Organic Light-emitting Diodes Research Articles

Strategic Design of Anion-Responsive Triarylboranes Exhibiting Colorimetric and Fluorometric Red-Shift for Sensing and Optoelectronic Applications.

Triarylboranes (TABs) have been employed as colorimetric and/or fluorometric anion sensors. The majority of TAB-based anion sensors exhibit blue-shift modes of absorption and photoluminescence (PL) or turn off of PL, attributed to the intrinsic electronic polarity of the trivalent boron unit in their molecular designs. In this Concept article, we introduce a novel approach to modulating the photophysical properties of TABs toward a red-shift mode by balancing the dual, opposing roles of the amine-bridged TAB (phenazaborine). This molecular design strategy enables significant changes in color and emission response to anions, shifting to the lower energy regime in solution. Additionally, this approach is applicable to the solid-state modulation of PL in films and organic light-emitting diodes (OLEDs).

A Dynamic Hybrid Luminescent Display for Multilevel Anticounterfeiting

AbstractIncorporating specific motifs to provide tangible evidence of authenticity is a direct and effective measure against counterfeiting. However, achieving multi‐level anticounterfeiting through multiple motifs requires utilizing numerous stimulus sources to configure region‐specific emissions with customizable colors, which is complex, costly, and inaccessible. To address this challenge, a hybrid luminescent display is developed by integrating an internal down‐conversion layer with an organic light‐emitting diode (OLED). The internal down‐conversion layer can effectively extract the substrate and waveguide modes, resulting in a very rare outcome where the efficiency of a hybrid down‐conversion white OLED exceeds that of the pump light source. More importantly, by combining voltage‐modulated color‐tunable electroluminescence (EL) with EL‐induced down‐conversion luminescence, this unique design can precisely create dynamic and configurable multi‐color display patterns using only electrical stimulation. For anticounterfeiting purposes, the further amalgamation of the dynamic hybrid luminescent display device with the Internet of Things for digital authentication, and with fingerprint features for physical unclonable functions showcases unprecedented security. These results herald a new generation of multilevel luminescent anticounterfeiting technology.

Stable Xanthene Radicals and Their Heavy Chalcogen Analogues Showing Tunable Doublet Emission from Green to Near-infrared.

Organic luminescent radicals, unlike traditional closed-shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand their emission spectra. In this study, we report the synthesis of stable 9-aryl-substituted xanthene radicals and their heavy chalcogen analogues (1a-c and 2a-c), which exhibited excellent chemical stability and emission ranging from green to near-infrared (527~714 nm). Notably, the selenium-substituted radical (1c) demonstrates a significantly enhanced photoluminescence quantum yield of 41% when doped into its precursor solid. Additionally, the introduction of methoxyphenyl groups has largely enhanced the stability of the radical, showcasing an excellent photostability with the longest half-life of around 1792 h. The high internal quantum efficiency of up to 81% was further validated in organic light-emitting diode. This study introduces a novel class of stable carbon-centered radicals with high tunability and functionality for photoelectric applications.

Highly Enhanced Light Recycling in Quantum Dot Displays by Sidewall Reflectors

AbstractQuantum dot (QD) color conversion‐based displays have emerged as one of the most promising next‐generation devices due to their superior emission properties in terms of color expression. To date, however, existing QD color conversion layer (QD‐CCL) technologies have suffered from low luminance and power efficiency, mainly due to significant light absorption by the bank structure. Here, the color conversion efficiency of QD‐CCL has been significantly enhanced by fabricating a highly reflective metal layer on the side surface of the bank structure. Using a high‐aspect‐ratio silver reflector fabricated through a secondary sputtering lithographic technique involving argon ion bombardment, the fabricated QD‐CCL is combined with a blue organic light‐emitting diode (OLED) serving as a light source. As a result, light recycling from the reflector significantly enhances color conversion efficiency and luminance by up to 4.60‐fold and 4.29‐fold, respectively. Optical simulation reveals that higher pixel resolution provides greater reflection probabilities during extraction. This photomask‐free approach is not only simple but also highly compatible with existing semiconductor fabrication processes, making it a viable commercial alternative for all color‐converting structures that utilize light‐emitting materials with omnidirectional emission characteristics.

RGB-Single-Chip OLEDs for High-Speed Visible-Light Communication by Wavelength-Division Multiplexing.

Organic light-emitting diodes (OLEDs) have been developed for high-speed transmitters of visible-light communication (VLC) but so far the possibility of direct fabrication of multiple colors on a single substrate has not been exploited for multi-Gbps data transmission. Very fast red-, green-, and blue (RGB)-emitting OLEDs are developed on a single substrate to realize high data transmission speed by wavelength division multiplexing (WDM). -6dB electrical bandwidth of over 100MHz is achieved for all colors by selecting fluorescent materials with nanosecond emission lifetimes and little overlap between their emission spectra and incorporating them into OLEDs designed for high-speed operation. Optical microcavities in top-emitting OLED structures are used to minimize spectral overlap. A record data transmission rate for an OLED transmitter system of 3.2Gbps is demonstrated, by transmitting data with the 3 colors simultaneously and separating each data by dichroic mirrors. The results show that WDM with integrated RGB pixels is a useful way to increase the data transmission rate of a VLC system based on OLED transmitters, which has the potential to enable multi-gigabit transmission by displays. The availability of high-speed multiple-color devices as developed here also expands applications of OLEDs for spectroscopy, sensing, and ranging.

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.

Lead-Free Perovskite Light-Emitting Diodes.

Metal halide perovskites have been identified as a promising class of materials for light-emitting applications. The development of lead-based perovskite light-emitting diodes (PeLEDs) has led to substantial improvements, with external quantum efficiencies (EQEs) now surpassing 30% and operational lifetimes comparable to those of organic LEDs (OLEDs). However, the concern over the potential toxicity of lead has motivated a search for alternative materials that are both eco-friendly and possess excellent optoelectronic properties, with lead-free perovskites emerging as a strong contender. In this review, the properties of various lead-free perovskite emitters are analyzed, with a particular emphasis on the more well-reported tin-based variants. Recent progress in enhancing device efficiencies through refined crystallization processes and the optimization of device configurations is also discussed. Additionally, the remaining challenges are examined, and propose strategies that may lead to stable device operation. Looking forward, the potential future developments for lead-free PeLEDs are considered, including the extension of spectral range, the adoption of more eco-friendly deposition techniques, and the exploration of alternative materials.

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores.

The development of organic light-emitting devices has driven demand for new luminescent materials, particularly after the 2001 discovery of aggregation-induced emission. This study focuses on fluorinated diphenylacetylene-based luminescent molecules, revealing that specific molecular modifications can enhance fluorescence and achieve a wide range of photoluminescence colors. A simple and effective luminescence color-tuning method is proposed to investigate the photoluminescence behavior of two-component polymer dispersion films blended with two types of fluorinated diphenylacetylenes, namely blue- and yellow- or red-fluorescent fluorinated diphenylacetylenes. It is confirmed that if blue and green-yellow or yellow fluorophores are blended in appropriate ratios, a binary blend with color coordinates (0.20, 0.32) can be achieved, which approaches the white point of pure white emission. These findings contribute to the development of effective lighting and display devices as new white-light-emitting materials.

Recent progress in circularly polarized multi-resonance thermally activated delayed fluorescence materials for organic light-emitting diodes

Recent progress in circularly polarized multi-resonance thermally activated delayed fluorescence materials for organic light-emitting diodes

Molecular dynamics study of N,N'-di-n-alkyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI)/rubrene interface: Why the charge transfer at the interface is optimized depending on the alkyl chain length of PTCDI.

Molecular dynamics simulations were performed to investigate the interfacial structure of the N,N'-di-n-alkyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI)/rubrene interface, which represents the donor/acceptor interface in new types of organic light-emission diodes. In particular, the interfacial structure was examined for different alkyl chain lengths of PTCDI (Cn-PTCDI) at n = 4, 8, and 13, in order to elucidate the observed maximum charge transfer efficiency at the C8-PTCDI/rubrene interface in a recent experiment. The results revealed that the molecular conformation of the acceptor (Cn-PTCDI) molecules at the interface undergoes changes depending on the alkyl chain length when interacting with the rubrene molecule. It was found that the closest complex between Cn-PTCDI and rubrene is formed at n = 8, consistent with the experimental observation. In addition, the interfacial structures of Cn-PTCDI/air and rubrene/air were examined and compared to gain insights into the inherent stability associated with the intermolecular interactions at the interface.

Sterically Tuned Ortho-Phenylene-Linked Donor-Acceptor Benzothiazole-Based Boron Difluoride Complexes as Thermally-Activated Delayed Fluorescence Emitters for Organic Light-Emitting Diodes.

Two donor-acceptor dyes with an ortho-phenylene-linked carbazole electron donor and a benzothiazole-fused boron heterocyclic acceptor were designed, synthesized, and spectroscopically investigated. Due to the steric effects of boron heterocyclic units, the dyes demonstrate different conformations in the crystalline state. The presence of numerous hydrogen-bonding intermolecular interactions and the very weak π-π stacking in the molecular packing results in intense solid-state emission with photoluminescence quantum yields of 40 and 18% for crystals and 50 and 42% for host-based light-emitting layers. The compounds show aggregation-induced emission and thermally activated delayed fluorescence (TADF). The received ionization potential and electron affinity values suggested good charge-injecting ability and bipolar charge-transporting properties of the developed dyes. Transport of holes and electrons was detected in layers of one dye by the time-of-flight measurements. The benzothiazole-based boron difluoride complexes showed high electron mobility of 1.5 × 10-4 and 0.7 × 10-4 cm2 V-1 s-1 at an electric field of 1.35 × 106 V cm-1. Therefore, these dyes were successfully applied as emitters in organic light-emitting diodes with external quantum efficiencies of 15 and 13%, respectively. Our study marks a critical advancement in the area of solid-state emissive boron difluoride dyes, which can be applied as TADF emitters into organic light-emitting diodes. The obtained results reveal that the orientation of the acceptor unit in the ortho-phenylene-linked donor-acceptor dyes makes a significant impact on the TADF activity.

Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

AbstractConstructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V‐shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich‐structured molecules, and a series of novel and robust TADF materials with regular U‐shaped sandwich conformations are constructed by using 11,12‐dihydroindolo[2,3‐a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9‐phenylcarbazole and indolo[3,2,1‐JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556–563 °C), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86 %–97 %). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through‐space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited‐state energy. The organic light‐emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6 %, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12‐dihydroindolo[2,3‐a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.

High‐Efficiency Deep‐Blue Solution‐Processed Organic Light‐Emitting Diodes Using Carbazole Dendrons Modified Hybridized Local and Charge‐Transfer Emitters

In the pursuit of efficient and cost‐effective organic light‐emitting diodes (OLEDs), the development of solution‐processed hybridized local and charge transfer (HLCT) emitters presents a promising approach. HLCT materials uniquely integrate the advantages of both singlet and triplet excitons, surpassing the traditional spin statistical limit of 25% while offering high photoluminescence efficiency and balanced charge transport properties. Herein, we report the synthesis and characterization of two new deep blue, solution‐processable HLCT fluorophores, G1FTPI and G2FTPI. These compounds incorporate fluorenyl carbazole dendron units into the HLCT luminogenic triphenylamine‐phenanthroimidazole (TPI) molecule. Their HLCT and photoluminescence (PL) properties were experimentally and theoretically investigated using solvation effects and density functional theory (DFT) calculations. The molecules exhibit deep blue emission with a high solid‐state fluorescence quantum yield, good solution‐processed film‐forming quality, and high hole mobility values of 2.18 – 2.61 × 10‐6 cm2 V‐1s‐1. Both compounds were successfully employed as non‐doped emissive layers in solution‐processed OLEDs, demonstrating excellent electroluminescent (EL) performance. Notably, the G2FTPI‐based device emitted a deep blue light at 432 nm with CIE coordinates of (0.158, 0.098) and achieved a a maximum current efficiency (CEmax) of 3.13 cd A‐1 and a maximum external quantum efficiency (EQEmax) of 5.30%.

De(sulfon)amidative Cyclization: The Synthesis of Dibenzolactams and Dibenzosultams for Organic Light Emitting Diode Materials

This study addresses a challenge in organic synthetic chemistry: the direct cleavage of amide bonds, which is typically hampered by the thermodynamic stability of the C(Ar)–C(acyl) bond. Previous methods often rely on “CO” extrusion‐jointing transition metal‐catalyzed process and require activated tertiary amides, limiting their applicability due to incompatibility with reactive functional groups such as halogens. Herein, we report a transition metal‐free approach for the deamidative cyclization of biaryl diamides via a radical process, yielding dibenzolactam derivatives. Along this line, we have developed the desulfonamidative cyclization of biaryl disulfonamides to produce dibenzosultams through direct nucleophilic aromatic substitution, demonstrating high selectivity for unsymmetrical structures. Additionally, unsymmetrical sulfamoyl biaryl amides, containing both amide and sulfonamide functionalities, can selectively undergo desulfonamidative coupling with the amide to form dibenzolactams, which offers a complementary synthetic pathway to unsymmetric dibenzolactams. These protocols exhibit excellent compatibility with reactive functional groups, including halogens, providing an innovative synthetic toolbox for the development of thermally activated delayed fluorescence (TADF) materials used in organic light emitting diodes (OLEDs). DMAC‐PDO, incorporating a dibenzolactam as the acceptor unit, serves as an efficient blue TADF emitter with a maximum external quantum efficiency (EQEmax) of 23.4%.

De(sulfon)amidative Cyclization: The Synthesis of Dibenzolactams and Dibenzosultams for Organic Light Emitting Diode Materials.

This study addresses a challenge in organic synthetic chemistry: the direct cleavage of amide bonds, which is typically hampered by the thermodynamic stability of the C(Ar)-C(acyl) bond. Previous methods often rely on "CO" extrusion-jointing transition metal-catalyzed process and require activated tertiary amides, limiting their applicability due to incompatibility with reactive functional groups such as halogens. Herein, we report a transition metal-free approach for the deamidative cyclization of biaryl diamides via a radical process, yielding dibenzolactam derivatives. Along this line, we have developed the desulfonamidative cyclization of biaryl disulfonamides to produce dibenzosultams through direct nucleophilic aromatic substitution, demonstrating high selectivity for unsymmetrical structures. Additionally, unsymmetrical sulfamoyl biaryl amides, containing both amide and sulfonamide functionalities, can selectively undergo desulfonamidative coupling with the amide to form dibenzolactams, which offers a complementary synthetic pathway to unsymmetric dibenzolactams. These protocols exhibit excellent compatibility with reactive functional groups, including halogens, providing an innovative synthetic toolbox for the development of thermally activated delayed fluorescence (TADF) materials used in organic light emitting diodes (OLEDs). DMAC-PDO, incorporating a dibenzolactam as the acceptor unit, serves as an efficient blue TADF emitter with a maximum external quantum efficiency (EQEmax) of 23.4%.

Dual Sulfone-Bridged Triphenylamine Heteroaromatics for High-Performance Blue Organic Electroluminescence.

Polycyclic heteroaromatics (PHAs) are a highly versatile class of functional materials, especially applicable as efficient luminophores in organic light-emitting diodes (OLEDs). Those constructed by tethered phenyl surrounding the main group center attract extensive attention due to their excellent OLED device performance. However, the development of such a class of emitters is often limited to boron, nitrogen-doped π-conjugated heterocycles. Herein, we proposed a novel kind of blue emitter by constructing a donor-acceptor molecular configuration, utilizing a dual sulfone-bridged triphenylamine (BTPO) core and mono/di-diphenylamine (DPA) substituents. The twisted D-A molecular structures and appropriate donor strength facilitate the effective separation of natural transition orbitals, endowing the emitters with charge-transfer dominant hybridized local and charge-transfer characteristics for the excited states. Both BTPO-DPA and BTPO-2DPA own small S1-T1 splitting energy, thus demonstrating blue thermally activated delayed fluorescence. The more symmetrical structure and enhanced CT features brought by additional DPA moiety confer BTPO-2DPA with a shorter delayed fluorescence lifetime, a higher fluorescence quantum yield and narrower emission. Therefore, BTPO-2DPA based OLED devices exhibit superior blue electroluminescence performance, with external quantum efficiencies reaching 12.31 %.

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

Advanced 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.

Dimesitylborane as Electron Accepting Unit in High Performance Yellow Single-Layer Phosphorescent Organic Light Emitting Diode.

A new host material for Single-Layer Phosphorescent Organic Light-Emitting Diodes (SL-PhOLED) is reported, namely SPA-2-FDMB, using the dimesitylborane (DMB) fragment as an acceptor unit. The molecular design is constructed on the general donor-spiro-acceptor architecture, which consists of connecting, via a spiro bridge, a donor and an acceptor units in order to avoid strong interaction between them. The DMB fragment is known for many electronic applications (notably Aggregation-Induced Emission) but has not been used yet for SL-PhOLED applications. This appears particularly interesting, as the development of this simplified technology has shown that only a few electron-accepting fragments such as diphenylphosphine oxide can provide high-performance devices. Herein, the yellow-emitting SL-PhOLED using SPA-2-FDMB as host presents an External Quantum Efficiency of 8.1% (Current Efficiency of 24.9cd.A-1) with a low threshold voltage of 2.6V. As SPA-2-FDMB presents a sharp HOMO/LUMO difference, the good matching of HOMO and LUMO energy levels with the Fermi level of the electrodes is responsible for these performances. The low LUMO level of -2.61eV also appears particularly important. These performances are, to date, the highest reported for a yellow/orange-emitting SL-PhOLED and show the potential of DMB unit in the single-layer technology.

A New Organic Laser Material Design Toward Ultra-Low Amplified Spontaneous Red Emission and Ultra-Bright Electroluminescence.

Significant efforts are dedicated to developing new classes of organic semiconductor materials to achieve electrically pumped lasing. However, further advancements are necessary to understand the relationship between the structure and property for the creation of innovative laser materials with high stability, low triplet yield, ultra-low lasing threshold, and low-efficiency roll-off at ultra-bright electroluminescence. Here, a new design principle is validated for organic semiconductor laser materials, demonstrating simultaneous enhancement in the key figures of merit of low amplified spontaneous emission thresholds (Eth), efficient electroluminescence, and low triplet yields. By applying the Einstein stimulated emission rate equation and Strickler-Berg approximation, Two red-emitting laser dimers of Cibalackrot with different linkers are constructed, leading to giant enhancement (≈250%) in oscillator strengths, and stimulated emission cross-sections. When blended in poly(9,9-dioctylfluorene-alt-benzothiadiazole), the new dimers achieve an ultra-low Eth (4.5±0.3µJcm-2) in the deep red region (λASE=655nm), among the lowest reported for deep-red emitters. Organic light-emitting diodes (OLEDs) utilizing the dimer blend exhibit low-efficiency roll-off under DC mode. Under pulse operation, the OLEDs achieve high current densities (90Am-2) and ultrahigh brightness (≈710000cdm-2). These findings highlight the dimerization design as an excellent platform to advance organic semiconductor laser materials.

Conformational Modulation of Efficient Macrocyclic Emitters Featuring Delayed Fluorescence by Conjugation Length and Cavity Dimensions.

The π-conjugated macrocyclic emitters with thermally activated delayed fluorescence (TADF) characteristics have attracted widespread attention in the field of organic electroluminescence (EL) materials due to their unique geometries and excellent luminescence performance. Despite the significant impact of conjugation length and cavity dimensions on molecular conformation, the influence of these factors on the excited-state properties remains understudied. Herein, we formulated a strategy aimed at modulating the conformation of TADF macrocyclic molecules containing aniline as the donor (D) unit, and triazine as the acceptor (A), linked in D-A and D-π-A alternative macrocyclic construction (MC-TNT and MC-TST). Corroborated by experimental and theoretical analyses, the compact and conformationally twisted MC-TNT exhibits efficient blue luminescence in crystalline state, facilitating EL at high doping concentrations with maximum external quantum efficiency (EQEmax) of 13.9%, leading the field of blue macrocyclic emitters. Notably, MC-TST with π-bridge and flat conformation, demonstrates diminished Coulombic repulsion, achieving nearly 100% photoluminescence quantum yield and superior horizontal dipole orientation of 85% in 5 wt% doped films, and the corresponding device's EQEmax reaches record-high 32.7% within the TADF macrocyclic domain.