Department of Chemistry and ‡Department of Materials Science and Engineering, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.
J Am Chem Soc. 2014 Apr 2;136(13):5106-15. doi: 10.1021/ja500871j. Epub 2014 Mar 24.
We have developed a generalized seeded-growth methodology for the synthesis of monodisperse metal-doped plasmonic oxide heterodimer nanocrystals (NCs) with a near-unity morphological yield. Using indium-doped cadmium oxide (ICO) as an example, we show that a wide variety of preformed metal NCs (Au, Pt, Pd, FePt, etc.) can serve as the seeds for the tailored synthesis of metal-ICO heterodimers with exquisite size, shape, and composition control, facilitated by the delayed nucleation mechanism of the CdO phase. The metal-ICO heterodimers exhibit broadly tunable near-infrared localized surface plasmon resonances, and dual plasmonic bands are observed for Au-ICO heterodimers. We further demonstrate that the oxide domain of the Au-ICO heterodimers can be selectively and controllably transformed into a series of partially and completely hollow cadmium chalcogenide nanoarchitectures with unprecedented structural complexity, leaving the metal domain intact. Our work not only represents an exciting addition to the rapidly expanding library of chemical reactions that produce colloidal hybrid NCs, but it also provides a general route for the bottom-up chemical design of multicomponent metal-oxide-semiconductor NCs in a rational and sequential manner.
我们开发了一种通用的种子生长方法,用于合成具有近 100%形态产率的单分散金属掺杂等离子体氧化物异质二聚体纳米晶体(NCs)。以掺铟氧化镉(ICO)为例,我们表明,各种预先形成的金属 NC(金、铂、钯、FePt 等)可以作为种子,通过 CdO 相的延迟成核机制,实现具有精致尺寸、形状和组成控制的金属-ICO 异质二聚体的定制合成。金属-ICO 异质二聚体表现出广泛可调谐的近红外局域表面等离子体共振,并且对于 Au-ICO 异质二聚体观察到双等离子体带。我们进一步证明,Au-ICO 异质二聚体的氧化物域可以选择性和可控地转化为一系列具有前所未有的结构复杂性的部分和完全空心的镉硫属化物纳米结构,而金属域保持完整。我们的工作不仅代表了在产生胶体杂化 NCs 的快速扩展的化学反应库中令人兴奋的补充,而且还为以合理和顺序的方式,从下至上设计多组分金属-氧化物-半导体 NCs 提供了一种通用途径。