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A Comparative Study Of The Growth Of Octadecyltrichlorosilane And 3-mercaptopropyltrimethoxysilane Self-assembled Monolayers On Hydrophilic Silicon Surfaces

机译:亲水硅表面上十八烷基三氯硅烷和3-巯基丙基三甲氧基硅烷自组装单分子膜的生长比较研究

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摘要

Self-assembled monolayers of two different organosilane precursors, methyl-terminated nonpolar n-octadecyltrichlorosilane(OTS, Cl_3Si(CH_2)_(17)CH_3) and thiol-terminated polar 3-mercaptopropyltrimethox-ysilane (MPTMS, (CH_3O)_3SiCH_2CH_2CH_2SH), were prepared separately on hydrophilic silicon surfaces by immersion in millimolar solutions of the respective precursors in toluene at room temperature. Ex situ atomic force microscopy (AFM), lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to study the growth and the properties of OTS and MPTMS SAMs. For OTS SAMs, generally speaking, small islands surrounded large dendrite-shaped islands. But for MPTMS SAMs, sporadic small round islands appeared, but no dendrites. The impact of the solution age was more significant on the growth of OTS SAMs than MPTMS SAMs. At the same precursor concentration and solution age, the growth of OTS SAMs was much faster than MPTMS SAMs due to the greater hydrolysis ability of Si-Cl bonds in OTS as compared with that of Si-OCH_3 bonds in MPTMS. The difference in hydrolysis ability was confirmed by the absence of a Cl signal in the XP spectrum of OTS SAMs and the existence of a C_(1s) peak corresponding to unhydrolyzed Si-OCH_3 bonds in the XP spectrum of MPTMS SAMs. This trend together with the difference in alkyl chain length had a strong influence on the surface morphology and coverage of these two SAMs. According to the individual adsorption behavior of the components, the predictable kinetic difficulty of preparing OTS/MPTMS mixed SAMs by co-adsorption is pointed out. Furthermore, a potential reaction condition for stepwise adsorption is suggested.
机译:两种不同有机硅烷前体的自组装单层,分别是甲基封端的非极性正十八烷基三氯硅烷(OTS,Cl_3Si(CH_2)_(17)CH_3)和硫醇封端的极性3-巯基丙基三甲氧基-硅烷(MPTMS,(CH_3O)_3SiCH_2CH_2CH_2SH)通过在室温下将各前体的毫摩尔溶液浸入甲苯中而在亲水性硅表面上分别制备。利用异位原子力显微镜(AFM),横向力显微镜(LFM)和X射线光电子能谱(XPS)来研究OTS和MPTMS SAM的生长及其性能。一般来说,对于OTS SAM,小岛包围着大树状的岛。但是对于MPTMS SAM,出现了零星的小圆形岛,但没有树突。解决方案年龄的影响对OTS SAM的增长比MPTMS SAM更为重要。在相同的前体浓度和溶液年龄下,由于OTS中Si-Cl键的水解能力比MPTMS中Si-OCH_3键的水解能力强,因此OTS SAMs的生长比MPTMS SAMs快得多。通过在OTS SAM的XP光谱中没有Cl信号和在MPTMS SAM的XP光谱中存在对应于未水解的Si-OCH_3键的C_(1s)峰,可以确认水解能力的差异。这种趋势以及烷基链长度的差异对这两种SAM的表面形态和覆盖率都有很大影响。根据组分的个别吸附行为,指出了通过共吸附制备OTS / MPTMS混合SAMs的可预测动力学困难。此外,提出了逐步吸附的潜在反应条件。

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