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Thermally activated delayed fluorescence (TADF) emitters potentially can provide organic light‐emitting diodes with 100% internal quantum efficiency by harvesting triplet excitons. Generally, TADF emitters are small molecules that are not applicable for solution processability. The addition of tert‐butyl groups to the periphery of TADF emitters has proven to improve their solubility in various organic solvents, reduce aggregation‐induced quenching, and enhance the photoluminescence quantum yield (PLQY). This article studies the photophysical influence of the tert‐butyl group attached to an emitter with a carbazole acceptor and a triazine donor. The resulting t3CzTrz‐F is a blue–green TADF emitter, in which the addition of a tert‐butyl group increases the rate of reverse intersystem crossing (rISC), while simultaneously decreasing the nonradiative decay rate substantially. In addition, dilution of t3CzTrz‐F in a host matrix in film results in an enhanced PLQY, which is associated with a decrease in the nonradiative decay constant, while there is no change in the rISC rate. Through a solid‐state NMR study, the change in rISC and nonradiative rate upon tert‐butylation by enlarged intermolecular spacing and reduced vibrational and rotational freedom is rationalized, resulting in improved photophysical performance.

Abstract Many wide-gap organic semiconductors exhibit imbalanced electron and hole transport, therefore efficient organic light-emitting diodes require a multilayer architecture of electron- and hole-transport materials to confine charge recombination to the emissive layer. Here, we show that even for emitters with imbalanced charge transport, it is possible to obtain highly efficient single-layer organic light emitting diodes (OLEDs), without the need for additional charge-transport and blocking layers. For hole-dominated emitters, an inverted single-layer device architecture with ohmic bottom-electron and top-hole contacts moves the emission zone away from the metal top electrode, thereby more than doubling the optical outcoupling efficiency. Finally, a blue-emitting inverted single-layer OLED based on thermally activated delayed fluorescence is achieved, exhibiting a high external quantum efficiency of 19% with little roll-off at high brightness, demonstrating that balanced charge transport is not a prerequisite for highly efficient single-layer OLEDs.

Abstract Bimolecular charge recombination is one of the most important loss processes in organic solar cells. However, the bimolecular recombination rate in solar cells based on novel non-fullerene acceptors is mostly unclear. Moreover, the origin of the reduced-Langevin recombination rate in bulk heterojunction solar cells in general is still poorly understood. Here, we investigate the bimolecular recombination rate and charge transport in a series of high-performance organic solar cells based on non-fullerene acceptors. From steady-state dark injection measurements and drift–diffusion simulations of the current–voltage characteristics under illumination, Langevin reduction factors of up to over two orders of magnitude are observed. The reduced recombination is essential for the high fill factors of these solar cells. The Langevin reduction factors are observed to correlate with the quadrupole moment of the acceptors, which is responsible for band bending at the donor–acceptor interface, forming a barrier for charge recombination. Overall these results therefore show that suppressed bimolecular recombination is essential for the performance of organic solar cells and provide design rules for novel materials.

Charge transport is one of the key factors in the operation of organic solar cells. Here, we investigate the electron and hole transport in the non-fullerene acceptor (NFA) IT-4F, by a combination of space-charge-limited current measurements and multiscale molecular simulations. The electron and hole mobilities are fairly balanced, amounting to 2.9 × 10−4 cm2 V−1 s−1 for electrons and 2.0 × 10−5 cm2 V−1 s−1 for holes. Orientational ordering and electronic couplings facilitate a better charge-percolating network for electrons than for holes, while ambipolarity itself is due to sufficiently high electron affinity and low ionization energy typical for narrow-gap NFAs. Our findings provide a molecular-level understanding of the balanced hole and electron transport in an archetypical NFA, which may play a key role in exciton diffusion and photogenerated hole transfer in organic solar cells.

Abstract Excellent performance has been reported for organic light‐emitting diodes (OLEDs) based on small molecule emitters that exhibit thermally activated delayed fluorescence. However, the necessary vacuum processing makes the fabrication of large‐area devices based on these emitters cumbersome and expensive. Here, the authors present high performance OLEDs, based on novel, TADF polymers that can be readily processed from a solution. These polymers are based on the acridine‐benzophenone donor–acceptor motif as main‐chain TADF chromophores, linked by various conjugated and non‐conjugated spacer moieties. The authors’ extensive spectroscopic and electronic analysis shows that in particular in case of alkyl spacers, the properties and performance of the monomeric TADF chromophores are virtually left unaffected by the polymerization. They present efficient solution‐processed OLEDs based on these TADF polymers, diluted in oligostyrene as a host. The devices based on the alkyl spacer‐based TADF polymers exhibit external quantum efficiencies (EQEs) ≈12%, without any outcoupling‐enhancing measures. What's more, the EQE of these devices does not drop substantially upon diluting the polymer down to only ten weight percent of active material. In contrast, the EQE of devices based on the monomeric chromophore show significant losses upon dilution due to loss of charge percolation.

Space-charge-limited currents are widely used to characterize charge transport in semiconductors. Here, the authors characterize space-charge-limited electron and hole currents in metal-halide perovskites, applicable in emerging solar cells. The currents are strongly influenced by the high permittivity and ion motion.

Thermally-activated delayed fluorescence (TADF) is a concept which helps to harvest triplet excitations, boosting the efficiency of an organic light-emitting diode. TADF can be observed in molecules with spatially separated donor and acceptor groups with a reduced triplet-singlet energy level splitting. TADF materials with balanced electron and hole transport are attractive for realizing efficient single-layer organic light emitting diodes, greatly simplifying their manufacturing and improving their stability. Our goal here is to computationally screen such materials and provide a comprehensive database of compounds with a range of emission wavelengths, ionization energies, and electron affinities.

Charge transport in the amorphous organic small molecules α-NPD (N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine) and Spiro-TAD (2,2′,7,7′-tetrakis(N,N-diphenylamino)-9,9-spirobifluorene) is investigated in solution-processed films and compared to charge transport in vacuum-deposited films of the same molecule. By optimizing the solution-deposition conditions, such as solvent and concentration, equal charge-transport parameters for solution-processed and vacuum-deposited films are demonstrated. Modeling of the charge carrier transport characteristics was performed by drift-diffusion simulations. The dependence of the charge carrier mobility on temperature, carrier density, and electric field was found to be the same for vacuum deposition and solution processing. In both material processing cases, hole mobilities of 4 × 10−8 m2 V−1 s−1 for spiro-TAD and 0.9 × 10−8 m2 V−1 s−1 for α-NPD are obtained, demonstrating that solution processing can be a viable alternative to vacuum deposition in terms of charge transport.

Abstract Amorphous small‐molecule hole‐transporting materials are commonly used in organic light‐emitting diodes and perovskite solar cells. Characterization of their main functionality, hole transport, has been complicated by the presence of large contact barriers. Using a recently developed technique to establish Ohmic hole contacts, the bulk hole transport in a series of molecules with a broad range of ionization energies is investigated. The measured charge‐carrier mobility dependence on charge concentration, electric field, and temperature is used to extract the energetic disorder and molecular site spacing. Excellent agreement of these parameters as well as ionization energies with multiscale simulations paves the way to predictive charge‐transport simulations from the molecular level.

Ferroelectricity has been proposed as one of the potential origins of the observed hysteresis in photocurrent-voltage characteristics of perovskite based solar cells. Measurement of ferroelectric properties on perovskite solar cells is hindered by the presence of (in)organic charge transport layers. Here we fabricate metal-perovskite-metal capacitors and unambiguously show that methylammonium lead iodide is not ferroelectric at room temperature. We propose that the hysteresis originates from the movement of positive ions rather than ferroelectric switching.