Yan Chang, Byrne Dana, Ondry Justin C, Kahnt Axel, Moreno-Hernandez Ivan A, Kamat Gaurav A, Liu Zi-Jie, Laube Christian, Crook Michelle F, Zhang Ye, Ercius Peter, Alivisatos A Paul
Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Sci Adv. 2022 Aug 12;8(32):eabq1700. doi: 10.1126/sciadv.abq1700. Epub 2022 Aug 10.
The size and shape of semiconductor nanocrystals govern their optical and electronic properties. Liquid cell transmission electron microscopy (LCTEM) is an emerging tool that can directly visualize nanoscale chemical transformations and therefore inform the precise synthesis of nanostructures with desired functions. However, it remains difficult to controllably investigate the reactions of semiconductor nanocrystals with LCTEM, because of the highly reactive environment formed by radiolysis of liquid. Here, we harness the radiolysis processes and report the single-particle etching trajectories of prototypical semiconductor nanomaterials with well-defined crystalline facets. Lead selenide nanocubes represent an isotropic structure that retains the cubic shape during etching via a layer-by-layer mechanism. The anisotropic arrow-shaped cadmium selenide nanorods have polar facets terminated by either cadmium or selenium atoms, and the transformation trajectory is driven by etching the selenium-terminated facets. LCTEM trajectories reveal how nanoscale shape transformations of semiconductors are governed by the reactivity of specific facets in liquid environments.
半导体纳米晶体的尺寸和形状决定了它们的光学和电子性质。液池透射电子显微镜(LCTEM)是一种新兴工具,它可以直接观察纳米级的化学转变,从而为精确合成具有所需功能的纳米结构提供信息。然而,由于液体辐射分解形成的高反应性环境,利用LCTEM可控地研究半导体纳米晶体的反应仍然很困难。在这里,我们利用辐射分解过程,报告了具有明确晶面的典型半导体纳米材料的单粒子蚀刻轨迹。硒化铅纳米立方体代表一种各向同性结构,在通过逐层机制蚀刻过程中保持立方形状。各向异性的箭形硒化镉纳米棒具有由镉或硒原子终止的极性晶面,其转变轨迹是由蚀刻硒终止的晶面驱动的。LCTEM轨迹揭示了半导体的纳米级形状转变是如何由液体环境中特定晶面的反应性所决定的。