Nonlinear Boost of Optical Angular Momentum Selectivity by Hybrid Nanolaser Circuits.

Selective control of light is essential for optical science and technology, with numerous applications. However, optical selectivity in the angular momentum of light has been quite limited, remaining constant by increasing the incident light power on previous passive optical devices. Here, we demonstrate a nonlinear boost of optical selectivity in both the spin and orbital angular momentum of light through near-field selective excitation of single-mode nanolasers. Our designed hybrid nanolaser circuits consist of plasmonic metasurfaces and individually placed perovskite nanowires, enabling subwavelength focusing of angular-momentum-distinctive plasmonic fields and further selective excitation of nanolasers in nanowires. The optically selected nanolaser with a nonlinear increase of light emission greatly enhances the baseline optical selectivity offered by the metasurface from about 0.4 up to near unity. Our demonstrated hybrid nanophotonic platform may find important applications in all-optical logic gates and nanowire networks, ultrafast optical switches, nanophotonic detectors, and on-chip optical and quantum information processing.

Space-Confined Growth of Ultrathin P-Type GeTe Nanosheets for Broadband Photodetectors.

As p-type phase-change degenerate semiconductors, crystalline and amorphous germanium telluride (GeTe) exhibit metallic and semiconducting properties, respectively. However, the massive structural defects and strong interface scattering in amorphous GeTe films significantly reduce their performance. In this work, two-dimensional (2D) p-type GeTe nanosheets are synthesized via a specially designed space-confined chemical vapor deposition (CVD) method, with the thickness of the GeTe nanosheets reduced to 1.9 nm. The space-confined CVD method improves the crystallinity of ultrathin GeTe by lowering the partial pressure of the reactant gas, resulting in GeTe nanosheets with excellent p-type semiconductor properties, such as a satisfactory on/off ratio of 105 . Temperature-dependent electrical measurements demonstrate that variable-range hopping and optical-phonon-assisted hopping mechanisms dominate transport behavior at low and high temperatures, respectively. GeTe devices exhibit significantly high responsivity (6589 and 2.2 A W-1 at 633 and 980 nm, respectively) and detectivity (1.67 × 1011 and 1.3 × 108 Jones at 633 and 980 nm, respectively), making them feasible for broadband photodetectors in the visible to near-infrared range. Furthermore, the fabricated GeTe/WS2 diode exhibits a rectification ratio of 103 at zero gate voltage. These satisfactory p-type semiconductor properties demonstrate that ultrathin GeTe exhibits enormous potential for applications in optoelectronic interconnection circuits.

Interlayer Coupling in Anisotropic/Isotropic Van der Waals Heterostructures of ReS2 and WS2.

Van der Waals (vdW) heterostructures are composed of atomically thin layers assembled through weak (vdW) force, which have opened a new era for integrating materials with distinct properties and specific applications. However, few studies have focused on whether and how anisotropic materials affect heterostructure system. The study introduces anisotropic and isotropic materials in a heterojunction system to change the in-plane symmetry, offering a new degree of freedom for modulating its properties. The sample is fabricated by manually stacking ReS2 and WS2 flakes prepared by mechanical exfoliation. Raman spectra and photoluminescence measurements confirm the formation of an effective heterojunction, indicating interlayer coupling of the system. The anisotropy and asymmetry of the WS2 -ReS2 heterostructure system can be adjusted by the introduction of isotropic WS2 and anisotropic ReS2 , which can be proved by the change of the polarized Raman pattern. In the transient absorption measurement, the transient absorption spectra of WS2 -ReS2 heterostructure are red-shifted compared to those of WS2 monolayer, and the charge transfer is observed in the heterostructure. These results show the potential of anisotropic 2D materials in anisotropy modulation of heterostructures, which may promote future electronic or photonic application.

Growth of single-crystal black phosphorus and its alloy films through sustained feedstock release.

Black phosphorus (BP), a fascinating semiconductor with high mobility and a tunable direct bandgap, has emerged as a candidate beyond traditional silicon-based devices for next-generation electronics and optoelectronics. The ability to grow large-scale, high-quality BP films is a prerequisite for scalable integrated applications but has thus far remained a challenge due to unmanageable nucleation events. Here we develop a sustained feedstock release strategy to achieve subcentimetre-size single-crystal BP films by facilitating the lateral growth mode under a low nucleation rate. The as-grown single-crystal BP films exhibit high crystal quality, which brings excellent field-effect electrical properties and observation of pronounced Shubnikov-de Haas oscillations, with high mobilities up to ~6,500 cm2 V-1 s-1 at low temperatures. We further extend this approach to the growth of single-crystal BP alloy films, which broaden the infrared emission regime of BP from 3.7 µm to 6.9 µm at room temperature. This work will greatly facilitate the development of high-performance electronics and optoelectronics based on BP family materials.

Enhancing photoluminescence of WSe2 in vapor grown WSe2/VOCl bilayer heterojunctions via surface passivation.

Monolayer tungsten selenide (WSe2) has attracted attention due to its direct bandgap-generated strong light emission and light-matter interaction. Herein, vertical WSe2/VOCl bilayer heterojunctions with enhanced PL of WSe2 were synthesized by the vapor growth method. The morphology, crystal structure, and chemical composition of the WSe2/VOCl heterojunctions were systematically investigated, which confirmed the successful formation of the heterojunctions. The PL emission intensity of WSe2 obtained from the WSe2/VOCl heterojunction was about 2.4 times higher than that of the WSe2 monolayer, demonstrating the high optical quality of the WSe2/VOCl heterojunction, which was further confirmed by time-resolved PL measurements. The insulator top VOCl, which was deposited on the surface of the semiconductor bottom WSe2 as a surface passivation material, reducing the impurities and resulting in an atomically clean surface, successfully enhanced the PL emission of the bottom WSe2. This vertical WSe2/VOCl bilayer heterojunction with PL enhancement could provide a promising platform for optical 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.

Electrically Controlling Vortices in a Neutral Exciton-Polariton Condensate at Room Temperature.

Manipulating bosonic condensates with electric fields is very challenging as the electric fields do not directly interact with the neutral particles of the condensate. Here we demonstrate a simple electric method to tune the vorticity of exciton-polariton condensates in a strong coupling liquid crystal (LC) microcavity with CsPbBr_{3} microplates as active material at room temperature. In such a microcavity, the LC molecular director can be electrically modulated giving control over the polariton condensation in different modes. For isotropic nonresonant optical pumping we demonstrate the spontaneous formation of vortices with topological charges of +1, +2, -2, and -1. The topological vortex charge is controlled by a voltage in the range of 1 to 10 V applied to the microcavity sample. This control is achieved by the interplay of a built-in potential gradient, the anisotropy of the optically active perovskite microplates, and the electrically controllable LC molecular director in our system with intentionally broken rotational symmetry. Besides the fundamental interest in the achieved electric polariton vortex control at room temperature, our work paves the way to micron-sized emitters with electric control over the emitted light's phase profile and quantized orbital angular momentum for information processing and integration into photonic circuits.

Scalable-doped Nanoporous 1T″ ReSe2 via a General Surface Co-Alloy Strategy.

Reliable and controllable doping of 2D transition metal dichalcogenides is an efficient approach to tailor their physicochemical properties and expand their functional applications. However, precise control over dopant distribution and scalability of the process remains a challenge. Here, we report a general method to achieve scalable in situ doping of centimeter-sized bicontinuous nanoporous ReSe2 films with transition metal atoms via surface coalloy growth. The distinct strains induced by the bending curvature of nanoporous structures and uniform dopants result in a local 1T' to 1T″ structure phase transition over nanoporous ReSe2 films. The as-prepared nanoporous Ru-ReSe2 with high 1T″ phase exhibits preferable electrochemical activity in hydrogen evolution reaction. The work demonstrates a unique and general approach to synthesize uniformly-doped transition metal dichalcogenides with 3D bicontinuous nanoporous structure, which can be scaled up to batch production for various applications.

Morphology Deformation and Giant Electronic Band Modulation in Long-Wavelength WS2 Moiré Superlattices.

As a lattice interference effect, moiré superlattices feature a magnification effect that they respond sensitively to both the extrinsic mechanical perturbations and intrinsic atomic reconstructions. Here, using scanning tunneling microscopy and spectroscopy, we observe that long-wavelength WS2 superlattices are reconstructed into various moiré morphologies, ranging from regular hexagons to heavily deformed ones. We show that a dedicated interplay between the extrinsic nonuniform heterostrain and the intrinsic atomic reconstruction is responsible for this interesting moiré structure evolution. Importantly, the interplay between these two factors also introduces a local inhomogeneous intralayer strain within a moiré. Contrary to the commonly reported electronic modulation that occurred at the valence band edge due to interlayer hybridization, we find that this local intralayer strain induces a strong modulation at K point of the conduction band, reaching up to 300 meV in the heavily deformed moiré. Our microscopic explorations provide valuable information in understanding the intriguing physics in TMD moirés.

Photoluminescence Lightening: Extraordinary Oxygen Modulated Dynamics in WS2 Monolayers.

Transition metal dichalcogenide monolayers exhibit ultrahigh surface sensitivity since they expose all atoms to the surface and thereby influence their optoelectronic properties. Here, we report an intriguing lightening of the photoluminescence (PL) from the edge to the interior over time in the WS2 monolayers grown by physical vapor deposition method, with the whole monolayer brightened eventually. Comprehensive optical studies reveal that the PL enhancement arises from the p doping induced by oxygen adsorption. First-principles calculations unveil that the dissociation of chemisorbed oxygen molecule plays a significant role; i.e., the dissociation at one site can largely promote the dissociation at a nearby site, facilitating the photoluminescence lightening. In addition, we further manipulate such PL brightening rate by controlling the oxygen concentration and the temperature. The presented results uncover the extraordinary surface chemistry and related mechanism in WS2 monolayers, which deepens our insight into their unique PL evolution behavior.

Band Alignment Engineering by Twist Angle and Composition Modulation for Heterobilayer.

Atomically thin monolayer semiconducting transition metal dichalcogenides (TMDs), exhibiting direct band gap and strong light-matter interaction, are promising for optoelectronic devices. However, an efficient band alignment engineering method is required to further broaden their practical applications as versatile optoelectronics. In this work, the band alignment of two vertically stacked monolayer TMDs using the chemical vapor deposition (CVD) method is effectively tuned by two strategies: 1) formulating the compositions of MoS2(1-x) Se2x alloys, and 2) varying the twist angles of the stacked heterobilayer structures. Photoluminescence (PL) results combined with density functional theory (DFT) calculation show that by changing the alloy composition, a continuously tunable band alignment and a transition of type II-type I-type II band alignment of TMD heterobilayer is achieved. Moreover, only at moderate (10°-50°) twist angles, a PL enhancement of 28%-110% caused by the type I alignment is observed, indicating that the twist angle is coupled with the global band structure of heterobilayer. A heterojunction device made with MoS0.76 Se1.24 /WS2 of 14° displays a significantly high photoresponsivity (55.9 A W-1 ), large detectivity (1.07 × 1010 Jones), and high external quantum efficiency (135%). These findings provide engineering tools for heterostructure design for their application in optoelectronic devices.

Unidirectional Rashba spin splitting in single layer WS2(1-x)Se2xalloy.

Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS1.4Se0.6alloys. The electronic structure of this alloy, explored using angle resolved photoemission spectroscopy, shows a clear valence band structure anisotropy characterized by two paraboloids shifted in one direction of thek-space by a constant in-plane vector. This band splitting is a signature of a unidirectional Rashba spin splitting with a related giant Rashba parameter of 2.8 ± 0.7 eV Å. The combination of angle resolved photoemission spectroscopy with piezo force microscopy highlights the link between this giant unidirectional Rashba spin splitting and an in-plane polarization present in the alloy. These peculiar anisotropic properties of the WS1.4Se0.6alloy can be related to local atomic orders induced during the growth process due the different size and electronegativity between S and Se atoms. This distorted crystal structure combined to the observed macroscopic tensile strain, as evidenced by photoluminescence, displays electric dipoles with a strong in-plane component, as shown by piezoelectric microscopy. The interplay between semiconducting properties, in-plane spontaneous polarization and giant out-of-plane Rashba spin-splitting in this 2D material has potential for a wide range of applications in next-generation electronics, piezotronics and spintronics devices.

Moiré superlattices and related moiré excitons in twisted van der Waals heterostructures.

Recent advances in moiré superlattices and moiré excitons, such as quantum emission arrays, low-energy flat bands, and Mott insulators, have rapidly attracted attention in the fields of optoelectronics, materials, and energy research. The interlayer twist turns into a degree of freedom that alters the properties of the systems of materials, and the realization of moiré excitons also offers the feasibility of making artificial exciton crystals. Moreover, moiré excitons exhibit many exciting properties under the regulation of various external conditions, including spatial polarisation, alternating dipolar to alternating dipolar moments and gate-dependence to gate voltage dependence; all are pertinent to their applications in nano-photonics and quantum information. But the lag in theoretical development and the low-efficiency of processing technologies significantly limit the potential of moiré superlattice applications. In this review, we systematically summarise and discuss the recent progress in moiré superlattices and moiré excitons, and analyze the current challenges, and put forward relevant recommendations. There is no doubt that further research will lead to breakthroughs in their application and promote reforms and innovations in traditional solid-state physics and materials science.

Orbital-Angular-Momentum-Controlled Hybrid Nanowire Circuit.

Plasmonic nanostructures can enable compact multiplexing of the orbital angular momentum (OAM) of light; however, strong dissipation of the highly localized OAM-distinct plasmonic fields in the near-field region hinders on-chip OAM transmission and processing. Superior transmission efficiency is offered by semiconductor nanowires sustaining highly confined optical modes, but only the polarization degree of freedom has been utilized for their selective excitation. Here we demonstrate that incident OAM beams can selectively excite single-crystalline cadmium sulfide (CdS) nanowires through coupling OAM-distinct plasmonic fields into nanowire waveguides for long-distance transportation. This allows us to build an OAM-controlled hybrid nanowire circuit for optical logic operations including AND and OR gates. In addition, this circuit enables the on-chip photoluminescence readout of OAM-encrypted information. Our results open exciting new avenues not only for nanowire photonics to develop OAM-controlled optical switches, logic gates, and modulators but also for OAM photonics to build ultracompact photonic circuits for information processing.

Strain-Stabilized Metastable Face-Centered Tetragonal Gold Overlayer for Efficient CO2 Electroreduction.

Synthesis of the unconventional phase of noble metal nanocrystals may create new opportunities in exploring intriguing physicochemical properties but remains challenging. In the research field of thin film growth, the interface strain offers a general driving force to stabilize the metastable phase of epitaxial film. Herein we extend this concept to the field of noble metal nanocrystals and report the solution synthesis of metastable face-centered tetragonal Au that has not been discovered before. The successful synthesis relies on the formation of intermetallic AuCu3@Au core-shell structure, where the interface strain stabilizes the metastable fct Au overlayer. Compared with the face-centered cubic Au counterpart, the metastable fct Au shows greatly improved catalytic activity toward CO2 reduction to CO. The density functional theory calculations and spectroscopic studies reveal that the metastable fct Au upshifts the d-band center, which lowers the energy barrier of key intermediate COOH* formation and thus facilitates the reaction kinetics.

An Efficient Deep-Subwavelength Second Harmonic Nanoantenna Based on Surface Plasmon-Coupled Dilute Nitride GaNP Nanowires.

High-index semiconductor nanoantennae represent a powerful platform for nonlinear photon generation. Devices with reduced footprints are pivotal for higher integration capacity and energy efficiency in photonic integrated circuitry (PIC). Here, we report on a deep subwavelength nonlinear antenna based on dilute nitride GaNP nanowires (NWs), whose second harmonic generation (SHG) shows a 5-fold increase by incorporating ∼0.45% of nitrogen (N), in comparison with GaP counterpart. Further integrating with a gold (Au) thin film-based hybrid cavity achieves a significantly boosted SHG output by a factor of ∼380, with a nonlinear conversion efficiency up to 9.4 × 10-6 W-1. In addition, high-density zinc blende (ZB) twin phases were found to tailor the nonlinear radiation profile via dipolar interference, resulting in a highly symmetric polarimetric pattern well-suited for coupling with polarization nano-optics. Our results manifest dilute nitride nanoantenna as promising building blocks for future chip-based nonlinear photonic technology.

Strong Second- and Third-Harmonic Generation in 1D Chiral Hybrid Bismuth Halides.

Breaking the symmetry of a crystal structure can enable even-order nonlinear activities, including second-harmonic generation (SHG). The emerging chiral hybrid organic-inorganic metal halides feature unique optical and electronic properties and flexible crystal structures, making them a class of promising nonlinear optical materials. However, their nonlinear response performances are currently inferior to traditional nonlinear crystals, because of the lack of research on resonant enhancement and third-harmonic generation (THG). Herein, we designed chiral hybrid bismuth halides with naturally nonsymmetrical structure to enable SHG. Simultaneously, these chiral compounds preserve 1D crystal structures to create strong free exciton, broad self-trapped exciton (STE), and discrete band energy levels, which facilitate the resonant enhancement of SHG and THG susceptibilities. These new chiral films showcase superior effective SHG susceptibility (χ(2) ∼ 130.5 pm V-1 at an interesting wavelength of 1550 nm), exceeding that of the reference, a commercial LiNbO3 (χ(2) ∼ 83.4 pm V-1) single-crystal film. Furthermore, their THG intensities are even higher than their SHG intensities, with effective THG susceptibility (χ(3)) being ∼9.0 × 106 pm2 V-2 at 1550 nm (37 times that of the reference monolayer WS2). Their high SHG and THG performances indicate the promising future of these 1D chiral hybrid bismuth halides toward nonlinear optical applications.

Twist-angle-dependent interlayer exciton diffusion in WS2-WSe2 heterobilayers.

The nanoscale periodic potentials introduced by moiré patterns in semiconducting van der Waals heterostructures have emerged as a platform for designing exciton superlattices. However, our understanding of the motion of excitons in moiré potentials is still limited. Here we investigated interlayer exciton dynamics and transport in WS2-WSe2 heterobilayers in time, space and momentum domains using transient absorption microscopy combined with first-principles calculations. We found that the exciton motion is modulated by twist-angle-dependent moiré potentials around 100 meV and deviates from normal diffusion due to the interplay between the moiré potentials and strong exciton-exciton interactions. Our experimental results verified the theoretical prediction of energetically favourable K-Q interlayer excitons and showed exciton-population dynamics that are controlled by the twist-angle-dependent energy difference between the K-Q and K-K excitons. These results form a basis to investigate exciton and spin transport in van der Waals heterostructures, with implications for the design of quantum communication devices.

Mechanism of Extreme Optical Nonlinearities in Spiral WS2 above the Bandgap.

Layered two-dimensional transition-metal dichalcogenides (2D-TMDs) are promising building blocks for ultracompact optoelectronic applications. Recently, a strong second harmonic generation (SHG) was observed in spiral stacked TMD nanostructures which was explained by its low crystal symmetry. However, the relationship between the efficiency of SHG signals and the electronic band structure remains unclear. Here, we show that the SHG signal in spiral WS2 nanostructures is strongly enhanced (∼100 fold increase) not only when the second harmonic signal is in resonance with the exciton states but also when the excitation energy is slightly above the electronic band gap, which we attribute to a large interband Berry connection associated with certain optical transitions in spiral WS2. The giant SHG enhancement observed and explained in this study could promote the understanding and utility of TMDs as highly efficient nonlinear optical materials and potentially lead to a new pathway to fabricate more efficient optical energy conversion devices.

Observation and Active Control of a Collective Polariton Mode and Polaritonic Band Gap in Few-Layer WS2 Strongly Coupled with Plasmonic Lattices.

Two-dimensional semiconductors host excitons with very large oscillator strengths and binding energies due to significantly reduced carrier screening. Two-dimensional semiconductors integrated with optical cavities are emerging as a promising platform for studying strong light-matter interactions as a route to explore a variety of exotic many-body effects. Here, in few-layered WS2 coupled with plasmonic nanoparticle lattices, we observe the formation of a collective polaritonic mode near the exciton energy and the formation of a complete polariton band gap with energy scale comparable to the exciton-plasmon coupling strength. A coupled oscillator model reveals that the collective mode arises from the cooperative coupling of the excitons to the plasmonic lattice diffraction orders via exciton-exciton interactions, leading to ultrastrong coupling. The emergence of the collective mode is accompanied by a superlinear increase of the polariton mode splitting as a function of the square root of the exciton oscillator strength. The presence of these many body effects, which are enhanced in systems which lack bulk polarization, not only allows the formation of a collective mode with periodically varying field profiles, but also further enhances the exciton-plasmon coupling. By integrating the hybrid WS2-plasmonic lattice device with a field-effect transistor, we demonstrate active tuning of the collective mode and the polariton band gap. We also report electrically tunable waveguiding in the polariton band gap region through a line defect, which can be turned off with gate bias that can extinguish the collective mode and the polariton band gap. These systems provide new opportunities for obtaining a deeper and systematic understanding of many body cooperative phenomena in two-dimensional materials coupled with periodic photonic systems and for designing more complex and actively controllable polaritonic devices including switchable polariton lasers, waveguides, and optical logical elements.