Two-Dimensional Lanthanide Metal-Organic Framework Heterostructures for Noninvasively Photoresponsive High-Security Photonic Barcodes.

Stimuli-responsive micro/nanoscale photonic barcodes show great capacity for encryption and anticounterfeiting technologies due to multiple authentications, yet their application is commonly restricted by invasive stimuli. Herein, we report noninvasive light-stimulated high-security photonic barcodes based on spatially assembled photoresponsive two-dimensional (2D) 1,3,5-benzenetribenzoate (BTB)@Ln-MOF host-guest heterostructures. The photoluminescence (PL) spectra information on BTB@Ln-MOF heterostructures could be precisely controlled by the different wavelengths of ultraviolet (UV) light trigger. By using the PL properties and 2D heterostructures as cryptographic primitives, spatially resolved smart photonic barcodes based on both spectral and graphical coding are realized in BTB@Ln-MOF host-guest materials. These results will pave an avenue for the development of smart stimuli-responsive photonic barcodes for anticounterfeiting applications.

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.

Exciton Chirality Transfer Empowers Self-Triggered Spin-Polarized Amplified Spontaneous Emission from 1D-Anchoring-3D Perovskites.

Spin-polarized lasers, arising from stimulated emission of imbalanced spin populations, play a vital role in spin-optoelectronics. It is usually tackled by external spin injection, inevitably suffering from additional losses across the barriers from injection sources to gain materials. Herein, spin-polarized coherent light emission is self-triggered from the 1D-anchoring-3D perovskites, where the imbalanced populations in achiral 3D perovskites are endowed with the spin selectivity of exciton chirality (EC) underpinned by chiral 1D perovskites. Efficient transfer of EC is enabled by rapid energy transfer, thereby creating an imbalance of the spin population of excited states. Stimulated emission of such populations brings self-triggered spin-polarized amplified spontaneous emission in the composite perovskites, yielding a higher degree of polarization (DOP) than that based on optical spin injection into bare achiral 3D perovskites. Chemical diversity of composite perovskites not only enables to adjust band gap for broadband output of spin-polarized light signals but also promises to manipulate radiative decay and spin relaxation toward remarkably increased DOP. These results highlight the importance of EC transfer mechanism for spin-polarized lasing and represent a crucial step toward the development of chiral-spintronics.

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.

Thickness control of organic semiconductor-incorporated perovskites.

Two-dimensional organic semiconductor-incorporated perovskites are a promising family of hybrid materials for optoelectronic applications, owing in part to their inherent quantum well architecture. Tuning their structures and properties for specific properties, however, has remained challenging. Here we report a general method to tune the dimensionality of phase-pure organic semiconductor-incorporated perovskite single crystals during their synthesis, by judicious choice of solvent. The length of the conjugated semiconducting organic cations and the dimensionality (n value) of the inorganic layers can be manipulated at the same time. The energy band offsets and exciton dynamics at the organic-inorganic interfaces can therefore be precisely controlled. Furthermore, we show that longer and more planar π-conjugated organic cations induce a more rigid inorganic crystal lattice, which leads to suppressed exciton-phonon interactions and better optoelectronic properties as compared to conventional two-dimensional perovskites. As a demonstration, optically driven lasing behaviour with substantially lower lasing thresholds was realized.

Revealing molecular diffusion dynamics in polymer microspheres by optical resonances.

Understanding the diffusion of small molecules in polymer microsystems is of great interest in diverse fundamental and industrial research. Despite the rapidly advancing optical imaging and spectroscopic techniques, entities under investigation are usually limited to flat films or bulky samples. We demonstrate a route to in situ detection of diffusion dynamics in polymer micro-objects by means of optical whispering-gallery mode resonances. Through mode tracking, interactions between solvent molecules and polymer microspheres, including sorption, diffusion, and swelling can be quantitatively analyzed. A turning point of mode response is observed, while the diffusion exceeds the sub-wavelength-thick outermost layer as the radial extent of resonances and starts penetrating the inner core. The estimated solubility in the glassy polymer is consistent with the predicted value using Flory-Huggins theory. Besides, the non-Fickian contribution is analyzed in such a glassy polymer-penetrant system. Our work represents a high-precision and label-free approach to describing characteristics in diffusion dynamics.

Photoisomerization-controlled wavelength-tunable plasmonic lasers.

We demonstrate photoisomerization-controlled wavelength-tunable plasmonic lasers by integrating spiropyran derivative-doped PMMA films with two-dimensional Ag nanoparticle arrays. The controllable transformation between spiropyran derivatives and its isomers with different refractive indices by photoexcitation allows for a dynamical and continuous change of the refractive index in the host PMMA film, which is able to tune the lattice plasmon resonance, and hence the lasing wavelength. This result opens up a new avenue for engineering wavelength tunable plasmonic lasers toward practical photonic integration.

Bubble wall confinement-driven molecular assembly toward sub-12 nm and beyond precision patterning.

Patterning is attractive for nanofabrication, electron devices, and bioengineering. However, achieving the molecular-scale patterns to meet the demands of these fields is challenging. Here, we propose a bubble-template molecular printing concept by introducing the ultrathin liquid film of bubble walls to confine the self-assembly of molecules and achieve ultrahigh-precision assembly up to 12 nanometers corresponding to the critical point toward the Newton black film limit. The disjoining pressure describing the intermolecular interaction could predict the highest precision effectively. The symmetric molecules exhibit better reconfiguration capacity and smaller preaggregates than the asymmetric ones, which are helpful in stabilizing the drainage of foam films and construct high-precision patterns. Our results confirm the robustness of the bubble template to prepare molecular-scale patterns, verify the criticality of molecular symmetry to obtain the ultimate precision, and predict the application potential of high-precision organic patterns in hierarchical self-assembly and high-sensitivity sensors.

Organic Synthetic Photonic Systems with Reconfigurable Parity-Time Symmetry Breaking for Tunable Single-Mode Microlasers.

Synthetic photonic materials exploiting the quantum concept of parity-time (PT) symmetry lead to an emerging photonic paradigm-non-Hermitian photonics, which is revolutionizing the photonic sciences. The non-Hermitian photonics dealing with the interplay between gain and loss in PT synthetic photonic material systems offers a versatile platform for advancing microlaser technology. However, current PT-symmetric microcavity laser systems only manipulate imaginary parts of the refractive indices, suffering from limited laser spectral bandwidth. Here, an organic composite material system is proposed to synthesize reconfigurable PT-symmetric microcavities with controllable complex refractive indices for realizing tunable single-mode laser outputs. A grayscale electron-beam direct-writing technique is elaborately designed to process laser dye-doped polymer films in one single step into microdisk cavities with periodic gain and loss distribution, which enables thresholdless PT-symmetry breaking and single-mode laser operation. Furthermore, organic photoisomerizable compounds are introduced to reconfigure the PT-symmetric systems in real-time by tailoring the real refractive index of the polymer microresonators, allowing for a dynamically and continuously tunable single-mode laser output. This work fundamentally enhances the PT-symmetric photonic systems for innovative design of synthetic photonic materials and architectures.

Magnetic-Field-Driven Reconfigurable Microsphere Arrays for Laser Display Pixels.

Reconfigurable microlaser arrays are essential to the construction of display panels where the individual pixel should be highly tunable in resonance mode, optical polarization, and lasing wavelength upon external control signals. Here we demonstrate a facile yet reliable approach to fabrication of organic microlaser pixels, in which the assembly of microsphere arrays on each pixel is controlled according to the near-field magnetostatic confinement. The geometrical configuration of diamagnetic microspheres could be readily modulated with the near-field potential traps by using the external field to alternate the saturation magnetization of the underneath micromagnet. The motion of microspheres can be modulated among several states upon applied field, and the reconfigurable microsphere array is thus achieved with high spatial precision and rapid temporal response. Moreover, both isolated and coupled spheres serve as low-threshold microlasers with tunable optical resonance modes, whereas the switching between the vertical and horizontal alignments of coupled spheres manipulates the polarization of lasing outputs. By repeating the magnetostatic confinement on the same substrate, the full-color laser display pixels with magnetically tunable color expression capability are successfully achieved.

Nonconfinement growth of edge-curved molecular crystals for self-focused microlasers.

Synthesis of single-crystalline micro/nanostructures with curved shapes is essential for developing extraordinary types of optoelectronic devices. Here, we use the strategy of liquid-phase nonconfinement growth to controllably synthesize edge-curved molecular microcrystals on a large scale. By varying the molecular substituents on linear organic conjugated molecules, it is found that the steric hindrance effect could minimize the intrinsic anisotropy of molecular stacking, allowing for the exposure of high-index crystal planes. The growth rate of high-index crystal planes can be further regulated by increasing the molecular supersaturation, which is conducive to the cogrowth of these crystal planes to form continuously curved-shape microcrystals. Assisted by nonrotationally symmetric geometry and optically smooth curvature, edge-curved microcrystals can support low-threshold lasing, and self-focusing directional emission. These results contribute to gaining an insightful understanding of the design and growth of functional molecular crystals and promoting the applications of organic active materials in integrated photonic devices and circuits.

Evolutionary trends in human mandibles and dentition from Neolithic to current Chinese.

OBJECTIVES: This study aimed to systematically compare Neolithic mandibles and dentition with modern Chinese, and thereby discern human evolutionary trends. MATERIALS AND METHODS: Neolithic remains of 45 adults unearthed at the Zhangqiu Jiaojia site, were compared with clinical records of 48 patients at Shandong University. All samples were scanned by cone beam computed tomography (CBCT) using identical parameters. Digital imaging and communications in medicine images were collected, three-dimensional models reconstructed, and morphology measurements obtained using Mimics software. RESULTS: Neolithic mandibles were significantly larger in their vertical and sagittal dimensions (P < .05), but similar in horizontal width to modern humans. Their condyles had fewer bird beak and crooked finger shaped morphologies than modern mandibles (P < .05). Neolithic third molars were more often erupted than in modern mandibles, and their Position A, class I and II, and vertical impactions were more common (P < .05). Neolithic teeth were generally smaller in crown lengths and in cross-sectional areas, than their modern counterparts (P < .05). CONCLUSIONS: Neolithic mandibles were larger than modern humans, who have refined diets and mandibular atrophy. They had fewer abnormally shaped condylar morphologies, and much fewer third molar impactions than in modern humans. However, modern dentition particularly their crowns are larger, likely through genetic influx from migrations.

Single-Crystalline Perovskite p-n Junction Nanowire Arrays for Ultrasensitive Photodetection.

Highly sensitive photodetectors play significant roles in modern optoelectronic integrated circuits. Constructing p-n junctions has been proven to be a particularly powerful approach to realizing sensitive photodetection due to their efficient carrier separation. Recently, p-n-junction photodetectors based on organic-inorganic hybrid perovskites, which combine favorable optoelectronic performance with facile processability, hold great potential in practical applications. So far, these devices have generally been made of polycrystalline films, which exhibit poor carrier-transport efficiency, impeding the further improvement of their photoresponsivities. Here, a type of ultrasensitive photodetector based on single-crystalline perovskite p-n-junction nanowire arrays is demonstrated. The single-crystalline perovskite p-n-junction nanowire arrays not only possess high crystallinity that enables efficient carrier transport but also form a built-in electric field facilitating effective carrier separation. As a result, the devices show excellent photosensitivity over a wide spectral range from 405 to 635 nm with an outstanding responsivity of 2.65 × 102  A W-1 at 532 nm. These results will provide new insights into the design and construction of high-performance photodetectors for practical optoelectronic applications.

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.

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.

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.

Organic donor-acceptor heterojunctions for high performance circularly polarized light detection.

Development of highly efficient and stable lateral organic circularly polarized light photodetector is a fundamental prerequisite for realization of circularly polarized light integrated applications. However, chiral semiconductors with helical structure are usually found with intrinsically low field-effect mobilities, which becomes a bottleneck for high-performance and multi-wavelength circularly polarized light detection. To address this problem, here we demonstrate a novel strategy to fabricate multi-wavelength circularly polarized light photodetector based on the donor-acceptor heterojunction, where efficient exciton separation enables chiral acceptor layer to provide differentiated concentration of holes to the channel of organic field-effect transistors. Benefitting from the low defect density at the semiconductor/dielectric interface, the photodetectors exhibit excellent stability, enabling current roll-off of about 3-4% over 500 cycles. The photocurrent dissymmetry value and responsivity for circularly polarized light photodetector in air are 0.24 and 0.28 A W-1, respectively. We further demonstrate circularly polarized light communication based on a real-time circularly polarized light detector by decoding the light signal. As the proof-of-concept, the results hold the promise of large-scale circularly polarized light integrated photonic applications.

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.

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.