8 October 2014 TADF for singlet harvesting: next generation OLED materials based on brightly green and blue emitting Cu(I) and Ag(I) compounds
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Abstract
Detailed photophysical studies are presented for Cu2Cl2(dppb)2 and Ag2Cl2(dppb)2. Both compounds show very effective thermally activated delayed fluorescence (TADF) at ambient temperature with an emission quantum yield of the Ag(I) complex of ΦPL(300 K) = 93 %. This emission is blue shifted by 65 nm (2500 cm-1) with respect to the emission of the Cu(I) complex, demonstrating a valuable strategy for engineering blue light emitters. Potentially, these materials are well suited for taking advantage of the singlet harvesting effect in an OLED device. Moreover, both compounds do not show effects of concentration quenching at high emitter concentration, a property which might be attractive for reducing the efficiency roll-off at higher current densities. Investigations down to T = 1.6 K show that spin-orbit coupling (SOC) is particularly weak. This is displayed in the very long emission decay times of the triplet states (T1 states) of metal-toligand charge transfer (3MLCT) character, amounting to τ(Ag2Cl2(dppb)2) = 1.1 ms and τ(Cu2Cl2(dppb)2) = 2.2 ms. According to the TADF mechanism, which leads to the additional decay channel at ambient temperature via the S1 state (of 1MLCT character), an increase of the radiative rate by a factor of 70 and almost 500 for Ag2Cl2(dppb)2 and Cu2Cl2(dppb)2, respectively, is induced. This results in radiative rates at ambient temperature of kr = 6.2 ∙ 104 s-1r = 16 μs, Ag(I) complex) and 11.7 ∙ 104 s-1r = 8.5 μs, Cu(I) complex). Simple approaches are presented that allow us to understand the weakness of SOC on the basis of results from DFT and TD-DFT calculations. Investigations of the emission decay properties down to T = 1.6 K further support the conclusions with respect to the SOC strength.
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Hartmut Yersin, Markus J. Leitl, Rafal Czerwieniec, "TADF for singlet harvesting: next generation OLED materials based on brightly green and blue emitting Cu(I) and Ag(I) compounds", Proc. SPIE 9183, Organic Light Emitting Materials and Devices XVIII, 91830N (8 October 2014); doi: 10.1117/12.2061010; https://doi.org/10.1117/12.2061010
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