The widespread application of III-V colloidal quantum dots (QDs) as nontoxic, highly tunable emitters is stymied by their high density of trap states. Here, we utilize density functional theory (DFT) to investigate trap state formation in a diverse set of realistically passivated core-only InP and GaP QDs. Through orbital localization techniques, we deconvolute the dense manifold of trap states to allow for detailed assignment of surface defects. We find that the three-coordinate species dominate trapping in III-V QDs and identify features in the geometry and charge environment of trap centers capable of deepening, or sometimes passivating, traps. Furthermore, we observe stark differences in surface reconstruction between InP and GaP, where the more labile InP reconstructs to passivate three-coordinate indium at the cost of distortion elsewhere. These results offer explanations for experimentally observed trapping behavior and suggest new avenues for controlling trap states in III-V QDs.
Imposing quantum confinement has the potential to significantly modulate both the structural and optical parameters of interest in many material systems. In this work, we investigate strongly confined ultrathin perovskite nanoplatelets APbBr3. We compare the all-inorganic and hybrid compositions with the A-sites cesium and formamidinium, respectively. Compared to each other and their bulk counterparts, the materials show significant differences in variable-temperature structural and optical evolution. We quantify and correlate structural asymmetry with the excitonic transition energy, spectral purity, and emission rate. Negative thermal expansion, structural and photoluminescence asymmetry, photoluminescence full width at half-maximum, and splitting between bright and dark excitonic levels are found to be reduced in the hybrid composition. This work provides composition- and structure-based mechanisms for engineering of the excitons in these materials.
Mechanistic studies of the morphology of lead halide perovskite nanocrystals (LHP-NCs) are hampered by a lack of generalizable suitable synthetic strategies and ligand systems. Here, the synthesis of zwitterionic CsPbBr3 NCs is presented with controlled anisotropy using a proposed "surface-selective ligand pairs" strategy. Such a strategy provides a platform to systematically study the binding affinity of capping ligand pairs and the resulting LHP morphologies. By using zwitterionic ligands (ZwL) with varying structures, majority ZwL-capped LHP NCs with controlled morphology are obtained, including anisotropic nanoplatelets and nanorods, for the first time. Combining experiments with density functional theory calculations, factors that govern the ligand binding on the different surface facets of LHP-NCs are revealed, including the steric bulkiness of the ligand, the number of binding sites, and the charge distance between binding moieties. This study provides guidance for the further exploration of anisotropic LHP-NCs.
Quantum confined lead halide perovskite nanoplatelets are anisotropic materials displaying strongly bound excitons with spectrally pure photoluminescence. We report the controlled assembly of CsPbBr3 nanoplatelets through varying the evaporation rate of the dispersion solvent. We confirm the assembly of superlattices in the face-down and edge-up configurations by electron microscopy, as well as X-ray scattering and diffraction. Polarization-resolved spectroscopy shows that superlattices in the edge-up configuration display significantly polarized emission compared to face-down counterparts. Variable-temperature X-ray diffraction of both face-down and edge-up superlattices uncovers a uniaxial negative thermal expansion in ultrathin nanoplatelets, which reconciles the anomalous temperature dependence of the emission energy. Additional structural aspects are investigated by multilayer diffraction fitting, revealing a significant decrease in superlattice order with decreasing temperature, with a concomitant expansion of the organic sublattice and increase of lead halide octahedral tilt.
Zero strain insertion, high cycling stability, and a stable charge/discharge plateau are promising properties rendering Lithium Titanium Oxide (LTO) a possible candidate for an anode material in solid state Li ion batteries. However, the use of pristine LTO in batteries is rather limited due to its electronically insulating nature. In contrast, reduced LTO shows an electronic conductivity several orders of magnitude higher. Studying bulk reduced LTO, we could show recently that the formation of polaronic states can play a major role in explaining this improved conductivity. In this work, we extend our study toward the lithium-terminated LTO (111) surface. We investigate the formation of polarons by applying Hubbard-corrected density functional theory. Analyzing their relative stabilities reveals that positions with Li ions close by have the highest stability among the different localization patterns.
Lithium titanium oxide Li4Ti5O12 is an intriguing anode material promising particularly long-life batteries, due to its remarkable phase stability during (dis)charging of the cell. However, its usage is limited by its low intrinsic electronic conductivity. Introducing oxygen vacancies can be one method for overcoming this drawback, possibly by altering the charge carrier transport mechanism. We use Hubbard corrected density functional theory to show that polaronic states in combination with a possible hopping mechanism can play a crucial role in the experimentally observed increase in electronic conductivity. To gauge polaronic charge mobility, we compute the relative stabilities of different localization patterns and estimate polaron hopping barrier heights.
We implemented the popular Hubbard density-functional theory + U (DFT+U) method in its spherically averaged form in the all-electron, full-potential DFT code FHI-aims. There, electronic states are expressed on a basis of highly localized numeric atomic orbitals (NAO), which straightforwardly lend themselves as projector functions for the DFT+U correction, yielding the necessary occupations of the correlated Hubbard subspace at no additional cost. We establish the efficacy of our implementation on the prototypical bulk NiO and obtain the well-known band gap opening effect of DFT+U. As a more stringent, real world test system, we then study polaron formation at the rutile TiO2(110) surface, where our results are in line with both experimental data as well as hybrid functional calculations. At this TiO2 test system, yet in the bulk, we analyze some of the intricacies of using the DFT+U correction in a localized, numeric atomic orbital basis set. Specifically, we find that multiple localized radial basis functions of the same angular momentum can lead to highly erroneous predictions of ground-state properties. We also demonstrate a number of remedies to this problem. Finally, we highlight the critical influence of the exact choice of projector functions on DFT+U results using a number of projector functions of different spatial extent and composed of linear combinations of NAO basis functions. All of our efforts serve to highlight that, contrary to its deceptive ease of use, the DFT+U is far from the "black-box" approach it is sometimes made out to be.
