The design and characterization of thermally activated delayed fluorescence (TADF) materials for optoelectronic applications represents an active area of recent research in organoelectronics. Noble metal-free TADF molecules offer unique optical and electronic properties arising from the efficient transition and interconversion between the lowest singlet (S1 ) and triplet (T1 ) excited states. Their ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T1 →S1 ) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic devices. TADF-based organic light-emitting diodes, oxygen, and temperature sensors show significantly upgraded device performances that are comparable to the ones of traditional rare-metal complexes. Here we present an overview of the quick development in TADF mechanisms, materials, and applications. Fundamental principles on design strategies of TADF materials and the common relationship between the molecular structures and optoelectronic properties for diverse research topics and a survey of recent progress in the development of TADF materials, with a particular emphasis on their different types of metal-organic complexes, D-A molecules, and fullerenes, are highlighted. The success in the breakthrough of the theoretical and technical challenges that arise in developing high-performance TADF materials may pave the way to shape the future of organoelectronics.
The control of the emission properties of synthetic organic molecules through molecular design has led to the development of high-performance optoelectronic devices with tunable emission colours, high quantum efficiencies and efficient energy/charge transfer processes. However, the task of generating excited states with long lifetimes has been met with limited success, owing to the ultrafast deactivation of the highly active excited states. Here, we present a design rule that can be used to tune the emission lifetime of a wide range of luminescent organic molecules, based on effective stabilization of triplet excited states through strong coupling in H-aggregated molecules. Our experimental data revealed that luminescence lifetimes up to 1.35 s, which are several orders of magnitude longer than those of conventional organic fluorophores, can be realized under ambient conditions. These results outline a fundamental principle to design organic molecules with extended lifetimes of excited states, providing a major step forward in expanding the scope of organic phosphorescence applications.
Developing organic optoelectronic materials with desired photophysical properties has always been at the forefront of organic electronics. The variation of singlet-triplet splitting (ΔEST) can provide useful means in modulating organic excitons for diversified photophysical phenomena, but controlling ΔEST in a desired manner within a large tuning scope remains a daunting challenge. Here, we demonstrate a convenient and quantitative approach to relate ΔEST to the frontier orbital overlap and separation distance via a set of newly developed parameters using natural transition orbital analysis to consider whole pictures of electron transitions for both the lowest singlet (S1) and triplet (T1) excited states. These critical parameters revealed that both separated S1 and T1 states leads to ultralow ΔEST; separated S1 and overlapped T1 states results in small ΔEST; and both overlapped S1 and T1 states induces large ΔEST. Importantly, we realized a widely-tuned ΔEST in a range from ultralow (0.0003 eV) to extra-large (1.47 eV) via a subtle symmetric control of triazine molecules, based on time-dependent density functional theory calculations combined with experimental explorations. These findings provide keen insights into ΔEST control for feasible excited state tuning, offering valuable guidelines for the construction of molecules with desired optoelectronic properties.
Processing-structure-oxygen surface exchange kinetics relationships in perovskite (Sr,Ti)FeO3−x were clarified by non-contact optical transmission relaxation, with kinetics optimized upon crystallization.
Despite
the high ionic conductivity and good machinability, the
application of sulfide solid electrolytes (SEs) is severely limited
by the poor compatibility of oxide cathodes with Li metals. Herein,
a ZnO co-doping strategy is proposed to enhance the chemical and electrochemical
performance of sulfide SEs. Given the synergistic effect by incorporation
of ZnO, the argyrodite electrolyte achieves superior interfacial stability
and Li dendrite suppression capability. By in-depth ex situ analyses,
the enhancement is ascribed to LiZn and Li3OBr formed in
the argyrodite/Li interface and a reduced electronic conductivity
arising from the ZnO doping. In addition, O doping improves the air
stability for argyrodite without degrading the ionic conductivity
because of the compensation by Zn doping. Hence, all-solid-state batteries
with ZnO-doped electrolytes achieve higher initial Coulombic efficiency
and a larger specific capacity than those of the ZnO-free electrolyte.
ZnO-doped sulfide SEs are promising to develop all-solid-state Li-metal
batteries.
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