CN105548277A - 一种基于方酸衍生物的氨气传感器及其制备方法和用途 - Google Patents
一种基于方酸衍生物的氨气传感器及其制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种基于方酸衍生物的氨气传感器及其制备方法和用途。具体而言，本发明的氨气传感器包括叉指电极和镀膜材料，该镀膜材料为如式I所示的方酸衍生物MSA，其通过真空镀膜技术镀于叉指电极上，并且其厚度为100~200nm。本发明的氨气传感器制备便捷，操作简单，选择性高，对于氨气的传感强度远高于其他分子；另外，本发明的氨气传感器灵明度高，对极小变化的氨气均有电流响应，并且最低检测限极低，可测试ppb级别的氨气。
Description
技术领域
本发明属于有机半导体材料技术领域，具体涉及一种基于方酸衍生物的氨气传感器，其制备方法，及其在空气质量检测中，特别是在氨气检测中的用途。
背景技术
随着环境污染日益严重，当今社会对于环境问题的关注度不断增高，尤其是与人体健康息息相关的小环境内的大气环境问题备受关注。氨气是一种无色但却具有强烈刺激性臭味的气体，其密度比空气轻（相对比重约为0.5），人体可感觉的最低浓度为5.3 ppm。当氨气与人体的皮肤组织接触时，不仅产生刺激作用，而且还会腐蚀皮肤。氨气可以通过吸收皮肤中的水分，使蛋白变性，并使组织脂肪皂化，破坏细胞膜结构。由于氨气的溶解度极高，因此其主要对动物或人体的上呼吸道产生刺激和腐蚀作用，减弱人体抵抗疾病的能力。当其浓度过高时，还可以通过三叉神经末梢的反射作用诱发心脏骤停和呼吸停止。然而，目前常见的氨气传感器的检测限高、选择性差，并且制备工艺较为复杂，因此迫切需要一种检测限低、选择性高、灵敏度高、制备过程简单易行的新型氨气传感器。
发明内容
针对上述情况，本发明采用一种方酸衍生物MSA（其结构如下所示）来制备氨气传感器，并且通过在不同气体浓度下观察传感器的I-V曲线变化来检测不同浓度的氨气。为了检测传感器的选择性，本发明还在相同温度下对多种有机物蒸气进行了检测，结果证明传感器具有稳定性好、检测限低、选择性高等优点，检测级别能够达到ppb级别，并且其制备工艺简单，具有很强的商业应用价值和广阔的市场前景。
具体而言，本发明采用如下技术方案：
如式（I）所示的方酸衍生物在制备氨气传感器中的用途。
上述基于方酸衍生物的氨气传感器包括叉指电极和镀膜材料，所述镀膜材料为上述如式（I）所示的方酸衍生物，其通过真空镀膜技术镀于所述叉指电极上，并且其厚度为100~200
nm。
优选的，在上述基于方酸衍生物的氨气传感器中，所述叉指电极以自下而上依次为硅、二氧化硅（厚度为270~330
nm，优选300 nm）、铬（厚度为9~11
nm，优选10 nm）的层状结构为基底，其上设置有金电极（厚度为90~110
nm，优选100 nm）；所述叉指电极的叉指宽度为3~8 μm（优选5 μm），叉指间距为2~5 μm（优选3 μm）
上述基于方酸衍生物的氨气传感器通过包括如下步骤的制备方法制得：
（1）清洁基板，并将叉指电极固定在所述基板上；
（2）将步骤（1）中固定有叉指电极的基板置于真空镀膜装置中，并向所述真空镀膜装置中装入作为镀膜材料的上述如式（I）所示的方酸衍生物；
（3）按照如下条件设置真空镀膜参数：蒸镀速度为5~6
Å/s，蒸镀压力为1E-6~1E-5 mbar，蒸镀温度为120~140℃；
（4）参数设置完成后，开启减压装置来降低所述真空镀膜装置的腔内气压，当腔内气压小于5.0
mbar时，开启分子泵，当气压达到蒸镀压力时，开始蒸镀薄膜，直至镀膜达到所需的厚度，即得基于方酸衍生物的氨气传感器。
优选的，在上述制备方法中，步骤（1）中所述固定通过双面胶粘合的方式来完成。
优选的，在上述制备方法中，步骤（2）中所述真空镀膜装置为真空镀膜机。
优选的，在上述制备方法中，步骤（3）中所述真空镀膜参数设置如下：蒸镀速度为5 Å/s，蒸镀压力为1E-5 mbar，蒸镀温度为120℃。
优选的，在上述制备方法中，步骤（4）中所述减压装置为真空泵。
上述基于方酸衍生物的氨气传感器在空气质量检测中，特别是在氨气检测中的用途。
与现有技术相比，利用上述技术方案的本发明具有如下优点：
（1）器件制备便捷，操作简单；
（2）选择性高，对于氨气的传感强度远高于其他分子；
（3）灵明度高，对极小变化的氨气均有电流响应；
（4）最低检测限极低，可测试ppb级别的氨气。
附图说明
图1为MSA分子的紫外光谱图。
图2为基于MSA薄膜的传感器的结构示意图。
图3为基于MSA薄膜的传感器对浓度为10ppb~64ppm的氨气的I/V曲线。
图4为基于MSA薄膜的传感器对浓度在10ppb~64ppm氨气传感的电阻变化。
图5为基于MSA薄膜的传感器的可回复性实验结果。
图6为基于MSA薄膜的传感器的选择性实验结果。
具体实施方式
下文将结合附图和具体实施例来进一步说明本发明的技术方案。除非另有说明，下列实施例中所使用的试剂、材料、仪器等均可通过商业手段获得。
实施例1：MSA的合成与氨气传感器的制备。
（1）MSA分子的合成：
称取对甲基苯胺（1.00 g，8.76 mmol）和方酸（1.88 g，17.52 mmol），并置于正丁醇与甲苯的等体积混合溶液（40 mL）中，加热并回流反应12 h，反应结束后过滤，固体用氯仿及正己烷各洗涤三次，并在真空烘箱内于60℃干燥24 h，得到亮黄色固体MSA（2.7 g，产率93.75%）。
相应的理化鉴定数据如下所示：
1H-NMR (400 MHz, DMSO-d 6)
δ 9.81 (s, 1H), 9.16 (s, 1H), 7.52 (d, J
= 7.6 Hz, 2H), 7.38 (d, J = 7.6 Hz, 2H), 7.18 (d, J = 7.3 Hz,
2H), 6.97 (d, J = 7.7 Hz, 2H), 2.27 (s, 3H), 2.19 (s, 3H)；
UV光谱图如图1所示。
（2）传感器的制备：
（a）清洁玻璃基板，并通过双面胶将叉指电极粘合在基板上，该叉指电极以自下而上依次为硅、二氧化硅（300 nm）、铬（10 nm）的层状结构为基底，其上设置有金电极（100
nm），叉指宽度为5 μm，叉指间距为3 μm；
（b）将步骤（1）中固定有叉指电极的基板置于真空镀膜机中，称取MSA分子35 mg，置于石英坩埚内，并装入真空镀膜机中，备用；
（c）按照如下条件设置真空镀膜参数：蒸镀速度为5 Å/s，蒸镀压力为1E-5 mbar，蒸镀温度为120℃；
（d）参数设置完成后，开启真空泵来降低真空镀膜机的腔内气压，当腔内气压小于5.0
mbar时，开启分子泵（如果分子泵开启时压力过大，则会直接损伤分子泵，使得镀膜压力达不到，导致镀膜质量过差），当气压达到1E-5
mbar时，开始蒸镀薄膜，直至镀膜厚度达到100
nm，即得基于方酸衍生物的氨气传感器，其结构示意图如图2所示。
实施例2：MSA薄膜传感器在不同气体浓度下的I-V曲线测定实验。
通过将1000 ppm氨气用氮气稀释得到不同浓度的氨气，并通过动态配气装置保持气体浓度为所需要的浓度，进而对MSA薄膜传感器在不同气体浓度下的I-V曲线进行测定实验，其结果如图3所示。
从图3中可以看出，对于不同浓度的氨气，MSA传感器均有不同的电流响应。浓度越高，相应的电流越小，但随着浓度提高至4 ppm以上，电流值变化较小，基本趋于平衡。
实施例3：MSA薄膜传感器在不同气体浓度下的电阻变化测定实验。
为了探索MSA器件的传感规律性，本发明测试了器件的电阻变化（(I0-I)/I）与气体浓度变化之间的关系以及电流与浓度的变化关系，通过将1000 ppm的氨气标准气用高纯氮稀释成不同浓度，并将器件放置于不同浓度的气体氛围内，测试电流变化并转换为电阻变化，其结果如图4所示。
从图4中可以看出，随着氨气浓度的不断增高，器件的电阻变化也在不断增高，电流值（电压取19.5
V时）则下降明显，并具有一定的函数关系。
实施例4：MSA薄膜传感器的可回复性测试。
控制电压为10 V，向器件通入浓度为60 ppb的氨气1 min后，再向器件内通入氮气，再依次通入不同浓度的氨气与氮气，用于测试器件的可回复性，其结果如图5所示。
从图5中可以看出，通入不同浓度（60 ppb~2 ppm）的氨气后，电流均会有所下降，但通入氮气后，器件电流又迅速上升到基线位置。由此可以证明，MSA薄膜传感器是可回复的，适合于长期且稳定地检测空气中的氨气。
实施例5：MSA传感器的选择性测试。
为了检测气体传感器的选择性，在相同温度下分别选取100 ppm的乙醇、四氯化碳、氯仿、乙醚、苯、乙酸乙酯等气体，测试器件对其响应强度，其结果如图6所示。
从图6中可以看出，对于高浓度（100 ppm）的乙醇、四氯化碳等气体而言，本发明的MSA薄膜传感器的响应强度低，有的几乎没有任何响应，而对于极低浓度（0.1
ppm）的氨气而言，其响应强度则可达到非常高的水平。由此可见，本发明的MSA薄膜传感器不仅检测限低，而且选择性高。
综上所述，本发明通过将一种方酸衍生物制作成结构简单的电阻式薄膜传感器，实现了针对极低浓度的氨气进行检测，并且选择性很高，解决了目前缺乏低检测限氨气传感器的难题，本发明的基于方酸衍生物的氨气传感器对于未来治理大气污染具有很高的应用价值。
Claims (10)
1.如式I所示的方酸衍生物在制备氨气传感器中的用途，
。
2.一种基于方酸衍生物的氨气传感器，其包括叉指电极和镀膜材料，所述镀膜材料为根据权利要求1所述的如式I所示的方酸衍生物，所述镀膜材料通过真空镀膜技术镀于所述叉指电极上，并且所述镀膜材料的厚度为100~200 nm。
3.根据权利要求2所述的基于方酸衍生物的氨气传感器，其特征在于：
所述叉指电极以自下而上依次为硅、二氧化硅、铬的层状结构为基底，所述基底上设置有金电极；
所述二氧化硅的厚度为270~330
nm，所述铬的厚度为9~11
nm，所述金电极的厚度为90~110
nm。
4.根据权利要求2所述的基于方酸衍生物的氨气传感器，其特征在于：
所述叉指电极的叉指宽度为3~8
μm，叉指间距为2~5 μm。
5.一种根据权利要求2所述的基于方酸衍生物的氨气传感器的制备方法，其包括如下步骤：
1）清洁基板，并将叉指电极固定在所述基板上；
2）将步骤1）中固定有叉指电极的基板置于真空镀膜装置中，并向所述真空镀膜装置中装入作为镀膜材料的根据权利要求1所述的如式I所示的方酸衍生物；
3）按照如下条件设置真空镀膜参数：蒸镀速度为5~6 Å/s，蒸镀压力为1E-6~1E-5 mbar，蒸镀温度为120~140℃；
4）参数设置完成后，开启减压装置来降低所述真空镀膜装置的腔内气压，当腔内气压小于5.0 mbar时，开启分子泵，当气压达到蒸镀压力时，开始蒸镀薄膜，直至镀膜达到所需的厚度，即得基于方酸衍生物的氨气传感器。
6.根据权利要求5所述的制备方法，其特征在于：
步骤1）中所述固定通过双面胶粘合的方式来完成。
7.根据权利要求5所述的制备方法，其特征在于：
步骤2）中所述真空镀膜装置为真空镀膜机。
8.根据权利要求5所述的制备方法，其特征在于：
步骤3）中所述真空镀膜参数设置如下：蒸镀速度为5 Å/s，蒸镀压力为1E-5 mbar，蒸镀温度为120℃。
9.根据权利要求5所述的制备方法，其特征在于：
步骤4）中所述减压装置为真空泵。
10.根据权利要求2所述的基于方酸衍生物的氨气传感器在氨气检测中的用途。
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