H. Sevincli

Control of Thermal and Electronic Transport in Defect-Engineered Graphene Nanoribbons

The influence of the structural detail and defects on the thermal and electronic transport properties of graphene nanoribbons (GNRs) is explored by molecular dynamics and non-equilibrium Greens function methods. A variety of randomly oriented and distributed defects, single and double vacancies, Stone-Wales defects, as well as two types of edge form (armchair and zigzag) and different edge roughnesses are studied for model systems similar in sizes to experiments (>100 nm long and >15 nm wide). We observe substantial reduction in thermal conductivity due to all forms of defects, whereas electrical conductance reveals a peculiar defect-type-dependent response. We find that a 0.1% single vacancy concentration and a 0.23% double vacancy or Stone-Wales concentration lead to a drastic reduction in thermal conductivity of GNRs, namely, an 80% reduction from the pristine one of the same width. Edge roughness with an rms value of 7.28 Å leads to a similar reduction in thermal conductivity. Randomly distributed bulk vacancies are also found to strongly suppress the ballistic nature of electrons and reduce the conductance by 2 orders of magnitude. However, we have identified that defects close to the edges and relatively small values of edge roughness preserve the quasi-ballistic nature of electronic transport. This presents a route of independently controlling electrical and thermal transport by judicious engineering of the defect distribution; we discuss the implications of this for thermoelectric performance.

Enhanced thermoelectric figure of merit in edge-disordered zigzag graphene nanoribbons

We investigate electron and phonon transport through edge disordered zigzag graphene nanoribbons based on the same methodological tool of nonequilibrium Green functions. We show that edge disorder dramatically reduces phonon thermal transport while being only weakly detrimental to electronic conduction. The behavior of the electronic and phononic elastic mean free paths points to the possibility of realizing an electron-crystal coexisting with a phonon-glass. The calculated thermoelectric figure of merit (ZT) values qualify zigzag graphene nanoribbons as a very promising material for thermoelectric applications.

A bottom-up route to enhance thermoelectric figures of merit in graphene nanoribbons

We propose a hybrid nano-structuring scheme for tailoring thermal and thermoelectric transport properties of graphene nanoribbons. Geometrical structuring and isotope cluster engineering are the elements that constitute the proposed scheme. Using first-principles based force constants and Hamiltonians, we show that the thermal conductance of graphene nanoribbons can be reduced by 98.8% at room temperature and the thermoelectric figure of merit, ZT, can be as high as 3.25 at T = 800 K. The proposed scheme relies on a recently developed bottom-up fabrication method, which is proven to be feasible for synthesizing graphene nanoribbons with an atomic precision.

Phonon engineering in carbon nanotubes by controlling defect concentration

Outstanding thermal transport properties of carbon nanotubes (CNTs) qualify them as possible candidates to be used as thermal management units in electronic devices. However, significant variations in the thermal conductivity (κ) measurements of individual CNTs restrict their utilizations for this purpose. In order to address the possible sources of this large deviation and to propose a route to solve this discrepancy, we systematically investigate the effects of varying concentrations of randomly distributed multiple defects (single and double vacancies, Stone-Wales defects) on the phonon transport properties of armchair and zigzag CNTs with lengths ranging between a few hundred nanometers to several micrometers, using both nonequilibrium molecular dynamics and atomistic Greens function methods. Our results show that, for both armchair and zigzag CNTs, κ converges nearly to the same values with different types of defects, at all lengths considered in this study. On the basis of the detailed mean free path analysis, this behavior is explained with the fact that intermediate and high frequency phonons are filtered out by defect scattering, while low frequency phonons are transmitted quasi-ballistically even for several micrometer long CNTs. Furthermore, an analysis of variances in κ for different defect concentrations indicates that defect scattering at low defect concentrations could be the source of large experimental variances, and by taking advantage of the possibility to create a controlled concentration of defects by electron or ion irradiation, it is possible to standardize κ with minimizing the variance. Our results imply the possibility of phonon engineering in nanostructured graphene based materials by controlling the defect concentration.

Prediction of quantum interference in molecular junctions using a parabolic diagram: Understanding the origin of Fano and anti- resonances

The effects of quantum interference on electron transport play a crucial role in molecular electronics and their explicit understanding still remains a major challenge. We devise a simple analytic model for transport through molecular junctions with side groups and introduce a graphical explanation to understand the relations between the influential parameters for quantum interference. Conditions for Fano resonance and anti-resonance line shapes in transmission spectra are derived. As a practical example, using the derived conditions, we demonstrate the line shapes (Fano and anti- resonance) for realistic molecules using a DFT-based quantum transport approach.Recently the interest in quantum interference (QI) phenomena in molecular devices (molecular junctions) has been growing due to the unique features observed in the transmission spectra. In order to design single molecular devices exploiting QI effects as desired, it is necessary to provide simple rules for predicting the appearance of QI effects such as anti-resonances or Fano line shapes and for controlling them. In this study, we derive a transmission function of a generic molecular junction with a side group (T-shaped molecular junction) using a minimal toy model. We developed a simple method to predict the appearance of quantum interference, Fano resonances or anti- resonances, and its position in the conductance spectrum by introducing a simple graphical representation (parabolic model). Using it we can easily visualize the relation between the key electronic parameters and the positions of normal resonant peaks and anti-resonant peaks induced by quantum interference in the conductance spectrum. We also demonstrate Fano and anti-resonance in T-shaped molecular junctions using a simple tight-binding model. This parabolic model enables one to infer on-site energies of T-shaped molecules and the coupling between side group and main conduction channel from transmission spectra.

Quartic dispersion, strong singularity, magnetic instability, and unique thermoelectric properties in two-dimensional hexagonal lattices of group-VA elements

The critical points and the corresponding singularities in the density of states of crystals were first classified by Van Hove with respect to their dimensionality and energy-momentum dispersions. Here, different from saddle-point Van Hove singularities, the occurrence of a continuum of critical points, which give rise to strong singularities in two-dimensional elemental hexagonal lattices, is shown using a minimal tight-binding formalism. The model predicts quartic energy-momentum dispersions despite quadratic or linear ones, which is also the origin of the strong singularity. Starting with this model and using first-principles density functional theory calculations, a family of novel two-dimensional materials that actually display such singularities are identified and their extraordinary features are investigated. The strong singularity gives rise to ferromagnetic instability with an inverse-square-root temperature dependence and the quartic dispersion is responsible for a steplike transmission spectrum, which is a characteristic feature of one-dimensional systems. Because of the abrupt change in transmission at the band edge, these materials have temperature-independent thermopower and enhanced thermoelectric efficiencies. Nitrogene has exceptionally high thermoelectric efficiencies at temperatures down to 50 K, which could make low-temperature thermoelectric applications possible.