CN1271096A - Nitrogen oxide sensor made of doped polyaniline and its making process - Google Patents
Nitrogen oxide sensor made of doped polyaniline and its making process Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 12
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229920000592 inorganic polymer Polymers 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229920000447 polyanionic polymer Polymers 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052737 gold Inorganic materials 0.000 abstract description 4
- 239000010931 gold Substances 0.000 abstract description 4
- 229910001252 Pd alloy Inorganic materials 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000002241 glass-ceramic Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
本发明公开了一种掺杂态聚苯胺的氧化氮气体传感器及其制备方法。掺杂态聚苯胺的氧化氮气体传感器是由基片、电极、聚苯胺敏感膜和导电引出端组成。基片为长方形、方形或圆形的微晶玻璃片、陶瓷片、绝缘性能好的聚合物或高阻硅片,经清洗后在其一侧表面烧制或蒸发一对叉指电极,电极材料为金或银钯合金。其制备方法是在含叉指电极的基片部分上采用掺杂诱导沉积自组装法或原位聚合沉积法生长成较高导电率的聚苯胺敏感膜,在两个电极端引出导线。本发明具有抗干扰能力强、器件长期稳定性好、使用方便等优点。可以广泛应用于汽车尾气检测、大气环境检测以及工厂及仓库的氧化氮气体泄漏报警装置以及军事战地环境、卫星发射现场的氧化氮气体浓度的检控等。
The invention discloses a doped polyaniline nitrogen oxide gas sensor and a preparation method thereof. The doped polyaniline nitrogen oxide gas sensor is composed of a substrate, an electrode, a polyaniline sensitive film and a conductive lead-out end. The substrate is a rectangular, square or circular glass-ceramic sheet, ceramic sheet, polymer with good insulating properties or high-resistance silicon sheet. After cleaning, a pair of interdigitated electrodes are fired or evaporated on one side of the surface. The electrode material is For gold or silver palladium alloy. The preparation method is to grow a polyaniline sensitive film with higher conductivity on the substrate part containing the interdigitated electrodes by doping-induced deposition self-assembly method or in-situ polymerization deposition method, and lead out wires at the two electrode ends. The invention has the advantages of strong anti-interference ability, good long-term stability of the device, convenient use and the like. It can be widely used in vehicle exhaust detection, atmospheric environment detection, nitrogen oxide gas leakage alarm devices in factories and warehouses, military battlefield environments, and detection and control of nitrogen oxide gas concentration at satellite launch sites.
Description
本发明属气体传感器领域。The invention belongs to the field of gas sensors.
氧化氮(NOX)气体是大气中对环境和人类健康危害十分严重的污染物。因此，研制氧化氮气体传感器以便及时准确地获知环境中和有关污染源的NOX气体及其浓度，对环境监测和环境保护意义重大。目前文献所报道的NOX气体传感器，多采用无机氧化物如SnO2、WO3敏感材料，工作温度一般都较高(200～500℃)，不便传感器的实际应用。Nitrogen oxide (NO X ) gas is a very serious pollutant in the atmosphere that is harmful to the environment and human health. Therefore, it is of great significance for environmental monitoring and environmental protection to develop a nitrogen oxide gas sensor in order to know the NOx gas and its concentration in the environment and related pollution sources in a timely and accurate manner. Currently, the NOx gas sensors reported in the literature mostly use inorganic oxides such as SnO 2 and WO 3 sensitive materials, and the working temperature is generally high (200-500°C), which is inconvenient for the practical application of the sensor.
近年来，可在室温工作的有机材料尤其是导电聚合物材料用作气体敏感材料日益得到重视。在导电聚合物中，聚苯胺由于其制备相对较简单、成本低、导电性能较稳定，因此采用聚苯胺制作NOX气体敏感材料更具优势。1996年7月16日公开的Monkman等人的美国专利“Polyaniline Gas Sensor”(“聚苯胺气体传感器”，专利号：US05536473)中首次将聚苯胺用于氧化氮气体传感器。但是Monkman等人采用的敏感膜是本征态聚苯胺，而本征态聚苯胺的电导率很低，大约为10-11S/cm，用它制作的传感器的电阻大于1千兆欧姆，给敏感信号的检测及后端信号处理带来很大困难，抗干扰能力差。另外，他们的制膜方法是通过旋涂法及真空蒸发等工艺，制得的膜与基片的附着力较差，使得传感器的稳定性降低。In recent years, organic materials that can work at room temperature, especially conductive polymer materials, have attracted increasing attention as gas-sensitive materials. Among conductive polymers, polyaniline is relatively simple to prepare, low in cost, and stable in conductivity, so it is more advantageous to use polyaniline to make NO x gas sensitive materials. In the U.S. patent "Polyaniline Gas Sensor"("polyaniline gas sensor", patent number: US05536473) published by Monkman et al. on July 16, 1996, polyaniline was used for the nitrogen oxide gas sensor for the first time. However, the sensitive film used by Monkman et al. is intrinsic polyaniline, and the conductivity of intrinsic polyaniline is very low, about 10 -11 S/cm, and the resistance of the sensor made by it is greater than 1 gigaohm, giving Sensitive signal detection and back-end signal processing bring great difficulties and poor anti-interference ability. In addition, their film-making method is through processes such as spin coating and vacuum evaporation, and the adhesion between the film and the substrate is poor, which reduces the stability of the sensor.
本发明的目的在于提供一种新的聚苯胺氧化氮气体传感器及其制备方法。The object of the present invention is to provide a new polyaniline nitrogen oxide gas sensor and a preparation method thereof.
本发明所述的掺杂态聚苯胺氧化氮气体传感器的工作原理是掺杂态聚苯胺的电导率与其自身的氧化程度有关，氧化程度愈高，电导率愈低。氧化氮是一种氧化性气体，与掺杂态聚苯胺接触后，使聚苯胺的氧化程度升高，因此敏感元件的电阻增大。氧化氮气体的浓度愈大，聚苯胺的氧化程度就愈高，电阻升高就愈大。因此通过检测元件的电阻，就可以探测到环境中氧化氮气体的浓度。The working principle of the doped polyaniline nitrogen oxide gas sensor of the present invention is that the electrical conductivity of the doped polyaniline is related to its own oxidation degree, and the higher the oxidation degree, the lower the electrical conductivity. Nitrogen oxide is an oxidizing gas. After contacting with doped polyaniline, the degree of oxidation of polyaniline will increase, so the resistance of the sensitive element will increase. The greater the concentration of nitrogen oxide gas, the higher the degree of oxidation of polyaniline and the greater the increase in resistance. Therefore, the concentration of nitrogen oxide gas in the environment can be detected by detecting the resistance of the element.
本发明所述的掺杂态聚苯胺氧化氮气体传感器是由基片、电极、聚苯胺敏感膜和导电引出端组成。基片为长方形、方形或圆形的微晶玻璃片、陶瓷片、绝缘性能好的聚合物或高阻硅片，经清洗后在其一侧表面烧制或蒸发一对叉指电极，电极材料为金或银钯合金。在含叉指电极的基片部分上采用掺杂诱导沉积自组装法或原位聚合沉积法生长掺杂态聚苯胺敏感膜，在两个电极端引出导线。其中掺杂态聚苯胺是指质子酸掺杂的半氧化半还原状态的聚苯胺。The doped polyaniline nitrogen oxide gas sensor of the invention is composed of a substrate, an electrode, a polyaniline sensitive film and a conductive lead-out end. The substrate is a rectangular, square or round glass-ceramic sheet, ceramic sheet, polymer with good insulating properties or high-resistance silicon sheet. After cleaning, a pair of interdigitated electrodes are fired or evaporated on one side of the surface. The electrode material is For gold or silver palladium alloy. A doped polyaniline sensitive film is grown on the substrate part containing interdigitated electrodes by doping-induced deposition self-assembly method or in-situ polymerization deposition method, and wires are drawn out at two electrode ends. The doped polyaniline refers to polyaniline in a semi-oxidized and semi-reduced state doped with a protonic acid.
掺杂诱导沉积自组装法的制膜过程是将表面酸性化的基片交替浸入本征态聚苯胺的N-甲基吡咯烷酮的溶液和聚合物酸的水溶液中，一定时间后取出，分别用有机溶剂和去离子水冲洗，吹干。详细过程见中国专利(“掺杂诱导沉积制备聚苯胺超薄膜的制备方法”，申请号：98121862.8，1998年)。原位聚合沉积法的制膜过程类似文献(李永明， 万梅香，浸渍聚合法制备透明聚苯胺薄膜的研究，高分子学报，2(1998)，177-183)报道的过程：先分别配置pH值约为0的0.05M苯胺酸性溶液和0.025M过硫酸铵的水溶液，随后将这两种溶液等体积混合，插入基片，搅拌，反应约3～5小时，提出基片，用酸性溶液冲洗，浸泡20分钟，再用去离子水冲洗后，吹干，得到质子酸掺杂的聚苯胺薄膜。所用的酸可以是盐酸、硫酸或对甲苯磺酸。与文献不同的是如此制得的膜要用浓度为1～10％的氨水浸泡处理脱掺杂，再将聚苯胺薄膜浸入聚合物酸的水溶液中1～5小时，使聚苯胺被聚合物酸掺杂。聚合物酸可以是聚苯乙烯磺酸、聚丙烯酸等有机聚合物酸，也可以是钼、钨等过渡金属的同多酸或杂多酸等无机聚合物酸。实验表明，聚合物酸掺杂的聚苯胺膜的稳定性较好。The film-making process of the doping-induced deposition self-assembly method is to alternately immerse the surface acidified substrate into the solution of N-methylpyrrolidone of intrinsic polyaniline and the aqueous solution of polymer acid, take it out after a certain period of time, and use organic Rinse with solvent and deionized water, and blow dry. For the detailed process, see the Chinese patent ("Preparation method of polyaniline ultra-thin film prepared by doping-induced deposition", application number: 98121862.8, 1998). The film-making process of the in-situ polymerization deposition method is similar to the process reported in the literature (Li Yongming, Wan Meixiang, Preparation of Transparent Polyaniline Films by Dip Polymerization, Acta Polymerica Sinica, 2 (1998), 177-183): first configure the pH value respectively 0.05M aniline acidic solution at about 0 and 0.025M ammonium persulfate aqueous solution, then mix the two solutions in equal volumes, insert the substrate, stir, react for about 3 to 5 hours, take out the substrate, rinse with acidic solution, Soak for 20 minutes, rinse with deionized water, and dry to obtain a protonic acid-doped polyaniline film. The acid used may be hydrochloric acid, sulfuric acid or p-toluenesulfonic acid. Different from the literature, the film prepared in this way needs to be soaked in ammonia water with a concentration of 1 to 10% for dedoping, and then the polyaniline film is immersed in the aqueous solution of polymer acid for 1 to 5 hours, so that the polyaniline is soaked by the polymer acid. doping. The polymer acid may be an organic polymer acid such as polystyrene sulfonic acid or polyacrylic acid, or may be an inorganic polymer acid such as an isopoly acid or a heteropoly acid of a transition metal such as molybdenum or tungsten. Experiments show that the stability of polyaniline membrane doped with polymer acid is better.
为了进一步提高聚苯胺薄膜与基片的附着力，基片表面可以先用聚合物电解质进行处理。处理方法是先将基片清洗干净后，在聚阳离子聚二丙烯基二甲基氯化铵的水溶液中浸泡5～30分钟，取出后用去离子水冲洗干净得到聚阳离子处理的表面；阳离子化的基片还可以浸入聚苯乙烯磺酸、聚丙烯酸或其它聚合物酸的溶液中浸泡5～30分钟，取出后用去离子水冲洗干净得到聚阴离子处理的表面。基片经如此处理可以增强聚苯胺敏感膜的附着力。In order to further improve the adhesion between the polyaniline film and the substrate, the surface of the substrate can be treated with a polymer electrolyte first. The treatment method is to clean the substrate first, soak it in the aqueous solution of polycation polydipropylene dimethyl ammonium chloride for 5 to 30 minutes, take it out and rinse it with deionized water to obtain the surface treated with polycation; cationization The substrate can also be immersed in polystyrene sulfonic acid, polyacrylic acid or other polymer acid solutions for 5-30 minutes, and then rinsed with deionized water to obtain a polyanion-treated surface. The substrate can be treated in this way to enhance the adhesion of the polyaniline sensitive film.
附图及附图说明：Drawings and descriptions of drawings:
图1：掺杂态聚苯胺氧化氮气体传感器基片的平面示意图：1是基片；2是叉指电极；4是电极引线；Figure 1: Plane schematic diagram of doped polyaniline nitrogen oxide gas sensor substrate: 1 is the substrate; 2 is the interdigitated electrode; 4 is the electrode lead;
图2：掺杂态聚苯胺氧化氮气体传感器的侧面示意图：1是基片；2是叉指电极；3是掺杂态聚苯胺敏感膜；4是电极引线；Figure 2: The side schematic diagram of the doped polyaniline nitrogen oxide gas sensor: 1 is the substrate; 2 is the interdigitated electrode; 3 is the doped polyaniline sensitive film; 4 is the electrode lead;
图3：聚苯乙烯磺酸掺杂的聚苯胺氧化氮气体传感器的敏感特性曲线：敏感膜由掺杂诱导沉积法制备；Figure 3: Sensitive characteristic curve of polyaniline nitrogen oxide gas sensor doped with polystyrene sulfonic acid: the sensitive film is prepared by doping-induced deposition method;
图4：聚苯乙烯磺酸掺杂的聚苯胺氧化氮气体传感器的敏感特性曲线：敏感膜由原位聚合沉积法制备；Figure 4: Sensitive characteristic curve of polyaniline nitrogen oxide gas sensor doped with polystyrene sulfonic acid: the sensitive film is prepared by in-situ polymerization deposition method;
图5：钨酸掺杂的聚苯胺氧化氮气体传感器的敏感特性曲线：敏感膜由掺杂诱导沉积法制备；Figure 5: Sensitive characteristic curve of polyaniline nitrogen oxide gas sensor doped with tungstic acid: the sensitive film is prepared by doping-induced deposition method;
图6：钨酸掺杂的聚苯胺氧化氮气体传感器的敏感特性曲线：敏感膜由原位聚合沉积法制备。Figure 6: Sensitive characteristic curve of polyaniline nitrogen oxide gas sensor doped with tungstic acid: the sensitive film is prepared by in-situ polymerization deposition method.
在图3、图4、图5、图6中的敏感特性曲线中，其横坐标为NO2浓度，单位是ppm(百万分之一)，纵坐标是聚苯胺氧化氮气体传感器的电阻，单位是KΩ(千欧姆)。In the sensitive characteristic curves in Fig. 3, Fig. 4, Fig. 5 and Fig. 6, its abscissa is NO Concentration, the unit is ppm (one part per million), and the ordinate is the resistance of the polyaniline nitrogen oxide gas sensor, The unit is KΩ (kiloohm).
本发明所述的掺杂态聚苯胺氧化氮气体传感器电阻在几百欧姆～几十千欧姆范围，比本征态聚苯胺制作的气体传感器的电阻低6个数量级以上，因此其输出的信号很容易采集和进一步处理，抗干扰能力强，敏感膜与基片的附着力强，器件长期稳定性好；此外还具有使用方便，不需加热器、体积小等优点。可以广泛应用于汽车尾气检测，大气环境检测、工厂及仓库的氧化氮气体泄漏报警装置以及军事战地环境、卫星发射现场的氧化氮气体浓度的检控等。The resistance of the doped polyaniline nitric oxide gas sensor of the present invention is in the range of hundreds of ohms to tens of thousand ohms, which is more than 6 orders of magnitude lower than that of the gas sensor made of intrinsic polyaniline, so the output signal is very low. It is easy to collect and further process, has strong anti-interference ability, strong adhesion between the sensitive film and the substrate, and good long-term stability of the device; in addition, it has the advantages of convenient use, no need for heaters, and small size. It can be widely used in vehicle exhaust detection, atmospheric environment detection, nitrogen oxide gas leakage alarm devices in factories and warehouses, military battlefield environments, and detection and control of nitrogen oxide gas concentration at satellite launch sites, etc.
实施例一：Embodiment one:
将如图1所示的蒸有叉指金电极的基片经表面酸性化处理后(详见前期专利：98121862.8)，将基片电极部分交替浸入0.2％的聚苯胺的N-甲基吡咯烷酮溶液及1％聚苯乙烯磺酸的水溶液中60分钟，分别用二甲基甲酰胺和去离子水冲洗，吹干，如此循环8次，最后在50～80℃处理2小时，即得采用掺杂诱导沉积法制造的聚苯乙烯磺酸掺杂的聚苯胺氧化氮气体传感器。图3为其敏感特性曲线。实施例二：After the surface of the substrate steamed with interdigitated gold electrodes as shown in Figure 1 is acidified (see the previous patent: 98121862.8 for details), the electrode parts of the substrate are alternately immersed in 0.2% polyaniline N-methylpyrrolidone solution and 1% polystyrene sulfonic acid aqueous solution for 60 minutes, rinsed with dimethylformamide and deionized water respectively, and dried, and so circulated 8 times, and finally treated at 50-80°C for 2 hours, that is, the doped Polystyrene sulfonic acid doped polyaniline nitrogen oxide gas sensor fabricated by induced deposition method. Figure 3 is its sensitive characteristic curve. Embodiment two:
将清洗干净的如图1所示的蒸有叉指金电极的基片在1％的聚二丙烯基二甲基氯化铵的水溶液中浸泡30分钟，取出后用去离子水冲洗干净。分别配置20ml苯胺酸性溶液和0.025M的过硫酸铵水溶液，苯胺溶液中苯胺的浓度为0.05M，对甲苯磺酸的浓度为0.5M。随后将这两种溶液混合，插入基片，搅拌，反应约5小时，提出基片，用0.05M的对甲苯磺酸溶液冲洗，浸泡20分钟，再冲洗后，放入5％的氨水溶液中处理1小时，取出后用去离子水冲洗干净，在1％聚苯乙烯磺酸的水溶液中处理2小时，取出，用去离子水冲洗干净，最后在50～80℃处理2小时，即得采用原位聚合沉积法制造的聚苯乙烯磺酸掺杂的聚苯胺氧化氮气体传感器。图4为其敏感特性曲线。实施例三：Soak the cleaned substrate with interdigitated gold electrodes steamed as shown in Figure 1 in 1% polydipropylene dimethyl ammonium chloride aqueous solution for 30 minutes, take it out and rinse it with deionized water. Prepare 20ml of aniline acidic solution and 0.025M ammonium persulfate aqueous solution respectively, the concentration of aniline in the aniline solution is 0.05M, and the concentration of p-toluenesulfonic acid is 0.5M. Then mix the two solutions, insert the substrate, stir, react for about 5 hours, take out the substrate, rinse with 0.05M p-toluenesulfonic acid solution, soak for 20 minutes, rinse again, and put it in 5% ammonia solution Treat for 1 hour, take it out and rinse it with deionized water, treat it in an aqueous solution of 1% polystyrene sulfonic acid for 2 hours, take it out, rinse it with deionized water, and finally treat it at 50-80°C for 2 hours, and you can use it Polystyrene sulfonic acid doped polyaniline nitrogen oxide gas sensor fabricated by in situ polymerization deposition method. Figure 4 is its sensitive characteristic curve. Embodiment three:
以1％的钨酸取代聚苯乙烯磺酸，同实施例一的方法，即得采用掺杂诱导沉积法制造的钨酸掺杂的聚苯胺氧化氮气体传感器。图5为其敏感特性曲线。实施例四：Substituting 1% tungstic acid for polystyrene sulfonic acid, the method of Example 1 was used to obtain a tungstic acid-doped polyaniline nitrogen oxide gas sensor manufactured by the doping-induced deposition method. Figure 5 is its sensitive characteristic curve. Embodiment four:
以1％的钨酸取代聚苯乙烯磺酸，同实施例一的方法，即得采用原位聚合沉积法制造的钨酸掺杂的聚苯胺氧化氮气体传感器。图6为其敏感特性曲线。Substituting 1% tungstic acid for polystyrene sulfonic acid, the method of Example 1 was used to obtain a tungstic acid-doped polyaniline nitrogen oxide gas sensor manufactured by in-situ polymerization deposition method. Figure 6 is its sensitive characteristic curve.
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