Strong Exciton-Exciton Scattering of Exfoliated van der Waals InSe toward Efficient Continuous-Wave Near-Infrared P-Band Emission.

P-band emission is a superlinear low-coherence emission through exciton-exciton (X-X) scattering into photon-like states. It occurs without the prerequisites of population inversion or macroscopical coherence, rendering lower power consumption than the widely explored superlinear low-coherence emissions including superfluorescence, amplified spontaneous emission, and random lasing, and holds great potential for speckle-free imaging and interferometric sensing. However, competition processes including exciton dissociation and annihilation undermine its operation at room temperature and/or low excitation conditions. Here we report room-temperature P-band emission from InSe microflakes with excitation density of 1010 cm-2, offering 2-orders-of-magnitude lower operation density compared to the state-of-the-art superlinear low-coherence emissions. The efficient P-band emission is attributed to a large X-X scattering strength of 0.25 µeV µm2 due to enhanced spatial confinement along with intrinsic material metrics of 3D/2D exciton complex and asymmetric electron/hole mass. These findings open an avenue toward strong low-coherence near-infrared light sources based on van der Waals semiconductors.

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.

Water-Assisted Growth of Twisted 3R-Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations.

Enhanced second-harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX2 , M: Mo, W; X: S, Se) due to the broken symmetries. The 3R-like stacked MX2 spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on-chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R-stacked chiral molybdenum diselenide (MoSe2 ) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water-assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe2 spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe2 spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light-matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R-stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on-chip nonlinear optical devices.

Ultrafast Internal Exciton Dissociation through Edge States in MoS2 Nanosheets with Diffusion Blocking.

Edge states of two-dimensional transition-metal dichalcogenides (TMDCs) are crucial to quantum circuits and optoelectronics. However, their dynamics are pivotal but remain unclear due to the edge states being obscured by their bulk counterparts. Herein, we study the state-resolved transient absorption spectra of ball-milling-produced MoS2 nanosheets with 10 nm lateral size with highly exposed free edges. Electron energy loss spectroscopy and first-principles calculations confirm that the edge states are located in the range from 1.23 to 1.78 eV. Upon above bandgap excitations, excitons populate and diffuse toward the boundary, where the potential gradient blocks excitons and the edge states are formed through interband transitions within 400 fs. With below bandgap excitations, edge states are slowed down to 1.1 ps due to the weakened valence orbital coupling. These results shed light on the fundamental exciton dissociation processes on the boundary of functionalized TMDCs, enabling the ground work for applications in optoelectronics and light-harvesting.

All Optical Switching through Anistropic Gain of CsPbBr3 Single Crystal Microplatelet.

Perovskite micro/nanostructures have recently emerged as a highly attractive gain material for nanolasers. To explore their applications and further improve performance, it is essential to understand the optical gain and the anisotropic properties. Herein, we obtained high quality CsPbBr3 microplatelets (MP) with anisotropic orthorhombic phase. Optical gain of CsPbBr3 single crystal MP was investigated via microscale variable stripe-length measurement. A polarization-dependent optical gain was observed, and the gain along [002] was larger than that of [1-10]. The behavior was attributed to the lowest energy transition dipole moment of [002] induced by the smaller deviation of Br-Pb-Br bond from the perfect lattice. Along the [002] direction, we obtained the optical gain value up to 5077 cm-1, which is the record value ever reported. Moreover, all optical switching of lasing is realized by periodical polarized excitation. Our results provide new perceptions in the design of novel functional anisotropic devices based on perovskite micro/nanostructures.

Ultrafast Antisolvent Growth of Single-Crystalline CsPbCl3 Microcavity for Low-Threshold Room Temperature Blue Lasing.

All-inorganic perovskite CsPbCl3 has recently attracted considerable attention due to its great potentials for the development of high-efficiency, deep-blue optoelectronic devices. Particularly, single-crystalline CsPbCl3 planar microstructures provide good platforms for both fundamental studies and nanophotonics applications from lasers and detectors to amplifiers. In this study, we report an ultrafast antisolvent deposition route to fabricate single-crystalline CsPbCl3 microplatelets (MPs). The as-grown MPs exhibit uniform morphology, strong emission, and outstanding gain property. Room temperature photoluminescence lasing is realized at 428 nm with a low threshold of 11.5 µJ cm-2 and high net optical gain up to 720 cm-1. These findings advance fundamental understanding on the fabrication and optoelectronic applications of low-dimensional CsPbCl3 perovskite structures.

Pattern-Selective Molecular Epitaxial Growth of Single-Crystalline Perovskite Arrays toward Ultrasensitive and Ultrafast Photodetector.

The emergence of organic-inorganic perovskite has provided great flexibility for creating optoelectronic devices with unprecedented performance or unique functionality. However, the perovskite films explored so far have been difficult to be patterned to arrays owing to their poor solvent and moisture stability, which usually lead to serious structural damage of perovskites. The successful preparation of perovskite microarrays with uniform shape and size is more challenging. Here we report a straightforward approach to realize single-crystalline perovskite arrays through a relatively simple pattern-selective molecular epitaxial growth. This approach is applied to create diverse shaped perovskite arrays, such as hexagon, triangle, circle, square, and rectangle. A vertically aligned perovskite photodetector displays both an ultrasensitive and ultrafast photoresponse arising from the reduction in carrier diffusion paths and the high optical absorption. This work demonstrates a general approach to creating perovskite arrays with uniform shape, size, and morphology and provides a rich platform for producing high-performance photodetectors and photovoltage devices.

Room-temperature Near-infrared Excitonic Lasing from Mechanically Exfoliated InSe Microflake.

The development of chip-level near-infrared laser sources using two-dimensional semiconductors is imperative to maintain the architecture of van der Waals integrated optical interconnections. However, the established two-dimensional semiconductor lasers may have either the disadvantages of poor controllability of monolayered gain media, large optical losses on silicon, or complicated fabrication of external optical microcavities. This study demonstrates room-temperature near-infrared lasing from mechanically exfoliated γ-phase indium selenide (InSe) microflakes free from external optical microcavities at a center wavelength of ∼1030 nm. The lasing action occurs at the sub-Mott density level and is generated by exciton-exciton scattering with a high net modal optical gain of ∼1029 cm-1. Moreover, the lasing is sustained for microdisks fabricated by a simple laser printing with a reduced threshold. These results suggest that InSe is a promising material for near-infrared microlasers and can be employed in a wide range of applications, including imaging, sensing, and optical interconnects.

Full-color enhanced second harmonic generation using rainbow trapping in ultrathin hyperbolic metamaterials.

Metasurfaces have provided a promising approach to enhance the nonlinearity at subwavelength scale, but usually suffer from a narrow bandwidth as imposed by sharp resonant features. Here, we counterintuitively report a broadband, enhanced second-harmonic generation, in nanopatterned hyperbolic metamaterials. The nanopatterning allows the direct access of the mode with large momentum, rendering the rainbow light trapping, i.e. slow light in a broad frequency, and thus enhancing the local field intensity for boosted nonlinear light-matter interactions. For a proof-of-concept demonstration, we fabricated a nanostructured Au/ZnO multilayer, and enhanced second harmonic generation can be observed within the visible wavelength range (400-650 nm). The enhancement factor is over 50 within the wavelength range of 470-650 nm, and a maximum conversion efficiency of 1.13×10-6 is obtained with a pump power of only 8.80 mW. Our results herein offer an effective and robust approach towards the broadband metasurface-based nonlinear devices for various important technologies.

Halide Perovskite Semiconductor Lasers: Materials, Cavity Design, and Low Threshold.

Solution-processable semiconductor lasers have been a long-standing challenge for next-generation displays, light sources, and communication technologies. Metal halide perovskites, which combine the advantages of inorganic and organic semiconductors, have recently emerged not only as excellent candidates for solution-processable lasers but also as potential complementary gain materials for filling the "green gap" and supplement industrial nanolasers based on classic II-VI/III-V semiconductors. Numerous perovskite lasers have been developed successfully with superior performance in terms of cost-effectiveness, low threshold, high coherence, and multicolor tunability. This mini review surveys the development, current status, and perspectives of perovskite lasers, categorized into thin film lasers, nanocrystals lasers, microlasers, and device concepts including polariton and bound-in-continuum lasers with a focus on material fundamentals, cavity design, and low-threshold devices in addition to critical issues such as mass fabrication and applications.

Large-Scale Thin CsPbBr3 Single-Crystal Film Grown on Sapphire via Chemical Vapor Deposition: Toward Laser Array Application.

Single-crystal perovskites with excellent photophysical properties are considered to be ideal materials for optoelectronic devices, such as lasers, light-emitting diodes and photodetectors. However, the growth of large-scale perovskite single-crystal films (SCFs) with high optical gain by vapor-phase epitaxy remains challenging. Herein, we demonstrated a facile method to fabricate large-scale thin CsPbBr3 SCFs (∼300 nm) on the c-plane sapphire substrate. High temperature is found to be the key parameter to control low reactant concentration and sufficient surface diffusion length for the growth of continuous CsPbBr3 SCFs. Through the comprehensive study of the carrier dynamics, we clarify that the trapped-related exciton recombination has the main effect under low carrier density, while the recombination of excitons and free carriers coexist until free carriers plays the dominate role with increasing carrier density. Furthermore, an extremely low-threshold (∼8 µJ cm-2) amplified spontaneous emission was achieved at room temperature due to the high optical gain up to 1255 cm-1 at a pump power of 20 times threshold (∼20 Pth). A microdisk array was prepared using a focused ion beam etching method, and a single-mode laser was achieved on a 3 µm diameter disk with the threshold of 1.6 µJ cm-2. Our experimental results not only present a versatile method to fabricate large-scale SCFs of CsPbBr3 but also supply an arena to boost the optoelectronic applications of CsPbBr3 with high performance.

Role of the Exciton-Polariton in a Continuous-Wave Optically Pumped CsPbBr3 Perovskite Laser.

Lead halide perovskites have emerged as excellent optical gain materials for solution-processable and flexible lasers. Recently, continuous-wave (CW) optically driven lasing was established in perovskite crystals; however, the mechanism of low-threshold operation is still disputed. In this study, CW-pumped lasing from one-dimensional CsPbBr3 nanoribbons (NBs) with a threshold of ∼130 W cm-2 is demonstrated, which can be ascribed to the large refractive index induced by the exciton-polariton (EP) effect. Increasing the temperature reduces the exciton fraction of EPs, which decreases the group and phase refractive indices and inhibits lasing above 100 K. Thermal management, including reducing the NB height to ∼120 ± 60 nm and adopting a high-thermal-conductivity sink, e.g., sapphire, is critical for CW-driven lasing, even at cryogenic temperatures. These results reveal the nature of ultralow-threshold lasing with CsPbBr3 and provide insights into the construction of room-temperature CW and electrically driven perovskite macro/microlasers.

Enhanced Optical Absorption and Slowed Light of Reduced-Dimensional CsPbBr3 Nanowire Crystal by Exciton-Polariton.

Metallic halide perovskites are promising for low-cost, low-consumption, flexible optoelectronic devices. However, research is lacking on light propagation and dielectric behaviors as fundamental properties for optoelectronic perovskite applications, particularly the mechanism supporting a strong light-matter interaction and the different properties of low-dimensional structures from their bulk counterparts. We use spatially resolved photoluminescence (SRPL) spectroscopy to explore light propagation and measure the refractive index of CsPbBr3 nanowires (NWs). Owing to strong exciton-photon interactions, light is guided as an exciton-polariton inside the NWs at room temperature. Remarkable spatial dispersion is confirmed, in which both the real and imaginary parts of the refractive index increase dramatically approaching exciton resonance, thus slowing light and enhancing absorption, respectively. Reducing the NWs dimension increases exciton-photon coupling and the exciton fraction, increasing the light absorption coefficient and group index 5- and 3-fold, respectively, relative to those of bulk films and slowing the light group velocity by ∼74%. Furthermore, dispersive absorption induces an energy redshift to the propagating PL at 4.1-5.5 meV µm-1 until the bottleneck region. These findings clarify light-matter interaction in confined perovskite structures to improve their optoelectronic device performance.

Controlled Growth and Thickness-Dependent Conduction-Type Transition of 2D Ferrimagnetic Cr2 S3 Semiconductors.

2D magnetic materials have attracted intense attention as ideal platforms for constructing multifunctional electronic and spintronic devices. However, most of the reported 2D magnetic materials are mainly achieved by the mechanical exfoliation route. The direct synthesis of such materials is still rarely reported, especially toward thickness-controlled synthesis down to the 2D limit. Herein, the thickness-tunable synthesis of nanothick rhombohedral Cr2 S3 flakes (from ≈1.9 nm to tens of nanometers) on a chemically inert mica substrate via a facile chemical vapor deposition route is demonstrated. This is accomplished by an accurate control of the feeding rate of the Cr precursor and the growth temperature. Furthermore, it is revealed that the conduction behavior of the nanothick Cr2 S3 is variable with increasing thickness (from 2.6 to 4.8 nm and >7 nm) from p-type to ambipolar and then to n-type. Hereby, this work can shed light on the scalable synthesis, transport, and magnetic properties explorations of 2D magnetic materials.

Atomically Dispersed Co-P3 on CdS Nanorods with Electron-Rich Feature Boosts Photocatalysis.

The development of highly efficient photocatalytic systems with rapid photogenerated charge separation and high surface catalytic activity is highly desirable for the storage and conversion of solar energy, yet remains a grand challenge. Herein, a conceptionally new form of atomically dispersed Co-P3 species on CdS nanorods (CoPSA-CdS) is designed and synthesized for achieving unprecedented photocatalytic activity for the dehydrogenation of formic acid (FA) to hydrogen. X-ray absorption near edge structure, X-ray photoelectron spectroscopy, and time-resolved photoluminescence results confirm that the Co-P3 species have a unique electron-rich feature, greatly improving the efficiency of photogenerated charge separation through an interface charge effect. The in situ attenuated total reflection infrared spectra reveal that the Co-P3 species can achieve much better dissociation adsorption of FA and activation of CH bonds than traditional sulfur-coordinated Co single atom-loaded CdS nanorods (CoSSA-CdS). These two new features make CoPSA-CdS exhibit the unprecedented 50-fold higher activity in the photocatalytic dehydrogenation of FA than CoSSA-CdS, and also much better activity than the Ru-, Rh-, Pd-, or Pt-loaded CdS. Besides, CoPSA-CdS also shows the highest mass activity (34309 mmol gCo -1 h-1 ) of Co reported to date. First-principles simulation reveals that the Co-P3 species herein can form an active PHCOO intermediate for enhancing the rate-determining dissociation adsorption of FA.

Lasing from reduced dimensional perovskite microplatelets: Fabry-Pérot or whispering-gallery-mode?

Cesium lead bromide (CsPbBr3) perovskite has attracted great attention recently for its potentials for next-generation green-color lasing devices owing to the relatively high structural stability and the high emission efficiency among the perovskite family. Herein, we explore the origins of cavity modes in CsPbBr3 microplatelets (MPs) lasers by using angle-resolved microphotoluminescence Fourier imaging technique, which is still controversial so far. In-plane Fabry-Pérot (F-P) mode lasing transition to whispering-gallery-mode (WGM) lasing is verified at room temperature, which mostly occurs in large MPs with edge length (L) over 13 µm. The F-P lasing is suppressed upon decreasing L or increasing excitation density, and the WGM lasing is predominant for all MPs at high excitation density. Furthermore, the parity and symmetry of in-plane F-P modes are classified. These results advance the fundamental understanding of lasing modes in planar microcavities as well as their applications in on-chip interconnection and quantum optics.

Intercalation-Mediated Synthesis and Interfacial Coupling Effect Exploration of Unconventional Graphene/PtSe2 Vertical Heterostructures.

Vertical heterostructures formed by stacks of two-dimensional (2D) layered materials with disparate electronic properties have attracted tremendous attention for their versatile applications. The targeted fabrication of such vertical stacks with clean interfaces and a specific stacking sequence remains challenging. Herein, we design a two-step chemical vapor deposition route for the direct synthesis of unconventional graphene/PtSe2 vertical stacks (Gr/PtSe2) on conductive Au foil substrates. Monolayer PtSe2 (1L-PtSe2) was detected to preferentially grow at the interface of the predeposited Gr layer and the Au foil substrate rather than on the Gr surface. The concurrent effect from the strong interaction of PtSe2/Au and the space confinement effect of Gr/Au are proposed to be the essential mechanisms. Particularly, this unique growth system allows us to uncover the intrinsic property of 1L-PtSe2 and the interfacial coupling effect using scanning tunneling microscopy/spectroscopy. Our work should hereby enable significant advances in the synthesis of 2D-based vertical heterostructures and in the exploration of their intrinsic interface properties.

Lasing from Mechanically Exfoliated 2D Homologous Ruddlesden-Popper Perovskite Engineered by Inorganic Layer Thickness.

2D Ruddlesden-Popper perovskites (RPPs) have aroused growing attention in light harvesting and emission applications owing to their high environmental stability. Recently, coherent light emission of RPPs was reported, however mostly from inhomologous thin films that involve cascade intercompositional energy transfer. Lasing and fundamental understanding of intrinsic laser dynamics in homologous RPPs free from intercompositional energy transfer is still inadequate. Herein, the lasing and loss mechanisms of homologous 2D (BA)2 (MA)n -1 Pbn I3 n +1 RPP thin flakes mechanically exfoliated from the bulk crystal are reported. Multicolor lasing is achieved from the large-n RPPs (n ≥ 3) in the spectral range of 620-680 nm but not from small-n RPPs (n ≤ 2) even down to 78 K. With decreasing n, the lasing threshold increases significantly and the characteristic temperature decreases as 49, 25, and 20 K for n = 5, 4, and 3, respectively. The n-engineered lasing behaviors are attributed to the stronger Auger recombination and exciton-phonon interaction as a result of the enhanced quantum confinement in the smaller-n perovskites. These results not only advance the fundamental understanding of loss mechanisms in both inhomologous and homologous RPP lasers but also provide insights into developing low-threshold, substrate-free, and multicolor 2D semiconductor microlasers.

Vapor-Phase Incommensurate Heteroepitaxy of Oriented Single-Crystal CsPbBr3 on GaN: Toward Integrated Optoelectronic Applications.

Integrating metallic halide perovskites with established modern semiconductor technology is significant for promoting the development of application-level optoelectronic devices. To realize such devices, exploring the growth dynamics and interfacial carrier dynamics of perovskites deposited on the core materials of semiconductor technology is essential. Herein, we report the incommensurate heteroepitaxy of highly oriented single-crystal cesium lead bromide (CsPbBr3) on c-wurtzite GaN/sapphire substrates with atomically smooth surface and uniform rectangular shape by chemical vapor deposition. The CsPbBr3 microplatelet crystal exhibits green-colored lasing under room temperature and has a structural stability comparable with that grown on van der Waals mica substrates. Time-resolved photoluminescence spectroscopy studies show that the type-II CsPbBr3-GaN heterojunction effectively enhances the separation and extraction of free carriers inside CsPbBr3. These findings provide insights into the fabrication and application-level integrated optoelectronic devices of CsPbBr3 perovskites.

Charge-Transfer-Induced Photoluminescence Properties of WSe2 Monolayer-Bilayer Homojunction.

The charge-transfer process in transition-metal dichalcogenides (TMDCs) lateral homojunction affects the electron-hole recombination process of in optoelectronic devices. However, the optical properties of the homojunction reflecting the charge-transfer process has not been observed and studied. In this work, we investigated the charge-transfer-induced emission properties based on monolayer (1L)-bilayer (2L) WSe2 lateral homojunction with dozens of nanometer monolayer region. On the one hand, the photoluminescence (PL) emission of bilayer WSe2 from the homojunction area blue shifts ∼23 and ∼31 meV for direct and indirect bandgap emission, respectively, compared with the bare WSe2 bilayer region. The blue shift of the emission spectrum in the bilayer WSe2 is ascribed to the decrease in binding energy induced by charge transfer from monolayer to bilayer. On the other hand, the energy shift shows a tendency to increase as the temperature decreases. The energy blue shift is ∼57 meV for direct bandgap emission at 80 K, which is larger than that (∼23 meV) at room temperature. The larger-energy blue shift at low temperature is derived from the larger driving force under larger band offset. Our observations of the unique optical properties induced by efficient charge transfer are very helpful for exploring novel TMDC-based optoelectronic devices.