RESUMO
Development of emissive materials for utilization in organic light-emitting diodes (OLEDs) remains a highly relevant research field. One of the most important aspects in the development of efficient emitters for OLEDs is the efficiency of triplet-to-singlet exciton conversion. There are many concepts proposed for the transformation of triplet excitons to singlet excitons, among which thermally activated delayed fluorescence (TADF) is the most efficient and widespread. One of the variations of the TADF concept is the hot exciton approach according to which the process of exciton relaxation into the lowest energy electronic state (internal conversion as usual) is slower than intersystem crossing between high-lying singlets and triplets. In this paper, we present the donor-acceptor materials based on 2-pyridone acceptor coupled to the different donor moieties through the phenyl linker demonstrating good performance as components of sky-blue, green-yellow, and white OLEDs. Despite relatively low photoluminescence quantum yields, the compound containing 9,9-dimethyl-9,10-dihydroacridine donor demonstrated very good efficiency in sky-blue OLED with the single emissive layer, which showed an external quantum efficiency (EQE) of 3.7%. It also forms a green-yellow-emitting exciplex with 4,4',4â³-tris[phenyl(m-tolyl)amino]triphenylamine. The corresponding OLED showed an EQE of 6.9%. The white OLED combining both exciplex and single emitter layers demonstrated an EQE of 9.8% together with excellent current and power efficiencies of 16.1 cd A-1 and 6.9 lm W-1, respectively. Quantum-chemical calculations together with the analysis of photoluminescence decay curves confirm the ability of all of the studied compounds to exhibit TADF through the hot exciton pathway, but the limiting factor reducing the efficiency of OLEDs is the low photoluminescence quantum yields caused mainly by nonradiative intersystem crossing dominating over the radiative fluorescence pathway.
RESUMO
INTRODUCTION: Evolution of organic light-emitting diodes (OLEDs) reached the point, which allows to obtain maximum internal quantum efficiency of 100% partly using heavy-metal-free emitters exhibiting thermally activated delayed fluorescence (TADF). Such emitters are also predictively perfect candidates for new generation of optical sensors since triplet harvesting can be sensitive to different analytes (at least to oxygen). Although many organic TADF emitters have been reported so far as OLED emitters, the investigation of materials suitable for both OLEDs and optical sensors remains extremely rare. OBJECTIVES: Aiming to achieve high photoluminescence quantum yields in solid-state and triplet harvesting abilities of organic semiconductors with efficient bipolar charge transport required for application in both blue OLEDs and optical sensors, symmetrical donor-acceptor-donor organic emitters containing pyrimidine-5-carbonitrile electron-withdrawing scaffold and carbazole, tert-butylcarbazole and methoxy carbazole donor moieties were designed, synthesized and investigated as the main objectives of this study. METHODS: New compounds were tested by many experimental methods including optical and photoelectron spectroscopy, time of flight technique, electrochemistry and thermal analyses. RESULTS: Demonstrating advantages of the molecular design, the synthesized emitters exhibited sky-blue efficient TADF with reverse intersystem crossing rates exceeding 106 s-1, aggregation-induced emission enhancement with photoluminescence quantum yields in solid state exceeding 50%, hole and electron transporting properties with charge mobilities exceeding 10-4 cm2/V·s, glass-forming properties with glass transition temperatures reaching 177 °C. Sky-blue OLEDs with non-doped light-emitting layers of the synthesized emitter showed maximum external efficiency of 12.8% while the doped device with the same emitter exhibited maximum external efficiency of 14%. The synthesized emitters were also used as oxygen probes for optical sensors with oxygen sensitivity estimated by the Stern-Volmer constant of 3.24·10-5 ppm-1. CONCLUSION: The developed bipolar TADF emitters with pyrimidine-5-carbonitrile and carbazole moieties showed effective applicability in both blue OLEDs and optical sensors.