High-Resolution Afterglow Patterning Using Cooperative Vapo- and Photo-Stimulation.

Bright afterglow room-temperature phosphorescence (RTP) soon after ceasing excitation is a promising technique for greatly increasing anti-counterfeiting capabilities. The development of a process for rapid high-resolution afterglow patterning of crystalline materials can improve both high-speed fabrication of anti-counterfeiting afterglow media and stable afterglow readout compared with those achieved with amorphous materials. Here, the high-resolution afterglow patterning of crystalline materials via cooperative organic vapo- and photo-stimulation is reported. A single crystal of (S)-(-)-2,2'-bis(diphenylphosphino)-5,5',6,6',7,7'8,8'-octahydro-1,1'-binaphthyl [(S)-H8-BINAP] doped with (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [(S)-BINAP] shows green afterglow RTP. Crystals of (S)-BINAP-doped (S)-H8-BINAP changed to an amorphous state with no afterglow capability on weak continuous photoirradiation under dichloromethane (DCM) vapor. Photoirradiation induced oxidation of the (S)-H8-BINAP host molecule in the crystal. The oxidized (S)-H8-BINAP forms on the crystal surface strongly interacted with DCM molecules, which induces melting of the (S)-BINAP-doped (S)-H8-BINAP crystal and trigger formation of an amorphous state without an afterglow capability. High-resolution afterglow patterning of the crystalline film is rapidly achieved by using cooperative organic vapo- and photo-stimulation. In addition to the benefit of rapid afterglow patterning, the formed afterglow images of the crystalline film can be repeatedly read out under ambient conditions without DCM vapor.

Organic-Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission.

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material. Remarkably, the presented (4-methylpiperidium)CdCl3 also shows noticeable antiferroelectric behavior. The implementation of cationic customization and halogen engineering not only enables a dramatic enhancement of Curie temperature of 114.4 K but also brings a record longest emission lifetime up to 117.11 ms under ambient conditions, realizing a leapfrog improvement of at least two orders of magnitude compared to reported hybrid ferroelectrics so far. This finding would herald the emergence of novel application potential, such as multi-level density data storage or multifunctional sensors, towards the future integrated optoelectronic devices with multitasking capabilities.

Tunable Afterglow and Self-Trapped Exciton Emissions in Zr (IV)-Based Organic-Inorganic Metal Halide Hybrids by Metal-Ion Doping.

Low-dimensional hybrid metal halide (LDHMH) materials have attracted considerable attention owing to their intriguing optical properties. To the best of the knowledge, this is the first study to successfully demonstrate both self-trap exciton (STE) and afterglow emissions in Zr-based LDHMH materials. The obtained pure (Ph3 S)2 ZrCl6 crystals showed near-ultraviolet phosphorescence and a green afterglow owing to the organic cation Ph3 S+ , while the Bi-doped and Sb-doped crystals exhibited both STE and afterglow emissions. However, the Te-doped crystals showed only a broad yellow STE emission owing to the [TeCl6 ]2- octahedron. In addition, all the crystals showed good stability. Notably, Sb-doped crystals produced white light, which can be adjusted between cold white and warm white using different excitations. Finally, this strategy for both STE and afterglow emissions can be applied to other LDHMH materials for optical applications.

White Light Afterglow in Carbon Dots Achieved via Synergy between the Room-Temperature Phosphorescence and the Delayed Fluorescence.

Carbon dot (CD) based long-lived afterglow emission materials have attracted attention in recent years, but demonstration of white-light room-temperature afterglow remains challenging, due to the difficulty of simultaneous generation of multiple long-lived excited states with distinct chromatic emission. In this work, a white-light room-temperature long-lived afterglow emission from a CD powder with a high efficiency of 5.8% and Commission International de l'Eclairage (CIE) coordinates of (0.396, 0.409) is realized. The afterglow of the CDs originates from a synergy between the phosphorescence of the carbon core and the delayed fluorescence associated with the surface CN moieties, which is accomplished by matching the singlet state of the surface groups of the CDs with the long-lived triplet state of the carbon core, resulting in an efficient energy transfer. It is demonstrated how the long-lived afterglow emission of CDs can be utilized for fabrication of white light emitting devices and in anticounterfeiting applications.

Highly Efficient and Ultralong Afterglow Emission with Anti-Thermal Quenching from CsCdCl3 : Mn Perovskite Single Crystals.

Triplet exciton-based long-lived phosphorescence is severely limited by the thermal quenching at high temperature. Herein, we propose a novel strategy based on the energy transfer from triplet self-trapped excitons to Mn2+ dopants in solution-processed perovskite CsCdCl3 . It is found the Mn2+ doped hexagonal phase CsCdCl3 could simultaneously exhibit high emission efficiency (81.5 %) and long afterglow duration time (150 s). Besides, the afterglow emission exhibits anti-thermal quenching from 300 to 400 K. In-depth charge-carrier dynamics studies and density functional theory (DFT) calculation provide unambiguous evidence that carrier detrapping from trap states (mainly induced by Cl vacancy) to localized emission centers ([MnCl6 ]4- ) is responsible for the afterglow emission with anti-thermal quenching. Enlightened by the present results, we demonstrate the application of the developed materials for optical storage and logic operation applications.

Sustainable Afterglow Room-Temperature Phosphorescence Emission Materials Generated Using Natural Phenolics.

Long-lived afterglow room-temperature phosphorescence (RTP) from natural phenolics has seldom been reported yet this is essential for the development of sustainable afterglow RTP materials. With this research, we have prepared sustainable afterglow RTP materials (GA@SA) with a lifetime of up to ≈934.7 ms by embedding gallic acid (GA) within a Ca2+ -crosslinked sodium alginate (SA) matrix. Theoretical simulations indicate that the restricted carbonyl moieties of the GA and H-type aggregates of GA in a SA matrix promoted the spin orbit coupling (SOC) of GA and induced afterglow emission. Moreover, afterglow RTP emission could be produced by embedding different types of natural phenolics such as, tannic acid, caffeic acid and chlorogenic acid into Ca2+ -crosslinked networks of SA. As an illustration of potential applications, GA@SA was used to prepare anti-counterfeit afterglow clothing and paper. This work provides an innovative method for the activation of long-lived afterglow RTP from sustainable phenolics.

A Descriptor for Accurate Predictions of Host Molecules Enabling Ultralong Room-Temperature Phosphorescence in Guest Emitters.

Although doping can induce room-temperature phosphorescence (RTP) in heavy-atom free organic systems, it is often challenging to match the host and guest components to achieve efficient intersystem crossing for activating RTP. In this work, we developed a simple descriptor ΔE to predict host molecules for matching the guest RTP emitters, based on the intersystem crossing via higher excited states (ISCHES) mechanism. This descriptor successfully predicted five commercially available host components to pair with naphthalimide (NA) and naphtho[2,3-c]furan-1,3-dione (2,3-NA) emitters with a high accuracy of 83 %. The yielded pairs exhibited bright yellow and green RTP with the quantum efficiency up to 0.4 and lifetime up to 1.67 s, respectively. Using these RTP pairs, we successfully achieved multi-layer message encryption. The ΔE descriptor could provide an efficient way for developing doping-induced RTP materials.

Continuous Condensed Triplet Accumulation for Irradiance-Induced Anticounterfeit Afterglow.

Afterglow room-temperature emission that is independent of autofluorescence after ceasing excitation is a promising technology for state-of-the-art bioimaging and security devices. However, the low brightness of the afterglow emission is a current limitation for using such materials in a variety of applications. Herein, the continuous formation of condensed triplet excitons for brighter afterglow room-temperature phosphorescence is reported. (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ((S)-BINAP) incorporated in a crystalline host lattice showed bright green afterglow room-temperature phosphorescence under strong excitation. The small triplet-triplet absorption cross-section of (S)-BINAP in the whole range of visible wavelengths greatly suppressed the deactivation caused by Förster resonance energy transfer from excited states of (S)-BINAP to the accumulated triplet excitons of (S)-BINAP under strong continuous excitation. The steady-state concentration of the triplet excitons for (S)-BINAP reached 2.3 × 10-2  M, producing a bright afterglow. Owing to the brighter afterglow, afterglow detection using individual particles with sizes approaching the diffraction limit in aqueous conditions and irradiance-dependent anticounterfeiting can be achieved.

Modulating the Carbonization Degree of Carbon Dots for Multicolor Afterglow Emission.

Organic afterglow materials based on carbon dots (CDs) have aroused extensive attention for their potential applications in sensing, photoelectric devices, and anticounterfeiting. Effective methods to control the CD structure and modulate the energy levels are critical but still challenging. Here, we demonstrate a method to modulate the afterglow emission of CDs@SiO2 composites by controlling the carbonization degree of CDs with variable calcining temperatures. The CDs@SiO2-Raw prepared with a hydrothermal bottom-up synthesis method shows a more polymerized structure of CDs with low carbonization degree, which emits long-lived thermally activated delayed fluorescence (TADF) with the lifetime of 252 ms. After calcination at 550 °C, CDs@SiO2-550 exhibits a larger conjugated π-domain structure with higher carbonization degree, thus inducing room-temperature phosphorescence (RTP) emission with a lifetime of 451 ms. The transformation of the carbonization degree of CD structures leads to changes in energy levels and ΔEST, which affect their afterglow luminescence behaviors. This work proposes a new concept to modulate the afterglow emission of CDs@SiO2 composites and forecasts potential applications of CD-based afterglow materials.

Integrated Afterglow and Self-Trapped Exciton Emissions in Hybrid Metal Halides for Anti-Counterfeiting Applications.

0D hybrid metal halides (0D HMHs) are considered to be promising luminescent emitters. 0D HMHs commonly exhibit self-trapped exciton (STE) emissions originating from the inorganic metal halide anion units. Exploring and utilizing the emission features of the organic cation units in 0D HMHs is highly desired to enrich their optical properties as multifunctional luminescent materials. Here, tunable emissions from organic and inorganic units are successfully achieved in triphenylsulfonium (Ph3 S+ )-based 0D HMHs. Notably, integrated afterglow and STE emissions with adjustable intensities are obtained in (Ph3 S)2 Sn1- x Tex Cl6 (x = 0-1) via the delicate combination of [SnCl6 ]2- and [TeCl6 ]2- . Moreover, such a strategy can be readily extended to develop other HMH materials with intriguing optical properties. As a demonstration, 0D (Ph3 S)2 Zn1- x Mnx Cl4 (x = 0-1) are constructed to achieve integrated afterglow and Mn2+ d-d emissions with high efficiency. Consequently, these novel 0D HMHs with colorful afterglow and STE emissions are applied in multiple anti-counterfeiting applications.