Organic Light-emitting Diodes Research Articles

Efficient and stable hybrid perovskite-organic light-emitting diodes with external quantum efficiency exceeding 40 per cent

Light-emitting diodes (LEDs) based on perovskite semiconductor materials with tunable emission wavelength in visible light range as well as narrow linewidth are potential competitors among current light-emitting display technologies, but still suffer from severe instability driven by electric field. Here, we develop a stable, efficient and high-color purity hybrid LED with a tandem structure by combining the perovskite LED and the commercial organic LED technologies to accelerate the practical application of perovskites. Perovskite LED and organic LED with close photoluminescence peak are selected to maximize photon emission without photon reabsorption and to achieve the narrowed emission spectra. By designing an efficient interconnecting layer with p-type interface doping that provides good opto-electric coupling and reduces Joule heating, the resulting green emitting hybrid LED shows a narrow linewidth of around 30 nm, a peak luminance of over 176,000 cd m−2, a maximum external quantum efficiency of over 40%, and an operational half-lifetime of over 42,000 h.

Multireference Ab Initio Calculations on Excited Electronic States of Carbazole-Based Organic Compounds for Thermally Activated Delayed Fluorescence.

The emerging technology of organic light-emitting diodes takes advantage of the thermally activated delayed fluorescence (TADF) mechanism for improved efficiency. Carbazole-based organic molecules are suitable for TADF emission because of charge transfer excitations between the electron-donor carbazole and an electron-acceptor unit. Computational design of new TADF molecules with the desired properties is challenging because charge-transfer excitations cannot be predicted accurately by time-dependent density functional theory. Four groups of carbazole-based donor-acceptor molecules have been studied using multireference ab initio methods to understand the nature of excited electronic states. The state-averaged complete active space self-consistent field (SA-CASSCF) and the N-electron valence state perturbation theory (NEVPT2) were used to calculate energies and oscillator strengths for multiple excited electronic states. The number of active electrons and orbitals and the number of excited states included in state-averaged CASSCF were selected such that the accuracy of ab initio predictions could be improved systematically. The procedure introduced here for the calculation of multiple excited electronic states of TADF candidates can be used to accelerate the computational search for efficient TADF materials.

Highly Efficient Organic Light–Emitting Diode Using DNA as Scattering Layer

AbstractHerein, an organic light–emitting diode (OLED) is fabricated with increased luminous efficiency and biocompatibility by topographic DNA film. In addition to the natural abundance and biocompatibility of DNA, its semi‐flexible characteristics facilitated the emergence of the liquid crystal phase, allowing the formation of a periodic wavy undulation structure by applying shear force. The resultant zigzag structure possesses sufficient periodicity and roughness, enhancing the effective scattering of emitted light. Furthermore, the DNA‐coated red OLED demonstrates cell proliferative effects and exhibits high electrical and thermal stability even in a bent state, suggesting its potential application in attachable OLED‐based light therapy.

Purely Organic Room‐Temperature Phosphorescence Molecule for High‐Performance Non‐Doped Organic Light‐Emitting Diodes

AbstractPurely organic molecules with room‐temperature phosphorescence (RTP) are potential luminescent materials with high exciton utilization for organic light‐emitting diodes (OLEDs), but those exhibiting superb electroluminescence (EL) performances are rarely explored, mainly due to their long phosphorescence lifetimes. Herein, a robust purely organic RTP molecule, 3,6‐bis(5‐phenylindolo[3,2‐a]carbazol‐12(5H)‐yl)‐xanthen‐9‐one (3,2‐PIC‐XT), is developed. The neat film of 3,2‐PIC‐XT shows strong green RTP with a very short lifetime (2.9 μs) and a high photoluminescence quantum yield (72 %), and behaviors balanced bipolar charge transport. The RTP nature of 3,2‐PIC‐XT is validated by steady‐state and transient absorption and emission spectroscopies, and the working mechanism is deciphered by theoretical simulation. Non‐doped multilayer OLEDs using thin neat films of 3,2‐PIC‐XT furnish an outstanding external quantum efficiency (EQE) of 24.91 % with an extremely low roll‐off (1.6 %) at 1000 cd m−2. High‐performance non‐doped top‐emitting and tandem OLEDs are also achieved, providing remarkable EQEs of 24.53 % and 42.50 %, respectively. Delightfully, non‐doped simplified OLEDs employing thick neat films of 3,2‐PIC‐XT are also realized, furnishing an excellent EQE of 17.79 % and greatly enhanced operational lifetime. The temperature‐dependent and transient EL spectroscopies demonstrate the electrophosphorescence attribute of 3,2‐PIC‐XT. These non‐doped OLEDs are the best devices based on purely organic RTP materials reported so far.

Purely Organic Room-Temperature Phosphorescence Molecule for High-Performance Non-Doped Organic Light-Emitting Diodes.

Purely organic molecules with room-temperature phosphorescence (RTP) are potential luminescent materials with high exciton utilization for organic light-emitting diodes (OLEDs), but those exhibiting superb electroluminescence (EL) performances are rarely explored, mainly due to their long phosphorescence lifetimes. Herein, a robust purely organic RTP molecule, 3,6-bis(5-phenylindolo[3,2-a]carbazol-12(5H)-yl)-xanthen-9-one (3,2-PIC-XT), is developed. The neat film of 3,2-PIC-XT shows strong green RTP with a very short lifetime (2.9 μs) and a high photoluminescence quantum yield (72 %), and behaviors balanced bipolar charge transport. The RTP nature of 3,2-PIC-XT is validated by steady-state and transient absorption and emission spectroscopies, and the working mechanism is deciphered by theoretical simulation. Non-doped multilayer OLEDs using thin neat films of 3,2-PIC-XT furnish an outstanding external quantum efficiency (EQE) of 24.91 % with an extremely low roll-off (1.6 %) at 1000 cd m-2. High-performance non-doped top-emitting and tandem OLEDs are also achieved, providing remarkable EQEs of 24.53 % and 42.50 %, respectively. Delightfully, non-doped simplified OLEDs employing thick neat films of 3,2-PIC-XT are also realized, furnishing an excellent EQE of 17.79 % and greatly enhanced operational lifetime. The temperature-dependent and transient EL spectroscopies demonstrate the electrophosphorescence attribute of 3,2-PIC-XT. These non-doped OLEDs are the best devices based on purely organic RTP materials reported so far.

Boosting Hole Mobility: Indenofluorene-Arylamine Copolymers and Their Impact on Solution-Processed OLED Performance.

We introduce three newly designed thermally cross-linkable hole transport copolymers (PIF-TPD, PIF-F2PCz, and PIF-TPAPCz) for improving the performance of solution-processed organic light-emitting diodes (s-OLEDs). These copolymers, designed through a strategic molecular approach with benzocyclobutene (BCB) and styrene-based cross-linking monomers, show high solvent resistance at a low cross-linking temperature (150 °C). Furthermore, these conjugated copolymers based on planar indenofluorene with three different hole transport (HT) units, exhibit outstanding charge carrier mobility (1.61 × 10-2 cm2 V-1s-1), demonstrated by comparing hole reorganization energy and electronic coupling strength of HT units. Despite these copolymers showing the overall vertical orientation in the horizontal dipole moment measurement results, we demonstrated that the HT units can exhibit the preferred orientation, contributing to high hole transport properties. As a result, they perform exceptionally well as hole transport layers in green phosphorescent s-OLEDs, achieving a maximum external quantum efficiency of 15.3% and a maximum current efficiency of 53.9 cd A-1 with a small efficiency roll-off despite their relatively low triplet energy levels. These results are comparable to vacuum-deposited OLEDs, highlighting the potential of these copolymers in advancing OLED technology for display panels and lighting applications.

Efficient and ultra-high luminance orange-red organic light emitting diode (OLED) based on triphenylamine-benzothiadiazole-phenoxazine hybrid molecule with hybrid local and charge-transfer (HLCT) characteristic

Due to the energy gap law, red emission needs relatively narrow energy gap, thus the nonradiative transition rate (knr) grows exponentially and eventually impacts the materials fluorescent efficiency. Here, an orange-red emission donor-acceptor-π-donor (D-A-π-D’) material N, N-diphenyl-4-(7-(4-(10-phenyl-10 H-phenoxazin-3-yl) phenyl) benzo [c] (Huang et al., 2019; Park et al., 2008; Caspar et al., 1982) [1,2,5] thiadiazol-4-yl) aniline (TBphPP) was designed and synthesized. Introducing a benzene π-bridge between the strong donor 10-phenyl-10H-phenoxazin (PPOX) and acceptor 2,1,3-benzothiadiazole (BTZ) not only is able to stretch the molecular conjugation so as to increase the proportion of LE state in hybrid local and charge-transfer (HLCT) state but also increase the overlap area of the electron cloud to improve luminous efficiency. As a result, the non-doped organic light-emitting diode (OLED) of TBphPP exhibited high luminance of 17,886 cd m−2 and relatively high exciton utilization efficiency (EUE) of 44 % with a standard red electroluminescent peak at 620 nm. Importantly, the optimized doped device based on TBphPP achieved high performance that the maximum external quantum efficiency (EQEmax) was up to 9.86 % with a higher EUE of 66.2 % and the efficiency roll-off (ηroll-off) at 100,000 cd m−2 was only 3.55 %. Simultaneously, it has reached ultra-high luminescence of 180,583 cd m−2, high current efficiency of 29.02 cd A−1 and power efficiency of 16.47 l m W−1. To our knowledge, the TBphPP device with such ultra-high luminance and high efficiency is one of the best performance orange-red materials based on HLCT characteristic.

Single-crystalline hole-transporting layers for efficient and stable organic light-emitting devices

Efficient charge-carrier injection and transport in organic light-emitting devices (OLEDs) are essential to simultaneously achieving their high efficiency and long-term stability. However, the charge-transporting layers (CTLs) deposited by various vapor or solution processes are usually in amorphous forms, and their low charge-carrier mobilities, defect-induced high trap densities and inhomogeneous thickness with rough surface morphologies have been obstacles towards high-performance devices. Here, organic single-crystalline (SC) films were employed as the hole-transporting layers (HTLs) instead of the conventional amorphous films to fabricate highly efficient and stable OLEDs. The high-mobility and ultrasmooth morphology of the SC-HTLs facilitate superior interfacial characteristics of both HTL/electrode and HTL/emissive layer interfaces, resulting in a high Haacke’s figure of merit (FoM) of the ultrathin top electrode and low series-resistance joule-heat loss ratio of the SC-OLEDs. Moreover, the thick and compact SC-HTL can function as a barrier layer against moisture and oxygen permeation. As a result, the SC-OLEDs show much improved efficiency and stability compared to the OLEDs based on amorphous or polycrystalline HTLs, suggesting a new strategy to developing advanced OLEDs with high efficiency and high stability.

Effect of Red Emissive Ligand Number on Dendronized Solution‐Processable Iridium(III) Complexes for Organic Light‐Emitting Diodes

AbstractTris‐bidentate iridium(III) complexes used in organic light‐emitting diodes (OLEDs) are typically homoleptic or heteroleptic with three or two identical emissive ligands, respectively. Herein red phosphorescence emitting dendrimers composed of first generation biphenyl dendrons, 2‐ethylhexyloxy surface groups and an iridium(III) complex core with three, two or one emissive [4‐phenyl]−2‐[thiophen‐2‐yl]quinoline ligands are reported. The dendrimers have similar photoluminescence quantum yields (PLQYs) in solution (84–88%), neat film (23–25%) and when blended with tris(4‐carbazoyl‐9‐ylphenyl)amine (72–73%), enabling the effect of the number of emissive ligands on OLED performance to be determined. The external quantum efficiency (EQE) of OLEDs composed of neat dendrimer films increased with decreasing number of emissive ligands, with the device composed of the dendrimer having a single emissive ligand having an EQE of 9.2%, which is almost double that expected from a bottom emitting device and a film PLQY of 25 ± 3.6%. The emission is Lambertian and the higher‐than‐expected EQE is ascribed to alignment of the single emissive ligand being optimal for light‐outcoupling. The EQE of OLEDs containing the blend film also increased with decreasing emissive number of ligands (maximum EQE = 15.4%).

Impact of Spontaneous Orientational Polarization on Triplet-Triplet Upconversion-Based Blue Organic Light-Emitting Diodes.

The spontaneous orientation polarization (SOP) of a permanent dipole moment of the molecule induces a giant surface potential (GSP) in an organic semiconductor film, and GSP is expected to be a crucial parameter for understanding the operational mechanism of organic light-emitting diodes (OLEDs). This study demonstrates that the voltage-dependent migration of a carrier recombination zone induced by a polar electron transporting layer (ETL) having a positive SOP causes a decline in the overall performance of the OLED in triplet-triplet upconversion (TTU) based on OLEDs. Specifically, the TTU efficiency in an OLED with 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) as the ETL decreased by 20% due to the reduction of electrically generated triplet exciton density. This decrease resulted in a lower external electroluminescence (EL) quantum efficiency (EQE) of 5.4% at 1 mA cm-2, while the OLED with a nonpolar ETL resulted in an EQE of around 8.1% at 1 mA cm-2. We confirmed a shift in the recombination zone from the current density dependence of the EL spectra in the OLEDs. Our results indicate that the fixed carrier recombination zone near a hole transport layer and an emitting layer (HTL/EML) strongly enhanced the TTU process, while the polar EML/ETL interface induced the migration of the recombination zone depending on voltage, resulting in the decrease of triplet exciton density.

Uncovering the Aggregation-Induced Emission Mechanisms of Phenoxazine and Phenothiazine Groups.

Molecules with both aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) properties are potential organic light-emitting diode materials; however, the AIE and TADF mechanisms are still debatable. In this work, four molecules incorporating carbazole (Cz), phenoxazine (PXZ), and phenothiazine (PTZ) as donor groups to the diphenylsulfone acceptor were investigated. The experiment results indicate that a molecule containing Cz exhibits solely TADF properties, whereas molecules containing PXZ and PTZ demonstrate both TADF and AIE characteristics. As for DPS-PTZ, the result indicates that the thin-film environment restricts molecular twisting, consequently reducing nonradiative decay, thereby attributing to the AIE property by density functional theory and molecular dynamics simulation. As for DPS-PXZ, the result suggests that the restricted access to a conical intersection in a singlet excited via an expansion in the C-S-C angle is the pivotal factor for the AIE characteristic. The C-S-C angle twist of DPS-PXZ is impeded in the aggregate state and resulted in luminescence. Understanding the mechanisms serves as a valuable guide for the development of new AIE systems, enabling their application in various practical domains.

Multiple resonance delayed fluorescence emitter with C3 symmetry for high-performance solution-processed OLEDs

Solution-processed organic materials that exhibit both high emission efficiency and narrowband emission characteristics are rare, and the performance of corresponding solution-processed organic light-emitting diodes (sOLEDs) remains inadequate for practical applications. This study proposes a proof-of-concept design aimed at enhancing both solution processing capability and emission efficiency in multiple-resonance induced thermally activated delayed fluorescence (MR-TADF) materials through the integration of multiple emitting units. A unique emitter named TriBNCz is synthesized and characterized, incorporating three MR-building blocks onto a single phenyl ring, resulting in sky-blue emission with a peak at 490 nm and a small full width at half maximum (FWHM) of 25 nm. Significant improvements in solution processing attributes, including solubility and film-forming properties, are achieved. Moreover, except for the MR effect of the excited states, long-range charge transfer properties of excited states are also obtained. The multiple charge transfer channels contribute to higher rate of reverse intersystem crossing (kRISC). The optimized sOLED device exhibits a maximum external quantum efficiency (EQEmax) of 17.8 %. Furthermore, by employing 5TCzBN as a sensitizer, the sensitized sOLED achieves an EQEmax of 28.8 % and a high-level EQE of 26.1 % at 1000 cd m−2, with an FWHM of 30 nm and Commission Internationale de I’Éclairage (CIE) coordinates of (0.103, 0.497), representing one of the best results among narrowband emission sOLEDs. This research opens a new avenue to develop high-performance solution-processed organic materials and sOLED devices.

Highly Stable Silver Nanowire Plasmonic Electrodes for Flexible Polymer Light-Emitting Devices.

Silver nanowire (AgNW) transparent electrodes are considered as a promising candidate for applications in flexible optoelectronic devices. However, it remains a great challenge to obtain flexible AgNW electrodes with excellent optoelectrical properties and mechanical flexibility. Here, highly stable Ag nanoparticle (AgNP)-enhanced plasmonic AgNW electrodes are demonstrated via the controllable in situ growth of AgNPs at the AgNW junctions and introduction of an l-histidine (l-His) wrapping layer. The flexible transparent electrodes of AgNW-AgNP/l-His possess a low sheet resistance (Rsh) of ∼17.5 Ω sq-1, a high transmittance of ∼92.5% (550 nm), and a robust mechanical stability (100,000 bending cycles). Benefiting from plasmon-coupling effects, flexible polymer light-emitting devices (FPLEDs) with AgNW-AgNP/l-His electrodes present a current efficiency (CE) of ∼14.8 cd A-1 and an external quantum efficiency (EQE) of ∼5.6%, constituting ∼80% and ∼75% increases compared to those of the reference devices with AgNW electrodes, respectively. Additionally, the laminated flexible transparent PLEDs (FT-PLEDs) are demonstrated by integrating polydimethylsiloxane/AgNW-AgNP anodes by a soft lamination process. The FT-PLEDs present a CE of ∼7.1 cd A-1 (cathode side: ∼3.9 cd A-1; anode side: ∼3.2 cd A-1) and an EQE of ∼2.7% (cathode side: ∼1.5%; anode side: ∼1.2%). Furthermore, the FPLEDs and FT-PLEDs exhibit robust mechanical durability, maintaining ∼89% and ∼86% of their initial luminance after 1000 bending cycles at a bending radius of 2 mm, respectively. This work opens up a new avenue for the development of high performance and stable flexible optoelectronic devices.

Stretchable OLEDs based on a hidden active area for high fill factor and resolution compensation

Stretchable organic light-emitting diodes (OLEDs) have emerged as promising optoelectronic devices with exceptional degree of freedom in form factors. However, stretching OLEDs often results in a reduction in the geometrical fill factor (FF), that is the ratio of an active area to the total area, thereby limiting their potential for a broad range of applications. To overcome these challenges, we propose a three-dimensional (3D) architecture adopting a hidden active area that serves a dual role as both an emitting area and an interconnector. For this purpose, an ultrathin OLED is first attached to a 3D rigid island array structure through quadaxial stretching for precise, deformation-free alignment. A portion of the ultrathin OLED is concealed by letting it ‘fold in’ between the adjacent islands in the initial, non-stretched condition and gradually surfaces to the top upon stretching. This design enables the proposed stretchable OLEDs to exhibit a relatively high FF not only in the initial state but also after substantial deformation corresponding to a 30% biaxial system strain. Moreover, passive-matrix OLED displays that utilize this architecture are shown to be configurable for compensation of post-stretch resolution loss, demonstrating the efficacy of the proposed approach in realizing the full potential of stretchable OLEDs.

Annealing temperature-dependent induced supramolecular chiroptical response of copolymer thin films studied by pump-modulated transient circular dichroism spectroscopy

Copolymer thin films showing induced supramolecular chirality are of considerable interest for optoelectronic applications such as organic light-emitting diodes. Here, we introduce a new helicene-like chiral additive with two octyloxy substituents which displays excellent chiral induction properties in an achiral polyfluorene copolymer, leading to a circular dichroism (CD) response of up to 10,000 mdeg. This chiral inducer also displays very good thermal stability, which enables us to perform an extended study on the induced chiroptical properties of the cholesteric copolymer thin films annealed at different temperatures in the range 140–260 °C. Starting from about 180 °C, a distinct change in the morphology of the CD-active film is observed by CD microscopy, from micrometre-size granular to extended CD-active regions, where the latter ones display skewed distributions of the dissymmetry parameter gabs. Broadband Müller matrix spectroscopy finds a pronounced CD and circular birefringence (CB) response and only weak linear dichroism (LD, LD’) and linear birefringence (LB, LB’). Ultrafast transient CD spectroscopy with randomly polarised excitation reveals a clean mirror-image-type transient response, which shows a second-order decay of the S1 population due to singlet–singlet annihilation processes.

Synthesis and Electron Transporting Properties of Diblock Copolymers Consisting of Polyfluorene and Polystyrene.

Poly(9,9-di-n-octylfluorene) (PFO) is a promising material for polymer light-emitting diodes (PLEDs) due to its advantageous properties. To enhance its electron transporting capabilities, diblock polymers were synthesized by attaching polystyrene (PSt) chains of varying lengths to one end of the PFO molecule. In a comparative study with PFO homopolymer, the diblock polymers maintained similar thermal properties, absorption spectra, and photoluminescent stability, while exhibiting slightly deeper lowest unoccupied molecular orbital (LUMO) levels and higher crystallinity. Notably, diblock polymers with shorter polystyrene blocks demonstrated higher electron mobility than the PFO homopolymer and diblock polymers with excessively long polystyrene blocks. These findings suggest that the optimal chain length of the polystyrene block is crucial for maximizing electron mobility, thus offering valuable insights for designing high-performance PLED materials.

29‐2: Distinguished Paper: High Efficiency and High Color Purity Deep‐Blue Organic Light‐Emitting Diodes with Blue Index >500

Thermally activated delayed fluorescent (TADF) and phosphorescent blue organic light‐emitting diodes (OLEDs) have been developed to overcome the relatively low triplet exciton utilization of traditional fluorescent OLEDs. However, broad emission spectra originating from charge transfer process limits the commercial application of such blue OLEDs. Herein, an effective phosphor‐sensitized fluorescent (PSF) OLED device structure was designed. PSF OLED exhibited a maximum blue index (BI) of 508 cd/A/CIEy with CIEy of 0.060, which has been the highest efficiency result reported for PSF deep‐blue OLEDs. Impressively, the sensitized OLEDs maintained blue index of 407 cd/A/CIEy, narrow emission spectra (FWHM = 17 nm) and high color purity (CIEy = 0.046), revealing the attractive technical advantages and commercial application potential.

21‐2: Modulus Spectroscopy and Capacitance‐Voltage Measurement of OLEDs as Tools for Estimating Charge Dynamics

In the past few decades, the injection and transporting characteristics of charge carriers in organic light emitting diodes (OLEDs) have been analyzed using hole‐only and electron‐only devices (HODs and EODs). However, such methods cannot fully explain the dynamic characteristics of OLEDs such as charge accumulation and recombination. In this study, we well‐established the combination of modulus spectroscopy and capacitance‐voltage measurement and applied it to describe the carrier dynamics in OLED devices.

Photoluminescence of Platinum(II) Complexes with Diazine-Based Ligands.

In the last past twenty years, research on luminescent platinum (II) complexes has been intensively developed for useful application such as organic light emitting diodes (OLEDs). More recently, new photoluminescent complexes based on diazine ligands (pyrimidine, pyrazine, pyridazine, quinazoline and quinoxaline) have been developed in this context. This review will summarize the photophysical properties of most of the phosphorescent diazine Pt(II) complexes described in the literature and compare the results to pyridine analogues whenever possible. Based on the emission color, and the photoluminescence quantum yield (PLQY) values, the relationship between structure modification, and photophysical properties are highlighted. Tuning of emission color, quantum yields in solution and solid state and, for some complexes, aggregation induced emission (AIE) or thermally activated delayed fluorescence (TADF) properties are described. When emitting OLEDs have been built from diazine Pt(II) complexes, the external quantum efficiency (EQE) values and luminance for different emission wavelengths and in some cases, chromaticity coordinates obtained from devices, are given. Finally, this review highlights the growing interest in studies of new luminescent diazine Pt(II) complexes for OLED applications.

P‐251: Late‐News Poster: OLED Lifetime Optimization in Lower Current‐Density Region

The Organic Light Emitting Diode (OLED) lifetime property was investigated in the lower current‐density region. The OLED display is required for an equivalent long lifetime performance in higher and lower current‐density regions. It was clarified that hole accumulation at the interface between electron blocking layer (EBL) and emissive layer (EML) is important for the Blue OLED lifetime property at lower current densities. The device simulation showed that the appropriate EML hole barrier affects the carrier distribution.