Yamanoi Yoshinori, Shirahata Naoto, Yonezawa Tetsu, Terasaki Nao, Yamamoto Noritaka, Matsui Yoshitaka, Nishio Kazuyuki, Masuda Hideki, Ikuhara Yuichi, Nishihara Hiroshi
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Chemistry. 2005 Dec 16;12(1):314-23. doi: 10.1002/chem.200500455.
The modification of flat semiconductor surfaces with nanoscale materials has been the subject of considerable interest. This paper provides detailed structural examinations of gold nanoparticles covalently immobilized onto hydrogen-terminated silicon surfaces by a convenient thermal hydrosilylation to form Si-C bonds. Gold nanoparticles stabilized by omega-alkene-1-thiols with different alkyl chain lengths (C3, C6, and C11), with average diameters of 2-3 nm and a narrow size distribution were used. The thermal hydrosilylation reactions of these nanoparticles with hydrogen-terminated Si(111) surfaces were carried out in toluene at various conditions under N2. The obtained modified surfaces were observed by high-resolution scanning electron microscopy (HR-SEM). The obtained images indicate considerable changes in morphology with reaction time, reaction temperature, as well as the length of the stabilizing omega-alkene-1-thiol molecules. These surfaces are stable and can be stored under ambient conditions for several weeks without measurable decomposition. It was also found that the aggregation of immobilized particles on a silicon surface occurred at high temperature (> 100 degrees C). Precise XPS measurements of modified surfaces were carried out by using a Au-S ligand-exchange technique. The spectrum clearly showed the existence of Si-C bonds. Cross-sectional HR-TEM images also directly indicate that the particles were covalently attached to the silicon surface through Si-C bonds.
用纳米级材料对平面半导体表面进行修饰一直是备受关注的课题。本文详细研究了通过便捷的热硅氢化反应将金纳米颗粒共价固定在氢终止的硅表面上以形成Si-C键的情况。使用了由不同烷基链长度(C3、C6和C11)的ω-烯烃-1-硫醇稳定的金纳米颗粒,其平均直径为2-3nm且尺寸分布狭窄。这些纳米颗粒与氢终止的Si(111)表面的热硅氢化反应在氮气氛围下于甲苯中在各种条件下进行。通过高分辨率扫描电子显微镜(HR-SEM)观察得到的修饰表面。所获得的图像表明,随着反应时间、反应温度以及稳定化的ω-烯烃-1-硫醇分子的长度不同,形态发生了显著变化。这些表面是稳定的,可在环境条件下储存数周而无明显分解。还发现固定在硅表面的颗粒在高温(>100℃)下会发生聚集。通过使用金-硫配体交换技术对修饰表面进行了精确的XPS测量。光谱清楚地显示了Si-C键的存在。横截面HR-TEM图像也直接表明颗粒通过Si-C键共价连接到硅表面。