Blue Phosphorescent Organic Light-emitting Diodes Research Articles

Interfacial Exciton-Polaron Quenching in Organic Light-Emitting Diodes

In organic light-emitting diodes (OLEDs), understanding the efficiency loss mechanism known as exciton-polaron quenching (EPQ) has been a longstanding challenge. Traditionally, EPQ was believed to occur mainly the bulk of the OLED emission layer (EML) due to the coexistence of polarons and excitons, limiting our understanding of its full impact. Here, we report a previously overlooked phenomenon termed “interfacial EPQ (Inf. EPQ),” which occurs at the heterointerface between the EML and the adjacent charge transport layer (CTL). We observe the transfer of EML excitons to CTL polarons across this interface, spanning distances of up to 4 nm. Notably, Inf. EPQ exceeds EPQ within the EML bulk, even in devices with a interfacial energy barrier (>0.2 eV). We propose a methodology that enables independent probing of Inf. EPQ, systematic validation of its essential parameters, and the identification of Dexter energy transfer as its governing mechanism. Importantly, our findings highlight Inf. EPQ as a phenomenon across devices with various luminescent mechanisms, wavelengths, and injection levels. By effectively addressing Inf. EPQ, we achieve efficiency enhancements in red, green, and blue phosphorescent OLEDs, by 70%±8%, 47%±5%, and 66%±6%, respectively. Our work advances the physical understanding of exciton and polaron dynamics at organic heterointerfaces, providing applicable solutions to Inf. EPQ-related issues in practical devices. Published by the American Physical Society 2024

Enhanced Emitting Dipole Orientation Based on Asymmetric Iridium(III) Complexes for Efficient Saturated-Blue Phosphorescent OLEDs.

Three novel asymmetric Ir(III) complexes have been rationally designed to optimize their emitting dipole orientations (EDO) and enhance light outcoupling in blue phosphorescent organic light-emitting diodes (OLEDs), thereby boosting their external quantum efficiency (EQE). Bulky electron-donating groups (EDGs), namely: carbazole (Cz), di-tert-butyl carbazole (tBuCz), and phenoxazine (Pxz) are incorporated into the tridentate dicarbene pincer chelate to induce high degree of packing anisotropy, simultaneously enhancing their photophysical properties. Angle-dependent photoluminescence (ADPL) measurements indicate increased horizontal transition dipole ratios of 0.89 and 0.90 for the Ir(III) complexes Cz-dfppy-CN and tBuCz-dfppy-CN, respectively. Analysis of the single crystal structure and density functional theory (DFT) calculation results revealed an inherent correlation between molecular aspect ratio and EDO. Utilizing the newly obtained emitters, the blue OLED devices demonstrated exceptional performance, achieving a maximum EQE of 30.7% at a Commission International de l'Eclairage (CIE) coordinate of (0.140, 0.148). Optical transfer matrix-based simulations confirmed a maximum outcoupling efficiency of 35% due to improved EDO. Finally, the tandem OLED and hyper-OLED devices exhibited a maximumEQE of 44.2% and 31.6%, respectively, together with good device stability. This rational molecular design provides straightforward guidelines to reach highly efficient and stable saturated blue emission.

Unveiling the ligand effects on Pt(Ⅱ) carbene complexes for rapid, efficient and narrow-spectra blue phosphorescence

Tetradentate Pt(II) complexes, comprising of benzoimidazolyl N-heterocyclic carbene (BI-NHC) coordination, have shown superior performance in blue phosphorescent organic light-emitting diodes (PhOLEDs). Here, four frame-structured complexes were synthesized to explore the intrinsic ligand effect for rapid, efficient and narrow-spectra blue phosphorescence through experimental analyses and theoretical calculations. We found carbazolylpridine (CzPy) chelating part in Pt(II) BI-NHC complexes dominates the phosphorescence with the suppression of metal-centered transition and electron-vibration coupling. Consequently, the CzPy chelated complexes (PtN-dip and PtN-dtb) achieved high luminescent efficiency, rapid radiative decay rate (kr) and narrow emission spectra. The peripheral substituent 2,6-di-iso-propylphenyl (dip) on NHC of PtN-dip constrains the molecule, significantly reducing the non-radiative decay rate (knr) and enhancing the efficiency. The 3,5-di-tert-butylphenyl (dtb) in PtN-dtb could enhances low-frequency vibration coupling that could expedite the excitons decay, resulting in higher kr and knr. This work unveils the intrinsic factors behind the ligand effects of Pt(II) BI-NHC based complexes, leading to a rapid, efficient and narrow-spectra phosphorescence.

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.

Narrow-emitting pyridoimidazole functionalized N-heterocyclic carbene based tetradentate Pt(II) complexes for blue phosphorescent organic light-emitting diodes

Two novel classes of N-heterocyclic carbene (NHC) based tetradentate Pt(II) complexes possessing bulky benzyl groups and pyridoimidazole ligands were designed and synthesized to produce efficient blue phosphorescent organic light-emitting diodes (PHOLEDs). Two blue Pt(II) complexes are reported, namely, platinum (II) [2-(3-(1-(4-(tert-butyl)benzyl)-1H-imidazo [4,5-b]pyridin-3(2H)-yl)phenoxy)-9-(pyridin-2-yl)-9H-carbazole] (Pt(t-BuBnOCzPy)) and platinum (II) [3-(3-(1-benzyl-1H-imidazo [4,5-b]pyridin-3(2H)-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole] (Pt(BnOCz4t-BuPy)), respectively. Notably, pyridoimidazole and bulky benzyl groups efficiently reduced steric hindrance, vibrational peaks, and intermolecular interactions. The photophysical and electrochemical properties of the two Pt(II) complexes were analytically examined experimentally and theoretically. The complexes exhibited blue electroluminescence (EL) emission at 466 nm with a small full-width half maximum (FWHM) of 26 nm and completely suppressed vibrational emission peaks. Blue PHOLEDs, at 5 wt% Pt(t-BuBnOCzPy) and Pt(BnOCz4t-BuPy) doping ratios exhibited maximum external quantum efficiencies (EQEmax) of 19 and 18.6 %, maximum power efficiencies (PEmax) of 25.5 and 24.9 cd m−2, and maximum current efficiencies (CEmax) of 24.3 and 24.3 cd m−2 with Commission International de I'Eclairage (CIEx,y) color coordinates of (0.13, 0.17) and (0.13, 0.17), respectively. These superior results suggest that the designed benzylated NHC pyridoimidazole tetradentate Pt(II) complexes provide a novel means of reducing steric hindrance and intermolecular interactions.

Operando analysis for understanding the parasite exciton dynamics in blue phosphorescent OLEDs using electrically pumped spectroscopy

Operando analysis for understanding the parasite exciton dynamics in blue phosphorescent OLEDs using electrically pumped spectroscopy

Dye-based nanoarchitectonics for the effective bandgap and stability of blue phosphorescent organic light-emitting diodes

Dye-based nanoarchitectonics for the effective bandgap and stability of blue phosphorescent organic light-emitting diodes

Synthesis and characterization of a novel thermally stable silane-based host material for blue phosphorescent organic light-emitting diodes

We report a novel thermally stable host material, namely, bis[3-(2-indolo[3,2,1-jk]carbazolyl)phenyl)diphenylsilane (Si-IDCz), for use in blue phosphorescent organic light-emitting diodes (PhOLEDs). Here, Si-IDCz exhibits a high glass transition temperature (Tg) of 151 °C as it contains a thermally stable silane moiety. Additionally, the rigid silicon core within Si-IDCz effectively suppresses molecular interactions, resulting in a wide bandgap and high triplet energy. Here, we used Si-IDCz as the single host for the blue PhOLEDs. The blue PhOLED with the single-host Si-IDCz exhibited an external quantum efficiency (EQE) of over 15%; an EQE of over 11% was maintained at a high luminance of 5000 cd/m2 owing to the high thermal stability of the Si-IDCz. Furthermore, an improved EQE of more than 20% was achieved by introducing a mixed-host system to enhance the photoluminescence quantum yield; the efficiency roll-off was reduced as well.

Highly Efficient Ultra-Thin EML Blue PHOLEDs with an External Light-Extraction Diffuser.

In this study, various diffusers are applied to highly efficient ultra-thin emission layer (EML) structure-based blue phosphorescent organic light-emitting diodes (PHOLEDs) to improve the electroluminescence (EL) characteristics and viewing angle. To achieve highly efficient blue PHOLEDs, the EL characteristics of ultra-thin EML PHOLEDs with the various diffusers having different structures of pattern-shape (hemisphere/sphere), size (4~75 μm), distribution (surface/embedded), and packing (close-packed/random) were systematically analyzed. The diffusers showed different enhancements in the overall EL characteristics of efficiencies, viewing angle, and others. The EL characteristics showed apparent dependency on their structure. The external quantum efficiency (EQE) was enhanced mainly by following the orders of pattern, size, and shape. Following the pattern size, the EQE enhancement gradually increased; the largest-sized diffuser with a 75 μm closed-packed hemisphere (diffuser-1) showed a 1.47-fold EQE improvement, which was the highest. Meanwhile, the diffuser with a ~7 μm random embedded sphere with a low density (diffuser 5) showed the lowest 1.02-fold-improved EQE. The reference device with ultra-thin EML structure-based blue PHOLEDs showed a maximum EQE of 16.6%, and the device with diffuser 1 achieved a maximum EQE of 24.3% with a 5.1% wider viewing angle compared to the reference device without a diffuser. For the in-depth analysis, the viewing angle profile of the ultra-thin EML PHOLED device and fluorescent green OLEDs were compared. As a result, the efficiency enhancement characteristics of the diffusers show a difference in the viewing angle profile. Finally, the application of the diffuser successfully demonstrated that the EL efficiency and viewing angle could be selectively improved. Additionally, we found that it was possible to realize a wide viewing angle and achieve considerable EQE enhancement by further investigations using high-density and large-sized embedded structures of light-extraction film.

1,2,4-Triazole-Ligand-based Iridium(III) complex and its use in blue phosphorescent organic light-emitting diodes

Organic light-emitting diodes (OLEDs) play a key role in modern flexible displays. Although stable and efficient red- and green-emitting phosphors have been developed, the applications of blue emitters are limited due to their poor chemical and electrochemical stability, and thus, they require further development. Herein, we report the preparation and full characterization of IrTrz, a 3-methyl-5-phenyl-1H-1,2,4-triazole-ligand-based facial-homoleptic iridium complex. Single-crystal X-ray diffractometry results suggested that the complex is a facial isomer with C3 point symmetry. The complex exhibited a blue emission band centered at ∼450 nm in both solution and the film state at ambient temperature; moreover, it showed a very narrow full-width at half maximum value (55 nm) and a moderate photoluminescence quantum yield (33%). The complex showed high thermal stability, with 5%-weight-loss and glass-transition temperatures of 324 and 210 °C, respectively. Consecutive cyclic voltammetry measurements revealed outstanding electrochemical stability of the complex. Therefore, multilayer phosphorescent OLEDs that use IrTrz as the blue emitter were fabricated with two types of host material: (3,3′-di(9H-carbazol-9-yl)-1,1′-biphenyl (mCBP) and 9-(dibenzo[b,d]thiophen-4-yl)-9H-3,9′-bicarbazole (4DBTCz)). In particular, the 4DBTCz-based devices exhibited low turn-on voltages (∼5.0 V) and high external quantum efficiencies (>11%) with a Commission Internationale de l’Eclairage y-coordinate of 0.2. Moreover, the devices demonstrated stable operational lifetimes that exceeded 690 h (for mCBP) and 390 h (for 4DBTCz) at 100 cd/m2. Therefore, we believe that the 1,2,4-triazole-ligand-based Ir(III) complex is a promising blue-phosphorescent emitter material for applications in stable and efficient OLED devices.

A symmetrical carbazole/benzonitrile-based high triplet energy bipolar host designed by a para-linkage strategy for efficient blue and green phosphorescent organic light-emitting diodes

Based on a para-linkage concept, a symmetrical carbazole-benzonitrile derivative of 4-(9H-carbazol-9-yl)-3,5-diphenyl-2,6-difluoronitrile (CzPhFBN) was designed and prepared as a host for phosphorescent organic light-emitting diodes (PhOLEDs). In the CzPhFBN molecular, a cyano (CN) unit and a carbazole (Cz) unit were attached to the central phenyl ring at the para positions. Simultaneously, the Cz group was surrounded by two phenyl units to increase structure distortion for high triplet energy and CN unit was surrounded by two F units to improve electron transporting behavior. The photophysical properties and carrier transport behavior of CzPhFBN were investigated. The results demonstrated that CzPhFBN offered a high triplet energy of exceeding 3.0 eV and bipolar carrier transporting property. By incorporating CzPhFBN as the host, the blue FIrpic- and green Ir(ppy)3-based PhOLEDs with a common device configuration delivered the maximum efficiencies of 11.1%/19.7 cd A−1/12.1 lm W−1 and/13.1%/43.6 cd A−1/28.6 lm W−1, respectively. These results indicate that this study provides a potential design strategy of high triplet energy bipolar host materials with a simple and elegant structure.

Asymmetric Decoration of a meta-Linked Bitriazine-Based Host for Highly Efficient and Stable Blue Phosphorescent Organic Light-Emitting Diodes

High triplet energy hosts for blue phosphorescent organic light-emitting diodes were developed by decorating a meta-linked bitriazine core with carbazole and tetraphenylsilyl functional groups. A symmetric host with two carbazole units as the two triazine units of the core and an asymmetric host with one carbazole unit and one tetraphenylsilyl unit as the two triazine units were prepared. The triplet energy of these two hosts was 2.97 eV, suitable for triplet exciton harvesting of blue phosphors. Comparing the two host designs, the asymmetric decoration of the two triazine units with carbazole and tetraphenylsilyl units was superior to the symmetric decoration of the two triazine units with two carbazoles in terms of high external quantum efficiency (EQE) and long-term device stability. A high EQE of 19.7% and a long device lifetime of 2093.6 h at 100 cd m-2 were achieved using the asymmetrical host.

Steric modulation of thermally activated delayed fluorescence-type host for high quantum efficiency in blue phosphorescent organic light-emitting diodes

In organic light-emitting diodes (OLEDs), host engineering is important in improving the device performance. however, it remains as a big challenge in blue phosphorescent OLEDs because of the high triplet energy of blue phosphors. In this work, we develop a sterically modulated thermally activated delayed fluorescence-type host based on an ortho-linked carbazole–triazine backbone structure. An additional π-spacer spatially twisting the two moieties delivers a short delayed decay time of 5.0 μs without any loss of the photoluminescence quantum yield while realizing high triplet and small singlet-triplet energy splitting. The photophysical modulation enables a more efficient utilization of the triplet excitons of the two blue phosphorescent emitters in OLEDs. The fabricated blue phosphorescent OLEDs exhibit a significantly improved device performance in all efficiency parameters compared to reference devices with a maximum external quantum efficiency of 23.6%. This work demonstrates a simple and powerful thermally activated delayed fluorescence host design strategy to realize high efficiency blue-phosphorescence OLEDs.

Carbazole-benzonitrile derivatives as universal hosts for triplet-harvesting blue organic light-emitting diodes

In this study, we proposed two carbazole-benzonitrile-based bipolar hosts, namely 2,6-bis(3-(9H-carbazol-9-yl)phenoxy)benzonitrile and 2,6-bis(4-(9H-carbazol-9-yl)phenoxy)benzonitrile, for improving the efficiency of blue phosphorescent organic light-emitting diodes.

Highly Efficient Solution-Processed Blue Phosphorescent Organic Light-Emitting Diodes Based on Co-Dopant and Co-Host System.

The low-lying HOMO level of the blue emitter and the interfacial miscibility of organic materials result in inferior hole injection, and long exciton lifetime leads to triplet-triplet annihilation (TTA) and triplet-polaron annihilation (TPA), so the efficiencies of blue phosphorescent organic light-emitting diodes (PhOLEDs) are still unsatisfactory. Herein, we design co-host and co-dopant structures to improve the efficiency of blue PhOLEDs by means of solution processing. TcTa acts as hole transport ladder due to its high-lying HOMO level, and bipolar mCPPO1 helps to balance carriers’ distribution and weaken TPA. Besides the efficient FIr6, which acts as the dominant blue dopant, FCNIrPic was introduced as the second dopant, whose higher HOMO level accelerates hole injection and high triplet energy facilitates energy transfer. An interesting phenomenon caused by microcavity effect between anode and cathode was observed. With increasing thickness of ETL, peak position of electroluminescence (EL) spectrum red shifts gradually. Once the thickness of ETL exceeded 140 nm, emission peak blue-shifts went back to its original position. Finally, the maximum current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE) of blue phosphorescent organic light-emitting diode (PhOLED) went up to 20.47 cd/A, 11.96 lm/W, and 11.62%, respectively.

Blue phosphorescent platinum(II) complexes based on tetradentate ligand with rigid and highly distorted linkage for efficient organic light-emitting diodes

Blue phosphorescent Pt(II) complexes comprising two C^N chelates, namely, 2,3′-bipyridine that are connected by a rigid linker, were designed and synthesized. In order to examine the effects of substitution of C^N ligands on the intermolecular interactions in solid-state, optical properties and electroluminescence, the electron withdrawing atom (F) or electron donor group (methoxy unit) as the substituents were introduced into the C-coordinated pyridine ring. The molecular structures of both complexes were confirmed by single crystal X-ray diffraction analysis. The coordination sphere of the Pt(II) cation in both complexes displayed a highly distorted square-planar geometry. The fluorine substituted Pt(II) compound (1) exhibited bright blue emission with λmax = 458 nm, whereas the red-shifted bluish-green emissions with λmax = 482 nm are observed in the methoxy-functionalized Pt(II) compound (2). The time-dependent density-functional theory (TD-DFT) calculations suggest that the electronic transition for both complexes arise from intraligand charge transfer (ILCT) (πbpy−π*bpy) mixed with metal-to-ligand charge transfer (MLCT) (Ptd−π*bpy) in the absence of contribution from the phenyl linker. Thus, multi-layered blue phosphorescent organic light-emitting diodes (PHOLEDs) were successfully fabricated using both Pt(II) compounds as the dopants. The PHOLEDs at 10% doping level displayed bright sky-blue emission with an external quantum efficiency of approximately 7.8–8.0% at 100 cd/m2.

Pure Hydrocarbon Materials as Highly Efficient Host for White Phosphorescent Organic Light-Emitting Diodes: A New Molecular Design Approach.

To date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high‐performance white and blue PhOLEDs. With EQE of 27.7 %, the PHC‐based white PhOLEDs display similar efficiency as the best reported with heteroatom‐based hosts. Incorporated as a host in a blue PhOLED, which are still the weakest links of the technology, a very high EQE of 25.6 % is reached, surpassing, for the first time, the barrier of 25 % for a PHC and FIrpic blue emitter. This performance shows that the PHC strategy represents an effective alternative for the future development of the OLED industry.

Pure Hydrocarbon Materials as Highly Efficient Host for White Phosphorescent Organic Light‐Emitting Diodes: A New Molecular Design Approach

AbstractTo date, all efficient host materials reported for phosphorescent OLEDs (PhOLEDs) are constructed with heteroatoms, which have a crucial role in the device performance. However, it has been shown in recent years that the heteroatoms not only increase the design complexity but can also be involved in the instability of the PhOLED, which is nowadays the most important obstacle to overcome. Herein, we design pure aromatic hydrocarbon materials (PHC) as very efficient hosts in high‐performance white and blue PhOLEDs. With EQE of 27.7 %, the PHC‐based white PhOLEDs display similar efficiency as the best reported with heteroatom‐based hosts. Incorporated as a host in a blue PhOLED, which are still the weakest links of the technology, a very high EQE of 25.6 % is reached, surpassing, for the first time, the barrier of 25 % for a PHC and FIrpic blue emitter. This performance shows that the PHC strategy represents an effective alternative for the future development of the OLED industry.

More than 25,000 h device lifetime in blue phosphorescent organic light-emitting diodes via fast triplet up-conversion of n-type hosts with sub μs triplet exciton lifetime

Understanding and retardation of materials degradation phenomena in blue phosphorescent organic-light emitting diodes (PhOLEDs) are crucial to replace a fluorescent device with an efficient phosphorescent device in practical applications. Among the organic functional materials in the blue PhOLEDs, the host in the emitting layer is the most populated and fragile region in view of its density of states since singlet, triplet excitons, and polarons are continuously accumulated and consumed during operation. In this work, we presented novel n-type hosts which have thermally activated delayed fluorescence (TADF) features without loss of triplet energy even in the p-n mixed host structure. Both high triplet energy of mixed host and triplet up-conversion of a new n-type host within sub μs range allowed to demonstrate highly efficient and operationally stable blue PhOLEDs. Introducing 3,3-di(9H-carbazol-9-yl)biphenyl and 3-[bis(9H-carbazol-9-yl)-1,3,5-triazin-2-yl]-5-(triphenylsilyl)benzonitrile as a mixed host, blue PhOLEDs exhibited maximum external quantum efficiency of 20.9%, color coordinate of (0.16, 0.29), and device lifetime of 13,573 h at 100 cd m−2, which was 4.2 times longer than that of state of the art blue device. Furthermore, the optimized blue PhOLEDs demonstrated device lifetime longer than 25,000 h, which is one of the longest device lifetimes of blue PhOLEDs without any sensitization or outcoupling enhancement. This result indicated that triplet exciton recycling via TADF mechanism in the n-type host is one of the effective approaches to enhance the operational stability of blue PhOLEDs.

Superbly long lifetime over 13,000 h for multiple energy transfer channels in deep blue phosphorescence organic light-emitting diodes with Ir complex under CIEy of 0.17

Despite over two decades of relentless endeavor, the industrial application of blue phosphorescent organic light-emitting diodes (PhOLEDs) has not been realized due to extremely short lifetime. The degradation of PhOLEDs is generally accelerated at high current levels since high triplet energy with long exciton lifetime are mostly concentrated on host molecules and transferred to dopant via slow Dexter energy transfer (DET) processes rather than fast Förster resonance energy transfer (FRET) processes. Herein, we propose a novel device architecture that creates multiple energy transfer channels by employing an Ir-complex intermediate energy carrier (IEC). Unlike exciplex or electroplex, no excitons were generated between the host and the IEC even though the IEC also behaves as a p-type host. The most crucial role of the IEC is to diversify the energy transfer channels. By introducing the IEC in deep blue PhOLEDs, both FRET and DET channels were additionally created between the IEC and the host, and the IEC and the dopant. Consequently, an unprecedentedly long half luminance lifetime of 13,830 h at an initial luminance of 100 cd/m2 was obtained with a high efficiency of 14.4% and CIEy = 0.17. To our best knowledge, the lifetime in our report is the longest with a deep blue phosphorescent Ir complex.