Visible Light-Activated Ultralong-Lived Triplet Excitons of Carbon Dots for White-Light Manipulated Anti-Counterfeiting.

Room temperature phosphorescence (RTP) has emerged as an interesting but rare phenomenon with multiple potential applications in anti-counterfeiting, optoelectronic devices, and biosensing. Nevertheless, the pursuit of ultralong lifetimes of RTP under visible light excitation presents a significant challenge. Here, new phosphorescent materials that can be excited by visible light with record-long lifetimes are demonstrated, realized through embedding nitrogen doped carbon dots (N-CDs) into a poly(vinyl alcohol) (PVA) film. The RTP lifetime of the N-CDs@PVA film is remarkably extended to 2.1 s excited by 420 nm, representing the highest recorded value for visible light-excited phosphorescent materials. Theoretical and experimental studies reveal that the robust hydrogen bonding interactions can effectively reduce the non-radiative decay rate and radiative transition rate of triplet excitons, thus dramatically prolong the phosphorescence lifetime. Notably, the RTP emission of N-CDs@PVA film can also be activated by easily accessible low-power white-light-emitting diode. More significantly, the practical applications of the N-CDs@PVA film in state-of-the-art anti-counterfeiting security and optical information storage domains are further demonstrated. This research offers exciting opportunities for utilizing visible light-activated ultralong-lived RTP systems in a wide range of promising applications.

Directional Self-Assembly of Facet-Aligned Organic Hierarchical Super-Heterostructures for Spatially Resolved Photonic Barcodes.

Organic multicolor heterostructures with spatially resolved luminescent colors and identifiable patterns have exhibited considerable potential for achieving micro-/nanoscale photonic barcodes. Nevertheless, such types of barcodes reported thus far are exclusively based on a single heterostructure with limited coding elements. Here, a directional self-assembly strategy is proposed to achieve high-coding-capacity spatially resolved photonic barcodes through rationally constructing organic hierarchical super-heterostructures, where numerous subheterostructure blocks with flat hexagonal facets are precisely oriented with their specific facets via a reconfigurable capillary force. The building blocks were prepared through a one-pot sequential heteroepitaxial growth, which enables the effective modulation of the structural and color characteristics in coding structures. Significantly, a directional facet-to-facet attraction between particles via facet registration leads to the formation of well-defined 1D super-heterostructures, which contain multiple coding elements, thus providing a good platform for constructing the high-coding-capacity photonic barcodes. The results may be useful in fabricating organic hierarchical hybrid super-heterostructures for security labels and optical data recording.

Suppressing phase disproportionation in quasi-2D perovskite light-emitting diodes.

Electroluminescence efficiencies and stabilities of quasi-two-dimensional halide perovskites are restricted by the formation of multiple-quantum-well structures with broad and uncontrollable phase distributions. Here, we report a ligand design strategy to substantially suppress diffusion-limited phase disproportionation, thereby enabling better phase control. We demonstrate that extending the π-conjugation length and increasing the cross-sectional area of the ligand enables perovskite thin films with dramatically suppressed ion transport, narrowed phase distributions, reduced defect densities, and enhanced radiative recombination efficiencies. Consequently, we achieved efficient and stable deep-red light-emitting diodes with a peak external quantum efficiency of 26.3% (average 22.9% among 70 devices and cross-checked) and a half-life of ~220 and 2.8 h under a constant current density of 0.1 and 12 mA/cm2, respectively. Our devices also exhibit wide wavelength tunability and improved spectral and phase stability compared with existing perovskite light-emitting diodes. These discoveries provide critical insights into the molecular design and crystallization kinetics of low-dimensional perovskite semiconductors for light-emitting devices.

Solid-State Fluorescent Carbon Dots with Unprecedented Efficiency from Visible to Near-Infrared Region.

Developing solid-state luminescent materials with bright long-wavelength emissions is of considerable practical importance in light-emitting diodes (LEDs) but remains a formidable challenge. Here, a novel structure engineering strategy is reported to realize solid-state fluorescence (FL)-emitted carbon dots (CDs) from visible to near-infrared region. This is the first report of such an extended wavelength emission of self-quenching-resistant solid-state CDs. Notably, the quantum yields of these CDs are remarkably improved up to 67.7%, which is the highest value for solid-state CDs. The surface polymer chains of CDs can efficiently suppress the conjugated sp2 carbon cores from π-π stacking inducing aggregation caused FL quenching, and the redshift of FL emissions is attributed to narrowing bandgap caused by an enlarged sp2 carbon core. Using these CDs as conversion phosphors, the fabrication of white LEDs with adjustable correlated color temperatures of 1882-5019 K is achieved. Moreover, a plant growth LED device is assembled with a blue-LED chip and deep-red/near-infrared-emitted CDs. Compared with sunlight and white LEDs, the peanuts irradiated by plant growth LED lamp show higher growth efficiency in terms of branches and leaves. This work provides high-quality solid-state CD-based phosphors for LED lighting sources that are required for diverse optoelectronic applications.

2D/3D heterostructure derived from phase transformation of 0D perovskite for random lasing applications with remarkably improved water resistance.

Phase transformation between metal halide perovskites serves as a promising route to create new optoelectronic functionalities. Nevertheless, the transformation reported thus far mainly involves the transition between two individual phases (e.g., 0D-3D and 3D-2D), while the transition from one phase to a heterostructure with distinct phases has been rarely disclosed. Here, we report a straightforward one-step procedure to directly convert 0D perovskite to 2D/3D heterostructures and demonstrate the application of the derivatives in random lasing beyond 0D perovskite. This phase transformation was triggered by exposing the 0D perovskite to a water environment and the resultant 2D/3D heterostructure showed much improved water resistance compared to that of its corresponding 3D counterpart as for chemical stability and photoluminescence performance. In addition, we demonstrated that the derived 2D/3D heterostructure readily exhibited random lasing characteristic of incoherent feedback upon optical pumping, while the parent 0D Cs4PbBr6 exhibited no sign of light amplification even pumped much harder. The pump threshold and the PL spectral profile were well maintained upon recycling treatment with water, implying the water resistance capability of the developed random lasing. The results suggest that the 2D/3D perovskite composites derived from the phase transformation of their 0D counterpart can serve as promising platforms for nanophotonic applications.

Laterally Engineering Lanthanide-MOFs Epitaxial Heterostructures for Spatially Resolved Planar 2D Photonic Barcoding.

Metal-organic frameworks (MOFs) heterostructures with domain-controlled emissive colors have shown great potential for achieving high-throughput sensing, anti-counterfeit and information security. Here, a strategy based on steric-hindrance effect is proposed to construct lateral lanthanide-MOFs (Ln-MOFs) epitaxial heterostructures, where the channel-directed guest molecules are introduced to rebalance in-plane and out-of-plane growth rates of the Ln-MOFs microrods and eventually generate lateral MOF epitaxial heterostructures with controllable aspect ratios. A library of lateral Ln-MOFs heterostructures are acquired through a stepwise epitaxial growth procedure, from which rational modulation of each domain with specific lanthanide doping species allows for definition of photonic barcodes in a two-dimensional (2D) domain with remarkably enlarged encoding capacity. The results provide molecular-level insight into the use of modulators in governing crystallite morphology for spatially assembling multifunctional heterostructures.

Topological-Distortion-Driven Amorphous Spherical Metal-Organic Frameworks for High-Quality Single-Mode Microlasers.

Metal-organic frameworks (MOFs) have recently emerged as appealing platforms to construct microlasers owing to their compelling characters combining the excellent stability of inorganic materials and processable characters of organic materials. However, MOF microstructures developed thus far are generally composed of multiple edge boundaries due to their crystalline nature, which consequently raises significant scattering losses that are detrimental to lasing performance. In this work, we propose a strategy to overcome the above drawback by designing spherically shaped MOFs microcavities. Such spherical MOF microstructures are constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks into the growth environment. With an ultra-smooth surface and excellent circular boundaries, the acquired spherical microcavities possess a Q factor as high as ≈104 and can provide sufficient feedback for high-quality single-mode lasing oscillations. We hope that these results will pave an avenue for the construction of new types of flexible MOF-based photonic components.

Spatially Responsive Multicolor Lanthanide-MOF Heterostructures for Covert Photonic Barcodes.

Micro/nanoscale photonic barcodes based on multicolor luminescent segmented heterojunctions hold potential for applications in information security. However, such multicolor heterojunctions reported thus far are exclusively based on static luminescent signals, thus restricting their application in advanced confidential information protection. Reported here is a strategy to design responsive photonic barcodes with heterobimetallic (Tb3+ /Eu3+ ) metal-organic framework multicolor heterostructures. The spatial colors could be precisely controlled by thermally manipulating the energy-transfer process between the two lanthanides, thus achieving responsive covert photonic barcodes. Also demonstrated is that spatially resolved responsive barcodes with multi-responsive features could be created in a single heterostructure. These findings offer unique opportunities to purposely design highly integrated responsive microstructures and smart devices toward advanced anti-counterfeiting applications.

Dynamically wavelength-tunable random lasers based on metal-organic framework particles.

We propose a strategy to construct dynamically tunable random lasers by continuously adjusting the excited state of gain molecules spatially confined in the nanoporous channels of metal-organic framework particles. Wavelength-tunable random lasers are achieved by thermally manipulating the intramolecular charge transfer process of gain molecules. The wavelength-tunable response to thermal stimuli exhibits excellent reversible behavior. We envisage that such random lasers based on metal-organic frameworks will raise new fundamental issues regarding light-matter interactions in complex photonic media and open up a new avenue toward highly efficient light-emitting devices.

Gram-Scale Synthesis of 41% Efficient Single-Component White-Light-Emissive Carbonized Polymer Dots with Hybrid Fluorescence/Phosphorescence for White Light-Emitting Diodes.

Fluorescent carbon dots (CDs) are compelling optical emitters to construct white light-emitting diodes (WLEDs). However, it remains a challenge to achieve large-scale and highly efficient single-component white-light-emissive CDs suitable for WLED applications. Herein, a low cost, fast processable, environmentally friendly, and one-step synthetic approach is developed for the preparation of gram-scale and highly efficient single-component white-light-emissive carbonized polymer dots (SW-CPDs). It is revealed that hybrid fluorescence/phosphorescence components cooperatively contribute to the emergence of white light emission. The SW-CPDs exhibit a record quantum yield (QY) of ≈41% for the white light emission observed in solid-state CD systems, while the QY of the phosphorescence is ≈23% under ambient conditions. Heavy doping of N and P elements as well as presence of covalently cross-linked polymer frameworks is suggested to account for the emergence of hybrid fluorescence/phosphorescence, which is supported by the experimental results and theoretical calculations. A WLED is fabricated by applying the SW-CPDs on an UV-LED chip, showing favorable white-light-emitting characteristics with a high luminous efficacy of 18.7 lm W-1 that is comparable to that of state-of-the-art WLEDs reported before.

Porous Core-Shell CuCo2 S4 Nanospheres as Anode Material for Enhanced Lithium-Ion Batteries.

Porous core-shell CuCo2 S4 nanospheres that exhibit a large specific surface area, sufficient inner space, and a nanoporous shell were synthesized through a facile solvothermal method. The diameter of the core-shell CuCo2 S4 nanospheres is approximately 800 nm" the radius of the core is about 265 nm and the thickness of the shell are approximately 45 nm, respectively. On the basis of the experimental results, the formation mechanism of the core-shell structure is also discussed. These CuCo2 S4 nanospheres show excellent Li storage performance when used as anode material for lithium-ion batteries. This material delivers high reversible capacity of 773.7 mA h g-1 after 1000 cycles at a current density of 1 A g-1 and displays a stable capacity of 358.4 mA h g-1 after 1000 cycles even at a higher current density of 10 A g-1 . The excellent Li storage performance, in terms of high reversible capacity, cycling performance, and rate capability, can be attributed to the synergistic effects of both the core and shell during Li+ ion insertion/extraction processes.

Enabling random lasing in an ultrabroad spectral range with robust platforms based on amorphous media.

Random lasing with coherent feedback has been achieved in an ultrabroad spectral range of 533-870 nm when employing robust platforms based on amorphous media to provide optical feedback and modulating the gain curve. The pump threshold of the resultant random lasing is comparable to those reported with strongly scattering centers in crystalline forms and highly efficient microfiber systems. The findings suggest that amorphous media could serve as the base of robust platforms to investigate light-matter interactions in complex media and to create highly efficient light-emitting devices.

Controlling Random Lasing with Three-Dimensional Plasmonic Nanorod Metamaterials.

Plasmonics has brought revolutionary advances to laser science by enabling deeply subwavelength nanolasers through surface plasmon amplification. However, the impact of plasmonics on other promising laser systems has so far remained elusive. Here, we present a class of random lasers enabled by three-dimensional plasmonic nanorod metamaterials. While dense metallic nanostructures are usually detrimental to laser performance due to absorption losses, here the lasing threshold keeps decreasing as the volume fraction of metal is increased up to ∼0.07. This is ∼460 times higher than the optimal volume fraction reported thus far. The laser supports spatially confined lasing modes and allows for efficient modulation of spectral profiles by simply tuning the polarization of the pump light. Full-field speckle-free imaging at micron-scales has been achieved by using plasmonic random lasers as the illumination sources. Our findings show that plasmonic metamaterials hold potential to enable intriguing coherent optical sources.

Wavelength-tunable spasing in the visible.

A SPASER, short for surface plasmon amplification by stimulated emission of radiation, is key to accessing coherent optical fields at the nanoscale. Nevertheless, the realization of a SPASER in the visible range still remains a great challenge because of strong dissipative losses. Here, we demonstrate that room-temperature SPASER emission can be achieved by amplifying longitudinal surface plasmon modes supported in gold nanorods as plasmon nanocavities and utilizing laser dyes to supply optical gain for compensation of plasmon losses. By choosing a particular organic dye and adjusting the doping level, the resonant wavelength of the SPASER emission can be tuned from 562 to 627 nm with a spectral line width narrowed down to 5-11 nm. This work provides a versatile route toward SPASERs at extended wavelength regimes.

Unidirectional spaser in symmetry-broken plasmonic core-shell nanocavity.

The spaser, a quantum amplifier of surface plasmons by stimulated emission of radiation, is recognized as a coherent light source capable of confining optical fields at subwavelength scale. The control over the directionality of spasing has not been addressed so far, especially for a single-particle spasing nanocavity where optical feedback is solely provided by a plasmon resonance. In this work we numerically examine an asymmetric spaser - a resonant system comprising a dielectric core capped by a metal semishell. The proposed spaser emits unidirectionally along the axis of the semishell; this directionality depends neither on the incident polarization nor on the incident angle of the pump. The spasing efficiency of the semishell-capped resonator is one order of magnitude higher than that in the closed core-shell counterpart. Our calculations indicate that symmetry breaking can serve as a route to create unidirectional, highly intense, single-particle, coherent light sources at subwavelength scale.

Plasmonically controlled lasing resonance with metallic-dielectric core-shell nanoparticles.

We experimentally demonstrate the capability of tailoring lasing resonance properties by manipulating the coupling between surface plasmons and photons in random lasing media composed of metallic-dielectric core-shell nanoparticles and organic dyes. It is revealed that core-shell nanoparticle-based systems exhibit optical feedback features distinctive from those containing pure metallic nanoparticles, provided that the scattering strength is weak enough. The pump threshold increases with an increment in the shell thickness, which can provide a direct proof that the local field enhancement plays a central role in the emergence of coherent feedback. The anomalous behavior in both threshold and optical feedback is discussed in terms of the modification of fluorescent properties of fluorophores close to metallic surface.

Random lasing in ballistic and diffusiveregimes for macroporous silica-based systems with tunable scattering strength.

We have systematically investigated random lasing properties in weakly scattering systems composed of a macroporous silica disk immersed in a dye solution where the solvent is a mixture of two alcohols. Controlling the refractive index of the mixed solvent allows us to vary the scattering strength over a wide range. We have found two different scattering regimes where sharp spectral spikes with linewidth less than 1.0 nm, i.e., random laser with coherent feedback, appear in emission spectra. When the refractive index contrast between the solvent and the silica is very small, random lasing with coherent feedback is observed although the system appears nearly transparent. The coherent feedback vanishes when the refractive index contrast is increased up to a critical value, while further increase in the refractive index contrast results in the revival of the coherent feedback. We suggest that the existence of underlying microcavities plays an important role in the very weakly scattering regime (ballistic) while other mechanisms such as amplified extended modes may lead to the coherent feedback in lasing oscillation when the scattering strength increases.

Two-photon-excited fluorescence from silicate glass containing tantalum ions pumped by a near-infrared femtosecond pulsed laser.

We report a novel phenomenon in sodium-calcium-silicate glass doped with Ta(5+). Under irradiation with a 780 nm femtosecond pulsed laser, strong blue emission centered at about 420 nm could be observed. The spectral characteristics are similar to those pumped by ultraviolet photons. The log-log correlation between integrated emission intensity and pump power reveals that a two-photon absorption process is involved in the phenomenon. It is suggested that the presence of localized Ta(5+)5d(0) energy levels is responsible for the appearance of the blue emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into glass hosts.

Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses.

Near-infrared broadband emission from bismuth-tantalum-codoped germanium oxide glasses was observed at room temperature when the glasses were pumped by an 808 nm laser diode. The emission band covered the O, E, S, C, and L bands (1260-1625 nm), with a maximum peak at approximately 1310 nm, a FWHM broader than 400 nm, and a lifetime longer than 200 micros. The observed broadband luminescence was attributed to bismuth clusters in the glasses. Bismuth-tantalum-codoped germanium oxide glass might be promising as amplification media for broadly tunable lasers and wideband amplifiers in optical communications.

Near infrared broadband emission of bismuth-doped aluminophosphate glass.

Near infrared broadband emission characteristics of bismuth-doped aluminophosphate glass have been investigated. Broad infrared emissions peaking at 1210nm, 1173nm and 1300nm were observed when the glass was pumped by 405nm laser diode (LD), 514nm Ar+ laser and 808nm LD, respectively. The full widths at half maximum (FWHMs) are 235nm, 207nm and 300nm for the emissions at 1210nm, 1173nm and 1300nm, respectively. Based on the energy matching conditions, it is suggested that the infrared emission may be ascribed to 3P1? 3P0 transition of Bi+. The broadband infrared luminescent characteristics of the glasses indicate that they are promising for broadband optical fiber amplifiers and tunable lasers.