Huashan Li

Efficient Exciton Transport Between Strongly Quantum-Confined Silicon Quantum Dots

Many-body Green function analysis and first-order perturbation theory are used to quantify the influence of size, surface reconstruction, and surface treatment on exciton transport between small silicon quantum dots. Competing radiative processes are also considered in order to determine how exciton transport efficiency is influenced. The analysis shows that quantum confinement causes small (~1 nm) Si quantum dots to exhibit exciton transport efficiencies far exceeding that of their larger counterparts for the same center-to-center separation. This surprising result offers the prospect of designing assemblies of quantum dots through which excitons can travel for long distances, a game-changing paradigm shift for next-generation solar energy harvesting. We also find that surface reconstruction significantly influences the absorption cross section and leads to a large reduction in both transport rate and efficiency. Further, exciton transport efficiency is higher for hydrogen-passivated dots as compared with those terminated with more electronegative ligands, a result not predicted by Förster theory.

Bandgap Tuning of Silicon Quantum Dots by Surface Functionalization with Conjugated Organic Groups.

The quantum confinement and enhanced optical properties of silicon quantum dots (SiQDs) make them attractive as an inexpensive and nontoxic material for a variety of applications such as light emitting technologies (lighting, displays, sensors) and photovoltaics. However, experimental demonstration of these properties and practical application into optoelectronic devices have been limited as SiQDs are generally passivated with covalently bound insulating alkyl chains that limit charge transport. In this work, we show that strategically designed triphenylamine-based surface ligands covalently bonded to the SiQD surface using conjugated vinyl connectivity results in a 70 nm red-shifted photoluminescence relative to their decyl-capped control counterparts. This suggests that electron density from the SiQD is delocalized into the surface ligands to effectively create a larger hybrid QD with possible macroscopic charge transport properties.

Optimal size regime for oxidation-resistant silicon quantum dots.

First-principles computations have been carried out to predict that appropriately terminated silicon quantum dots with diameters in the range of 1.2-2 nm will offer a superb resistance to oxidation. This is because surface treatments can produce dangling bond defect densities sufficiently low that dots of this size are unlikely to have any defect at all. On the other hand, these dots are large enough that the severe angles between facets do not expose bonds that are vulnerable to subsequent oxygen attack. The absence of both surface defects and geometry-related vulnerabilities allows even very short passivating ligands to generate an effective barrier, an important consideration for charge and exciton transport within quantum dot assemblies. Our computations, which employ many-body perturbation theory using Green functions, also indicate that dots within this size regime have optical and electronic properties that are robust to small amounts of inadvertent oxidation, and that any such oxygen incorporation is essentially frozen in place.

First principles analysis of the initial oxidation of Si(001) and Si(111) surfaces terminated with H and CH3

Transition state analyses have been carried out within a density functional theory setting to explain and quantify the distinctly different ways in which hydrogen and methyl terminations serve to protect silicon surfaces from the earliest onset of oxidation. We find that oxidation occurs via direct dissociative adsorption, without any energy barrier, on Si(111) and reconstructed Si(001) that have been hydrogen terminated; oxidation initiates with a barrier of only 0.05 eV on unreconstructed Si(001). The commonly measured protection afforded by hydrogen is shown to derive from a coverage-dependent dissociation rate combined with barriers to the hopping of adsorbed oxygen atoms. Methyl termination, in contrast, offers an additional level of protection because oxygen must first undergo interactions with these ligands in a three-step process with significant energy barriers: adsorption of O(2) into a C-H bond to form a C-O-O-H intermediate; decomposition of C-O-O-H into C-O-H and C=O intermediates; and, finally, hopping of oxygen atoms from ligands to the substrate.

Double superexchange in quantum dot mesomaterials

A new optoelectronic mesomaterial is proposed in which a network of quantum dots is covalently connected via organic molecules. Optically generated excitons are rapidly dissociated with electrons subsequently hopping from dot to dot while holes transit via the connecting moieties. The molecules serve as efficient mediators for electron superexchange between the dots, while the dots themselves play the complementary role for hole transport between molecules. The network thus exhibits a double superexchange. In addition to enhancing carrier hopping rates, double superexchange plays a central role in mediating efficient polaron dissociation. Photoluminescence, dissociation, and transport dynamics are quantified from first-principles for a model system composed of small silicon quantum dots connected by organic moieties. The results demonstrate that double superexchange can be practically employed to significantly improve charge generation and transport. These are currently viewed as the critical obstacles to dramatic enhancements in the energy conversion efficiency of photovoltaic cells based on quantum dots.

Charge separation at nanoscale interfaces: Energy-level alignment including two-quasiparticle interactions

The universal and fundamental criteria for charge separation at interfaces involving nanoscale materials are investigated. In addition to the single-quasiparticle excitation, all the two-quasiparticle effects including exciton binding, Coulomb stabilization, and exciton transfer are considered, which play critical roles on nanoscale interfaces for optoelectronic applications. We propose a scheme allowing adding these two-quasiparticle interactions on top of the single-quasiparticle energy level alignment for determining and illuminating charge separation at nanoscale interfaces. Employing the many-body perturbation theory based on Greens functions, we quantitatively demonstrate that neglecting or simplifying these crucial two-quasiparticle interactions using less accurate methods is likely to predict qualitatively incorrect charge separation behaviors at nanoscale interfaces where quantum confinement dominates.