Enhancing Layer-Engineered Interlayer Exciton Emission and Valley Polarization in van der Waals Heterostructures via Strain.

Layer-engineered interlayer excitons from heterostructures of transition-metal dichalcogenides (TMDCs) exhibit a rich variety of emissive states and intriguing valley spin-selection rules, the effective modulation of which is crucial for excitonic physics and related device applications. Strain or high pressure provides the possibility to tune the energy of the interlayer excitons; however, the reported emission intensity is substantially quenched, which greatly limits their practical application in optoelectronic devices. Here, via applying uniaxial strain based on polyvinyl alcohol (PVA) encapsulation technique, we report enhanced layer-engineered interlayer exciton emission intensity with largely modulated emission energy in WSe2/WS2 heterobilayer and heterotrilayer. Both momentum-direct and momentum-indirect interlayer excitons were observed, and their emission energies show an opposite shift tendency upon applied strain, which agrees with our DFT calculations. We further demonstrate that intralayer and interlayer exciton states with low phonon interactions can be modulated through the mechanical strain applied to the PVA substrate at low temperatures. Due to strain-induced breaking of the 3-fold rotational symmetry, we observe the enhanced valley polarization of interlayer excitons. Our study contributes to the understanding and modulation of the optical properties of interlayer excitons, which could be exploited for optoelectronic device applications.

Defect Engineering of 2D Semiconductors for Dual Control of Emission and Carrier Polarity.

2D transition metal dichalcogenides (TMDCs) are considered as promising materials in post-Moore technology. However, the low photoluminescence quantum yields (PLQY) and single carrier polarity due to the inevitable defects during material preparation are great obstacles to their practical applications. Here, an extraordinary defect engineering strategy is reported based on first-principles calculations and realize it experimentally on WS2 monolayers by doping with IIIA atoms. The doped samples with large sizes possess both giant PLQY enhancement and effective carrier polarity modulation. Surprisingly, the high PL emission maintained even after one year under ambient environment. Moreover, the constructed p-n homojunctions shows high rectification ratio (≈2200), ultrafast response times and excellent stability. Meanwhile, the doping strategy is universally applicable to other TMDCs and dopants. This smart defect engineering strategy not only provides a general scheme to eliminate the negative influence of defects, but also utilize them to achieve desired optoelectronic properties for multifunctional applications.

Observation and Modulation of High-Temperature Moiré-Locale Excitons in van der Waals Heterobilayers.

Transition metal dichalcogenide heterobilayers feature strong moiré potentials with multiple local minima, which can spatially trap interlayer excitons at different locations within one moiré unit cell (dubbed moiré locales). However, current studies mainly focus on moiré excitons trapped at a single moiré locale. Exploring interlayer excitons trapped at different moiré locales is highly desirable for building polarized light-emitter arrays and studying multiorbital correlated and topological physics. Here, via enhancing the interlayer coupling and engineering the heterointerface, we report the observation and modulation of high-temperature interlayer excitons trapped at separate moiré locales in WS2/WSe2 heterobilayers. These moiré-locale excitons are identified by two emission peaks with an energy separation of ∼60 meV, exhibiting opposite circular polarizations due to their distinct local stacking registries. With the increase of temperature, two momentum-indirect moiré-locale excitons are observed, which show a distinct strain dependence with the momentum-direct one. The emission of these moiré-locale excitons can be controlled via engineering the heterointerface with different phonon scattering, while their emission energy can be further modulated via strain engineering. Our reported highly tunable interlayer excitons provide important information on understanding moiré excitonic physics, with possible applications in building high-temperature excitonic devices.

Highly Anisotropic Second-Order Nonlinear Optical Effects in the Chiral Lead-Free Perovskite Spiral Microplates.

Chiral metal halide perovskites with intrinsic asymmetric structures have drawn increased research interest for the application of second-order nonlinear optics (NLO). However, designing chiral perovskites with the features of a large NLO coefficient, high laser-induced damage thresholds (LDT), and environmental friendliness remains a major challenge. Herein, we have synthesized two chiral hybrid bismuth halides: (R/S-MBA)4Bi2Br10 spiral structure microplates, templated by chiral (R/S)-methylbenzylamine (R/S-MBA). The as-grown chiral lead-free perovskite spiral microplates exhibit a recorded second harmonic generation (SHG) effect with a large effective second-order NLO coefficient (deff) of 11.9 pm V-1 and a high LDT of up to 59.2 mJ cm-2. More importantly, the twisted screw structures show competitive circular polarization sensitivity at 1200 nm with an anisotropy factor (gSHG-CD) of 0.58, which is about 3 times higher than that of reported Pb-based chiral perovskites. These findings provide a new platform to design multifunctional lead-free chiral perovskites for nonlinear photonic applications.

Van der Waals epitaxial growth and optoelectronics of a vertical MoS2/WSe2 p-n junction.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted extensive attention due to their unique electronic and optical properties. In particular, TMDs can be flexibly combined to form diverse vertical van der Waals (vdWs) heterostructures without the limitation of lattice matching, which creates vast opportunities for fundamental investigation of novel optoelectronic applications. Here, we report an atomically thin vertical p-n junction WSe2/MoS2 produced by a chemical vapor deposition method. Transmission electron microscopy and steady-state photoluminescence experiments reveal its high quality and excellent optical properties. Back gate field effect transistor (FET) constructed using this p-n junction exhibits bipolar behaviors and a mobility of 9 cm2/(V·s). In addition, the photodetector based on MoS2/WSe2 heterostructures displays outstanding optoelectronic properties (R = 8 A/W, D* = 2.93 × 1011 Jones, on/off ratio of 104), which benefited from the built-in electric field across the interface. The direct growth of TMDs p-n vertical heterostructures may offer a novel platform for future optoelectronic applications.

Strain-controlled synthesis of ultrathin hexagonal GaTe/MoS2 heterostructure for sensitive photodetection.

Ultrathin hexagonal GaTe, with relatively high charge density, holds great potential in the field of optoelectronic devices. However, the thermodynamical stability limits it fabrications as well as applications. Here, by introducing two-dimensional MoS2 as the substrate, we successfully realized the phase-controlled synthesis of ultrathin h-GaTe, leading to high-quality h-GaTe/MoS2 heterostructures. Theoretical calculation studies reveal that GaTe with hexagonal phase is more thermodynamically stable on MoS2 templates, which can be attributed to the strain stretching and the formation energy reduction. Based on the achieved p-n heterostructures, optoelectronic devices are designed and probed, where remarkable photoresponsivity (32.5 A/W) and fast photoresponse speed (<50 µs) are obtained, indicating well-behaved photo-sensing behaviors. The study here could offer a good reference for the controlled growth of the relevant materials, and the achieved heterostructure will find promising applications in future integrated electronic and optoelectronic devices and systems.

Room temperature near unity spin polarization in 2D Van der Waals heterostructures.

The generation and manipulation of spin polarization at room temperature are essential for 2D van der Waals (vdW) materials-based spin-photonic and spintronic applications. However, most of the high degree polarization is achieved at cryogenic temperatures, where the spin-valley polarization lifetime is increased. Here, we report on room temperature high-spin polarization in 2D layers by reducing its carrier lifetime via the construction of vdW heterostructures. A near unity degree of polarization is observed in PbI2 layers with the formation of type-I and type-II band aligned vdW heterostructures with monolayer WS2 and WSe2. We demonstrate that the spin polarization is related to the carrier lifetime and can be manipulated by the layer thickness, temperature, and excitation wavelength. We further elucidate the carrier dynamics and measure the polarization lifetime in these heterostructures. Our work provides a promising approach to achieve room temperature high-spin polarizations, which contribute to spin-photonics applications.

Near-Unity Polarization of Valley-Dependent Second-Harmonic Generation in Stacked TMDC Layers and Heterostructures at Room Temperature.

With unique valley-dependent optical and optoelectronic properties, 2D transition metal dichalcogenides (2D TMDCs) are promising materials for valleytronics. Second-harmonic generation (SHG) in 2D TMDCs monolayers has shown valley-dependent optical selection rules. However, SHG in monolayer TMDCs is generally weak; it is important to obtain materials with both strong SHG signals and a large degree of polarization. In the work, a variety of inversion-symmetry-breaking (3R-like phase) TMDCs (WSe2 , WS2 , MoS2 ) atomic layers, spiral structures, and heterostructures are prepared, and their SHG polarization is studied. Through circular-polarization-resolved SHG experiments, it is demonstrated that the SHG intensity is enhanced in thicker samples by breaking inversion symmetry while maintaining the degree of polarization close to unity at room temperature. By studying TMDCs with different twist angles and the spiral structures, it is found that there is no significant effect of multilayer interlayer interaction on valley-dependent SHG. The realization of strong SHG with high degree of polarization may pave the way toward a new platform for nonlinear optical valleytronics devices based on 2D semiconductors.

Large-Scale Growth of Ultrathin Low-Dimensional Perovskite Nanosheets for High-Detectivity Photodetectors.

Low-dimensional organic-inorganic hybrid perovskites have demonstrated to be promising semiconductor materials due to their unique optoelectronic properties, however, the controllable growth of high-quality ultrathin 2D perovskites with large lateral dimension still faces great challenges. Herein, we report the controllable growth of large-scale ultrathin 2D (C6H5(CH2)3NH3)3Pb2I7 ((PPA)3Pb2I7) perovskite nanosheets (NSs) using a facile antisolvent-assisted crystallization approach under mild condition. As a result, the well-defined regular-shaped (PPA)3Pb2I7 NSs, with the largest lateral size over 100 µm, have been successfully synthesized, which is more than several ten times larger than that of other 2D perovskite NSs previously reported. Moreover, the thickness of the achieved 2D perovskite NSs can be well-tuned by altering the concentration of the precursor solution, with the smallest thickness down to ∼4.7 nm. More importantly, the photodetectors based on the high-quality (PPA)3Pb2I7 perovskites exhibit fascinating performance, including an extremely low dark current (∼1.5 pA), fast response/recovery rate (∼850/780 µs), and high detectivity (∼1.2 × 1010 Jones). This work provides a simple and promising strategy to controllably grow large-scale and ultrathin 2D perovskite NSs for low-cost and high-performance optoelectronic devices.