Excitation-Selective and Double-Emissive Lead-Free Binary Hybrid Metal Halides for White Light-Emitting Diode and X-Ray Scintillation.

Zero-dimensional (0D) organic metal halides comprising heterogeneous metal cations in single phase can achieve multiple luminous emissions enabling them toward multifunctional light-emitting applications. Herein, A novel single crystal of (C8H20N)4SbMnCl9 containing two luminescent centers of [SbCl5]2- pentahedrons and [MnCl4]2- tetrahedrons is reported. The large distance between Sb-Sb, Mn-Mn, and Sb-Mn as well as theory calculation indicate negligible interaction between individual centers, thus endowing (C8H20N)4SbMnCl9 with excitation-dependable and efficient luminescence. Under near-UV excitation, only orange emission originates from self-trapped excitons recombination in [SbCl5]2- pentahedron occurs with photoluminescence quantum yield (PLQY) of 91.5%. Under blue-light excitation, only green emission originating from 4T1-6A1 transition of Mn2+ in [MnCl4]2- tetrahedrons occurs with PLQY of 66.8%. Interestingly, upon X-ray illumination, both emissions can be fully achieved due to the high-energy photon absorption. Consequently, (C8H20N)4SbMnCl9 is employed as phosphors to fabricate white light-emitting diodes optically pumped by n-UV chip and blue-chip thanks to its excitation-dependable property. Moreover, it also shows promising performance as X-ray scintillator with low detection limit of 60.79 nGyair S-1, steady-state light yield ≈54% of commerical scintillaotr LuAG:Ce, high resolution of 13.5 lp mm-1 for X-ray imaging. This work presents a new structural design to fabricate 0D hybrids with multicolor emissions.

Long-Range Hot Charge Transfer Exciton Dissociation in an Organic/2D Semiconductor Hybrid Excitonic Heterostructure.

Whether and how an electron-hole pair at the donor-acceptor interface separates from their mutual Coulombic interaction has been a long-standing question for both fundamental interests and optoelectronic applications. This question is particularly interesting but yet to be unraveled in the emerging mixed-dimensional organic/2D semiconductor excitonic heterostructures where the Coulomb interaction is poorly screened. Here, by tracking the characteristic electroabsorption (Stark effect) signal from separated charges using transient absorption spectroscopy, we directly follow the electron-hole pair separation process in a model organic/2D heterostructure, vanadium oxide phthalocyanine/monolayer MoS2. After sub-100 fs photoinduced interfacial electron transfer, we observe a barrier-less long-range electron-hole pair separation to free carriers within 1 ps by hot charge transfer exciton dissociation. Further experiment reveals the key role of the charge delocalization in organic layers sustained by the local crystallinity, while the inherent in-plane delocalization of the 2D semiconductor has a negligible contribution to charge pair separation. This study reconciles the seemingly contradicting charge transfer exciton emission and dissociation process and is important to the future development of efficient organic/2D semiconductor optoelectronic devices.

Thermally activated delayed fluorescence (TADF) organic molecules for efficient X-ray scintillation and imaging.

X-ray detection, which plays an important role in medical and industrial fields, usually relies on inorganic scintillators to convert X-rays to visible photons; although several high-quantum-yield fluorescent molecules have been tested as scintillators, they are generally less efficient. High-energy radiation can ionize molecules and create secondary electrons and ions. As a result, a high fraction of triplet states is generated, which act as scintillation loss channels. Here we found that X-ray-induced triplet excitons can be exploited for emission through very rapid, thermally activated up-conversion. We report scintillators based on three thermally activated delayed fluorescence molecules with different emission bands, which showed significantly higher efficiency than conventional anthracene-based scintillators. X-ray imaging with 16.6 line pairs mm-1 resolution was also demonstrated. These results highlight the importance of efficient and prompt harvesting of triplet excitons for efficient X-ray scintillation and radiation detection.

Accurate optical optimization of light-emitting diodes with consideration of coupling between Purcell factor and transmittance coefficient.

The calculation method for light emission efficiency splits external quantum efficiency (EQE) into internal quantum efficiency (IQE) and light extraction efficiency (LEE) independently. Consequently, the IQE connected to Purcell factor and the LEE are calculated separately. This traditional method ignores the interplays between the Purcell factor and transmittance coefficient in spectral domain, which all strongly depend on emitting directions. In this work, we propose a new figure of merit to describe the light emission process accurately by using the direction-dependent Purcell factor and transmittance coefficient simultaneously. We use a specific LED structure as a numerical example to illustrate the calculation method and optimization procedure.

Influence of Isomerism on Radioluminescence of Purely Organic Phosphorescence Scintillators.

There are few reports about purely organic phosphorescence scintillators, and the relationship between molecular structures and radioluminescence in organic scintillators is still unclear. Here, we presented isomerism strategy to study the effect of molecular structures on radioluminescence. The isomers can achieve phosphorescence efficiency of up to 22.8 % by ultraviolet irradiation. Under X-ray irradiation, both m-BA and p-BA show excellent radioluminescence, while o-BA has almost no radioluminescence. Through experimental and theoretical investigation, we found that radioluminescence was not only affected by non-radiation in emissive process, but also highly depended on the material conductivity caused by the different molecular packing. This study not only allows us to clearly understand the relationship between the molecular structures and radioluminescence, but also provides a guidance to rationally design new organic scintillators.

Integrated perovskite/bulk-heterojunction toward efficient solar cells.

We successfully demonstrated an integrated perovskite/bulk-heterojunction (BHJ) photovoltaic device for efficient light harvesting and energy conversion. Our device efficiently integrated two photovoltaic layers, namely a perovskite film and organic BHJ film, into the device. The device structure is ITO/TiO2/perovskite/BHJ/MoO3/Ag. A wide bandgap small molecule DOR3T-TBDT was used as donor in the BHJ film, and a power conversion efficiency (PCE) of 14.3% was achieved in the integrated device with a high short circuit current density (JSC) of 21.2 mA cm(-2). The higher JSC as compared to that of the traditional perovskite/HTL (hole transporting layer) device (19.3 mA cm(-2)) indicates that the BHJ film absorbs light and contributes to the current density of the device. Our result further suggests that the HTL in traditional perovskite solar cell, even with good light absorption capability, cannot contribute to the overall device photocurrent, unless this HTL becomes a BHJ layer (by adding electron transporting material like PC71BM).

Multifunctional Fullerene Derivative for Interface Engineering in Perovskite Solar Cells.

In perovskite based planar heterojunction solar cells, the interface between the TiO2 compact layer and the perovskite film is critical for high photovoltaic performance. The deep trap states on the TiO2 surface induce several challenging issues, such as charge recombination loss and poor stability etc. To solve the problems, we synthesized a triblock fullerene derivative (PCBB-2CN-2C8) via rational molecular design for interface engineering in the perovskite solar cells. Modifying the TiO2 surface with the compound significantly improves charge extraction from the perovskite layer. Together with its uplifted surface work function, open circuit voltage and fill factor are dramatically increased from 0.99 to 1.06 V, and from 72.2% to 79.1%, respectively, resulting in 20.7% improvement in power conversion efficiency for the best performing devices. Scrutinizing the electrical properties of this modified interfacial layer strongly suggests that PCBB-2CN-2C8 passivates the TiO2 surface and thus reduces charge recombination loss caused by the deep trap states of TiO2. The passivation effect is further proven by stability testing of the perovskite solar cells with shelf lifetime under ambient conditions improved by a factor of more than 4, from ∼40 h to ∼200 h, using PCBB-2CN-2C8 as the TiO2 modification layer. This work offers not only a promising material for cathode interface engineering, but also provides a viable approach to address the challenges of deep trap states on TiO2 surface in planar perovskite solar cells.

Excited State Dynamics and Transport of Self-Trapped Excitons in Bi-Doped Cs2Na0.4Ag0.6In(1-y)BiyCl6 Double Perovskites.

Lead-free double perovskites (DPs) have become notable in white light emission applications due to the self-trapped exciton (STE) formation in the excited state. However, the mechanism understanding of the excited state dynamics and transport of STE remains ambiguous. Here, we demonstrate a new STE (Bi-STE) forming in tiny Bi-doped Cs2Na0.4Ag0.6InCl6, alongside its intrinsic STE (i-STE), resulting in the DPs photoluminescence quantum yield (PLQY) increasing to as high as >90%. The i-STE exhibits faster formation (60 fs) and slower relaxation dynamics (2.8 µs) compared to the Bi-STE. Moreover, we unveil that the Bi doping can augment the i-STE diffusion properties to attain a diffusion coefficient (diffusion length) of 0.012 cm2 s-1 (1.7 µm) at room temperature, indicating their promise in photovoltaic applications. Our results shed light on significant STE dynamics and transport mechanisms in DPs, providing a new roadmap for advancing existing and crafting new DPs in light emission applications.

Enhancing Efficiency of Large-Area Wide-Bandgap Perovskite Solar Modules with Spontaneously Formed Self-Assembled Monolayer Interfaces.

Wide-bandgap (WBG) perovskites play a crucial role in perovskite-based tandem cells. Despite recent advances using self-assembled monolayers (SAMs) to facilitate efficiency breakthroughs, achieving precise control over the deposition of such ultrathin layers remains a significant challenge for large-scale fabrication of WBG perovskite and, consequently, for the tandem modules. To address these challenges, we propose a facile method that integrates MeO-2PACz and Me-4PACz in optimal proportions (Mixed SAMs) into the perovskite precursor solution, enabling the simultaneous codeposition of WBG perovskite and SAMs. This technique promotes the spontaneous formation of charge-selective contacts while reducing defect densities by coordinating phosphonic acid groups with the unbonded Pb2+ ions at the bottom interface. The resulting WBG perovskite solar cells (PSCs) demonstrated a power conversion efficiency of 19.31% for small-area devices (0.0585 cm2) and 17.63% for large-area modules (19.34 cm2), highlighting the potential of this codeposition strategy for fabricating high-performance, large-area WBG PSCs with enhanced reproducibility. These findings offer valuable insights for advancing WBG PSCs and the scalable fabrication of modules.

Quantitative Dual-Energy X-ray Imaging Based on K-Edge Absorption Difference.

Conventional flat panel X-ray imaging (FPXI) employs a single scintillator for X-ray conversion, which lacks energy spectrum information. The recent innovation of employing multilayer scintillators offers a route for multispectral X-ray imaging. However, the principles guiding optimal multilayer scintillator configuration selection and quantitative analysis models remain largely unexplored. Here, we propose to adopt the K-edge absorption coefficient as a key parameter for selecting tandem scintillator combinations and to utilize the coefficient matrix to calculate the absorption efficiency spectrum of the sample. Through a dual scintillator example comprising C4H12NMnCl3 and Cs3Cu2I5, we establish a streamlined quantitative framework for deducing X-ray spectra from scintillation spectra, with an average relative error of 6.28% between the calculated and measured sample absorption spectrum. This insight forms the foundation for our quantitative method to distinguish the material densities. Leveraging this tandem scintillator configuration, in conjunction with our analytical tools, we successfully demonstrate the inherent merits of dual-energy X-ray imaging for discerning materials with varied densities and thicknesses.

Organic and Inorganic Metal Halide Tandem Scintillator for Dual-Energy Flat-Panel X-ray Imaging.

Traditional indirect flat-panel X-ray imaging (FPXI) uses inorganic scintillators with high-Z elements, which lack spectral information about X-ray photons and reflect only integrated X-ray intensity. To address this issue, we developed a stacked scintillator structure that combines organic and inorganic materials. This structure allows X-ray energies to be distinguished in a single shot by using a color or multispectral visible camera. However, the resolution of the resulting dual-energy image is primarily limited by the top scintillator layer. We inserted a layer of anodized aluminum oxide (AAO) between the double scintillators. This layer limits the lateral propagation of scintillation light, improves imaging resolution, and acts as a filter for X-rays. Our research demonstrates the advantages of stacked organic-inorganic scintillator structures for dual-energy X-ray imaging and provides novel and practical applications for relatively low-Z organic scintillators with high internal X-ray-to-light conversion efficiency.

Bifunctional Hole-Transport Materials with Modification and Passivation Effect for High-Performance Inverted Perovskite Solar Cells.

Hole-transport materials (HTMs) play an important role in perovskite solar cells (PSCs) to enhance the power conversion efficiency (PCE). The innovation of HTMs can increase the hole extraction ability and reduce interfacial recombination. Three organic small molecule HTMs with 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) as the central unit was designed and synthesized, namely, CPDTE-MTP (with the 2-ethylhexyl substituent and diphenylamine derivative end-group), CPDT-MTP (with the hexyl substituent and diphenylamine derivative end-group), and CPDT-PMTP (with the hexyl substituent and triphenylamine derivative end-group), which can form bifunctional and robust hole transport layer (HTL) on ITO and is tolerable to subsequent solvent and thermal processing. The X-ray photoelectron spectroscopy (XPS) results proved that CPDT-based HTMs can both interact with ITO through the nitrogen element in them and the tin element in ITO and passivate the upper perovskite layer. It is worth noting that the champion efficiency of MAPbI3 PSCs based on CPDT-PMTP achieved 20.77%, with an open circuit voltage (VOC) of 1.10 V, a short-circuit current (JSC) of 23.39 mA cm-2, and a fill factor (FF) of 80.83%, as three new materials were introduced into p-i-n PSCs as dopant-free HTMs.

Near-infrared absorbing acceptor with suppressed triplet exciton generation enabling high performance tandem organic solar cells.

Reducing the energy loss of sub-cells is critical for high performance tandem organic solar cells, while it is limited by the severe non-radiative voltage loss via the formation of non-emissive triplet excitons. Herein, we develop an ultra-narrow bandgap acceptor BTPSeV-4F through replacement of terminal thiophene by selenophene in the central fused ring of BTPSV-4F, for constructing efficient tandem organic solar cells. The selenophene substitution further decrease the optical bandgap of BTPSV-4F to 1.17 eV and suppress the formation of triplet exciton in the BTPSV-4F-based devices. The organic solar cells with BTPSeV-4F as acceptor demonstrate a higher power conversion efficiency of 14.2% with a record high short-circuit current density of 30.1 mA cm-2 and low energy loss of 0.55 eV benefitted from the low non-radiative energy loss due to the suppression of triplet exciton formation. We also develop a high-performance medium bandgap acceptor O1-Br for front cells. By integrating the PM6:O1-Br based front cells with the PTB7-Th:BTPSeV-4F based rear cells, the tandem organic solar cell demonstrates a power conversion efficiency of 19%. The results indicate that the suppression of triplet excitons formation in the near-infrared-absorbing acceptor by molecular design is an effective way to improve the photovoltaic performance of the tandem organic solar cells.

Realizing nearly-zero dark current and ultrahigh signal-to-noise ratio perovskite X-ray detector and image array by dark-current-shunting strategy.

Although perovskite X-ray detectors have revealed promising properties, their dark currents are usually hundreds of times larger than the practical requirements. Here, we report a detector architecture with a unique shunting electrode working as a blanking unit to suppress dark current, and it theoretically can be reduced to zero. We experimentally fabricate the dark-current-shunting X-ray detector, which exhibits a record-low dark current of 51.1 fA at 5 V mm-1, a detection limit of 7.84 nGyair s-1, and a sensitivity of 1.3 × 104 µC Gyair-1 cm-2. The signal-to-noise ratio of our polycrystalline perovskite-based detector is even outperforming many previously reported state-of-the-art single crystal-based X-ray detectors by serval orders of magnitude. Finally, the proof-of-concept X-ray imaging of a 64 × 64 pixels dark-current-shunting detector array is successfully demonstrated. This work provides a device strategy to fundamentally reduce dark current and enhance the signal-to-noise ratio of X-ray detectors and photodetectors in general.

Enabling low-drift flexible perovskite photodetectors by electrical modulation for wearable health monitoring and weak light imaging.

Metal halide perovskites are promising for next-generation flexible photodetectors owing to their low-temperature solution processability, mechanical flexibility, and excellent photoelectric properties. However, the defects and notorious ion migration in polycrystalline metal halide perovskites often lead to high and unstable dark current, thus deteriorating their detection limit and long-term operations. Here, we propose an electrical field modulation strategy to significantly reduce the dark current of metal halide perovskites-based flexible photodetector more than 1000 times (from ~5 nA to ~5 pA). Meanwhile, ion migration in metal halide perovskites is effectively suppressed, and the metal halide perovskites-based flexible photodetector shows a long-term continuous operational stability (~8000 s) with low signal drift (~4.2 × 10-4 pA per second) and ultralow dark current drift (~1.3 × 10-5 pA per second). Benefitting from the electrical modulation strategy, a high signal-to-noise ratio wearable photoplethysmography sensor and an active-matrix photodetector array for weak light imaging are successfully demonstrated. This work offers a universal strategy to improve the performance of metal halide perovskites for wearable flexible photodetector and image sensor applications.

Bright Transparent Scintillators with High Fraction BaCl2 : Eu2+ Nanocrystals Precipitation: An Ionic-Covalent Hybrid Network Strategy toward Superior X-Ray Imaging Glass-Ceramics.

Metal halide crystals are bright but hygroscopic scintillator materials that are widely used in X-ray imaging and detectors. Precipitating them in situ in glass to form glass ceramics (GCs) scintillator offers an efficient avenue for large-scale preparation, high spatial resolution, and excellent stability. However, precipitating a high fraction of metal halide nanocrystals in glass to maintain high light yield remains a challenge. Herein, an ionic-covalent hybrid network strategy for constructing GCs scintillator with high crystallinity (up to ≈37%) of BaCl2 : Eu2+ nanocrystals is presented. Experimental data and simulations of glass structure reveal that the Ba2+ -Cl- clustering promotes the high crystallization of BaCl2 nanocrystals. The ultralow phonon energy (≈200 cm-1 ) of BaCl2 nanocrystals and good Eu reduction effect enable high photoluminescence inter quantum efficiency (≈80.41%) in GC. GCs with varied crystallinity of BaCl2 : Eu2+ nanocrystals demonstrate efficient radioluminescence and tunable scintillator performance. They either outperform Bi4 Ge3 O14 single crystal by over 132% steady-state light yield or provide impressive X-ray imaging resolutions of 20 lp mm-1 . These findings provide a new design strategy for developing bright transparent GCs scintillators with a high fraction of metal halide nanocrystals for X-ray high-resolution imaging applications.

In Situ Fabrication of Cs3Cu2I5: Tl Nanocrystal Films for High-Resolution and Ultrastable X-ray Imaging.

Cs3Cu2I5 nanocrystals (NCs) are considered to be promising materials due to their high photoluminescence efficiency and X-ray hardness. However, the present strategy depends on tedious fabrication with excessive chemical waste. The evasive iodide ion dissociation, inadaptable ligand system, low stability, and relatively low light yield severely impede their applications. Herein, we develop an in situ fabrication strategy for a flexible and large-area Tl-doped Cs3Cu2I5 NC-polymer composite scintillation film with a high light yield (∼48800 photons/MeV) and improved stability. Tween 80 and phosphinic acid successfully inhibit the oxidation of iodide ions, and the films can be stored for at least six months. As a result, a high spatial resolution of 16.3 lp mm-1 and a low detection limit of 305 nGyair s-1 were achieved. A radioluminescence intensity of >80% was maintained after a total irradiation dose of 604.8 Gy. These results indicate the promising application of these copper halide NCs in low-cost, flexible, and high-performance medical imaging.

Molecular Triplet Sensitization of Monolayer Semiconductors in 2D Organic/Inorganic Hybrid Heterostructures.

Hybrid heterostructures (HSs) comprising organic and two-dimensional (2D) monolayer semiconductors hold great promise for optoelectronic applications. So far, research efforts on organic/2D HSs have exclusively focused on coupling directly photoexcited singlets to monolayer semiconductors. It remains unexplored whether and how the optically dark triplets in organic semiconductors with intriguing properties (e.g., long lifetime) can be implemented for modulating light-matter interactions of hybrid HSs. Herein, we investigate the triplet sensitization of monolayer semiconductors by time-resolved spectroscopic studies on Pd-octaethylporphyrin (PdOEP)/WSe2 and PdOEP/WS2 HSs with type I and type II band alignment, respectively. We show that PdOEP triplets formed in ∼5 ps from intersystem crossing can transfer energy or charge to WSe2 or WS2 monolayers, respectively, leading to a significant photoluminescence enhancement (180%) in WSe2 or long-lived charge separation (>2 ns) in WS2. The triplet transfer occurs in ∼100 ns, which is more than 3 orders of magnitude slower than singlet and can be attributed to its tightly localized nature. Further study of thickness dependence reveals the dictating role of triplet diffusion for triplet sensitization in organic/2D HSs. This study shows the great promise of much less explored molecular triplets on sensitizing 2D monolayer semiconductors and provides the guidance to achieve long-range light harvesting and energy migration in organic/2D HSs for enhanced optoelectronic applications.

Top-Emitting Microcavity Light-Emitting Diodes Based on All-Thermally Evaporated Lead-Free Copper Halide Self-Trapped-Exciton Emitters.

Lead-free metal halide light-emitting diodes (LEDs) based on cesium copper halide (CsCu2I3) self-trapped-exciton (STE) emissions show great potential in lighting and color display applications, especially because of their nontoxicity and earth abundance. However, so far, the efficiency and color purity of CsCu2I3-based LEDs remain low. Here we demonstrate the emission of a CsCu2I3 emitter can be enhanced and narrowed in a top-emitting microcavity device. Consequently, the CsCu2I3-based LED device with the assistance of a top-emitting microcavity has significantly narrowed and enhanced the emission spectrum with a full width at half-maximum of 59 nm and a maximum forward brightness of 14767 cd m-2. To the best of our knowledge, this work achieves the narrowest CsCu2I3 LED spectra and demonstrates the potential of employing the microcavity effect to increase the efficiency and color purity of STE-based light-emitting devices.