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.

A novel non-chemically amplified resist based on polystyrene-iodonium derivatives for electron beam lithography.

To break the resolution limitation of traditional resists, more work is needed on non-chemically amplified resists (non-CARs). Non-CARs based on iodonium salt modified polystyrene (PS-I) were prepared with controllable molecular weight and structure. The properties of the resist can be adjusted by the uploading of iodonium salts on the polymer chain, the materials with a higher proportion of iodonium salts show better lithography performance. By comparing contrast curves and quality of the lithographic patterns, the optimum developing condition of 4-methyl-2-pentanone and ethyl alcohol (v:v = 1:7) was selected. The high-resolution stripes of 15 nm half-pitch (HP) can be achieved by PS-I0.58in e-beam lithography (EBL). PS-I0.58shows the advanced lithography performance in the patterns of 16 nm HP and 18 nm HP stripes with low line edge roughness (3.0 nm and 2.4 nm). The resist shows excellent potential for further pattern transfer, the etch selectivity of resist PS-I0.58to the silicon was close to 12:1. The lithographic mechanism of PS-I was investigated by experimental and theoretical calculation, which indicates the polarity of materials changes results in the solubility switch. This work provides a new option and useful guidelines for the development of high-resolution resist.

Boosting exciton mobility approaching Mott-Ioffe-Regel limit in Ruddlesden-Popper perovskites by anchoring the organic cation.

Exciton transport in two-dimensional Ruddlesden-Popper perovskite plays a pivotal role for their optoelectronic performance. However, a clear photophysical picture of exciton transport is still lacking due to strong confinement effects and intricate exciton-phonon interactions in an organic-inorganic hybrid lattice. Herein, we present a systematical study on exciton transport in (BA)2(MA)n-1PbnI3n+1 Ruddlesden-Popper perovskites using time-resolved photoluminescence microscopy. We reveal that the free exciton mobilities in exfoliated thin flakes can be improved from around 8 cm2 V-1 s-1 to 280 cm2V-1s-1 by anchoring the soft butyl ammonium cation with a polymethyl methacrylate network at the surface. The mobility of the latter is close to the theoretical limit of Mott-Ioffe-Regel criterion. Combining optical measurements and theoretical studies, it is unveiled that the polymethyl methacrylate network significantly improve the lattice rigidity resulting in the decrease of deformation potential scattering and lattice fluctuation at the surface few layers. Our work elucidates the origin of high exciton mobility in Ruddlesden-Popper perovskites and opens up avenues to regulate exciton transport in two-dimensional materials.

Photophysics and its application in photon upconversion.

Photoluminescence (PL) upconversion is a phenomenon involving light-matter interaction, where the energy of the emitted photons is higher than that of the incident photons. PL upconversion has promising applications in optoelectronic devices, displays, photovoltaics, imaging, diagnosis and treatment. In this review, we summarize the mechanism of PL upconversion and ultrafast PL physical processes. In particular, we highlight the advances in laser cooling, biological imaging, volumetric displays and photonics.

Giant Out-of-Plane Exciton Emission Enhancement in Two-Dimensional Indium Selenide via a Plasmonic Nanocavity.

Out-of-plane (OP) exciton-based emitters in two-dimensional semiconductor materials are attractive candidates for novel photonic applications, such as radially polarized sources, integrated photonic chips, and quantum communications. However, their low quantum efficiency resulting from forbidden transitions limits their practicality. In this work, we achieve a giant enhancement of up to 34000 for OP exciton emission in indium selenide (InSe) via a designed Ag nanocube-over-Au film plasmonic nanocavity. The large photoluminescence enhancement factor (PLEF) is attributed to the induced OP local electric field (Ez) within the nanocavity, which facilitates effective OP exciton-plasmon interaction and subsequent tremendous enhancement. Moreover, the nanoantenna effect resulting from the effective interaction improves the directivity of spontaneous radiation. Our results not only reveal an effective photoluminescence enhancement approach for OP excitons but also present an avenue for designing on-chip photonic devices with an OP dipole orientation.

Sulfonium-Cations-Assisted Intermediate Engineering for Quasi-2D Perovskite Solar Cells.

Quasi-2D Ruddlesden-Popper (RP) perovskites with superior stability are admirable candidates for perovskite solar cells (PSCs) toward commercialization. However, the device performance remains unsatisfactory due to the disordered crystallization of perovskites. In this work, the effects of sulfonium cations on the evolution of intermediates and photovoltaic properties of 2D RP perovskites are investigated. The introduction of sulfonium cations leads to preferred intermediate transformation and improved film quality of perovskites. The resulting devices deliver a champion efficiency of 19.08% at room temperature and 20.52% at 180 K, due to reduced recombination and enhanced charge transport. More importantly, the unencapsulated device maintains 84% of the initial efficiency under maximum power point (MPP) tracking at 40 °C for 1000 h. This work helps to gain a comprehensive understanding of the crystallization process of quasi-2D perovskites and provides a simple strategy to modulate the intermediates of perovskites.

Solvent Effect on Film Formation and Trap States of Two-Dimensional Dion-Jacobson Perovskite.

Two dimensional Dion-Jacobson (2D DJ) perovskite has emerged as a potential photovoltaic material because of its unique optoelectronic characteristics. However, due to its low structural flexibility and high formation energy, extra assistance is needed during crystallization. Herein, we study the solvent effect on film formation and trap states of 2D DJ perovskite. It is found that the nucleation process of 2D DJ perovskite can be retarded by extra coordination, which is proved by in situ optical spectra. As a benefit, out-of-plane oriented crystallization and ordered phase distribution are realized. Finally, in 1,5-pentanediammonium (PeDA) based 2D DJ perovskite solar cells (PSCs), one of the highest reported open-circuit voltage (VOC) values of 1.25 V with state-of-the-art efficiency of 18.41% is obtained due to greatly shallowed trap states and suppressed nonradiative recombination. The device also exhibits excellent heat tolerance, which maintains 80% of its initial efficiency after being kept under 85 °C after 3000 h.

Giant Enhancement and Directional Second Harmonic Emission from Monolayer WS2 on Silicon Substrate via Fabry-Pérot Micro-Cavity.

Two-dimensional transition metal dichalcogenides (TMDs) possess large second-order optical nonlinearity, making them ideal candidates for miniaturized on-chip frequency conversion devices, all-optical interconnection, and optoelectronic integration components. However, limited by subnanometer thickness, the monolayer TMD exhibits low second harmonic generation (SHG) conversion efficiency (<0.1%) and poor directionality, which hinders their practical applications. Herein, we proposed a Fabry-Pérot (F-P) cavity formed by coupling an atomically thin WS2 film with a silicon hole matrix to enhance the SH emission. A maximum enhancement (∼1580 times) is achieved by tuning the excitation wavelength to be resonant with the microcavity modes. The giant enhancement is attributed to the strong electric field enhancement in the F-P cavity and the oscillator strength enhancement of excitons from suspended WS2. Moreover, directional SH emission (divergence angle ∼5°) is obtained benefiting from the resonance of the F-P microcavity. Our research results can provide a practical sketch to develop both high-efficiency and directional nonlinear optical devices for silicon-based on-chip integration optics.

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.

Ultrafast interfacial charge evolution of the Type-II cadmium Sulfide/Molybdenum disulfide heterostructure for photocatalytic hydrogen production.

The interfacial charge dynamics was crucial for semiconductor heterostructure photocatalysis. Through the rational design of the heterostructure interface, heterojunction expressed variable recombination and migration dynamics for excited carriers. Herein, followed by a typical chemical bath strategy with the hexagonal cadmium sulfide (CdS) overlapped on the exfoliated molybdenum disulfide (MoS2) film, we developed a cadmium sulfide/molybdenum disulfide (CdS-MoS2) nano-heterojunction and investigated the interfacial charge dynamics for photocatalytic hydrogen evolution. Photoelectron spectroscopy detected an energetic offset between CdS and MoS2, revealing the formation of an interfacial electric field with efficient charges separation. Through transient absorption spectra, we demonstrated the type-II contact at the CdS-MoS2 interface. Driven by the electric field, the excited carriers separated and rapidly migrated to sub-band defects of CdS within the first 500 fs. The carriers-restricted defects provided catalytic active sites, endowing CdS-MoS2 a highly efficient photocatalytic capability. Consequentially, the CdS-MoS2 achieved an enhanced hydrogen evolution rate of 2.3 mmol·g-1·h-1 with significantly stronger photocurrent density. This work gave an insight to the channel of interfacial separation and migration for excited carriers, which could contribute to the interfacial engineering of advanced heterojunction photocatalysts.

Edge Raman enhancement at layered PbI2platelets induced by laser waveguide effect.

As a two-dimensional (2D) layered semiconductor, lead iodide (PbI2) has been widely used in optoelectronics owing to its unique crystal structure and distinctive optical and electrical properties. A comprehensive understanding of its optical performance is essential for further application and progress. Here, we synthesized regularly shaped PbI2platelets using the chemical vapor deposition method. Raman scattering spectroscopy of PbI2platelets was predominantly enhanced when the laser radiated at the edge according to Raman mapping spectroscopy. Combining the outcome of polarized Raman scattering spectroscopy and finite-difference time domain simulation analysis, the Raman enhancement was proven to be the consequence of the enhancement effects inherent to the high refractive index contrast waveguide, which is naturally formed in well-defined PbI2platelets. Because of the enlarged excited area determined by the increased propagation length of the laser in the PbI2platelet formed waveguide, the total Raman enhancements are acquired rather than a localized point enhancement. Finally, the Raman enhancement factor is directly related to the thickness of the PbI2platelet, which further confirms the waveguide-enhanced edge Raman. Our investigation of the optical properties of PbI2platelets offers reference for potential 2D layered-related optoelectronic applications.

Zone-Folded Longitudinal Acoustic Phonons Driving Self-Trapped State Emission in Colloidal CdSe Nanoplatelet Superlattices.

Colloidal CdSe nanoplatelets (NPLs) have substantial potential in light-emitting applications because of their quantum-well-like characteristics. The self-trapped state (STS), originating from strong electron-phonon coupling (EPC), is promising in white light luminance because of its broadband emission. However, achieving STS in CdSe NPLs is extremely challenging because of their intrinsic weak EPC nature. Herein, we developed a strong STS emission in the spectral range of 450-600 nm by building superlattice (SL) structures with colloidal CdSe NPLs. We demonstrated that STS is generated via strong coupling of excitons and zone-folded longitudinal acoustic phonons with formation time of ∼450 fs and localization length of ∼0.56 nm. The Huang-Rhys factor, describing the EPC strength in SL structure, is estimated to be ∼19.9, which is much larger than that (∼0.1) of monodispersed CdSe NPLs. Our results provide an in-depth understanding of STS and a platform for generating and manipulating STS by designing SL structures.

Inch-Scale Ball-in-Bowl Plasmonic Nanostructure Arrays for Polarization-Independent Second-Harmonic Generation.

Second-harmonic generation (SHG) in plasmonic nanostructures has been investigated for decades due to their wide applications in photonic circuit, quantum optics and biosensing. Development of large-scale, uniform, and efficient plasmonic nanostructure system with tunable modes is desirable for their feasible utilizations. Herein, we design an efficient inch-scale SHG source by a solution-processed method instead of traditional high-cost processes. By assembling the gold nanoparticles with the porous anodic alumina templates, multiresonance in both visible and near-infrared regions can be achieved in hexagonal plasmonic nanostructure arrays, which provide strong electric field enhancement at the gap region. Polarization-independence SHG radiation has been realized owing to the in-plane isotropic characteristic of assembled unit. The tilt-angle dependent and angle-resolved measurement showed that wide-angle nonlinear response is achieved in our device because of the gap geometry of ball-in-bowl nanostructure with nonlinear emission electric dipoles distributed on the concave surface, which makes it competitive in practical applications. Our progress not only makes it possible to produce uniform inch-scale nonlinear arrays through low-cost solution process; and also advances the understanding of the SHG radiation in plasmonic nanostructures.

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.

Enhanced type I photoreaction of indocyanine green via electrostatic-force-driven aggregation.

Owing to the strong NIR absorbance, indocyanine green (ICG) has attracted new attention in emerging photo-theranostics. However, ICG has a very low ROS production efficiency and mainly works through the type II photoreaction via its monomer. The aggregation tendency of ICG in aqueous milieus further worsens the scenario. Herein, ICG aggregates show an enhanced type I photoreaction pathway and have much better photooxidizing capability than its monomer, which improves the performance of ICG in the photodynamic inactivation of bacteria. This finding provides a feasible way to tackle the contradiction of ROS generation and ICG aggregation. Finally, the photodynamic effect of ICG aggregates was combined with the photothermal effect of gold nanorods to achieve an effective treatment of bacterial infection.

High-Quality Hexagonal Nonlayered CdS Nanoplatelets for Low-Threshold Whispering-Gallery-Mode Lasing.

Low threshold micro/nanolasers have attracted extensive attention for wide applications in high-density storage and optical communication. However, constrained by quantum efficiency and crystalline quality, conventional semiconductor small-sized lasers are still subjected to a high lasing threshold. In this work, a low-threshold planar laser based on high-quality single-crystalline hexagonal CdS nanoplatelets (NPLs) using a self-limited epitaxial growth method is demonstrated. The as-grown CdS NPLs show multiple whispering-gallery-mode lasing at room temperature with a threshold of ≈0.6 µJ cm-2 , which is the lowest value among reported CdS-based lasers. Through power-dependent lasing studies at 77 K, the lasing action is demonstrated to originate from a exciton-exciton scattering process. Furthermore, the edge length- and thickness-dependent lasing threshold studies reveal that the threshold is inversely proportional to the second power of lateral edge length while partially affected by vertical thickness, and the lasing modes can be sustained in NPLs as thin as 60 nm. The lowest threshold emerges with the thickness of ≈110 nm due to stronger energy confinement in the vertical Fabry-Pérot cavity. The results not only open up a new avenue to fabricate nonlayered material-based coherent light sources, but also advocate the promise of nonlayered semiconductor materials for the development of novel optoelectronic devices.

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.

Unveiling lasing mechanism in CsPbBr3 microsphere cavities.

Recently, the light-matter interaction of perovskite microcavities has been widely explored for its great potential in low-threshold lasing devices. However, the mechanism of perovskite lasing remains unclear to date. In this study, we demonstrated high-quality single-mode excitonic lasing in CsPbBr3 microspheres, providing an ideal platform to study the underlying physics of lasing behavior. We show that the lasing mechanism shifts from the exciton-exciton scattering to the exciton-phonon scattering with the increase in temperature from 77 to 300 K, which was verified by temperature-dependent photoluminescence (PL), time-resolved photoluminescence (TRPL) as well as temperature-dependent Raman spectroscopy. Furthermore, by analyzing PL line width broadening with varied temperatures, we found that two different phonon modes were involved in the exciton-phonon scattering process. The scattering from the low-energy phonon (∼8.6 meV) is the dominant source of exciton-phonon coupling in the intermediate temperature range (77 to 230 K), while the high-energy phonon (∼15.3 meV) dominates from 230 K to room temperature. These results confirm the lasing mechanism in such perovskite-based micro/nano-cavities and significantly influence the development of future low-threshold lasers.

Recent Progress of Strong Exciton-Photon Coupling in Lead Halide Perovskites.

The semiconductor exciton-polariton, arising from the strong coupling between excitons and confined cavity photon modes, is not only of fundamental importance in macroscopic quantum effects but also has wide application prospects in ultralow-threshold polariton lasers, slowing-light devices, and quantum light sources. Very recently, metallic halide perovskites have been considered as a great candidate for exciton-polariton devices owing to their low-cost fabrication, large exciton oscillator strength, and binding energy. Herein, the latest progress in exciton-polaritons and polariton lasers of perovskites are reviewed. Polaritons in planar and nanowires Fabry-Pérot microcavities are discussed with particular reference to material and photophysics. Finally, a perspective on the remaining challenges in perovskite polaritons research is given.