溶解氧传感器微电极的制作及测试
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摘要
随着各种水质问题的出现，水资源的保护越来越受到人们的关注与重视。溶解氧作为衡量水体自净能力的一个重要指标，一直是人们对于水体检测的重点。传统的溶解氧检测方法有很多，但是由于其检测仪器结构复杂，成本较高，不能实现对水体及时连续监测等问题，给人们水体检测带来了诸多不便。因此，手持式，小型化的溶解氧检测仪器已成为人们研究的重点。本论文提出基于Clark溶解氧检测原理，利用MEMS微加工技术制作出了两个平行的微电极，然后通过对微电极位点的表面修饰，制备出了Clark型溶解氧传感器微电极，并完成了修饰后微电极的相关电化学测试，提高了对溶解氧的响应。本论文主要完成了以下相关工作：
1微电极的设计与制作：基于微电极在电化学反应中相对于宏观电极的优势，以Clark型溶解氧测定原理为基础，对微电极的图形进行了设计，通过标准MEMS工艺流程以及等离子体处理，制作出了铂金微电极位点上附有铝膜的微电极。
2微电极的表面修饰：将裸铂微电极位点处进行CV电化学沉积银，并通过盐酸处理，成功制备出银-氯化银薄膜电极，将此作为溶解氧传感器微电极的阳极；对附有铝膜的铂微电极进行阳极氧化处理，选择30V作为最合适的氧化电压，通过监测反应过程中的电流变化来控制阳极氧化的时间，从而制备出铂金微电极位点上纳米孔道，最后在氯铂酸与盐酸的混合溶液中利用电化学沉积法完成对其表面的纳米级修饰，此微电极作为溶解氧传感器微电极的阴极。
3微电极的测试：首先对纳米级修饰前后的铂微电极进行相关的电化学测试，发现修饰后的铂微电极电化学阻抗明显降低，CV扫描对一些电活性物质及溶解氧的响应电流从40μA增大道130μA，峰位明显正移；然后对纳米级修饰后制作的Clark溶解氧电极进行了相关溶解氧的测试，回路中的电流信号有显著的提高，达到几十微安，其对溶解氧的电催化性能增强。
表明该溶解氧微电极经过纳米级修饰，其对溶解氧测定的电化学活性和灵敏度都有明显的提高。同时，由于该微电极检测时所得信号是电信号，不需要繁琐的信号转换，因此可以用于制作小型化的溶解氧传感器。
With the appearance of water problem, people pay more attention to theprotection of water resource. Dissolved oxygen, which is an important parameter ofwater self-depuration capability, is always a significant part of water detection. Thereare many traditional DO detection methods which make the detection inconvenientdue to some disadvantages such as complicated detection structures, expensive cost,not be used for continuously in-situ detection and so on. Therefore, it is a trend for usto research small size and handheld DO detection instrument. In this dissertation, onthe basis of Clark principle for DO detection, we take advantage of MEMStechnology to fabricate two parallel microelectrodes. Then we successfully makeClark DO sensor microelectrodes through modifying surface and carry out somerelative electrochemistry tests that indicate the response of DO strengthens. The topicsof this dissertation are discussed as follows:
1. Design and fabrication of microelectrode. On the basis of microelectrodesuperiority, we designed the microelectrode pattern. Through MEMS and plasmatechnology, we fabricated Pt microelectrode which was deposited by aluminum film.
2. The modification for the surface of microelectrode. The anticathode of DO sensormicroelectrode is an Ag-AgCl electrode which was prepared by CV electrochemicaldeposition of Ag and treatment of HCl; the aluminum film on the Pt cathode wasprepared under30V by anodization and the curve of current-time. Finally,electrochemical deposition of Pt was carried out through porous alumina templateabove.
3. The test of microelectrode. According to the microelectrode before and afternano-modification, we carried out some relative electrochemistry test. It is foundout that electrochemical impedance of nano-modified microelectrode reducedobviously and the response current for DO improved dramatically, from40μA to130μA. Then we detected DO using nano-modified Clark DO electrode. The currentsignal was improved evidently relative to un-modified DO electrode.
It was proved that through nano-modified DO microelectrode, theelectrochemistry activation and sensitivity enhance obviously. In addition, thedetection signal is direct electrical signal that complicated signal conversion is notneeded, and the DO microelectrodes can be used for miniaturized DO sensor.
1微电极的设计与制作：基于微电极在电化学反应中相对于宏观电极的优势，以Clark型溶解氧测定原理为基础，对微电极的图形进行了设计，通过标准MEMS工艺流程以及等离子体处理，制作出了铂金微电极位点上附有铝膜的微电极。
2微电极的表面修饰：将裸铂微电极位点处进行CV电化学沉积银，并通过盐酸处理，成功制备出银-氯化银薄膜电极，将此作为溶解氧传感器微电极的阳极；对附有铝膜的铂微电极进行阳极氧化处理，选择30V作为最合适的氧化电压，通过监测反应过程中的电流变化来控制阳极氧化的时间，从而制备出铂金微电极位点上纳米孔道，最后在氯铂酸与盐酸的混合溶液中利用电化学沉积法完成对其表面的纳米级修饰，此微电极作为溶解氧传感器微电极的阴极。
3微电极的测试：首先对纳米级修饰前后的铂微电极进行相关的电化学测试，发现修饰后的铂微电极电化学阻抗明显降低，CV扫描对一些电活性物质及溶解氧的响应电流从40μA增大道130μA，峰位明显正移；然后对纳米级修饰后制作的Clark溶解氧电极进行了相关溶解氧的测试，回路中的电流信号有显著的提高，达到几十微安，其对溶解氧的电催化性能增强。
表明该溶解氧微电极经过纳米级修饰，其对溶解氧测定的电化学活性和灵敏度都有明显的提高。同时，由于该微电极检测时所得信号是电信号，不需要繁琐的信号转换，因此可以用于制作小型化的溶解氧传感器。
With the appearance of water problem, people pay more attention to theprotection of water resource. Dissolved oxygen, which is an important parameter ofwater self-depuration capability, is always a significant part of water detection. Thereare many traditional DO detection methods which make the detection inconvenientdue to some disadvantages such as complicated detection structures, expensive cost,not be used for continuously in-situ detection and so on. Therefore, it is a trend for usto research small size and handheld DO detection instrument. In this dissertation, onthe basis of Clark principle for DO detection, we take advantage of MEMStechnology to fabricate two parallel microelectrodes. Then we successfully makeClark DO sensor microelectrodes through modifying surface and carry out somerelative electrochemistry tests that indicate the response of DO strengthens. The topicsof this dissertation are discussed as follows:
1. Design and fabrication of microelectrode. On the basis of microelectrodesuperiority, we designed the microelectrode pattern. Through MEMS and plasmatechnology, we fabricated Pt microelectrode which was deposited by aluminum film.
2. The modification for the surface of microelectrode. The anticathode of DO sensormicroelectrode is an Ag-AgCl electrode which was prepared by CV electrochemicaldeposition of Ag and treatment of HCl; the aluminum film on the Pt cathode wasprepared under30V by anodization and the curve of current-time. Finally,electrochemical deposition of Pt was carried out through porous alumina templateabove.
3. The test of microelectrode. According to the microelectrode before and afternano-modification, we carried out some relative electrochemistry test. It is foundout that electrochemical impedance of nano-modified microelectrode reducedobviously and the response current for DO improved dramatically, from40μA to130μA. Then we detected DO using nano-modified Clark DO electrode. The currentsignal was improved evidently relative to un-modified DO electrode.
It was proved that through nano-modified DO microelectrode, theelectrochemistry activation and sensitivity enhance obviously. In addition, thedetection signal is direct electrical signal that complicated signal conversion is notneeded, and the DO microelectrodes can be used for miniaturized DO sensor.
引文
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