • Figure 2 is a schematic view showing the steps of preparing a two-layer and multi-layer metal oxide porous film gas sensing material
  • Example 3 is a topographical view of a scanning electron microscope (SEM) of the self-assembled polystyrene microspheres in a single layer film in Example 1;
  • SEM scanning electron microscope
  • SEM scanning electron microscope
  • Example 5 is a topographical view of a scanning electron microscope (SEM) after a metal oxide film is deposited successively after etching the styrene microspheres in Example 1.
  • SEM scanning electron microscope
  • Example 6 is a topographical view of a scanning electron microscope (SEM) of a two-layer metal oxide porous film prepared by removing a template and then annealed in Example 1.
  • SEM scanning electron microscope
  • Example 7 is a 2D topographical view of an atomic force microscope (AFM) of a two-layer metal oxide polyfluorene film L prepared in Example 1;
  • AFM atomic force microscope
  • Example 8 is an X-ray diffraction (XD) spectrum of a porous film of different metal oxides prepared in Example 1; 9 is a comparison chart of sensitivity curves of different metal oxide porous films prepared in Example 1 to 1000 ppm ethanol at different temperatures;
  • XD X-ray diffraction
  • Fig. 10 is a graph showing the sensitivity of a multilayer metal oxide porous film prepared in Example 1 of the present invention to different concentrations of ethanol at a temperature of 15 CTC.
  • Figure 11 is a graph showing the selectivity of a multilayer metal oxide polyfluorene film L prepared in Example 1 at a temperature of 15 CTC to 100 ppm of ethanol;
  • Figure 12 is a topographical view of a scanning electron microscope (SEM) of a three-layered metal oxide polyfluorene film L prepared in Example 2, which is similar in morphology to the multilayer metal oxide porous film prepared in Example 1;
  • SEM scanning electron microscope
  • Figure 13 is a graph comparing the sensitivity of different multilayer metal oxide porous films prepared in Example 2 to 100 ppm of ethanol at a temperature of 150 °C;
  • a method for preparing a multilayer metal oxide porous film nano gas sensing material comprising the following steps:
  • Step 1) self-assembling the microsphere template through a LB film method, a solution evaporation method, a spin coating method or a dip coating method on a substrate covered with an insulating layer to form a dense single-layer array 1 template;
  • Step 2) reducing the pitch of the microspheres by etching, and the pitch ranges from 1 nm to 1 ⁇ m;
  • Step 3 physically depositing a metal oxide film
  • Step 4) removing the template, preparing a porous array metal oxide film, and annealing to obtain a metal oxide porous film gas sensing material.
  • the insulating layer in the step 1 is preferably SiO x , 1 ⁇ x ⁇ 2, the insulating layer has a thickness of between 100 nm and 10 ⁇ m, and the substrate is Si, SiC s Si 3 N 4 , ceramic. one kind of sheet, preferably a Si substrate 2 Si ⁇ .
  • the microsphere template in the step 1 is one of an aqueous solution of polystyrene microspheres or an aqueous solution of silica microspheres, preferably an aqueous solution of polystyrene microspheres, and a volume of the aqueous solution of the polystyrene microspheres.
  • the mass concentration is from 0.5% to 3% mg/ml, preferably 1% mg/ml
  • the microsphere template has a diameter of from 100 nm to 5 ⁇ m, preferably 500 nm.
  • the etching method of the step 2 includes a plasma dry etching or a wet etching of an HF solution, wherein the microsphere template is an aqueous solution of polystyrene microspheres, and plasma dry etching is used.
  • the ball template is a wet etching or plasma dry etching of an aqueous solution of silica microspheres selected from a plasma etching machine or a reactive ion etching machine.
  • the physical deposition in the step 3 is physical deposition by magnetron sputtering or physical deposition by electron beam evaporation.
  • the microsphere template is an aqueous solution of polystyrene microspheres, and the template is removed by ultrasonic treatment using an organic solvent.
  • the microsphere template is an aqueous solution of silica microspheres, ultrasonic treatment is performed using an HF solution, and annealing is performed in the step 4.
  • the temperature is from 200 ° C to 1000 ° C and the time is from 0.5 h to 10 h.
  • FIG. 1 is a preparation step of a single-layer metal oxide porous film, and in the schematic diagram of the preparation steps of the double-layer metal oxide porous film shown in FIG. 2, the substrate of the obtained metal oxide porous film is covered with a single crystal Si ⁇ 2 oxide having a thickness of 150 nm. Layer of silicon substrate.
  • the PS microsphere template used was a non-functionalized PS7JC solution having a diameter of 500 nm, and the mass volume concentration of the aqueous solution was 1% mg/ml.
  • the power of the Ar plasma was 80 W, and the pressure of the cavity was 3 mTorr.
  • the sample was then sonicated in toluene for 2 min, the PS template was removed, and finally annealed at 550 ° C for 4 h in an air atmosphere.
  • the targets used for magnetron sputtering are ceramic targets of titanium oxide and zinc oxide, respectively.
  • the morphology of the porous film after the template is shown in Figures 3, 4, 5, 6, and 7. It can be seen from the figure that the prepared porous metal oxide film has a very uniform pore diameter of about 450 nm.
  • the X-ray film diffraction of a plurality of metal oxide porous film gas sensing materials prepared by this method is shown in Fig. 8. As can be seen from the figure, the prepared metal oxide porous film has a relatively good crystal form.
  • the substrate of the obtained porous metal oxide film is a silicon wafer substrate covered with a single crystal Si 2 oxide layer having a thickness of 150 nm.
  • the PS microsphere template used was a non-functionalized polystyrene (PS) 7 ⁇ solution having a diameter of 500 nm, and the aqueous solution had a mass volume concentration of 1% mg/ml.
  • PS polystyrene
  • the polystyrene microsphere single-layer template was self-assembled on a Si substrate covered with Si ⁇ 2 by solution evaporation method, and the PS template was etched by reactive ion etching to reduce the spacing between PS.
  • the flow rate is controlled at 40 sccm
  • the pressure of the chamber is controlled at 37 mTorr
  • the power applied by the excitation ⁇ 2 plasma is controlled at 90 W
  • the time of the ⁇ 2 plasma etching is controlled at 1 min.
  • 40 nm Cu 2 0+ 40 nm In 2 ⁇ 3 indium oxide in the lower layer, cuprous oxide in the upper layer
  • 40 nm ln 2 0 3 + 40 nm Cu respectively, deposited on the treated four substrates using a physical deposition method of magnetron sputtering 2 0 (cuprous oxide in the lower layer, indium oxide on the upper layer Layer)
  • 30 nm In 2 ⁇ 3 + 20 nm Cu 2 0 + 30 nm ln 2 0 3 copper oxide is an intermediate layer).
  • the targets used for magnetron sputtering were respectively a ceramic target of indium oxide and cuprous oxide.
  • the power for exciting the Ar plasma was 80 W, and the pressure of the chamber was 3 mTorr.
  • the sample was then sonicated in toluene, the PS template was removed, and finally annealed at 55 CTC for 4 h in an air atmosphere.
  • the morphology of the metal oxide porous film gas sensing material prepared by this method is shown in Fig. 12. It can be seen from Fig. 12 that the morphology of the prepared multilayer metal oxide porous film gas sensing material is similar to that of the method of Example 1.
  • the comparison of the gas-sensing response of the two-layer metal oxide porous film gas sensing material and the three-layer metal oxide porous film using this method is shown in Fig. 13. From Fig. 13, the gas of the three-layer metal oxide porous film gas sensing material can be seen. The sensitivity response is higher than the gas-sensitive response of the two-layer metal oxide porous film.

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Abstract

一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法，将微球水溶液自组装在覆盖有绝缘层（B）的基底（A）上，形成致密的单层阵列模板（C），用等离子刻蚀的方法刻蚀微球的表面，减小微球的间距，然后用物理沉积的方法沉积金属氧化物薄膜，之后用溶剂超声处理，去除模板，制备出多孔阵列金属氧化物薄膜，在空气气氛下退火处理即得到金属氧化物多孔薄膜气敏材料（D）。用该方法制备出规整的多孔阵列薄膜气敏材料，制得的多孔薄膜材料的孔径大小均一，材料的组合可控，孔径大小可控。

Description

一种多层金属氧化物多孔薄膜纳米气敏材料的制备 方法 技术领域
说
本发明涉及气体传感器的气敏材料领域 ,具体涉及的是一种多 层金属氧化物多孔薄膜纳米气敏材料的制备方法。
背景技术 书 随着人类生活水平的提高，生活中的有毒有害气体遍布生活的 每个角落，这些有毒气体给人们的身体带来很大的伤害。 所以，研 究出高性能 (高灵敏，高选择性，很好的稳定性 )的毒性气体传感 器对于研究工作者来说是一项很艰巨的任务。 金属氧化物作为一种 成熟的气敏材料，由于其具有成本低，性能稳定，对多种气体能达 到低检测极限的敏感检测的优点 ,现在越来越受到研究者的追捧。 气敏材料的气敏性能与材料的比表面积有着很大的关系，材料的比 表面积越大，与气体接触的反应位点越多，反应灵敏度在一定程度 上会越高。 因此把金属氧化物做成更小尺寸以增大其比表面积来提 高气敏材料响应是现代研究气敏材料的一种研究趋势。 金属氧化物多孔薄膜材料作为一种很好的气敏材料，因其比表 面积比块体薄膜材料大，其对气体的灵敏度有很大的提高。 所以近 几年 ,把金属氧化物薄膜做成多孔的结构从而提高气敏材料的气敏 响应也慢慢成为一种趋势，同时也越来越受到研究者的重视。
有序的多孔阵列薄膜材料因为有很高的比表面积和很完美，规 整的孔状阵列结构所以可以很好的应用于气敏传感器中，也使其在 气体传感器方面的应用也越来越成为一种趋势。 在污染性气体检测 方面 ,期望用金属氧化物微孔材料作为气敏材料来提高气体传感器 的选择性 ,重复性和稳定性对于污染性气体检测来说也是一种挑 战。 但这种完美的策略是需要先合成出这种完美的微孔结构材料， 所以这种微孔材料的合成就成为制约其在高效气敏器件中广泛应 用的十分重要的因素。 现阶段，一些金属氧化物多孔材料也陆续用 水热法 ,模板法等制备出来 ,金属氧化物多孔材料 ,金属掺杂的金 属氧化物多孔材料和混合金属氧化物多孔材料也陆续有人报道。 根 据多种气敏材料的互增理论 ,两种不同金属氧化物的共同协助效应 使得两种不同金属氧化物气敏材料组合的气敏响应比单一气敏材 料的气敏响应更高，各种气敏参数有所提高。 因此制备出两种或多 种不同材料的多层多孔薄膜在气敏材料的研究中也慢慢成为一种 焦点，在未来的气敏传感器的领域也有很大的应用前景。
发明内容
本发明的目的在于克服现有技术存在的以上问题，提供一种多 层金属氧化物多孔薄膜纳米气敏材料的制备方法 ,能够制备出规整 多孔阵列薄膜气敏材料 ,并通过不同材料的组合来提高材料的气敏 性能。
为实现上述技术目的，达到上述技术效果，本发明通过以下技 术方案实现：
一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法 ,包括 以下步骤：
步骤 1 )将微球模板通过 LB膜法、 溶液蒸发法、 旋涂法或浸 涂法中的一种自组装在覆盖有绝缘层的基底上，形成致密的单层阵 歹1」模板；
步骤 2 )用刻蚀的方法减小微球的间距 ,间距范围为 lnm- 1 μ m；
步骤 3 )物理沉积金属氧化物薄膜； 步骤 4 )去除模板 ,制备出多孔阵列金属氧化物薄膜 ,退火处 理即得到金属氧化物多孔薄膜气敏材料。
进一步的，所述步骤 1中的绝缘层优选为 SiOx , 1≤ x≤ 2 ,所 述绝缘层的厚度为 lOOnm- 10μ m之间，所述基底为 Si、 SiCs Si3N4、 陶瓷片中的一种，优选为 Si〇2的 Si基片。
进一步的，所述步骤 1中的微球模板为聚苯乙烯微球水溶液或 二氧化硅微球水溶液中的一种 ,优选为聚苯乙烯微球水溶液 ,所述 聚苯乙烯微球水溶液的体积质量浓度为 0.5%- 3%mg/ml,优选为 l%mg/ml , 所述微球模板的直径为 lOOnm- 5 μ m , 优选为 500nm。
进一步的，所述步骤 2 的刻蚀的方法包括等离子干法刻蚀或
HF 溶液的湿法刻蚀 ,所述微球模板为聚苯乙烯微球水溶液 ,选用 等离子干法刻蚀 ,所述微球模板为二氧化硅微球水溶液 '选用 HF 溶液的湿法刻蚀或等离子干法刻蚀，所述等离子干法刻蚀的等离子 体来自等离子体刻蚀机或反应离子刻蚀机。
进一步的，所述步骤 3中的物理沉积为磁控溅射物理沉积或电 子束蒸发物理沉积。 进一步的，所述微球模板为聚苯乙烯微球水溶液，选用有机溶 剂超声处理去除模板 ,所述微球模板为二氧化硅微球水溶液 ,选用
HF溶液超声处理，所述步骤 4中退火处理的温度为 200°C- 1000 °C ,时间为 0.5h- 10h。
本发明的方法制备的金属氧化物多孔薄膜气敏材料的气敏响 应取决于材料的组合方式，孑 L状薄膜中的孔洞的直径大小。 孑 L洞的 直径大小取决于等离子刻蚀的时间的特征。 如，若使用 500nm的 PS小球，用 90W的〇2等离子体激发功率，刻蚀 lmin以后， PS的 直径变成 450nm ,刻蚀 2min后， PS微球的直径为 400nm 。 当 多孔薄膜是单纯的一种金属氧化物时 ,多孔薄膜的孔径越大 ,得到 的气敏响应越高。 当孔状薄膜的孔洞直径 ,薄膜的厚度相同时 ,制 备出的两层不同的金属氧化物的多孔薄膜的气敏响应比单纯的一 种金属氧化物时高，制备出的三层不同的金属氧化物的多孑 L薄膜的 气敏响应比两层金属氧化物时有所提高。
本发明的有益效果是：
本发明能够制备出高质量单层或多层金属氧化物多孔薄膜气 敏材料 ,制备的金属氧化物多孔薄膜气敏材料完整性好 ,孔状结构 直径均一，气敏性能优越。 附图说明
图 1 为制备单层金属氧化物多孔薄膜气敏材料的的步骤示意 图；
图 2为制备双层和多层金属氧化物多孔薄膜气敏材料的的步骤 示意图；
图 3为实施例 1中聚苯乙烯微球自组装为单层薄膜后的扫描电 子显微镜 ( SEM )的形貌图；
图 4为实施例 1中聚苯乙烯微球经过等离子体刻蚀后的扫描电 子显微镜 ( SEM )的形貌图；
图 5为实施例 1中刻蚀完苯乙烯微球后先后沉积了金属氧化物 薄膜后的扫描电子显微镜 ( SEM )的形貌图；
图 6为实施例 1中去除模板再退火后制备的两层金属氧化物多 孔薄膜的扫描电子显微镜 ( SEM )的形貌图；
图 7为实施例 1中制备出的两层金属氧化物多孑 L薄膜的原子力 显微镜（ AFM )的 2D形貌图；
图 8为实例 1中制备的不同金属氧化物多孔薄膜的 X射线衍射 ( X D )谱图； 图 9为实例 1中制备的不同金属氧化物多孔薄膜在不同温度下 对 lOOOppm 乙醇的灵敏度曲线对比图；
图 10 为本发明实例 1 中制备的多层金属氧化物多孔薄膜在 15CTC的温度下对不同浓度的乙醇的灵敏度曲线图。
图 11为实例 1中制备的多层金属氧化物多孑 L薄膜在 15CTC的 温度下对 lOOOppm乙醇的的选择性图表；
图 12为实施例 2中制备的三层金属氧化物多孑 L薄膜的扫描电 子显微镜 ( SEM )的形貌图 ,其形貌类似于实例 1制备出的多层金 属氧化物多孔薄膜；
图 13为实例 2中制备的不同多层金属氧化物多孔薄膜在 150 °C的温度下对 lOOOppm的乙醇的灵敏度比较图；
具体实施方式
下面将参考附图并结合实施例，来详细说明本发明。
一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法 ,包括 以下步骤：
步骤 1 )将微球模板通过 LB膜法、 溶液蒸发法、 旋涂法或浸 涂法中的一种自组装在覆盖有绝缘层的基底上，形成致密的单层阵 歹1」模板； 步骤 2 )用刻蚀的方法减小微球的间距，间距范围为 lnm- 1 μ m；
步骤 3 )物理沉积金属氧化物薄膜；
步骤 4 )去除模板 ,制备出多孔阵列金属氧化物薄膜 ,退火处 理即得到金属氧化物多孔薄膜气敏材料。
进一步的，所述步骤 1中的绝缘层优选为 SiOx , 1≤ x≤ 2 ,所 述绝缘层的厚度为 lOOnm- 10μ m之间，所述基底为 Si、 SiCs Si3N4、 陶瓷片中的一种，优选为 Si〇2的 Si基片。
进一步的，所述步骤 1中的微球模板为聚苯乙烯微球水溶液或 二氧化硅微球水溶液中的一种 ,优选为聚苯乙烯微球水溶液 ,所述 聚苯乙烯微球水溶液的体积质量浓度为 0.5%- 3%mg/ml,优选为 l%mg/ml , 所述微球模板的直径为 lOOnm- 5 μ m , 优选为 500nm。
进一步的，所述步骤 2 的刻蚀的方法包括等离子干法刻蚀或 HF 溶液的湿法刻蚀 ,所述微球模板为聚苯乙烯微球水溶液 ,选用 等离子干法刻蚀 ,所述微球模板为二氧化硅微球水溶液 '选用 HF 溶液的湿法刻蚀或等离子干法刻蚀，所述等离子干法刻蚀的等离子 体来自等离子体刻蚀机或反应离子刻蚀机。 进一步的，所述步骤 3中的物理沉积为磁控溅射物理沉积或电 子束蒸发物理沉积。
进一步的 ,所述微球模板为聚苯乙烯微球水溶液 ,选用有机溶 剂超声处理去除模板 ,所述微球模板为二氧化硅微球水溶液 ,选用 HF溶液超声处理，所述步骤 4中退火处理的温度为 200°C- 1000 °C ,时间为 0.5h- 10h。
实施例 1
图 1为单层金属氧化物多孔薄膜制备步骤图 ,图 2 所示的双 层金属氧化物多孔薄膜制备步骤示意图中 ,所得金属氧化物多孔薄 膜的基底是覆盖有 150nm厚度单晶 Si〇2氧化层的硅片基底。 使用 的 PS微球模板是直径为 500nm的非功能化 PS7JC溶液，其水溶液的 质量体积浓度是 1% mg/ml。使用溶液蒸发法把聚苯乙烯微球单层 模板自组装在覆盖有 Si02的 Si基底上，使用反应离子刻蚀方法刻蚀 PS模板，减小 PS的间距，使用反应离子刻蚀机的过程中所通〇2的 流量控制在 40sccm ,腔体的压力控制在 37mTorr ,激发 02等离子 体所加的功率控制在 90W , 02等离子体刻蚀的时间控制在 lmin。 使用磁控溅射的物理沉积方法在处理完的四个基底上分别沉积 80nm的 Zn〇， 80nm Ti02 , 40nm Ζη〇+ 40nm Τ1Ο2 (氧化铁在 下层，氧化锌在上层）， 40nm Ti〇2+ 40nm ZnO (氧化锌在下层， 氧化钛在上层 )。 磁控溅射物理沉积金属氧化物薄膜的过程中激发 Ar等离子体的功率为 80W ,腔体的压力为 3mTorr。 然后把样品放 在甲苯里超声处理 2min ,去除 PS模板，最后在 550°C的温度，空 气的气氛下退火处理 4h。 磁控溅射使用的靶材分别是氧化钛和氧 化锌的陶瓷靶材。
使用此法制备金属氧化物多孔薄膜气敏材料的过程中所的到 的 PS模板自组装的形貌，等离子体处理完 PS后的形貌，沉积完金 属氧化物后的形貌，和去除 PS模板后的多孔薄膜的形貌见图 3、 4、 5、 6、 7 ,由图中可以看到，制备的金属氧化物多孔薄膜的孔状直 径非常均齐，在 450nm左右。 使用此法制备多种金属氧化物多孔 薄膜气敏材料的 X射线薄膜衍射见图 8 ,由图中可以看到，制备出 的金属氧化物多孔薄膜的拥有比较好的晶型。 使用此法制备金属氧 化物多孔薄膜气敏材料在不同温度下的乙醇气敏响应 ,双层金属氧 化物多孔薄膜在不同浓度乙醇下的气敏响应和双层金属氧化物多 孔薄膜在一定温度下对一定浓度乙醇的选择性图表见图 9、 10、 11 , 由图 9可以看出制备出的单层金属氧化物多孔薄膜的气敏响应要低 于双层金属氧化物多孔薄膜的气敏响应，也可以看出材料的气敏响 应在一定的温度范围内随着温度的增加而有所提高且三种金属氧 化物多孔薄膜的气敏响应都满足以上关系 ,在一定的温度范围内温 度越高他们的气敏响应越高。 由图 10可以看出制备出的金属氧化 物多孔薄膜的气敏响应随着气体浓度的增加而有所提高的。由图 11 可以看出制备出的双层金属氧化物多孔薄膜的对乙醇有很好的选 择性。
实施例 2
图 2所示的多层金属氧化物多孔薄膜制备步骤示意图中，所得 金属氧化物多孔薄膜的基底是覆盖有 150nm厚度单晶 Si〇2氧化层 的硅片基底。 使用的 PS微球模板是直径为 500nm的非功能化聚苯 乙烯小球 ( PS ) 7_Κ溶液，其水溶液的质量体积浓度是 1% mg/ml。 使用溶液蒸发法把聚苯乙烯微球单层模板自组装在覆盖有 Si〇2的 Si 基底上，使用反应离子刻蚀方法刻蚀 PS模板，减小 PS之间的间距， 所通〇2的流量控制在 40sccm ,腔体的压力控制在 37mTorr ,激发 〇2等离子体所加的功率控制在 90W ,〇2等离子体刻蚀的时间控制 在 lmin。 使用磁控溅射的物理沉积方法在处理完的四个基底上分 别沉积 40nm Cu20+ 40nm In2〇3 (氧化铟在下层，氧化亚铜在上 层）， 40nm ln203+ 40nm Cu20 (氧化亚铜在下层，氧化铟在上 层）， 30nm Cu2〇+20nm ln203 + 30nm Cu20 (氧化铟为中间 层 ) , 30nm In2〇3+20nm Cu20 + 30nm ln203 (氧化亚铜为中间 层 )。 磁控溅射使用的靶材分别是氧化铟，氧化亚铜的陶瓷靶材， 激发 Ar等离子体的功率为 80W ,腔体的压力为 3mTorr。 然后把样 品放在甲苯里超声处理，去除 PS模板，最后在 55CTC的温度，空气 的气氛下退火处理 4h。
使用此法制备出的金属氧化物多孔薄膜气敏材料形貌见图 12 , 由图 12可以看出制备出的多层金属氧化物多孔薄膜气敏材料的形 貌类似于实例 1方法制备出来的金属氧化物多孔薄膜的形貌。使用 此法制备双层金属氧化物多孔薄膜气敏材料与三层金属氧化物多 孔薄膜的气敏响应对比图见图 13 ,由图 13可以看出三层金属氧化 物多孔薄膜气敏材料的气敏响应高于两层金属氧化物多孔薄膜的 气敏响应。

Claims

权 利 要 求 书
1、 一种多层金属氧化物多孔薄膜纳米气敏材料的制备方法， 其特征在于，包括以下步骤：
步骤 1 )将微球模板通过 LB膜法、 溶液蒸发法、 旋涂法或浸 涂法中的一种自组装在覆盖有绝缘层的基底上，形成致密的单层阵 歹1」模板；
步骤 2 )用刻蚀的方法减小微球的间距 ,间距范围为 lnm- 1 μ m；
步骤 3 )物理沉积金属氧化物薄膜；
步骤 4 )去除模板 ,制备出多孔阵列金属氧化物薄膜 ,退火处 理即得到金属氧化物多孔薄膜气敏材料。
2、 根据权利要求 1所述的多层金属氧化物多孔薄膜纳米气敏 材料的制备方法其特征在于所述步骤 1中的绝缘层优选为 Si〇x , 1< χ< 2 ,所述绝缘层的厚度为 lOOnm- 10μ m之间，所述基底为 Si、 SiC Si3N4、陶瓷片中的一种，优选为 Si〇2的 Si基片。
2、 根据权利要求 1所述的多层金属氧化物多孔薄膜纳米气敏 材料的制备方法 ,其特征在于：所述步骤 1中的微球模板为聚苯乙 烯微球水溶液或二氧化硅微球水溶液中的一种，优选为聚苯乙烯微 球水溶液 ， 所述聚苯乙烯微球水溶液的体积质量浓度为
0.5%- 3%mg/ml,优选为 l%mg/ml , 所述微球模板的直径为 100ηηη-5μ m ,优选为 500nm。
3、 根据权利要求 1所述的多层金属氧化物多孔薄膜纳米气敏 材料的制备方法 ,其特征在于：所述步骤 2的刻蚀的方法包括等离 子干法刻蚀或 HF溶液的湿法刻蚀 ,所述微球模板为聚苯乙烯微球 7_Κ溶液，选用等离子干法刻蚀，所述微球模板为二氧化硅微球水溶 液，选用 HF溶液的湿法刻蚀或等离子干法刻蚀，所述等离子干法 刻蚀的等离子体来自等离子体刻蚀机或反应离子刻蚀机。
4、 根据权利要求 1所述的多层金属氧化物多孔薄膜纳米气敏 材料的制备方法 ,其特征在于：所述步骤 3中的物理沉积为磁控溅 射物理沉积或电子束蒸发物理沉积。
5、 根据权利要求 1所述的多层金属氧化物多孔薄膜纳米气敏 材料的制备方法，其特征在于：所述微球模板为聚苯乙烯微球水溶 液 ,选用有机溶剂超声处理去除模板 ,所述微球模板为二氧化硅微 球水溶液 '选用 HF溶液超声处理，所述步骤 4中退火处理的温度 为 200°C-1000°C ,日寸间为 0.5h- 10h。
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