Organic Light-emitting Diodes Research Articles

Towards the accurate simulation of multi-resonance emitters using mixed-reference spin-flip time-dependent density functional theory

Multi-resonant Thermally Activated Delayed Fluorescent (MR-TADF) materials have received significant research interest owing to their potential use as emitters in high-performance Organic Light Emitting Diodes (OLEDs). Despite their advantages, including narrow emission spectra leading to high colour purity, several challenges remain in optimising the performance of these materials. One key issue is the typically long delayed fluorescence lifetime which arises from a large gap and weak coupling between the lowest lying singlet and triplet states. To develop high-performing materials, in silico design is an important step and consequently it is crucial to develop and deploy computational methods that accurately model their excited state properties. Previous studies have highlighted the importance of double excitations, which are not accounted for within the framework of Linear Response Time-Dependent Density Functional Theory (LR-TDDFT), contributing to the poor performance of this method for these materials. Consequently, in this work, we employ Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) to calculate the properties of MR-TADF materials. Our findings indicate that this approach accurately predicts the excited state properties including the crucial ΔEST, the energy difference between the lowest singlet (S1) and triplet (T1) excited states. We further use this method to explore the excited state properties of systems designed to enhance the coupling between singlet and triplet states by increasing the density of states and enhancing spin–orbit coupling through metal perturbation. The results in this work sets the foundation for computationally efficient in silico development high-performing MR-TADF materials within the framework of MRSF-TDDFT.

Delocalizing electron distribution in thermally activated delayed fluorophors for high-efficiency and long-lifetime blue electroluminescence.

Blue thermally activated delayed fluorescent emitters are promising for the next generation of organic light-emitting diodes, yet their performance still cannot meet the requirements for commercialization. Here we establish a design rule for highly efficient and stable thermally activated delayed fluorescent emitters by introducing an auxiliary acceptor that could delocalize electron distributions, enhancing molecular stability in both the negative polaron and triplet excited state, while also accelerating triplet-to-singlet up-conversion and singlet radiative processes simultaneously. Proof-of-concept thermally activated delayed fluorescent compounds, based on a multi-carbazole-benzonitrile structure, exhibit near-unity photoluminescent quantum yields, short-lived delays and improved photoluminescent and electroluminescent stabilities. A deep-blue organic light-emitting diode using one of these molecules as a sensitizer for a multi-resonance emitter achieves a remarkable time to 95% of initial luminance of 221 h at an initial luminance of 1,000 cd m-2, a maximum external quantum efficiency of 30.8% and Commission Internationale de l'Eclairage coordinates of (0.14, 0.17).

Spin-Valley-Locked Electroluminescence for High-Performance Circularly Polarized Organic Light-Emitting Diodes.

Circularly polarized (CP) organic light-emitting diodes (OLEDs) have attracted attention in potential applications, including novel display and photonic technologies. However, conventional approaches cannot meet the requirements of device performance, such as high dissymmetry factor, high directionality, narrowband emission, simplified device structure, and low costs. Here, we demonstrate spin-valley-locked CP-OLEDs without chiral emitters but based on photonic spin-orbit coupling, where photons with opposite CP characteristics are emitted from different optical valleys. These spin-valley-locked OLEDs exhibit a narrowband emission of 16 nm, a high external quantum efficiency of 3.65%, a maximum luminance of near 98,000 cd/m2, and a gEL of up to 1.80, which are among the best performances of active single-crystal CP-OLEDs, achieved with a simple device structure. This strategy opens an avenue for practical applications toward three-dimensional displays and on-chip CP-OLEDs.

One new [Ir(C^N)2(N^O)] Ir(III)-complex with efficient deep-red light: Forwards to high-performance all-solution-processed polymer light-emitting diodes

Despite continuous progress to Ir(III)-complex-based deep-red OLEDs/PLEDs, the realization of their all-solution-processed ones with satisfactory performance is highly challenging. In this work, through the doping of a new Ir(III)-complex ([Ir(dpqx)2(pbi)] (2) with efficient dee-red light (λem = 661 nm, ΦPL = 0.48), two kinds of high-performance all-solution-processed deep-red PLEDs-A/B, differentially configurated with Ba/Al and Poly(vinyl-PBD)-assisted LiF/Al as the composite cathodes, were realized, respectively. Meanwhile, their electroluminescent result shows that owing to an optimized carries’ injection/transport, the deep-red PLED-B with Poly(vinyl-PBD)-assisted LiF/Al has the better performance (ηEQEMax = 3.44 %) than that (ηEQEMax = 2.76 %) of the PLED-A. Therefore, the PLED-B Poly(vinyl-PBD)-assisted LiF/Al maybe paves one way to Ir(III)-complexes for deep-red all-solution-processed PLEDs.

Singlet-Triplet Inversion in Triangular Boron Carbon Nitrides.

The discovery of singlet-triplet (ST) inversion in some π-conjugated triangle-shaped boron carbon nitrides is a remarkable breakthrough that defies Hund's first rule. Deeply rooted in strong electron-electron interactions, ST inversion has garnered significant interest due to its potential to revolutionize triplet harvesting in organic LEDs. Using the well-established Pariser-Parr-Pople model for correlated electrons in π-conjugated systems, we employ a combination of CISDT and restricted active space configuration interaction calculations to investigate the photophysics of several triangular boron carbon nitrides. Our findings reveal that ST inversion in these systems is primarily driven by a network of alternating electron-donor and electron-acceptor groups in the molecular rim, rather than by the triangular molecular structure itself.

Superbly Efficient and Stable Ultrapure Blue Phosphorescent Organic Light-Emitting Diodes with Tetradentate Pt(II) Complex with Vibration Suppression Effect.

Blue phosphorescent organic light-emitting diodes (PHOLEDs) are on the brink of commercialization for decades. However, the external quantum efficiency (EQE) and operational lifetime of PHOLEDs are not yet reached industrial standards. Here, a novel tetradentate Pt(II) emitter with a spirofluorene onto the carbazole unit that minimizes the vibration modes, corresponding to the structural relaxation during the de-excitation, called the vibration suppression effect is reported. This modification reduces the intensity of the second peak in the spectrum and Shockley-Read-Hall recombination by blocking direct hole injection into the emitter while enhancing Förster resonance energy transfer, resulting in 451h of LT50 (the time until a 50% decrease in initial luminance at 1000cdm-2) and 25.1% of the maximum EQE (EQEmax). Thanks to the vibration suppression effect, an extremely narrow full width at half a maximum of 22nm is obtained. In phosphor-sensitized thermally activated delayed fluorescent OLED, ultra-pure blue emission with Commission internationale de l'Eclairage (CIE) coordinates of (0.136, 0.096) is obtained with 28.1% of EQEmax. Furthermore, 50.3% of the EQEmax and 589h of LT70 are simultaneously recorded with the two-stack tandem PHOLED, which is the highest EQEmax among 2-tandem and bottom-emission PHOLEDs with CIEy<0.15.

Efficient Folded Molecules with Intramolecular Through-Space Charge Transfer for Near-Ultraviolet Organic Light-Emitting Diodes

Efficient Folded Molecules with Intramolecular Through-Space Charge Transfer for Near-Ultraviolet Organic Light-Emitting Diodes

Theoretical insight on electronic and optical properties of some phosphorescent iridium(III) complexes for organic light-emitting diode devices

Organic light-emitting diode (OLED) structures have been extensively investigated because of their potential applications in various fields. It is known that organic or metal-mediated organic compounds are used in the layers of OLEDs. Within OLED materials, iridium(III) compounds have attract much attention owing to their many advantages. Therefore, we predicted the OLED behaviors of twenty-five phosphorescent iridium(III) complexes using theoretical chemical methods. All theoretical calculations were performed with the B3LYP hybrid functional using Gaussian 16 and Amsterdam Modeling Suite 2023 programs. While the 6–31G(d) basis set for non-metal atoms and LANL2DZ basis set for iridium metal was preferred in the computations carried out by using Gaussian program, whereas in the calculations performed with the Amsterdam Modelling Suite program, the TZP basis set was used for all atoms. From the theoretically obtained results, it is seen that Ir6, Ir7, Ir22-Ir25 complexes can be proposed as good candidate for hole injection layer materials in OLED based on indium tin oxide as an anode. Within complexes investigated, it has been determined that Ir16 and Ir17 complexes are the most suitable candidates for electron transport layer materials, whereas Ir16 complex can be used as both a hole transfer layer and ambipolar materials. Furthermore, it has been predicted that Ir4, Ir7, Ir8, and Ir23 complexes could be preferred as hole blocking layer compounds. From the detailed analysis of the singlet-triplet transitions of the complexes studied, it could be said that all iridium(III) complexes investigated could be used as highly efficient phosphorescent OLED molecules.

Efficient thermally activated delayed fluorescence materials from symmetric anthraquinone derivatives for high-performance red OLEDs

Constructing efficient red thermally activated delayed-fluorescence (TADF) materials for high-performance organic light-emitting diodes (OLEDs) remains challenging due to the formidable barrier of energy gap law. In this work, a design strategy of connecting two donor units to the adjacent positions of electron acceptor is proposed for creating red luminescent materials, and four Y-shaped TADF molecules consisting of strong electron-withdrawing anthraquinone (AQ) acceptor and triphenylamine or acridine-based donors are designed and synthesized. They exhibit strong red emissions (604−618 nm) in toluene solutions and orange/red emissions (566−608 nm) with good photoluminescence quantum yields (43−68%) in doped films, and enjoy small singlet-triplet energy gaps (0.02−0.10 eV) and fast reverse intersystem crossing processes (1.5–7.3 × 105 s−1), which are attributed to the unique Y-shape structure. A maximum external quantum efficiency of 19.5% with an electroluminescence peak at 616 nm is achieved for AQ-PTPA-based red doped device, representing the highest level for red TADF-OLEDs based on AQ acceptor in the literature. This work can provide guidance for the design of efficient red delayed-fluorescence molecules for the application in OLEDs.

Construction frontier molecular orbital prediction model with transfer learning for organic materials

The frontier molecular orbitals of organic semiconductor materials play a crucial role in the performance of photoelectric devices, including organic photovoltaics (OPVs), organic light-emitting diodes (OLEDs), and organic photodetectors (OPDs). In this work, a model for predicting frontier molecular orbital of organic materials, including HOMO and LUMO levels, is established with the extreme gradient boosting algorithm and Klekota-Roth fingerprints. The correlation coefficients of HOMO or LUMO energy levels in the testing set are 0.75 and 0.84 in the transfer model from 11,626 DFT data in Harvard Energy database to 1198 experimental data in literature. The difference between the ML predicted value and the experimental value is smaller than the difference between ML prediction and DFT calculation, always less than 10%. Moreover, based on correlation and SHAP interpretability analysis, 13 key structural fragments influencing energy levels are selected to further verify the effective regulation of the frontier molecular orbital by the key structural fragments in practical applications. Considering the completely opposite regulatory functions of key structural fragments on HOMO and LUMO energy levels, four new Y6 derivatives, Y-PCP, Y-P6F, Y-PCF, and Y-P4FC, are designed to flexibly modify the HOMO and LUMO energy levels. The prediction trends of ML align closely with the computational trends from DFT. It is worth noting that the accuracy of LUMO energy level prediction by the prediction model makes up for the instability of DFT calculation on LUMO energy level. This work offers a cost-effective method to accelerate the acquisition of electronic properties of organic materials.

Clar's Aromatic π-Sextet Rule for the Construction of Red Multiple Resonance Emitter.

Despite the proliferation of multiple resonance (MR) materials in the blue to green spectral ranges, red MR emitters remain scarce in the literature, an area that certainly warrants attention for future applications. Here, through a clever application of classic Clar's aromatic π-sextet rule, we triumphantly constructed the first red MR emitter by substituting the conventional benzene ring core with anthracene (fewer π-sextets). Theoretical studies indicate that the quantity of π-sextets ultimately determines the optical bandgap of a molecule, rather than the number of fused benzene rings. Benefiting from the high photoluminescence quantum yield of ~94% and horizontal dipole ratio of ~90%, the corresponding narrowband red (luminescence wavelength: 608 nm) organic light-emitting diode shows a high external quantum efficiency of 27.3%, with only a slight decrease of 3.7% at an elevated luminance level of 100,000 cd/m2.

To Maximize Luminescence for an Efficient Organic Solar Cell†

Comprehensive SummaryWith the continuous development of photovoltaic materials, organic solar cells (OSCs) have made remarkable advancements, surpassing a power conversion efficiency (PCE) of 20%. However, the PCEs of OSCs remain lower than that of inorganic solar cells due to significant energy losses, mainly stemming from the relatively large non‐radiative recombination losses (usually be expressed as ∆E3), resulting in low open‐circuit voltages. This can be achieved by reducing non‐radiative recombination, and hereby increasing the electroluminescence quantum efficiency (EQEEL) of the photo‐active layer. This review analyzes the significance of luminescence efficiency in achieving high‐performance OSCs by examining the reciprocal relationship between ∆E3 and EQEEL. High‐efficiency organic solar cells can also be used as effective organic light‐emitting diodes (OLEDs). The discussion provides insights into the influencing factors of EQEEL and the mechanisms for adjusting various parameters, which include enhancements in photoluminescence quantum yield and the proportion of radiative excitons. The objective is to offer insights into the crucial role of luminescence performance in OSC development, guiding researchers toward developing novel photovoltaic materials or optimization strategies to enhance the luminescence performance of the active layer in OSCs, fostering the simultaneous advancement of OSCs and OLEDs. Key Scientists

Efficient Deep-Blue Organic Light-Emitting Diodes Employing Doublet Sensitization.

Fast and efficient exciton utilization is a crucial solution and highly desirable for achieving high-performance blue organic light-emitting diodes (OLEDs). However, the rate and efficiency of exciton utilization in traditional OLEDs, which employ fully closed-shell materials as emitters, are inevitably limited by spin statistical limitations and transition prohibition. Herein, a new sensitization strategy, namely doublet-sensitized fluorescence (DSF), is proposed to realize high-performance deep-blue electroluminescence. In the DSF-OLED, a doublet-emitting cerium(III) complex, Ce-2, is utilized as sensitizer for multi-resonance thermally activated delayed fluorescence emitter ν-DABNA. Experimental results reveal that holes and electrons predominantly recombine on Ce-2 to form doublet excitons, which subsequently transfer energy to the singlet state of ν-DABNA via exceptionally fast (over 108s-1) and efficient (≈100%) Förster resonance energy transfer for deep-blue emission. Due to the circumvention of spin-flip in the DSF mechanism, near-unit exciton utilization efficiency and remarkably short exciton residence time of 1.36µs are achieved in the proof-of-concept deep-blue DSF-OLED, which achieves a Commission Internationale de l'Eclairage coordinate of (0.13, 0.14), a high external quantum efficiency of 30.0%, and small efficiency roll-off of 14.7% at a luminance of 1000cdm-2. The DSF device exhibits significantly improved operational stability compared with unsensitized reference device.

Creating highly efficient stretchable OLEDs with nanowavy structures for angle-independent narrow band emission

Stretchable organic light-emitting diodes (SOLEDs) have been the challenging class of OLEDs as they have limited processability to fabricate a design that can withstand external deformation. Herein, we demonstrated the highly efficient top-emitting geometrical stretchable OLED (GSOLED) by incorporating the prestretched elastomer with optical adhesive film. The experimental and theoretical characterizations verified the enhancement of device efficiencies with the light extraction phenomenon brought by nanowavy corrugated structures. Furthermore, GSOLED shows stability in stretchable conditions and displays narrower emission spectrum with improved color purity. The full width at half maximum (FWHM) of 21 nm shows narrowband emission with a high current efficiency and EQE of 221 cd A−1 and 39.50%. This work marks a significant step forward, providing unprecedented insights into the factors influencing device performance in current and future material systems for stretchable organic light-emitting diodes.

Construction of Concentration Quenching‐Resistant Multi‐Resonance TADF Emitters via Positional Isomerization for OLEDs

AbstractMultiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters are promising for high‐definition organic light‐emitting diodes (OLEDs) due to their high exciton utilization and color purity. However, strong interchromophore interactions cause most MR‐TADF emitters with planar structures to aggregate at high doping concentrations, leading to degraded efficiencies. Herein, using benzenesulfonyl‐functionalized dibenzothiophene sulfoximine with steric effects, three MR‐TADF emitters (2SBN, 3SBN, and 4SBN) are synthesized by coupling the classic DtBuCzB skeleton at different sites. Three emitters exhibit green or blue‐green emission with full width at half maximum (FWHM) values less than 29 nm and photoluminescence quantum yields exceeding 90%. OLEDs based on 2SBN, 3SBN, and 4SBN achieve high maximum external quantum efficiency (EQEmax) values of 30.1%, 27%, and 33.8%, respectively, at a 5 wt.% doping concentration. Notably, due to the distorted conformation of 4SBN and suppressed intermolecular interaction, the OLED remains high EQEmax of 28.9% at a doping concentration of 20 wt.%. These results demonstrate the feasibility of molecular design to modulate spatial conformations via positional isomerism to develop MR‐TADF emitters with reduced concentration quenching.

Regulating the photoluminescence of aluminium complexes from non-luminescence to room-temperature phosphorescence by tuning the metal substituents

Although luminescent aluminum compounds have been utilized for emitting and electron transporting layers in organic light-emitting diodes, most of them often exhibit not phosphorescence but fluorescence with lower photoluminescent quantum yields in the aggregated state than those in the amorphous state due to concentration quenching. Here we show the synthesis and optical properties of β-diketiminate aluminum complexes, such as crystallization-induced emission (CIE) and room-temperature phosphorescence (RTP), and the substituent effects of the central element. The dihaloaluminum complexes were found to exhibit the CIE property, especially RTP from the diiodo complex, while the dialkyl ones showed almost no emission in both solution and solid states. Theoretical calculations suggested that undesired structural relaxation in the singlet excited state of dialkyl complexes should be suppressed by introducing electronegative halogens instead of alkyl groups. Our findings could provide a molecular design not only for obtaining luminescent complexes but also for achieving triplet-harvesting materials.

Dual‐Core Engineering for Efficient Deep‐Blue Multiple Resonance Thermally Activated Delayed Fluorescent Materials

AbstractDeveloping narrowband blue multiple resonance (MR) organic emitters with Commission Internationale de L'Eclairage (CIE) y coordinates &lt;0.1 is essential for advanced display technologies. This study proposes a deep‐blue thermally activated delayed fluorescence (TADF) emitter, named 2BNO, which integrates two independent MR cores. Unlike many TADF materials with single‐bonded dual emitting cores, 2BNO utilizes a steric hindrance‐assisted fluorene bridge to achieve an orthorhombic molecular structure. The dual‐core MR‐TADF emitter shows enhanced light absorption and a high photoluminescence quantum yield. Notably, the emission of 2BNO is not significantly redshifted compared to single‐core compounds and maintains a narrow full width at half‐maximum (FWHM) of 24 nm with CIE coordinates of (0.147, 0.041) in 2Me‐THF solution, nearing the BT.2020 blue standard. Organic light‐emitting diodes (OLEDs) incorporating 2BNO as the emitter exhibit deep‐blue emission at 460 nm with a narrow FWHM of 29 nm and CIE coordinates of (0.14, 0.09). The dual emitting core design significantly improves device efficiency, achieving a high external quantum efficiency (EQE) of 19.8%. The dual‐core molecular design strategy in this work is demonstrated to be effective in promoting the efficiency of the TADF emitters while preserving deep‐blue color purity.

Exploration of red and deep red Thermally activated delayed fluorescence molecules constructed via intramolecular locking strategy

Red and deep red (DR) organic light-emitting diodes (OLEDs) have garnered increasing attention due to their widespread applications in display technology and lighting devices. However, most red OLEDs exhibit low luminescence efficiency, severely limiting their practical applications. To address this challenge, we theoretically design four novel TADF molecules with red and DR luminescence using intramolecular locking strategies building upon the experimental findings of DCN-DLB and DCN-DSP, and their crystal structures are predicted with the lower energy and higher packing density. The photophysical properties and luminescence mechanism of six molecules in toluene and crystal are clarified using the first principles calculation and thermal vibration correlation function (TVCF) method. The proposed design strategy is anticipated to offer several advantages: enhanced electron-donating capabilities, more rigid structures, longer emission wavelengths and higher luminescence efficiency. Specifically, we introduce oxygen atoms and nitrogen atoms as intramolecular locks, and the newly developed DCN-DBF and DCN-PHC have redshifted emission, narrow singlet–triplet energy gap (ΔEST), fast reverse intersystem crossing rate and enhanced photoluminescence quantum yield (PLQY). Notably, DCN-DBF achieves both long wavelength emission and high efficiency, with emission peaks at 598 nm and 587 nm corresponding to PLQY of 52.13 % and 43.42 % in toluene and crystal, respectively. Our work not only elucidates the relationship between molecular structures and photophysical properties, but also proposes feasible intramolecular locking design strategies and four promising red and DR TADF molecules, which could provide a valuable reference for the design of more efficient red and DR TADF emitters.

Modulating Charge‐Transfer Excited States of Multiple Resonance Emitters via Intramolecular Covalent Bond Locking

AbstractAdvanced multiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters with high efficiency and color purity have emerged as a research focus in the development of ultra‐high‐definition displays. Herein, we disclose an approach to modulate the charge‐transfer excited states of MR emitters via intramolecular covalent bond locking. This strategy can promote the evolution of strong intramolecular charge‐transfer (ICT) states into weak ICT states, ultimately narrowing the full‐width at half‐maximum (FWHM) of emitters. To modulate the ICT intensity, two octagonal rings are introduced to yield molecule m‐DCzDAz‐BNCz. Compounds m‐CzDAz‐BNCz and m‐DCzDAz‐BNCz exhibit bright light‐green and green fluorescence in toluene, with emission maxima of 504 and 513 nm, and FWHMs of 28 and 34 nm, respectively. Sensitized organic light‐emitting diodes (OLEDs) employing emitters m‐CzDAz‐BNCz and m‐DCzDAz‐BNCz exhibit green emission with peaks of 508 and 520 nm, Commission Internationale de L'Eclairage (CIE) coordinates of (0.12, 0.65) and (0.19, 0.69), and maximum external quantum efficiencies (EQEs) of 30.2 % and 32.6 %, respectively.

Multiple Enol-Keto Isomerization and Excited-State Unidirectional Intramolecular Proton Transfer Generate Intense, Narrowband Red OLEDs.

A novel series of excited-state intramolecular proton transfer (ESIPT) emitters, namely, DPNA, DPNA-F, and DPNA-tBu, endowed with dual intramolecular hydrogen bonds, were designed and synthesized. In the condensed phase, DPNAs exhibit unmatched absorption and emission spectral features, where the minor 0-0 absorption peak becomes a major one in the emission. Detailed spectroscopic and dynamic approaches conclude fast ground-state equilibrium among enol-enol (EE), enol-keto (EK), and keto-keto (KK) isomers. The equilibrium ratio can be fine-tuned by varying the substitutions in DPNAs. Independent of isomers and excitation wavelength, ultrafast ESIPT takes place for all DPNAs, giving solely KK tautomer emission maximized at >650 nm. The spectral temporal evolution of ESIPT was resolved by a state-of-the-art technique, namely, the transient grating photoluminescence (TGPL), where the rate of EK* → KK* is measured to be (157 fs)-1 for DPNA-tBu, while a stepwise process is resolved for EE* → EK* → KK*, with a rate of EE* → EK* of (72 fs)-1. For all DPNAs, the KK tautomer emission shows a narrowband emission with high photoluminescence quantum yields (PLQY, ∼62% for DPNA in toluene) in the red, offering advantages to fabricate deep-red organic light-emitting diodes (OLED). The resulting OLEDs give high external quantum efficiency with a spectral full width at half-maximum (FWHM) as narrow as ∼40 nm centered at 666-670 nm for DPNAs, fully satisfying the BT. 2020 standard. The unique ESIPT properties and highly intense tautomer emission with a small fwhm thus establish a benchmark for reaching red narrowband organic electroluminescence.