Disorder and Halide Distributions in Cesium Lead Halide Nanocrystals as Seen by Colloidal 133Cs Nuclear Magnetic Resonance Spectroscopy

Colloidal nuclear magnetic resonance (cNMR) spectroscopy on inorganic cesium lead halide nanocrystals (CsPbX3 NCs) is found to serve for noninvasive characterization and quantification of disorder within these structurally soft and labile particles. In particular, we show that Cs-133 cNMR is highly responsive to size variations from 3 to 11 nm or to altering the capping ligands on the surfaces of CsPbX3 NCs. Distinct Cs-133 signals are attributed to the surface and core NC regions. Increased heterogeneous broadening of Cs-133 signals, observed for smaller NCs as well as for long-chain zwitterionic capping ligands (phosphocholines, phosphoethanol(propanol)amine, and sulfobetaines), can be attributed to more significant surface disorder and multifaceted surfaces (truncated cubes). On the contrary, capping with dimethyl-didodecyl-ammonium bromide (DDAB) successfully reduces signal broadening owing to better surface passivation and sharper (001)-bound cuboid shape. DFT calculations on various sizes of NCs corroborate the notion that the surface disorder propagates over several octahedral layers. Cs-133 NMR is a sensitive probe for studying halide gradients in mixed Br/Cl NCs, indicating bromide-rich surfaces and chloride-rich cores. On the contrary, mixed Br/I NCs exhibit homogeneous halide distributions.