Excitation-Dependent Emission in Sb3+-Doped All-Inorganic Rare-Earth Double Perovskites for Anticounterfeiting Applications.

Achieving high-efficiency tunable emission in a single phosphor remains a significant challenge. Herein, we report a series of Sb3+-doped all-inorganic double perovskites, Sb3+:Cs2NaScCl6, with efficient excitation-dependent emission. In 0.5%Sb3+:Cs2NaScCl6, strong blue emission with a high photoluminescence quantum yield (PLQY) of 85% is obtained under 265 nm light irradiation, which turns into bright neutral white light with a PLQY of 56% when excited at 303 nm. Spectroscopic and computational investigations were performed to reveal the mechanism of this excitation-dependent emission. Sb3+ doping induces two different excitation channels: the internal transition of Sb3+: 5s2 → 5s5p and the electron transfer transition of Sb3+: 5s → Sc3+ 3d. The former one generates excited Sb3+ ions, which can undergo efficient energy transfer to populate the host self-trapped exciton (STE) state, yielding enhanced blue emission. The latter one leads to the formation of a new STE state with the hole localized on Sb3+ and the electron delocalized on the nearest Sc3+, which accounts for the newly exhibited low-energy emission. The difference in the excitation pathways of the two emitting STE states results in the highly efficient excitation-dependent emission, making the doped systems promising anticounterfeiting materials.

Sb-Doped Cs3 TbCl6 Nanocrystals for Highly Efficient Narrow-Band Green Emission and X-Ray Imaging.

Metal halide nanocrystals (NCs) with high photoluminescence quantum yield (PLQY) are desirable for lighting, display, and X-ray detection. Herein, the novel lanthanide-based halide NCs are committed to designing and optimizing the optical and scintillating properties, so as to unravel the PL origin, exciton dynamics, and optoelectronic applications. Sb-doped zero-dimensional (0D) Cs3 TbCl6 NCs exhibit a green emission with a narrow full width of half maximum of 8.6 nm, and the best PLQY of 48.1% is about three times higher than that of undoped NCs. Experiments and theoretical calculations indicate that 0D crystalline and electronic structures make the exciton highly localized on [TbCl6 ]3- octahedron, which boosts the Cl- -Tb3+ charge transfer process, thus resulting in bright Tb3+ emission. More importantly, the introduction of Sb3+ not only facilitates the photon absorption transition, but also builds an effective thermally boosting energy transfer channel assisted by [SbCl6 ]3- -induced self-trapped state, which is responsible for the PL enhancement. The high luminescence efficiency and negligible self-absorption of the Cs3 TbCl6 : Sb nanoscintillator enable a more sensitive X-ray detection response compared with undoped sample. The study opens a new perspective to deeply understand the excited state dynamics of metal halide NCs, which helps to design high-performance luminescent lanthanide-based nanomaterials.

Cs2 SnCl6 : To Emit or to Catalyze? Te4+ Ion Calls the Shots.

A low concentration of Te4+ doping is found to be capable of endowing the lead-free Cs2 SnCl6 perovskites with excellent photoluminescence quantum yield (PLQY), while further increasing Te4+ concentration leads to PLQY deterioration. The mechanism behind the improved PLQY is intensively studied and reported elsewhere. However, little work is conducted to understand the decreased PLQY at high doping levels and to explore its implications for non-PL-related applications. Here, it is demonstrated that the Te4+ -incorporated Cs2 SnCl6 can be promising candidate for efficient CO2 photocatalysis. An optimum photocatalytic performance is achieved when Te4+ concentration reaches as high as 50%, at which point significant PL quenching has occurred. Through a detailed spectral characterization, such concentration-dependent functionality is attributed to systematic changes in both electronic and local crystal structure, which allow a robust regulation of excitation energy relaxation channels. These findings expand the scope of available photocatalysts for CO2 reduction and also inform synthetic planning for the preparation of multifunctional Pb-free metal halide perovskites.

All-Inorganic Zero-Dimensional Sb3+-Doped Rb2ScCl5(H2O) Perovskite Single Crystals: Efficient Self-Trapped Exciton Emission and X-ray Detection.

Zero-dimensional (0D) halide perovskites have attracted extensive attention for their potential applications in solid-state lighting and X-ray detection due to their fascinating optoelectronic properties and convenient solution processability. Herein, we report the synthesis and photophysical properties of high-quality Sb3+-doped 0D Rb2ScCl5(H2O) perovskite single crystals. The pristine crystals exhibit weak yellow self-trapped exciton (STE) emission peaking at 632 nm. The emission quantum yield can be dramatically enhanced from less than 1% to about 53% via Sb3+ doping. Spectroscopic characterizations indicate that the photoluminescence enhancement is a result of the efficient energy transfer from Sb3+ to the emissive STEs. Additionally, 0.2%Sb3+:Rb2ScCl5(H2O) single crystals exhibit potential application in direct X-ray detection with a high sensitivity of 58.5 µC Gy-1 cm-2.

Highly Luminescent One-Dimensional Organic-Inorganic Hybrid Double-Perovskite-Inspired Materials for Single-Component Warm White-Light-Emitting Diodes.

Double perovskites (DPs) are one of the most promising candidates for developing white light-emitting diodes (WLEDs) owing to their intrinsic broadband emission from self-trapped excitons (STEs). Translation of three-dimensional (3D) DPs to one-dimensional (1D) analogues, which could break the octahedral tolerance factor limit, is so far remaining unexplored. Herein, by employing a fluorinated organic cation, we report a series of highly luminescent 1D DP-inspired materials, (DFPD)2 MI InBr6 (DFPD=4,4-difluoropiperidinium, MI =K+ and Rb+ ). Highly efficient warm-white photoluminescence quantum yield of 92 % is achieved by doping 0.3 % Sb3+ in (DFPD)2 KInBr6 . Furthermore, single-component warm-WLEDs fabricated with (DFPD)2 KInBr6 :Sb yield a luminance of 300 cd/m2 , which is one of the best-performing lead-free metal-halides WLEDs reported so far. Our study expands the scope of In-based metal-halides from 3D to 1D, which exhibit superior optical performances and broad application prospects.

Spatiotemporal imaging of charge transfer in photocatalyst particles.

The water-splitting reaction using photocatalyst particles is a promising route for solar fuel production1-4. Photo-induced charge transfer from a photocatalyst to catalytic surface sites is key in ensuring photocatalytic efficiency5; however, it is challenging to understand this process, which spans a wide spatiotemporal range from nanometres to micrometres and from femtoseconds to seconds6-8. Although the steady-state charge distribution on single photocatalyst particles has been mapped by microscopic techniques9-11, and the charge transfer dynamics in photocatalyst aggregations have been revealed by time-resolved spectroscopy12,13, spatiotemporally evolving charge transfer processes in single photocatalyst particles cannot be tracked, and their exact mechanism is unknown. Here we perform spatiotemporally resolved surface photovoltage measurements on cuprous oxide photocatalyst particles to map holistic charge transfer processes on the femtosecond to second timescale at the single-particle level. We find that photogenerated electrons are transferred to the catalytic surface quasi-ballistically through inter-facet hot electron transfer on a subpicosecond timescale, whereas photogenerated holes are transferred to a spatially separated surface and stabilized through selective trapping on a microsecond timescale. We demonstrate that these ultrafast-hot-electron-transfer and anisotropic-trapping regimes, which challenge the classical perception of a drift-diffusion model, contribute to the efficient charge separation in photocatalysis and improve photocatalytic performance. We anticipate that our findings will be used to illustrate the universality of other photoelectronic devices and facilitate the rational design of photocatalysts.

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.

Organic-Inorganic Hybrid Cuprous-Based Metal Halides for Warm White Light-Emitting Diodes.

Single-component emitters with stable and bright warm white-light emission are highly desirable for high-efficacy warm white light-emitting diodes (warm-WLEDs), however, materials with such luminescence properties are extremely rare. Low-dimensional lead (Pb) halide perovskites can achieve warm white photoluminescence (PL), yet they suffer from low stability and PL quantum yield (PLQY). While Pb-free air-stable perovskites such as Cs2 AgInCl6 emit desirable warm white light, sophisticated doping strategies are typically required to increase their PL intensity. Moreover, the use of rare metal-bearing compounds along with the typically required vacuum-based thin-film processing may greatly increase their production cost. Herein, organic-inorganic hybrid cuprous (Cu+ )-based metal halide MA2 CuCl3 (MA = CH3 NH3 + ) that meets the requirements of i) nontoxicity, ii) high PLQY, and iii) dopant-free is presented. Both single crystals and thin films of MA2 CuCl3 can be facilely prepared by a low-cost solution method, which demonstrate bright warm white-light emission with intrinsically high PLQYs of 90-97%. Prototype electroluminescence devices and down-conversion LEDs are fabricated with MA2 CuCl3 thin films and single crystals, respectively, which show bright luminescence with decent efficiencies and operational stability. These findings suggest that MA2 CuCl3 has a great potential for the single-component indoor lighting and display applications.

Boosting the Self-Trapped Exciton Emission in Cs2NaYCl6 Double Perovskite Single Crystals and Nanocrystals.

Halide double perovskites have aroused substantial research interest because of their unique optical properties and intriguing flexibility for various compositional adjustments. Herein, we report the synthesis and photophysics of rare-earth element yttrium (Y)-based double perovskite single crystals (SCs) and nanocrystals (NCs). The pristine Cs2NaYCl6 bulk SCs exhibit a weak sky-blue emission with a low photoluminescence quantum yield (PLQY) of 7.68% based on the self-trapped exciton (STE), while no PL emission was observed for NCs. Excitingly, the STE emission of SCs and NCs is greatly enhanced via Sb3+ doping. The optimized Cs2NaYCl6:Sb3+ SCs and NCs exhibit high PLQYs up to 82.5% and 51.8%, respectively. Theoretical calculations and charge-carrier dynamic studies demonstrate that the giant emission enhancement after Sb3+ doping is related with the enhancement of the sensitization of the emissive STE states, the passivating of the nonradiative carrier trapping processes, and the regulation of carrier-phonon coupling.

Filling Chlorine Vacancy with Bromine: A Two-Step Hot-Injection Approach Achieving Defect-Free Hybrid Halogen Perovskite Nanocrystals.

Mixed-halide (Cl and Br) perovskite nanocrystals (NCs) are of particular interest because they hold great potential for use in high-efficiency blue light-emitting diodes (LEDs). Generally, mixed-halide compounds are obtained by either a one-step synthesis with simultaneous addition of both halide precursors or a postsynthetic anion exchange using the opposite halogen. However, both strategies fail to prevent the formation of deep-level Cl vacancy defects, rendering the photoluminescence quantum yields (PLQYs) typically lower than 30%. Here, by optimizing both thermodynamic and kinetic processes, we devise a two-step hot-injection approach, which simultaneously realizes Cl vacancy filling and efficient anion exchange between Cl- and Br-. Both the identity of Br precursors and their injection temperature are revealed to be critical in transforming those highly defective CsPbCl3 NCs to defect-free CsPb(Cl/Br)3. The optimally synthesized NCs exhibit a saturated blue emission at ∼460 nm with a near-unity PLQY and a narrow emission bandwidth of 18 nm, which represents one of the most efficient blue emitters reported so far. The turn-on voltage of the ensuing LEDs is ∼4.0 V, which is lower than those of most other mixed-halide perovskites. In addition, LEDs exhibit a stable electroluminescence peak at 460 nm under a high bias voltage of 8.0 V. We anticipate that our findings will provide new insights into the materials design strategies for producing high-optoelectronic-quality Cl-containing perovskites.

Unraveling the Key Role of the Benzyl Group in the Synthesis of CL-20 Precursor HBIW.

As one of the most important energetic material molecules, hexanitrohexaazaisowurtzitane (CL-20) can only be synthesized using an amine with a benzyl group. Moreover, the reaction mechanism remains unexplored and the special role of the benzyl group has not been revealed. To address these issues, we perform an extensive theoretical study to investigate the synthesis mechanism of CL-20 precursor HBIW by employing density functional theory. Our calculated results demonstrate that the benzyl group can reduce the energy of the intermediate and the energy barrier of the rate-determining step due to the π-π stack interaction between two benzene rings of the benzyl group. For the first time, we revealed that the reactions can produce 16 intermediates with different chiralities during the formation of the first two side five-membered rings and only two of which can further form the bottom six-membered ring and finally obtain the product HBIW. The steric hindrance effect of the benzyl group leads to the formation of a higher-energy intermediate first, thereby providing an opportunity to correct the wrong chirality. All of these factors make the diimine with the benzyl group the most suitable reactant for the synthesis of CL-20.

Organo-Metal Halide Scintillator with Weak Thermal Quenching Up to 200 °C.

The prominent thermal quenching (TQ) effect of organic-inorganic metal halides limits their applications for lighting and imaging. Herein, we report an organo-metal halide scintillator (TTPhP)2MnCl4 (TTPhP+ = tetraphenylphosphonium cation), which exhibits a weak TQ effect up to 200 °C under ultraviolet-visible light (efficiency loss of 5.5%) and X-ray radiation (efficiency loss of 37%). The light yield of the (TTPhP)2MnCl4 scintillator (37 000 photons MeV-1 at 200 °C) under X-ray radiation is >2 times that of the commercial scintillator LuAG:Ce (15 000 photons MeV-1 at 200 °C). The microscopic mechanism of the weak TQ effect is demonstrated to be the scintillator having the ability to compensate for the emission losses from trapped charges and the large Mn-Mn distance (10.233 Å) suppressing nonradiative recombination at high temperatures. We further demonstrate the applications of (TTPhP)2MnCl4 as high-power white-light-emitting diodes operated at currents of ≤300 mA and X-ray imaging at 200 °C with a high spatial resolution.

Germanium Halides Serving as Ideal Precursors: Designing a More Effective and Less Toxic Route to High-Optoelectronic-Quality Metal Halide Perovskite Nanocrystals.

The three-precursors approach has proven to be advantageous for obtaining high-quality metal halide perovskite nanocrystals (PNCs). However, the current halide precursors of choice are mainly limited to those highly toxic organohalides, being unfavorable for large-scale and sustainable use. Moreover, most of the resulting PNCs still suffer from low quality in terms of photoluminescence quantum yield (PLQY). Herein we present all-inorganic germanium salts, GeX4 (X = Cl, Br, I), serving as robust and less hazardous alternatives that are capable of ensuring improved material properties for both Pb-based and Pb-free PNCs. Importantly, unlike most of the other inorganic halide sources, the GeX4 compound does not deliver the Ge element into the final compositions, whereas the PLQY and phase stability of the resulting nanocrystals are significantly improved. Theoretical calculations suggest that Ge halide precursors provide favorable conditions in both dielectric environment and thermodynamics, which jointly contribute to the formation of size-confined defect-suppressed nanoparticles.

Profiling Cystathionine ß/γ-Lyase in Complex Biosamples Using Novel Activatable Fluorogens.

Cystathionine lyase, the key enzyme in transsulfuration and reverse transsulfuration pathways, is involved in a wide array of physiological and pathophysiological processes in both mammals and nonmammals. Though the biological significance of the hydrogen sulfide/cystathionine lyase system in disease states is extensively discussed, the absence of molecular methods for direct monitoring of cystathionine lyase in complex biosamples renders the result unreliable and perplexing. Here, we present the first attempt at designing and developing effective activatable fluorescent probes for cystathionine lyase based on the naphthylamide scaffold. CBLP and CSEP were designed based on the catalytic preference of cystathionine ß-lyase (CBL) and cystathionine γ-lyase (CSE). Briefly, incorporation of cysteine/homocysteine as the recognition moiety and a carbamate ethyl sulfide group as a self-immolated linker proved to be an effective strategy for cystathionine lyase fluorescence reporting. CBLP exhibits high selectivity and sensitivity in vitro in semiquantifying CBL levels in roots of wild-type Arabidopsis thaliana and cbl mutants (cbl knockout: SALK_014740C, overexpressed: OE-CBL). Meanwhile, CSEP successfully detected CSE levels in HCC-LM3 cells, zebrafish models, and upregulated CSE in frozen section slides from the liver tissue of cecal ligation and puncture (CLP)-induced septic rats, which was also validated by Western blotting and immunohistochemical analysis. In summary, the practical design strategy facilitates profiling of cystathionine lyase activity in biological processes. It may pave the way for the development of accurate and efficient methods for the direct estimation of cystathionine lyase.

New Cy5 photosensitizers for cancer phototherapy: a low singlet-triplet gap provides high quantum yield of singlet oxygen.

Highly efficient triplet photosensitizers (PSs) have attracted increasing attention in cancer photodynamic therapy where photo-induced reactive oxygen species (ROSs, such as singlet oxygen) are produced via singlet-triplet intersystem crossing (ISC) of the excited photosensitizer to kill cancer cells. However, most PSs exhibit the fatal defect of a generally less-than-1% efficiency of ISC and low yield of ROSs, and this defect strongly impedes their clinical application. In the current work, a new strategy to enhance the ISC and high phototherapy efficiency has been developed, based on the molecular design of a thio-pentamethine cyanine dye (TCy5) as a photosensitizer. The introduction of an electron-withdrawing group at the meso-position of TCy5 could dramatically reduce the singlet-triplet energy gap (ΔE st) value (from 0.63 eV to as low as 0.14 eV), speed up the ISC process (τ ISC = 1.7 ps), prolong the lifetime of the triplet state (τ T = 319 µs) and improve singlet oxygen (1O2) quantum yield to as high as 99%, a value much higher than those of most reported triplet PSs. Further in vitro and in vivo experiments have shown that TCy5-CHO, with its efficient 1O2 generation and good biocompatibility, causes an intense tumor ablation in mice. This provides a new strategy for designing ideal PSs for cancer photo-therapy.

Directionally Modified Fluorophores for Super-Resolution Imaging of Target Enzymes: A Case Study with Carboxylesterases.

In the need for improving the labeling quality of super-resolution imaging, multifarious fluorescent labeling strategies have sprang up. Among them, a small molecule inhibitor-probe (SMI-probe) shows its advancement in fine mapping due to its smaller size and its specific binding to a specific site. Herein, we report a novel protocol of mechanism-guided directional modification of fluorophores into fluorescent inhibitors for enzyme targeting, which could half the size of the SMI-probe. To confirm the feasibility of the strategy, carboxylesterase (hCE) inhibitors are designed and developed. Among the constructed molecule candidates, NIC-4 inhibited both isoforms of hCE1 and hCE2, with IC50 values of 4.56 and 4.11 µM. The CE-targeting specificity of NIC-4 was confirmed by colocalizing with an immunofluorescent probe in fixed-cell confocal imaging. Moreover, NIC-4 was used in live-cell super-resolution microscopy, which indicates dotlike structures instead of the larger staining with the immunofluorescent probe. Moreover, it enables the real-time tracking of dynamic flow of carboxylesterases in live cells.

Extending the Legible Time of Light-Responsive Rewritable Papers with a Tunable Photochromic Diarylethene Molecule.

Inkless printing based on rewritable papers has recently made great progress because it can improve the utilization rate of papers, which is of great significance for saving resources and protecting the environment. Among them, light-responsive rewritable papers (LRPs) are a hot research topic because light is clean, easily available, wavelength and intensity adjustable, and noncontacting. However, the photochromic material, as the imaging substance of LRPs, is easily affected by environmental conditions, resulting in insufficient time to read the information. In view of this, we designed and constructed an acid/base tunable diarylethene molecular system that can effectively adjust the photochromic properties by reversibly changing the electron density of the diarylethene photoreaction center through protonation and demonstrated its potential as an imaging material with a longer legible time. What makes us more satisfied is that the acidification can not only extend the legible time of carrying information but also bring a clear and stable absorption/fluorescence imaging dual mode, which can better reflect details and improve contrast. Therefore, we believe that this tunable photochromic diarylethene molecule is a potential imaging material for the development of new LRPs.

Bright Triplet Self-Trapped Excitons to Dopant Energy Transfer in Halide Double-Perovskite Nanocrystals.

For inorganic semiconductor nanostructure, excitons in the triplet states are known as the "dark exciton" with poor emitting properties, because of the spin-forbidden transition. Herein, we report a design principle to boost triplet excitons photoluminescence (PL) in all-inorganic lead-free double-perovskite nanocrystals (NCs). Our experimental data reveal that singlet self-trapped excitons (STEs) experience fast intersystem crossing (80 ps) to triplet states. These triplet STEs give bright green color emission with unity PL quantum yield (PLQY). Furthermore, efficient energy transfer from triplet STEs to dopants (Mn2+) can be achieved, which leads to white-light emitting with 87% PLQY in both colloidal and solid thin film NCs. These findings illustrate a fundamental principle to design efficient white-light emitting inorganic phosphors, propelling the development of illumination-related applications.

Controlling Photoluminescence and Photocatalysis Activities in Lead-Free Cs2 Ptx Sn1-x Cl6 Perovskites via Ion Substitution.

Lead-free halide perovskites have triggered interest in the field of optoelectronics and photocatalysis because of their low toxicity, and tunable optical and charge-carrier properties. From an application point of view, it is desirable to develop stable multifunctional lead-free halide perovskites. We have developed a series of Cs2 Ptx Sn1-x Cl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2 Ptx Sn1-x Cl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2 Ptx Sn1-x Cl6 solid solution with a small amount of Pt4+ substitution exhibits photocatalytic hydrogen evolution activity. An optical spectroscopy study reveals that the switch between photoluminescence and photocatalysis functions is controlled by sub-band gap states. Our finding provides a new way to develop lead-free multifunctional halide perovskites with high stability.

Ultrafast Dynamics of Self-Trapped Excitons in Lead-Free Perovskite Nanocrystals.

Lead-free halide perovskite nanocrystals (NCs) have received increasing attention owing to their low toxicity and high stability. Localized charge distribution and strong carrier-phonon coupling in lead-free perovskite NCs facilitates the formation of self-trapped excitons (STEs), which typically give a broadband photoluminescence (PL) emission with a large Stokes shift. In this Perspective, we highlight how PL modulations can give rise to an efficient white-light emission by understanding and tuning the ultrafast dynamics of STEs in lead-free perovskite NCs. We then present the exciton energy transfer mediated by STEs to provide an efficient thermally activated delayed fluorescence and dopant PL. We also illustrate promising directions for future applications based on STEs. We hope that this Perspective can provide a new viewpoint for researchers to understand the ultrafast dynamics of STEs and promote lead-free perovskite NCs for optoelectronic applications.