自上而下可控合成单分散金属纳米颗粒及其duv-lspr性能研究-study on top - down controllable synthesis of monodisperse metal nanoparticles and their duv - lspr properties.docxVIP

万方数据 万方数据 摘 要 金属纳米颗粒具有随形貌和尺寸显著变化的光、电、磁等物理化学性能，形 貌和尺寸的均一性——即单分散性对金属纳米颗粒的应用来讲至关重要。自下而 上的化学法是目前制备单分散金属纳米颗粒的主要方式。但这种方式通常需要高 反应活性的有机金属前驱体或强还原剂，且反应过程条件繁琐、污染较大，因此 开发一种自上而下的物理方式制备单分散金属纳米颗粒具有重要意义。 本文采用纳秒脉冲激光液相烧蚀/辐照法在常温常压下直接以金属靶材为原 料成功制备了单分散的胶体镉纳米颗粒，实现了 6.5-16.8nm 范围内的尺寸可控调 节，并研究了单分散镉纳米颗粒的形成机制。实验结果和相关热力学计算均表明， 胶体镉纳米颗粒通过激光选择性表面逐层气化的方式迅速从尺寸各异的多分散 体系变为尺寸统一的单分散体系，且最终尺寸可通过改变激光能量密度来调节。 另外，体系中作为表面活性剂的油酸在均匀化过程中也发挥了重要作用。该工艺 操作简单，环境友好，是一种快速高效的自上而下可控制备单分散胶体金属纳米 颗粒的方法。 此外，本文利用同样方法实现了单分散胶体锌纳米颗粒的可控制备，验证了 激光选择性表面逐层气化机制的正确性和普适性，并且成功以胶体锌纳米颗粒为 模板合成出硒化锌纳米空心球。 最后，本工作合成的单分散镉纳米颗粒在深紫外区域表现出较强的局域表面 等离子体共振特性，FDTD 数值仿真吸收谱与测试结果吻合，这表明单分散镉纳 米颗粒是一种潜在的高灵敏度生物分子探测的理想衬底材料。 关键词：激光辐照；单分散金属纳米颗粒；表面气化；局域表面等离子体共振 ABSTRACT Metal nanoparticles possess optical, electrical, magnetic, and other physical and chemical properties which will be significantly tunedt with the change of morphology and size uniformity. High uniformity in terms of shape and particle sizes, i.e., monodisperse, is critical to their applications. Chemical methods, bottom-up routes, are mainly adopted to synthesize monodisperse metal nanoparticles. However, it usually requires organometallic precursors with high reactivity or reducing agents, and the processes are complicated and contaminated. Therefore, the development of a top-down physical method to synthesize monodisperse metal nanoparticles is important. In this work, we converted directly bulky IIB metals to ligand-protected, highly crystalline, monodisperse spherical colloidal Cd nanoparticles with precisely controlled sizes (6.5–16.8 nm, size dispersion ?? 10%), using nanosecond pulsed laser ablation/irradiation in liquid. We have also studied formation mechanism of the monodisperse Cd nanoparticles. The experimental results and related thermodynamic calculations show that it is based on near-IR-laser-induced size-selectively layer-by-layer surface vaporization, and the size can controlled by laser fluence. In addition, the use of OA made a big difference in the process of homogenization. In