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.

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.

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.

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.

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.

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.

Continuous-Wave Pumped Perovskite Lasers with Device Area Below 1 µm2.

Continuous-wave (CW) pumped lasers with device areas below 1 µm2 constitute a key step to meeting the energy efficiency requirement for on-chip optical communications. However, a debate about whether a sub-micrometer device size and low threshold can be simultaneously satisfied has persisted owing to insurmountable radiation losses when approaching the optical diffraction limit. Herein, a record-small CW optically pumped perovskite laser with a device area of 0.65 µm2 is demonstrated. The thresholds of sub-micrometer lasers can be found lower than those of several-micrometer counterparts, and are ascribed to the enlarged group refractive index and modal confinement resulting from the enhanced exciton-photon coupling. Moreover, the operation temperature is elevated to 150 K through the reduction in heat generation. These findings unveil the potential of exciton-polaritons in laser miniaturization, providing an alternative for developing low-threshold semiconductor lasers without artificial optical cavities, to approach the optical diffraction limit.

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.

Exciton polariton interactions in Van der Waals superlattices at room temperature.

Monolayer transition-metal dichalcogenide (TMD) materials have attracted a great attention because of their unique properties and promising applications in integrated optoelectronic devices. Being layered materials, they can be stacked vertically to fabricate artificial van der Waals lattices, which offer unique opportunities to tailor the electronic and optical properties. The integration of TMD heterostructures in planar microcavities working in strong coupling regime is particularly important to control the light-matter interactions and form robust polaritons, highly sought for room temperature applications. Here, we demonstrate the systematic control of the coupling-strength by embedding multiple WS2 monolayers in a planar microcavity. The vacuum Rabi splitting is enhanced from 36 meV for one monolayer up to 72 meV for the four-monolayer microcavity. In addition, carrying out time-resolved pump-probe experiments at room temperature we demonstrate the nature of polariton interactions which are dominated by phase space filling effects. Furthermore, we also observe the presence of long-living dark excitations in the multiple monolayer superlattices. Our results pave the way for the realization of polaritonic devices based on planar microcavities embedding multiple monolayers and could potentially lead the way for future devices towards the exploitation of interaction-driven phenomena at room temperature.

Localized Bound Multiexcitons in Engineered Quasi-2D Perovskites Grains at Room Temperature for Efficient Lasers.

Reducing the excitation threshold to minimize the Joule heating is critical for the realization of perovskite laser diodes. Although bound excitons are promising for low threshold laser, how to generate them at room temperature for laser applications is still unclear in quasi-2D perovskite-based devices. In this work, via engineering quasi-2D perovskite PEA2 (CH3 NH3 )n -1 Pbn Br3 n +1 microscopic grains by the anti-solvent method, room-temperature multiexciton radiative recombination is successfully demonstrated at a remarkably low pump density of 0.97 µJ cm-2 , which is only one-fourth of that required in 2D CdSe nanosheets. In addition, the well-defined translational momentum in quasi-2D perovskite grains can restrict the Auger recombination which is detrimental to radiative emission. Furthermore, the quasi-2D perovskite grains are favorable for increasing binding energies of excitons and biexcitons and so as the related radiative recombination. Consequently, the prepared phase quasi-2D perovskite film renders a threshold of room-temperature stimulated emission as low as 13.7 µJ cm-2 , reduced by 58.6% relative to the amorphous counterpart with larger grains. The findings in this work are expected to facilitate the development of solution-processable perovskite multiexcitonic laser diodes.

A Fano Cavity-Photon Interface for Directional Suppression of Spectral Diffusion of a Single Perovskite Nanoplatelet.

Colloidal nanocrystals that are capable of mass production with wet chemical synthesis have long been proposed as color-tunable, scalable quantum emitters for information processing and communication. However, they constantly suffer from spectral diffusion due to being exposed to a noisy electrostatic environment. Herein we demonstrate a cavity-photon interface (CPI) which effectively suppresses the temperature-activated spectral diffusion (SD) of a single perovskite nanoplatelet (NPL) up to 40 K. The spectrally stabilized single-photon emission is achieved at a specific emission direction corresponding to an inhibited dipole moment of the NPL as the result of the Fano coupling between the two photon dissipation channels of the NPL. Our results shed light on the nature of the SD of perovskite nanocrystals and offer a general cavity quantum electrodynamic scheme that controls the brightness and spectral dynamics of a single-photon emitter.

Simultaneous electrical and thermal rectification in a monolayer lateral heterojunction.

Efficient waste heat dissipation has become increasingly challenging as transistor size has decreased to nanometers. As governed by universal Umklapp phonon scattering, the thermal conductivity of semiconductors decreases at higher temperatures and causes heat transfer deterioration under high-power conditions. In this study, we realized simultaneous electrical and thermal rectification (TR) in a monolayer MoSe2-WSe2 lateral heterostructure. The atomically thin MoSe2-WSe2 heterojunction forms an electrical diode with a high ON/OFF ratio up to 104. Meanwhile, a preferred heat dissipation channel was formed from MoSe2 to WSe2 in the ON state of the heterojunction diode at high bias voltage with a TR factor as high as 96%. Higher thermal conductivity was achieved at higher temperatures owing to the TR effect caused by the local temperature gradient. Furthermore, the TR factor could be regulated from maximum to zero by rotating the angle of the monolayer heterojunction interface. This result opens a path for designing novel nanoelectronic devices with enhanced thermal dissipation.

Unveiling the Enhancement of Spontaneous Emission at Exceptional Points.

Exceptional points (EPs), singularities of non-Hermitian physics where complex spectral resonances degenerate, are one of the most exotic features of nonequilibrium open systems with unique properties. For instance, the emission rate of quantum emitters placed near resonators with EPs is enhanced (compared to the free-space emission rate) by a factor that scales quadratically with the resonance quality factor. Here, we verify the theory of spontaneous emission at EPs by measuring photoluminescence from photonic-crystal slabs that are embedded with a high-quantum-yield active material. While our experimental results verify the theoretically predicted enhancement, they also highlight the practical limitations on the enhancement due to material loss. Our designed structures can be used in applications that require enhanced and controlled emission, such as quantum sensing and imaging.

Signature of Ultrafast Formation and Annihilation of Polaronic States in a Layered Ferromagnet.

The strong interaction between charge and lattice vibration gives rise to a polaron, which has a profound effect on optical and transport properties of matters. In magnetic materials, polarons are involved in spin dependent transport, which can be potentially tailored for spintronic and opto-spintronic device applications. Here, we identify the signature of ultrafast formation of polaronic states in CrBr3. The polaronic states are long-lived, having a lifetime on the time scale of nanoseconds to microseconds, which coincides with the emission lifetime of ∼4.3 µs. Transition of the polaronic states is strongly screened by the phonon, generating a redshift of the transition energy ∼0.2 eV. Moreover, energy-dependent localization of polaronic states is discovered followed by transport/annihilation properties. These results shed light on the nature of the polarons and their formation and transport dynamics in layered magnetic materials, which paves the way for the rational design of two-dimensional magnetic devices.