Daniel Rhodes

New First Order Raman-active Modes in Few Layered Transition Metal Dichalcogenides

Although the main Raman features of semiconducting transition metal dichalcogenides are well known for the monolayer and bulk, there are important differences exhibited by few layered systems which have not been fully addressed. WSe2 samples were synthesized and ab-initio calculations carried out. We calculated phonon dispersions and Raman-active modes in layered systems: WSe2, MoSe2, WS2 and MoS2 ranging from monolayers to five-layers and the bulk. First, we confirmed that as the number of layers increase, the E′, E″ and E2g modes shift to lower frequencies, and the A′1 and A1g modes shift to higher frequencies. Second, new high frequency first order A′1 and A1g modes appear, explaining recently reported experimental data for WSe2, MoSe2 and MoS2. Third, splitting of modes around A′1 and A1g is found which explains those observed in MoSe2. Finally, exterior and interior layers possess different vibrational frequencies. Therefore, it is now possible to precisely identify few-layered STMD.

Field-Effect Transistors Based on Few-Layered α-MoTe2

Here we report the properties of field-effect transistors based on a few layers of chemical vapor transport grown α-MoTe2 crystals mechanically exfoliated onto SiO2. We performed field-effect and Hall mobility measurements, as well as Raman scattering and transmission electron microscopy. In contrast to both MoS2 and MoSe2, our MoTe2 field-effect transistors are observed to be hole-doped, displaying on/off ratios surpassing 10(6) and typical subthreshold swings of ∼140 mV per decade. Both field-effect and Hall mobilities indicate maximum values approaching or surpassing 10 cm(2)/(V s), which are comparable to figures previously reported for single or bilayered MoS2 and/or for MoSe2 exfoliated onto SiO2 at room temperature and without the use of dielectric engineering. Raman scattering reveals sharp modes in agreement with previous reports, whose frequencies are found to display little or no dependence on the number of layers. Given that MoS2 is electron-doped, the stacking of MoTe2 onto MoS2 could produce ambipolar field-effect transistors and a gap modulation. Although the overall electronic performance of MoTe2 is comparable to those of MoS2 and MoSe2, the heavier element Te leads to a stronger spin-orbit coupling and possibly to concomitantly longer decoherence times for exciton valley and spin indexes.

Intrinsic carrier mobility of multi-layered MoS2 field-effect transistors on SiO2

By fabricating and characterizing multi-layered MoS2-based field-effect transistors in a four terminal configuration, we demonstrate that the two terminal-configurations tend to underestimate the carrier mobility μ due to the Schottky barriers at the contacts. For a back-gated two-terminal configuration, we observe mobilities as high as 91 cm2 V−1 s−1 which is considerably smaller than 306.5 cm2 V−1 s−1 as extracted from the same device when using a four-terminal configuration. This indicates that the intrinsic mobility of MoS2 on SiO2 is significantly larger than the values previously reported, and provides a quantitative method to evaluate the charge transport through the contacts.

Hall and field-effect mobilities in few layered p-WSe2 field-effect transistors

Here, we present a temperature (T) dependent comparison between field-effect and Hall mobilities in field-effect transistors based on few-layered WSe2 exfoliated onto SiO2. Without dielectric engineering and beyond a T-dependent threshold gate-voltage, we observe maximum hole mobilities approaching 350 cm2/Vs at T = 300 K. The hole Hall mobility reaches a maximum value of 650 cm2/Vs as T is lowered below ~150 K, indicating that insofar WSe2-based field-effect transistors (FETs) display the largest Hall mobilities among the transition metal dichalcogenides. The gate capacitance, as extracted from the Hall-effect, reveals the presence of spurious charges in the channel, while the two-terminal sheet resistivity displays two-dimensional variable-range hopping behavior, indicating carrier localization induced by disorder at the interface between WSe2 and SiO2. We argue that improvements in the fabrication protocols as, for example, the use of a substrate free of dangling bonds are likely to produce WSe2-based FETs displaying higher room temperature mobilities, i.e. approaching those of p-doped Si, which would make it a suitable candidate for high performance opto-electronics.

High Photoresponsivity and Short Photoresponse Times in Few-Layered WSe2 Transistors

Here, we report the photoconducting response of field-effect transistors based on three atomic layers of chemical vapor transport grown WSe2 crystals mechanically exfoliated onto SiO2. We find that trilayered WSe2 field-effect transistors, built with the simplest possible architecture, can display high hole mobilities ranging from 350 cm(2)/(V s) at room temperature (saturating at a value of ∼500 cm(2)/(V s) below 50 K) displaying a strong photocurrent response, which leads to exceptionally high photoresponsivities up to 7 A/W under white light illumination of the entire channel for power densities p < 10(2) W/m(2). Under a fixed wavelength of λ = 532 nm and a laser spot size smaller than the conducting channel area, we extract photoresponsitivities approaching 100 mA/W with concomitantly high external quantum efficiencies up to ∼40% at room temperature. These values surpass values recently reported from more complex architectures, such as graphene and transition metal dichalcogenides based heterostructures. Also, trilayered WSe2 phototransistors display photoresponse times on the order of 10 μs. Our results indicate that the addition of a few atomic layers considerably decreases the photoresponse times, probably by minimizing the interaction with the substrates, while maintaining a very high photoresponsivity.

Atypical Exciton–Phonon Interactions in WS2 and WSe2 Monolayers Revealed by Resonance Raman Spectroscopy

Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic).

Superconductivity with extremely large upper critical fields in Nb2Pd0.81S5

Here, we report the discovery of superconductivity in a new transition metal-chalcogenide compound, i.e. Nb2Pd0.81S5, with a transition temperature Tc ≅ 6.6 K. Despite its relatively low Tc, it displays remarkably high and anisotropic superconducting upper critical fields, e.g. μ0Hc2 (T → 0 K) > 37 T for fields applied along the crystallographic b-axis. For a field applied perpendicularly to the b-axis, μ0Hc2 shows a linear dependence in temperature which coupled to a temperature-dependent anisotropy of the upper critical fields, suggests that Nb2Pd0.81S5 is a multi-band superconductor. This is consistent with band structure calculations which reveal nearly cylindrical and quasi-one-dimensional Fermi surface sheets having hole and electron character, respectively. The static spin susceptibility as calculated through the random phase approximation, reveals strong peaks suggesting proximity to a magnetic state and therefore the possibility of unconventional superconductivity.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

Role of spin-orbit coupling and evolution of the electronic structure of WTe 2 under an external magnetic field

Here, we present a detailed study on the temperature and angular dependence of the Shubnikovde-Haas (SdH) effect in the semi-metal WTe2. This compound was recently shown to display a very large non-saturating magnetoresistance which was attributed to nearly perfectly compensated densities of electrons and holes. We observe four fundamental SdH frequencies and attribute them to spin-orbit split, electron- and hole-like, Fermi surface (FS) cross-sectional areas. Their angular dependence is mildly consistent with ellipsoidal FSs with volumes implying an excess of � 7 % in the density of electrons with respect to that of the holes. Nevertheless, we show that density functional theory (DFT) calculations can reasonably describe the experimentally determined electron FSs but fail to accurately describe the hole FSs. When their cross-sectional areas are adjusted to reflect the experimental data, the resulting volumes of the electron/hole FSs obtained from the DFT would imply a strong imbalance between the densities of electrons and holes. We observe a severe fieldinduced renormalization of the effective masses suggesting that the electronic structure of WTe2 is particularly sensitive to the Zeeman-effect. By combining the results of our DFT calculations with our analysis of the experimental results we conclude that WTe2 is unlikely to remain compensated under an external field.

Evaluating the potential for high thermoelectric efficiency of silver selenide

Measurements and modeling of electronic transport properties of n-type Ag2+xSe suggest that this material could have a thermoelectric figure of merit zT greater than 1 at 300 K and above. The exceptional performance can be traced to the exceptionally high mobility, higher than other optimized thermoelectric materials. Although zT decreases at high temperature because of a transition to a phase with high carrier concentration, our model indicates that reducing the carrier concentration will lead to high thermoelectric performance at room temperature for cooling applications as well as up to 600 K for waste heat recovery.