Two-dimensional-lattice-confined single-molecule-like aggregates.

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes1,2, lasers3-5 and quantum technologies6,7, among others8-10. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. This two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

Exceptionally High-glum Circularly Polarized Lasers Empowered by Strong 2D-Chiroptical Response in a Host-Guest Supramolecular Microcrystal.

Circularly polarized (CP) lasers hold tremendous potential for advancing spin information communication and display technologies. Organic materials are emerging candidates for high-performance CP lasers because of their abundant chiral structures and excellent gain characteristics. However, their dissymmetry factor (glum) in CP emission is typically low due to the weak chiral light matter interactions. Here, we presented an effective approach to significantly amplifying glum by leveraging the intrinsic 2D-chiroptical response of an anisotropic organic supramolecular crystal. The organic complex microcrystal was designed to exhibit large 2D-chiroptical activities through strong coupling interactions between their remarkable linear birefringence (LB) and high degree of fluorescence linear polarization. Such 2D-chiroptical response can be further enhanced by the stimulated emission resulted from an increased degree of linear polarization, yielding a nearly pure CP laser with an exceptionally high glum of up to 1.78. Moreover, exploiting the extreme susceptibility of LB to temperature, we demonstrate a prototype of temperature-controlled chiroptical switches. These findings offer valuable insights for harnessing organic crystals to facilitate the development of high-performance CP lasers and other chiroptical devices.

Dimension Evolution of Self-Assembled Organic Microcrystal for Laser and Polarization-Rotation Function.

Multidimensional integrated micro/nanostructures are vitally important for the implementation of versatile photonic functionalities, whereas current material structures still suffer undesired surface defects and contaminations in either multistep micro/nanofabrications or extreme synthetic conditions. Herein, the dimension evolution of organic self-assembled structures 2D microrings and 3D microhelixes for multidimensional photonic devices is realized via a protic/aprotic solvent-directed molecular assembly method based on a multiaxial confined-assisted growth mechanism. The 2D microrings with consummate circle boundaries and molecular-smooth surfaces function as high-quality whispering-gallery-mode microcavities for dual-wavelength energy-influence-dependent switchable lasing. Moreover, the 3D microhelixes with smooth surfaces and natural twistable characteristics act as active photon-transport materials and polarization rotators. These results will broaden the horizon of constructing multidimensional microstructures for integrated photonic circuits.

Adaptive Helical Chirality in Supramolecular Microcrystals for Circularly Polarized Lasing.

Chiral organic molecules offer a promising platform for exploring circularly polarized lasing, which, however, faces a great challenge that the spatial separation of molecular chiral and luminescent centers limits chiroptical activity. Here we develop a helically chiral supramolecular system with completely overlapped chiral and luminescent units for realizing high-performance circularly polarized lasing. Adaptive helical chirality is obtained by incorporating chiral agents into organic microcrystals. Benefiting from the efficient coupling of stimulated emission with the adaptive helical chirality, the supramolecular microcrystals enable high-performance circularly polarized lasing emission with dissymmetry factors up to ~0.7. This work opens up the way to rational design of chiral organic materials for circularly polarized lasing.

Circularly Polarized Lasing from Helical Superstructures of Chiral Organic Molecules.

Chiral supramolecular aggregates have the potential to explore circularly polarized lasing with large dissymmetry factors. However, the controllable assembly of chiral superstructures towards deterministic circularly polarized laser emission remains elusive. Here, we design a pair of chiral organic molecules capable of stacking into a pair of definite helical superstructures in microcrystals, which enables circularly polarized lasing with deterministic chirality and high dissymmetry factors. The microcrystals function as optical cavities and gain media simultaneously for laser oscillations, while the supramolecular helices endow the laser emission with strong and opposite chirality. As a result, the microcrystals of two enantiomers allow for circularly polarized laser emission with opposite chirality and high dissymmetry factors up to ~1.0. This work demonstrates the chiral supramolecular assemblies as an excellent platform for high-performance circularly polarized lasers.

Continuous-Wave Raman Lasing from Metal-Linked Organic Dimer Microcrystals.

Stimulated Raman scattering offers an alternative strategy to explore continuous-wave (c.w.) organic lasers, which, however, still suffers from the limitation of inadequate Raman gain in organic material systems. Here we propose a metal-linking approach to enhance the Raman gain of organic molecules. Self-assembled microcrystals of the metal linked organic dimers exhibit large Raman gain, therefore allowing for c.w. Raman lasing. Furthermore, broadband tunable Raman lasing is achieved in the organic dimer microcrystals by adjusting excitation wavelengths. This work advances the understanding of Raman gain in organic molecules, paving a way for the design of c.w. organic lasers.

Spatially Resolved Organic Whispering-Gallery-Mode Hetero-Microrings for High-Security Photonic Barcodes.

Whispering-gallery-mode (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. However, such kind of barcodes developed hitherto are primarily based on microcavities wherein multiple gain medias were blended into a single matrix, thus resulting in the limited and indistinguishable coding elements. Here, a surface tension assisted heterogeneous assembly strategy is proposed to construct the spatially resolved WGM hetero-microrings with multiple spatial colors along its circular direction. Through precisely regulating the charge-transfer (CT) strength, full-color microrings covering the entire visible range were effectively acquired, which exhibit a series of sharp and recognizable peaks and allow for the effective construction of high-quality photonic barcodes. Notably, the spatially resolved WGM hetero-microrings with multiple coding elements were finally acquired through heterogeneous nucleation and growth controlled by the directional diffusion between the hetero-emulsion droplets, thus remarkably promoting the security strength and coding capacity of the barcodes. The results would be useful to fabricate new types of organic hierarchical hybrid WGM heterostructures for optical information recording and security labels.

3D-Printed Möbius Microring Lasers: Topology Engineering in Photonic Microstructures.

Manipulating photons in artificially structured materials is highly desired in modern photonic technology. Nontrivial topological structures are rapidly emerging as a state-of-art platform for achieving unprecedented fascinating phenomena of photon manipulation. However, the current studies mainly focus on planar structures, and the fabrication of photonic microstructures with specific topological geometric features still remains a great challenge. Extending the topological photonics to 3D microarchitectures is expected to enrich the photon manipulation capabilities and further advance the topological photonic devices. Here, a femtosecond laser direct writing technique is employed to fabricate 3D topological Möbius microring resonators from dye-doped polymer. The high-quality-factor Möbius microring resonator supports a unique spin-orbit coupled lasing at very low threshold. Due to the spin-orbit coupling induced geometric/Berry phase, the Möbius microrings, in striking contrast with ordinary microrings, output laser signals with all polarization states. The manipulation of miniaturized coherent light sources in the fabricated Möbius microrings represents a significant step forward toward 3D topological photonics that offers a novel design philosophy for functional photonic and optoelectronic devices.

Geometry-Programmable Perovskite Microlaser Patterns for Two-Dimensional Optical Encryption.

Lasing signals with easily distinguishable readout and cavity-geometry-dependent output are emerging as novel cryptographic primitives for two-dimensional (2D) optical encryption, while their practical application is restricted by the challenge of integrating different lasing elements onto an identical 2D pattern. Herein, a lithographic template-confined crystallization approach was proposed to prepare large-scale perovskite microstructures with any desired geometries and locations, which enabled them to serve as 2D lasing patterns for reliable encryption and authentication. These prepatterned perovskite microstructures realized whispering-gallery-mode lasing and also demonstrated outstanding reproducibility of lasing actions. Benefiting from the feature of their cavity-geometry-dependent lasing thresholds, we achieved controllable laser output from different shaped elements, which was further utilized for the proof-of-concept demonstration of a cryptographic implementation. The remarkable lasing performance and feasible preparation of 2D microlaser patterns with customized geometries and locations provide us deep insights into the concepts and fabrication technologies for 2D optical encryption.

Simulating the Structure of Carbon Dots via Crystalline π-Aggregated Organic Nanodots Prepared by Kinetically Trapped Self-Assembly.

This work reports the successful preparation of a new type of crystalline luminescent organic nanodot (<3.5 nm) by kinetically trapped self-assembly, which is then used as a simplified π-packing model to simulate the structure of CDs. The precise structure and J-aggregation-induced photoluminescence (PL) of the nanodots are revealed by investigating the structural relationship between the nanodots and the corresponding single crystals and their properties. Compared with the single crystals, crystalline organic nanodots show longer PL lifetime, higher PL quantum yield, and narrower PL peak, indicating that they are potential organic quantum nanodots. In addition, the efficient π-stacking environment in the corresponding single crystals can promote π-aggregation-induced PL anisotropy. This work indicates crystalline organic nanodots with precise structures to be potentially useful for understanding the structures of CDs and to be attractive potential luminescent materials.

Interfacial Chemistry Triggers Ultrafast Radiative Recombination in Metal Halide Perovskites.

Efficient radiative recombination is essential for perovskite luminescence, but the intrinsic radiative recombination rate as a basic material property is challenging to tailor. Here we report an interfacial chemistry strategy to dramatically increase the radiative recombination rate of perovskites. By coating aluminum oxide on the lead halide perovskite, lead-oxygen bonds are formed at the perovskite-oxide interface, producing the perovskite surface states with a large exciton binding energy and a high localized density of electronic state. The oxide-bonded perovskite exhibits a ≈500 fold enhanced photoluminescence with a ≈10 fold reduced lifetime, indicating an unprecedented ≈5000 fold increase in the radiative recombination rate. The enormously enhanced radiative recombination promises to significantly promote the perovskite optoelectronic performance.

Organoplatinum(II) Cruciform: A Versatile Building Block to Fabricate 2D Microcrystals with Full-Color and White Phosphorescence and Anisotropic Photon Transport.

Conventional square-planar platinum complexes typically form one-dimensional assemblies as a result of unidirectional metallophilic and/or π⋅⋅⋅π intermolecular interactions. Organoplatinum(II) complexes with a cruciform shape are presented herein to construct two-dimensional (2D) microcrystals with full-color and white phosphorescence. These 2D crystals show unique monocomponent π⋅⋅⋅π stacking, from either the cyclometalating or noncyclometalating ligand, and the bicomponent alternate π⋅⋅⋅π stacking from both ligands along different facet directions. Anisotropic tri-directional waveguiding is further implemented on a single hexagonal microcrystal. These results demonstrate the great capability of the organoplatinum(II) cruciform as a general platform to fabricate 2D phosphorescent micro-/nanocrystals for advanced photonic applications.

Selective, Anisotropic, or Consistent Polarized-Photon Out-Coupling of 2D Organic Microcrystals.

Nano- and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out-coupled light, with respect to that of the source luminescence, has never been explored in active optical-waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized-photon out-coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly-polarized luminescence. It is found that the polarization direction and degree of the luminescence out-coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi-channel polarized photon transport.

Accumulated Lattice Strain as an Internal Trigger for Spontaneous Pathway Selection.

Multicomponent crystallization is universally important in various research fields including materials science as well as biology and geology, and presents new opportunities in crystal engineering. This process includes multiple kinetic and thermodynamic events that compete with each other, wherein "external triggers" often help the system select appropriate pathways for constructing desired structures. Here we report an unprecedented finding that a lattice strain accumulated with the growth of a crystal serves as an "internal trigger" for pathway selection in multicomponent crystallization. We discovered a "spontaneous" crystal transition, where the kinetically preferred layered crystal, initially formed by excluding the pillar component, carries a single dislocation at its geometrical center. This crystal "spontaneously" liberates a core region to relieve the accumulated lattice strain around the dislocation. Consequently, the liberated part becomes dynamic and enables the pillar ligand to invade the crystalline lattice, thereby transforming into a thermodynamically preferred pillared-layer crystal.

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.

Controlled Shape Evolution of Pure-MOF 1D Microcrystals towards Efficient Waveguide and Laser Applications.

MOF-based one-dimensional materials have received increasing attention in the nanophotonics field, but it is still difficult in the flexible shape evolution of MOF micro/nanocrystals for desired optical functionalities due to the susceptible solvothermal growth process. Herein, we report on the well-controlled shape evolution of pure-MOF microcrystals with optical waveguide and lasing performances based on a bottom-up and top-down synergistic method. The MOF microcrystals from solvothermal synthesis (bottom-up) enable the evolution from microrods via microtubes to nanowires through a chelating agent-assisted etching process (top-down). The three types of MOF 1D-microstructures with high crystallinity and smooth surfaces all exhibit efficient optical waveguide performance. Furthermore, MOF nanowire with lowest propagation loss served as low-threshold pure-MOF nanolasers with Fabry-Pérot resonance. These results advance the fundamental understanding on the controlled MOF evolution mechanism, and offer a valuable route for the development of pure-MOF-based photonic components with desired functionalities.

Materials chemistry and engineering in metal halide perovskite lasers.

The invention and development of the laser have revolutionized science, technology, and industry. Metal halide perovskites are an emerging class of semiconductors holding promising potential in further advancing the laser technology. In this Review, we provide a comprehensive overview of metal halide perovskite lasers from the viewpoint of materials chemistry and engineering. After an introduction to the materials chemistry and physics of metal halide perovskites, we present diverse optical cavities for perovskite lasers. We then comprehensively discuss various perovskite lasers with particular functionalities, including tunable lasers, multicolor lasers, continuous-wave lasers, single-mode lasers, subwavelength lasers, random lasers, polariton lasers, and laser arrays. Following this a description of the strategies for improving the stability and reducing the toxicity of metal halide perovskite lasers is provided. Finally, future research directions and challenges toward practical technology applications of perovskite lasers are provided to give an outlook on this emerging field.

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.

Pure Metal-Organic Framework Microlasers with Controlled Cavity Shapes.

Metal-organic frameworks (MOFs) are an emerging kind of laser material, yet they remain a challenge in the controlled fabrication of crystal nanostructures with desired morphology for tuning their optical microcavities. Herein, the shape-engineering of pure MOF microlasers was demonstrated based on the coordination-mode-tailored method. The one-dimensional (1D) microwires and 2D microplates were selectively fabricated through changing the HCl concentration to tailor the coordination modes. Both the single-crystalline microwires and microplates with strong optical confinement functioned as low-threshold MOF microlasers. Moreover, distinct lasing behaviors of 1D and 2D MOF microcrystals confirm a typical shape-dependent microcavity effect: 1D microwires serve as Fabry-Pérot (FP) resonators, and 2D microplates lead to the whispering-gallery-mode (WGM) microcavities. These results provide a special pathway for the exploitation of MOF-based micro/nanolasers with on-demand functions.

Supercrystallographic Reconstruction of 3D Nanorod Assembly with Collectively Anisotropic Upconversion Fluorescence.

Constructing three-dimensional (3D) metamaterials from functional nanoparticles endows them with emerging collective properties tailored by the packing geometries. Herein, we report 3D supercrystals self-assembled from upconversion nanorods (NaYF4:Yb,Er NRs), which exhibit both translational ordering of NRs and orientational ordering between constituent NRs in the superlattice (SL). The construction of 3D reciprocal space mappings (RSMs) based on synchrotron-based X-ray scattering measurements was developed to uncover the complex structure of such an assembly. That is, the two main orthogonal sets of hexagonal close-packing (hcp)-like SLs share the [110]SL axis, and NRs within the SL possess orientational relationships of [120]NR//[100]SL, [210]NR//[010]SL, and [001]NR//[001]SL. Notably, these supercrystals containing well-aligned NRs exhibit collectively anisotropic upconversion fluorescence in two perpendicular directions. This study not only demonstrates novel crystalline superstructures and functionality of NR-based 3D assemblies but also offers a unique tool for deciphering a wide range of complex nanoparticle supercrystals.