Designing barrier-free metal/MoS2 contacts through electrene insertion.

Transition-metal dichalcogenides (TMDCs), including MoS2, have great potential in electronics applications. However, achieving low-resistance metal contacts is a challenge that impacts their performance in nanodevices due to strong Fermi-level pinning and the presence of a tunnelling barrier. As a solution, we explore a strategy of inserting monolayers of alkaline-earth sub-pnictide electrenes with a general formula of [M2X]+e- (M = Ca, Sr, Ba; X = N, P, As, Sb) between the TMDC and the metal. These electrenes possess two-dimensional sheets of charge on their surfaces that can be readily donated when interfaced with a TMDC semiconductor, thereby lowering its conduction band below the Fermi level and eliminating the Schottky and tunnelling barriers. In this work, density-functional theory (DFT) calculations were performed for metal/electrene/MoS2 heterojunctions for all stable M2X electrenes and both Au and Cu metals. To identify the material combinations that provide the most effective Ohmic contact, the charge transfer, band structure, and electrostatic potential were computed. Linear correlations were found between the charge donated to the MoS2 and both the electrene surface charge and work function. Overall, Ca2N appears to be the most promising electrene for achieving an Ohmic metal/MoS2 contact due to its high surface charge density.

Low thermal expansion of layered electrides predicted by density-functional theory.

Layered electrides are a unique class of materials with anionic electrons bound in interstitial regions between thin, positively charged atomic layers. While density-functional theory is the tool of choice for computational study of electrides, there has to date been no systematic comparison of density functionals or dispersion corrections for their accurate simulation. There has also been no research into the thermomechanical properties of layered electrides, with computational predictions considering only static lattices. In this work, we investigate the thermomechanical properties of five layered electrides using density-functional theory to evaluate the magnitude of thermal effects on their lattice constants and cell volumes. We also assess the accuracy of five popular dispersion corrections with both planewave and numerical atomic orbital calculations.

A density-functional benchmark of vibrational free-energy corrections for molecular crystal polymorphism.

Many crystal structure prediction protocols only concern themselves with the electronic energy of molecular crystals. However, vibrational contributions to the free energy (Fvib) can be significant in determining accurate stability rankings for crystal candidates. While force-field studies have been conducted to gauge the magnitude of these free-energy corrections, highly accurate results from quantum mechanical methods, such as density-functional theory (DFT), are desirable. Here, we introduce the PV17 set of 17 polymorphic pairs of organic molecular crystals, for which plane wave DFT is used to calculate the vibrational free energies and free-energy differences (ΔFvib) between each pair. Our DFT results confirm that the vibrational free-energy corrections are small, having a mean value of 1.0 kJ/mol and a maximum value of 2.3 kJ/mol for the PV17 set. Furthermore, we assess the accuracy of a series of lower-cost DFT, semi-empirical, and force-field models for computing ΔFvib that have been proposed in the literature. It is found that calculating Fvib using the Γ-point frequencies does not provide ΔFvib values of sufficiently high quality. In addition, ΔFvib values calculated using various approximate methods have mean absolute errors relative to our converged DFT results of equivalent or larger magnitude than the vibrational free-energy corrections themselves. Thus, we conclude that, in a crystal structure prediction protocol, it is preferable to forego the inclusion of vibrational free-energy corrections than to estimate them with any of the approximate methods considered here.