Revealing the Optical Transition Properties of Interlayer Excitons in Defective WS2/WSe2 Heterobilayers.

Manipulation of physical properties in multidimensional tunable moiré superlattice systems is a key focus in nanophotonics, especially for interlayer excitons (IXs) in two-dimensional materials. However, the impact of defects on IXs remains unclear. Here, we thoroughly study the optical properties of WS2/WSe2 heterobilayers with varying defect densities. Low-temperature photoluminescence (PL) characterizations reveal that the low-energy IXs are more susceptible to defects compared to the high-energy IXs. The low-energy IXs also show much faster PL quenching rate with temperature, faster peak width broadening rate with laser power, shorter lifetime, and lower circular polarization compared to the low-energy IXs in the region with fewer defects. These effects are attributed to the combined effects of increased electron scattering, exciton-phonon interactions, and nonradiative channels introduced by the defects. Our findings aid in optimizing moiré superlattice structures.

Three-dimensional hidden phase probed by in-plane magnetotransport in kagome metal CsV3Sb5 thin flakes.

Transition metal compounds with kagome structure have been found to exhibit a variety of exotic structural, electronic, and magnetic orders. These orders are competing with energies very close to each other, resulting in complex phase transitions. Some of the phases are easily observable, such as the charge density wave (CDW) and the superconducting phase, while others are more challenging to identify and characterize. Here we present magneto-transport evidence of a new phase below ~ 35 K in the kagome topological metal CsV3Sb5 (CVS) thin flakes between the CDW and the superconducting transition temperatures. This phase is characterized by six-fold rotational symmetry in the in-plane magnetoresistance (MR) and is connected to the orbital current order in CVS. Furthermore, the phase is characterized by a large in-plane negative magnetoresistance, which suggests the existence of a three-dimensional, magnetic field-tunable orbital current ordered phase. Our results highlight the potential of magneto-transport to reveal the interactions between exotic quantum states of matter and to uncover the symmetry of such hidden phases.

Chirality-Dependent Dynamic Evolution for Trions in Monolayer WS2.

Monolayer transition metal dichalcogenides exhibit valley-dependent excitonic characters with a large binding energy, acting as the building block for future optoelectronic functionalities. Herein, combined with pump-probe ultrafast transient transmission spectroscopy and theoretical simulations, we reveal the chirality-dependent trion dynamics in h-BN encapsulated monolayer tungsten disulfide. By resonantly pumping trions in a single valley and monitoring their temporal evolution, we identify the temperature-dependent competition between two relaxation channels driven by chirality-dependent scattering processes. At room temperature, the phonon-assisted upconversion process predominates, converting excited trions to excitons within the same valley on a sub-picosecond (ps) time scale. As temperature decreases, this process becomes less efficient, while alternative channels, notably valley depolarization process for trions, assume importance, leading to an increase of trion density in the unpumped valley within a ps time scale. Our time-resolved valley-contrast results provide a comprehensive insight into trion dynamics in 2D materials, thereby advancing the development of novel valleytronic devices.

Impact of Bright-Dark Exciton Thermal Population Mixing on the Brightness of CsPbBr3 Nanocrystals.

Understanding the interplay between bright and dark exciton states is crucial for deciphering the luminescence properties of low-dimensional materials. The origin of the outstanding brightness of lead halide perovskites remains elusive. Here, we analyze temperature-dependent time-resolved photoluminescence to investigate the population mixing between bright and dark exciton sublevels in individual CsPbBr3 nanocrystals in the intermediate confinement regime. We extract bright and dark exciton decay rates and show quantitatively that the decay dynamics can only be reproduced with second-order phonon transitions. Furthermore, we find that any exciton sublevel ordering is compatible with the most likely population transfer mechanism. The remarkable brightness of lead halide perovskite nanocrystals rather stems from a reduced asymmetry between bright-to-dark and dark-to-bright conversion originating from the peculiar second-order phonon-assisted transitions that freeze bright-dark conversion at low temperatures together with the very fast radiative recombination and favorable degeneracy of the bright exciton state.

Exciton polariton condensation from bound states in the continuum at room temperature.

Exciton-polaritons (polaritons) resulting from the strong exciton-photon interaction stimulates the development of novel low-threshold coherent light sources to circumvent the ever-increasing energy demands of optical communications1-3. Polaritons from bound states in the continuum (BICs) are promising for Bose-Einstein condensation owing to their theoretically infinite quality factors, which provide prolonged lifetimes and benefit the polariton accumulations4-7. However, BIC polariton condensation remains limited to cryogenic temperatures ascribed to the small exciton binding energies of conventional material platforms. Herein, we demonstrated room-temperature BIC polariton condensation in perovskite photonic crystal lattices. BIC polariton condensation was demonstrated at the vicinity of the saddle point of polariton dispersion that generates directional vortex beam emission with long-range coherence. We also explore the peculiar switching effect among the miniaturized BIC polariton modes through effective polariton-polariton scattering. Our work paves the way for the practical implementation of BIC polariton condensates for integrated photonic and topological circuits.

Ultrastrong exciton-plasmon couplings in WS2 multilayers synthesized with a random multi-singular metasurface at room temperature.

Van der Waals semiconductors exemplified by two-dimensional transition-metal dichalcogenides have promised next-generation atomically thin optoelectronics. Boosting their interaction with light is vital for practical applications, especially in the quantum regime where ultrastrong coupling is highly demanded but not yet realized. Here we report ultrastrong exciton-plasmon coupling at room temperature in tungsten disulfide (WS2) layers loaded with a random multi-singular plasmonic metasurface deposited on a flexible polymer substrate. Different from seeking perfect metals or high-quality resonators, we create a unique type of metasurface with a dense array of singularities that can support nanometre-sized plasmonic hotspots to which several WS2 excitons coherently interact. The associated normalized coupling strength is 0.12 for monolayer WS2 and can be up to 0.164 for quadrilayers, showcasing the ultrastrong exciton-plasmon coupling that is important for practical optoelectronic devices based on low-dimensional semiconductors.

Energy transfer driven brightening of MoS2 by ultrafast polariton relaxation in microcavity MoS2/hBN/WS2 heterostructures.

Energy transfer is a ubiquitous phenomenon that delivers energy from a blue-shifted emitter to a red-shifted absorber, facilitating wide photonic applications. Two-dimensional (2D) semiconductors provide unique opportunities for exploring novel energy transfer mechanisms in the atomic-scale limit. Herein, we have designed a planar optical microcavity-confined MoS2/hBN/WS2 heterojunction, which realizes the strong coupling among donor exciton, acceptor exciton, and cavity photon mode. This configuration demonstrates an unconventional energy transfer via polariton relaxation, brightening MoS2 with a record-high enhancement factor of ~440, i.e., two-order-of-magnitude higher than the data reported to date. The polariton relaxation features a short characteristic time of ~1.3 ps, resulting from the significantly enhanced intra- and inter-branch exciton-exciton scattering. The polariton relaxation dynamics is associated with Rabi energies in a phase diagram by combining experimental and theoretical results. This study opens a new direction of microcavity 2D semiconductor heterojunctions for high-brightness polaritonic light sources and ultrafast polariton carrier dynamics.

Total Syntheses of ß-Carboline Alkaloids Manzamine C, Orthoscuticelline C, and Quassidine S.

A regioselective olefin hydrofunctionalization reaction of pavettine (4) with various nucleophiles was developed and used as the key step in the total syntheses of ß-carboline natural products manzamine C (3), orthoscuticelline C (5), and quassidine S (6). In the 6-step total synthesis of manzamine C (3), an efficient two-step procedure, comprising a Wittig olefination reaction and a Fukuyama-Mitsunobu reaction, was devised for the synthesis of the N-macrocycle with a Z-olefin.

Realization of Robust and Ambient-Stable Room-Temperature Ferromagnetism in Wide Bandgap Semiconductor 2D Carbon Nitride Sheets.

Due to their weak intrinsic spin-orbit coupling and a distinct bandgap of 3.06 eV, 2D carbon nitride (CN) flakes are promising materials for next-generation spintronic devices. However, achieving strong room-temperature (RT) and ambient-stable ferromagnetism (FM) remains a huge challenge. Here, we demonstrate that the strong RT FM with a high Curie temperature (TC) up to ∼400 K and saturation magnetization (Ms) of 2.91 emu/g can be achieved. Besides, the RT FM exhibits excellent air stability, with Ms remaining stable for over 6 months. Through the magneto-optic Kerr effect, Hall device, X-ray magnetic circular dichroism, and magnetic force microscopy measurements, we acquired clear evidence of magnetic behavior and magnetic domain evolutions at room temperature. Electrical and optical measurements confirm that the Co-doped CN retains its semiconductor properties. Detailed structural characterizations confirm that the single-atom Co coordination and nitrogen defects as well as C-C covalent bonds are simultaneously introduced into CN. Density functional theory calculations reveal that introducing C-C bonds causes carrier spin polarization, and spin-polarized carrier-mediated magnetic exchange between adjacent Co atoms leads to long-range magnetic ordering in CN. We believe that our findings provide a strong experimental foundation for the enormous potential of 2D wide bandgap semiconductor spintronic devices.

Syntheses of Substituted α,ß-Unsaturated δ-Lactams from N-Boc-2,4-dioxopiperidine.

A method for the syntheses of substituted α,ß-unsaturated δ-lactams (2) from the commercially available compound N-Boc-2,4-dioxopiperidine (1) has been developed. The α-substituents were introduced by a reductive Knoevenagel condensation reaction, and the ß-substituents were installed by palladium-catalyzed cross coupling reactions. More than 20 diverse examples were prepared in 2-3 steps. The synthesis was operationally simple, user-friendly, and easy to scale up.

Room-temperature high-speed electrical modulation of excitonic distribution in a monolayer semiconductor.

Excitons in monolayer semiconductors, benefitting from their large binding energies, hold great potential towards excitonic circuits bridging nano-electronics and photonics. However, achieving room-temperature ultrafast on-chip electrical modulation of excitonic distribution and flow in monolayer semiconductors is nontrivial. Here, utilizing lateral bias, we report high-speed electrical modulation of the excitonic distribution in a monolayer semiconductor junction at room temperature. The alternating charge trapping/detrapping at the two monolayer/electrode interfaces induces a non-uniform carrier distribution, leading to controlled in-plane spatial variations of excitonic populations, and mimicking a bias-driven excitonic flow. This modulation increases with the bias amplitude and eventually saturates, relating to the energetic distribution of trap density of states. The switching time of the modulation is down to 5 ns, enabling high-speed excitonic devices. Our findings reveal the trap-assisted exciton engineering in monolayer semiconductors and offer great opportunities for future two-dimensional excitonic devices and circuits.

Unraveling the Ultrafast Coherent Dynamics of Exciton Polariton Propagation at Room Temperature.

Exciton polaritons are widely considered as promising platforms for developing room-temperature polaritonic devices, owing to the high-speed propagation and nonlinear interactions. However, it remains challenging to explore the dynamics of exciton polaritons specifically at room temperature, where the lifetime could be as small as a few picoseconds and the prevailing time-averaged measurement cannot give access to the true nature of it. Herein, by using the time-resolved photoluminescence, we have successfully traced the ultrafast coherent dynamics of a moving exciton polariton condensate in a one-dimensional perovskite microcavity. The propagation speed is directly measured to be ∼12.2 ± 0.8 µm/ps. Moreover, we have developed a time-resolved Michelson interferometry to quantify the time-dependent phase coherence, which reveals that the actual coherence time of exciton polaritons could be much longer (nearly 100%) than what was believed before. Our work sheds new light on the ultrafast coherent propagation of exciton polaritons at room temperature.

Manipulating nonlinear exciton polaritons in an atomically-thin semiconductor with artificial potential landscapes.

Exciton polaritons in atomically thin transition-metal dichalcogenide microcavities provide a versatile platform for advancing optoelectronic devices and studying the interacting Bosonic physics at ambient conditions. Rationally engineering the favorable properties of polaritons is critically required for the rapidly growing research. Here, we demonstrate the manipulation of nonlinear polaritons with the lithographically defined potential landscapes in monolayer WS2 microcavities. The discretization of photoluminescence dispersions and spatially confined patterns indicate the deterministic on-site localization of polaritons by the artificial mesa cavities. Varying the trapping sizes, the polariton-reservoir interaction strength is enhanced by about six times through managing the polariton-exciton spatial overlap. Meanwhile, the coherence of trapped polaritons is significantly improved due to the spectral narrowing and tailored in a picosecond range. Therefore, our work not only offers a convenient approach to manipulating the nonlinearity and coherence of polaritons but also opens up possibilities for exploring many-body phenomena and developing novel polaritonic devices based on 2D materials.

Berry Curvature Dipole Induced Giant Mid-Infrared Second-Harmonic Generation in 2D Weyl Semiconductor.

Due to its inversion-broken triple helix structure and the nature of Weyl semiconductor, 2D Tellurene (2D Te) is promising to possess a strong nonlinear optical response in the infrared region, which is rarely reported in 2D materials. Here, a giant nonlinear infrared response induced by large Berry curvature dipole (BCD) is demonstrated in the Weyl semiconductor 2D Te. Ultrahigh second-harmonic generation response is acquired from 2D Te with a large second-order nonlinear optical susceptibility (χ(2) ), which is up to 23.3 times higher than that of monolayer MoS2 in the range of 700-1500 nm. Notably, distinct from other 2D nonlinear semiconductors, χ(2) of 2D Te increases extraordinarily with increasing wavelength and reaches up to 5.58 nm V-1 at ≈2300 nm, which is the best infrared performance among the reported 2D nonlinear materials. Large χ(2) of 2D Te also enables the high-intensity sum-frequency generation with an ultralow continuous-wave (CW) pump power. Theoretical calculations reveal that the exceptional performance is attributed to the presence of large BCD located at the Weyl points of 2D Te. These results unravel a new linkage between Weyl semiconductor and strong optical nonlinear responses, rendering 2D Te a competitive candidate for highly efficient nonlinear 2D semiconductors in the infrared region.

Controllable vortex lasing arrays in a geometrically frustrated exciton-polariton lattice at room temperature.

Quantized vortices appearing in topological excitations of quantum phase transition play a pivotal role in strongly correlated physics involving the underlying confluence of superfluids, Bose-Einstein condensates and superconductors. Exciton polaritons as bosonic quasiparticles have enabled studies of non-equilibrium quantum gases and superfluidity. Exciton-polariton condensates in artificial lattices intuitively emulate energy-band structures and quantum many-body effects of condensed matter, underpinning constructing vortex lattices and controlling quantum fluidic circuits. Here, we harness exciton-polariton quantum fluids of light in a frustrated kagome lattice based on robust metal-halide perovskite microcavities, to demonstrate vortex lasing arrays and modulate their configurations at room temperature. Tomographic energy-momentum spectra unambiguously reveal massless Dirac bands and quenched kinetic-energy flat bands coexisting in kagome lattices, where polariton condensates exhibit prototypical honeycomb and kagome spatial patterns. Spatial coherence investigations illustrate two types of phase textures of polariton condensates carrying ordered quantized-vortex arrays and π-phase shifts, which could be selected when needed using lasing emission energy. Our findings offer a promising platform on which it is possible to study quantum-fluid correlations in complex polaritonic lattices and highlight feasible applications of structured light.

Ultrafast exciton fluid flow in an atomically thin MoS2 semiconductor.

Excitons (coupled electron-hole pairs) in semiconductors can form collective states that sometimes exhibit spectacular nonlinear properties. Here, we show experimental evidence of a collective state of short-lived excitons in a direct-bandgap, atomically thin MoS2 semiconductor whose propagation resembles that of a classical liquid as suggested by the nearly uniform photoluminescence through the MoS2 monolayer regardless of crystallographic defects and geometric constraints. The exciton fluid flows over ultralong distances (at least 60 µm) at a speed of ~1.8 × 107 m s-1 (~6% the speed of light). The collective phase emerges above a critical laser power, in the absence of free charges and below a critical temperature (usually Tc ≈ 150 K) approaching room temperature in hexagonal-boron-nitride-encapsulated devices. Our theoretical simulations suggest that momentum is conserved and local equilibrium is achieved among excitons; both these features are compatible with a fluid dynamics description of the exciton transport.

Higher-order topological polariton corner state lasing.

Unlike conventional laser, the topological laser is able to emit coherent light robustly against disorders and defects because of its nontrivial band topology. As a promising platform for low-power consumption, exciton polariton topological lasers require no population inversion, a unique property that can be attributed to the part-light-part-matter bosonic nature and strong nonlinearity of exciton polaritons. Recently, the discovery of higher-order topology has shifted the paradigm of topological physics to topological states at boundaries of boundaries, such as corners. However, such topological corner states have never been realized in the exciton polariton system yet. Here, on the basis of an extended two-dimensional Su-Schrieffer-Heeger lattice model, we experimentally demonstrate the topological corner states of perovskite polaritons and achieved polariton corner state lasing with a low threshold (approximately microjoule per square centimeter) at room temperature. The realization of such polariton corner states also provides a mechanism of polariton localization under topological protection, paving the way toward on-chip active polaritonics using higher-order topology.

Ultrafast charge transfer in mixed-dimensional WO3-x nanowire/WSe2 heterostructures for attomolar-level molecular sensing.

Developing efficient noble-metal-free surface-enhanced Raman scattering (SERS) substrates and unveiling the underlying mechanism is crucial for ultrasensitive molecular sensing. Herein, we report a facile synthesis of mixed-dimensional heterostructures via oxygen plasma treatments of two-dimensional (2D) materials. As a proof-of-concept, 1D/2D WO3-x/WSe2 heterostructures with good controllability and reproducibility are synthesized, in which 1D WO3-x nanowire patterns are laterally arranged along the three-fold symmetric directions of 2D WSe2. The WO3-x/WSe2 heterostructures exhibited high molecular sensitivity, with a limit of detection of 5 × 10-18 M and an enhancement factor of 5.0 × 1011 for methylene blue molecules, even in mixed solutions. We associate the ultrasensitive performance to the efficient charge transfer induced by the unique structures of 1D WO3-x nanowires and the effective interlayer coupling of the heterostructures. We observed a charge transfer timescale of around 1.0 picosecond via ultrafast transient spectroscopy. Our work provides an alternative strategy for the synthesis of 1D nanostructures from 2D materials and offers insights on the role of ultrafast charge transfer mechanisms in plasmon-free SERS-based molecular sensing.

Spectral Fingerprint of Quantum Confinement in Single CsPbBr3 Nanocrystals.

Lead halide perovskite nanocrystals are promising materials for classical and quantum light emission. To understand these outstanding properties, a thorough analysis of the band-edge exciton emission is needed, which is not reachable in ensemble and room-temperature studies because of broadening effects. Here, we report on a cryogenic-temperature study of the photoluminescence of single CsPbBr3 nanocrystals in the intermediate quantum confinement regime. We reveal the size-dependence of the spectral features observed: the bright triplet exciton energy splittings, the trion and biexciton binding energies, and the optical phonon replica spectrum. In addition, we show that bright triplet energy splittings are consistent with a pure exchange model and that the variety of polarization properties and spectra recorded can be rationalized simply by considering the orientation of the emitting dipoles and the populations of the emitting states.

Compact spin-valley-locked perovskite emission.

Circularly polarized light sources with free-space directional emission play a key role in chiroptics1, spintronics2, valleytronics3 and asymmetric photocatalysis4. However, conventional approaches fail to simultaneously realize pure circular polarization, high directionality and large emission angles in a compact emitter. Metal-halide perovskite semiconductors are promising light emitters5-8, but the absence of an intrinsic spin-locking mechanism results in poor emission chirality. Further, device integration has undermined the efficiency and directionality of perovskite chiral emitters. Here we realize compact spin-valley-locked perovskite emitting metasurfaces where spin-dependent geometric phases are imparted into bound states in the continuum via Brillouin zone folding, and thus, photons with different spins are selectively addressed to opposite valleys. Employing this approach, chiral purity of 0.91 and emission angle of 41.0° are simultaneously achieved, with a beam divergence angle of 1.6°. With this approach, we envisage the realization of chiral light-emitting diodes, as well as the on-chip generation of entangled photon pairs.