Ultralong Lifetimes Research Articles

Mechanochemical Synthesis of Carbazole Isomer Phosphors.

The 1H-benzo[f]indole (Bd[f]), a carbazole (Cz) isomer is first reported as the source of Cz-based phosphors in 2020. In this work, the novel carbazole isomers, 1H-benzo[g]indole (Bd[g]) based derivatives, are synthesized by a one-step solvent-free mechanical ball milling reaction, establishing a facile, efficient, and environmentally friendly method for the synthesis of new Cz isomer phosphorescent derivatives with high yields compared to previously reported multi-step solvent-based thermochemical synthesis routes of Bd[f] derivatives with low yields. Six Bd[g] derivatives with different substituents, namely OCH3-Bd, In-Bd, Bn-Bd, F-Bd, Cl-Bd, and Br-Bd, are synthesized, which exhibit distinctly different single-crystal structures and phosphorescent properties. After irradiation with 365nm UV light, Bd[g] derivatives-doped poly (methyl methacrylate) (PMMA) films exhibit photoactivated green room-temperature phosphorescence with ultra-long lifetimes up to 1.65s. Interestingly, the phosphorescence is stable in seawater along with good bactericidal properties, which also provide new candidates for indole-based marine antifoulants. This study demonstrates that mechanical ball milling is an efficient method for the synthesis of benzoindole heterocycles. Bd[g], as new members of the benzoindole family, are new building units to construct carbazole isomer phosphorescent molecules besides Bd[f].

Dynamics of Photoinduced Charge Carriers in Metal-Halide Perovskites

The measurement and description of the charge-carrier lifetime (τc) is crucial for the wide-ranging applications of lead-halide perovskites. We present time-resolved microwave-detected photoconductivity decay (TRMCD) measurements and a detailed analysis of the possible recombination mechanisms including trap-assisted, radiative, and Auger recombination. We prove that performing injection-dependent measurement is crucial in identifying the recombination mechanism. We present temperature and injection level dependent measurements in CsPbBr3, which is the most common inorganic lead-halide perovskite. In this material, we observe the dominance of charge-carrier trapping, which results in ultra-long charge-carrier lifetimes. Although charge trapping can limit the effectiveness of materials in photovoltaic applications, it also offers significant advantages for various alternative uses, including delayed and persistent photodetection, charge-trap memory, afterglow light-emitting diodes, quantum information storage, and photocatalytic activity.

In situ Cyclization of Aromatic Thioethers in Emissive Materials to Generate Phosphorescent Dibenzothiophenes

AbstractIn this contribution, we explored the photocyclization of thioethers to highly substituted dibenzothiophenes (DBT) using solely UV‐light without any need for additives. This cost‐effective, robust and environmentally friendly approach yielded phosphorescent compounds, which were characterized by X‐ray crystallography and state‐of‐the‐art photophysical methods. The resulting DBTs feature ultralong photoluminescence lifetimes and quantum yields close to unity in frozen glassy matrices. The reaction mechanism was elucidated in detail through a combination of quantum chemical calculations and experimental results, providing evidence that triplet states are involved in the cyclization process. Additionally, the photoreaction can also be induced within materials. For this purpose, the precursors were integrated into polymer films or polymer resins suitable for 3D printing. Irradiation of these polymeric objects allows motifs with ultralong phosphorescence to be irreversibly inscribed through the proceeding photocyclization. The in situ photogeneration of DBTs from aromatic thioethers overcomes the observed incompatibilities regarding solubility in polymer resins for 3D printing.

Inherent Water Competition Effect-Enabled Colloidal Electrode for Ultra-stable Aqueous Zn-I Batteries.

Electrode material stability is crucial for the development of next-generation ultralong-lifetime batteries. However, current solid- and liquid-state electrode materials face challenges such as rigid atomic structure collapse and uncontrolled species migration, respectively, which contradict the theoretical requirements for ultralong operation lifetimes. Herein, we present a design concept for a soft colloid polyvinylpyrrolidone iodine (PVP-I) electrode, leveraging the inherent water molecule competition effect between (SO4)2- from the electrolyte and PVP-I from the cathode in an aqueous Zn||PVP-I battery. Electrochemical demonstrations measured under various simulated and practical (integrated with photovoltaic solar panel) conditions highlight the potential for an ultralong battery lifetime. The PVP-I colloid exhibits a dynamic response to the electric field during battery operation. More importantly, the water competition effect between (SO4)2- from the electrolyte and water-soluble polymer cathode materials establishes a new electrolyte/cathode interfacial design platform for advancing ultralong-lifetime aqueous batteries.

Effect of ionic bonding on luminescence properties of histidine maleic anhydride derivatives

Polymeric materials exhibiting room-temperature phosphorescent (RTP) have attracted wide attention for their easy synthesis, low toxicity, and applications in various fields such as data encryption, cell imaging, information security and other fields. Nevertheless, the conventional ways of preparing such materials are mainly focused on doping, which may suffer from phase separation, poor compatibility, and lack of effective methods to promote intersystem crossing and suppress the nonradiative deactivation rates. Herein, a series of polymers with fluorescence and phosphorescence dual emission were prepared by simple radical solution copolymerization. Through rigid ion-bonded cross-linked networks and cross-linked hydrogen-bonded networks between the polymer chains, the non-radiative jumps and achieve ultra-long phosphorescence lifetimes were able to suppress. By suppressing non-radiative transitions through rigid ion-bonded cross-linked networks and intermolecular hydrogen-bonding networks between polymer chains, ultra-long phosphorescence is achieved. Impressively, a LRTP lifetime of up to 815.38 ms in polymers under ambientconditions is set up. Moreover, in this study, phosphorescence emission can be easily tuned by balancing ion radius and charge states. These results outline the construction of polymeric materials, endowing traditional polymers with new characteristics and promising potential applications.

Stable Persistent Room-Temperature Phosphorescent Hydrogels Based on Ionically Crosslinked Nonaromatic Carboxylate Polymers.

Developing pure organic room-temperature phosphorescent (RTP) hydrogels is important for expanding the practical applications of phosphorescent materials. However, most of the reported RTP hydrogels containing aromatic phosphors suffer from short phosphorescent lifetimes, unstable underwater RTP emissions, and complex preparation processes. Herein, novel nonaromatic RTP hydrogels are prepared by using two types of non-traditional luminescent polymers, sodium alginate and a polymeric carboxylate, which are not RTP emissive or very weakly emissive in aqueous environments. The prepared hydrogels exhibit the following features: I) color-tunable RTP emissions with ultra-long lifetimes up to 451.1ms, II) excellent anti-swelling properties and stable persistent RTP emission even after being immersed in deionized water for months, III) efficient and large-scale preparation of hydrogel fibers by wet spinning technique. Experiment results and theoretical calculations show that the stable and long-lifetime RTP emissions of the hydrogels originate from the introduction of more nonconventional chromophores which are strongly crosslinked with ionic bonding between carboxylate groups and calcium ions and enhanced through-space interactions between them. This work provides a reliable strategy for designing nonaromatic hydrogels with stable and persistent RTP.

In situ Cyclization of Aromatic Thioethers in Emissive Materials to Generate Phosphorescent Dibenzothiophenes.

In this contribution, we explored the photocyclization of thioethers to highly substituted dibenzothiophenes (DBT) using solely UV-light without any need for additives. This cost-effective, robust and environmentally friendly approach yielded phosphorescent compounds, which were characterized through X-ray crystallography and state-of-the-art photophysical methods. The resulting DBTs feature ultralong photoluminescence lifetimes and quantum yields close to unity in frozen glassy matrices. The reaction mechanism was investigated in detail through a combination of quantum chemical calculations and experimental results, providing evidence that triplet states are involved in the cyclization process. Additionally, the photoreaction can also be induced within materials. For this purpose, the precursors can be integrated into polymer films or polymer resins suitable for 3D printing. Irradiation of these polymeric objects allows motifs with ultralong phosphorescence to be irreversibly inscribed through the proceeding photocyclization. The in situ photogeneration of DBTs from aromatic thioethers overcomes the observed incompatibilities regarding solubility in polymer resins for 3D printing.

Color-tunable ultralong-lifetime room temperature phosphorescence using phenylalanine derivative doped poly(vinyl alcohol) films

Doping chromophores in polymer matrixes to deliver room temperature phosphorescence (RTP) is well established. However, there are few examples of polymer-based RTP materials with ultralong phosphorescent lifetimes (>4 s) and afterglow (>30 s) under ambient conditions. We report a series of ultralong-lived RTP films by doping Phenylalanine (Phe) derivatives in a poly (vinyl alcohol) (PVA) matrix. The phosphorescence lifetime and efficiency of these films can be increased by introducing pentaerythritol (PER), an effect that is attributed to enhanced hydrogen-bonding interactions. The Fmoc-L-Phe@PER/PVA film exhibits a phosphorescence lifetime of 4.42 s and an afterglow duration of 46 s. Co-doping the PVA system with (Rhodamine B and Sulforhodamine B sodium salt) fluorescent dyes allows an adjustment of the afterglow from blue to red and pink. These films have been successfully applied in flexible luminescent materials, silk-screen printing, and multicolor afterglow light-emitting diode (LED) arrays.

Chiral Polymer‐Organic Molecule Composite with Circularly Polarized Thermally Activated Delayed Fluorescence and Room‐Temperature Phosphorescence by Bridging Effect of Hydrogen Bond

AbstractCircularly polarized luminescence is essential to chiral and photonic science, but achieving circularly polarized thermally activated delayed fluorescence (CP‐TADF) and circularly polarized room‐temperature phosphorescence (CP‐RTP) simultaneously remains a great challenge. This is because it is difficult to satisfy simultaneously the stable triplet exciton, appropriate energy gap, and the regular chiral environment. Herein, a simple strategy is reported to construct a persistent photoluminescent system, which can achieve TADF and RTP simultaneously by suppressing the non‐radiative transition decay of the triplet exciton through intermolecular hydrogen bonding between acridine flavin (AF) and rigid polymer network. The persistent photoluminescent composite exhibited ultra‐long lifetimes and high quantum yields. Then, a rarely multi‐circularly polarized photoluminescence system containing CP‐TADF and CP‐RTP is constructed by the co‐assembly of cellulose nanocrystals, polyvinyl alcohol, and AF. By utilizing the cholesteric structure, photonic band gap of chiral photonic crystals, and the stabilization mechanism of triplet exciton by intermolecular hydrogen bonding between the light emitter and rigid polymer, chiral photoluminescent films exhibited rare optical properties simultaneously: multi‐circularly polarized photoluminescence emission, high and tunable dissymmetric factor, significant quantum yield, and ultralong lifetimes, which are not reported before and broaden the perspective for multi‐circularly polarized luminescence.

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries.

Traditional Li-ion intercalation chemistry into graphite anodes exclusively utilizes the cointercalation-free or cointercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfactory cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in situ synthesis of t-GIC in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GIC (b-GIC) and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional cointercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles, even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10 000 cycles. Full cells coupled with a layered cathode display remarkable cycling stability upon a 15 min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach for achieving fast-charging and low-temperature batteries.

Nylons with Highly-Bright and Ultralong Organic Room-Temperature Phosphorescence

Endowing the widely-used synthetic polymer nylon with high-performance organic room-temperature phosphorescence would produce advanced materials with a great potential for applications in daily life and industry. One key to achieving this goal is to find a suitable organic luminophore that can access the triplet excited state with the aid of the nylon matrix by controlling the matrix-luminophore interaction. Herein we report highly-efficient room-temperature phosphorescence nylons by doping cyano-substituted benzimidazole derivatives into the nylon 6 matrix. These homogeneously doped materials show ultralong phosphorescence lifetimes of up to 1.5 s and high phosphorescence quantum efficiency of up to 48.3% at the same time. The synergistic effect of the homogeneous dopant distribution via hydrogen bonding interaction, the rigid environment of the matrix polymer, and the potential energy transfer between doped luminophores and nylon is important for achieving the high-performance room-temperature phosphorescence, as supported by combined experimental and theoretical results with control compounds and various polymeric matrices. One-dimensional optical fibers are prepared from these doped room-temperature phosphorescence nylons that can transport both blue fluorescent and green afterglow photonic signals across the millimeter distance without significant optical attenuation. The potential applications of these phosphorescent materials in dual information encryption and rewritable recording are illustrated.

Isostructural doping for organic persistent mechanoluminescence.

Mechanoluminescence, featuring light emission triggered by mechanical stimuli, holds immense promise for diverse applications. However, most organic Mechanoluminescence materials suffer from short-lived luminescence, limiting their practical applications. Herein, we report isostructural doping as a valuable strategy to address this challenge. By strategically modifying the host matrices with specific functional groups and simultaneously engineering guest molecules with structurally analogous features for isostructural doping, we have successfully achieved diverse multicolor and high-efficiency persistent mechanoluminescence materials with ultralong lifetimes. The underlying persistent mechanoluminescence mechanism and the universality of the isostructural doping strategy are also clearly elucidated and verified. Moreover, stress sensing devices are fabricated to show their promising prospects in high-resolution optical storage, pressure-sensitive displays, and stress monitoring. This work may facilitate the development of highly efficient organic persistent mechanoluminescence materials, expanding the horizons of next-generation smart luminescent technologies.

A novel group of N,N-diaryl-1,2-benzenediamine room temperature phosphors based on structural engineering

Room temperature phosphorescence (RTP) has gained new momentum as a long-term topic along with the appearance of novel phosphors with versatile application potentials. Compared to traditional RTP materials, innovative pure organic phosphors have become promising alternatives due to their superiority in cost and processibility. However, the development of single-component organic phosphors with ultralong emission lifetimes and simple structures is still ongoing. Despite several kinds of organic phosphors being developed, the ones utilizing arylamine skeletons are barely reported. In this paper, we present a novel family of N,N-diaryl-1,2-benzenediamine phosphors with varying numbers of methyl substituents on terminal phenyl rings based on structural engineering. These molecules exhibited bright phosphorescence in the region of green to yellow light with a remarkably long lifetime up to 684 ms in crystalline states under ambient conditions. Comprehensive experimental and theoretical studies revealed that diverse intermolecular interactions and weak intramolecular hydrogen bonds co-contribute to the long-lived RTP emission. An encryption QR code was constructed, which displayed great potential in anti-counterfeiting applications. This work offered a novel structural motif for ultralong RTP material design and is constructive for material pool expansion.

Deterministic placement and effective-mass pinning of topological polariton bound states in the continuum

The exciton-polaritons derived from the light-matter interaction of an optical bound state in the continuum (BIC) with the strong excitonic resonance in a transition metal dichalcogenide (TMD) monolayer can inherit ultra-long radiative lifetimes and significant nonlinearities up to room temperature. Yet such realization can be challenging with conventional approaches to the photonic cavity design, typically due to poorly-resolved Rabi splittings at room temperature and an unstable energy positioning of the BIC state. We show and experimentally validate a strategy to dramatically improve the state-of-the-art on both points, by embedding a tungsten disulfide (WS2) monolayer deep within a Bloch-surface-wave stack, where the photonic mode is moulded by a 1D photonic crystal with a compound periodicity. In particular, we introduce a deterministic placement principle to the design of the PhC, allowing to stabilize the energy positioning of a topologically-protected BIC polariton eigenstate, with an effective mass which we can robustly pre-assign at choice as either positive or negative. This is in stark contrast to typical waveguide realizations of polariton BICs: only negative polariton effective masses can be commonly achieved, while sudden jumps to a weaker-interacting positive-effective-mass BIC are at the same time possible upon small perturbations, in fact hijacking the advantage from a topological protection when present.

Synergy of Dendrites-Impeded Atomic Clusters Dissociation and Side Reactions Suppressed Inert Interface Protection for Ultrastable Zn Anode.

The sluggish ions-transfer and inhomogeneous ions-nucleation induce the formation of randomly oriented dendrites on Zn anode, while the chemical instability at anode-electrolyte interface triggers detrimental side reactions. Herein, this report in situ designs a multifunctional hybrid interphase of Bi/Bi2O3, for the first time resulting in a novel synergistic regulation mechanism involving: (i) chemically inert interface protection mechanism suppresses side reactions; and more fantastically, (ii) innovative thermodynamically favorable Zn atomic clusters dissociation mechanism impedes dendrites formation. Assisted by collaborative modulation behavior, the Zn@Bi/Bi2O3 symmetry cell delivers an ultrahigh cumulative plating capacity of 1.88 Ah cm-2 at 5mA cm-2 and ultralong lifetimes of 300h even at high current density and depth of discharge (10mA cm-2, DODZn: 60%). Furthermore, under a low electrolyte-to-capacity ratio (E/C: 45µL mAh-1) and negative-to-positive capacity ratio (N/P: 6.3), Zn@Bi/Bi2O3||MnO2 full-cell exhibits a superior capacity retention of 86.7% after 500 cycles at 1 A g-1, which outperforms most existing interphases. The scaled-up Zn@Bi/Bi2O3||MnO2 battery module (6V, 1 Ah), combined with the photovoltaic panel, presents excellent renewable-energy storage ability and long output lifetime (12h). This work provides a fantastic synergistic mechanism to achieve the ultrastable Zn anode and can be greatly promised to apply it into other metal-based batteries.

Achieving Ultralong Room-Temperature Phosphorescence in Covalent Organic Framework System.

The combination of room-temperature phosphorescence (RTP) and covalent organic frameworks (COFs) would give rise to a new class of functional materials with sensing and responsive properties. However, such organic materials have been rarely reported, especially for those with long phosphorescence lifetimes. Here we report the incorporation of RTP emitters into COFs either via chemical decoration or noncovalent doping to achieve ultralong RTP in a COF system. The RTP emitters are designed with small phosphorescence rates and consequently exhibit ultralong phosphorescence lifetimes when nonradiative decay and oxygen quenching are suppressed in COF system. The RTP-COF materials have been found to possess oxygen sensing properties with large response of phosphorescence lifetimes.

Na+: the key to ultra-long afterglow lifetimes of CDs in dense SiO2 matrices

This work demonstrates that Na+ is the key to ultra-long afterglow lifetimes of CDs in dense silica matrices.

High-Quality Circularly Polarized Organic Afterglow from Nonconjugated Amorphous Chiral Copolymers.

Organic materials featuring circularly polarized luminescence (CPL) and/or afterglow emission represent an active research frontier with promising applications in various fields, but the achievement of high-performance CPL organic afterglow (CPOA) remains a huge challenge due to the intrinsic contradictions between the luminescent lifetime/dissymmetry factor (glum) and phosphorescent quantum efficiency (PhQY). Herein, we report a simple and universal approach to design efficient CPOA from amorphous copolymers by incorporating chiral chromophores into a nonconjugated clusterization-triggered emissive polymer with plenty of hydron-bonding interactions, followed by aggregation engineering using water dissolution and evaporation. With this chiral copolymerization and aggregation engineering (CCAE) strategy, high-performance CPOA polymers with PhQYs of up to 6.32%, ultralong lifetimes of over 650 ms, glum values of 3.54 × 10-3, and the highest figure-of-merit were achieved at room temperature. Given the impressive CPOA performance of these polymers, the applications in multilevel data anticounterfeiting and reversible displays with high stability were demonstrated. These findings through the CCAE strategy to overcome the inherent restraints of CPOA materials lay the foundation for the development of amorphous polymers with superior CPOA, significantly expanding the understanding of CPL and the design of organic afterglow materials.

Triplet Orbital Coupling: Achieving Ultralong Lifetime and Color Control in Upconversion Luminescence

AbstractLanthanide‐doped nanocrystals typically exhibit limited time‐gated nonlinear luminescence with microsecond lifetimes because of their parity‐forbidden 4f–4f transitions. Here the direct observation of ultralong‐lived upconversion luminescence by coupling molecular triplet orbitals to lanthanide‐doped nanocrystals is reported. Through careful manipulation of the molecular triplet states, nanohybrids capable of producing ultralong upconversion lifetimes up to 1.37 s and tunable color output are constructed, surpassing the intrinsic lifetime of lanthanide ions by a factor of 4500. In addition to the exciton migration pathway from the 4f levels of lanthanide ions to the molecular singlet and then to triplet states, direct activation of the triplet state by exciton from the 4f levels is observed. This phenomenon significantly reduces the required photon energy (by more than 0.83 eV) for stimulation of the triplet state compared to the process involving intersystem crossing. Taking advantage of the unique properties of these nanohybrids, a pulsed laser‐pumped encryption system with enhanced security is developed by embedding additional passwords that contain information about pulse frequency and width. This work provides a new perspective on time‐resolved nonlinear luminescence with an ultrawide time dimension by engineering molecular triplet states.

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 2.1s excited by 420nm, 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.