Emitters In Organic Light-emitting Diodes Research Articles

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of F- and Cl-substituted 8-quinolinolato ligands: synthesis, molecular and electronic structures, fluorescence and application in OLED devices.

Six new four-coordinate tetrahedral boron complexes, containing 9-borafluoren-9-yl and diphenylboron cores attached to orthogonal fluorine- and chlorine-substituted 8-quinolinolato ligand chromophores, have been synthesised, characterised, and applied as emitters in organic light-emitting diodes (OLEDs). An extensive steady-state and time-resolved photophysical study, in solution and in the solid state, resulted in the first-time report of delayed fluorescence (DF) in solid films of 8-quinolinolato boron complexes. The DF intensity dependence on excitation dose suggests that this emission originates from triplet-triplet annihilation (TTA). Density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies give insight into the ground and excited state geometries, electronic structures, absorption energies, and singlet-triplet gaps in these new organoboron luminophores. Finally, given their highly luminescent behaviour, organic light-emitting diode (OLED) devices were produced using the synthesised organoboron compounds as emissive fluorescent dopants. The best OLED displays green-blue (λmaxEL = 489 nm) electroluminescence with an external quantum efficiency (EQE) of 3.3% and a maximum luminance of 6300 cd m-2.

Indole-fused BN-heteroarenes as narrowband blue emitters for organic light-emitting diodes

Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters based on a novel indole-fused BN-heteroarene (InBN) are developedviaa π-truncation strategy. Narrowband blue-emitting OLEDs are demonstrated with high EQEs of up to 16.8%.

Double-locked narrowband hybrid locally-excited and charge-transfer emitter exhibiting amplified spontaneous emission

<p>Hybrid Locally-excited and Charge-Transfer (HLCT) materials have garnered significant attention for their high exciton utilization efficiency in organic light-emitting diodes (OLEDs). However, conventional HLCT materials suffer from broad emission, which limits their applications. In this study, we report a narrowband HLCT emitter, namely 10-(dimesitylboranyl)-8,8,12,12-tetraphenyl-8,12-dihydrobenzo[9,1]quinolizino[3,4,5,6,7-<i>klmn</i>]phenoxazine (PXZ-DL), incorporated by double-locked intramolecular connection. PXZ-DL exhibits a narrow emission spectrum with a small full width at half-maximum (FWHM) of 35 nm and 47 nm in solution and as an OLED emitter, respectively. Moreover, PXZ-DL demonstrates a high photoluminescence quantum yield of 100% and an external quantum efficiency of 8.0%. Additionally, PXZ-DL demonstrates excellent performance in amplified spontaneous emission with a low threshold of 5.7 ��J cm<sup>-2</sup> and a narrow FWHM of 11 nm. The intramolecular lock strategy offers a promising approach for the development of HLCT materials with high color purity.</p>

Deep-Blue Triplet-Triplet Annihilation Organic Light-Emitting Diode (CIEy ≈ 0.05) Using Tetraphenylimidazole and Benzonitrile Functionalized Anthracene/Chrysene Emitters.

Herein, new deep-blue triplet-triplet annihilation (TTA) molecules, namely 4-(10-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)anthracen-9-yl)benzonitrile (TPIAnCN) and 4-(12-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)chrysen-6-yl)benzonitrile (TPIChCN), are designed, synthesized, and investigated as emitters for organic light-emitting diodes (OLED). TPIAnCN and TPIChCN are composed of polyaromatic hydrocarbons of anthracene (An) and chrysene (Ch) as the cores functionalized with tetraphenylimidazole (TPI) and benzonitrile (CN) moieties, respectively. The experimental and theoretical results verify their excellent thermal properties, photophysical properties, as well as electrochemical properties. Particularly, their emissions are in the deep blue region, with TTA emissions being observed in their thin films. By utilization of these molecules as emitters, deep blue TTA OLEDs with CIE coordinates of (0.15, 0.05), high external quantum efficiency of 6.84%, and high exciton utilization efficiency (ηs) of 48% were fabricated. This result manifests the potential use of chrysene as an alternate building block to formulate new TTA molecules for accomplishing high-performance TTA OLEDs.

Anomalous circularly polarized light emission in organic light-emitting diodes caused by orbital–momentum locking

Chiral circularly polarized (CP) light is central to many photonic technologies, from optical communication of spin information to novel display and imaging technologies. As such, there has been significant effort in the development of chiral emissive materials that allow for the emission of strongly dissymmetric CP light from organic light-emitting diodes (OLEDs). A consensus for chiral emission in such devices is that the molecular chirality of the active layer determines the favored light handedness of CP emission, regardless of the light-emitting direction. Here, we discover that, unconventionally, oppositely propagating CP light exhibits opposite handedness, and reversing the current-flow in OLEDs also switches the handedness of the emitted CP light. This direction-dependent CP emission boosts the net polarization rate by orders of magnitude by resolving an established issue in CP-OLEDs, where the CP light reflected by the back electrode typically erodes the measured dissymmetry. Through detailed theoretical analysis, we assign this anomalous CP emission to a ubiquitous topological electronic property in chiral materials, namely the orbital-momentum locking. Our work paves the way to design new chiroptoelectronic devices and probes the close connections between chiral materials, topological electrons, and CP light in the quantum regime.

Correlating Exciton Dynamics of Thermally Activated Delayed-Fluorescence Emitters to Efficiency Roll-Off in OLEDs

Physical parameters, such as decay rates and photoluminescence (PL) quantum efficiencies, associated with thermally activated delayed fluorescence (TADF) emitters play a critical role in determining the performance of organic light-emitting diodes (OLEDs). Herein, we investigate the impact of TADF decay rates and PL quantum efficiencies on external quantum efficiency (EQE) roll-off. Our analysis reveals that a high EQE with suppressed efficiency roll-off in TADF OLEDs can be achieved by shortening the delayed lifetime with an increasing delayed contribution or by shortening the prompt lifetime with increasing prompt contribution simultaneously. We further show that TADF compounds with long delayed and/or prompt lifetimes can give rise to multiple spin cycling and subsequently result in significant exciton quenching and efficiency roll-off in OLEDs. These results provide universal selection criteria for TADF emitters in OLEDs to concurrently achieve a high maximum EQE and low-efficiency roll-off.

Bulky Iridium NHC Complexes for Bright, Efficient Deep‐Blue OLEDs

AbstractFour new deep‐blue‐emitting iridium(III) NHC complexes containing sterically demanding ligands are synthesized. The four complexes show bright, deep‐blue emission, with emission maxima between 420 and 427 nm in both acetonitrile solution and 30 wt% doped films in TSPO1; the two meridional isomers showing photoluminescence quantum yields, ΦPL, in doped films of 80% and 89%. The two meridional isomers are used to assess the impact of emitters containing bulky, sterically demanding ligands on the performance of organic light‐emitting diodes (OLEDs). OLEDs employing a stepped doping profile with mer‐Ir(tfpi_tmBn)3 as the emitter produce the highest performing devices in this study, with these devices exhibiting deep‐blue [λEL = 429 nm, CIE = (0.16, 0.08)] emission and a maximum external quantum efficiency (EQEmax) of 14.9%, which decreases to 11.7% at 100 cd m−2. The performance of the OLEDs shows very good efficiencies and moderate efficiency roll‐offs in comparison to reported phosphorescent deep‐blue OLEDs with CIEy ≤ 0.08, as required for commercial displays. The promising results suggest that the design strategy of adding steric bulk to blue emitting iridium complexes containing NHC ligands is a useful strategy for reducing intermolecular interactions between emitters in OLEDs.

Highly Efficient Green and Red Narrowband Emissive Organic Light-Emitting Diodes Employing Multi-Resonant Thermally Activated Delayed Fluorescence Emitters.

Herein, we demonstrate how judicious selection of the donor decorating a central multi-resonant thermally activated delayed fluorescence (MR-TADF) core based on DiKTa can lead to very high-performance OLEDs. By decorating the DiKTa core with triphenylamine (TPA) and diphenylamine (DPA), 3TPA-DiKTa and 3DPA-DiKTa exhibit bright, narrowband green and red emission in doped films, respectively. The OLEDs based on these emitters showed record-high performance for this family of emitters with maximum external quantum efficiencies (EQEmax ) of 30.8 % for 3TPA-DiKTa at λEL of 551 nm and 16.7 % for 3DPA-DiKTa at λEL =613 nm. The efficiency roll-off in the OLEDs was improved significantly by using 4CzIPN as an assistant dopant in hyperfluorescence (HF) devices. The outstanding device performance has been attributed to preferential horizontal orientation of the transition dipole moments of 3TPA-DiKTa and 3DPA-DiKTa.

A Thermally Activated Delayed Fluorescence Emitter Investigated by Time-Resolved Near-Infrared Spectroscopy.

Emitters for organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) require small singlet (S1 )-triplet (T1 ) energy gaps as well as fast intersystem crossing (ISC) transitions. These transitions can be mediated by vibronic mixing with higher excited states Sn and Tn (n=2, 3, 4, …). For a prototypical TADF emitter consisting of a triarylamine and a dicyanobenzene moiety (TAA-DCN) it is shown that these higher states can be located energetically by time-resolved near-infrared (NIR) spectroscopy.

Dense Local Triplet States and Steric Shielding of a Multi-Resonance TADF Emitter Enable High-Performance Deep-Blue OLEDs.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) molecules based on boron and nitrogen atoms are emerging as next-generation blue emitters for organic light-emitting diodes (OLEDs) due to their narrow emission spectra and triplet harvesting properties. However, intermolecular aggregation stemming from the planar structure of typical MR-TADF molecules that leads to concentration quenching and broadened spectra limits the utilization of the full potential of MR-TADF emitters. Herein, a deep-blue MR-TADF emitter, pBP-DABNA-Me, is developed to suppress intermolecular interactions effectively. Furthermore, photophysical investigation and theoretical calculations reveal that adding biphenyl moieties to the core body creates dense local triplet states in the vicinity of S1 and T1 energetically, letting the emitter harvest excitons efficiently. OLEDs based on pBP-DABNA-Me show a high external quantum efficiency (EQE) of 23.4% and a pure-blue emission with a Commission Internationale de L'Eclairage (CIE) coordinate of (0.132, 0.092), which are maintained even at a high doping concentration of 100wt%. Furthermore, by incorporating a conventional TADF sensitizer, deep-blue OLEDs with a CIE value of (0.133, 0.109) and an extremely high EQE of 30.1% are realized. These findings provide insight into design strategies for developing efficient deep-blue MR-TADF emitters with fast triplet upconversion and suppressed self-aggregation.

Highly Efficient Au(I) Alkynyl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs.

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %.

Photo- and electro-luminescent properties of difluoroboron complexes based on the carbazole-functionalized 2-(benzo[d]thiazol-2-yl)phenol ligands

This article describes the synthesis and luminescent properties of two carbazole-functionalized 2-(benzo[d]thiazol-2-yl)phenol ligands (BTZ-Cz-OH and BTZ-DCz-OH) and their difluoroboron complexes (BTZ-Cz-BF and BTZ-DCz-BF) as the emitting materials. All of the emitting materials were characterized by NMR (1H and 13C) spectroscopy, high-resolution mass spectroscopy and elemental analysis, and they possess good thermal and electrochemical stabilities. The ligands exhibit green emission in solution and solid thin films due to the characteristics of excited-state intramolecular proton-transfer (ESIPT). Upon coordination to the difluoroboron complexes, a significant blue-shift and enhanced emission is observed due to the restricted conformation change. These materials are successfully used as the doped emitters in organic light-emitting diodes (OLEDs), and all the doped devices exhibit strong emission with low turn-on voltages (3.9–4.8 V), and the doped devices based on the difluoroboron complexes exhibit better EL performances than that of the ligands. Especially, the doped device of BTZ-Cz-BF with the dopant concentration of 10 wt% shows the best EL performances with a maximum luminescence of 3940 cd/m2, a maximum current efficiency of 8.26 cd/A and a maximum external quantum efficiency (EQE) of 3.34%.

Towards Efficient Blue Delayed-Fluorescence Molecules by Modulating Torsion Angle Between Electron Donor and Acceptor

Towards Efficient Blue Delayed-Fluorescence Molecules by Modulating Torsion Angle Between Electron Donor and Acceptor

Oxalamide/Amide Ligands: Enhanced and Copper-Catalyzed C-N Cross-Coupling for Triarylamine Synthesis.

Triarylamines are privileged core structures that are found in versatile optoelectronic materials. New methods are constantly being sought for their preparation. Herein, a new protocol for triarylamine synthesis is presented where a wide range of diarylamines couple smoothly with aryl bromides mediated by a copper oxalamide (or amide) catalytic system. Notably, a new non-C2-symmetric 1-isoquinolinamide-based N,N-/N,O-bidentate ligand was introduced that could tolerate bulky diarylamines. Plenty of known optoelectronic functional molecules could be synthesized in good to excellent yields. The practicality of this C-N cross-coupling was illustrated by the gram-scale synthesis of a patented thermally activated delayed fluorescence emitter for organic light-emitting diodes.

3-(N,N-Diphenylamino)carbazole Donor Containing Bipolar Derivatives with Very High Glass Transition Temperatures as Potential TADF Emitters for OLEDs

Well-defined electroactive bipolar derivatives of new structure have been synthesized from 3-(N,N-diphenylamino)-9H-carbazole and bis(4-fluorophenyl)sulfone, 4-fluorophenylsulfone or 4,4′-difluorobenzophenone, respectively. The full characterization of their structure is described. The amorphous materials with very high glass transition temperatures of 111–173 °C also possess high thermal stability, with onset decomposition temperatures of 351–398 °C. Some of the compounds having the best solubility were tested as the emitters dispersed in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) host for preparation of organic light emitting diodes (OLEDs). A device containing 15 wt% of the guest bis[4-{3-(N,N-diphenylamino)carbazol-9-yl}phenyl] sulfone demonstrated the best overall characteristics with maximum brightness exceeding 2630 cd/m2, current efficiency of 3.2 cd/A, power efficiency of 2.2 lm/W, and external quantum efficiency exceeding 1.7% at 100 cd/m2.

The Selection of Anode and Cathode Materials for Top Emission Organic Light-Emitting Diodes

In this study top emission organic light-emitting diodes (TE-OLED) were successfully fabricated on flexible PET/multilayer disordered silver nanonetwork (MDSN) substrate with conventional LiF/Al as a semitransparent cathode and Ag as a reflective anode. The effects of the hole injection layer, anode buffer layer, and an electron injection layer on the luminescence characteristics of TE-OLEDs were investigated. At first, the thickness of cathode Al is adjusted based upon the overall transmittance of the top-emission cathode and its conductivity. There is a high energy barrier for the hole between the work function of the anode Ag (4.2 eV) and the NPB highest occupied molecular orbital (HOMO) energy level (5.5 eV), which is not favorable for hole injection. This study tested four types of hole injection layer (HIL) materials. Finally, MoO3 was selected as an optimal HIL material, and the optimum thickness was adjusted, enabling the hole to be injected smoothly from the anode to the NPB and then to an emitting layer. The TE-OLED luminance reached 268 cd/m2. There is a high energy barrier between the work function of Ag and MoO3 HOMO (5.3 eV)—about 1.1 eV—which is still not conducive to the hole injection, so a thin layer of high work function metal Au (work function 5.1 eV) was added to the top of the anode silver, which more matches with the MoO3 energy level. It can make the hole easier to inject from the anode to MoO3 (HIL) and protect the silver from oxidation. At 8 V, the luminance is increased to 413.7 cd/m2, and the current efficiency is 0.81 cd/A. The luminance is significantly improved. An electron transport/hole blocking layer TPBi (10 nm) was added to enhance the electron transport capability and effectively block the holes with higher electron mobility and a higher HOMO energy level of TPBi. So that more holes can remain in the emitting layer and increase the chance of the electron-hole recombination to improve the luminance and current efficiency of TE-OLED. At 8 V, the luminance and current efficiency can reach 611.4 cd/m2 and 0.95 cd/A, respectively.

Plasmon loss improved top emission organic light-emitting diode with multi capping layer

Here, we report surface plasmon (SP) loss improved top-emitting organic light emitting diodes (TEOLEDs) by applying our unique cathode unit structure. Generally, the TEOLED has high optical loss portion of SP mode compared to the bottom emitting OLED and it causes low out-coupling efficiency in the TEOLED. Commonly used TEOLED structure uses Ag:Mg (10:1, 22 nm) cathode with high refractive index single capping layer, which has high optical loss portion of SP mode. To reduce SP mode loss in the TEOLED, we applied thin Ag:Mg (10:1, 12 nm) cathode with multi-capping layer. Our cathode unit reduces 55% of SP loss and enhances about 20% efficiency. Our approach to enhance out-coupling efficiency will be useful to make high efficiency TEOLEDs.

Hydroxy-Tetraphenylimidazole Derivatives as Efficient Blue Emissive Materials for Electroluminescent Devices.

Herein, three hydroxy-tetraphenylimidazole (HPI)-based fluorophores (HPI-TPA, HPI-PCz, and HPI-CzP) are designed and synthesized by disubstituted HPI core with arylamine units of triphenylamine (TPA), phenyl carbazole (PCz), and carbazole phenyl (CzP) at 3,5-positions of the N-phenyl ring of HPI, respectively. Their photophysical properties are theoretically and experimentally examined. HPI-TPA shows a hybridized local and charge transfer (HLCT) excited state characteristic and emits deep blue color via an HLCT mechanism, while both HPI-PCz and HPI-CzP exhibit excited-state intramolecular proton transfer (ESIPT) property and display pure keto form emissions. They possess high thermal stability and are successfully fabricated as emitters in organic light-emitting diodes (OLEDs). All devices exhibit intense blue color emissions with low turn-on voltages (3.5-3.7 V). Particularly, HPI-TPA-based OLED emits light in the deep-blue region with a high maximum external quantum efficiency (EQEmax ) of 3.77% and a decent efficiency roll-off.

Chrysene-Cored Fluorescent Dendrimers as Nondoped Deep-Blue Emitters for Solution-Processable Electroluminescent Devices

AbstractNew solution-processable chrysene-basked deep-blue fluorescent dendrimers consisting of chrysene as a core end-capped by carbazole dendrons were designed, synthesized, and characterized. These dendrimers exhibit strong deep-blue emissions in solution or thin-film states with decent hole mobility and high thermal and electrochemical stability. They can be effectively used as nondoped emitters in organic light-emitting diodes (OLEDs). The nondoped OLEDs, which have a simple structure, showed good electroluminescence (EL) performance (luminance: 2334–2400 cd m–2; external quantum efficiency: 1.88-2.51%; turn-on voltage: 3.8–4.0 V) and deep-blue EL spectra (CIE y: 0.065–0.075) with a narrow full width at half maximum of 61–65 nm.

Rare Earth Complexes with 5d-4f Transition: New Emitters in Organic Light-Emitting Diodes.

Organic light-emitting diodes (OLEDs) are considered as next-generation displays and lighting technologies. During the past three decades, various luminescent materials such as fluorescence, phosphorescence, and thermally activated delayed fluorescence materials have been subsequently investigated as emitters. To date, blue OLEDs are still the bottleneck as compared to red and green ones because of the lack of efficient emitters with simultaneous high exciton utilization efficiency and long-term stability. Recently, d-f transition rare earth complexes have been reported as new emitters in OLEDs with potential high efficiency and stability. In this Perspective, we present a brief introduction to OLEDs and an overview of the previous electroluminescence study on d-f transition rare earth complexes. This is followed by our recent developments in cerium(III) complex- and europium(II) complex-based OLEDs. We finally discuss the challenges and opportunities for OLED study based on d-f transition rare earth complexes.