Efficient Fluorescent Organic Light-emitting Diodes Research Articles

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

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

Dimethyl-dihydroindenocarbazole-anthracene-phenanthroimidazole based hybridized local and charge-transfer molecules as efficient nondoped deep-blue emitters for highly efficient fluorescent organic light-emitting diodes

The pursuit of hybridized local and charge transfer (HLCT) excited state-based emitters is a promising strategy to achieve high external quantum efficiency in blue organic light-emitting diodes (OLEDs). Two isomeric dimethyl-dihydroindenocarbazole-anthracene-phenanthroimidazole-based emissive molecules (PhAnsIn and PhAnoIn) were designed and explored based on the HLCT scheme. All molecules possessed the HLCT excited-state characters, according to the photophysical investigation and density functional theory calculations. Consequently, PhAnsIn and PhAnoIn showed good blue emission with peaks at 457 and 464 nm and photoluminescence quantum yield of 80.6% and 56.5% in neat films, respectively. The fabricated blue OLEDs with PhAnsIn and PhAnoIn as emitters also realized the corresponding blue emission with electroluminescence peaks at 458 and 457 nm, respectively. The nondoped devices based on PhAnsIn and PhAnoIn exhibited maximum external quantum efficiencies of 8.2% and 8.5% with CIE coordinates of (0.14, 0.12) and (0.14, 0.11), respectively.

(Invited) Structural Analysis of Organic Semiconducting Materials By Solid State NMR

Recently, our group have successfully developed several blue and green thermally activated delayed fluorescence (TADF) emitters showing high external quantum efficiencies in OLEDs through high-throughput screening based on quantum chemical calculations. Although a number of highly efficient TADF emitters have been reported, the study about their conformation and aggregated structure in an amorphous states, which is expected to be the origin of high device performance, is still limited. Thus we have carried out multiscale simulations and solid-state NMR (ssNMR) analysis of organic amorphous thin films. The ssNMR is one of the powerful technique to acquire the structural information of amorphous aggregated materials, which has been difficult by diffraction techniques due to the lack of long range order for amorphous state. In this presentation, we demonstrate ssNMR analysis of amorphous organic semiconducting materials.Reference(1) “Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy”, Suzuki, K.; Kubo, S.; Aussenac, F.; Engelke, F.; Fukushima, T.; Kaji, H. Angew. Chem. Int. Ed. 2017, 56, 14842.(2) “Efficient blue thermally activated delayed fluorescence emitters showing very fast reverse intersystem crossing”, Ren, Y., Wada, Y., Suzuki, K., Kusakabe, Y., Geldsetzer, J. and Kaji, H. Appl. Phys. Express, 2021, 14, 071003.(3) “Solution-processable thermally activated delayed fluorescence emitters for application in organic light emitting diodes”, Suzuki, K.; Adachi, C.; Kaji, H. J. Soc. Inf. Disp. 2017, 25, 480.(4) “Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching”, Moon, C.-K.; Suzuki, K.; Shizu, K.; Adachi, C.; Kaji, H.; Kim, J.-J. Adv. Mater. 2017, 131, 6614.(5) “Triarylboron-based Fluorescent Organic Light-emitting Diodes with External Quantum Efficiencies Exceeding 20%”, Suzuki, K.; Kubo, S.; Shizu, K.; Fukushima, T.; Wakamiya, A.; Murata, Y.; Adachi, C.; Kaji, H.; Angew. Chem. Int. Ed. 2015, 54, 15231.(5) “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, Kaji, H.; Suzuki, H.; Fukushima, T.; Shizu, K.; Suzuki, K.; Kubo, S.; Komino, T.; Oiwa, H.; Suzuki, F.; Wakamiya, A.; Murata, Y.; Adachi, C. Nat. Commun. 2015, 6, 8476.

(Invited) Structural Analysis of Organic Semiconducting Materials Using Solid-State NMR

Our research group is currently conducting basic research on organic light-emitting diodes (OLEDs). Recently, we have successfully developed a series of blue and green TADF emitters for OLEDs realizing high external quantum efficiencies through high-throughput screening based on quantum chemical calculations. However, even using highly efficient emitting materials, the device performance depends on the device structure and aggregated state of organic molecules in the device. To understand the origin of the device performance, both theoretical and experimental approaches are important. In this regards, we have also carried out multiscale simulations and solid-state NMR (ssNMR) analysis of organic amorphous thin films. The ssNMR is the powerful technique for the detailed experimental analysis of amorphous aggregated materials, which has been difficult by typical diffraction methods because organic molecules in OLEDs are in the amorphous state. In this presentation, we demonstrate the structural analysis of organic semiconducting materials using ssNMR. Also, we we show the analysis of molecular orientation of an organic semiconducting material in an amorphous thin film state using DNP-ssNMR, which is one of the most powerful sensitivity enhancement technique of NMR.Reference(1) “Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy”, Suzuki, K.; Kubo, S.; Aussenac, F.; Engelke, F.; Fukushima, T.; Kaji, H. Angew. Chem. Int. Ed. 2017, 56, 14842.(2) “Solution-processable thermally activated delayed fluorescence emitters for application in organic light emitting diodes”, Suzuki, K.; Adachi, C.; Kaji, H. J. Soc. Inf. Disp. 2017, 25, 480.(3) “Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching”, Moon, C.-K.; Suzuki, K.; Shizu, K.; Adachi, C.; Kaji, H.; Kim, J.-J. Adv. Mater. 2017, 131, 6614.(4) “Triarylboron-based Fluorescent Organic Light-emitting Diodes with External Quantum Efficiencies Exceeding 20%”, Suzuki, K.; Kubo, S.; Shizu, K.; Fukushima, T.; Wakamiya, A.; Murata, Y.; Adachi, C.; Kaji, H.; Angew. Chem. Int. Ed. 2015, 54, 15231.(5) “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, Kaji, H.; Suzuki, H.; Fukushima, T.; Shizu, K.; Suzuki, K.; Kubo, S.; Komino, T.; Oiwa, H.; Suzuki, F.; Wakamiya, A.; Murata, Y.; Adachi, C. Nat. Commun. 2015, 6, 8476.

Two-channel singlet exciton harvesting for high efficiency fluorescent organic light-emitting diodes using dual thermally activated delayed fluorescence mechanism

A two-channel singlet exciton harvesting device was developed to improve the external quantum efficiency (EQE) of the fluorescent organic light-emitting diodes (OLEDs) using a dual, thermally activated delayed fluorescence (TADF) mechanism. The emitting layer consisted of two TADF materials, the 10,10'-(sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine) (DMAC-DPS) TADF emitter and the TADF exciplex formed between DMAC-DPS and ((1,3,5-triazine-2,4,6-triyl)tris(benzene-3,1-diyl))tris(diphenylphosphine oxide) (POT2T), and a green fluorophore. The DMAC-DPS serves as the main TADF matrix, which transports carriers, forms excitons, and harvests the singlet excitons of the fluorophore, whereas the DMAC-DPS:POT2T exciplex played a role of a second TADF material harvesting the singlet excitons of the fluorophore while suppressing the Dexter energy transfer. The exciplex was dispersed in the DMAC-DPS by managing the POT2T content, which reduced triplet-triplet-annihilation of the exciplex while suppressing Dexter energy transfer to the fluorophore. The two-channel singlet exciton harvesting mechanism maximized the singlet exciton formation, which enhanced the EQE of the fluorescent OLEDs from 10.3% to 15.0% compared to the conventional singlet exciton harvesting device using either TADF compound or TADF exciplex.

Triazolotriazine-based thermally activated delayed fluorescence materials for highly efficient fluorescent organic light-emitting diodes (TSF-OLEDs)

Thermally activated delayed fluorescence (TADF) sensitized fluorescent organic light-emitting diodes (TSF-OLEDs) have shown great potential for the realization of high efficiency with low efficiency roll-off and good color purity. However, the superior examples of TSF-OLEDs are still limited up to now. Herein, a trade-off strategy is presented for designing efficient TADF materials and achieving high-performance TSF-OLEDs via the construction of a new type of triazolotriazine (TAZTRZ) acceptor. The enhanced electron-withdrawing ability of TAZTRZ acceptor, fused by triazine (TRZ) and triazole (TAZ) together, enables TADF luminogens with small singlet-triplet energy gap (ΔEST) values. Meanwhile, the increased planarity from the TRZ-phenyl linkage (6:6 system) to the TAZ-phenyl linkage (5:6 system) can compensate the decrease of oscillator strength (f) while lowing ΔEST, thus achieving a trade-off between small ΔEST and high f. As a result, the related TSF-OLED achieved an extremely low turn-on voltage of 2.1 V, an outstanding maximum external quantum efficiency (EQEmax) of 23.7% with small efficiency roll-off (EQE1000 of 23.2%; EQE5000 of 20.6%) and an impressively high maximum power efficiency of 82.1 lm W−1, which represents the state-of-the-art performance for yellow TSF-OLEDs.

Combined Inter- and Intramolecular Charge-Transfer Processes for Highly Efficient Fluorescent Organic Light-Emitting Diodes with Reduced Triplet Exciton Quenching.

Inter- and intramolecular charge-transfer processes are combined using an exciplex-forming host and a thermally activated delayed fluorescent dopant, for fabricating efficient fluorescent organic light-emitting diodes along with the reduced efficiency roll-off at high current densities. Extra conversion on the host from triplet exciplexes to singlet exciplexes followed by energy transfer to the dopant reduces population of triplet excitons on dopant molecules, thereby reducing the triplet exciton annihilations at high current densities.

Triplet-triplet annihilation in highly efficient fluorescent organic light-emitting diodes: current state and future outlook.

Studies of delayed electroluminescence in highly efficient fluorescent organic light-emitting diodes (OLEDs) of many dissimilar architectures indicate that the triplet-triplet annihilation (TTA) significantly increases yield of excited singlet states-emitting molecules in this type of device thereby contributes substantially to their efficiency. Towards the end of the 2000s, the essential role of TTA in realizing highly efficient fluorescent devices was widely recognized. Analysis of a diverse set of fluorescent OLEDs shows that high efficiencies are often cor-related to TTA extents. It is therefore likely that it is the long-term empirical optimization of OLED efficiencies that has resulted in fortuitous emergence of TTA as a large and ubiquitous contributor to efficiency. TTA contributions as high as 20-30% are common in the state-of-the-art OLEDs, and even become dominant in special cases, where TTA is shown to substantially exceed the spin-statistical limit. The fundamental features of OLED efficiency enhancement via TTA-molecular structure-dependent contributions, current density-dependent intensities in practical devices and frequently observed antagonistic relationships between TTA extent and OLED lifetime-came to be understood over the course of the next few years. More recently, however, there was much less reported progress with respect to all-important quantitative details of the TTA mechanism. It should be emphasized that, to this day and despite the decades of work on improving blue phosphorescent OLEDs as well as the recent advent of thermally activated delayed fluorescence OLEDs, the majority of practical blue OLEDs still rely on TTA. Considering such practical importance of fluorescent blue OLEDs, the design of blue OLED-compatible materials capable of substantially exceeding the spin-statistical limit in TTA, elimination of the antagonistic relationship between TTA-related efficiency gains and lifetime losses, and designing devices with an extended range of current densities producing near-maximum TTA electroluminescence are the areas where future improvements would be most beneficial.

Enhanced efficiency in nondoped, blue organic light-emitting diodes utilizing simultaneously local excition and two charge-transfer exciton from benzimidazole-based donor–acceptor molecules

The simultaneous utilization of all charge-transfer excitons and local excitons is the pathway to obtain the high efficiency fluorescent organic light-emitting diodes (FOLEDs). Here, a twisted intramolecular charge transfer state (TICT-state), a planar intramolecular charge transfer state (ICT-state), and a locally excited state (LE-state) are demonstrated to enhance the occurrence of singlet excitons in the fluorescent emitters, which are based on benzimidazole and triphenylamine donor–acceptor derivatives. The synthesis, photophysics and electroluminescent (EL) performance are studied systematically. The fluorescence emitters (TPABBBI and TPABBI) with the special TICT and ICT characteristics realize the electron–hole (e–h) recombination via intramolecular conversion from charge-transfer excitons to radiative singlet exciton. The devices based on them show high efficiency (5.1 cd/A, 5.77 lm/W, 5.66% of EQEm for TPABBBI and 3.56 cd/A, 3.11 lm/W, 4.23% for TPABBI), low efficiency roll-off at high luminance and stable blue emission.

C60:LiF nanocomposite for high power efficiency fluorescent organic light-emitting diodes

To reduce the driving voltage, and hence enhance the power efficiency of OLEDs, the mobility of the various carrier transport layers needs to be increased. Buckminsterfullerene (C60) has been proposed to be one possible alternative conductive electron transport layer (ETL) to enhance the power efficiency in OLEDs, due to its high conductivity and the formation of an ohmic contact with the LiF/Al cathode. The optical properties of a nanocomposite of C60 with LiF (C60:LiF) and its potential as an efficient ETL in OLEDs was studied. With proper optimization of the device structure, a more than 50% improvement in the power efficiency, without sacrificing the high EQE, in optimized fluorescent OLEDs with the use of C60:LiF nanocomposite ETL was achieved.

Triplet annihilation exceeding spin statistical limit in highly efficient fluorescent organic light-emitting diodes

We have demonstrated that the exemplary red fluorescent organic light-emitting diodes (OLEDs) gain as much as half of their electroluminescence from annihilation of triplet states generated by recombining charge carriers. The magnitude of triplet-triplet annihilation (TTA) contribution in combination with the remarkably high total efficiencies [>11% external quantum efficiency (EQE)] indicates that the absolute amount of electroluminescence attributable to TTA substantially exceeds the limit imposed by spin statistics, which was independently confirmed by studying magnetic field effects on delayed luminescence. We determined the value of 1.3 for the ratio of the rate constants of singlet and triplet channels of annihilation, which is indeed substantially higher than the value of 0.33 expected for a purely statistical annihilation process. It is, however, in an excellent quantitative agreement with the extent of the experimental contribution of delayed luminescence to steady-state electroluminescence. The nonstatistical branching ratio of the two annihilation channels is attributed to the favorable relationship between the energies of the excited singlet and triplet states of rubrene—emissive layer host. We surmise that, with the appropriate emissive layer materials, the fluorescent OLED devices are capable of using a considerably larger fraction of triplet states than was previously believed. In principle, the upper limit for the singlet excited state yield in the TTA process is 0.5, which makes the maximum internal quantum efficiency of fluorescent OLEDs to be 25%+0.5×75%=62.5%. The estimates of maximum EQE of the fluorescent OLEDs should be revised to at least 0.2×62.5%=12.5% and, likely, even higher to account for optical outcoupling exceeding 0.2.