Aggregation induced intermolecular charge transfer in simple nonconjugated donor–acceptor system

The exploration of exciplex for organic light-emitting diodes (OLEDs) has been fleetly developed. However, many of them confront with the problems like phase separation and poor solubility, hampering their utilization in solution process. Hence, a series of soluble exciplex luminophores with the simple architecture of D-spacer-A (mCP-6C-TRZ, phCz-6C-TRZ and 2phCz-6C-TRZ) are synthesized and characterized, in which, the alkyl chain as ample spacer breaks the molecular backbone conjugation, induces intermolecular charge transfer process instead of intramolecular charge transfer in solid state. These materials are endowed with narrowed singlet−triplet splitting energy (ΔE_ST), efficient reverse intersystem crossing (RISC) process, and distinct thermally activated delayed fluorescence (TADF) characteristics. In view of their high triplet energy level (E_T) and bipolar carrier transport ability, where efficient exciplexes are applied as the host, the solution-processed phosphorescence devices realize a low efficiency roll-off of 7.0% at 1000 cd m⁻², high luminance, current efficiency (CE) and external quantum efficiency (EQE) of 25,990 cd m⁻², 20.0 cd A⁻¹ and 6.7%, respectively. These results offer a promising tactic to the establishment of exciplex with TADF feature as host for fabricating efficient solution processed OLEDs.     

Management of Host–Guest Triplet Exciton Distribution for Stable,High-Efficiency,Low Roll-Off Solution-Processed Blue Organic Light-Emitting Diodes by Employing Triplet-Energy-Mediated Hosts

High-quality hosts are indispensable for simultaneously realizing stable, high efficiency, and low roll-off blue solution-processed organic light-emitting diodes (OLEDs). Herein, three solution processable bipolar hosts with successively reduced triplet energies approaching the T₁ state of thermally activated delayed fluorescence (TADF) emitter are developed and evaluated for high-performance blue OLED devices. The smaller T₁ energy gap between host and guest allows the quenching of long-lived triplet excitons to reduce exciton concentration inside the device, and thus suppresses singlet-triplet and triplet-triplet annihilations. Triplet-energy-mediated hosts with high enough T₁ and better charge balance in device facilitate high exciton utilization efficiency and uniform triplet exciton distribution among host and TADF guest. Benefited from these synergetic factors, a high maximum external quantum efficiency (EQE_max) of 20.8%, long operational lifetime (T₅₀ of 398.3 h @ 500 cd m⁻²), and negligible efficiency roll-off (EQE of 20.1% @ 1000 cd m⁻²) are achieved for bluish-green TADF OLEDs. Additionally introducing a narrowband emission multiple-resonance TADF material as terminal emitter to accelerate exciton dynamic and improve exciton utilization, a higher EQE_max of 23.1%, suppressed roll-off and extended lifetime of 456.3 h are achieved for the sky-blue sensitized OLEDs at the same brightness.     

High performance doping-free WOLEDs based on rationally designed asymmetric orange-red Ir(III) emitter with balanced charge mobility

Doping-free organic light-emitting diodes (OLEDs) have attracted continuous attention owing to reduced phase separation, better repeatability, and low cost. Despite demonstrating great potential for white OLEDs (WOLEDs), development of phosphorescent materials capable of achieving high performance with low voltage, high luminance, and low efficiency roll-off simultaneously, still remains a significant challenge. Herein, we design three orange-red Ir(III) phosphors employing functionalized 1,2-diphenylbenzimidazole as main ligands. Clear relationship between structures and electroluminescence (EL)-performances has been established by comprehensively studying their emission properties and intrinsic carrier transporting abilities. Designed phosphor SFIrbiq with spirobifluorene moiety showing negligible intermolecular interactions and balanced carrier transporting ability, not only achieves favorable monochromatic doping-free device but also high-performance doping-free WOLEDs. Optimized WOLED realizes low voltages (2.5 V at 1 cd m⁻², 3.3 V at 100 cd m⁻², and 4.2 V at 1000 cd m⁻²), maximum brightness of 34 505 cd m⁻² and efficiencies of 24.2 cd A⁻¹, 21.7 lm W⁻¹, 10.3%. Such doping-free hybrid WOLED also achieves low efficiency roll-off of 5% for external quantum efficiency (EQE) at 1000 cd m⁻². The device performance can be further improved by employing doping-free all-phosphorescent device structure, achieving maximum efficiencies of 33.3 cd A⁻¹, 32.4 lm W⁻¹, and 16.9%. The results are promising among reported doping-free three-color WOLEDs, paving a feasible way to development of efficient Ir(III) phosphors and doping-free WOLEDs.     

Ultraefficient Non-Doped Deep Blue Fluorescent OLED: Achieving a High EQE of 10.17% at 1000 cd m−2 with CIEy<0.08

The pursuit for efficient deep blue material is an ever-increasing issue in organic optoelectronics field. It is a long-standing challenge to achieve high external quantum efficiency (EQE) exceed 10% at brightness of 1000 cd m⁻² with a Commission International de L'Eclairage (CIE_y) <0.08 in non-doped organic light-emitting diodes (OLEDs). Herein, this study reports a deep blue luminogen, PPITPh, by bonding phenanthro[9,10-d]imidazole moiety with m-terphenyl group via benzene bridge. The non-doped OLED based on PPITPh exhibits an exceptionally high EQE of 11.83% with a CIE coordinate of (0.15, 0.07). The EQE still maintains 10.17% at the brightness of 1000 cd m⁻², and even at a brightness as high as 10000 cd m⁻², an EQE of 7.5% is still remained, representing the record-high result among non-doped deep-blue OLEDs at 1000 cd m⁻². The unprecedented device performance is attributed to the reversed intersystem crossing process through hot exciton mechanism. Besides, the maximum EQE of orange phosphorescent OLED with PPITPh as host is 32.02%, and remains 31.17% at the brightness of 1000 cd m⁻². Such minimal efficiency roll-off demonstrates that PPITPh is also an excellent phosphorescent host material. The result offers a new design strategy for the enrichment of high-efficiency deep blue luminogen.     

Carbazole-bridged triphenylamine-bipyridine bipolar hosts for high-efficiency low roll-off multi-color PhOLEDs

Three new bipolar molecules composed of carbazole, triarylamine, and bipyridine were synthesized and utilized as host materials in multi-color phosphorescent OLEDs (PhOLEDs). These carbazole-based materials comprise a hole-transport triarylamine at C3 and an electron-transport 2,4′- or 4,4′-bipyridine at N9. The different bipyridine isomers and linking topology of the bipyridine with respect to carbazole N9 not only allows fine-tuning of physical properties but also imparts conformational change which subsequently affects molecular packing and carrier transport properties in the solid state. PhOLEDs were fabricated using green [(ppy)₂Ir(acac)], yellow [(bt)₂Ir(acac)], and red [(mpq)₂Ir(acac)] as doped emitters, which showed low driving voltage, high external quantum efficiency (EQE), and extremely low efficiency roll-off. Among these new bipolar materials, the 2Cz-44Bpy-hosted device doping with 10% (ppy)₂Ir(acac) as green emitting layer showed a high EQE of 22% (79.8 cd A⁻¹) and power efficiency (PE) of 102.5 lm W⁻¹ at a practical brightness of 100 cd m⁻². In addition, the device showed limited efficiency roll-off (21.6% EQE) and low driving voltage (2.8 V) at a practical brightness of 1000 cd m⁻².     

Cascade Chirality Transfer Through Diastereomeric Interaction Enables Efficient Circularly Polarized Electroluminescence

Organic light-emitting diodes (OLEDs) with circularly polarized emission can bring a breakthrough innovation in display technologies. However, it remains challenging due to the difficulty in obtaining high efficiency and large dissymmetry factor simultaneously. Herein, it is demonstrated that robust circularly polarized (CP) electroluminescence can be induced by cascade chirality transfer within the emitting layer. Through spectroscopic data and theoretical analysis, the initiation of this chirality transfer process is assigned to diastereomeric interaction. Utilizing this interaction and excellent Förster resonance energy transfer ability to the well-known racemic emitter, CP-OLEDs with an electroluminescence dissymmetry factor (|g_EL|) up to 3.2 × 10⁻³ and high external quantum efficiency (EQE) of 32% are successfully fabricated. These devices also show ultra-low efficiency roll-off at high brightness, with EQE ≥ 20% at 128 000 cd m⁻². This study paves the way for the future development of CP-OLEDs through synergistic materials and device engineering.     

Highly twisted organic molecules with ortho linkage as the efficient bipolar hosts for sky-blue thermally activated delayed fluorescence emitter in OLEDs

Two new host materials, CzDPPy and tCzDPPy, were designed and synthesized through the Ullmann-coupling reaction between carbazole/3,6-di-tert-butyl-carbazole and 2,6-bis(2-bromophenyl)pyridine. Their single-crystal structure, thermal, electrochemical, opt-electronic and bipolar carrier-transporting properties were fully investigated. Due to the steric hindrance of carbazole at the ortho positions of diphenylpyridine, both CzDPPy and tCzDPPy adapted highly twisted molecular conformation, which could effectively minimize their π conjugation and endow them the high triplet energies of 2.67 and 2.64 eV, respectively. Organic light-emitting devices (OLEDs) were fabricated by using CzDPPy and tCzDPPy as the host materials and 1,2-bis(carbazol-9-yl)-4,5-dicyanobenzene (2CzPN) as the sky-blue TADF emitter. The peak current efficiency of 34.8 cd A⁻¹, power efficiency of 33.1 lm W⁻¹ and external quantum efficiency of 16.0% were realized for the CzDPPy-based TADF OLED, along with the satisfactory CIE coordinate of (0.18, 0.34) at 100 cd m⁻².     

Improved efficiency,stable spectra and low efficiency roll-off achieved simultaneously in white phosphorescent organic light-emitting diodes by strategic exciton management

Despite their merits of high efficiency and environmental friendliness, phosphor based white organic light-emitting diodes (WOLEDs) for commercial applications still face tough challenges of efficiency roll-off and color stability. Herein, we fabricated high-efficiency phosphor WOLEDs with extremely low roll-off and stable white emission by employing mixed spacer layer between the two complementary emissions as well as mixed host in the orange layer. The strategic exciton management in our proposed device structure greatly balanced the transport of charge carriers due to the excellent exciton manipulation of the mixed spacer, and significantly suppressed the exciton quenching owing to the extended exciton recombination region, which significantly minimized the efficiency roll-off of the fabricated WOLEDs. The resulting phosphor WOLED exhibited the maximum current efficiency (CE) and power efficiency (PE) of 47.5 cd A⁻¹ and 44.7 lm W⁻¹, respectively, and the CE still had 43.1 cd A⁻¹ at 5000 cd m⁻², showing a suppressed efficiency roll-off of only 9.2%. Additionally, the device achieved fairly stable spectra over a wide range of luminance with suitable CIE coordinates for indoor lighting and outdoor displays.     

Acceptor-Donor-Acceptor-Configured Delayed Fluorescence Emitters for Efficient Orange-Red and White Devices with Low Roll-off

Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) materials are promising for the realization of highly efficient emitters. However, severe efficiency roll-off at high brightness still remains as a huge challenge for TADF-based OLEDs. Herein, rod-like orange-red TADF emitters of 2BNCz-PZ and 2BNtCz-PZ with acceptor-donor-acceptor (A-D-A) configuration are developed by bearing dihydrophenazine donor and discoidal rigid boron, nitrogen-contained polycyclic aromatic hydrocarbons acceptors. Both emitters exhibit hybrid long-range/short-range charge-transfer excitation for small singlet-triplet energy splitting, short delayed lifetime, and high photoluminescence quantum yield, leading to fast singlet radiation rate over 10⁷ s⁻¹ and fast reverse intersystem crossing rate over 10⁶ s⁻¹. Furthermore, a horizontal emitting dipole orientation factor over 90% is realized. The optimized orange-red OLED based on 2BNtCz-PZ presents a maximum external quantum efficiency (EQE) of 31.0% and a slight EQE roll-off to 22.2% at 1 000 cd m⁻² with emission peak over 600 nm. In addition, the single-emitting layer white OLEDs achieve a maximum EQE of 30.6% due to the use of these orange-red dopants with intense charge-transfer absorption band. This work reveals the potential of the rod-like A-D-A configuration for constructing highly efficient orange-red TADF emitters with low-efficiency roll-off.     

Simplified and high-efficiency warm/cold phosphorescent white organic light-emitting diodes based on interfacial exciplex co-host

Possessing the reverse intersystem crossing (RISC) process, exciplex system has vast potential to enhance the efficiency of the white organic light-emitting diodes (WOLEDs). Nevertheless, general structures of the emitting layer always employ triple-doping in a long range (20–30 nm) which is complicated on fabrication progress. In this paper, based on the interfacial exciplex co-host, a flexible and simplified structure design is proposed to realize both warm and cold phosphorescent WOLEDs. In the two devices, with strategically locating the ultrathin orange phosphorescent emitting layers at two sides of the blue phosphorescent emitting layer (2 nm), respectively, multiple energy transfer channels are created to carry out highly efficient exciton utilization. Owing to the different energy transfer mechanisms, different organic emission ratios are obtained in two WOLEDs. The cold WOLEDs exhibited superior maximum external quantum efficiency (EQE), current efficiency (CE) and power efficiency (PE) of 28.37%, 72.17 cd A⁻¹ and 87.17 lm W⁻¹, respectively. Also, the warm WOLEDs showed high values as EQE of 23.80%, CE of 67.70 cd A⁻¹ and PE of 81.10 lm W⁻¹. Furthermore, both the devices presented rather stable color output in the luminance range from 2000 cd m⁻² to 10000 cd m.⁻²     

Molecular engineering of “A-D-D-A” dual-emitting-cores emitters with thermally activated delayed fluorescence and aggregation-induced emission characteristics

Endowing thermally activated delayed fluorescence (TADF) emitter with aggregation-induced emission (AIE) peculiarity is of great significance for realizing more promising commercial applications. Herein, two new dual-emitting-cores emitters with a structure of acceptor-donor-donor-acceptor (A-D-D-A), namely 2DBT-BZ-2Cz and 2DFT-BZ-2Cz, were designed and synthesized to explore their luminescence trait. The emitters, adopting dual carbazole as donor segments and dual phenyl ketone in peripheral skeleton as electron acceptor units, were featured with small singlet (S₁)–triplet (T₁) splitting energy (ΔE_ST) of 0.02 eV and 0.01 eV. The efficient thermally activated delayed fluorescence (TADF) characteristics and aggregation-induced emission property make them suitable for nondoped OLED devices. The solution-processed green OLEDs based on 2DBT-BZ-2Cz demonstrated greater device performance with current efficiency of 20.7 cd A⁻¹ and maximum luminescence of 10,000 cd m⁻². This work thus provides the direction to explore luminogens of dual-emitting-cores with TADF and AIE features as promising candidates in solid state lighting.     

The synthesis,crystal structures,aggregation-induced emission and electroluminescence properties of two novel green-yellow emitters based on carbazole-substituted diphenylethene and dimesitylboron

Introducing the hole-transporting carbazole moiety into an aggregation-induced emissive tetraarylethene skeleton and attaching electron-transporting dimesitylboron groups to the periphery, we obtain two novel electroluminescent materials. Their structures are fully characterized by elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Furthermore, their thermal, electrochemical, as well as photophysical properties including AIE-behavior are systematically investigated not only by experimental methods but also by DFT computation. Thereby, we show that the two compounds possess high thermal and electrochemical stability with a remarkable AIE-behavior. X-ray crystal analyses aided by DFT calculations provide insights in the origin of the luminescent properties and AIE features. Ultimately, two non-doped OLEDs (Device A and Device B) were fabricated by using PDPBCE and BDPBCE as light-emitting layer, respectively. Device A showed yellowish-green light with a turn-on voltage of 3.8 V, a maximum brightness of 59130 cd m⁻² and a maximum current efficiency of 6.43 cd A⁻¹. Device B exhibited greenish-yellow light with a turn-on voltage of 3.0 V, a maximum brightness of 67,500 cd m⁻² and a maximum current efficiency of 11.2 cd A⁻¹.     

Indolo[3,2,1-jk]carbazole based planarized CBP derivatives as host materials for PhOLEDs with low efficiency roll-off

Three novel planarized CPB derivatives (ICzCz, ICzPCz, ICzICz) have been synthesized and characterized concerning applications as host materials for PhOLEDs. The incorporation of fully planar indolo[3,2,1-jk]carbazole (ICz) in the CBP scaffold has been systematically investigated, revealing a significant impact on molecular properties, such as improved thermal stability (t_g > 110 °C), high triplet energies (E_T > 2.81 eV) and charge transport properties. Employing the newly developed materials as host materials, efficient green PhOLEDs (CE_max: 60.1 cd A⁻¹, PE_max: 42.1 lm W⁻¹, EQE_max: 15.9%) with a remarkably low efficiency roll-off of 5% at 1000 cd m⁻² as well as blue PhOLEDs (ICzCz) with a high PE of 26.1 lm W⁻¹ have been realized. Hence, the first comprehensive report on the application of ICz as integral building block for electroluminescent materials is presented, establishing this particular structural motive as versatile structural motive in this field.     

Tuning electron injection/transporting properties of 9,10-diphenylanthracene based electron transporters via optimizing the number of peripheral pyridine for highly efficient fluorescent OLEDs

By incorporating different number of pyridine rings to the periphery of the 9,10-diphenylanthracene (DPA) core, four new pyridine-containing DPA derivatives, 3-(4-(10-phenylanthracen-9-yl)phenyl)pyridine (AnPy), 9,10-bis(4-(pyridin-3-yl)phenyl)anthracene (AnDPy), 3,3'-((2-(pyridin-3-yl)anthracene-9,10-diyl)bis(4,1-phenylene))dipyridine (AnTPy), 3,3'-(9,10-bis(4-(pyridin-3-yl)phenyl)anthracene-2,6-diyl)dipyridine (AnFPy) were designed and synthesized as electron transporters. Their photophysical properties, energy levels and electron mobilities can be readily regulated through tuning the quantity of the pyridine ring. Through optimizing electron injection/transporting properties, AnTPy exhibits not only a suitable lowest unoccupied molecular orbital (LUMO) energy level for electron injection into light-emitting layer (EML), but also a relatively high electron mobility of around 10⁻³ cm² V⁻¹ s⁻¹, which is about two orders of magnitude higher than that of the widely used material Alq₃. As expected, the blue fluorescent OLEDs with AnPy, AnTPy and AnFPy as an electron-transporting layer (ETL) exhibited superior performance compared to that using Alq₃, remarkably lowering the driving voltages and improving efficiencies. In particular, the device with AnTPy as an ETL showed a maximum current efficiency of 14.4 cd A⁻¹, a maximum power efficiency of 12.1 lm W⁻¹, a maximum external quantum efficiency (EQE) of 8.15% and low efficiency roll-off even at an illumination-relevant luminance of 10,000 cd m⁻². These results clearly demonstrated that tuning electron injection/transporting properties by optimizing the number of peripheral electron-withdrawing groups was an efficient strategy to achieve high-performance ETMs.     

Thermal annealing effect on light emission profile of polyfluorenes containing double bond subunit

We presented comprehensive photoluminescence (PL) and electroluminescence (EL) studies of polyfluorene based electroactive polymer (SF4) containing double bond side chain to investigate its characteristics as a function of temperature. Annealing treatment was conducted for thin films on glass substrates and also for the organic light emitting diodes (OLEDs) at different temperatures. While polymer thin film coated on to glass substrate annealed at < 150 °C exhibited green color emission, OLEDs that annealed at >150 °C shifted white color emission. It was implying that the emission was taking place interchain interaction. Phase modulation at higher annealing temperatures was occurred on the thin film as shown AFM images. Further, annealed polymer film with 120 °C exhibited the best performance in OLED device with luminance 5241 cd m⁻², a maximum efficiency 1.54 cd A⁻¹ and external quantum efficiency 0.54% compared to other polymer films annealed with different temperatures.     

Suppression of efficiency roll-off in TADF-OLEDs using Ag-island nanostructures with localized surface plasmon resonance effect

Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) have emerged as promising alternatives to phosphorescent OLEDs for harvesting both singlet and triplet excitons. However, the development of TADF-OLEDs meets a thorny problem of serious efficiency roll-off at high luminance. Here, we demonstrate an approach to suppress the efficiency roll-off characteristics in TADF-OLEDs by localized surface plasmon resonance (LSPR) effect of easy-fabricated Ag-island nanostructures. Compared with the common TADF-OLEDs at a high current density of 100 mA cm⁻², the efficiency roll-off ratio of the TADF-OLEDs with Ag-island nanostructures decreases from 49.75% to 35.76% significantly, and the maximum current efficiency is increased by 10.5%. The performance enhancement is mainly attributed to the coupling between excitons and localized surface plasmons (LSPs), which could alter the excited state kinetic characteristics of TADF molecules.     

Efficient deep-red electroluminescent donor-acceptor copolymers based on 6,7-dichloroquinoxaline

Since the large steric hindrance caused by chlorine atoms not only suppresses the aggregation but also results in large stokes shift and low self-absorption, a series of donor-acceptor alternating copolymers based on 6,7-dichloroquinoxaline have been synthesized by modifying the structures of oligothiophenes. All the polymers have been well characterized to study the effects of the length of oligothiophenes and the steric hindrance on the optical, electronic and electroluminescent properties. It was observed that the intramolecular charge transfer absorption was weakened by steric hindrance. Unlike non-chloride analogues, prolonged conjugated length resulted in smaller bandgap, given similar steric hindrance. Deep-red emission centered at 678 nm with brightness about 1800 cd m⁻² was achieved with external quantum efficiency 1.34% using dopant/host technic.     

Two trans-1-(9-anthryl)-2-phenylethene derivatives as blue-green emitting materials for highly bright organic light-emitting diodes application

1-(9-Anthryl)-2-phenylethene (t-APE) is a blue-green material with high fluorescence quantum yield (Ф_f 0.44). However, it is easily crystallized. Herein, Two asymmetric blue-green emitting materials based on t-APE, (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-1-yl)anthracene (6) and (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-2-yl)anthracene (7) were firstly designed and synthesized. The two compounds possess high thermal stability, morphological durability, and bipolar characteristics. The non-doped blue-green organic light-emitting diodes (OLEDs) using 6 and 7 as emitting layers showed emission at 495 nm, full width at half maximum of 80 nm, maximum brightness of 13,814, 10,579 cd m⁻², maximum current efficiency of 3.62, 7.16 cd A⁻¹, and Commission Internationale de L'Eclairage (CIE) coordinate of (0.20, 0.43), respectively. Furthermore, when employing 6 and 7 as blue-green emitting layers and rubrene doped in tris-(8-hydroxyquinolinato)aluminum (Alq3) as the orange emitting layers to fabricate white OLEDs (WOLEDs), the WOLEDs exhibit a maximum brightness of 10,984, 14,652 cd m⁻², maximum current efficiency of 2.04, 2.70 cd A⁻¹, and CIE coordinate of (0.30, 0.40), (0.37, 0.47), Color Rendering Index (CRI) of 65, 60, stable EL spectra, respectively. This study demonstrates that the t-APE-type derivatives have the excellent properties for the emitting materials of OLEDs.     

Triarylphosphine oxide–phenanthroline molecular conjugate as a promising doped electron-transport layer for organic light-emitting diodes

Over the past three decades, transparent high electron mobility molecular materials have attracted intensive research efforts for organic light-emitting diodes as electron-transport layer for the sake of low working voltage, high power efficiency and operational stability. However, developing high-performing electron-transport materials presents a demanding challenge owing to difficulties in synthesis, purification and/or processing. In this contribution, we show that n-doping a simple and facilely available phenanthroline derivative, namely 3-(6-diphenylphosphinylnaphth-2-yl)-1,10-phenanthroline Phen-NaDPO with a high T_g of 116 °C, is capable of greatly increasing the electron conductivity up to 3.3 × 10⁻⁴ S m⁻¹. The characterization of the blue sky fluorescent and green phosphorescent OLEDs involving this doped electron-transport layer Phen-NaDPO:50% wt Cs₂CO₃ revealed comparable performances to the analogue BPhen (T_g ≈ 66 °C) OLEDs. For instance, the resulting sky blue fluorescent OLEDs provided ca. 15 cd/A, 13 lm/W @1000 cd m⁻² & t₉₅ ≈ 167 h @1000 cd m⁻². The present finding shows that the doped Phen-NaDPO may be a robust electron-transport material for optoelectronics.     

Steric Rooted Multi-Resonant Thermally Activated Delayed Fluorescent Emitters for Pure Blue Organic Light Emitting Diodes with Ultralow Efficiency Roll-Off

Multi-resonant thermally activated delayed fluorescent ( MR-TADF ) materials are blooming for high-resolution organic light-emitting diodes (OLEDs). However, boron/nitrogen (B/N)-integrated MR-TADF emitters suffer severe efficiency roll-off from their strong inter-molecular π–π interactions. Herein, versatile narrowband pure blue emitters ( mono-mx-CzDABNA and tri-mx-CzDABNA ) are demonstrated featuring a ring-fused extended π-skeleton: a classic steric hindrance and rigidity accessed by integrating with meta-xylene (mx) rotors. tri-mx-CzDABNA shows a narrowband (FWHM, 26 nm) pure blue emission (λ_max, 462 nm) with substantial hypsochromic shift (12 nm) while maintaining MR-TADF characteristics. The key solid-state analyses conclude that they conceivably suppress the non-radiative energy loss, thus improving the photoluminescence quantum yield (PLQY > 90%) and rate of reverse intersystem crossing (RISC) (k_RISC ≈2.85 × 10⁵ s⁻¹). The integration of tri meta-xylene significantly leads to an enhanced horizontal dipole ratio (HDR) from 65% to 85%. Hyperfluorescent-OLEDs are fabricated using designed MR-TADF as terminal emitter, achieving a narrowband (FWHM, 34 nm) pure blue electroluminescence (λ_max, 472 nm) and maximum external quantum efficiency (EQE_max) of 26.97% with magnificently suppressed efficiency roll-off (7.8%) at 1000 cd m⁻². So, it is believed that regulation of internal efficiencies and high color purity can amplify the route to achieving a narrowband pure blue emission through new synthetic MR-TADF approaches.