Joonki Suh

Point defects in semiconductors can trap free charge carriers and localize excitons. The interaction between these defects and charge carriers becomes stronger at reduced dimensionalities, and is expected to greatly influence physical properties of the hosting material. We investigated effects of anion vacancies in monolayer transition metal dichalcogenides as two-dimensional (2D) semiconductors where the vacancies density is controlled by α-particle irradiation or thermal-annealing. We found a new, sub-bandgap emission peak as well as increase in overall photoluminescence intensity as a result of the vacancy generation. Interestingly, these effects are absent when measured in vacuum. We conclude that in opposite to conventional wisdom, optical quality at room temperature cannot be used as criteria to assess crystal quality of the 2D semiconductors. Our results not only shed light on defect and exciton physics of 2D semiconductors, but also offer a new route toward tailoring optical properties of 2D semiconductors by defect engineering.

Band offsets between different monolayer transition metal dichalcogenides are expected to efficiently separate charge carriers or rectify charge flow, offering a mechanism for designing atomically thin devices and probing exotic two-dimensional physics. However, developing such large-area heterostructures has been hampered by challenges in synthesis of monolayers and effectively coupling neighboring layers. Here, we demonstrate large-area (>tens of micrometers) heterostructures of CVD-grown WS2 and MoS2 monolayers, where the interlayer interaction is externally tuned from noncoupling to strong coupling. Following this trend, the luminescence spectrum of the heterostructures evolves from an additive line profile where each layer contributes independently to a new profile that is dictated by charge transfer and band normalization between the WS2 and MoS2 layers. These results and findings open up venues to creating new material systems with rich functionalities and novel physical effects.

Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS2) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p-n junctions of MoS2, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS2 by substitutional niobium (Nb) doping, leading to a degenerate hole density of ∼ 3 × 10(19) cm(-3). Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS2 by replacing the Mo cations in the host lattice. van der Waals p-n homojunctions based on vertically stacked MoS2 layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS2. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.

In electrically conductive solids, the Wiedemann-Franz law requires the electronic contribution to thermal conductivity to be proportional to electrical conductivity. Violations of the Wiedemann-Franz law are typically an indication of unconventional quasiparticle dynamics, such as inelastic scattering, or hydrodynamic collective motion of charge carriers, typically pronounced only at cryogenic temperatures. We report an order-of-magnitude breakdown of the Wiedemann-Franz law at high temperatures ranging from 240 to 340 kelvin in metallic vanadium dioxide in the vicinity of its metal-insulator transition. Different from previously established mechanisms, the unusually low electronic thermal conductivity is a signature of the absence of quasiparticles in a strongly correlated electron fluid where heat and charge diffuse independently.

Black phosphorus attracts enormous attention as a promising layered material for electronic, optoelectronic and thermoelectric applications. Here we report large anisotropy in in-plane thermal conductivity of single-crystal black phosphorus nanoribbons along the zigzag and armchair lattice directions at variable temperatures. Thermal conductivity measurements were carried out under the condition of steady-state longitudinal heat flow using suspended-pad micro-devices. We discovered increasing thermal conductivity anisotropy, up to a factor of two, with temperatures above 100 K. A size effect in thermal conductivity was also observed in which thinner nanoribbons show lower thermal conductivity. Analysed with the relaxation time approximation model using phonon dispersions obtained based on density function perturbation theory, the high anisotropy is attributed mainly to direction-dependent phonon dispersion and partially to phonon-phonon scattering. Our results revealing the intrinsic, orientation-dependent thermal conductivity of black phosphorus are useful for designing devices, as well as understanding fundamental physical properties of layered materials.