Thermally Activated Delayed Fluorescence Compounds Research Articles

Rational Design of Organic Emitters with Inverted Singlet-Triplet Gaps for Enhanced Exciton Management.

In organic light-emitting diodes (OLEDs), the pursuit of efficient molecular emitters has led to the development of thermally activated delayed fluorescence (TADF) molecules. While TADF compounds have promising properties, they face challenges such as energy gap constraints and uphill exciton transfer. Inverted emitters (INVEST) offer a novel solution with an inverted singlet-triplet energy (ΔEST) gap, enabling efficient utilization of excitons. This study examines the design and computational analysis of an array of molecules, including 23 INVEST emitters and remaining with positive energy gaps. Within the STEOM-DLPNO-CCSD framework, we explore the role of various molecular fragments in determining ΔEST. We also assess the importance of dynamic spin-polarization (DSP) obtained via the Pariser-Parr-Pople (PPP) scheme in energy gap determination. Exciting trends emerged from our results, with pentalene-containing compounds consistently manifesting negative ΔEST values while their naphthalene counterparts exhibited contrasting behavior. Moreover, we observed a negative DSP correlates with inverted singlet-triplet gaps. Overall, this research advances OLED materials through molecular design and computational analysis, offering avenues for optimizing exciton management and enhancing device performance.

Chiral Sulfonyl Binaphthalene‐Based Thermally Activated Delayed Fluorescence Materials for Circularly Polarized Electroluminescence

AbstractChiral emitters capable of producing circularly polarized luminescence (CPL) with high dissymmetry factors (g) are crucial for circularly polarized organic light‐emitting diodes (CP‐OLEDs) and 3D display. Herein, sulfonyl binaphthalene is incorporated as both electron acceptor and chiral source into three pairs of thermally activated delayed fluorescence (TADF) enantiomers, (R/S)‐BPSTCZ, (R/S)‐BPSDMAC, and (R/S)‐BPSPXZ, for the first time, combining tert‐butylcarbazole, 9,9‐dimethyl‐9,10‐dihydro‐acridine and phenoxazine electron donors, respectively. These TADF compounds exhibit tunable emissions spanning from deep blue to green, accompanied by high photoluminescence quantum yields. Due to the large distorted angles caused by two sulfonyl units, all enantiomers exhibit pronounced CPL with |gPL| factors of up to 6.0 × 10−3 in doped films. The corresponding CP‐OLEDs display good performances with external quantum efficiencies of up to 28.5% and notable |gEL| factors of up to 8.8 × 10−3, surpassing most CP‐OLEDs based on chiral TADF materials.

Synthetic progress of organic thermally activated delayed fluorescence emitters via C-H activation and functionalization.

Thermally activated delayed fluorescence (TADF) emitters have become increasingly prominent due to their promising applications across various fields, prompting a continuous demand for developing reliable synthetic methods to access them. This review aims to highlight the progress made in the last decade in synthesizing organic TADF compounds through C-H bond activation and functionalization. The review begins with a brief introduction to the basic features and design principles of TADF emitters. It then provides an overview of the advantages and concise development of C-H bond transformations in constructing TADF emitters. Subsequently, it summarizes both transition-metal-catalyzed and non-transition-metal-promoted C-H bond transformations used for the synthesis of TADF emitters. Finally, the review gives an outlook on further challenges and potential directions in this field.

Reverse intersystem crossing mechanisms in doped triangulenes.

Thermally activated delayed fluorescence (TADF) has emerged as one of the most promising strategies in the quest for organic light emitting diodes with optimal performance. This computational study dissects the mechanistic intricacies of the central photophysical step, reverse intersystem crossing (rISC) in N and B doped triangulenes as potential multi-resonance TADF compounds. Optimal molecular patterns conducive to efficient rISC, encompassing dopant atom size, number, and distribution, are identified. Additionally, we assess various electronic structure methods for characterizing TADF-relevant molecular systems. The findings identify the distinct role of the direct and mediated mechanisms in rISC, and provide insights into the design of advanced TADF chromophores for next-generation OLED technology.

Modulation of nonradiative emission decay rate by spacer unit in donor-acceptor TADF compounds

Highly emissive thermally activated delayed fluorescence (TADF) compounds typically are constructed from twisted donor and acceptor units, usually with the help of an additional spacer unit. Such molecular structure ensures low singlet-triplet energy gap, enabling the utilization of triplet states and boosting the emission yield. Here we show that emission yield also depends on the molecular structure of spacer unit. Selecting structurally flexible biphenyl spacer unit instead of rigid fluorene was shown to selectively enhance the nonradiative decay rate of triplet states (kNRT), leading to the lowered yield of delayed fluorescence (from 0.55 to 0.43). However, more rapid kNRT led in weaker OLED external quantum efficiency (EQE) roll-off due to lowered triplet lifetime, though at the cost of lower peak efficiency. The presented work highlights the need of careful design of spacer fragments for efficient TADF emitters.

Multiple donor–acceptor design for highly luminescent and stable thermally activated delayed fluorescence emitters

A considerable variety of donor–acceptor (D–A) combinations offers the potential for realizing highly efficient thermally activated delayed fluorescence (TADF) materials. Multiple D–A type compounds are one of the promising families of TADF materials in terms of stability as well as efficiencies. However, those emitters are always composed of carbazole-based donors despite a wide choice of moieties used in linearly linked single D–A molecules. Herein, we developed a multiple D–A type TADF compound with two distinct donor units of 9,10-dihydro-9,9-dimethylacridine (DMAC) and carbazole as the hetero-donor design. The new emitter exhibits high photoluminescence quantum yield (PLQY) in various conditions including polar media blend and high concentrations. Organic light-emitting diodes (OLEDs) showed a reasonably high external quantum efficiency (EQE). In addition, we revealed that the multiple-D–A type molecules showed better photostability than the single D–A type molecules, while the operational stability in OLEDs involves dominant other factors.

Highly Efficient Solution-Processed Bluish-Green Thermally Activated Delayed Fluorescence Compounds Using Di(pyridin-3-yl)methanone as Acceptor

Solution-processed devices with thermally activated delayed fluorescence (TADF) compounds have gained great attention due to their low cost and high performance. Here, two solution-processable TADF emitters named ACCz-DPyM and POxCz-DPyM were synthesized by coupled 9,10-dihydro-9,9-dimethylacridine or phenoxazine modified carbazole as donor with di(pyridin-3-yl)methanone as acceptor. Both TADF compounds show same small ΔΕST of 0.04 eV and high PLQY of 66.2% and 58.2%. The devices fabricated by ACCz-DPyM and POxCz-DPyM as emitters show excellent performance as solution-processed with low turn-on voltage of 4.0 and 3.4 V, high luminance of 6209 and 3248 cd m−2 at 8 V, the maximum current efficiency of 9.9 and 15.9 cd A−1, the maximum external quantum efficiency of 6.6% and 6.5% and low efficiency roll-off. The solution-processed device based on ACCz-DPyM shows bluish-green emission. These results show that ACCz-DPyM and POxCz-DPyM are suitable for solution processing devices.

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.

Donor-Acceptor Type of Fused-Ring Thermally Activated Delayed Fluorescence Compounds Constructed through an Oxygen-Containing Six-Membered Ring.

Nowadays, thermally activated delayed fluorescence (TADF) compounds with a fused-ring core skeleton are getting increasing research interest because of their use in high-performance organic light-emitting diodes (OLEDs). In this study, TADF compounds featuring a D-A-type fused-ring core skeleton are developed. The challenging compatibility of a planarized D-A arrangement and the TADF property is achieved through linking the D and A moieties with two oxygen atoms within a six-membered ring. Compared with a single-oxygen analogue possessing a flexible skeleton and a twisted D-A arrangement, these fused-ring compounds with higher skeleton rigidity show higher photoluminescence quantum yields and narrower emission spectra in toluene and in doped thin films. Their electroluminescent devices achieve high external quantum efficiencies (up to 19.4%), suggesting the potential of rarely achieved D-A-type fused-ring TADF systems to serve as high-performance emitters of OLEDs.

Achieving over 36% EQE in blue OLEDs using rigid TADF emitters based on spiro-donor and spiro-B-heterotriangulene acceptors

The design of robust thermally activated delayed fluorescence (TADF) emitters is crucial in realizing highly efficient and stable blue TADF-organic light-emitting diodes (OLEDs). Here boron-based donor–acceptor-type blue TADF compounds incorporating a triply-bridged, spiro-type boron acceptor; namely, spiro-fluorenyl B-heterotriangulene, and 9,9-diphenyl-9,10-dihydroacridine (DPAC, 1) or 10H-spiro[acridine-9,9′-fluorene] (sAC, 2) donors are presented. Their doped host films show blue emissions with narrow full width at half maximum values of 52 nm (0.29 eV) and unitary photoluminescence quantum yields. The compounds exhibit short-lived delayed fluorescence (τd = 1.8–2.7 μs) and undergo fast reverse intersystem crossing with the rate constants of ∼106 s−1 in the film state. These are attributable to the small singlet–triplet energy splitting of ∼40 meV and the effective spin–orbit coupling between the singlet (1CT, S1) and local triplet (3LE, T2) excited states. From outstanding horizontal transition dipole orientation ratios of 0.89 and 0.90 for the host films of 1 and 2, respectively, high-efficiency blue TADF-OLEDs showing maximum external quantum efficiencies (EQEs) of over 30% are realized. Notably, the device with the fully spiro 2 achieves a state-of-the-art EQEmax of 36.4% and a suppressed efficiency roll-off, with a high EQE of 26.3% even at 1,000 cd/m2, highlighting the synergistic effect between the spiro-structure and the B-heterotriangulene acceptor skeleton.

Moving Beyond Cyanoarene Thermally Activated Delayed Fluorescence Compounds as Photocatalysts: An Assessment of the Performance of a Pyrimidyl Sulfone Photocatalyst in Comparison to 4CzIPN.

Carbazolyl dicyanobenzene (CDCB) derivates exhibiting thermally activated delayed fluorescence (TADF) have shown themselves to be excellent photocatalysts over recent years, particularly 4CzIPN, although investigation into organic TADF compounds as photocatalysts outside of the CDCB group has been limited. Herein, we report an alternative donor-acceptor TADF structure, 9,9'-(sulfonylbis(pyrimidine-5,2-diyl))bis(3,6-di-tert-butyl-9H-carbazole), pDTCz-DPmS, for use as a photocatalyst (PC). A comparison of the electrochemical and photophysical properties of pDTCz-DPmS with 4CzIPN in a range of solvents identifies the former as a better ground state reducing agent and photoreductant, while both exhibit similar oxidation capabilities in the ground and excited state. The increased conjugation of pDTCz-DPmS relative to 4CzIPN presents a more intense CT band in the UV-vis absorption spectrum, aiding in the light absorption of this molecule. Prompt and delayed emission lifetimes are observed for pDTCz-DPmS, confirming the TADF nature, both of which are sufficiently long-lived to participate in productive photochemistry. These combined properties make pDTCz-DPmS useful in photocatalysis reactions, covering a range of photoredox oxidative and reductive quenching reactions, as well as those involving a dual Ni(II) cocatalyst, alongside energy transfer processes. The higher triplet energy and increased photostability of pDTCz-DPmS compared with 4CzIPN were found to be advantages of this organic PC.

Substituent effect on TADF properties of 2-modified 4,6-bis(3,6-di-tert-butyl-9-carbazolyl)-5-methylpyrimidines.

The interest in organic materials exhibiting thermally activated delayed fluorescence (TADF) significantly increased in recent years owing to their potential application as emitters in highly efficient organic light emitting diodes (OLEDs). Simple modification of the molecular structure of TADF compounds through the selection of different electron-donating or accepting fragments opens great possibilities to tune the emission properties and rates. Here we present the synthesis of a series of novel pyrimidine–carbazole emitters and their photophysical characterization in view of effects of substituents in the pyrimidine ring on their TADF properties. We demonstrate that electron-withdrawing substituents directly connected to the pyrimidine unit have greater impact on the lowering of the energy gap between singlet and triplet states (ΔEST) for efficient TADF as compared to those attached through a phenylene bridge. A modification of the pyrimidine unit with CN, SCH3, and SO2CH3 functional groups at position 2 is shown to enhance the emission yield up to 0.5 with pronounced TADF activity.

High-efficiency and low roll-off deep-blue OLEDs enabled by thermally activated delayed fluorescence emitter with preferred horizontal dipole orientation

• Molecular engineering by linear extension resulted in two blue TADF emitters. • The two emitters exhibited high photoluminescence quantum yields and preferred horizontal dipole orientation. • Deep-blue TADF OLEDs achieved external quantum efficiency of up to 29.3% and low efficiency roll-off. Highly efficient blue thermally activated delayed fluorescence (TADF) materials with high horizontal dipole orientation (Θ // ) remain a big challenge due to the concentration quenching effects and serious efficiency roll-offs in their corresponding organic light-emitting diodes (OLEDs). We herein report two novel TADF compounds, namely 2TDBA-SBA and TDBA-SBA, which were facilely synthesized by utilizing a rigid oxygen-bridged cyclized triarylboron-based unit (TDBA) as the acceptor and a spiro acridine (SBA) as the donor. Benefiting from the rigid and planar skeleton of the acceptor and the linear molecular shape, high Θ // s and photoluminescence quantum yields (PLQYs) of ∼ 90% were achieved. Significantly, TDBA-SBA exhibited excellent TADF properties with a short delayed fluorescence lifetime of only 684 ns and narrow full-width at half-maximum (FWHM) of 44 nm in solution state, accompanied by the high PLQYs of over 80% at high doping concentrations, manifesting the alleviated exciton quenching effects. Consequently, OLEDs based on TDBA-SBA achieved a high maximum external quantum efficiency (EQE) of 29.3% and a maximum brightness of 27663 cd cm −2 . Importantly, an EQE over 20% was realized even at the high brightness of 10000 cd cm −2 , signifying a small efficiency roll-off.

Computational descriptor analysis on excited state behaviours of a series of TADF and non-TADF compounds.

The thermally activated delayed fluorescence (TADF) behaviours of seventeen organic TADF emitters and two non-TADF chromophores bearing various donor and acceptor moieties were investigated, focusing on their torsion angles, singlet-triplet gap (ΔEST), spin orbit couplings (SOC) and topological ΦS index. Electronic structure calculations were performed in the framework of the Tamm-Dancoff approximation (TDA) allowing the possible reverse intersystem crossing (RISC) pathways to be characterized. The electronic density reorganization of the excited states was checked also with respect to the different exchange-correlation functional and absorption spectra were obtained by considering vibrational and dynamical effects through Wigner sampling of the ground state equilibrium regions. Examining all the parameters obtained in our computational study, we rationalized the influence of electron-donating and electron-accepting groups and the effects of geometrical factors, especially torsion angles, on a wide class of diverse compounds ultimately providing an easy and computationally effective protocol to assess TADF efficiencies.

Quantum simulations of thermally activated delayed fluorescence in an all-organic emitter.

We investigate the prototypical NAI-DMAC thermally activated delayed fluorescence (TADF) emitter in the gas phase- and high-packing fraction limits at finite temperature, by combining first principles molecular dynamics with a quantum thermostat to account for nuclear quantum effects (NQE). We find a weak dependence of the singlet-triplet energy gap (ΔEST) on temperature in both the solid and the molecule, and a substantial effect of packing. While the ΔEST vanishes in the perfect crystal, it is of the order of ∼0.3 eV in the molecule, with fluctuations ranging from 0.1 to 0.4 eV at 300 K. The transition probability between the HOMOs and LUMOs has a stronger dependence on temperature than the singlet-triplet gap, with a desirable effect for thermally activated fluorescence; such temperature effect is weaker in the condensed phase than in the molecule. Our results on ΔEST and oscillator strengths, together with our estimates of direct and reverse intersystem crossing rates, show that optimization of packing and geometrical conformation is critical to increase the efficiency of TADF compounds. Our findings highlight the importance of considering thermal fluctuations and NQE to obtain robust predictions of the electronic properties of NAI-DMAC.

Highly Efficient Thermally Activated Delayed Fluorescence from Pyrazine-Fused Carbene Au(I) Emitters.

Metal-based thermally activated delayed fluorescence (TADF) is conceived to inherit the advantages of both phosphorescent metal complexes and purely organic TADF compounds for high-performance electroluminescence. Herein a panel of new TADF Au(I) emitters has been designed and synthesized by using carbazole and pyrazine-fused nitrogen-heterocyclic carbene (NHC) as the donor and acceptor ligands, respectively. Single-crystal X-ray structures show linear molecular shape and coplanar arrangement of the donor and acceptor with small dihedral angles of <6.5°. The coplanar orientation and appropriate separation of the HOMO and LUMO in this type of molecules favour the formation of charge-transfer excited state with appreciable oscillator strength. Together with a minor but essential heavy atom effect of Au ion, the complexes in doped films exhibit highly efficient (Φ∼0.9) and short-lived (<1 μs) green emissions via TADF. Computational studies on this class of emitters have been performed to decipher the key reverse intersystem crossing (RISC) pathway. In addition to a small energy splitting between the lowest singlet and triplet excited states (ΔEST ), the spin-orbit coupling (SOC) effect is found to be larger at a specific torsion angle between the donor and acceptor planes which favours the RISC process the most. This work provides an alternative molecular design to TADF Au(I) carbene emitters for OLED application.

Tuning of HOMO-LUMO localization for achieving thermally activated delayed fluorescence

High emission yield and rapid reverse intersystem crossing are essential for efficient thermally activated delayed fluorescence (TADF) compounds. In this paper, we show that efficient TADF can be achieved by enhancing the localization of HOMO and LUMO in carbazole-pyrimidine compounds with rather flat molecular structure. Simple carbazole-pyrimidine Cbz-PYR was selected as a reference compound due to the pronounced room-temperature phosphorescence activity. The subsequent modifications of carbazole and pyrimidine units with diphenylamine and phenyl fragments resulted in weakened HOMO-LUMO communication, leading to the minimized singlet-triplet energy gap of only 111 meV. Due to the rather flat molecular geometry, TADF compounds showed remarkable radiative decay rate reaching 4.6 × 107 s−1 for the most efficient TADF-active carbazole-pyrimidine compound dCbz-pPYR, followed by high emission yield of 0.75. Efficient green electroluminescence with peak EQE of 18.3%. was shown for OLED device with dCbz-pPYR emitter.

Blue TADF Emitters Based on B-Heterotriangulene Acceptors for Highly Efficient OLEDs with Reduced Efficiency Roll-Off.

The design of robust boron acceptors plays a key role in the development of boron-based thermally activated delayed fluorescence (TADF) emitters for the realization of efficient and stable blue organic light-emitting diodes (OLEDs). Herein, we report a set of donor (D)-acceptor (A)-type blue TADF compounds (1-3) comprising triply bridged triarylboryl acceptors, the so-called B-heterotriangulenes, which differ depending on the identity of one of the bridging groups: methylene (1), dimethylmethylene (2), or oxo (3). The X-ray crystal structures of 2 and 3 reveal a highly twisted D-A connectivity and a completely planar geometry for the B-heterotriangulene rings. All compounds exhibit blue emissions with the unitary photoluminescence quantum yields and small singlet-triplet energy splitting (<0.1 eV) in their doped host films. The compounds exhibit a fast reverse intersystem crossing rate (kRISC ≈ 106 s-1) with short-lived delayed fluorescence (τd ≈ 2 μs), which is found to be promoted by the strong spin-orbit coupling between the local triplet excited state (3LE, T2) and singlet (S1) states. Using compounds 1-3 as the emitters, highly efficient blue TADF-OLEDs are realized. The devices based on the emitters with B-heterotriangulenes exhibit better performances than the device incorporating a singly bridged reference emitter over the whole luminance range. Notably, the device based on the fully dimethylmethylene-bridged emitter (2) achieves the highest maximum external quantum efficiency (EQE) of 28.2% and the lowest efficiency roll-off, maintaining a high EQE value of 21.2% at 1000 cd/m2.

Rational Utilization of Intramolecular Hydrogen Bonds to Achieve Blue TADF with EQEs of Nearly 30% and Single Emissive Layer All-TADF WOLED.

A series of highly efficient blue thermally activated delayed fluorescence (TADF) compounds, SON-Cz, SON-tBuCz, and SON-PhCz, were developed. Pyridinyl was introduced as the bridging unit between carbazole donors and sulfone acceptor. Intramolecular hydrogen bonds between the pyridine N atom and carbazole H atoms were detected in single crystals, which suppressed the twisting of carbazole rings and dramatically increased the molecular rigidity. At the same time, tert-butyl or phenyl were incorporated at the 3,6-sites of carbazole ring to tune electron donating ability or enlarge HOMO delocalization. All these hydrogen bonds featured TADF compounds exhibited much improved photoluminescence quantum yields (PLQYs) and excellent efficiencies in their doped blue organic light-emitting diodes. In particular, SON-tBuCz and SON-PhCz exhibited the maximum external quantum efficiencies (EQEs) of 29.59% and 28.22% with CIE coordinates of (0.17, 0.22) and (0.21, 0.36), respectively. The excellent performance benefits from the carbazole structure modification and the intramolecular hydrogen bonds, which bring more rigid structures and eliminate nonradiative transitions. Furthermore, a single emissive layer all-TADF white OLED was fabricated using SON-tBuCz as the blue emitter and 4CzTPN-Ph as the orange emitter to give an EQE of 23.51% with a high CRI of 71, which is among the top efficiencies ever reported for all-TADF WOLEDs so far.

Dicyano-Imidazole: A Facile Generation of Pure Blue TADF Materials for OLEDs.

A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9'-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔEST ) between the first excited singlet (S1 ) and the triplet (T1 ) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l'Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.