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.

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.

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.

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.

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.

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.

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.

Low Threshold Fabry-Pérot Mode Lasing from Lead Iodide Trapezoidal Nanoplatelets.

Lead Iodide (PbI2 ) is a layered semiconductor with direct band gap holding great promises in green light emission and detection devices. Recently, PbI2 planar lasers are demonstrated using hexagonal whispering-gallery-mode microcavities, but the lasing threshold is quite high. In this work, lasing from vapor phase deposition derived PbI2 trapezoidal nanoplatelets (NPs) with threshold that is at least an order of magnitude lower than the previous value is reported. The growth mechanism of the trapezoidal NPs is explored and attributed to the synergistic effects of van der Waals interactions and lattice mismatching. The lasing is enabled by the population inversion of n = 1 excitons and the optical feedback is provided by the Fabry-Pérot oscillation between the side facets of trapezoidal NPs. The findings not only advance the understanding of growth and photophysics mechanism of PbI2 nanostructures but also provide ideas to develop low threshold ultrathin lasers.

Fabry-Pérot Oscillation and Room Temperature Lasing in Perovskite Cube-Corner Pyramid Cavities.

Recently, organometal halide perovskite-based optoelectronics, particularly lasers, have attracted intensive attentions because of its outstanding spectral coherence, low threshold, and wideband tunability. In this work, high-quality CH3 NH3 PbBr3 single crystals with a unique shape of cube-corner pyramids are synthesized on mica substrates using chemical vapor deposition method. These micropyramids naturally form cube-corner cavities, which are eminent candidates for small-sized resonators and retroreflectors. The as-grown perovskites show strong emission ≈530 nm in the vertical direction at room temperature. A special Fabry-Pérot (F-P) mode is employed to interpret the light confinement in the cavity. Lasing from the perovskite pyramids is observed from 80 to 200 K, with threshold ranging from ≈92 µJ cm-2 to 2.2 mJ cm-2 , yielding a characteristic temperature of T0 = 35 K. By coating a thin layer of Ag film, the threshold is reduced from ≈92 to 26 µJ cm-2 , which is accompanied by room temperature lasing with a threshold of ≈75 µJ cm-2 . This work advocates the prospect of shape-engineered perovskite crystals toward developing micro-sized optoelectronic devices and potentially investigating light-matter coupling in quantum optics.

Defect-free InAsSb nanowire arrays on Si substrates grown by selective-area metal-organic chemical vapor deposition.

We report the realization of defect-free InAsSb nanowire (NW) arrays on Si substrates by selective-area metal-organic chemical vapor deposition. We studied the effects of growth temperature and the morphology of patterned Si/SiO2 substrates on the formation of InAsSb NW arrays, and found that both the morphology and the yield of the NW arrays were sensitive to the growth conditions. By optimizing the growth conditions, we achieved high-quality InAsSb NW arrays, which exhibited a pure zinc-blende crystal structure without any defects. In addition, based on the as-grown NWs, we fabricated back-gated field effect transistors devices that showed an electron mobility of 2000 cm2 V-1 s-1 at room temperature.

Cocrystals Strategy towards Materials for Near-Infrared Photothermal Conversion and Imaging.

A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near-infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self-assemble into new cocrystals through non-covalent interactions. The strong D-A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest-lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency (η=18.8 %), which is due to the active non-radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications.

Tuning Excitonic Properties of Monolayer MoS2 with Microsphere Cavity by High-Throughput Chemical Vapor Deposition Method.

Tuning the optical properties of 2D direct bandgap semiconductors is crucial for applications in photonic light source, optical communication, and sensing. In this work, the excitonic properties of molybdenum disulphide (MoS2 ) are successfully tuned by directly depositing it onto silica microsphere resonators using chemical vapor deposition method. Multiple whispering gallery mode (WGM) peaks in the emission wavelength range of ≈650-750 nm are observed under continuous wave excitation at room temperature. Time-resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) spectroscopy are conducted to study light-matter interaction dynamics of the MoS2 microcavities. TRPL study suggests radiative recombination rate of carrier-phonon scattering and interband transition processes in MoS2 is enhanced by a factor of ≈1.65 due to Purcell effect in microcavities. TA spectroscopy study shows modulation of the interband transition process mainly occurs at PB-A band with an estimated F ≈ 1.60. Furthermore, refractive index sensing utilizing WGM peaks of MoS2 is established with sensitivity up to ≈150 nm per refractive index unit. The present work provides a large-scale and straightforward method for coupling atomically thin 2D gain media with cavities for high-performance optoelectronic devices and sensors.

Selective-Area MOCVD Growth and Carrier-Transport-Type Control of InAs(Sb)/GaSb Core-Shell Nanowires.

We report the first selective-area growth of high quality InAs(Sb)/GaSb core-shell nanowires on Si substrates using metal-organic chemical vapor deposition (MOCVD) without foreign catalysts. Transmission electron microscopy (TEM) analysis reveals that the overgrowth of the GaSb shell is highly uniform and coherent with the InAs(Sb) core without any misfit dislocations. To control the structural properties and reduce the planar defect density in the self-catalyzed InAs core nanowires, a trace amount of Sb was introduced during their growth. As the Sb content increases from 0 to 9.4%, the crystal structure of the nanowires changes from a mixed wurtzite (WZ)/zinc-blende (ZB) structure to a perfect ZB phase. Electrical measurements reveal that both the n-type InAsSb core and p-type GaSb shell can work as active carrier transport channels, and the transport type of core-shell nanowires can be tuned by the GaSb shell thickness and back-gate voltage. This study furthers our understanding of the Sb-induced crystal-phase control of nanowires. Furthermore, the high quality InAs(Sb)/GaSb core-shell nanowire arrays obtained here pave the foundation for the fabrication of the vertical nanowire-based devices on a large scale and for the study of fundamental quantum physics.

Controlled-Direction Growth of Planar InAsSb Nanowires on Si Substrates without Foreign Catalysts.

We describe the controlled growth of planar InAsSb nanowires (NWs) on differently oriented Si substrates without any foreign catalysts. Interestingly, the planar InAsSb NWs grew along four criss-crossed ⟨110⟩ directions on an [100]-oriented substrate, two ⟨100⟩ directions plus four ⟨111⟩ directions on an [110]-oriented substrate, and six equivalent ⟨112⟩ directions on an [111]-oriented substrate, which correspond to the projections of ⟨111⟩ family crystal directions on the substrate planes. High-resolution transmission electron microscopy (HRTEM) reveals that the NWs experienced a transition from out-of-plane to in-plane growth at the early growth stage but still occurred on the {111} plane, which has the lowest surface energy among all the surfaces. Furthermore, the NWs exhibit a pure zinc-blende crystal structure without any defects. A growth model is presented to explain growth of the NWs. In addition, conductive atomic force microscopy shows that electrically rectifying p-n junctions form naturally between the planar InAsSb NWs and the p-type Si substrates. The results presented here could open up a new route way to fabricate highly integrated III-V nanodevices.

InAs/GaSb core-shell nanowires grown on Si substrates by metal-organic chemical vapor deposition.

We report the growth of InAs/GaSb core-shell heterostructure nanowires with smooth sidewalls on Si substrates using metal-organic chemical vapor deposition with no assistance from foreign catalysts. Sb adatoms were observed to strongly influence the morphology of the GaSb shell. In particular, Ga droplets form on the nanowire tips when a relatively low TMSb flow rate is used, whereas the droplets are missing and the radial growth of the GaSb is enhanced due to a reduction in the diffusion length of the Ga adatoms when the TMSb flow rate is increased. Moreover, transmission electron microscopy measurements revealed that the GaSb shell coherently grew on the InAs core. The results obtained here show that the InAs/GaSb core-shell nanowires grown using the Si platform have strong potential in the fabrication of future nanometer-scale devices and in the study of fundamental quantum physics.

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.

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.

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.

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.

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.