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.     

Modulating Backbone Conjugation of Polymeric Thermally Activated Delayed Fluorescence Emitters for High-Efficiency Blue OLEDs

Blue conjugated polymers-based OLEDs with both high efficiency and low efficiency roll-off are under big challenge. Herein, a strategy of local conjugation is proposed to construct high-efficiency blue-emitting conjugated polymers, in which the conjugation degree of polymeric backbones is adjusted by inserting different spacers. In this way, the energy level of triplet state and the energy transfer direction of the polymeric main-chains can be effectively regulated. Benefiting from such fine regulation, the prepared alternative copolymers Alt-PB36 with local conjugated main-chains can better suppress the accumulation of long-lived triplet excitons comparing with the complete conjugated polymers. The higher PLQY of Alt-PB36 also verifies the effective energy transfer from the polymeric main-chains to the TADF units. Accordingly, Alt-PB36 based solution-processed OLEDs achieve an EQE_max of 11.6% and a very low efficiency roll-off of 2.8% at 100 cd m⁻² and 15.2% at 500 cd m⁻². This result represents the best efficiency among blue light-emitting conjugated polymer-based OLEDs so far under high luminance.     

Highly efficient Organic Light-Emitting Diodes from thermally activated delayed fluorescence using a sulfone–carbazole host material

Organic Light-Emitting Diodes (OLEDs) using the thermally activated delayed fluorescence (TADF) emitter (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) are demonstrated using a novel ambipolar host 3,5-di(carbazol-9-yl)-1-phenylsulfonylbenzene (mCPSOB). When doped in a 5 wt.% concentration, OLEDs with EL efficiency values of more than 81 cd/A for current efficacy and 26.5% for external quantum efficiency are reported. These devices exhibit a low turn-on voltage of 3.2 V at 10 cd/m², as well as reduced efficiency roll-off at high current densities. To the best of our knowledge, these are among the highest ever reported efficiencies for TADF OLEDs, and are even comparable to the highest reported efficiencies for phosphorescent OLEDs.     

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.     

Enhancement of Reverse Intersystem Crossing in Charge-Transfer Molecule through Internal Heavy Atom Effect

Thermally activated delayed fluorescence (TADF) is beneficial for improving the efficiency of organic light-emitting diodes (OLEDs) by providing pathways to convert non-emissive triplet excitons into singlet excitons. To ensure TADF is efficient, it is critical to enhance the reverse intersystem crossing (RISC) rate. To this end, most approaches propose thus far have focused on reducing the energy difference between S₁ and T₁ states. The present study explores how incorporating the internal heavy atom (IHA) effect can impact the RISC and device performance. By introducing a series of halogen atoms to charge-transfer molecules, TADF molecules exhibiting RISC over 7 × 10⁷ s⁻¹ are realized. These molecules are then applied to OLEDs, and the effect of incorporating these moieties is investigated. The results show that efficiency roll-off is still significant even with RISC-enhanced TADF emitters. Spectroscopic and theoretical results indicate that a fast RISC may not be the sole factor important for reducing efficiency roll-off and that the spin-flip cycles considering both T₁→S₁ and S₁→T₁ should be carefully taken into account to derive a complete picture of the IHA effect on efficiency roll-off behavior.     

Copper(I) Complex as Sensitizer Enables High-Performance Organic Light-Emitting Diodes with Very Low Efficiency Roll-Off

Organic light-emitting diodes (OLEDs) utilizing purely organic thermally activated delayed fluorescence (TADF) sensitizers have recently achieved high efficiencies and narrow-band emissions. However, these devices still face intractable challenges of severe efficiency roll-off at practical luminance and finite operational lifetime. Herein, a carbene-Cu(I)-amide complex, (MAC*)Cu(Cz), is demonstrated as a TADF sensitizer for both fluorescent and TADF OLEDs. The (MAC*)Cu(Cz)-sensitized fluorescent OLED not only achieves a high external quantum efficiency (EQE) of 14.6% with an extremely low efficiency roll-off of 12% at the high luminance of 10 000 nits, but also delivers a 15 times longer operational lifetime than that of the non-sensitized reference device. More importantly, utilizing the (MAC*)Cu(Cz) sensitizer in the multi-resonance (MR) TADF OLED results in a record-high EQE of 26.5% together with a full-width at half maximum of 46 nm and an emission peak at 566 nm. This value is the state-of-the-art efficiency for yellow-emitting MR-TADF OLEDs. The photophysical analysis proved that the fast reverse intersystem crossing process of (MAC*)Cu(Cz) is the key factor to suppress triplet exciton involved quenching at high luminance. This finding firstly demonstrates the use of Cu(I) complex as an efficient TADF sensitizer and paves the way for practical applications of TADF sensitized OLEDs.     

Thermally activated delayed-fluorescence organic light-emitting diodes based on exciplex emitter with high efficiency and low roll-off

Highly efficient thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) based on exciplex are demonstrated in a blended system with commercially available 1,1-bis((di-4-tolylamino)phenyl)cyclohexane (TAPC) and 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T). By well adjusting the ratio between these two materials, the optimized device shows a low turn-on voltage of 2.4 V and a high external quantum efficiency (EQE) of 11.6%. More importantly, the device retains an EQE of 9.4% even at a high luminescence of 1000 cd/m². The low efficiency roll-off is attributed to the small singlet-triplet splitting and the short of the delayed fluorescence lifetime. Both EQE and efficiency roll-off are ones of the best performance among the reported TADF OLEDs based on exciplex.     

Highly efficient orange fluorescent OLEDs based on the energy transfer from bilayer interface exciplex

We demonstrated highly efficient traditional orange emission fluorescent OLEDs with simple device structure by utilizing energy transfer from bilayer interface TADF exciplex to dopant. With rubrene as the dopant, under the optimized concentration of 1.5%, the device achieved maximum current efficiency, power efficiency and EQE of 25.3 cd/A, 22.6 lm/W and 8.1%, respectively. Even at the luminance of 1000 cd/m², the EQE also remained 6.9%. The obtainment of so high efficiency could be attributed to highly efficient RISC efficiency of triplet excitons and energy transfer efficiency from TADF exciplex to dopant. The more detailed working mechanism was also argued.     

Achieving High‐Performance Nondoped OLEDs with Extremely Small Efficiency Roll‐Off by Combining Aggregation‐Induced Emission and Thermally Activated Delayed Fluorescence

Luminescent materials with thermally activated delayed fluorescence (TADF) can harvest singlet and triplet excitons to afford high electroluminescence (EL) efficiencies for organic light‐emitting diodes (OLEDs). However, TADF emitters generally have to be dispersed into host matrices to suppress emission quenching and/or exciton annihilation, and most doped OLEDs of TADF emitters encounter a thorny problem of swift efficiency roll‐off as luminance increases. To address this issue, in this study, a new tailor‐made luminogen (dibenzothiophene‐benzoyl‐9,9‐dimethyl‐9,10‐dihydroacridine, DBT‐BZ‐DMAC) with an unsymmetrical structure is synthesized and investigated by crystallography, theoretical calculation, spectroscopies, etc. It shows aggregation‐induced emission, prominent TADF, and interesting mechanoluminescence property. Doped OLEDs of DBT‐BZ‐DMAC show high peak current and external quantum efficiencies of up to 51.7 cd A^?1 and 17.9%, respectively, but the efficiency roll‐off is large at high luminance. High‐performance nondoped OLED is also achieved with neat film of DBT‐BZ‐DMAC, providing excellent maxima EL efficiencies of 43.3 cd A^?1 and 14.2%, negligible current efficiency roll‐off of 0.46%, and external quantum efficiency roll‐off approaching null from peak values to those at 1000 cd m^?2. To the best of the authors' knowledge, this is one of the most efficient nondoped TADF OLEDs with small efficiency roll‐off reported so far.     

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.     

Flexible all fluorescence white organic light emitting device with over 22% EQE by stepped reverse intersystem crossing channels based on ternary exciplex

Improvement of the utilization of triplet excitons for thermally activated delayed fluorescence (TADF) emitter-based white organic light emitting devices (WOLEDs) is a key scientific challenge. In this study, a new strategy with stepped reverse intersystem crossing (RISC) channels induced by new ternary exciplex was proposed to enhance up-conversion of non-radiative triplet excitons. A flexible TADF WOLED with external quantum efficiency (EQE) of 22.7% and a power efficiency of 62.5 lmW⁻¹ was demonstrated. At 1000 cdm⁻², the EQE still remained at 21.4%, showing low efficiency roll-off of 5.7%. It is attributed to the reduced non-radiative triplet excitons stack, which suppressed the triplet–triplet quenching. Moreover, the new ternary exciplex-based WOLED system mCP: DMAC-DPS:PO-T2T:4CZPNPh exhibited rate constant of RISC process of 2.5 × 10⁶ s⁻¹, and about 2 times photoluminescence quantum yield over binary exciplex. The high efficiency effectively demonstrated that the proposed multiple triplet excitons capture process is an effective strategy to improve the utilization of triplet excitons. Moreover, the novel strategy can be a promising approach for the further development of WOLED.     

Near-infrared thermally activated delayed fluorescent dendrimers for the efficient non-doped solution-processed organic light-emitting diodes

Two near-infrared (NIR) dendrimers with TADF characteristics are reported to develop the non-doped solution-processed OLED for the first time. The rigid ring end-capped aliphatic chain dendrons are introduced to improve the dissolvability and film-forming ability. The dendrimers possess excellent thermal and morphological stabilities. Simultaneously, the dendrimers exhibit self-host feature that the peripheral carbazole/tricarbazole dendrons can encapsulate the core to prevent concentration quenching. Employing MPPA-3Cz as the emitter, the non-doped solution-processed device exhibits a maximum external quantum efficiency (EQE) of 0.254% with a peak wavelength at 715 nm, which is comparable to the most-efficient solution-processed NIR FOLEDs with similar electroluminescent spectra. Moreover, the device shows negligible efficiency roll-off at high current density. Our results indicate that the design of long-wavelength TADF dendrimers will be a promising strategy for the efficient non-doped solution-processed NIR OLEDs.     

Ultra-Deep-Blue Aggregation-Induced Delayed Fluorescence Emitters: Achieving Nearly 16% EQE in Solution-Processed Nondoped and Doped OLEDs with CIEy < 0.1

Ultra-deep-blue aggregation-induced delayed fluorescence (AIDF) emitters (TB-tCz and TB-tPCz) bearing organoboron-based cores as acceptors and 3,6-substituted carbazoles as donors are presented. The thermally activated delayed fluorescence (TADF) properties of the two emitters are confirmed by theoretical calculations and time-resolved photoluminescence experiments. TB-tCz and TB-tPCz exhibit fast reverse intersystem crossing rate constants owing to efficient spin–orbit coupling between the singlet and triplet states. When applied in solution-processed organic light-emitting diodes (OLEDs), the TB-tCz- and TB-tPCz-based nondoped devices exhibit ultra-deep-blue emissions of 416–428 nm and high color purity owing to their narrow bandwidths of 42.2–44.4 nm, corresponding to the Commission International de l´Eclairage color coordinates of (x = 0.16–0.17, y = 0.05–0.06). They show a maximum external quantum efficiency (EQE_max) of 8.21% and 15.8%, respectively, exhibiting an unprecedented high performance in solution-processed deep-blue TADF-OLEDs. Furthermore, both emitters exhibit excellent device performances (EQE_max = 14.1–15.9%) and color purity in solution-processed doped OLEDs. The current study provides an AIDF emitter design strategy to implement high-efficiency deep-blue OLEDs in the future.     

High-efficiency phosphorescent organic light-emitting devices with low efficiency roll-off using a thermally activated delayed fluorescence material as host

Phosphorescent organic light-emitting devices (PHOLEDs) with high efficiency and low efficiency roll-off were fabricated. The emissive layer was composed of a thermally activated delayed fluorescence (TADF) material 4,5-bis(carbazol-9-yl)-1,2-dicyanobenzene (2CzPN) as host and an orange iridium complex bis(4-tert-butyl-2-phenylbenzothiozolato-N,C^2′)iridium(III)(acetylacetonate) [(tbt)₂Ir(acac)] as dopant. At a low dopant concentration of 1 wt%, a PHOLED without light extraction optimization achieved a maximum power efficiency of 42.1 lm/W, a luminance efficiency of 77.9 cd/A and an external quantum efficiency (EQE) of 26.8%, respectively. Meanwhile, the EQE maintained 26.6% at 1000 cd/m² and 25.8% at 5000 cd/m², respectively. Moreover, a critical current density of 300 mA/cm² was realized, indicating significantly improved efficiency roll-off. The efficient utilization of triplet excitons on 2CzPN for phosphorescence via reverse inter-system crossing of 2CzPN followed by Fӧrster resonance energy transfer from 2CzPN to (tbt)₂Ir(acac) is responsible for the superior performance.     

Achieving Narrow FWHM and High EQE Over 38% in Blue OLEDs Using Rigid Heteroatom-Based Deep Blue TADF Sensitized Host

Simultaneously obtaining high efficiency and deep blue emission in organic light emitting diodes (OLEDs) remains a challenge. To overcome the demands associated with deep blue thermally activated delayed fluorescence (TADF) emitters, two deep blue TADF materials namely, DBA–BFICz and DBA–BTICz, are designed and synthesized by incorporating oxygen-bridged boron (DBA) acceptor with heteroatoms, oxygen and sulphur-based donors, BFICz and BTICz, respectively. Both TADF materials show deep blue photoluminescence emissions below 450 nm by enhancing the optical band gap over 2.8 eV through deeper highest occupied molecular orbital (HOMO) level of heteroatom based donor moieties. At the same time, the photoluminescence quantum yields (PLQYs) of both TADF materials remain over 94%. The TADF device with DBA–BFICz as an emitter exhibits a good external quantum efficiency (EQE) of 33.2%. Since both new TADF materials show deep blue emissions and high efficiencies, hyperfluorescence (HF) OLED devices are fabricated using ν-DABNA as a fluorescence dopant. DBA–BFICz as a TADF sensitized host in HF–OLED reveals an outstanding EQE of 38.8% along with narrow full width at half maximum of 19 nm in the bottom emission pure blue OLEDs. This study provides an approach to develop deep blue TADF emitters for highly efficient OLEDs.     

Efficient Solution-Processed Hyperfluorescent OLEDs with Spectrally Narrow Emission at 840 nm

To reduce cost and improve environmental sustainability, there continues to be an important need for the development of efficient organic light-emitting diodes (OLEDs) that do not rely on heavy metal-containing compounds. In particular, the efficiency of fluorescent near-infrared (NIR) OLEDs continues to lag well-behind that of their platinum-containing counterparts. Low efficiencies in this spectral range mainly arise from the low quantum yields of fluorescent NIR emitters due to the energy gap law and inefficient harvesting of triplet excitons. In this paper, a thermally activated delayed fluorescent (TADF) material is used as the assistant dopant to demonstrate pure NIR-emitting fluorescent OLEDs with an external quantum efficiency of up to 3.8%, with an electroluminescence maximum at 840 nm and a spectral full-width at half-maximum of < 40 nm. The efficiency is more than three times higher than that of the best previously reported fluorescent OLEDs in this spectral range and approaches that achievable with the best platinum-containing phosphorescent emitters.     

High Performance NIR OLEDs with Low Efficiency Roll-Off by Leveraging Os(II) Phosphors and Exciplex Co-Host

Near-infrared (NIR) organic-light emitting devices (OLEDs) with high radiance are useful for applications including invisible marking, communication, and biomedical imaging. However, performances of NIR OLEDs are typically limited by their severe efficiency roll-offs at high current density. Herein, three isoquinolinyl azolate based Os(II) complexes (Isq-1–3) with short radiative decay lifetime (in hundreds of ns), and photoluminescence with peak wavelengths > 745 nm and quantum yield up to 48% as doped thin films, are reported. Upon concomitant employment of exciplex-forming co-host (tris(4-carbazoyl-9-ylphenyl)amine and 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), efficiency roll-off is greatly reduced, giving external quantum efficiency of 9.66% at a current density of 300 mA cm⁻². A maximum radiance over 170 W sr⁻¹ m⁻² is also achieved in devices based on Isq-2 and Isq-3.     

Analysis of exciton annihilation in high-efficiency sky-blue organic light-emitting diodes with thermally activated delayed fluorescence

We study external quantum efficiency (η_EQE) roll-off in organic light-emitting diodes (OLEDs) using thermally-activated delayed fluorescence (TADF) of 4,5-di (9H-carbazol-9-yl) phthalonitrile (2CzPN). Using 2CzPN intramolecular rate constants from optical analyses, we construct an exciton quenching model incorporating intersystem crossing and reverse intersystem crossing. The model indicates that singlet–triplet annihilation and triplet–triplet annihilation dominate η_EQE roll-off because of the relatively long 2CzPN triplet lifetime of 273 μs. This work yields a method to relax the exciton quenching process in TADF based OLEDs.     

Interplay between Singlet and Triplet Excited States in Interface Exciplex OLEDs with Fluorescence,Phosphorescence, and TADF Emitters

Interface exciplex represents a promising host material for organic light-emitting diodes (OLEDs) with barrier-free charge injection and highly confined recombination region. However, the efficiency of radiative recombination in pristine exciplex is usually low and needs to be improved by doping various emitters. In this study, the interface exciplex OLEDs doped with fluorescence, phosphorescence, and thermally activated delayed fluorescence (TADF) emitters is fabricated to investigate the relationship between their excited-state properties and electroluminescence efficiencies. A maximum external quantum efficiency of 20% is achieved in interface exciplex OLEDs doped with TADF emitter, which corresponds to nearly 100% exciton utilization and is superior to those of fluorescence and phosphorescence emitters. Furthermore, optical spectroscopy and magneto-electroluminescence method are used to study the advantages of TADF emitter in interface exciplex host. The large dipole of TADF emitter is beneficial for harvesting energy from the charge-transfer state at the interface, and its reverse intersystem crossing avoids the accumulation of triplet excitons that leads to triplet-triplet annihilation in interface exciplex OLEDs. These results demonstrate that the photophysical process needs to be carefully considered in designing high-performance emitters for exciplex host materials, and it may bring in-depth understanding on improving exciton utilization and electroluminescence efficiency in interface exciplex OLEDs.     

Enhancement of the current efficiency of organic light-emitting devices due to the surface plasmonic resonance effect of dodecanethilol-functionalized Au nanoparticles

The photoluminescence intensity of the dodecanethilol-functionalized Au (DDT-Au) nanoparticle (NP) layer/4,4′-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine] (TAPC)/4,4′-bis(N-carbazolyl)-1,1′-biphenyl:tris(2-phenylpyridine)iridium (III) (CPB:Ir(ppy)₃) film was increased by about 1.15 times compared to that of the TAPC/CPB:Ir(ppy)₃ film due to the effect of coupling between the excitons in the emitting layer and a localized surface plasmonic resonance (LSPR) in the DDT-Au NPs. The current efficiency of the organic light-emitting devices (OLEDs) with the DDT-Au NP layer at 100 cd/m² was 14.9 cd/A larger than that without the DDT-Au NP layer, resulting in an enhancement of the out-coupling efficiency. The increase in the current efficiency of the OLEDs with a DDT-Au NP layer was attributed to the enhanced out-coupling efficiency due to the existence of the LSPR generated by the DDT-Au NPs.