WO2013185440A1 - 一种基于色素敏化TiO2薄膜的气体传感器制作方法 - Google Patents

一种基于色素敏化TiO2薄膜的气体传感器制作方法 Download PDF

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WO2013185440A1
WO2013185440A1 PCT/CN2012/085448 CN2012085448W WO2013185440A1 WO 2013185440 A1 WO2013185440 A1 WO 2013185440A1 CN 2012085448 W CN2012085448 W CN 2012085448W WO 2013185440 A1 WO2013185440 A1 WO 2013185440A1
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dye
film
substrate
nanocrystalline
gas sensor
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PCT/CN2012/085448
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English (en)
French (fr)
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邹小波
黄晓玮
石吉勇
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江苏大学
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Priority to GB1421877.0A priority Critical patent/GB2518308B8/en
Publication of WO2013185440A1 publication Critical patent/WO2013185440A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector

Definitions

  • the present invention relates to a method for fabricating a gas sensor, and more particularly to a method for fabricating a gas sensor for adding a pigment to a magnetron sputtering titanium dioxide (Ti0 2 ) gas sensitive film.
  • the gas sensor is doped with other metal or oxide additives, and the composite metal oxide gas sensing material is prepared to obtain a desired effect.
  • Ti0 2 film has high refractive index, high dielectric constant and the like, for example: Chinese patent number ZL201010206483.2, the name is titanium dioxide porous film preparation method, Chinese patent number ZL200510012254.6, named electrophoretic deposition low temperature preparation of titanium dioxide A method for preparing a nanocrystalline porous film electrode.
  • pigment sensitizing materials are those that combined with the substrate material can effectively improve the conductivity of the substrate material.
  • synthetic dye sensitizing materials and natural pigment sensitizing materials synthetic dye sensitizing materials such as metal organic complexes and organic compounds, most of the coloring components of natural pigment sensitizing materials are anthocyanins, which can be at different pH values. Different colors appear in the lower or different redox systems.
  • the present invention provides a method for fabricating a gas sensor based on a dye-sensitized nanocrystalline TiO 2 film, which combines a dye-sensitized material with a nanocrystalline TiO 2 film to produce a gas sensor with high sensitivity and at room temperature. jobs.
  • the technical solution adopted by the present invention includes the following steps: (1) selecting a substrate suitable for subsequent coating, preparing an electrode by a coating method on the substrate, and preparing the nanometer by the magnetron sputtering method on the substrate coated with the electrode Crystal Ti0 2 film;
  • the method for preparing a nanocrystalline TiO 2 film by the magnetron sputtering method is as follows: placing an electrode coated substrate on a substrate stage, using titanium metal or titanium oxide as a target, and adjusting titanium the distance between the target and the substrate stage 20 ⁇ 30cm is, the rate of rotation of the stage 4 ⁇ 8rp, magnetron sputtering the reaction chamber a vacuum of at least pumped 10- 3 Pa, temperature of the heating The heat is 20 ⁇ 250°C, the inert gas flow is 60 ⁇ 100sccm, the magnetron sputtering power is 80 ⁇ 120w, and the sputtering is performed for 15 ⁇ 60min under 0.5 ⁇ 2.0Pa pressure.
  • the dye sensitizing material includes a synthetic dye sensitizing material and a natural dye sensitizing material, and when a synthetic dye sensitizing material is used, the concentration of the dye solution is 0.1 mol/L to 0.5 mol/ L. When a natural dye sensitizing material is used, the water content of the dye solution is 60% to 80%.
  • the present invention uses a magnetron sputtering to prepare a nanocrystalline TiO 2 film, a nanocrystalline Ti0 2 film as a base material, and a dye sensitizing material as an activating material to form a gas sensor; Fixed on the nanocrystalline Ti0 2 film, the pigment molecules encapsulate the Ti0 2 molecule while filling the gap between the Ti0 2 crystals, changing the lattice resistance of the Ti0 2 crystal, enhancing its sensitivity to gas molecules while making it It can work at room temperature, and can qualitatively and quantitatively analyze gas through the change of sensor resistance at room temperature. Compared with other gas sensors, it has higher sensitivity and wider detection range. It has good reproducibility and can detect human sense of smell. Undetectable gas concentration. DRAWINGS
  • 1 is a schematic view of a substrate plated with an electrode
  • Figure 2 is a schematic view of a sensor coated with thin films of nanocrystalline Ti0 and 2;
  • FIG. 3 is a schematic view of a sensor coated with thin films and nanocrystalline Ti0 2 pigment
  • the method for fabricating the gas sensor of the present invention comprises: selecting a substrate, fabricating an electrode, and preparing a nanocrystal by magnetron sputtering
  • Substrate selection refers to the selection of a substrate material suitable for subsequent coating, and the substrate may be a silicon wafer, a glass wafer, a conductive glass sheet, or a polytetrafluoroethylene sheet.
  • the fabrication of the electrode means that the electrode 2 is formed on the substrate 1 by a plating method.
  • a gold or platinum electrode is produced by a screen printing technique, such as a substrate 1 coated with a gold or platinum electrode 2 as shown in FIG.
  • sputtered nanocrystalline Ti0 2 film, a magnetron sputtering method Preparation of Nanocrystalline Ti0 2 film was as follows by a plasma sputtering method on the substrate with gold or platinum plating electrodes: the electrodes are plated with the substrate 1 Put it into the substrate stage, use titanium metal or titanium oxide as the target table, adjust the distance between the titanium target and the substrate stage to 20 ⁇ 30cm, and rotate the stage at 4 ⁇ 8rp, magnetron splash
  • the vacuum of the reaction chamber is at least 10 - 3 Pa, the temperature is heated to 20 ⁇ 250 ° C, the inert gas flow is 60 ⁇ 100 sccm, the magnetron sputtering power is 80 ⁇ 120w, and the sputtering is 15 ⁇ at 0.5 ⁇ 2.0Pa.
  • Selection and dissolution of the dye-sensitized material includes selecting a suitable dye-sensitized material for the gas to be detected and dissolving the dye-sensitized material in a suitable solvent.
  • select those oxidizing redox indicators such as phenol saffron, methylene blue, tetrasulfonate indigo, and dissolve the selected dye sensitizing material into a solvent compatible with it.
  • a pigment solution is prepared.
  • the dye sensitizing material includes a synthetic dye sensitizing material and a natural dye sensitizing material.
  • the concentration of the dye solution formed is 0.1 m O l/L to 0.5 mol/L.
  • the natural dye sensitizing material is concentrated so that the water content of the dye solution is 60% to 80%.
  • the dye sensitizing material fixing method is as follows: the prepared nanocrystalline Ti0 2 film 3 is placed in the prepared pigment solution for 12 to 48 hours, and then taken out, and the impurities are rinsed with absolute ethanol in a dry air. After drying, it is dried in an oven at 30-80 ° C for 1 ⁇ 5 hours, and a sensor coated with a nanocrystalline Ti0 2 film and a pigment as shown in FIG. 3 is obtained, and 4 is a pigment layer.
  • the electrode 2 is formed by ion plating on the substrate 1, and the nanocrystalline Ti0 2 film 3 is prepared by magnetron sputtering.
  • the dye-sensitized material is used as an excitation material to fabricate a novel gas sensor.
  • the nanocrystalline Ti0 2 film 3 is advantageous for the fixation of the dye-sensitized material and, on the other hand, for the enrichment of gas molecules.
  • the charge of the dye sensitizing material After the gas molecules adsorbed on the nanocrystalline Ti0 2 film 3 are in contact with the dye sensitizing material, the charge of the dye sensitizing material generates a charge transfer from the center ion to the ligand, and the transferred charge excites the lattice resistance of the Ti0 2 crystal, so that the lattice resistance of the Ti0 2 crystal is excited. Its sensitivity to gases changes. Therefore, when the novel gas sensor of the present invention reacts with an odor molecule, its conductivity changes at normal temperature.
  • a gas sensor is fabricated by using a synthetic dye sensitizing material in combination with a nanocrystalline 10 2 film, and the manufacturing steps are as follows:
  • One of a silicon wafer, a glass plate, a conductive glass plate, and a polytetrafluoroethylene sheet is selected as the substrate.
  • a gold or platinum electrode such as the substrate 1 and the electrode 2 shown in FIG. 1, is produced by a screen printing or plasma sputtering method.
  • magnetron sputtering method for preparing nanocrystalline Ti0 2 film the substrate 1 is placed on a substrate stage, metal titanium or titanium oxide as a target, adjusting the titanium target and the substrate between the substrate The distance is 20cm, the rotation speed of the stage is 4rp, the vacuum of the magnetron sputtering reaction chamber is at least 10 - 3 Pa, the temperature is heated to 20 ° C, the inert gas flow is 60 sccm, and the magnetron sputtering power is 80 W. Under Pa pressure, sputtering was performed for 15 minutes to obtain a sensor coated with the nanocrystalline TiO 2 film 3 as shown in FIG.
  • the dye-sensitized material is fixed: the nanocrystalline Ti0 2 film is placed in O.lmol / L methylene blue solution for 12 hours, taken out, rinsed with anhydrous ethanol, dried in dry air After drying, it was dried in an oven at 30 ° C for 1 h to obtain the desired sensor as shown in FIG.
  • the solution formed by the other synthetic dye sensitizing material is selected in the above step 4, the method of this step is unchanged.
  • a gas sensor is fabricated by using a natural pigment dye material in combination with a nanocrystalline Ti0 2 film, and the manufacturing steps are as follows:
  • Steps 1 to 3 are the same as in the first embodiment.
  • [0022] 4 the extraction and preparation of natural color sensitive materials: Take purple potato pigment as an example, take 10g purple potato washed, cut into a shape of diced into a tissue homogenizer, to obtain a slurry solution, the amount of volume Take 10 ml of purple sweet potato chopped liquid, pour into a triangular flask, add 100 ml of 1% citric acid, shake well, and dip in a constant temperature water bath at 50 °C for 1 hour. After the material was obviously faded, the extract was filtered through a qualitative filter paper having a diameter of 15 cm, and the extract was concentrated by evaporation on a rotary evaporator to a water content of 60% to obtain a desired concentrated purple potato pigment solution.
  • the fixing of the color sensitive material the prepared nanocrystalline 110 2 film is placed in the concentrated purple potato pigment solution for 12 hours, and then taken out, the impurities are rinsed with absolute ethanol, and dried in dry air. After drying, it was dried in an oven at 30 ° C for 1 h to obtain the desired sensor as shown in FIG.
  • the method of this step does not change.
  • a gas sensor is fabricated by using a synthetic dye sensitizing material in combination with a nanocrystalline Ti0 2 film, and the manufacturing steps are as follows:
  • One of a silicon wafer, a glass plate, a conductive glass plate, and a polytetrafluoroethylene sheet is selected as the substrate.
  • a gold or platinum electrode is formed by screen printing or plasma sputtering, such as substrate 1 and electrode 2 in FIG.
  • magnetron sputtering method for preparing nanocrystalline Ti0 2 film the substrate is placed on a substrate stage, titanium metal or titanium oxide as a target, adjusting the distance between the titanium target and the substrate stage 25cm, the rotation rate of the stage is 6rp, the vacuum of the magnetron sputtering reaction chamber is at least 10 - 3 Pa, the temperature is heated to 100 ° C, the inert gas flow is 80 sccm, and the magnetron sputtering power is 100 w. Under the pressure of OPa, sputtering was performed for 30 minutes to obtain a sensor coated with the nanocrystalline TiO 2 film 3 as shown in FIG. [0027] 4. Selection of a synthetic dye sensitizing material, taking methylene blue as an example, selecting methylene blue as a dye sensitizing material and dissolving it in water to form a 0.25 mol/L dye solution.
  • the present embodiment uses a natural combination of the pigment material, a gas sensor with nanocrystalline Ti0 2 film, prepared as follows: Step 1 ⁇ Step 3 in Example 3.
  • [0030] 4 the extraction and preparation of natural color sensitive materials: Take purple potato pigment as an example, take 15g purple potato washed, cut into a shape of diced into a tissue homogenizer, to obtain a slurry solution, the amount of volume Take 15 ml of purple potato mash, pour into a triangular flask, add 150 ml of 3% citric acid, shake well, and immerse in a 55 ° C constant temperature water bath for 1.5 hours. After the material was obviously faded, the extract was filtered through a qualitative filter paper having a diameter of 15 cm, and the extract was concentrated by evaporation on a rotary evaporator to a water content of 70% to obtain a desired concentrated purple potato pigment solution.
  • the fixing of the color sensitive material the prepared nanocrystalline 110 2 film is placed in the concentrated purple potato pigment solution for 24 hours, and then taken out, the impurities are rinsed with absolute ethanol, and dried in dry air. After drying, it was dried in an oven at 60 ° C for 4 h to obtain the desired sensor shown in FIG.
  • the method of this step does not change.
  • a gas sensor is fabricated by using a synthetic dye sensitizing material in combination with a nanocrystalline Ti0 2 film, and the manufacturing steps are as follows:
  • One of a silicon wafer, a glass plate, a conductive glass plate, and a polytetrafluoroethylene sheet is selected as the substrate.
  • a gold or platinum electrode is formed by screen printing or plasma sputtering, such as the substrate 1 and the electrode in FIG.
  • magnetron sputtering method for preparing nanocrystalline Ti0 2 film the substrate is placed on the substrate stage, metal titanium or titanium oxide as a target, adjusting the distance between the titanium target and the substrate stage 30cm, the rotation rate of the stage is 8rp, the vacuum of the magnetron sputtering reaction chamber is at least 10 - 3 Pa, the temperature is heated to 250 ° C, the inert gas flow is 100sccm, the magnetron sputtering power is 120w, at 2.0Pa Under pressure, sputter for 60 min. As shown in FIG 2 obtained coated nanocrystalline film sensor 3 Ti0 and 2. [0035] 4. Selection of a synthetic dye sensitizing material, taking methylene blue as an example, selecting methylene blue as a dye sensitizing material and dissolving it in water to form a 0.5 mol/L dye solution.
  • a gas sensor is fabricated by using a natural pigment dye material in combination with a nanocrystalline Ti0 2 film, and the manufacturing steps are as follows:
  • Step 1 to Step 3 are the same as in Embodiment 5.
  • [0038] 4 the extraction and preparation of natural color sensitive materials: Take purple potato pigment as an example, take 20g purple potato washed, cut into a shape of diced into a tissue homogenizer, to obtain a slurry solution, the amount of volume Take 20 ml of purple sweet potato chopped liquid, pour into a triangular flask, add 200 ml of 5% citric acid, shake well, and dip in a constant temperature water bath at 60 °C for 2 hours. After the material was obviously faded, the extract was filtered through a qualitative filter paper having a diameter of 15 cm, and the extract was concentrated by evaporation on a rotary evaporator to a water content of 80% to obtain a desired concentrated purple potato pigment solution.
  • the fixing of the color sensitive material the prepared nanocrystalline Ti0 2 film is placed in the concentrated purple potato pigment solution for 48 hours, and then taken out, the impurities are rinsed with absolute ethanol, and dried in dry air. After drying, it was dried in an oven at 80 ° C for 5 h to obtain the desired sensor as shown in FIG.
  • the method of this step does not change.

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Abstract

一种基于色素敏化TiO2薄膜的气体传感器制作方法。该方法包括：选择适合于后续镀膜的基片（1），在基片（1）上通过镀膜方法制作电极（2），将镀有电极（2）的基片（1）通过磁控溅射法制备纳米晶TiO2薄膜；针对所需检测的气体选择合适的色素敏化材料并将色素敏化材料溶解在与之相容的溶剂中制成色素溶液；将纳米晶TiO2薄膜放入色素溶液中浸泡12-48小时后取出，用无水乙醇将杂质冲洗干净，晾干后在30-80°C烘箱中烘1-5小时。本发明使用纳米晶TiO2薄膜为基底材料，色素敏化材料为激化材料，色素分子包裹了TiO2分子的同时填充了TiO2晶体之间的间隙。所制成的传感器可在室温下通过电阻的变化定性定量地分析气体。

Description

一种基于色素敏化 Ti02薄膜的气体传感器制作方法 技术领域
[0001] 本发明涉及一种气体传感器的制作方法， 特指用在磁控溅射二氧化钛 （Ti02) 气 体敏感膜中加入色素的气体传感器的制作方法。
背景技术
[0002] 近年来， 随着科技的发展， 人们对有害气体检测的要求越来越高， 对气体传感器 的需求也越来越多。 目前的气体传感器大多存在对低浓度气体检测灵敏度不够高的不足。 为克服以上的不足之处， 在气体传感器中掺杂其它金属或氧化物添加剂， 制备复合金属 氧化物气敏材料等取得了较理想的效果。 其中， Ti02膜具有高折射率， 高介电常数等特 点， 例如： 中国专利号为 ZL201010206483.2、 名称为二氧化钛多孔薄膜的制备方法， 中 国专利号 ZL200510012254.6、 名称为电泳沉积低温制备二氧化钛纳晶多孔薄膜电极的制 备方法。 磁控溅射法制备纳米晶 Ti02薄膜工艺简单， 制得的纳米晶 Ti02薄膜分布均匀、 厚度可控、 表面积大、 附着力强、 不开裂， 在大规模工业化生产中更加容易控制产品的 质量， 并降低综合生产成本， 但这种气体传感器需要高温 （200°C~600°C ) 下才能工作， 色素敏化材料是指那些与基底材料结合后能有效提高基底材料导电性能的色素， 包括合 成色素敏化材料和天然色素敏化材料， 合成色素敏化材料如金属有机配合物和有机化合 物，天然色素敏化材料的显色成分大多是花青素，他们均可在不同的 pH值下或不同的氧 化还原系统中呈现不同的颜色。
发明内容
[0003] 本发明提供一种基于色素敏化的纳米晶 Ti02薄膜的气体传感器制作方法，将色素 敏化材料与纳米晶 Ti02薄膜相结合， 所制作的气体传感器灵敏度高且可在室温下工作。
[0004] 本发明采用的技术方案是包括以下步骤： （1 ) 选择适合于后续镀膜的基片， 在基 片上通过镀膜方法制作电极， 将镀有电极的基片通过磁控溅射法制备纳米晶 Ti02薄膜；
(2)针对所需检测的气体选择合适的色素敏化材料并将色素敏化材料溶解在与之相容的 溶剂中， 制成色素溶液； （3)将所述纳米晶 Ti02薄膜放入所述色素溶液中浸泡 12~48小 时后取出， 用无水乙醇将杂质冲洗干净， 晾干后在 30~80°C烘箱中烘 l~5h即可。
[0005] 进一步地， 所述磁控溅射法制备纳米晶 Ti02薄膜的方法如下： 将镀有电极的基片 放入基材载物台， 用金属钛或氧化钛作为靶台， 调节钛靶和基材载物台之间的距离为 20~30cm, 载物台的旋转速率为 4~8rp， 磁控溅射反应室真空度至少抽到 10—3Pa， 温度加 热到 20~250°C， 惰性气体流为 60~100sccm， 磁控溅射功率为 80~120w， 在 0.5~2.0Pa压 强下溅射 15~60min。
[0006] 进一步地， 所述色素敏化材料包括合成色素敏化材料和天然色素敏化材料， 当采 用合成色素敏化材料时， 制成的色素溶液的浓度为 0.1mol/L~0.5mol/L， 当采用天然色素 敏化材料时， 色素溶液含水率为 60% ~80%。
[0007] 本发明的有益效果： 本发明用磁控溅射制备纳米晶 Ti02薄膜， 使用纳米晶 Ti02 薄膜作为基底材料， 使用色素敏化材料作为激化材料制作气体传感器； 将色素敏化材料 固定于纳米晶 Ti02薄膜上， 色素分子包裹了 Ti02分子的同时填充了 Ti02晶体之间的间 隙， 改变了 Ti02晶体的晶格电阻， 增强其对气体分子的敏感性的同时使其能在常温下工 作， 可在室温下通过传感器电阻的变化定性定量地分析气体， 与其他的气体传感器相比 有较高的灵敏度和较宽的检测范围， 重现性好， 可检测出人嗅觉不能感知的气体浓度。 附图说明
[0008] 图 1为镀有电极的基片示意图；
图 2为涂有纳米晶 Ti02薄膜的传感器示意图；
图 3为涂有纳米晶 Ti02薄膜和色素的传感器示意图；
图中： 1.基片； 2.电极； 3.纳米晶 Ti02薄膜； 4.色素层。
具体实施方式
[0009] 本发明气体传感器的制作方法包括基片选择、 制作电极、 磁控溅射法制备纳米晶
Ti02薄膜、 色素敏化材料的选择与溶解、 色素敏化材料的固定这五个步骤。
[0010] 基片选择是指选择适合于后续镀膜的基片材料， 基片可以是硅片、 玻璃片、 导电 玻璃片、 或者是聚四氟乙烯片。
[0011] 制作电极是指在基片 1上通过镀膜方法制作电极 2。 如通过丝网印刷技术制作金 或铂金电极， 如图 1所示的镀有金或铂金电极 2的基片 1。
[0012] 通过等离子体溅射方法在镀有金或铂金电极的基片上溅射纳米晶 Ti02薄膜，磁控 溅射法制备纳米晶 Ti02薄膜的方法如下： 将镀有电极的基片 1放入基材载物台， 用金属 钛或氧化钛作为靶台， 调节钛靶和基材载物台之间的距离为 20~30cm， 载物台的旋转速 率为 4~8rp， 磁控溅射反应室真空度至少抽到 10-3Pa， 温度加热到 20~250°C， 惰性气体流 60~100sccm, 磁控溅射功率 80~120w， 在 0.5~2.0Pa压强下， 溅射 15~60min， 得到如图 2 所示的涂有纳米晶 Ti02薄膜 3的传感器。 [0013] 色素敏化材料的选择与溶解包括针对所需检测的气体选择合适的色素敏化材料并 将色素敏化材料溶解在合适的溶剂中。 检测还原性气体时选择那些敏化性较强的氧化还 原指示剂， 如酚藏花红、 亚甲基蓝、 四磺酸基靛蓝， 并将所选择的色素敏化材料溶解到 与之相容的溶剂中， 制成色素溶液。 色素敏化材料包括合成色素敏化材料和天然色素敏 化材料， 当采用合成色素敏化材料时， 形成的色素溶液的浓度为 0.1mOl/L~0.5mol/L， 当 采用天然色素敏化材料时， 要浓縮天然色素敏化材料使色素溶液含水率为 60% ~80%。
[0014] 色素敏化材料固定方法如下：将制成的纳米晶 Ti02薄膜 3放入制成的色素溶液中 浸泡 12~48小时后取出， 用无水乙醇将杂质冲洗干净， 在干燥空气中晾干后在 30~80°C 烘箱中烘干 l~5h即可， 得到如图 3所示的涂有纳米晶 Ti02薄膜和色素的传感器， 4是色 素层。
[0015] 本发明通过在基片 1上用离子喷镀的方法制作电极 2， 用磁控溅射法制备纳米晶 Ti02薄膜 3， 色素敏化材料作为激化材料制作新型的气体传感器。 纳米晶 Ti02薄膜 3— 方面有利于色素敏化材料的固定， 另一方面有利于气体分子的富集。 吸附在纳米晶 Ti02 薄膜 3上的气体分子与色素敏化材料接触后， 使色素敏化材料的电荷发生中心离子到配 体的电荷迁移， 转移的电荷激发 Ti02晶体的晶格电阻， 使其对气体的敏感性改变。 因此 本发明的新型气体传感器与气味分子反应时， 其导电性能在常温下改变。
[0016] 以下提供本发明的 6个实施例：
实施例 1
本实施例是使用合成色素敏化材料与纳米晶 1 02薄膜相结合制作气体传感器， 制作步骤 如下：
1、 选择硅片、 玻璃片、 导电玻璃片、 聚四氟乙烯片其中的一种作为基片。
[0017] 2、 通过丝网印刷或等离子体溅射方法制作金或铂金电极， 如图 1所示的基片 1和 电极 2。
[0018] 3、磁控溅射法制备纳米晶 Ti02薄膜： 将基片 1放入基材载物台， 金属钛或氧化钛 作为靶台， 调节钛靶和基材载物台之间的距离为 20cm， 载物台的旋转速率为 4rp， 磁控 溅射反应室真空度至少抽到 10— 3Pa， 温度加热到 20°C， 惰性气体流 60sccm， 磁控溅射功 率 80w， 在 0.5Pa压强下， 溅射 15min， 得到如图 2所示的涂有纳米晶 Ti02薄膜 3的传 感器。
[0019] 4、 合成色素敏化材料的选择， 以亚甲基蓝为例， 选择亚甲基蓝作为色素敏化材料 并将其溶解到水中形成 O.lmol/L的色素溶液。
[0020] 5、 色素敏化材料的固定： 将制成纳米晶 Ti02薄膜放入 O.lmol/L亚甲基蓝溶液中 浸泡 12小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 30°C烘箱中烘 干 lh即得到如图 3所示的所需的传感器。在本实施例中， 如果上述步骤 4中选择的是其 他合成色素敏化材料所形成的溶液， 本步骤方法不变。
[0021] 实施例 2
本实施例是使用天然色素色素材料与纳米晶 Ti02薄膜相结合制作气体传感器， 制作步骤 如下：
步骤 1〜步骤 3同实施例 1。
[0022] 4、 天然色敏材料的提取和制备： 以紫薯色素为例， 取 10g紫薯洗净， 切成丁状放 入组织匀浆机中捣碎，得到浆液状溶液，用量筒量取 10毫升紫薯捣碎液，倒入三角瓶中， 再加入 100毫升 1%的柠檬酸， 摇匀， 置于 50°C恒温水浴锅中浸提 1小时。 待原料明显 褪色后， 用直径 15cm的定性滤纸过滤出萃取液， 用旋转蒸发仪将萃取液蒸发浓縮， 浓縮 至含水率为 60%， 得到所需浓縮的紫薯色素溶液。
[0023] 5、 色敏材料的固定： 将制成的纳米晶 1102薄膜放入浓縮的紫薯色素溶液中浸泡 12小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 30°C烘箱中烘干 lh 即得到如图 3所示的所需的传感器。 在本实施例中， 如果步骤 4中提取的是其他天然色 敏材料所形成的溶液， 本步骤方法不变。
[0024] 实施例 3
本实施例是使用合成色素敏化材料与纳米晶 Ti02薄膜相结合制作气体传感器， 制作步骤 如下：
1、 选择硅片、 玻璃片、 导电玻璃片、 聚四氟乙烯片其中的一种作为基片。
[0025] 2、 通过丝网印刷或等离子体溅射方法制作金或铂金电极， 如图 1中的基片 1和电 极 2。
[0026] 3、磁控溅射法制备纳米晶 Ti02薄膜： 将基片放入基材载物台， 金属钛或氧化钛作 为靶台， 调节钛靶和基材载物台之间的距离为 25cm， 载物台的旋转速率为 6rp， 磁控溅 射反应室真空度至少抽到 10-3Pa， 温度加热到 100°C， 惰性气体流 80sccm， 磁控溅射功 率 100w， 在 l.OPa压强下， 溅射 30min， 得到如图 2所示的涂有纳米晶 Ti02薄膜 3的传 感器。 [0027] 4、 合成色素敏化材料的选择， 以亚甲基蓝为例， 选择亚甲基蓝作为色素敏化材料 并将其溶解到水中形成 0.25mol/L的色素溶液。
[0028] 5、 色素敏化材料的固定： 将制成纳米晶 Ti02薄膜放入 0.25mol/L亚甲基蓝溶液中 浸泡 24小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 60°C烘箱中烘 干 3h即得到图 3所示的所需的传感器。在本实施例中， 如果步骤 4中选择的是其他合成 色素敏化材料所形成的溶液， 本步骤方法不变。
[0029] 实施例 4
本实施例是使用天然色素材料与纳米晶 Ti02薄膜相结合制作气体传感器，制作步骤如下： 步骤 1〜步骤 3同实施例 3。
[0030] 4、 天然色敏材料的提取和制备： 以紫薯色素为例， 取 15g紫薯洗净， 切成丁状放 入组织匀浆机中捣碎，得到浆液状溶液，用量筒量取 15毫升紫薯捣碎液，倒入三角瓶中， 再加入 150毫升 3%的柠檬酸， 摇匀， 置于 55°C恒温水浴锅中浸提 1.5小时。 待原料明显 褪色后， 用直径 15cm的定性滤纸过滤出萃取液， 用旋转蒸发仪将萃取液蒸发浓縮， 浓縮 至含水率为 70%， 得到所需浓縮的紫薯色素溶液。
[0031] 5、 色敏材料的固定： 将制成的纳米晶 1102薄膜放入浓縮的紫薯色素溶液中浸泡 24小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 60°C烘箱中烘干 4h 即得到图 3所示的所需的传感器。 在本实施例中， 如果步骤 4中提取的是其他天然色敏 材料所形成的溶液， 本步骤方法不变。
[0032] 实施例 5
本实施例是使用合成色素敏化材料与纳米晶 Ti02薄膜相结合制作气体传感器， 制作步骤 如下：
1、 选择硅片、 玻璃片、 导电玻璃片、 聚四氟乙烯片其中的一种作为基片。
[0033] 2、 通过丝网印刷或等离子体溅射方法制作金或铂金电极， 如图 1中基片 1和电极
2。
[0034] 3、磁控溅射法制备纳米晶 Ti02薄膜： 将基片放入基材载物台， 金属钛或氧化钛作 为靶台， 调节钛靶和基材载物台之间的距离为 30cm， 载物台的旋转速率为 8rp， 磁控溅 射反应室真空度至少抽到 10-3Pa， 温度加热到 250°C， 惰性气体流 lOOsccm, 磁控溅射功 率 120w， 在 2.0Pa压强下， 溅射 60min。 得到如图 2所示的涂有纳米晶 Ti02薄膜 3的传 感器。 [0035] 4、 合成色素敏化材料的选择， 以亚甲基蓝为例， 选择亚甲基蓝作为色素敏化材料 并将其溶解到水中形成 0.5mol/L的色素溶液。
[0036] 5、 色素敏化材料的固定： 将制成纳米晶 Ti02薄膜放入 0.5mol/L亚甲基蓝溶液中 浸泡 48小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 80°C烘箱中烘 干 5h即得到如图 3所示的所需的传感器。在本实施例中， 如果步骤 4中选择的是其他合 成色素敏化材料所形成的溶液， 本步骤方法不变。
[0037] 实施例 6
本实施例是使用天然色素色素材料与纳米晶 Ti02薄膜相结合制作气体传感器， 制作步骤 如下：
步骤 1~ 步骤 3同实施例 5。
[0038] 4、 天然色敏材料的提取和制备： 以紫薯色素为例， 取 20g紫薯洗净， 切成丁状放 入组织匀浆机中捣碎，得到浆液状溶液，用量筒量取 20毫升紫薯捣碎液，倒入三角瓶中， 再加入 200毫升 5%的柠檬酸， 摇匀， 置于 60°C恒温水浴锅中浸提 2小时。 待原料明显 褪色后， 用直径 15cm的定性滤纸过滤出萃取液， 用旋转蒸发仪将萃取液蒸发浓縮， 浓縮 至含水率为 80%， 得到所需浓縮的紫薯色素溶液。
[0039] 5、 色敏材料的固定： 将制成的纳米晶 Ti02薄膜放入浓縮的紫薯色素溶液中浸泡 48小时后取出，用无水乙醇将杂质冲洗干净，在干燥空气中晾干后在 80°C烘箱中烘干 5h 即得到如图 3所示的所需的传感器。 在本实施例中， 如果步骤 4中提取的是其他天然色 敏材料所形成的溶液， 本步骤方法不变。

Claims

权利要求书
1. 一种基于色素敏化 Ti02薄膜的气体传感器制作方法， 其特征是包括以下步骤：
( 1 ) 选择适合于后续镀膜的基片， 在基片上通过镀膜方法制作电极， 将镀有电极的基片 通过磁控溅射法制备纳米晶 Ti02薄膜；
(2) 针对所需检测的气体选择合适的色素敏化材料并将色素敏化材料溶解在与之相容的 溶剂中， 制成色素溶液；
( 3 ) 将所述纳米晶 Ti02薄膜放入所述色素溶液中浸泡 12~48小时后取出， 用无水乙醇将 杂质冲洗干净， 晾干后在 30~80°C烘箱中烘 l~5h即可。
2. 根据权利要求 1 所述的气体传感器制作方法， 其特征是： 所述磁控溅射法制备纳米晶 Ti02薄膜的方法如下： 将镀有电极的基片放入基材载物台， 用金属钛或氧化钛作为靶 台， 调节钛靶和基材载物台之间的距离为 20~30cm， 载物台的旋转速率为 4~8rp， 磁控溅 射反应室真空度至少抽到 10—3Pa， 温度加热到 20~250°C， 惰性气体流为 60~100sccm， 磁 控溅射功率为 80~120w， 在 0.5~2.0Pa压强下溅射 15~60min。
3. 根据权利要求 1 所述的气体传感器制作方法， 其特征是： 所述色素敏化材料包括合成 色素敏化材料和天然色素敏化材料， 当采用合成色素敏化材料时， 制成的色素溶液的浓 度为 0.1mol/L~0.5mol/L， 当采用天然色素敏化材料时， 色素溶液含水率为 60% ~80%。
4. 根据权利要求 1 所述的气体传感器制作方法， 其特征是： 基片是硅片、 玻璃片、 导电 玻璃片或聚四氟乙烯片， 电极是金或铂金电极。
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CN114720511A (zh) * 2022-03-24 2022-07-08 浙江科技学院 一种验证多因素影响TiO2气敏性能机理的模拟方法

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