Grillo Fabio, La Zara Damiano, Mulder Paul, Kreutzer Michiel T, Ruud van Ommen J
Department of Chemical Engineering, Delft University of Technology, 2629 HZ Delft, The Netherlands.
J Phys Chem C Nanomater Interfaces. 2018 Aug 30;122(34):19981-19991. doi: 10.1021/acs.jpcc.8b05572. Epub 2018 Aug 2.
Understanding the spontaneous organization of atoms on well-defined surfaces promises to enable control over the shape and size of supported nanostructures. Atomic layer deposition (ALD) boasts atomic-scale control in the synthesis of thin films and nanoparticles. Yet, the possibility to control the shape of ALD-grown nanostructures remains mostly unexplored. Here, we report on the bottom-up formation of both linear and V-shaped anatase TiO nanorods (NRs) on graphene nanoplatelets during TiCl/HO ALD carried out at 300 °C. NRs as large as 200 nm form after only five ALD cycles, indicating that diffusional processes rather than layer-by-layer growth are behind the NR formation. In particular, high-resolution transmission electron microscopy reveals that the TiO NRs and graphene nanoplatelets are in rotational alignment as a result of lattice matching. Crucially, we also show that individual nanocrystals can undergo in-plane oriented attachment.
了解原子在明确界定的表面上的自发组织,有望实现对负载型纳米结构的形状和尺寸的控制。原子层沉积(ALD)在薄膜和纳米颗粒的合成中具有原子尺度的控制能力。然而,控制ALD生长的纳米结构形状的可能性仍大多未被探索。在此,我们报道了在300°C下进行的TiCl₄/H₂O ALD过程中,在石墨烯纳米片上自下而上形成线性和V形锐钛矿TiO₂纳米棒(NRs)的情况。仅经过五个ALD循环就形成了长达200 nm的NRs,这表明扩散过程而非逐层生长是NR形成的原因。特别是,高分辨率透射电子显微镜显示,由于晶格匹配,TiO₂ NRs与石墨烯纳米片呈旋转对齐。至关重要的是,我们还表明单个纳米晶体可以进行面内取向附着。