ConspectusSince the seminal work of Tang and Vanslyke in 1987 on small-molecule emitters and that of Friend and co-workers in 1990 on conjugated-polymer emitters, organic light-emitting diodes (OLEDs) have attracted much attention from academia as well as industry, as the OLED market is estimated to reach the $30 billion mark by the end of 2018. In these first-generation organic emitters, on the basis of simple spin statistics, electrical excitation resulted in the formation of ∼25% singlet excitons and ∼75% triplet excitons. Radiative decay of the singlet excitons to the singlet ground state leads to a prompt fluorescence emission, while the triplet excitons only lead to weak phosphorescence due to the very small spin-orbit couplings present in purely organic molecules. The consequence is a ca. 75% energy loss, which triggered wide-ranging efforts to try and harvest as many of the triplet excitons as possible. In 1998, Thompson, Forrest, and their co-workers reported second-generation OLED emitters based on coordination complexes with heavy transition metals (e.g., iridium or platinum). Here, the triplet excitons stimulate efficient and fast phosphorescence due to the strong spin-orbit couplings enabled by the heavy-metal atoms. Internal quantum efficiencies (IQE) up to 100% have been reported, which means that for every electron injected into the device, a photon is emitted. While these second-generation emitters are those mainly exploited in current OLED applications, there is strong impetus from both cost and environmental standpoints to find new ways of exploiting purely organic emitters, which in addition can offer greater flexibility to fine-tune the electronic and optical properties by exploiting the synthetic organic chemistry toolbox.In 2012, Adachi and co-workers introduced a promising strategy, based on thermally activated delayed fluorescence (TADF), to harvest the triplet excitons in purely organic molecular materials. These materials now represent the third generation of OLED emitters. Impressive photophysical properties and device performances have been reported, with internal quantum efficiencies also reaching nearly 100%.Our objectives in this Account are threefold: (i) to lay out a comprehensive description, at the molecular level, of the fundamental photophysical processes behind TADF emitters; (ii) to discuss some of the challenges facing the design of TADF emitters, such as the need to balance the efficiency of thermal activation of triplet excitons into the singlet manifold with the efficiency of radiative transition to the ground state; and (iii) to highlight briefly some of the recent molecular-design strategies that pave the way to new classes of TADF materials.
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