Exciton Utilization Research Articles

Pressure treatment enables white-light emission in Zn-IPA MOF via asymmetrical metal-ligand chelate coordination

Metal-organic frameworks that feature hybrid fluorescence and phosphorescence offer unique advantages in white-emitting communities based on their multiple emission centers and high exciton utilization. However, it poses a substantial challenge to realize superior white-light emission in single-component metal-organic frameworks without encapsulating varying chromophores or integrating multiple phosphor subunits. Here, we achieve a high-performance white-light emission with photoluminescence quantum yield of 81.3% via boosting triplet excitons distribution through pressure treatment in single-component Zn-IPA metal-organic frameworks. A novel metal-ligand asymmetrical chelate coordination is successfully integrated into the Zn-IPA after a high-pressure treatment over ~20.0 GPa. This modification unexpectedly endows the targeted sample with a new emergent electronic state to narrow the singlet-triplet energy gap, which effectively accelerates the spin-flipping process for boosted triplet excitons population. Time delay phosphor-converted light-emitting diodes are fabricated with long emission time up to ~7 s after switching off, providing significant advancements for white-light and time-delay lighting applications.

Hot-Exciton Mechanism with Diphenyl Anthracene Core Unit: A Detailed Theoretical Study.

Hot-exciton materials, among all kinds of organic light-emitting diode (OLED) emitters, have better exciton utilization efficiency and efficiency roll-off, making them possible for their practical applications. We studied the photophysical properties of a few hot-exciton molecules based on an anthracene core unit to efficiently harvest all triplet excitons to the lowest excited singlet state. The conversion of triplet exciton to singlet exciton utilizing hRISC can be enhanced due to the 1ππ*←3nπ* transition channel. The energy gap between the excited singlet and triplet excited states, spin-orbit coupling interaction, nature of excited states, rate constants of reverse intersystem crossing, and radiative process were calculated and analyzed to gain more insights into the hot-exciton mechanism. Additionally, we extended our study by substituting groups in the diphenyl anthracene core unit to find improved performance. We found that the combinations of triphenylamine (TPA) or 9-phenyl-9H-carbazole (CZP) acting as the electron donor, benzophenone as the acceptor, and the anthracene as the π-bridge is the most efficient hot-exciton emitter for improved OLED lighting application technology.

Versatile Thermally Activated Delayed Fluorescence Material Enabling High Efficiencies in both Photodynamic Therapy and Deep-Red/NIR Electroluminescence.

Thermally activated delayed fluorescence (TADF) materials have received increasing attention from organic electronics to other related fields, such as bioapplications and photocatalysts. However, it remains a challenging task for TADF emitters to showcase the versatility concurrent with high performance in multiple applications. Herein, we first present such a proof-of-concept TADF material, namely, QCN-SAC, through strategically manipulating exciton dynamics. On the one hand, QCN-SAC displays obvious aggregate-induced deep-red/near-infrared emission with a high radiative rate beyond 107 s-1, thereby demonstrating nearly 100% exciton utilization under oxygen-free conditions. In a QCN-SAC-based nondoped organic light-emitting diode (OLED), a superb external quantum efficiency of 16.4% can be reached with a peak at 708 nm. On the other hand, QCN-SAC also exhibits a high intersystem crossing rate over 108 s-1 without leveraging the heavy-atom effect, which makes QCN-SAC-based nanoparticles perform well in boosting reactive oxygen species generation for imaging-guided photodynamic therapy (PDT). This work presents a fundamental principle for designing high-performance all-in-one TADF molecules for OLED and PDT applications. This discovery holds promise for advancing the development of versatile TADF materials with a range of uses in the near future.

Regulating Spatial Configuration in Donor‐π‐Acceptor for through‐Space Exciton Transfer: Concentration‐Independent Emitter for OLEDs

AbstractThermally activated delayed fluorescence (TADF) emitters have garnered much attention due to 100% exciton utilization and toxic metal‐free design but often experience concentration‐quenching, requiring dispersion into the host matrix. Developing emitters that maintain consistent performance and emission wavelength irrespective of the concentration remains a significant challenge. Herein, two TADF emitters (2BPy‐pTC and 2BPy‐oTC) are designed and synthesized. The nature and energetics of the lowest excited singlet (S1) and triplet (T1) along with the extent of through‐bond exciton transfer (TBET) and through‐space exciton transfer (TSET) are unveiled using reliable quantum‐chemical calculations. While 2BPy‐pTC exhibits pre‐dominantly TBET, a greater extent of TSET is found in 2BPy‐oTC. Both emitters show a low singlet‐triplet energy gap (ΔEST), 0.21 eV for 2BPy‐pTC and 0.02 eV for 2BPy‐oTC. For 2BPy‐pTC, increasing the emitter concentration from 5 to 100 wt.% causes a bathochromic shift in the electroluminescence (EL) peak (467 to 495 nm) and a drop in maximum external quantum efficiency (EQEmax) from 12.0% to 5.5%. In contrast, 2BPy‐oTC maintains EL maxima of 500 nm and consistent EQEmax (24.0% – 27.2%) while increasing emitter concentration, acting as a universal emitter for both doped and non‐doped OLEDs and eliminating the need for tedious co‐deposition.

Efficiency Boost in Through Space Charge Transfer Emitters: Insights from Spiro Lateral Rocking Confinement.

Intramolecular through-space charge-transfer (TSCT) excited states have emerged as promising candidates for thermally activated delayed fluorescence (TADF) emitters. This study addresses the challenges in tuning excited state dynamics through conformational engineering, which significantly impacts exciton utilization. An effective strategy is presented to enhance the performance of TSCT-TADF molecules by restricting the lateral rocking of the spiro unit via immobilizing groups, which indirectly adjusts the conformations of the donor and acceptor subunits. This approach is successfully illustrated with two TSCT-TADF emitters, 8PhDM-B and 8PyDM-B, featuring sterical aryl phenyl and pyridine substitutions at the C8 site of a rigid spiro-fluorene bridge. Organic light-emitting diodes (OLEDs) utilizing these emitters demonstrated impressive maximum external quantum efficiencies of 33.1% and 31.0%, respectively. The findings underscore the importance of the rocking confined strategy in refining excited state dynamics, thereby providing valuable insights for the design of highly efficient OLED emitters.

A Novel Matrix-Free Hyperfluorescent System Based on Anti-Quenching TADF Host for High Color Purity MR-TADF Emitters.

Organic light-emitting diodes (OLEDs) based on hyperfluorescent system have attracted widespread attention due to their ability to simultaneously achieve improvements in efficiency, lifetime, and color purity by combining the advantages of high exciton utilization sensitizers and high-color purity emitters. Traditional hyperfluorescent systems typically involve three or four components and are severely sensitive to the doping concentration (≈0.5 wt%) of a terminal emitter, which inevitably causes high costs and difficulties in reproducibility. Here, a novel design concept for a matrix-free hyperfluorescent (MFHF) system that employs a combination of an anti-quenching TADF host and a high color purity MR-TADF emitter is proposed. This strategy allows traditional concentration-sensitive MR-TADF emitters to significantly improve exciton utilization and reduce exciton lifetime at high doping levels, without the need for complex molecular modifications. The OLEDs with binary emissive layer achieve pure-green emission, a maximum external quantum efficiency of over 30%, and a high maximum power efficiency of 145lmW-1. The approach offers a straightforward and universal method to achieve anti-quenching matrix-free hyperfluorescent OLEDs with high color purity, making them promising for commercial applications in low-cost ultra-high-definition (UHD) displays.

Ultrafast Spectroscopic Investigation of the Aggregation Induced TADF from High-Level Reversed Intersystem Crossing.

The thermally activated delayed fluorescence (TADF) originating from high-level intersystem crossing (hRISC) presents great potential in realizing a more full utilization of triplet excitons. In this study, DPA-FBP and TPA-FBP were doped in a PMMA film with different weight fractions to study the effect of aggregation on the luminescence properties. As a result, the TADF feature from hRISC was only found in the 50 wt % doped film, whereas the 1 wt % doped film only shows prompt fluorescence. The fs-TA spectroscopy results reveal that the 50 wt % film will generate charge transfer species to lower the energy gap, so that the high-lying triplet exciton can transition back to the singlet state, whereas that of the 1 wt % film will quickly transition to the lowest triplet state due to the unfavorable energy splitting. This study provides a new insight into aggregation effects on the excited-state properties of hot exciton materials and the solid-state photodynamic.

Molecular Engineering for High-Performance X-ray Scintillators.

X-ray scintillators, materials that convert high-energy radiation into detectable light in the ultraviolet to visible spectrum, are widely used in industrial and medical applications. Organic and organic-inorganic hybrid systems have emerged as promising alternatives for X-ray detection and imaging due to their mechanical flexibility, lightweight, tunable excited states, and solution processability for large-scale fabrication. However, these systems often suffer from weak X-ray absorption and insufficient exciton utilization, which seriously affects their scintillation performance, limiting their potential for broader application and commercialization. This review highlights recent advances in molecular engineering for developing high-performance X-ray scintillators. It focuses on molecular design principles, such as the heavy atom effect, donor-acceptor/host-guest strategies, hydrogen/halogen bonding, molecular sensitization, and crystal packing, for enhancing scintillation performance. By leveraging these approaches, researchers have made significant strides in improving X-ray scintillation efficiency and advancing the potential of these materials for commercial applications.

Short-Range Coulomb Interaction Is a Key to Switch the Utilization of Higher Triplet Excitons in Multiresonance Thermally Activated Delayed Fluorescence Doped Film.

Multiresonance thermally activated delayed fluorescence (MR-TADF) materials have attracted widespread attention due to ultrahigh definition display standards. However, many MR-TADF materials lack TADF properties in both the solution and solid states. Interestingly, the TADF characteristics appear once these MR-TADF compounds are doped in a suitable host film, but the precise mechanism involved in the host-guest interaction remains uncertain. Herein, we systematically investigated the role of host-guest interactions employing doped films (DABNA-1@mCBP and DABNA-1@DPEPO) with opposite phenomena. The results indicate that mCBP with a V-shape and enhanced rigidity could facilitate the formation of an energy spacing layer by employing short-range Coulomb energy through the MR luminescent core, which could offset the sensitivity of the stacking distance, enhancing the coupling between T1 and T2, and thus switch the reverse internal conversion and the higher T2 reverse intersystem crossing process. This work is a further development of luminescence mechanisms and an update of the host-guest interaction criteria for the targeted design of doped films.

Pure room temperature phosphorescence emission in nondoped OLEDs: adjustable oxidation states and excited-state modulation.

Purely organic room temperature phosphorescence (RTP) materials are a new kind of triplet emitter, which can harvest both singlet and triplet excitons in theory, thus showing great application potential for organic light-emitting diodes (OLEDs). However, nondoped OLEDs based on RTP emitters have been rarely explored owing to challenges in realizing efficient phosphorescence in single-component systems. Herein, three donor-acceptor-type luminogens were designed and synthesized in which phenothiazine, with different oxidation degrees, acted as the electron donor and acetophenone as the acceptor. The adjustable oxidation states of phenothiazine enabled the modulation of excited states, facilitating the transition from dual RTP and thermally activated delayed fluorescence emissions to pure RTP. A nondoped OLED device was then fabricated based on the pure RTP emitter, achieving a high exciton utilization efficiency of 86%, clearly demonstrating the enhancement of electroluminescence performance through RTP properties.

Blue-emission crystalline OLED doped with DMAC-DPS TADF material

Doping thermally activated delayed fluorescence (TADF) materials with high exciton utilization into crystalline hosts with high carrier mobility is an effective approach for developing novel OLEDs. This approach harnesses the strengths of both materials to realize high-performance blue light-emitting crystalline organic light-emitting diodes (C-OLEDs). Nevertheless, the high triplet energy levels of blue emitting TADF materials may facilitate the outflow of triplet excitons through Dexter energy transfer to the lower energy levels within the crystalline host, thus leading to efficiency losses in the device. In this study, we present a pioneering strategy designed to improve the exciton utilization efficiency of TADF materials in C-OLED by leveraging the up-conversion capability of TTA materials to reclaim triplet excitons. With a well-designed energy level structure, this device achieves a maximum EQE of 5.6 % and a low turn-on voltage of 2.7 V. The benefits of the crystalline host allowed for fast turn-on, and a rapid increase in brightness and current density, leading to significantly improved blue photon output and a lower series resistance Joule heat loss ratio. This work introduces a novel approach to employ TADF materials in crystalline hosts and manage excitons within the emissive layer of devices, aiming to develop high-performance C-OLEDs.

An efficient thermally activated delayed fluorophore featuring an oxygen-locked azaryl ketone acceptor

Thermally activated delayed fluorescence (TADF) dyes are promising for applications like bioimaging, sensing, and optoelectronic devices due to their efficient exciton utilization without noble metals, making them ideal for organic light-emitting diodes (OLEDs). In this contribution, we introduce a new TADF emitter, 3-(9,9-dimethylacridin-10(9H)-yl)-12H-chromeno[2,3-b]quinolin-12-one (CQLO-DMAC), which incorporates an intramolecular oxygen-locked azaryl ketone acceptor, CQLO. This design enhances molecular rigidity and electron-accepting strength. The CQLO-DMAC compound, featuring a bulky donor, shows significant intramolecular charge transfer and TADF emission. Comprehensive analyses, including spectroscopic studies and theoretical calculations, reveal high luminescence efficiency and reduced non-radiative losses. Utilizing CQLO-DMAC in OLEDs, we achieved a green-yellow emission peak at 548 nm and a maximum external quantum efficiency of 17.4 %. The findings highlight the potential of CQLQ as a highly effective acceptor in designing of TADF electroluminescent dyes.

Efficient Triplet Harvesting via Hot Exciton Utilization in Solution Processed OLEDs Employing Tetraphenyl Buta‐1,3‐Diene Based AIE Emitters

AbstractHigh photoluminescence quantum yield (PLQY) especially in solid‐state together with harvesting radiative triplet excitons are essential to achieve efficient organic light‐emitting diodes (OLEDs). Herein, the aggregation induced emission (AIE) active tetraphenyl buta‐1,3‐diene (TPB) moiety has been employed and tactfully modified to obtain orthogonally oriented donor‐acceptor (D‐A‐π‐A‐D) type derivatives (namely, TPB‐CHO‐TPA and TPB‐CN‐TPA) which possess additionally the hybridized local and charge transfer (HLCT) type excited‐state. Moreover, computational studies have revealed the possibility of triplet harvesting through hot exciton mechanism in these designed emitters. These key features along with excellent solubility in most of the organic solvents have encouraged to utilize these as light emitting materials for solution processed non‐doped and doped OLED devices. The optimal OLED device using TPB‐CHO‐TPA exhibits yellow light emission (ELmax = 572 nm and CIEx,y = 0.48, 0.51) having maximum external quantum efficiency (EQEmax) of 7.6% with power and current efficiency of 6.1 lm W−1 and 8.9 cd A−1 where the calculated exciton utilization efficiency (EUE) approaches to 97%, indicating efficient triplet harvesting in electroluminescence process. This work signifies a novel design strategy for AIE‐based HLCT type emitters having efficient hot exciton utilization which can pave the way for future development of TPB based highly efficient OLED devices.

Achieving Efficient X-ray Scintillation of Purely Organic Phosphorescent Materials by Chromophore Confinement.

Scintillators have attracted significant attention due to their wide-ranging applications in both industrial and medical fields. However, one of the ongoing challenges is the efficient utilization of triplet excitons to achieve high radioluminescence efficiency. Here, a series of purely organic phosphors is presented for X-ray scintillation, employing a combined rigid and flexible host-guest doping strategy. The doped crystals exhibit a remarkable maximum phosphorescence efficiency of 99.4% under UV excitation. Furthermore, upon X-ray irradiation, the radioluminescence intensities of the doped phosphors are markedly higher compared to their single-component crystal counterparts. Through systematic investigations, it is demonstrated the crucial role of confining isolated chromophores in enhancing scintillation efficiency. Additionally, a transparent scintillator screen fabricated with the doped phosphor exhibits excellent X-ray imaging performance, achieving a high spatial resolution of 18.0 lpmm-1. This work not only offers valuable insights into suppressing non-radiative transitions of triplet excitons during scintillation but also opens a new avenue for designing highly efficient purely organic phosphorescent scintillators.

Dendritic Oligomers‐Based Exciplex Emitters Realizing Solution‐Processed Organic Light‐Emitting Diodes with Nearly 30% External Quantum Efficiency

AbstractDue to the feature of the strong intermolecular interactions causing aggregation‐caused excitons quenching (ACQ) of solution process, realizing high‐performance solution‐processed organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) emitters remains a formidable challenge nowadays. To address this issue, herein, a novel strategy is proposed to construct solution‐processable ternary exciplex emitters by utilizing the dendritic oligomer as the substrate, simultaneously realizing excellent solution‐process adaptability, good dispersibility to restrain harmful ACQ, and improved exciton utilization with multiple reverse intersystem crossing channels. Accordingly, dendritic oligomer‐based exciplex systems are constructed by combining small‐molecule donor and acceptor components with the multi‐carbazole‐substituted tetraphenylsilane‐core analog as substrate. And their film morphologies, photoluminescence quantum yields (ΦPLs), and non‐radiative decay rates of triplet excitons (knrTs) are significantly improved. Among them, DMAC‐DPS:PO‐T2T:SimCP3 exhibits the highest ΦPL of 97.5% and the lowest knrT of 1.0 × 103 s−1, and realizes the best maximum external quantum efficiency of 29.7% in solution‐processed OLED, which is comparable with the highest electroluminescence efficiencies of all solution‐processable emitters. Therefore, this work will provide a prospective pathway to develop efficient solution‐processable exciplex emitters and promote the progress of solution‐processed OLEDs.

Insights into the Structural Modification of Selenium-Doped Derivatives with Narrowband Emissions: A Theory Study.

The research on boron/nitrogen (B/N)-based multiresonance thermally activated delayed fluorescence (MR-TADF) emitters has been a prominent topic due to their narrowband emission and high luminous efficiency. However, devices derived from the common types of narrowband TADF materials often experience an efficiency roll-off, which could be ascribed to their relatively slow triplet-singlet exciton interconversion. Since inserting the heavy Se atom into the B/N scheme has been a proven strategy to address the abovementioned issues, herein, extensive density functional theory (DFT) and time-dependent DFT (TD-DFT) simulations have been employed to explore the effects of the structural modification on a series of structurally modified selenium-doped derivatives. Furthermore, the two-layered ONIOM (QM/MM) model has been employed to study the pressure effects on the crystal structure and photophysical properties of the pristine CzBSe. The theoretical results found that the introduced tert-butyl units in Cz-BSeN could result in a shorter charge transfer distance and smaller reorganization energy than the parent CzBSe. In contrast to directly incorporating the o-carborane (Cb) unit to CzBSe, incorporating the bridged phenyl units is important in order to achieve narrowband emissions and high luminous efficiency. The lowest three triplet excited states of CzBSe, Cz-BSeN and PhCb-BSeN all contribute to their triplet-singlet exciton conversions, resulting in a high utilization of triplet excitons. The pressure has an evident influence on the photophysical properties of the aggregated CzBSe and is favored for obtaining narrowband emissions. Our work is promised to provide a feasible strategy for designing selenium-doped derivatives with narrowband emissions and rapid triplet-singlet exciton interconversions.

Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi-Mode Radioluminescence for Efficient X-Ray Imaging.

The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin-forbidden feature of X-ray-induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin-forbidden triplet excitons to spin-allowed singlet excitons, which enables singlet exciton-dominated multi-mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110nGys-1; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm-1. This study advances the fundamental understanding of exciton dynamics under X-ray excitation, significantly broadening the practical use of phosphorescent materials for safety-critical industries and medical diagnostics.

Efficient metal free organic radical scintillators

The development of high-performance metal-free organic X-ray scintillators (OXSTs), characterized by a synergistic combination of robust X-ray absorption, efficient exciton utilization, and short luminescence lifetimes, poses a considerable challenge. Here we present an effective strategy for achieving augmented X-ray scintillation through the utilization of halogenated open-shell organic radical scintillators. Our experimental results demonstrate that the synthesized scintillators exhibit strong X-ray absorption derived from halogen atoms, display efficacious X-ray stability, and theoretically achieve 100% exciton utilization efficiency with a short lifetime (∼18 ns) due to spin-allowed doublet transitions. The superior X-ray scintillation performance exhibited by these organic radicals is not only exploitable in X-ray radiography for contrast imaging of various objects but also applicable in a medical high-resolution micro-computer-tomography system for the clear visualization of fibrous veins within a bamboo stick. Our study substantiates the promise of organic radicals as prospective candidates for OXSTs, offering valuable insights and a roadmap for the development of advanced organic radical scintillators geared towards achieving high-quality X-ray radiography.

High Efficiency Non‐Doped Organic Light Emitting Diodes Based on Pure Organic Room Temperature Phosphorescence by High‐Lying Singlet Exciton Fission

AbstractHeavy‐metal‐free pure organic room temperature phosphorescence (ORTP) holds great potential in the field of organic optoelectronic devices owing to low economic cost, simple preparation techniques, and high exciton utilization. However, it is still filled with challenges in realizing high efficiency organic light‐emitting diodes (OLEDs) and exploring the internal physical mechanism based on these ORTP molecules. Here, a high‐performance OLED induced by an unexpected interfacial spin‐mixing process between the ORTP molecule and interlayers is demonstrated, and the high efficiency electroluminescence (EL) mechanism is studied through magneto–electroluminescence (MEL) and magneto–photoluminescence (MPL) measurements. The steady‐state and transient PL properties imply that the interfacial effect is related to a high‐lying singlet fission (HLSF) process in the ORTP molecule itself. Further, the HLSF process and the corresponding energy level position are confirmed by the incident wavelength‐ and temperature‐dependent PL spectra and the magnetic‐field‐dependent transient PL. Finally, by optimizing the interfacial material adjacent to the emissive layer to utilize this interfacial spin mixing effect, a high‐efficiency non‐doped ORTP‐OLED with external quantum efficiency of 16% and CIE coordinates of (0.27, 0.49) is developed. The proposed mechanism during the EL process will give insight to produce more efficient OLEDs based on ORTP materials in the future.

Hybrid Local and Charge-Transfer Material with Ultralong Room Temperature Phosphorescence for Efficient Organic Afterglow Light-Emitting Diodes.

Organic ultralong room temperature phosphorescence (OURTP) materials capable of combining various emission behaviors for diversified optoelectronic properties and applications have recently gained a vigorous development, but it remains a forbidden challenge in designing OURTP molecules with hybrid local and charge-transfer (HLCT) feature, possibly due to the elevated difficulties in simultaneously meeting the stringent requirements of both HLCT and OURTP emitters. Here, through introducing multiple heteroatoms into one-dimensional fused ring of coumarin with moderate charge transfer perturbation in donor-π-acceptor architecture, we demonstrate a HLCT-featured OURTP molecule showing both promoted fluorescence with a quantum yield of 77 % in solution and long-lived OURTP with a lifetime of 251 ms in conventional host material used in electroluminescent device. Thus, efficient OURTP organic light-emitting diodes (OLEDs) were fabricated, exhibiting bright electroluminescence with an exciton utilization efficiency of 85 % and yellow OURTP lasting over 2 s for afterglow. Impressively, the HLCT OURTP-OLEDs can be further optimized to reach an unprecedented total external quantum efficiency (EQE) of ~12 % and OURTP EQE up to 3.11 %, representing the highest performance among the reported OURTP-OLEDs. These impressive results highlight the significance to fuse HLCT and OURTP together in enriching OURTP materials and improving the afterglow OLED performances.