Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 637371, Singapore.
Nanoscale. 2013 Jul 21;5(14):6404-12. doi: 10.1039/c3nr00981e. Epub 2013 Jun 6.
Interfacial self-assembly of nanoparticles is capable of creating large-area close-packed structures for a variety of applications. However, monolayers of hydrophilic cetyltrimethylammonium bromide (CTAB)-coated Au nanoparticles are challenging to assemble via interfacial self-assembly. This report presents a facile and scalable process to fabricate large-area monolayer films of ultrathin CTAB-coated Au nanoprisms at the air-water interface using the Langmuir-Schaefer technique. This is first achieved by a one-step functionalization of Au nanoprisms with poly(vinylpyrrolidone) (PVP). PVP functionalization is completed within a short time without loss of nanoprisms due to aggregation. Uniform and near close-packed monolayers of the Au nanoprisms formed over large areas (∼1 cm(2)) at the air-water interface can be transferred to substrates with different wettabilities. The inter-prism gaps are tuned qualitatively through the introduction of dodecanethiol and oleylamine. The morphological integrity of the nanoprisms is maintained throughout the entire assembly process, without truncation of the nanoprism tips. The near close-packed arrangement of the nanoprism monolayers generates large numbers of hot spots in the 2D arrays in the tip-to-tip and edge-to-edge inter-particle regions, giving rise to strong surface-enhanced Raman scattering (SERS) signals. When deposited on an Au mirror film, additional hotspots are created in the 3(rd) dimension in the gaps between the 2D nanoprism monolayers and the Au film. SERS enhancement factors reaching 10(4) for non-resonant probe molecules are achieved.
纳米粒子的界面自组装能够为各种应用创造大面积的密堆积结构。然而,亲水十六烷基三甲基溴化铵(CTAB)包覆的 Au 纳米粒子的单层通过界面自组装进行组装是具有挑战性的。本报告提出了一种简便且可扩展的工艺,使用 Langmuir-Schaefer 技术在空气-水界面制备大面积的超薄 CTAB 包覆的 Au 纳米棱柱单层膜。这是通过 Au 纳米棱柱的一步聚(乙烯基吡咯烷酮)(PVP)功能化首次实现的。PVP 功能化在短时间内完成,不会因聚集而导致纳米棱柱损失。Au 纳米棱柱在空气-水界面上形成的大面积(约 1cm²)均匀且近乎密堆积的单层可以转移到具有不同润湿性的基底上。通过引入十二硫醇和油胺可以定性地调节棱柱间的间隙。在整个组装过程中,纳米棱柱的形态完整性得以保持,而不会截断纳米棱柱的尖端。纳米棱柱单层的近乎密堆积排列在尖端到尖端和颗粒间边缘到边缘的粒子区域中产生大量热点,从而产生强烈的表面增强拉曼散射(SERS)信号。当沉积在 Au 镜膜上时,在二维纳米棱柱单层和 Au 膜之间的间隙中,在 3 维(rd)中会产生额外的热点。对于非共振探针分子,实现了 10^4 的 SERS 增强因子。