Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Azaborine as a Versatile Weak Donor for Thermally Activated Delayed Fluorescence.

Extensive research has been devoted to the development of thermally activated delayed fluorescence emitters, especially those showing pure-blue emission for use in lighting and full-color display applications. Toward that goal, herein we report a novel weak donor, 1,4-azaborine (AZB), with complementary electronic and structural properties compared to the widely used dimethylacridan (DMAC) or carbazole (Cz) donors. Coupled with a triazine acceptor, AZB-Ph-TRZ is the direct structural analogue of the high-performance and well-studied green TADF emitter DMAC-TRZ and has ΔEST = 0.39 eV, a photoluminescence quantum yield (ΦPL) of 27%, and λPL = 415 nm in 10 wt % doped mCP films. The shortened analogue AZB-TRZ possesses red-shifted emission with a reduced singlet-triplet gap (ΔEST = 0.01 eV) and fast reverse intersystem crossing (kRISC of 5 × 106 s-1) in mCP. Despite a moderate ΦPL of 34%, OLEDs with AZB-TRZ in mCP showed sky-blue emission with CIE1931(x,y) of (0.22,0.39) and a maximum external quantum efficiency (EQEmax) of 10.5%. Expanding the chemist's toolkit for the design of blue donor-acceptor TADF materials will enable yet further advances in the future, as AZB is paired with a wider range of acceptor groups.

Thermally Activated Delayed Fluorescence: Polarity, Rigidity, and Disorder in Condensed Phases.

We present a detailed and comprehensive picture of the photophysics of thermally activated delayed fluorescence (TADF). The approach relies on a few-state model, parametrized ab initio on a prototypical TADF dye, that explicitly accounts for the nonadiabatic coupling between electrons and vibrational and conformational motion, crucial to properly address (reverse) intersystem crossing rates. The Onsager model is exploited to account for the medium polarity and polarizability, with careful consideration of the different time scales of relevant degrees of freedom. TADF photophysics is then quantitatively addressed in a coherent and exhaustive approach that accurately reproduces the complex temporal evolution of emission spectra in liquid solvents as well as in solid organic matrices. The different rigidity of the two environments is responsible for the appearance in matrices of important inhomogeneous broadening phenomena that are ascribed to the intertwined contribution from (quasi)static conformational and dielectric disorder.

Laplace Transform Fitting as a Tool To Uncover Distributions of Reverse Intersystem Crossing Rates in TADF Systems.

Donor-acceptor (D-A) thermally activated delayed fluorescence (TADF) molecules are exquisitely sensitive to D-A dihedral angle. Although commonly simplified to an average value, these D-A angles nonetheless exist as distributions across the individual molecules embedded in films. The presence of these angle distributions translates to distributions in the rates of reverse intersystem crossing (krISC), observed as time dependent spectral shifts and multiexponential components in the emission decay, which are difficult to directly quantify. Here we apply inverse Laplace transform fitting of delayed fluorescence to directly reveal these distributions. Rather than a single average value, the crucial krISC rate is instead extracted as a density of rates. The modes and widths of these distributions vary with temperature, host environment, and intrinsic D-A torsional rigidity of different TADF molecules. This method gives new insights and deeper understanding of TADF host-guest interactions, as well as verifies future design strategies that target D-A bond rigidity.

Diindolocarbazole - achieving multiresonant thermally activated delayed fluorescence without the need for acceptor units.

In this work we present a new multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter paradigm, demonstrating that the structure need not require the presence of acceptor atoms. Based on an in silico design, the compound DiICzMes4 possesses a red-shifted emission, enhanced photoluminescence quantum yield, and smaller singlet-triplet energy gap, ΔEST, than the parent indolocarbazole that induces MR-TADF properties. Coupled cluster calculations accurately predict the magnitude of the ΔEST when the optimized singlet and triplet geometries are used. Slow yet optically detectable reverse intersystem crossing contributes to low efficiency in organic light-emitting diodes using DiICzMes4 as the emitter. However, when used as a terminal emitter in combination with a TADF assistant dopant within a hyperfluorescence device architecture, maximum external quantum efficiencies of up to 16.5% were achieved at CIE (0.15, 0.11). This represents one of the bluest hyperfluorescent devices reported to date. Simultaneously, recognising that MR-TADF emitters do not require acceptor atoms reveals an unexplored frontier in materials design, where yet greater performance may yet be discovered.

Investigation of Intramolecular Through-Space Charge-Transfer States in Donor-Acceptor Charge-Transfer Systems.

Commonly, thermally activated delayed fluorescence (TADF) emitters present a twisted donor-acceptor structure. Here, electronic communication is mediated through-bond via π-conjugation between donor and acceptor groups. A second class of TADF emitters are those where electronic communication between donor and acceptor moieties is mediated through-space. In these through-space charge-transfer (TSCT) architectures, the donor and acceptor groups are disposed in a pseudocofacial orientation and linked via a bridging group that is typically an arene (or heteroarene). In most of these systems, there is no direct evidence that the TSCT is the dominant contributor to the communication between the donor and acceptor. Herein we investigate the interplay between through-bond localized excited (LE) and charge-transfer (CT) states and the TSCT in a rationally designed emitter, TPA-ace-TRZ, and a family of model compounds. From our photophysical studies, TSCT TADF in TPA-ace-TRZ is unambiguously confirmed and supported by theoretical modeling.

Hot Vibrational States in a High-Performance Multiple Resonance Emitter and the Effect of Excimer Quenching on Organic Light-Emitting Diodes.

The photophysics of multiple resonance thermally activated delayed fluorescence molecule ν-DABNA is described. We show coupling of a 285 cm-1 stretching/scissoring vibrational mode of peripheral phenyl rings to the S1 state, which dictates the ultimate emission full-width at half maximum. However, a separate high amplitude mode, 945 cm-1 of the N-biphenyl units, mediates the reverse intersystem crossing (rISC) mechanism. Concentration-dependent studies in solution and solid state reveal a second emission band that increases nonlinearly with concentration, independent of the environment assigned to excimer emission. Even at concentrations well below those used in devices, the excimer contribution affects performance. Using different solvents and solid hosts, rISC rates between 3-6 × 105 s-1 are calculated, which show negligible dependence on environmental polarity or host packing. At 20 K over the first 10 ns, we observe a broad Gaussian excimer emission band with energy on-set above the S1 exciton band. An optical singlet-triplet gap (ΔEST) of 70 meV is measured, agreeing with previous thermal estimates; however, the triplet energy is also found to be temperature-dependent. A monotonic increase of the exciton emission band full-width at half maximum with temperature indicates the role of hot transitions in forming vibrational excited states at room temperature (RT), and combined with an observed temperature dependency of ΔEST, we deduce that the rISC mechanism is that of thermally activated reverse internal conversion of T1 to TN (n ≥ 2) followed by rapid rISC of TN to S1. Organic light-emitting diodes with ν-DABNA as a hyperfluorescent emitter (0.5 wt % and 1 wt %) exhibit an increase of maximum external quantum efficiency, reaching 27.5% for the lower ν-DABNA concentration. On the contrary, a Förster radius analysis indicated that the energy transfer ratio is smaller because of higher donor-acceptor separation (>2.4 nm) with weak sensitizer emission observed in the electroluminescence. This indicates excimer quenching in 1 wt % devices.

Photophysics of TADF Guest-Host Systems: Introducing the Idea of Hosting Potential.

The thermally activated delayed fluorescence (TADF) donor-acceptor (D-A) molecule, DMAC-TRZ, is used as a TADF emitter "probe" to distinguish the environmental effects of a range of solid-state host materials in guest-host systems. Using the guest's photophysical behavior in solution as a benchmark, a comprehensive study using a variety of typical TADF organic light-emitting diode hosts with different characteristics provides a clearer understanding of guest-host interactions and what affects emitter performance in solid state. We investigate which are the key host characteristics that directly affect charge-transfer (CT) state energy and singlet triplet energy gaps. Using time-resolved photoluminescence measurements, we use the CT state energy distribution obtained from the full width at half-maximum (fwhm) of the emission band and correlate this with other photophysical properties such as the apparent dynamic red shift of CT emission on-set to estimate the disorder-induced heterogeneity of D-A dihedral angles and singlet triplet gaps. Further, the delayed emission stabilization energy value and time-dependent CT band fwhm are shown to be related to a combination of host's rigidity, emitter molecule packing, and the energy difference between guest and host lowest energy triplet states. Concentration dependence studies show that emitter dimerization/aggregation can improve as well as reduce emission efficiency depending on the characteristics of the host. Two similar host materials, mCPCN and mCBPCN, with optimum host characteristics show completely different behaviors, and their hosting potential is extensively explored. We demonstrate that type I and type III TADF emitters behave differently in the same host and that the materials with intrinsic small ΔE ST have the smallest disorder-induced CT energy and reverse intersystem crossing rate dispersion. We also present an optimized method to define the actual triplet energy of a guest-host system, a crucial parameter in understanding the overall mechanism of the TADF efficiency of the system.