High Performance Thermally Activated Delayed Fluorescence Sensitized Organic Light-Emitting Diodes.

Recently, organic light-emitting diodes (OLEDs) employing thermally activated delayed fluorescence (TADF) materials have aroused huge attention in both academia and industry. Compared with fluorescent and phosphorescent materials, TADF materials can theoretically capture 100 % excitons without incorporating noble metals, making them effective emitters and hosts for OLEDs simultaneously. Here, in this review, our recent works on mechanisms and materials of high performance TADF-sensitized phosphorescent (TSP) OLEDs, TADF-sensitized fluorescent (TSF) OLEDs and TADF-sensitized TADF (TST) OLEDs are summarized. Finally, we propose the outlook for the further development and application of TADF-sensitized OLEDs.

Stable Enantiomers Displaying Thermally Activated Delayed Fluorescence: Efficient OLEDs with Circularly Polarized Electroluminescence.

Aromatic-imide-based thermally activated delayed fluorescent (TADF) enantiomers, (+)-(S,S)-CAI-Cz and (-)-(R,R)-CAI-Cz, were efficiently synthesized by introducing a chiral 1,2-diaminocyclohexane to the achiral TADF unit. The TADF enantiomers exhibited high PLQYs of up to 98 %, small ΔEST  values of 0.06 eV, as well as obvious temperature-dependent transient PL spectra, thus demonstrating their excellent TADF properties. Moreover, the TADF enantiomers showed mirror-image CD and CPL activities. Notably, the CP-OLEDs with CPEL properties based on the TADF enantiomers not only achieved high EQE values of up to 19.7 and 19.8 %, but also displayed opposite CPEL signals with gEL  values of -1.7×10-3 and 2.3×10-3 , which represents the first CP-OLEDs, based on the enantiomerically pure TADF materials, having both high efficiencies and intense CPEL.

Towards highly efficient red thermally activated delayed fluorescence materials by the control of intra-molecular π-π stacking interactions.

Thermally activated delayed fluorescence (TADF) materials have attracted much attention as they can achieve 100% theoretical internal quantum efficiency without using expensive noble metals. However, efficient red TADF emitters are hard to realize according to the energy gap law. Here, three donor-acceptor-donor type TADF emitters with the same acceptor of o-phthalodinitrile (PN) but different donors (9, 9-dimethyl-9, 10-dihydroacridine (DMAC), phenoxazine (PXZ), and phenothiazine (PTZ) for DMAC-PN, PXZ-PN, and PTZ-PN, respectively) have been synthesized, and it is observed that the performance of the emitters can be improved by reducing the intra-molecular π-π stacking. DMAC-PN with reduced intra-molecular π-π stacking shows a photoluminescence quantum yield (PLQY) of 20.2% in degassed toluene solution, much higher than those of PXZ-PN, and PTZ-PN (0.8%, 0.2%, respectively). An organic light-emitting diode (OLED) employing DMAC-PN doped into 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP) as the emitting layer exhibits a maximum external quantum efficiency (EQE) of 10.2% with the emission peak at 564 nm. Moreover, when DMAC-PN is doped into a polar host, bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), the OLED shows a large redshift of the emission maximum to 594 nm, while maintaining a peak EQE as high as 7.2%, indicating that efficient red TADF OLEDs can be fabricated by doping orange TADF emitters into hosts with proper polarity.

How does interactive virtual reality enhance learning outcomes via emotional experiences? A structural equation modeling approach.

Introduction: Interest in interactive virtual reality (IVR) is increasing due to its potential for embodied learning and group-led teaching. However, few studies have investigated the internal mechanism by which IVR technology features and learning experiences affect learning outcomes in terms of psychological and emotional value. Based on media technology models and the control value theory of achievement emotions (CVTAE), this study uses structural equation modeling (SEM) to investigate the correlations among the internal elements of IVR technology features, learning experiences, and learning outcomes. It also emphasizes the role played by emotional experience in this context. Methods: The sample referenced by this study consisted of 480 college students (193 males) who were simultaneously engaged in guided inquiry and learning in an IVR-based COVID-19 pandemic science museum in groups of 10. Results: The findings suggest that presence and perceived enjoyment have a key mediating effect on the relationship between virtual reality (VR) features and perceived learning outcomes in an IVR-based learning simulation. In addition, the results indicate that presence is more strongly correlated with perceived learning effects, while enjoyment is more strongly correlated with learning satisfaction. Discussion: These findings provide intellectual support and theoretical backing for VR-based instructional design and environmental development. Moreover, this study has practical value with regard to the future large-scale application of IVR to experiential teaching, group-led teaching, and the promotion of the digital transformation and intelligence upgrading in education.

Efficient and Stable Deep-Blue Fluorescent Organic Light-Emitting Diodes Employing a Sensitizer with Fast Triplet Upconversion.

Multiple donor-acceptor-type carbazole-benzonitrile derivatives that exhibit thermally activated delayed fluorescence (TADF) are the state of the art in efficiency and stability in sky-blue organic light-emitting diodes. However, such a motif still suffers from low reverse intersystem crossing rates (kRISC ) with emission peaks <470 nm. Here, a weak acceptor of cyanophenyl is adopted to replace the stronger cyano one to construct blue emitters with multiple donors and acceptors. Both linear donor-π-donor and acceptor-π-acceptor structures are observed to facilitate delocalized excited states for enhanced mixing between charge-transfer and locally excited states. Consequently, a high kRISC of 2.36 × 106 s-1 with an emission peak of 456 nm and a maximum external quantum efficiency of 22.8% is achieved. When utilizing this material to sensitize a blue multiple-resonance TADF emitter, the corresponding device simultaneously realizes a maximum external quantum efficiency of 32.5%, CIEy ≈ 0.12, a full width at half maximum of 29 nm, and a T80 (time to 80% of the initial luminance) of > 60 h at an initial luminance of 1000 cd m-2 .

Exciplex System with Increased Donor-Acceptor Distance as the Sensitizing Host for Conventional Fluorescent OLEDs with High Efficiency and Extremely Low Roll-Off.

Exciplex systems with efficient thermally activated delayed fluorescence as the sensitizing hosts for fluorescent organic light-emitting diodes (OLEDs) have been flourished recently, while the device performances are still lagging behind. Here, a donor molecule sterically encapsulated with tert-butyl units is designed and synthesized to increase the donor-acceptor separation in an exciplex system, leading to reduced singlet-triplet energy gap (Δ ESTs) and improved reverse intersystem crossing (RISC) efficiency. OLEDs utilizing exciplexes with increased donor-acceptor distance ( rDA) as the hosts for conventional fluorescent dopants exhibit a maximum external quantum efficiency (EQEmax) as high as 16.5%, benefiting from the enhanced RISC process and suppressed exciton loss by the Dexter interaction. Furthermore, extremely low efficiency roll-off is obtained with EQEs of 16.2% at 5000 cd/m2 and 15.2% at 10 000 cd/m2. The results here represent the state-of-the-art performances for devices based on exciplexes as the hosts for conventional fluorescent dopants, manifesting the superiority of exciplexes with increased rDA as the sensitizing hosts for fluorescent dopants.

Unveiling the Role of Langevin and Trap-Assisted Recombination in Long Lifespan OLEDs Employing Thermally Activated Delayed Fluorophores.

Recent research studies on noble-metal-free thermally activated delayed fluorescent (TADF) materials have boosted the efficiencies of organic light-emitting diodes (OLEDs) to unity. However, the short lifespan still hinders their further practical application. Carrier recombination pathways have been reported to have a significant influence on the efficiencies of TADF devices, though their effects on device lifetimes remain rarely studied. Here, we have designed and synthesized five pyrimidine or pyrazine/carbazole isomers as hosts for TADF OLEDs to explore the inherent role of Langevin recombination (LR) and trap-assisted recombination (TAR) in device lifetimes. It is revealed that for LR dominant devices, lifetimes would increase by reducing the host triplet energy levels, whereas for TAR dominant devices, lifetimes are insensitive to the host triplet excitons as recombination mainly takes place on dopants. Still, LR dominant devices are favored as they offer more room for optimization. We further apply this concept in designing a stable LR dominant blue TADF device, achieving a long LT50 (lifespan up to 50% of the initial luminance) of 269 h and high external quantum efficiency of 17.9% at 1000 cd m-2 simultaneously.

Blocking Energy-Loss Pathways for Ideal Fluorescent Organic Light-Emitting Diodes with Thermally Activated Delayed Fluorescent Sensitizers.

Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence-sensitized fluorescence (TSF) offer the possibility of attaining an ultimate high efficiency with low roll-off utilizing noble-metal free, easy-to-synthesize, pure organic fluorescent emitters. However, the performances of TSF-OLEDs are still unsatisfactory. Here, TSF-OLEDs with breakthrough efficiencies even at high brightnesses by suppressing the competitive deactivation processes, including direct charge recombination on conventional fluorescent dopants (CFDs) and Dexter energy transfer from the host to the CFDs, are demonstrated. On the one hand, electronically inert terminal-substituents are introduced to protect the electronically active core of the CFDs; on the other hand, delicate device structures are designed to provide multiple energy-funneling paths. As a result, unprecedentedly high maximum external quantum efficiency/power efficiency of 24%/71.4 lm W-1 in a green TSF-OLED are demonstrated, which remain at 22.6%/52.3 lm W-1 even at a high luminance of 5000 cd m-2 . The work unlocks the potential of TSF-OLEDs, paving the way toward practical applications.

Versatile Indolocarbazole-Isomer Derivatives as Highly Emissive Emitters and Ideal Hosts for Thermally Activated Delayed Fluorescent OLEDs with Alleviated Efficiency Roll-Off.

Maintaining high efficiency at high brightness levels is an exigent challenge for real-world applications of thermally activated delayed fluorescent organic light-emitting diodes (TADF-OLEDs). Here, versatile indolocarbazole-isomer derivatives are developed as highly emissive emitters and ideal hosts for TADF-OLEDs to alleviate efficiency roll-off. It is observed that photophysical and electronic properties of these compounds can be well modulated by varying the indolocarbazole isomers. A photoluminescence quantum yield (ηPL ) approaching unity and a maximum external quantum efficiency (EQEmax ) of 25.1% are obtained for the emitter with indolo[3,2-a]carbazolyl subunit. Remarkably, record-high EQE/power efficiency of 26.2%/69.7 lm W-1 at the brightness level of 5000 cd m-2 with a voltage of only 3.74 V are also obtained using the same isomer as the host in a green TADF-OLED. It is evident that TADF hosts with high ηPL values, fast reverse intersystem crossing processes, and balanced charge transport properties may open the path toward roll-off-free TADF-OLEDs.

High-Performance Fluorescent Organic Light-Emitting Diodes Utilizing an Asymmetric Anthracene Derivative as an Electron-Transporting Material.

Fluorescent organic light-emitting diodes with thermally activated delayed fluorescent sensitizers (TSF-OLEDs) have aroused wide attention, the power efficiencies of which, however, are limited by the mutual exclusion of high electron-transport mobility and large triplet energy of electron-transporting materials (ETMs). Here, an asymmetric anthracene derivative with electronic properties manipulated by different side groups is developed as an ETM to promote TSF-OLED performances. Multiple intermolecular interactions are observed, leading to a kind of "cable-like packing" in the crystal and favoring the simultaneous realization of high electron-transporting mobility and good exciton-confinement ability, albeit the low triplet energy of the ETM. The optimized TSF-OLEDs exhibit a record-high maximum external quantum efficiency/power efficiency of 24.6%/76.0 lm W-1 , which remain 23.8%/69.0 lm W-1 at a high luminance of even 5000 cd m-2 with an extremely low operation voltage of 3.14 V. This work opens a new paradigm for designing ETMs and also paves the way toward practical application of TSF-OLEDs.

Multifunctional Materials for High-Performance Double-Layer Organic Light-Emitting Diodes: Comparison of Isomers with and without Thermally Activated Delayed Fluorescence.

Organic light-emitting diodes (OLEDs) with simple structures are attracting a lot of attention nowadays, though their performances are always inferior to those of the more complicated structures as multifunctional materials are rare. Here, we have designed and synthesized multifunctional isomers by combining electron-donating carbazole (Cz) and triphenylamine (TPA) units with electron-accepting triazine (Trz), namely, N-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-[1,1'-biphenyl]-4-amine (CzTPA-p-Trz) and N-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-[1,1'-biphenyl]-4-amine (CzTPA-m-Trz). The use of multiple electron-donating groups gives them suitable highest occupied molecular orbitals for hole injection and high mobilities for hole transport. Hole-only devices with CzTPA-m-Trz or CzTPA-p-Trz as the hole injection layers and hole transport layers show a higher hole current than the widely used 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile/4,4'-N,N'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl system. Interestingly, CzTPA-p-Trz is a fluorescent material with a high photoluminescence quantum yield (PLQY), while CzTPA-m-Trz shows weak thermally activated delayed fluorescence (TADF). As expected, a CzTPA-p-Trz-based undoped double-layer green device achieved a higher external quantum efficiency (EQE) of 4.4% and a higher power efficiency (PE) of 11.8 lm/W. On the other hand, among double-layer devices doped with an orange phosphorescent dopant, a device based on TADF material, CzTPA-m-Trz, achieved higher peak EQE (23.5%) and PE (68.3 lm/W) than those of CzTPA-p-Trz (20.8% and 60.2 lm/W). Even at a high luminance of 5000 cd m-2, a high EQE of 21.8% was retained for CzTPA-m-Trz-based devices. These results are even comparable to those for the state-of-the-art phosphorescent devices based on the same dopant with more complicated structures. The above results indicate that well-designed multifunctional materials are promising for high-performance OLEDs with simple structures.

Highly Efficient Full-Color Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes: Extremely Low Efficiency Roll-Off Utilizing a Host with Small Singlet-Triplet Splitting.

Numerous efforts have been devoted to boost the efficiency of thermally activated delayed fluorescence (TADF) devices; however, strategies to suppress the device efficiency roll-off are still in urgent need. Here, a general and effective approach to suppress the efficiency roll-off of TADF devices is proposed, that is, utilizing TADF materials as the hosts for TADF emitters. Bearing small singlet-triplet splitting (ΔEST) with donor and acceptor units, TADF materials as the hosts possess the potential to achieve matched frontier energy levels with the adjacent transporting layers, facilitating balanced charge injection as well as bipolar charge transport mobilities beneficial to the balanced charges transportation. Furthermore, an enhanced Förster energy transfer from the host to the dopant can be anticipated, helpful to reduce the exciton concentration. Based on the principles, a new TADF material based on indeno[2,1-b]carbazole/1,3,5-triazin derivation is synthesized and used as the universal host for the full-color TADF devices. Remarkable low efficiency roll-off was achieved with above 90% of the maximum external quantum efficiencies (EQEmax's) maintained even at a brightness of 2000 cd/m2, along with EQEmax's of 23.2, 21.0, and 19.2% for orange, green, and sky-blue TADF devices, respectively. Through computational simulation, we identified the suppressed exciton annihilation rates compared with devices adopting conventional hosts. The state-of-the-art low efficiency roll-off of those TADF devices manifests the great potential of such host design strategy, paving an efficient strategy toward their practical application.

Simultaneous Enhancement of Efficiency and Stability of Phosphorescent OLEDs Based on Efficient Förster Energy Transfer from Interface Exciplex.

Exciplex forming cohosts have been widely adopted in phosphorescent organic light-emitting diodes (PHOLEDs), achieving high efficiency with low roll-off and low driving voltage. However, the influence of the exciplex-forming hosts on the lifetimes of the devices, which is one of the essential characteristics, remains unclear. Here, we compare the influence of the bulk exciplex and interface exciplex on the performances of the devices, demonstrating highly efficient orange PHOLEDs with long lifetime at low dopant concentration by efficient Förster energy transfer from the interface exciplex. A bipolar host, (3'-(4,6-diphenyl-1,3,5-triazin-2-yl)-(1,1'-biphenyl)-3-yl)-9-carbazole (CzTrz), was adopted to combine with a donor molecule, tris(4-(9H-carbazol-9-yl)phenyl)amine (TCTA), to form exciplex. Devices with energy transfer from the interface exciplex achieve lifetime almost 2 orders of magnitude higher than the ones based on bulk exciplex as the host by avoiding the formation of the donor excited states. Moreover, a highest EQE of 27% was obtained at the dopant concentration as low as 3 wt % for a device with interface exciplex, which is favorable for reducing the cost of fabrication. We believe that our work may shed light on future development of ideal OLEDs with high efficiency, long-lifetime, low roll-off and low cost simultaneously.

Highly efficient blue thermally activated delayed fluorescent OLEDs with record-low driving voltages utilizing high triplet energy hosts with small singlet-triplet splittings.

The high driving voltage of blue organic light-emitting diodes (OLEDs) based on emitters with thermally activated delayed fluorescence (TADF) remains a constraint for their portable application. A major reason for this is that the high triplet (T1) of the host required to match the blue TADF emitters would always lead to inferiority in terms of carrier injection. Therefore, a suitable host should possess not only a high T1 but also a relatively low singlet (S1) for improved carrier injection, indicating that small singlet-triplet splittings (ΔESTs) are highly desired. Here, four carbazolyl benzonitrile derivatives are facilely prepared in a one-step approach with restrained conjugate lengths to maintain high triplet energies while their highly twisted structures spatially separate the frontier orbital distribution to achieve relatively low ΔESTs. Meanwhile, the charge transporting mobilities of these hosts are effectively tuned by the different linker types of the host moieties. Consequently, high-triplet-energy hosts with favorable carrier injection/transporting abilities are realized, endowing blue TADF devices with a maximum external quantum efficiency of 21.5%, a maximum power efficiency of 42.0 lm W-1 and an ultra-low onset voltage of 2.8 V. It is noteworthy that a driving voltage of 4.9 V is achieved at a practical luminance of 1000 cd m-2, which is the lowest among the doped blue TADF OLEDs reported until now. This work suggests that manipulation of the molecular topologies not only leads to the flexible and feasible design of novel bipolar host materials, but also affords a promising method for fine-tuning physical properties and thus obtaining state-of-the-art device performances.

Highly Efficient Simplified Single-Emitting-Layer Hybrid WOLEDs with Low Roll-off and Good Color Stability through Enhanced Förster Energy Transfer.

Single-emitting layer hybrid white organic light-emitting diodes (SEL-hybrid-WOLEDs) usually suffer from low efficiency, significant roll-off, and poor color stability, attributed to the incomplete energy transfer from the triplet states of the blue fluorophores to the phosphors. Here, we demonstrate highly efficient SEL-hybrid-WOLEDs with low roll-off and good color-stability utilizing blue thermally activated delayed fluorescence (TADF) materials as the host emitters. The triplet states of the blue TADF host emitter can be up-converted into its singlet states, and then the energy is transferred to the complementary phosphors through the long-range Förster energy transfer, enhancing the energy transfer from the host to the dopant. Simplified SEL-hybrid-WOLEDs achieve the highest forward-viewing external quantum efficiency (EQE) of 20.8% and power efficiency of 51.2 lm/W with CIE coordinates of (0.398, 0.456) at a luminance of 500 cd/m(2). The device EQE only slightly drops to 19.6% at a practical luminance of 1000 cd/m(2) with a power efficiency of 38.7 lm/W. Furthermore, the spectra of the device are rather stable with the raising voltage. The reason can be assigned to the enhanced Förster energy transfer, wide charge recombination zone, as well as the bipolar charge transporting ability of the host emitter. We believe that our work may shed light on the future development of highly efficient SEL-hybrid-WOLEDs with simultaneous low roll-off and good color stability.