RESUMEN
Quantum dot (QD) solids are emerging materials for many optoelectronic applications. To enhance interdot coupling and charge transport, surface ligands can be removed, allowing individual QDs to be attached along specific crystal orientations (termed "oriented attachment"). Optimizing the electronic and optical properties of QD solids demands a comprehensive understanding of the nanoscale energy flow in individual and attached QDs under photoexcitation. In this work, we employed ultrafast electron diffraction to directly measure how oriented attachment along ⟨100⟩ directions affects the nonequilibrium lattice dynamics of lead selenide QDs. The oriented attachment anisotropically alters the ultrafast energy relaxation along specific crystal axes. Along the ⟨100⟩ directions, both the lattice deformation and atomistic random motions are suppressed in comparison with those of individual QDs. Conversely, the effects are enhanced along the unattached ⟨111⟩ directions due to ligand removal. The oriented attachment switches the major lattice thermalization pathways from ⟨100⟩ to ⟨111⟩ directions.
RESUMEN
In addition to long-range periodicity, local disorder, with local structures deviating from the average lattice structure, dominates the physical properties of phonons, electrons, and spin subsystems in crystalline functional materials. Experimentally characterizing the 3D atomic configuration of such a local disorder and correlating it with advanced functions remains challenging. Using a combination of femtosecond electron diffraction, structure factor calculations, and time-dependent density functional theory molecular dynamics simulations, the static local disorder and its local anharmonicity in thermoelectric SnSe are identified exclusively. The ultrafast structural dynamics reveal that the crystalline SnSe is composed of multiple locally correlated configurations dominated by the static off-symmetry displacements of Sn (≈0.4 Å) and such a set of locally correlated structures is termed local disorder. Moreover, the anharmonicity of this local disorder induces an ultrafast atomic displacement within 100 fs, indicating the signature of probable THz Einstein oscillators. The identified local disorder and local anharmonicity suggest a glass-like thermal transport channel, which updates the fundamental insight into the long-debated ultralow thermal conductivity of SnSe. The method of revealing the 3D local disorder and the locally correlated interactions by ultrafast structural dynamics will inspire broad interest in the construction of structure-property relationships in material science.
RESUMEN
A thorough understanding of the photocarrier relaxation dynamics in semiconductor quantum dots (QDs) is essential to optimize their device performance. However, resolving hot carrier kinetics under high excitation conditions with multiple excitons per dot is challenging because it convolutes several ultrafast processes, including Auger recombination, carrier-phonon scattering, and phonon thermalization. Here, we report a systematic study of the lattice dynamics induced by intense photoexcitation in PbSe QDs. By probing the dynamics from the lattice perspective using ultrafast electron diffraction together with modeling the correlated processes collectively, we can differentiate their roles in photocarrier relaxation. The results reveal that the observed lattice heating time scale is longer than that of carrier intraband relaxation obtained previously using transient optical spectroscopy. Moreover, we find that Auger recombination efficiently annihilates excitons and speeds up lattice heating. This work can be readily extended to other semiconductor QDs systems with varying dot sizes.