PbS Nanocrystals Made with Excess PbCl₂ Have an Intrinsic Shell that Reduces Their Stokes Shift

The use of excess PbCl₂ in the synthesis of PbS nanocrystals has become a convenient route to produce narrow-line-width infrared emitters. However, these materials have found limited adoption in optoelectronic devices-even compared to PbS nanocrystals prepared with lead oleate. Here, using both transmission electron microscopy and small-angle X-ray scattering, we show that excess PbCl₂ results in larger-diameter PbS nanocrystals for the same excitonic features, which is consistent with the formation of an intrinsic insulating shell. We observe further differences in excess-lead-chloride nanocrystals consistent with a shell, including lattice strain and smaller Stokes shifts for intermediate sizes (⌀: 4.8-6.8 nm) that match the passivation/rigidification predicted for a chloride-terminate surface. Our results clarify and rationalize the divergent properties of PbS nanocrystals prepared using different synthetic methodologies, give guidance for device implementation, and offer a new target for synthetic control.