Two-dimensional (2D) materials

Huang D, Song C-L, Webb TA, Fang S, Chang C-Z, Moodera JS, Kaxiras E, Hoffman JE. Revealing the Empty-State Electronic Structure of Single-Unit-Cell FeSe /SrTiO3. Physical Review Letters. 2015;115 :017002.Abstract

We use scanning tunneling spectroscopy to investigate the filled and empty electronic states of superconducting single-unit-cell FeSe deposited on SrTiO3(001). We map the momentum-space band structure by combining quasiparticle interference imaging with decay length spectroscopy. In addition to quantifying the filled-state bands, we discover a Γ-centered electron pocket 75 meV above the Fermi energy. Our density functional theory calculations show the orbital nature of empty states at Γ and explain how the Se height is a key tuning parameter of their energies, with broad implications for electronic properties.

Ostadhossein A, Cubuk ED, Tritsaris GA, Kaxiras E, Zhang S, van Duin ACT. Stress effects on the initial lithiation of crystalline silicon nanowires: reactive molecular dynamics simulations using ReaxFF. Physical Chemistry Chemical Physics. 2015;17 :3832-3840.Abstract

Silicon (Si) has been recognized as a promising anode material for the next-generation high-capacity lithium (Li)-ion batteries because of its high theoretical energy density. Recent in situ transmission electron microscopy (TEM) revealed that the electrochemical lithiation of crystalline Si nanowires
(c-SiNWs) proceeds by the migration of the interface between the lithiated Si (LixSi) shell and the pristine unlithiated core, accompanied by solid-state amorphization. The underlying atomic mechanisms of Li insertion into c-Si remain poorly understood. Herein, we perform molecular dynamics (MD) simulations using the reactive force field (ReaxFF) to characterize the lithiation process of c-SiNWs. Our calculations show that ReaxFF can accurately reproduce the energy barriers of Li migration from DFT calculations in
both crystalline (c-Si) and amorphous Si (a-Si). The ReaxFF-based MD simulations reveal that Li insertion into interlayer spacing between two adjacent (111) planes results in the peeling-off of the (111) facets and subsequent amorphization, in agreement with experimental observations. We find that breaking of the Si–Si bonds between (111)-bilayers requires a rather high local Li concentration, which explains the atomically sharp amorphous–crystalline interface (ACI). Our stress analysis shows that lithiation induces compressive stress at the ACI layer, causing retardation or even the stagnation of the reaction front, also in good agreement with TEM observations. Lithiation at high temperatures (e.g. 1200 K) shows that Li insertion into c-SiNW results in an amorphous to crystalline phase transformation at Li : Si composition
of B4.2 : 1. Our modeling results provide a comprehensive picture of the effects of reaction and diffusion-induced stress on the interfacial dynamics and mechanical degradation of SiNW anodes under chemo-mechanical lithiation.

Sharmila Shirodkar

Sharmila Shirodkar

Sharmila is interested in studying the electronic and optical properties of two dimensional (2D) materials. 

Tritsaris GA, Malone BD, Kaxiras E. Structural stability and electronic properties of low-index surfaces of SnS. Journal of Applied Physics. 2014;115 :173702.Abstract

Thin film photovoltaic cells are increasingly important for cost-effective solar energy harvesting. Layered SnS is a promising absorber material due to its high optical absorption in the visible and good doping characteristics. We use first-principles calculations based on density functional theory to study structures of low-index surfaces of SnS using stoichiometric and oxygen-containing structural models, in order to elucidate their possible effect on the efficiency of the photovoltaic device. We find that the surface energy is minimized for the surface with orientation parallel to the layer stacking direction. Compared to stoichiometric surfaces, the oxygen-containing surfaces exhibit fewer electronic states near the band gap. This reduction of near-gap surface states by oxygen should reduce recombination losses at grain boundaries and interfaces of the SnS absorber, and should be beneficial to the efficiency of the solar cell.

Tritsaris GA, Kaxiras E, Meng S, Wang E. Adsorption and Diffusion of Lithium on Layered Silicon for Li-Ion Storage. Nano Letters. 2013;13 :2258-2263.Abstract

The energy density of Li-ion batteries depends critically on the specific charge capacity of the constituent electrodes. Silicene, the silicon analogue to graphene, being of atomic thickness could serve as high-capacity host of Li in Li-ion secondary batteries. In this work, we employ first-principles calculations to investigate the interaction of Li with Si in model electrodes of free-standing single-layer and double-layer silicene. More specifically, we identify strong binding sites for Li, calculate the energy barriers accompanying Li diffusion, and present our findings in the context of previous theoretical work related to Liion storage in other structural forms of silicon: the bulk and nanowires. The binding energy of Li is ∼2.2 eV per Li atom and shows small variation with respect to Li content and silicene thickness (one or two layers) while the barriers for Li diffusion are relatively low, typically less than 0.6 eV. We use our theoretical findings to assess the suitability of two-dimensional silicon in the form of silicene layers for Li-ion storage.

Tritsaris GA, Malone BD, Kaxiras E. Optoelectronic properties of single-layer, double-layer, and bulk tin sulfide: A theoretical study. Journal of Applied Physics. 2013;113 :233507.Abstract

SnS is a metal monochalcogenide suitable for use as absorber material in thin film photovoltaic cells. Its structure is an orthorhombic crystal of weakly coupled layers, each layer consisting of strongly bonded Sn-S units. We use first-principles calculations to study model single-layer, double-layer, and bulk structures of SnS in order to elucidate its electronic structure. We find that the optoelectronic properties of the material can vary significantly with respect to the number of layers and the separation between them: the calculated band gap is wider for fewer layers (2.72 eV, 1.57 eV, and 1.07 eV for single-layer, double-layer, and bulk SnS, respectively) and increases with tensile strain along the layer stacking direction (by ∼55 meV/1% strain).

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