Aggregation-induced emission organic metal halide complex for X-ray scintillation.

The expanding applications of X-ray scintillation across various areas, from healthcare to security detection call for the development of new-generation scintillators that offer enhanced sensitivity, efficiency, and versatility. Here, we report for the first time the use of organic metal halide complexes with aggregation-induced emission (AIE) for X-ray scintillation, which can be facilely synthesized and processed in the solution phase. By reacting an AIE organic molecule, 4-(4-(diphenylamino) phenyl)-1-(propyl)-pyridinium (TPA-PD) with zinc chloride (ZnCl2) in solution at room temperature, an organic metal halide complex, (TPA-PD)2ZnCl2, is produced with a high synthetic yield of 87%. Optical and radioluminescence characterizations find that (TPA-PD)2ZnCl2 exhibits bluish-green photoluminescence and radioluminescence peaked at around 450 nm, with a photoluminescence quantum efficiency (PLQE) of 65%, and an absolute light yield of 13 423 Photon per MeV. Moreover, short photoluminescence and radioluminescence decay lifetimes are recorded at 1.81 ns and 5.24 ns, respectively. For X-ray scintillation, an excellent response dose-response linearity and a low limit of detection of 80.23 nGyair S-1 are obtained for (TPA-PD)2ZnCl2. By taking advantage of the high X-ray absorption of metal halides and fast radioluminescence of AIE molecules, our design of covalently bonded organic metal halide complexes opens up new opportunities for the development of high-performance solution-processable scintillators.

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6 H5 )4 P]2 SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction.

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6 H5 )4 P]2 SbCl5 . In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic-inorganic hybrid systems.

One-dimensional organic metal halide nanoribbons with dual emission.

Organic metal halide hybrids with low-dimensional structures at the molecular level have received great attention recently for their exceptional structural tunability and unique photophysical properties. Here we report for the first time the synthesis and characterization of a one-dimensional (1D) organic metal halide hybrid, which contains metal halide nanoribbons with a width of three octahedral units. It is found that this material with a chemical formula C8H28N5Pb3Cl11 shows a dual emission with a photoluminescence quantum efficiency (PLQE) of around 25%. Photophysical studies and density functional theory (DFT) calculations suggest the coexisting of delocalized free excitons and localized self-trapped excitons in metal halide nanoribbons leading to the dual emission.

Molecular Sensitization Enabled High Performance Organic Metal Halide Hybrid Scintillator.

Scintillators, one of the essential components in medical imaging and security checking devices, rely heavily on rare-earth-containing inorganic materials. Here, a new type of organic-inorganic hybrid scintillators containing earth abundant elements that can be prepared via low-temperature processes is reported. With room temperature co-crystallization of an aggregation-induced emission (AIE) organic halide, 4-(4-(diphenylamino) phenyl)-1-(propyl)-pyrindin-1ium bromide (TPA-PBr), and a metal halide, zinc bromide (ZnBr2 ), a zero-dimensional (0D) organic metal halide hybrid (TPA-P)2 ZnBr4 with a yellowish-green emission peaked at 550 nm has been developed. In this hybrid material, dramatically enhanced X-ray scintillation of TPA-P+ is achieved via the sensitization by ZnBr4 2- . The absolute light yield (14,700 ± 800 Photons/MeV) of (TPA-P)2 ZnBr4 is found to be higher than that of anthracene (≈13,500 Photons/MeV), a well-known organic scintillator, while its X-ray absorption is comparable to those of inorganic scintillators. With TPA-P+ as an emitting center, short photoluminescence and radioluminescence decay lifetimes of 3.56 and 9.96 ns have been achieved. Taking the advantages of high X-ray absorption of metal halides and efficient radioluminescence with short decay lifetimes of organic cations, the material design paves a new pathway to address the issues of low X-ray absorption of organic scintillators and long decay lifetimes of inorganic scintillators simultaneously.

Efficient Red Light Emitting Diodes Based on a Zero-Dimensional Organic Antimony Halide Hybrid.

Zero-dimensional (0D) organic metal halide hybrids (OMHHs) have recently emerged as a new class of light emitting materials with exceptional color tunability. While near-unity photoluminescence quantum efficiencies (PLQEs) are routinely obtained for a large number of 0D OMHHs, it remains challenging to apply them as emitter for electrically driven light emitting diodes (LEDs), largely due to the low conductivity of wide bandgap organic cations. Here, the development of a new OMHH, triphenyl(9-phenyl-9H-carbazol-3-yl) phosphonium antimony bromide (TPPcarzSbBr4 ), as emitter for efficient LEDs, which consists of semiconducting organic cations (TPPcarz+ ) and light emitting antimony bromide anions (Sb2 Br8 2- ), is reported. By replacing one of the phenyl groups in a well-known tetraphenylphosphonium cation (TPP+ ) with an electroactive phenylcarbazole group, a semiconducting TPPcarz+ cation is developed for the preparation of red emitting 0D TPPcarzSbBr4 single crystals with a high PLQE of 93.8%. With solution processed TPPcarzSbBr4 thin films (PLQE of 86.1%) as light emitting layer, red LEDs are fabricated to exhibit an external quantum efficiency (EQE) of 5.12%, a peak luminance of 5957 cd m-2 , and a current efficiency of 14.2 cd A-1 , which are the best values reported to date for electroluminescence devices based on 0D OMHHs.

Point scintillator dosimetry in ultra-high dose rate electron "FLASH" radiation therapy: A first characterization.

FLASH radiation therapy is a novel technique combining ultra-high dose rates (UHDR) with very short treatment times to strongly decrease normal tissue toxicity while preserving the anti-tumoral effect. However, the radiobiological mechanisms and exact conditions for obtaining the FLASH-effect are still under investigation. There are strong indications that parameters defining the beam structure, such as dose per pulse, instantaneous dose rate and pulse repetition frequency (PRF) are of importance. UHDR irradiations therefore come with dosimetric challenges, including both dose assessment and temporal ones. In this work, a first characterization of 6 real-time point scintillating dosimeters with 5 phosphors (Al2O3:C,Mg; Y2O3:Eu; Al2O3:C; (C38H34P2)MnBr4 and (C38H34P2)MnCl4, was performed in an UHDR pulsed electron beam. The dose rate independence of the calibration was tested by calibrating the detector at conventional and UHDR. Dose rate dependence was observed, however, further investigation, including intermediate dose rates, is needed. Linearity of the response with dose was tested by varying the number of pulses and a linearity with R2> 0.9989 was observed up to at least 200 Gy. Dose per pulse linearity was investigated by variation of the pulse length and SSD. All point scintillators showed saturation effects up to some extent and the instantaneous dose rate dependence was confirmed. A PRF dependence was observed for the Al2O3:C,Mg and Al2O3:C- based point scintillators. This was expected as the luminescence decay time of these materials exceeds the inter-pulse time.

Metal Halide Scaffolded Assemblies of Organic Molecules with Enhanced Emission and Room Temperature Phosphorescence.

Ionically bonded organic metal halide hybrids have emerged as versatile multicomponent material systems exhibiting unique and useful properties. The unlimited combinations of organic cations and metal halides lead to the tremendous structural diversity of this class of materials, which could unlock many undiscovered properties of both organic cations and metal halides. Here we report the synthesis and characterization of a series benzoquinolinium (BZQ) metal halides with a general formula (BZQ)Pb2X5 (X = Cl, Br), in which metal halides form a unique two-dimensional (2D) structure. These BZQ metal halides are found to exhibit enhanced photoluminescence and stability as compared to the pristine BZQ halides, due to the scaffolding effects of 2D metal halides. Optical characterizations and theoretical calculations reveal that BZQ+ cations are responsible for the emissions in these hybrid materials. Changing the halide from Cl to Br introduces heavy atom effects, resulting in yellow room temperature phosphorescence (RTP) from BZQ+ cations.

Regulating Exciton-Phonon Coupling to Achieve a Near-Unity Photoluminescence Quantum Yield in One-Dimensional Hybrid Metal Halides.

Low-dimensional hybrid metal halides are emerging as a highly promising class of single-component white-emitting materials for their unique broadband emission from self-trapped excitons (STEs). Despite substantial progress in the development of these metal halides, many challenges remain to be addressed to obtain a better fundamental understanding of the structure-property relationship and realize the full potentials of this class of materials. Here, via pressure regulation, a near 100% photoluminescence quantum yield (PLQY) of broadband emission is achieved in a corrugated 1D hybrid metal halide C5 N2 H16 Pb2 Br6 , which possesses a highly distorted structure with an initial PLQY of 10%. Compression reduces the overlap between STE states and ground state, leading to a suppressed phonon-assisted non-radiative decay. The PL evolution is systematically demonstrated to be controlled by the pressure-regulated exciton-phonon coupling which can be quantified using Huang-Rhys factor S. Detailed studies of the S-PLQY relation for a series of 1D hybrid metal halides (C5 N2 H16 Pb2 Br6 , C4 N2 H14 PbBr4 , C6 N2 H16 PbBr4 , and (C6 N2 H16 )3 Pb2 Br10 ) reveal a quantitative structure-property relationship that regulating S factor toward 28 leads to the maximum emission.

Dual-Mechanism Quenched Fluorogenic Probe Provides Selective and Rapid Detection of Cathepsin L Activity*.

Cathepsin L (CTL) is a cysteine protease demonstrating upregulated activity in many disease states. Overlapping substrate specificity makes selective detection of CTL activity difficult to parse from that of its close homologue CTV and the ubiquitous CTB. Current probes of CTL activity have limited applications due to either poor contrast or extra assay steps required to achieve selectivity. We have developed a fluorogenic probe, CTLAP, that displays good selectivity for CTL over CTB and CTV while exhibiting low background fluorescence attributed to dual quenching mechanisms. CTLAP achieves optimum CTL selectivity in the first 10 min of incubation, thus suggesting that it is amenable for rapid detection of CTL, even in the presence of competing cathepsins.

Highly Efficient and Stable Perovskite Solar Cells Enabled by Low-Cost Industrial Organic Pigment Coating.

Surface passivation of perovskite solar cells (PSCs) using a low-cost industrial organic pigment quinacridone (QA) is presented. The procedure involves solution processing a soluble derivative of QA, N,N-bis(tert-butyloxycarbonyl)-quinacridone (TBOC-QA), followed by thermal annealing to convert TBOC-QA into insoluble QA. With halide perovskite thin films coated by QA, PSCs based on methylammonium lead iodide (MAPbI3 ) showed significantly improved performance with remarkable stability. A PCE of 21.1 % was achieved, which is much higher than 18.9 % recorded for the unmodified devices. The QA coating with exceptional insolubility and hydrophobicity also led to greatly enhanced contact angle from 35.6° for the pristine MAPbI3 thin films to 77.2° for QA coated MAPbI3 thin films. The stability of QA passivated MAPbI3 perovskite thin films and PSCs were significantly enhanced, retaining about 90 % of the initial efficiencies after more than 1000 hours storage under ambient conditions.

Reaching 90% Photoluminescence Quantum Yield in One-Dimensional Metal Halide C4N2H14PbBr4 by Pressure-Suppressed Nonradiative Loss.

Low-dimensional perovskite-related metal halides have emerged as a new class of light-emitting materials with tunable broadband emission from self-trapped excitons (STEs). Although various types of low-dimensional structures have been developed, fundamental understating of the structure-property relationships for this class of materials is still very limited, and further improvement of their optical properties remains greatly important. Here, we report a significant pressure-induced photoluminescence (PL) enhancement in a one-dimensional hybrid metal halide C4N2H14PbBr4, and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. Under a gigapascal pressure scale, the PL quantum yields (PLQYs) were quantitatively determined to show a dramatic increase from the initial value of 20% at ambient conditions to over 90% at 2.8 GPa. With in situ characterization of photophysical properties and theoretical analysis, we found that the PLQY enhancement was mainly attributed to the greatly suppressed nonradiative decay. Pressure can effectively tune the energy level of self-trapped states and increase the exciton binding energy, which leads to a larger Stokes shift. The resulting highly localized excitons with stronger binding reduce the probability for carrier scattering, to result in the significantly suppressed nonradiative decay. Our findings clearly show that the characteristics of STEs in low-dimensional metal halides can be well-tuned by external pressure, and enhanced optical properties can be achieved.

Metal Halide Regulated Photophysical Tuning of Zero-Dimensional Organic Metal Halide Hybrids: From Efficient Phosphorescence to Ultralong Afterglow.

The photophysical tuning is reported for a series of tetraphenylphosphonium (TPP) metal halide hybrids containing distinct metal halides, TPP2 MXn (MXn =SbCl5 , MnCl4 , ZnCl4 , ZnCl2 Br2 , ZnBr4 ), from efficient phosphorescence to ultralong afterglow. The afterglow properties of TPP+ cations could be suspended for the hybrids containing low band gap emissive metal halide species, such as SbCl5 2- and MnCl4 2- , but significantly enhanced for the hybrids containing wide band gap non-emissive ZnCl4 2- . Structural and photophysical studies reveal that the enhanced afterglow is attributed to stronger π-π stacking and intermolecular electronic coupling between TPP+ cations in TPP2 ZnCl4 than in the pristine organic ionic compound TPPCl. Moreover, the afterglow in TPP2 ZnX4 can be tuned by controlling the halide composition, with the change from Cl to Br resulting in a shorter afterglow due to the heavy atom effect.

Thiazol-2-thiolate-Bridged Binuclear Platinum(II) Complexes with High Photoluminescence Quantum Efficiencies of up to Near Unity.

Binuclear platinum(II) complexes with strong Pt-Pt interactions are an interesting class of luminescent materials, of which photophysical properties could be controlled via multiple ways through organic ligands and Pt-Pt distance. While a number of binuclear platinum(II) complexes have been developed with tunable emissions, achieving high photoluminescence quantum efficiency (PLQE) remains challenging and of great interest. Here we report the synthesis and characterization of a series of binuclear 2,4-difluorophenylpyridine platinum(II) complexes bridged by thiazol-2-thiolate ligands with different bulkiness. The three complexes were found to have short Pt-Pt distances ranging from 2.916 to 2.945 Å. The strong Pt-Pt interactions lead to pronounced metal-metal-to-ligand charge transfer (MMLCT) absorptions between 450 and 500 nm, and strong 3MMLCT emissions in the orange/red region. The PLQEs of the new complexes are in the ranges of 2-31% in solution and 26-100% in solid state. These complexes also exhibit excellent stability in halogenated solvents.

Phase Control and In Situ Passivation of Quasi-2D Metal Halide Perovskites for Spectrally Stable Blue Light-Emitting Diodes.

The fabrication of efficient and spectrally stable pure-blue perovskite light-emitting diodes (LEDs) has been elusive and remains of great interest. Herein, we incorporate diammonium salts into quasi-2D perovskite precursors for phase control of multiple quantum well structures to yield tunable and efficient emission in the blue region. With detailed characterizations and computational studies, we show that in situ passivation by the diammonium salts effectively modifies the surface energies of quasi-2D phases and inhibits the growth of low-band gap quasi-2D and 3D phases. Such phase control and in situ passivation could afford blue light-emitting perovskite thin films with high photoluminescence quantum efficiencies of, for instance, 75% for the emission peak at 471 nm. Using this perovskite thin film as an emitting layer, spectrally stable pure-blue LEDs with an emission peak at 474 nm and a full width at half-maximum of 26 nm could be fabricated to exhibit a brightness of 290 cd m-2 at 8 V and an external quantum efficiency of 2.17%.

Highly efficient eco-friendly X-ray scintillators based on an organic manganese halide.

Scintillation based X-ray detection has received great attention for its application in a wide range of areas from security to healthcare. Here, we report highly efficient X-ray scintillators with state-of-the-art performance based on an organic metal halide, ethylenebis-triphenylphosphonium manganese (II) bromide ((C38H34P2)MnBr4), which can be prepared using a facile solution growth method at room temperature to form inch sized single crystals. This zero-dimensional organic metal halide hybrid exhibits green emission peaked at 517 nm with a photoluminescence quantum efficiency of ~ 95%. Its X-ray scintillation properties are characterized with an excellent linear response to X-ray dose rate, a high light yield of ~ 80,000 photon MeV-1, and a low detection limit of 72.8 nGy s-1. X-ray imaging tests show that scintillators based on (C38H34P2)MnBr4 powders provide an excellent visualization tool for X-ray radiography, and high resolution flexible scintillators can be fabricated by blending (C38H34P2)MnBr4 powders with polydimethylsiloxane.

Hollow metal halide perovskite nanocrystals with efficient blue emissions.

Metal halide perovskite nanocrystals (NCs) have emerged as new-generation light-emitting materials with narrow emissions and high photoluminescence quantum efficiencies (PLQEs). Various types of perovskite NCs, e.g., platelets, wires, and cubes, have been discovered to exhibit tunable emissions across the whole visible spectrum. Despite remarkable advances in the field of perovskite NCs, many nanostructures in inorganic NCs have not yet been realized in metal halide perovskites, and producing highly efficient blue-emitting perovskite NCs remains challenging and of great interest. Here, we report the discovery of highly efficient blue-emitting cesium lead bromide (CsPbBr3) perovskite hollow NCs. By facile solution processing of CsPbBr3 precursor solution containing ethylenediammonium bromide and sodium bromide, in situ formation of hollow CsPbBr3 NCs with controlled particle and pore sizes is realized. Synthetic control of hollow nanostructures with quantum confinement effect results in color tuning of CsPbBr3 NCs from green to blue, with high PLQEs of up to 81%.

Multicomponent Organic Metal Halide Hybrid with White Emissions.

Zero-dimensional (0D) organic metal halide hybrids, in which organic and metal halide ions cocrystallize to form neutral species, are a promising platform for the development of multifunctional crystalline materials. Herein we report the design, synthesis, and characterization of a ternary 0D organic metal halide hybrid, (HMTA)4 PbMn0.69 Sn0.31 Br8 , in which the organic cation N-benzylhexamethylenetetrammonium (HMTA+ , C13 H19 N4 + ) cocrystallizes with PbBr4 2- , MnBr4 2- , and SnBr4 2- . The wide band gap of the organic cation and distinct optical characteristics of the three metal bromide anions enabled the single-crystalline "host-guest" system to exhibit emissions from multiple "guest" metal halide species simultaneously. The combination of these emissions led to near-perfect white emission with a photoluminescence quantum efficiency of around 73 %. Owing to distinct excitations of the three metal halide species, warm- to cool-white emissions could be generated by controlling the excitation wavelength.

Facile Formation of 2D-3D Heterojunctions on Perovskite Thin Film Surfaces for Efficient Solar Cells.

The interfaces between perovskite and charge transport layers greatly impact the device efficiency and stability of perovskite solar cells (PSCs). Inserting an ultrathin wide-band-gap layer between perovskite and hole transport layers (HTLs) has recently been shown as an effective strategy to enhance device performance. Herein, a small amount of an organic halide salt, N,N'-dimethylethylene-1,2-diammonium iodide, is used to create two-dimensional (2D)-three-dimensional (3D) heterojunctions on MAPbI3 thin film surfaces by facile solution processing. The formation of an ultrathin wide-band-gap 2D perovskite layer on top of 3D MAPbI3 changes the morphological and photophysical properties of perovskite thin films, effectively reduces the surface defects, and suppresses the charge recombination in the interfaces between perovskite and HTL. As a result, a power conversion efficiency of ∼20.2%, with an open-circuit voltage of 1.14 V, a short-circuit current density of 22.57 mA cm-2, and a fill factor of 0.78, is achieved for PSCs with enhanced stability.

Highly Emissive and Stable Organic-Perovskite Nanocomposite Thin Films with Phosphonium Passivation.

Organometal halide perovskite materials, in particular colloidal perovskite nanocrystals (NCs), have been investigated extensively as next-generation light-emitting materials. However, producing highly efficient and stable perovskite thin films from colloidal NCs is not trivial, as dissociation of surfactants often occurs during the thin-film formation. Here, we demonstrate a facile solution-processing approach to prepare perovskite nanocomposite thin films by using phosphonium as the capping ligand for methylammonium lead bromide (MAPbBr3) NCs. The photoluminescence and stability of thin films containing in situ formed perovskite NCs were greatly enhanced after phosphonium passivation, with the photoluminescence quantum efficiency reaching 78% and only 5% decrease of the intensity after one month's exposure in ambient conditions. Electrically driven light-emitting diodes (LEDs) based on pristine perovskite neat thin films and organic-perovskite nanocomposite thin films were fabricated, and we observed a 10-fold improvement in the external quantum efficiency of these LEDs (from 0.6% to 6.3%) resulting from the in situ formation of perovskite NCs with phosphonium passivation.

Ligand-Mediated Release of Halides for Color Tuning of Perovskite Nanocrystals with Enhanced Stability.

The rich chemistry of metal halide perovskites has enabled various methods of band structure control and surface passivation. Here we report a highly facile and efficient post-treatment approach for precise color tuning of cesium lead halide perovskite nanocrystals (NCs) with enhanced stability. By utilizing a special multifunctional organic ligand, triphenyl(9-phenyl-9H-carbazol-3-yl)phosphonium bromide (TPP-Carz), carbon-halide bond cleavage can be achieved to release halide ions from halogenated solvents in a controlled manner for color tuning of perovskite NCs via ion exchange. Besides controlled release of halide ions for anion exchange, TPP-Carz can effectively passivate the surfaces of perovskite NCs simultaneously. As a result, perovskite NCs prepared by this post-treatment method with tunable colors over the entire visible spectrum have shown significantly improved luminescence and stability in comparison to the ones prepared using reactive anion precursors without surface passivation by TPP-Carz.