Understanding and tuning the ligand shell composition in colloidal halide perovskite
nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while
much less is known on the surface of Pb-free perovskite systems. Here, we reveal the
ligand shell architecture of Bi-doped
Cs
2
Ag
1–
x
Na
x
InCl
6
NCs
via nuclear magnetic resonance analysis. This material, in its bulk form, was found to
have a photoluminescence quantum yield (PLQY) as high as 86%, a record value for halide
double perovskites. Our results show that both amines and carboxylic acids are present
and homogeneously distributed over the surface of the NCs. Notably, even for an
optimized surface ligand coating, achieved by combining dodecanoic acid and decylamine,
a maximum PLQY value of only 37% is reached, with no further improvements observed when
exploiting post-synthesis ligand exchange procedures (involving Cs-oleate, different
ammonium halides, thiocyanates and sulfonic acids). Our density functional theory
calculations indicate that, even with the best ligands combination, a small fraction of
unpassivated surface sites, namely undercoordinated Cl ions, is sufficient to create
deep trap states, opposite to the case of Pb-based perovskites that exhibit much higher
defect tolerance. This was corroborated by our transient absorption measurements, which
showed that an ultrafast trapping of holes (most likely mediated by surface Cl-trap
states) competes with their localization at the AgCl
6
octahedra, from where,
instead, they can undergo an optically active recombination yielding the observed PL
emission. Our results highlight that alternative surface passivation strategies should
be devised to further optimize the PLQY of double perovskite NCs, which might include
their incorporation inside inorganic shells.