Anomalous Behavior of 2D Janus Excitonic Layers under Extreme Pressures

Newly discovered 2D Janus transition metal dichalcogenides layers have gained much attention from a theory perspective owing to their unique atomic structure and exotic materials properties, but little to no experimental data are available on these materials. Here, experimental and theoretical studies establish the vibrational and optical behavior of 2D Janus S–W–Se and S–Mo–Se monolayers under high pressures for the first time. Chemical vapor deposition (CVD)-grown classical transition metal dichalcogenides (TMD) monolayers are first transferred onto van der Waals (vdW) mica substrates and converted to 2D Janus sheets by surface plasma technique, and then integrated into a 500 µm size diamond anvil cell for high-pressure studies. The results show that 2D Janus layers do not undergo phase transition up to 15 GPa, and in this pressure regime, their vibrational modes exhibit a nonmonotonic response to the applied pressures (dω/dP). Interestingly, these 2D Janus monolayers exhibit unique blueshift in photoluminescence (PL) upon compression, which is in contrast to many other traditional semiconductor materials. Overall theoretical simulations offer in-depth insights and reveal that the overall optical response is a result of competition between the ab-plane (blueshift) and c-axis (redshift) compression. The overall findings shed the very first light on how 2D Janus monolayers respond under extreme pressures and expand the fundamental understanding of these materials.     

High efficiency graphene solar cells by chemical doping

We demonstrate single layer graphene/n-Si Schottky junction solar cells that under AM1.5 illumination exhibit a power conversion efficiency (PCE) of 8.6%. This performance, achieved by doping the graphene with bis(trifluoromethanesulfonyl)amide, exceeds the native (undoped) device performance by a factor of 4.5 and is the highest PCE reported for graphene-based solar cells to date. Current-voltage, capacitance-voltage, and external quantum efficiency measurements show the enhancement to be due to the doping-induced shift in the graphene chemical potential that increases the graphene carrier density (decreasing the cell series resistance) and increases the cell's built-in potential (increasing the open circuit voltage) both of which improve the solar cell fill factor.     

Modulating Photoluminescence of Monolayer Molybdenum Disulfide by Metal–Insulator Phase Transition in Active Substrates

The atomic thickness and flatness allow properties of 2D semiconductors to be modulated with influence from the substrate. Reversible modulation of these properties requires an “active,” reconfigurable substrate, i.e., a substrate with switchable functionalities that interacts strongly with the 2D overlayer. In this work, the photoluminescence (PL) of monolayer molybdenum disulfide (MoS₂) is modulated by interfacing it with a phase transition material, vanadium dioxide (VO₂). The MoS₂ PL intensity is enhanced by a factor of up to three when the underlying VO₂ undergoes the thermally driven phase transition from the insulating to metallic phase. A nonvolatile, reversible way to rewrite the PL pattern is also demonstrated. The enhancement effect is attributed to constructive optical interference when the VO₂ turns metallic. This modulation method requires no chemical or mechanical processes, potentially finding applications in new switches and sensors.     

Phase Transition across Anisotropic NbS3 and Direct Gap Semiconductor TiS3 at Nominal Titanium Alloying Limit

Alloying selected layered transitional metal trichalcogenides (TMTCs) with unique chain-like structures offers the opportunities for structural, optical, and electrical engineering thus expands the regime of this class of pseudo-one-dimensional materials. Here, the novel phase transition in anisotropic Nb_(1−x)Ti_xS₃ alloys is demonstrated for the first time. Results show that Nb_(1−x)Ti_xS₃ can be fully alloyed across the entire composition range from triclinic-phase NbS₃ to monoclinic-phase TiS₃. Surprisingly, incorporation of a small concentration of Ti (x ≈ 0.05–0.18) into NbS₃ host matrix is sufficient to induce triclinic to monoclinic transition. Theoretical studies suggest that Ti atoms effectively introduce hole doping, thus rapidly decreases the total energy of monoclinic phase and induces the phase transition. When alloyed, crystalline and optical anisotropy are largely preserved as evidenced by high resolution transmission electron microscopy and angle-resolved Raman spectroscopy. Further Raman measurements identify Raman modes to determine crystalline anisotropy direction and offer insights into the degree of anisotropy. Overall results introduce Nb_(1−x)Ti_xS₃ as a new and easy phase change material and mark the first phase engineering in anisotropic van der Waals (vdW) trichalcogenide systems for their potential applications in two-dimensional superconductivity, electronics, photonics, and information technologies.     

Room-Temperature Synthesis of 2D Janus Crystals and their Heterostructures

Janus crystals represent an exciting class of 2D materials with different atomic species on their upper and lower facets. Theories have predicted that this symmetry breaking induces an electric field and leads to a wealth of novel properties, such as large Rashba spin–orbit coupling and formation of strongly correlated electronic states. Monolayer MoSSe Janus crystals have been synthesized by two methods, via controlled sulfurization of monolayer MoSe₂ and via plasma stripping followed thermal annealing of MoS₂. However, the high processing temperatures prevent growth of other Janus materials and their heterostructures. Here, a room-temperature technique for the synthesis of a variety of Janus monolayers with high structural and optical quality is reported. This process involves low-energy reactive radical precursors, which enables selective removal and replacement of the uppermost chalcogen layer, thus transforming classical transition metal dichalcogenides into a Janus structure. The resulting materials show clear mixed character for their excitonic transitions, and more importantly, the presented room-temperature method enables the demonstration of first vertical and lateral heterojunctions of 2D Janus TMDs. The results present significant and pioneering advances in the synthesis of new classes of 2D materials, and pave the way for the creation of heterostructures from 2D Janus layers.     

Controlling Structural Anisotropy of Anisotropic 2D Layers in Pseudo‐1D/2D Material Heterojunctions

Chemical vapor deposition and growth dynamics of highly anisotropic 2D lateral heterojunctions between pseudo‐1D ReS₂ and isotropic WS₂ monolayers are reported for the first time. Constituent ReS₂ and WS₂ layers have vastly different atomic structure, crystallizing in anisotropic 1T′ and isotropic 2H phases, respectively. Through high‐resolution scanning transmission electron microscopy, electron energy loss spectroscopy, and angle‐resolved Raman spectroscopy, this study is able to provide the very first atomic look at intimate interfaces between these dissimilar 2D materials. Surprisingly, the results reveal that ReS₂ lateral heterojunctions to WS₂ produce well‐oriented (highly anisotropic) Re‐chains perpendicular to WS₂ edges. When vertically stacked, Re‐chains orient themselves along the WS₂ zigzag direction, and consequently, Re‐chains exhibit six‐fold rotation, resulting in loss of macroscopic scale anisotropy. The degree of anisotropy of ReS₂ on WS₂ largely depends on the domain size, and decreases for increasing domain size due to randomization of Re‐chains and formation of ReS₂ subdomains. Present work establishes the growth dynamics of atomic junctions between novel anisotropic/isotropic 2D materials, and overall results mark the very first demonstration of control over anisotropy direction, which is a significant leap forward for large‐scale nanomanufacturing of anisotropic systems.