Mark T. Lusk

Nanoengineering defect structures on graphene.

We present a new way of nanoengineering graphene by using defect domains. These regions have ring structures that depart from the usual honeycomb lattice, though each carbon atom still has three nearest neighbors. A set of stable domain structures is identified by using density functional theory, including blisters, ridges, ribbons, and metacrystals. All such structures are made solely out of carbon; the smallest encompasses just 16 atoms. Blisters, ridges, and metacrystals rise up out of the sheet, while ribbons remain flat. In the vicinity of vacancies, the reaction barriers to formation are sufficiently low that such defects could be synthesized through the thermally activated restructuring of coalesced adatoms.

Graphene nanoengineering and the inverse Stone-Thrower-Wales defect

We analyze a new fundamental building block for monolithic nanoengineering on graphene: the Inverse-Stone-Thrower-Wales (ISTW) defect. The ISTW is formed from a pair of joined pentagonal carbon rings placed between a pair of heptagonal rings; the well-known Stone-Thrower-Wales (STW) defect is the same arrangement, but with the heptagonal rather than pentagonal rings joined. When removed and passivated with hydrogen, the structure constitutes a new molecule, diazulene, which may be viewed as the result of an ad-dimer defect on anthracene. Embedding diazulene in the honeycomb lattice, we study the effect of ad-dimers on planar graphene. Because the ISTW defect has yet to be experimentally identified, we examine several synthesis routes and find one for which the barrier is only slightly higher than that associated with adatom hopping on graphene. ISTW and STW defects may be viewed as fundamental building blocks for monolithic structures on graphene. We show how to construct extended defect domains on the surface of graphene in the form of blisters, bubbles, and ridges on a length scale as small as 2 angstroms by 7 angstroms. Our primary tool in these studies is density functional theory.

Defect engineering: Graphene gets designer defects

An extended one-dimensional defect that has the potential to act as a conducting wire has been embedded in another perfect graphene sheet.

Numerical simulation of ultrasonic wave propagation in anisotropic and attenuative solid materials

The axisymmetric elastodynamic finite element code developed is capable of predicting quantitatively accurate displacement fields for elastic wave propagation in isotropic and transversely isotropic materials. The numerical algorithm incorporates viscous damping by adding a time-dependent tensor to Hookes law. Amplitude comparisons are made between the geometric attenuation in the far field and the corresponding finite element predictions to investigate the quality and validity of the code. Through-transmission experimental measurements made with a 1 MHz L-wave transducer attached to an aluminum sample support the code predictions. The algorithm successfully models geometric beam spreading dispersion and energy absorption due to viscous damping. This numerical model is a viable tool for the study of elastic wave propagation in nondestructive testing applications.<<ETX>>

Size Dependence of the Multiple Exciton Generation Rate in CdSe Quantum Dots

The multiplication rates of hot carriers in CdSe quantum dots are quantified using an atomistic pseudopotential approach and first-order perturbation theory. We consider both the case of an individual carrier (electron or hole) decaying into a trion and the case of an electron-hole pair decaying into a biexciton. The dependence on quantum dot volume of multiplication rate, density of final states, and effective Coulomb interaction are determined. We show that the multiplication rate of a photogenerated electron-hole pair decreases with dot size for a given absolute photon energy. However, if the photon energy is rescaled by the volume-dependent optical gap, then smaller dots exhibit an enhancement in carrier multiplication rate for a given relative photon energy. We find that holes have much higher multiplication rates than electrons of the same excess energy due to the larger density of final states (positive trions). When electron-hole pairs are generated by photon absorption, however, the net carrier multiplication rate is dominated by electrons because they have much higher excess energy on average. We also find, contrary to earlier studies, that the effective Coulomb coupling governing carrier multiplication is energy-dependent.

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.

Embedded ribbons of graphene allotropes: an extended defect perspective

Four fundamental dimer manipulations can be used to produce a variety of localized and extended defect structures in graphene. Two-dimensional templates result in graphene allotropes, here viewed as extended defects, which can exhibit either metallic or semiconducting electrical character. Embedded allotropic ribbons?i.e. thin swaths of the new allotropes?can also be created within graphene. We examined these ribbons and found that they maintain the electrical character of their parent allotrope even when only a few atoms in width. Such extended defects may facilitate the construction of single atomic layer carbon circuitry.

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.

Synthesis of Group IV Clathrates for Photovoltaics

Although Si dominates the photovoltaics market, only two forms of Si have been thoroughly considered: amorphous Si and Si in the diamond structure ( d-Si). Silicon can also form in other allotropes, including clathrate structures. Silicon clathrates are inclusion compounds, which consist of an Si framework surrounding templating guest atoms (e.g., Na). After formation of the type II Na 24Si136 clathrate, the guest atoms can be removed (Si136), and the material transitions from degenerate to semiconducting behavior with a 1.9 eV direct band gap. This band gap is tunable in the range of 1.9-0.6 eV by alloying the host framework with Ge, enabling a variety of photovoltaic applications that include thin-film single-junction devices, Si136 top cells on d-Si for all-Si tandem cells, and multijunction cells with varying Si/Ge ratios. In this study, we present electronic structure calculations that show the evolution of the direct transition as a function of Si/Ge ratio across the alloy range. We demonstrate the synthesis of type II Si/Ge clathrates spanning the whole alloy range. We also demonstrate a technique for forming Si clathrate films on d-Si wafers and sapphire substrates.

Simulating Distortion and Residual Stresses in Carburized Thin Strips

This paper illustrates the application of a new multiphase material model for simulating distortion and residual stresses in carburized and quenched gear steels. Simulation is focused on thin, metallic strips that are heat treated to introduce a through-thickness carbon gradient. Because the material properties are strongly dependent on the carbon content. quenching causes significant transverse out-of-plane distortion. The material model accounts for a multiphase alloy structure where inelasticity in the individual phases is temperature and rate dependent. The model is fit to an extensive matrix of experimental data for low carbon steels (0.2-0.8 percent) whose transformation kinetics and mechanical response are similar to 4023 and 4620 alloys used in experiments. While residual stress data are limited, reasonable agreement with X-ray diffraction measurements was obtained. Comparisons of transverse deflections predicted numerically showed excellent agreement with those measured experimentally for all five thicknesses reported. Accurate transformation and lattice carburization strains are critical to correctly predict the sense and magnitude of these transverse distortions and in-plane residual stresses.