Reversible Facet Reconstruction of CdSe/CdS Core/Shell Nanocrystals by Facet–Ligand Pairing
Hairui Lei, Tenghui Li, Jiongzhao Li, Jie Zhu, Haibing Zhang, Haiyan Qin, Xueqian Kong, Linjun Wang, Xiaogang Peng
Abstract
Synthesis of colloidal semiconductor nanocrystals with defined facet structures is challenging, though such nanocrystals are essential for fully realizing their size-dependent optical and optoelectronic properties. Here, for the mostly developed colloidal wurtzite CdSe/CdS core/shell nanocrystals, facet reconstruction is investigated under typical synthetic conditions, excluding nucleation, growth, and interparticle ripening. Within the reaction time window, two reproducible sets of facets─each with a specific group of low-index facets─can be reversibly reconstructed by switching the ligand system, indicating thermodynamic stability of each set. With a unique <0001> axis, atomic structures of the low-index facets of wurtzite nanocrystals are diverse. Experimental and theoretical studies reveal that each facet in a given set is paired with a common ligand in the solution, namely, either fatty amine and/or cadmium alkanoate. The robust bonding modes of ligands are found to be strongly facet-dependent and often unconventional, instead of following Green's classification. Results suggest that facet-controlled nanocrystals can be synthesized by optimal facet-ligand pairing either in synthesis or after-synthesis reconstruction, implying semiconductor nanocrystal formation with size-dependent properties down to an atomic level.