Low Power Volatile and Nonvolatile Memristive Devices from 1D MoO2-MoS2 Core-Shell Heterostructures for Future Bio-Inspired Computing.

Memristors-based integrated circuits for emerging bio-inspired computing paradigms require an integrated approach utilizing both volatile and nonvolatile memristive devices. Here, an innovative architecture comprising of 1D CVD-grown core-shell heterostructures (CSHSs) of MoO2-MoS2 is employed as memristors manifesting both volatile switching (with high selectivity of 107 and steep slope of 0.6 mV decade-1) and nonvolatile switching phenomena (with Ion/Ioff ≈103 and switching speed of 60 ns). In these CSHSs, the metallic core MoO2 with high current carrying capacity provides a conformal and immaculate interface with semiconducting MoS2 shells and therefore it acts as a bottom electrode for the memristors. The power consumption in volatile devices is as low as 50 pW per set transition and 0.1 fW in standby mode. Voltage-driven current spikes are observed for volatile devices while with nonvolatile memristors, key features of a biological synapse such as short/long-term plasticity and paired pulse facilitation are emulated suggesting their potential for the development of neuromorphic circuits. These CSHSs offer an unprecedented solution for the interfacial issues between metallic electrodes and the layered materials-based switching element with the prospects of developing smaller footprint memristive devices for future integrated circuits.

Observation of positive trions in α-MoO3/MoS2 van der Waals heterostructures.

Mono-layer transition metal dichalcogenides (TMDCs) have emerged as an ideal platform for the study of many-body physics. As a result of their low dimensionality, these materials show a strong Coulomb interaction primarily due to reduced dielectric screening that leads to the formation of stable excitons (bound electron-hole pairs) and higher order excitons, including trions, and bi-excitons even at room temperature. van der Waals (vdW) heterostructures (HSs) of TMDCs provide an additional degree of freedom for altering the properties of 2D materials because charge carriers (electrons) in the different atomically thin layers are exposed to interlayer coupling and charge transfer takes place between the layers of vdW HSs. Astoundingly, it leads to the formation of different types of quasi-particles. In the present work, we report the synthesis of vdW HSs, i.e., α-MoO3/MoS2, on a 300 nm SiO2/Si substrate and investigate their temperature-dependent photoluminescence (PL) spectra. Interestingly, an additional PL peak is observed in the case of the HS, along with A and B excitonic peaks. The emergence of a new PL peak in the low-energy regime has been assigned to the formation of a positive trion. The formation of positive trions in the HS is due to the high work function of α-MoO3, which enables the spontaneous transit of electrons from MoS2 to α-MoO3 and injection of holes into the MoS2 layer. In order to confirm charge transfer in the α-MoO3/MoS2 HS, systematic power and wavelength-dependent Raman and PL studies, as well as first-principle calculations using Bader charge analysis, have been carried out, which clearly validate our mechanism. We believe that this study will provide a platform towards the integration of vdW HSs for next-generation excitonic devices.

Pulsed Carrier Gas Assisted High-Quality Synthetic 3R-Phase Sword-like MoS2: A Versatile Optoelectronic Material.

Synthesizing a material with the desired polymorphic phase in a chemical vapor deposition (CVD) process requires a delicate balance among various thermodynamic variables. Here, we present a methodology to synthesize rhombohedral (3R)-phase MoS2 in a well-defined sword-like geometry having lengths up to 120 µm, uniform width of 2-3 µm and thickness of 3-7 nm by controlling the carrier gas flow dynamics from continuous mode to pulsed mode during the CVD growth process. Characteristic signatures such as high degree of circular dichroism (∼58% at 100 K), distinct evolution of low-frequency Raman peaks and increasing intensity of second harmonic signals with increasing number of layers conclusively establish the 3R-phase of the material. A high value (∼844 pm/V) of second-order susceptibility for few-layer-thick MoS2 swords signifies the potential of MoS2 to serve as an atomically thin nonlinear medium. A field effect mobility of 40 cm2/V-s and Ion/Ioff ratio of ∼106 further confirm the electronic-grade standard of this 3R-phase MoS2. These findings are significant for the development of emerging quantum electronic devices utilizing valley-based physics and nonlinear optical phenomena in layered materials.

Symmetric domain segmentation in WS2flakes: correlating spatially resolved photoluminescence, conductance with valley polarization.

The incidence of intra-flake heterogeneity of spectroscopic and electrical properties in chemical vapour deposited (CVD) WS2flakes is explored in a multi-physics investigation via spatially resolved spectroscopic maps correlated with electrical, electronic and mechanical properties. The investigation demonstrates that the three-fold symmetric segregation of spectroscopic response, in topographically uniform WS2flakes are accompanied by commensurate segmentation of electronic properties e.g. local carrier density and the differences in the mechanics of tip-sample interactions, evidenced via scanning probe microscopy phase maps. Overall, the differences are understood to originate from point defects, namely sulfur vacancies within the flake along with a dominant role played by the substrate. While evolution of the multi-physics maps upon sulfur annealing elucidates the role played by sulfur vacancy, substrate-induced effects are investigated by contrasting data from WS2flake on Si and Au surfaces. Local charge depletion induced by the nature of the sample-substrate junction in case of WS2on Au is seen to invert the electrical response with comprehensible effects on their spectroscopic properties. Finally, the role of these optoelectronic properties in preserving valley polarization that affects valleytronic applications in WS2flakes, is investigated via circular polarization discriminated photoluminescence experiments. The study provides a thorough understanding of spatial heterogeneity in optoelectronic properties of WS2and other transition metal chalcogenides, which are critical for device fabrication and potential applications.

Twist-Dependent Tuning of Excitonic Emissions in Bilayer WSe2.

Monolayer (ML) transition metal dichalcogenides (TMDCs) have been rigorously studied to comprehend their rich spin and valley physics, exceptional optical properties, and ability to open new avenues in fundamental research and technology. However, intricate analysis of twisted homobilayer (t-BL) systems is highly required due to the intriguing twist angle (t-angle)-dependent interlayer effects on optical and electrical properties. Here, we report the evolution of the interlayer effect on artificially stacked BL WSe2, grown using chemical vapor deposition (CVD), with t-angle in the range of 0 ≤ θ ≤ 60°. Systematic analyses based on Raman and photoluminescence (PL) spectroscopies suggest intriguing deviations in the interlayer interactions, higher-energy exciton transitions (in the range of ∼1.6-1.7 eV), and stacking. In contrast to previous observations, we demonstrate a red shift in the PL spectra with t-angle. Density functional theory (DFT) is employed to understand the band-gap variations with t-angle. Exciton radiative lifetime has been estimated theoretically using temperature-dependent PL measurements, which shows an increase with t-angle that agrees with our experimental observations. This study presents the groundwork for further investigation of the evolution of various interlayer excitons and their dynamics with t-angle in homobilayer systems, critical for optoelectronic applications.

Anomalously polarised emission from a MoS2/WS2 heterostructure.

We report circularly polarised emission, with helicity opposite to the optical excitation, from a van der Waals heterostructure (HS) consisting of a monolayer MoS2 and three-layer WS2. Selective excitation of the MoS2 layer confirms that this cross-polarized emission is due to the charge transfer from the WS2 layers to the MoS2 layer. We propose that the high levels of n-doping in the constituent layers due to sulphur vacancies and defects give rise to an enhanced transition rate of electrons from the k valley of WS2 to the k' valley of MoS2, which leads to the emission, counter polarized to the excitation. Simulations based on the rate equation model support this conclusion.

High degree of circular polarization in WS2 spiral nanostructures induced by broken symmetry.

We present helicity resolved photoluminescence (PL) measurements of WS2 spiral (SPI) nanostructures. We show that very high degree of circular polarization (DCP) (~94 ± 4%) is obtained from multilayer SPI samples at room temperature upon excitation with a circularly polarized laser at a wavelength near-resonant with the A-exciton (633 nm). TEM analysis showed that these SPI nanostructures have AB stacking in which the inversion symmetry is broken, and hence this leads to very high DCP. Comparison with PL from monolayer and bi-layer WS2 samples, along with polarization resolved PL studies provide evidence for suppression of interlayer/intravalley scattering in the multilayer SPI samples.