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硅纳米线阵列的制备及其在生化传感器中的应用

Preparation of the Silicon Nanowires Array and Its Application in Chemical and Biological Sensors

【作者】 万丽娟

【导师】 张健;

【作者基本信息】 华东师范大学 , 微电子学与固体电子学, 2010, 博士

【摘要】 硅纳米线以其进入纳米尺度后所具有的独特的半导体性质与发展为各式纳米元件的极大潜力,受到学术界越来越多的关注。在本论文的第一部分中,针对利用“无电电镀”方法制备硅纳米线的形成机制的说法不统一的现状,我们从研究硅纳米线的形成机理入手,通过对无电电镀和伽伐尼置换两个概念的分析,借鉴其他小组的某些观点和经过大量的实验验证,提出一种新的硅纳米线的形成机制。在该机制中,伽伐尼置换过程中形成的金属-绝缘体-半导体(MIS)结构对硅纳米线阵列的形成起到至关重要的作用。MIS结构是一个动态平衡的过程,贵金属离子和HF溶液分别起到增厚和减薄二氧化硅层的作用。第二部分,考虑到以往的硅纳米线刻蚀需要在高温、高压等严苛的实验条件下进行,我们通过对实验条件的改进,在室温、常压等常态的实验条件下,成功地制备了线径均匀和垂直排布于硅衬底的硅纳米线阵列;同时,通过研究各实验条件对形成硅纳米线的影响,得到优化的制备硅纳米线阵列的实验条件。结合实验结果,对硅纳米线形成机理做进一步探讨,证实了第一部分中提出的机制的正确性。第三部分,为了实现硅纳米线阵列在微纳器件中的应用,我们通过把微电子加工工艺与伽伐尼置换相结合的方法,采用氮化硅做掩膜,成功地获得了图形化的硅纳米线。通过在氮化硅抗蚀能力之内,改变刻蚀时间的影响,得到优化的实验条件。另外,利用流体力学理论解释了图形化对形成硅纳米线长度的影响。最后,通过在硅纳米线阵列的表面修饰普鲁士蓝分子,制成了普鲁士蓝/硅纳米线电极,通过在三电极系统中把该电极应用到对过氧化氢的电化学行为方面的研究,发现该电极对过氧化氢有很好的催化响应能力,有制成生化传感器的希望。

【Abstract】 Recently, due to the unique semiconductor properties characteristics and the great potentials for developing various nano-devices such as nanoelectronics and nanosensors, silicon nanowires have attracted more and more attention.There exists a controversy about the formation mechanism of silicon nanowires (SiNWs) prepared by a chemical etching method assisted by metal ions (such as Ag+) in hydrogen fluoride-contained solution. To begin with, we discussed the difference between eletroless plating with galvanic displacement which is commonly adapted by others researches in the process of the SiNWs array preparation in HF solution containing noble metal ions.Firstly, a metal-insulator-semiductor (MIS) like structure had been put forward to explain the SiNWs array formation in the beginning of the thesis. In the galvanic displacement process, on one hand, the metal ions in the solution can extract the electrons from the silicon substrate and be reduced into metal nanoparticles or metal nanoclusters via the galvanic displacement. On the other hand, silicon substrates lose the electrons and are oxidized to silicon dioxide (SiO2). The reduced metal partcles located on the silicon oxide surface form the MIS-like structure. Hydrogen fluoride-contained solution will dissolve the silicon dioxide without metal covered and lead to the etching process to take place.Secondly, we succeeded in preparing the vertically aligned large-area SiNWs array in HF solution containing noble metal ions under the normal conditions (room temperature, latm.). Its expremental process is simple and the cost is decreased comparing with the the rigid experimental conditions, such as high temperature, high pressure, etc. in the previous literatures. Moreover, the optimal experimental parameters of prepaing SiNWs array are obtained by discussing the influence of various experimental conditions. These results further confirm that it is correct about the obove mentioned formation mechanism of SiNWs.Thirdly, in order to carry out the application in micro-and nano-devices and IC, the patterned SiNWs array is obtained by combining the pholithagraphy technology with chemical etching method. The silicon nitride layer is used as a mask. For silicon nitride layer will be etched away for a long etching time, we discuss the influence of etching time and obtain the optimal parameters during the process of prepaing SiNWs array. In addition, considering of the influence of patterns on the SiNWs etching, we put forward a fluid dynamics theory.Finally, the Prussian blue/silicon nanowires (PB/SiNWs) electrode is constructed successfully by modifying Prussian blue molecules on the surface of patterned SiNWs array. The electrochemical characteristic of this electrode was investigated by detecting hydrogen peroxide (H2O2) as a working electrode in a three-electrode electrochemical system. The results demonstrate that the electrode has an excellent catalytic resonse to H2O2 and is potential for electrochemical biosensors.

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