Fluorescent Organic Light-emitting Diodes Research Articles

Solid-State Fluorophores with Synergic Excited State Intramolecular Proton Transfer (ESIPT) and Aggregation-Induced Emission (AIE) Properties as Effective Non-Doped Emitters for Electroluminescent Devices

Here, we present the concept of combining excited-state intramolecular proton transfer (ESIPT) and aggregation-induced emission (AIE) features into a single molecule as a strategy to generate high-performance ESIPT-based non-doped organic light-emitting diodes (OLEDs). Two ESIPT-AIE-type green fluorophores, TBzHPI and TBzHI, are meticulously designed and synthesized by incorporating a conventional AIE moiety of triphenylethylene (TPE) with specific ESIPT cores of 2-(benzo[d]thiazol-2-yl)-6-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenol (BzHPI) and 2-(benzo[d]thiazol-2-yl)-6-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol (BzHI), respectively. The ESIPT and AIE properties are thoroughly validated through both theoretical calculations and experimental investigations. Both TBzHPI and TBzHI exhibit large Stokes shifted emissions (135-146 nm) and strong green emission of the pure keto form in the solid state owing to the collective effects of ESIPT and AIE properties in molecules. Their uses as non-doped emitters in OLEDs have been accomplished, with all devices showing strong keto-form emissions and low turn-on voltages of 2.8 V. Particularly, TBzHPI-based device demonstrates a remarkably high luminance of 54,825 cd m2, a current efficiency (CE) of 18.42 cd A-1, and an external quantum efficiency (EQE) of 5.76%, with only a slight decrease in efficiency. This finding is significant as it represents the highest EQE reported so far for ESIPT molecules used as non-doped emitters in fluorescent OLEDs.

Novel isocyanobenzene carbazole-based thermally activated delayed fluorophors towards solution-processed blue emitting OLED devices with high efficiency

Achieving efficient blue emission is an exigent challenge for the application of thermally activated delayed fluorescent organic light-emitting diodes (TADF-OLEDs). Carbazole benzonitrile-based TADF molecules exhibit promising performance in achieving the goal. Here, by replacing the cyano group in the sensitizer with the isocyano group, a 9 nm hypochromatic shift in photoluminescence spectra of the sensitizer and an enhanced efficiency of the Förster energy transfer (FET) in TADF-sensitized fluorescence (TSF) is found. By using the isocyano-based compounds as sensitizers, a maximum external quantum efficiency of 24.5% is obtained in solution-processed OLEDs, surpassing the cyano-based counterparts with similar structures. Moreover, the full width at half maximum (FWHM) of the emitter in the electroluminescence spectrum is also decreased from 47 nm to 38 nm, indicating a more complete energy transfer.

Anthracene derivatives with electron-transport units for non-doped blue fluorescent organic light-emitting diodes

Blue organic light-emitting diodes with non-doped emissive layer (EML) structures have been garnered increasing interest due to their convenience of manufacturing process. For this purpose, we designed and synthesized two novel anthracene derivatives, PO2PhAnTz and PO2PhAnBI. Both derivatives exhibited bright blue electroluminescence emission and a relatively low operating voltage with a simple bilayer device structure. The PO2PhAnBI with triphenyl-phosphine oxide moiety as host, anthracene core as dopant and benzimidazole as electron transport group, realized a balanced bipolar transport and attained a maximum external quantum efficiency of 5.74 %. The findings shed light on the molecule design role toward high-efficiency non-doped blue OLEDs.

Deuterated Multiple‐Resonance Thermally Activated Delayed Fluorescence Emitter and Their Application in Vacuum‐Deposited Organic Light‐Emitting Diodes

AbstractMultiple‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters have garnered significant attention in recent years due to their remarkable properties, such as high luminescent quantum yield, robustness, and their compliance with the Broadcast Television 2020 standard for the new generation of ultrahigh‐definition. Despite these advancements, the operational lifetimes of organic light‐emitting diodes (OLEDs) relying on MR‐TADF emitters still fall short for practical application. It is believed that the enhancement of the intrinsic molecular stability of tBu‐DABNA, a fundamental backbone of MR‐TADF emitters, holds great promise to be a universal strategy for all MR‐TADF emitters improving the operational lifetimes of OLEDs. Herein, the design and synthesis of targeted deuteration are reported on donor and/or backbone of MR‐TADF emitters, where the structure‐property relationship between intrinsic molecular stability upon isotopic effect and device operational stability are examined. The isotopic analogs show a gradual increase in the device operational stability and achieve long‐lifetime LT80 (80% of the initial luminance of 1000 cd m−2) of 24.3 h for TADF‐sensitized fluorescence OLED, representing a sevenfold enhancement when compared with the undeuterated counterpart. This strategic deuteration approach underlines the importance of structural modification on materials toward device operational stability.

Quantitative Analysis of Exciton Dynamics: Investigating the Role of the Efficiency-Enhancement Layer for Blue Fluorescent Organic Light-Emitting Diodes

Quantitative Analysis of Exciton Dynamics: Investigating the Role of the Efficiency-Enhancement Layer for Blue Fluorescent Organic Light-Emitting Diodes

Selective Enhancement of Viewing Angle Characteristics and Light Extraction Efficiency of Blue Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes through an Easily Tailorable Si3N4 Nanofiber Structure.

We selectively improved the viewing angle characteristics and light extraction efficiency of blue thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) by tailoring a nanofiber-shaped Si3N4 layer, which was used as an internal scattering layer. The diameter of the polymer nanofibers changed according to the mass ratio of polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) in the polymer solution for electrospinning. The Si3N4 nanofiber (SNF) structure was fabricated by etching an Si3N4 film using the PAN/PMMA nanofiber as a mask, making it easier to adjust parameters, such as the diameter, open ratio, and height, even though the SNF structure was randomly shaped. The SNF structures exhibited lower transmittance and higher haze with increasing diameter, showing little correlation with their height. However, all the structures demonstrated a total transmittance of over 80%. Finally, by applying the SNF structures to the blue TADF OLEDs, the external quantum efficiency was increased by 15.6%. In addition, the current and power efficiencies were enhanced by 23.0% and 25.6%, respectively. The internal light-extracting SNF structure also exhibited a synergistic effect with the external light-extracting structure. Furthermore, when the viewing angle changed from 0° to 60°, the peak wavelength and CIE coordinate shift decreased from 20 to 6 nm and from 0.0561 to 0.0243, respectively. These trends were explained by the application of Snell's law to the light path and were ultimately validated through finite-difference time-domain simulations.

Deep Learning Prediction of Triplet-Triplet Annihilation Parameters in Blue Fluorescent Organic Light-Emitting Diodes.

The triplet-triplet annihilation (TTA) ratio and the rate coefficient (kTT) of TTA are key factors in estimating the contribution of triplet excitons to radiative singlet excitons in fluorescent TTA organic light-emitting diodes. In this study, deep learning models are implemented to predict key factors from transient electroluminescence (trEL) data using new numerical equations. A new TTA model is developed that considers both polaron and exciton dynamics, enabling the distinction between prompt and delayed singlet decays with a fundamental understanding of the mechanism. In addition, deep learning models for predicting the kinetic coefficients and TTA ratio are established. After comprehensive optimization inspired by photophysics, determination coefficient values of 0.992 and 0.999 are achieved in the prediction of kTT and TTA ratio, respectively, indicating a nearly perfect prediction. The contribution of each kinetic parameter of polaron and exciton dynamics to the trEL curve is discussed using various deep-learning models.

Acceptor-σ-donor-σ-acceptor host material for red phosphorescent and thermally activated delayed fluorescent OLEDs

A novel bipolar host molecule di-spiro [fluorene-9,5′-quinolino [3,2,1-de] acridine-9′,9″-fluorene]-2,2″,7,7″-tetracarbonitrile (QACN) featuring an Acceptor-σ-Donor-σ-Acceptor structure was developed. Systematic investigations into its photophysical, electrochemical, and thermal properties unveiled exceptional thermal stability, a three-dimensional spatial configuration, and bipolar carrier transport capability. Employing QACN as the host material in red phosphorescent and thermally activated delayed fluorescent (TADF) organic light-emitting diodes (OLEDs) yielded a maximum external quantum efficiency of 25.3 % and 16.5 %, respectively. Compared with the commercial material TPBi (EQE = 12.0 %, λEL = 668 nm) and mCP (EQE = 14.5 %, λEL = 652 nm), the TADF OLEDs based on QACN achieved a higher EQE and a large red-shift emission (EQE = 16.5 %, λEL = 694 nm). These findings underscore the potential of QACN as an effective host material for red phosphorescent and TADF emitters and provide a new auxiliary finesse for realizing deep red and near-infrared (NIR) OLEDs.

High Efficiency Triplet‐Triplet Fusion Blue Fluorescence OLEDs by introducing a “Hot Exciton” Efficiency Enhancement Layer

AbstractTriplet‐triplet fusion (TTF) can effectively transfer triplet excitons to singlet energy level and exhibit good stability, making it widely used in blue fluorescence organic light emitting diodes (OLEDs) for practical application. However, the efficiency of the resulting blue fluorescence OLEDs is still fundamentally limited. Herein, this work introduces a hot exciton efficiency enhancement layer (EEL) between TTF emissive layer and electron‐transporting layer for the first time. It can be found that the triplet excitons are greatly utilized by the efficient hot exciton EEL. As a result, a high efficiency blue fluorescence OLED is successfully developed, exhibiting a maximum external quantum efficiency of 15.2% at the luminance of 4068.0 cd m−2, achieving a breakthrough in the efficiency of blue TTF‐OLEDs. Transient electroluminescence (TrEL) measurements and detailed theoretical calculations confirm the key role of the effective hot exciton process from the high‐lying triplet energy level (Tn, n ≥ 2) to S1 via a reverse intersystem crossing (hRISC). Furthermore, the device lifetime is also greatly improved owing to the fast and efficient hRISC in the introduced hot exciton EEL. This work has important guiding significance for constructing high efficiency blue fluorescence OLEDs by introducing hot exciton molecules.

Over 30% external quantum efficiency for doping-free D-A-type thermally activated delayed fluorescence organic light-emitting diodes

The application of doping-free emitting layers in organic light-emitting diodes (OLEDs) device fabrication has attracted extensive attention due to the simplified process and the low cost. Meanwhile, the application of interfacially doping layer (or ultrathin emissive layer, UEML) with a thickness below 1 nm showed great potential in achieving high device efficiency by reducing the aggregation-caused quenching (ACQ) effect, which was usually observed in neat film and highly doped dopant-host system. This work developed a simple molecular design strategy via peripheral decoration of TADF emissive core with multiple shielding groups (t-butyl and aryl units) to effectively alleviate the intermolecular interaction and the ACQ effect. The resulting OLEDs based on BIPH-TPA exhibited a record-setting external quantum efficiency (EQE) of 15.8 % at 640 nm with a conventional doping-free configuration (25 nm). Furthermore, the ultrathin doping-free (0.2 nm) OLEDs based on NA-TPA achieved unprecedented EQE of 33.1 % at 620 nm. The outstanding EL performance clearly demonstrated promising potential of this molecular design strategy for the exploration of doping-free OLEDs.

Highly efficient fluorescent and hybrid white organic light-emitting diodes based on a bimolecular excited system: publisher's note.

This publisher's note contains a correction to Opt. Lett.48, 5771 (2023)10.1364/OL.506371.

Effective exciplex host for solution-processed narrowband blue TADF-OLEDs using a 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole analogue with an adamantane substituent

Implementing an exciplex host system in the emitting layer is crucial for achieving highly efficient thermally activated delayed fluorescence (TADF) and phosphorescent organic light-emitting diodes (OLEDs). In this study, we successfully designed and synthesized 3-((3r,5r,7r)-adamantan-1-yl)-9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (AdCz-DBT) and 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (Cz-DBT) as p-type hosts for the exciplex host implementation, and 7-(4-(tert-butyl)phenyl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene (tPDBA) as an n-type host. The AdCz-DBT host incorporates a large and robust adamantane group into Cz-DBT, increasing molecular weight, film-forming properties and thermal stability. Additionally, AdCz-DBT maintains energy levels and photophysical properties similar to those of adamantane-free Cz-DBT. Efficient exciplex emission was observed in the blend film due to well-matched energy levels of the synthesized p- and n-type hosts. The introduction of adamantane into Cz-DBT did not hinder exciplex formation, resulting in a relatively high photoluminescence quantum yield and improved charge balance in the mixed host with tPDBA.Ultimately, the solution-processed blue TADF-OLED with the AdCz-DBT:tPDBA blend host demonstrated a relatively high external quantum efficiency of 8.00% and a long operational lifetime, exhibiting excellent performance compared to devices using the Cz-DBT:tPDBA blend host.

Strategic Insertion of Heavy Atom to Tailor TADF OLED Material for the Development of Type I Photosensitizing Catalytic Red Emissive Assemblies.

The work presented in the manuscript describes a simple strategy for transforming thermally activated delayed fluorescent organic light-emitting diodes (TADF OLEDs) compound 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenoxazine (DPZ-PXZ) into type I photosensitizer 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenothiazine (DPZ-PHZ) by strategically introducing sulfur atom in the photosensitizing core. The synthesized compound DPZ-PHZ exhibits aggregation-induced enhancement (AIE) and through-space charge transfer (TSCT) characteristics and generates red emissive assemblies in mixed aqueous media. The original compound DPZ-PXZ exhibits well-separated HOMO and LUMO levels and is reported to have highly efficient reverse intersystem crossing (RISC). In comparison, the incorporation of sulfur atom in the phenothiazine donor regulates the electronic communication between donor and acceptor units and promotes the intersystem crossing (ISC) in DPZ-PHZ molecules. Interestingly, compound DPZ-PHZ exhibits rapid activation of aerial oxygen for instant generation of superoxide radical anion. Backed by excellent type I photosensitizing activity, DPZ-PHZ assemblies have high catalytic potential for the synthesis of benzimidazoles, benzothiazoles and quinazolines derivatives under mild reaction conditions. The work presented in the manuscript provides an insight into the combination of heavy atom approach and TSCT for achieving adequate electronic communication between donor and acceptor units, balanced RISC/ISC, and stabilized-charge separated state for the development of efficient type I photosensitizing assemblies.

High-Efficiency and Narrowband Green Thermally Activated Delayed Fluorescence Organic Light-Emitting Diodes Based on Two Diverse Boron Multi-Resonant Skeletons.

Up to now, highly efficient narrowband thermally activated delayed fluorescence (TADF) molecules constructed by oxygen-bridged boron with an enhancing multiple resonance (MR) effect have been in urgent demand for solid-state lighting and full-color displays. In this work, a novel MR-TADF molecule, BNBO, constructed by the oxygen-bridged boron unit and boron-nitrogen core skeleton as an electron-donating moiety, is successfully designed and synthesized via a facile one-step synthesis. Based on BNBO as an efficient green emitter, the organic light-emitting diode (OLED) shows a sharp emission peak of 508 nm with a full-width at half-maximum (FWHM) of 36 nm and realizes quite high peak efficiency values, including an external quantum efficiency (EQEmax) of 24.3% and a power efficiency (PEmax) of 62.3 lm/W. BNBO possesses the intramolecular charge transfer (ICT) property of donor-acceptor (D-A) materials and multiple resonance characteristics, which provide a simple strategy for narrowband oxygen-boron materials.

Efficient Near‐Infrared Organic Light‐Emitting Diodes with Emission Peak Above 900 nm Enabled by Enhanced Photoluminescence Quantum Yields and Out‐Coupling Efficiencies

AbstractNear‐infrared organic light‐emitting diodes (NIR OLEDs) with emission peak above 900 nm are attractive for many emerging applications, spanning from bioimaging to light detection and ranging. However, the device performance of NIR OLEDs is generally limited by the low quantum efficiency of emitters because of the fast nonradiative transition process imposed by energy‐gap law and aggregation quenching. So far, only a few Pt(II) complexes delivering external quantum efficiency (EQE) over 1% are reported, while there is no comparable electroluminescence in heavy‐metal‐free fluorescent organic emitters. Here, NIR OLEDs centered at 934 nm by blending an acceptor–donor–acceptor type molecule Y11 into a polymer host poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐(4,4′‐(N‐(4‐sec‐butylphenyl)diphenylamine) (TFB) are reported. The OLEDs show a remarkably high EQE of 1.72%. Moreover, owing to a low turn‐on voltage (≈0.9 V), the resultant NIR OLEDs have an electricity‐to‐light power efficiency surpassing 20 mW W−1. The improved device performance can be attributed to enhanced photoluminescence quantum yields (PLQYs) of the blends owing to suppressed aggregation quenching, and favorable light extraction from the emissive layer. Such values are the highest among fluorescent OLEDs with electroluminescence above 900 nm.

Bicarbazole-Benzophenone-Based Twisted Donor-Acceptor-Donor Derivatives as Blue Emitters for Highly Efficient Fluorescent Organic Light-Emitting Diodes.

This paper delves into the development of a group of twisted donor-acceptor-donor (D-A-D) derivatives incorporating bicarbazole as electron donor and benzophenone as electron acceptor for potential use as blue emitters in OLEDs. The derivatives were synthesized in a reaction of 4,4'-difluorobenzophenone with various 9-alkyl-9'H-3,3'-bicarbazoles. The materials, namely, DB14, DB23, and DB29, were designed with different alkyl side chains to enhance their solubility and film-forming properties of layers formed using the spin-coating from solution method. The new materials demonstrate high thermal stabilities with decomposition temperatures >383 °C, glass transition temperatures in the range of 95-145 °C, high blue photoluminescence quantum yields (>52%), and short decay times, which range in nanoseconds. Due to their characteristics, the derivatives were used as blue emitters in OLED devices. Some of the OLEDs incorporating the DB23 emitter demonstrated a high external quantum efficiency (EQEmax) of 5.3%, which is very similar to the theoretical limit of the first-generation devices.

Robust luminogens as cutting-edge tools for efficient light emission in recent decades.

Blue luminogens play a vital role in white lighting and potential metal-free fluorescent materials and their high-lying excited states contribute to harvesting triplet excitons in devices. However, in TADF-OLEDs (ΔEST < 0.1 eV), although T1 excitons transfer to S1via RISC with 100% IQE, the longer lifetime of blue TADF suffers from efficiency roll-off (RO). In this case, hybridized local and charge transfer (HLCT) materials have attracted significant interest in lighting owing to their 100% hot exciton harvesting and enhanced efficiency. Both academics and industrialists widely use the HLCT strategy to improve the efficiency of fluorescent organic light-emitting diodes (FOLEDs) by harvesting dark triplet excitons through the RISC process. Aggregation-induced emissive materials (AIEgens) possess tight packing in the aggregation state, and twisted AIEgens with HLCT behaviour have a shortened conjugation length, inducing blue emission and making them suitable candidates for OLED applications. TTA-OLEDs are used in commercial BOLEDs because of their moderate efficiency and reasonable operation lifetime. In this review, we discuss the devices based on TTA fluorophores, TADF fluorophores, HLCT fluorophores, AIEgens and HLCT-sensitized fluorophores (HLCT-SF), which break through the statistical limitations.

Achieving efficient and stable blue thermally activated delayed fluorescence organic light-emitting diodes based on four-coordinate fluoroboron emitters by simple substitution molecular engineering.

Achieving both high efficiency and high stability in blue thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs) is challenging for practical displays and lighting. Here, we have successfully developed a series of sky-blue to pure-blue emitting donor-acceptor (D-A) type TADF materials featuring a four-coordinated boron with 2,2'-(pyridine-2,6-diyl)diphenolate (dppy) ligands, i.e.1-8. Synergistic engineering of substituents on the phenyl bridge as well as the electronic properties and the attached positions of heteroatom N-donors not only enables fine-tuning of the emission colors, but also modulates the nature and energies of their triplet excited states that are important for the reverse intersystem crossing (RISC). Particularly for the compound with two methyl substituents on the phenyl bridge (compound 8), RISC is significantly facilitated through the vibronic coupling of the energetically close-lying triplet charge transfer (3CT) and the triplet local excited (3LE) states, when compared to analogue 7. Efficient sky-blue to pure-blue OLEDs with electroluminescence peaks (λ EL) at 460-492 nm have been obtained, in which ca. five-fold higher external quantum efficiencies (EQEs) of 18.9% have been demonstrated by 8 than that by 7. Moreover, ca. thirty times longer device operational half-lifetimes (LT50) of 9113 hours for 8 than that for 7 as well as satisfactory LT50 reaching 26 643 hours for 6 at an initial luminance of 100 cd m-2 have also been demonstrated. To the best of our knowledge, these results represent one of the best high-performance blue OLEDs based on tetracoordinated boron TADF emitters. Moreover, the design strategy presented here has provided an attractive strategy for enhancing the device performance of blue TADF-OLEDs.

Highly efficient deep-red to near-infrared thermally activated delayed fluorescence organic light-emitting diodes using a 2,3-bis(4-cyanophenyl)quinoxaline-6,7-dicarbonitrile acceptor

The demand for deep-red (DR) or near-infrared (NIR) emitters has grown markedly owing to their essential roles in optical telecommunications, night vision-technologies, flat panel displays, bioimaging, photodynamic therapy, and sensors,...

Utilization of newly configured carbazole-cyanopyridone structural hybrids towards achieving high-performance cyan fluorescent organic light-emitting diodes

The study focuses on the novel D–A–D (donor–acceptor–donor) type cyanopyridone-based materials for cyan organic light-emitting diodes.