Organic light-emitting diodes (OLEDs) have their performance limited by the number of emissive singlet states created upon charge recombination (25%). Recently, a novel strategy has been proposed, based on thermally activated up-conversion of triplet to singlet states, yielding delayed fluorescence (TADF), which greatly enhances electroluminescence. The energy barrier for this reverse intersystem crossing mechanism is proportional to the exchange energy (ΔEST ) between the singlet and triplet states; therefore, materials with intramolecular charge transfer (ICT) states, where it is known that the exchange energy is small, are perfect candidates. However, here it is shown that triplet states can be harvested with 100% efficiency via TADF, even in materials with ΔEST of more than 20 kT (where k is the Boltzmann constant and T is the temperature) at room temperature. The key role played by lone pair electrons in achieving this high efficiency in a series of ICT molecules is elucidated. The results show the complex photophysics of efficient TADF materials and give clear guidelines for designing new emitters.

Knowing the underlying photophysics of thermally activated delayed fluorescence (TADF) allows proper design of high efficiency organic light-emitting diodes. We have proposed a model to describe reverse intersystem crossing (rISC) in donor–acceptor charge transfer molecules, where spin–orbit coupling between singlet and triplet states is mediated by one of the local triplet states of the donor (or acceptor). This second order, vibronically coupled mechanism describes the basic photophysics of TADF. Through a series of measurements, whereby the energy ordering of the charge transfer (CT) excited states and the local triplet are tuned in and out of resonance, we show that TADF reaches a maximum at the resonance point, substantiating our model of rISC. Moreover, using photoinduced absorption, we show how the populations of both singlet and triplet CT states and the local triplet state change in and out of resonance. Our vibronic coupling rISC model is used to predict this behaviour and describes how rISC and TADF are affected by external perturbation.

Factors influencing the rate of reverse intersystem crossing (k rISC) in thermally activated delayed fluorescence (TADF) emitters are critical for improving the efficiency and performance of third‐generation heavy‐metal‐free organic light‐emitting diodes (OLEDs). However, present understanding of the TADF mechanism does not extend far beyond a thermal equilibrium between the lowest singlet and triplet states and consequently research has focused almost exclusively on the energy gap between these two states. Herein, we use a model spin‐vibronic Hamiltonian to reveal the crucial role of non‐Born‐Oppenheimer effects in determining k rISC. We demonstrate that vibronic (nonadiabatic) coupling between the lowest local excitation triplet (3LE) and lowest charge transfer triplet (3CT) opens the possibility for significant second‐order coupling effects and increases k rISC by about four orders of magnitude. Crucially, these simulations reveal the dynamical mechanism for highly efficient TADF and opens design routes that go beyond the Born‐Oppenheimer approximation for the future development of high‐performing systems.

WOLEDs offer new design opportunities in practical solid-state lighting and could play a significant role in reducing global energy consumption. Obtaining white light from organic LEDs is a considerable challenge. Alongside the development of new materials with improved color stability and balanced charge transport properties, major issues involve the fabrication of large-area devices and the development of low-cost manufacturing technology. This Review will describe the types of materials (small molecules and polymers) that have been used to fabricate WOLEDs. A range of device architectures are presented and appraised.

Here, a comprehensive photophysical investigation of a the emitter molecule DPTZ‐DBTO2, showing thermally activated delayed fluorescence (TADF), with near‐orthogonal electron donor (D) and acceptor (A) units is reported. It is shown that DPTZ‐DBTO2 has minimal singlet–triplet energy splitting due to its near‐rigid molecular geometry. However, the electronic coupling between the local triplet (3LE) and the charge transfer states, singlet and triplet, (1CT, 3CT), and the effect of dynamic rocking of the D–A units about the orthogonal geometry are crucial for efficient TADF to be achieved. In solvents with low polarity, the guest emissive singlet 1CT state couples directly to the near‐degenerate 3LE, efficiently harvesting the triplet states by a spin orbit coupling charge transfer mechanism (SOCT). However, in solvents with higher polarity the emissive CT state in DPTZ‐DBTO2 shifts below (the static) 3LE, leading to decreased TADF efficiencies. The relatively large energy difference between the 1CT and 3LE states and the extremely low efficiency of the 1CT to 3CT hyperfine coupling is responsible for the reduction in TADF efficiency. Both the electronic coupling between 1CT and 3LE, and the (dynamic) orientation of the D–A units are thus critical elements that dictate reverse intersystem crossing processes and thus high efficiency in TADF.