Band Gap Engineering of MoxW1-xS2 Alloy Monolayers with Wafer-Scale Uniformity.

Modulating the band gap of two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors is critical for their application in a wider spectral range. Alloying has been demonstrated as an effective method for regulating the band gap of 2D TMDC semiconductors. The fabrication of large-area 2D TMDC alloy films with centimeter-scale uniformity is fundamental to the application of integrated devices. Herein, we report a liquid-phase precursor one-step chemical vapor deposition (CVD) method for fabricating a MoxW1-xS2 alloy monolayer with a large size and an adjustable band gap. Good crystalline quality and high uniformity on a wafer scale enable the continuous adjustment of its band gap in the range of 1.8-2.0 eV. Density functional theory calculations provided a deep understanding of the Raman-active vibration modes of the MoxW1-xS2 alloy monolayer and the change in the conductivity of the alloy with photon energy. The synthesis of large-area MoxW1-xS2 alloy monolayers is a critical step toward the application of 2D layered semiconductors in practical optoelectronic devices.

Dual Stabilization of a Tri-Metallofullerene Radical Er3@C80: Exohedral Derivatization and Endohedral Three-Center Bonding.

The enclosed space within fullerene molecules, capable of trapping metal clusters, offers an opportunity to investigate the behavior of metal atoms in a highly confined sub-nanometer environment. However, the studies on trimetallofullerenes M3@C80 have been very limited due to their difficult obtainability. In this paper, we present a new method for obtaining a tri-metallofullerene Er3@C80 through exohedral modification of the fullerene cage. Our findings reveal that Er3@C80 exhibits a radical character and can react with the dichlorobenzene radical to generate a stable derivative Er3@C80PhCl2. Theoretical calculations demonstrate the presence of a three-center two-electron metal-metal bond in the center of the fullerene cage. This bond serves to counterbalance the Coulomb repulsion between the Er ions. Consequently, both exohedral derivatization and endohedral three-center bonding contribute to the substantial stability of Er3@C80PhCl2. Furthermore, molecular dynamics simulations indicate that the Er3 cluster within the molecule possesses a rigid triangle structure. The availability of M3@C80 derivatives opens avenues for future investigations into interactions among metal atoms, such as magnetic coupling, within fullerene cages.

Stability and Electronic Properties of Mixed Rare-Earth Tri-Metallofullerenes YxDy3-x@C80 (x = 1 or 2).

Tri-metallofullerenes, specifically M3@C80 where M denotes rare-earth metal elements, are molecules that possess intriguing magnetic properties. Typically, only one metal element is involved in a given tri-metallofullerene molecule. However, mixed tri-metallofullerenes, denoted as M1xM23-x@C80 (x = 1 or 2, M1 and M2 denote different metal elements), have not been previously discovered. The investigation of such mixed tri-metallofullerenes is of interest due to the potential introduction of distinct properties resulting from the interaction between different metal atoms. This paper presents the preparation and theoretical analysis of mixed rare-earth tri-metallofullerenes, specifically YxDy3-x@C80 (x = 1 or 2). Through chemical oxidation of the arc-discharge produced soot, the formation of tri-metallofullerene cations, namely Y2Dy@C80+ and YDy2@C80+, has been observed. Density functional theory (DFT) calculations have revealed that the tri-metallofullerenes YxDy3-x@C80 (x = 1 or 2) exhibit a low oxidation potential, significantly lower than other fullerenes such as C60 and C70. This low oxidation potential can be attributed to the relatively high energy level of a singly occupied orbital. Additionally, the oxidized species demonstrate a large HOMO-LUMO gap similar to that of YxDy3-xN@C80, underscoring their high chemical stability. Theoretical investigations have uncovered the presence of a three-center two-electron metal-metal bond at the center of Y2DY@C80+ and YDy2@C80+. This unique multi-center bond assists in alleviating the electrostatic repulsion between the metal ions, thereby contributing to the overall stability of the cations. These mixed rare-earth tri-metallofullerenes hold promise as potential candidates for single-molecule magnets.

Theoretical Design of an Mox W1-x S2 /Graphene (x=0.25/0.75) Heterojunction with Adjustable Band Gap: Potential Candidate Materials for the Next Generation of Optoelectronic Devices.

Multicomponent two-dimensional (2D) transition metal dichalcogenides (TMDCs) semiconductors based on adjustable band gap are increasingly used to design optoelectronic devices with specific spectral response. Here, we have designed the Mox W1-x S2 /graphene heterostructure with adjustable band gap by adopting the combination idea of alloying and multiple heterogeneous recombination. The contact type, stability and photoelectric properties of Mox W1-x S2 /graphene heterojunction were investigated theoretically. At the same time, by applying external vertical electric field to Mox W1-x S2 /graphene, the regulate of heterojunction Schottky contact type was realized. The results show that Mox W1-x S2 /graphene heterojunction has broad application prospects in the field of photocatalysis and Schottky devices, and is suitable for being a potential candidate material for next generation of optoelectronic devices. The design of Mox W1-x S2 /graphene heterostructure enables it to obtain the advanced characteristics that are lacking in the one-component intrinsic 2D TMDCs semiconductors or graphene materials, and provides a theoretical basis for the experimental preparation of such heterojunctions.

All-Optical Synchronization of Remote Optomechanical Systems.

Synchronization and frequency locking between remote mechanical oscillators are of scientific and technological importance. The key challenges are to align the oscillation frequencies and realize strong nonlinear interaction of both oscillators to a common carrier capable of long-distance transmission. Here, we experimentally realize the all-optical synchronization between two different optomechanical systems, a microsphere and a microdisk. The mechanical oscillation of the microsphere induced by the radiation pressure is loaded onto the pump laser via the optomechanical interaction, which is directly transmitted through a 5-km-long single-mode fiber to excite the mechanical oscillation of the microdisk. By finely tuning both the optical and mechanical frequencies of the two microresonators, the oscillation of the microdisk is injection locked to the microsphere, resulting in a synchronized phase relation of the two systems. Our results push a step forward the long-distance synchronization network using optomechanical microresonators.

Realization of Single-Crystal Dye Lasers by Taming Charge Transfer in Molecular Self-Assemblies.

The large library of organic dye molecules offers almost infinite possibilities for laser design, but still faces a great challenge in achieving pure dye aggregate lasers due to intermolecular quenching. Here, we report a kinetically controlled molecular self-assembly strategy to synthesize unconventional dye microcrystals for lasing. By increasing temperature, the dye self-assembly is transformed from thermodynamic to kinetic control. Unlike the thermodynamic microcrystal products incapable of lasing due to intermolecular charge-transfer-mediated excimer formation, the kinetic dye microcrystals have large intermolecular distances and weak intermolecular interactions, supporting highly efficient intramolecular charge-transfer monomer emission and low-threshold lasing. This work demonstrates single-crystal dye lasers, promising to unleash the full potential of laser dyes in solid-state lasers.

Defect engineering in two-dimensional perovskite nanowire arrays by europium(III) doping towards high-performance photodetection.

We demonstrate high-performance photodetectors based on Eu-doped 2D perovskite nanowire arrays. The pure crystallographic orientation enables efficient carrier transport and the doped Eu ions effectively suppress the trap density in the nanowire arrays. As a result, the optimized Eu-doped photodetectors show an excellent responsivity of 6.24 A W-1, an outstanding specific detectivity of 5.83 × 1013 Jones and stable photo-switching behavior with a current on/off ratio of 103.

Vanadium-Doped Molybdenum Diselenide Atomic Layers with Room-Temperature Ferromagnetism.

Diluted two-dimensional magnetic semiconductors with high Curie temperature are highly sought after because of their potential applications in spintronics. Development of new techniques for preparation of high quality diluted magnetic semiconductors is critical for their applications. In this study, vanadium-doped molybdenum selenide, a new diluted magnetic semiconductor, was synthesized by a single-step chemical vapor deposition method. The merit of this method is that the molybdenum and vanadium precursors can be supplied to the growth substrate uniformly. Photoluminescence measurements reveal that the band gap of MoSe2 decreases after doping, which can be attributed to the formation of impurity energy band caused by p-type doping at the valence band maximum. Thus, the V-doped MoSe2 still maintains the semiconducting characteristics. Vibrating sample magnetometer studies clearly show the ferromagnetism of V-doped MoSe2 at room temperature. DFT calculations illustrates the joint contribution of V dopants and nearby atoms to the magnetic moments. This study provides future prospects for the multifunctional application of two-dimensional materials.

Theoretical design of SnS2-graphene heterojunctions with vacancy and impurity defects for multi-purpose photoelectric devices.

SnS2 with atomic thickness has attracted extensive attention in the field of photocatalysis due to its special physicochemical properties, suitable band gap, low cost and low environmental toxicity. However, the application of SnS2 in the field of optoelectronics is restricted by its low photocatalytic efficiency and carrier mobility. In this study, vacancies and transition metal atoms are introduced into a SnS2 monolayer to modulate its physicochemical properties. Meanwhile, the SnS2 monolayer modified by vacancies and transition metal atoms is combined with graphene to form a heterostructure, which promotes the separation of photogenerated electron-hole pairs. The results of theoretical calculations show that the SnS2/graphene heterojunction can promote the separation of photogenerated carriers in intrinsic monolayer SnS2, and improve the photocatalytic efficiency and carrier mobility. The modification of Sn vacancies and Fe, Co atoms not only expands the visible light response range of the SnS2/graphene heterojunction, but also introduces magnetism, which is expected to be applied in spin optoelectronic materials. In this work, defects, doping and heterojunction assembly are rationally integrated, which provides a new idea for the design and development of spin optoelectronic devices based on monolayer SnS2.

Recent advances in luminescent metal-organic frameworks and their photonic applications.

In recent years, metal-organic frameworks (MOFs) have been attracting ever more interest owing to their fascinating structures and widespread applications. Among the optoelectronic materials, luminescent MOFs (LMOFs) have become one of the most attractive candidates in the fields of optics and photonics thanks to the unique characteristics of their frameworks. Luminescence from MOFs can originate from either the frameworks, mainly including organic linkers and metal ions, or the encapsulated guests, such as dyes, perovskites, and carbon dots. Here, we systematically review the recent progress in LMOFs, with an emphasis on the relationships between their structures and emission behaviour. On this basis, we comprehensively discuss the research progress and applications of multicolour emission from homogeneous and heterogeneous structures, host-guest hybrid lasers, and pure MOF lasers based on optically excited LMOFs in the field of micro/nanophotonics. We also highlight recent developments in other types of luminescence, such as electroluminescence and chemiluminescence, from LMOFs. Future perspectives and challenges for LMOFs are provided to give an outlook of this emerging field. We anticipate that this article will promote the development of MOF-based functional materials with desired performance towards robust optoelectronic applications.

Thermally Activated Lasing in Organic Microcrystals toward Laser Displays.

Thermally activated delayed fluorescent (TADF) materials are promising to overcome triplet-induced optical loss in the pursuit of electrically pumped organic lasers. However, population inversion is difficult to establish in these materials due to the severe suppression of triplet-to-singlet upconversion in their condensed states. In this work, we report thermally activated lasing in solution-processed coassembled microcrystals, where TADF dyes were uniformly dispersed into crystalline matrices to ensure an efficient reverse intersystem crossing (RISC). The dark-state triplet excitons harvested by the RISC were effectively converted into radiative singlet excitons, which subsequently participated in the population inversion to boost lasing with an unusual temperature dependence. The lasing wavelength was tuned over the full visible spectrum by doping various TADF laser dyes, owing to the excellent compatibility. Trichromatic TADF microlasers were precisely patterned into periodic pixelated arrays by a template-confined solution-growth method. With as-prepared TADF microlaser arrays as display panels, vivid laser displays were achieved under programmable excitation. These results offer valuable enlightenment to minimize triplet state-related energy losses toward high-performance lasers.

Chiral Hybrid Perovskite Single-Crystal Nanowire Arrays for High-Performance Circularly Polarized Light Detection.

Circularly polarized light (CPL) detection has emerged as a key technology for various optoelectronics. Chiral hybrid perovskites (CHPs) that combine CPL-sensitive absorption induced by chiral organic ligands and superior photoelectric properties of perovskites are promising candidates for direct CPL detection. To date, most of the CHP detectors are made up of polycrystalline thin-film, which results in a rather limited discrimination of CPL due to the existence of redundant impurities and intrinsic defect states originating from rapid crystallization process. Here, it is developed a direct CPL detector with high photocurrent and polarization selectivity based on low-defect CHP single-crystal nanowire arrays. Large-scale CHP nanowires are obtained through a micropillar template-assisted capillary-bridge rise approach. Thanks to the high crystallinity and ordered crystallographic alignment of these arrays, a CPL photodetector with high light on/off ratio of 1.8 × 104 , excellent responsivity of 1.4 A W-1 , and an outstanding anisotropy factor of 0.24 for photocurrent has been achieved. These results would provide useful enlightenment for direct CPL detection in high-performance chiral optoelectronics.

Randomly Induced Phase Transformation in Silk Protein-Based Microlaser Arrays for Anticounterfeiting.

Anticounterfeiting labels based on physical unclonable functions (PUFs) exhibit high security with unreplicable code outputs, making them an ideal platform to realize unbreakable anticounterfeiting. Although various schemes are proposed for PUF labels, the utilization of natural randomness suffers from unpredictable signal extraction sites, which poses a challenge to efficient and convenient authentication for practical anticounterfeiting applications. Here, a covert optical PUF-based cryptographic protocol from silk protein-based microlaser (SML) arrays that possess hidden randomness of lasers for unclonable lasing signals as well as a defined location for efficient identification is proposed. The initial SMLs are patterned by casting laser dye-doped regenerated silk fibroin solution, resulting in a uniform microlaser array with regulated positions. With the SML array as substrate, random methanol microdroplets are stochastically sprayed on the SML array, which eventually induces uneven lasing signal changes of the patterned microlasers. The treated SML array possesses the deterministic readout sites of laser signals and unrepeatable signal distribution characteristics, which can guarantee efficient authentication and high security when serving as an anticounterfeiting label.

3D Laser Displays Based on Circularly Polarized Lasing from Cholesteric Liquid Crystal Arrays.

3D laser displays play an important role in next-generation display technologies owing to the ultimate visual experience they provide. Circularly polarized (CP) laser emissions, featuring optical rotatory power and invariability under rotations, are attractive for 3D displays due to potential in enhancing contrast ratio and comfortability. However, the lack of pixelated self-emissive CP microlaser arrays as display panels hinders the implementation of 3D laser displays. Here, full-color 3D laser displays are demonstrated based on CP lasing with inkjet-printed cholesteric liquid crystal (CLC) arrays as display panels. Individual CP lasers are realized by embedding fluorescent dyes into CLCs with their left-/right-handed helical superstructures serving as distributed feedback microcavities, bringing in ultrahigh circular polarization degree values (gem  = 1.6). These CP microlaser pixels exhibit excellent far-field color-rendering features and a relatively large color gamut for high-fidelity displays. With these printed CLC red-green-blue (RGB) microlaser arrays serving as display panels, proof-of-concept full-color 3D laser displays are demonstrated via delivering images with orthogonal CP laser emissions into one's left and right eyes. These results provide valuable enlightenment for the development of 3D laser displays.

Optically Pumped Lasing in Microscale Light-Emitting Electrochemical Cell Arrays for Multicolor Displays.

Laser displays, which offer wide achievable color gamut and excellent color rendering, have emerged as a promising next-generation display technology. Constructing display panels composed of pixelated microlaser arrays is of great significance for the actualization of laser displays in the flat-panel sector. Here, we report microscale light-emitting electrochemical cell (LEC) arrays that operate as both optically pumped lasers and electroluminescence devices, which can be applied as self-emissive panels for high quality displays. Optically pumped red, green, and blue laser emissions were achieved in individual circular microcells consisting of corresponding conjugated polymers and electrolytes, suggesting that the microstructures can act as resonators for coherent outputs. As-prepared microstructures possess a narrowed recombination region, which dramatically increases the current density by 3 orders of magnitude under pulsed operation, compared with the corresponding thin-film devices, representing a promising solution-processed device platform for electrical pumping. Under programmable electrical excitation, both static and dynamic displays were demonstrated with such microscale LEC arrays as display panels. The prominent performance of the demonstrated structures (microlaser arrays embedded in LEC devices) provide us deep insight into the concepts and device constructions of electrically driven laser displays.

Experimentally Observed Reverse Intersystem Crossing-Boosted Lasing.

Thermally activated delayed-fluorescent (TADF) materials are anticipated to overcome triplet-related losses towards electrically driven organic lasers. Thus far, contributions from triplets to lasing have not yet been experimentally demonstrated owing to the limited knowledge about the excited-state processes. Herein, we experimentally achieve reverse intersystem crossing (RISC)-boosted lasing in organic microspheres with uniformly dispersed TADF emitters. In these materials, triplets are continuously converted to radiative singlets through RISC, giving rise to reduced losses in stimulated emission. The involvement of regenerated singlets in population inversion results in a thermally activated lasing; that is, the lasing intensity increases with increasing temperature, accompanied by accelerated depletion of the excited-state population. Benefiting from the suppression of triplet accumulations by RISC processes, a high-repetition-rate microlaser was achieved.

A Photoisomerization-Activated Intramolecular Charge-Transfer Process for Broadband-Tunable Single-Mode Microlasers.

Miniaturized lasers with high spectral purity and wide wavelength tunability are crucial for various photonic applications. Here we propose a strategy to realize broadband-tunable single-mode lasing based on a photoisomerization-activated intramolecular charge-transfer (ICT) process in coupled polymer microdisk cavities. The photoisomerizable molecules doped in the polymer microdisks can be quantitatively transformed into a kind of laser dye with strong ICT character by photoexcitation. The gain region was tailored over a wide range through the self-modulation of the optically activated ICT isomers. Meanwhile, the resonant modes shifted with the photoisomerization because of a change in the effective refractive index of the polymer microdisk cavity. Based on the synergetic modulation of the optical gain and microcavity, we realized the broadband tuning of the single-mode laser. These results offer a promising route to fabricate broadband-tunable microlasers towards practical photonic integrations.

Organic Printed Core-Shell Heterostructure Arrays: A Universal Approach to All-Color Laser Display Panels.

A universal approach is demonstrated for realizing dual-wavelength lasing in organic core-shell structured microlaser arrays, which show great promise in serving as all-color laser display panels. By alternately printing hydrophilic and hydrophobic laser dye solutions on preprocessed substrates, precisely patterned core-shell heterostructure arrays were obtained. The spatially separated core and shell independently function as optical resonators to support dual-wavelength tunable lasing in each heterostructure. Such a general method enables to flexibly control the lasing wavelength of the core-shell microlasers across a wide spectral range by systematically designing the gain media. Using as-prepared microlaser arrays as display panels, full-color laser displays were achieved with a color gamut much larger than that of standard RGB space. These results provide insights for design concepts and device construction for novel optoelectronic applications.

Controllable Growth of High-Quality Inorganic Perovskite Microplate Arrays for Functional Optoelectronics.

Inorganic perovskite single crystals have emerged as promising vapor-phase processable structures for optoelectronic devices. However, because of material lattice mismatch and uncontrolled nucleation, vapor-phase methods have been restricted to random distribution of single crystals that are difficult to perform for integrated device arrays. Herein, an effective strategy to control the vapor-phase growth of high-quality cesium lead bromide perovskite (CsPbBr3 ) microplate arrays with uniform morphology as well as controlled location and size is reported. By introducing perovskite seeds on substrates, intractable lattice mismatches and random nucleation barriers are surpassed, and the epitaxial growth of perovskite crystals is accurately controlled. It is further demonstrated that CsPbBr3 microplate arrays can be monolithically integrated on substrates for the fabrication of high-performance lasers and photodetectors. This strategy provides a facile approach to fabricate high-quality CsPbBr3 microplates with controllable size and location, which offers new opportunities for the scalable production of integrated optoelectronic devices.

Exciton funneling in light-harvesting organic semiconductor microcrystals for wavelength-tunable lasers.

Organic solid-state lasers are essential for various photonic applications, yet current-driven lasing remains a great challenge. Charge transfer (CT) complexes formed with p-/n-type organic semiconductors show great potential in electrically pumped lasers, but it is still difficult to achieve population inversion owing to substantial nonradiative loss from delocalized CT states. Here, we demonstrate the lasing action of CT complexes based on exciton funneling in p-type organic microcrystals with n-type doping. The CT complexes with narrow bandgap were locally formed and surrounded by the hosts with high-lying energy levels, which behave as artificial light-harvesting systems. Excitation light energy captured by the hosts was delivered to the CT complexes, functioning as exciton funnels to benefit lasing actions. The lasing wavelength of such composite microcrystals was further modulated by varying the degree of CT. The results offer a comprehensive understanding of exciton funneling in light-harvesting systems for the development of high-performance organic lasing devices.