Reversible Shift from Excitonic to Excimer Emission in Fluorescent Organic Light-Emitting Diodes: Dependence on Deposition Parameters and Electrical Bias.

Organic light-emitting diodes (OLEDs), in general, require multilayer devices and microcavity structures for emission tuning, which increases the complexity and cost of production. Hence, it is imperative to develop techniques for spectral tuning, which employ simplified device structures. In this study, we have selected a tris(8-hydroxyquinolinato)aluminum (Alq3): 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-(1)benzopyropyrano (6,7-8-i,j)quinolizin-11-one (C545T)-based OLED and investigated the dependence of the OLED emission on various deposition parameters and the electrical bias. The concentration of the dopant in the emissive layer (EML) was varied from 3 to 50%, and the single dopant emitter as a limiting case was also studied along with studies on the varied deposition rates and EML thickness. By varying the deposition parameters, the emission was observed to change from excitonic green to excimeric yellow. With increased doping concentration, reduction in pure exciton emission with an increase in excimer emission was observed, resulting in electroluminescent spectral red shift. Similarly, electroluminescence spectra have shown different levels of broadening, depending on the deposition rate and thickness of the EML. These effects could be reversed with increasing applied electric field. Thus, it is indicated that, by suitably optimizing the deposition parameters of the dopant material, spectral tuning can easily be obtained, which may form the basis of simplified and cost-effective device structures.

Photokinetic study on remarkable excimer phosphorescence from heteroleptic cyclometalated platinum(ii) complexes bearing a benzoylated 2-phenylpyridinate ligand.

Novel heteroleptic cyclometalated platinum(ii) complexes consisting of 5'-benzoylated 2-phenylpyridinate (ppy) cyclometalated and acetylacetonate ancillary ligands were synthesized, and their photoluminescence (PL) properties were investigated. The 5'-benzoylated complex without any other substituents exhibited phosphorescence-based monomer emission at 479 nm in dichloromethane (10 µM, rt) with a PL quantum yield of 0.28. On the other hand, in poly(methyl methacrylate) (PMMA) film, remarkable excimer emission additionally emerged at ca. 600 nm with a relatively high PL quantum yield of 0.47 as the doping level increased to 0.20 mmmol g-1, which was comparably intense in comparison with the monomer emission. In the case of the complexes with unsubstituted, 4'-benzoylated, and 5'-fluorinated ppy cyclometalated ligands, excimer emission was modestly generated at the same doping level, and thus the introduction of a benzoyl group to the 5'-position is effective to obtain remarkable excimer emission. The combination of benzoyl and fluoro groups was more effective at inducing excimer emission, and the intensity of excimer emission of the 2-(5-benzoyl-4,6-difluorophenyl)pyridinate-based complex was 3.5 times larger than that of monomer emission at a doping level of 0.20 mmmol g-1 in PMMA. From the analysis of PL lifetimes at varying concentrations, photokinetic profiles were fully analyzed according to the model system for the irreversible excimer formation, and the excimer formation rate constant of the 5'-benzoylated complex was determined in dichloromethane as 2.2 × 109 M-1 s-1, which is 4.4 times larger than that of the unsubstituted complex. We also fabricated an organic light-emitting diode using the 2-(5-benzoyl-4,6-difluorophenyl)pyridinate-based complex as a single emitter. The device exhibited pseudo-white EL with the Commission internationale de l'éclairage chromaticity coordinates of (0.42, 0.42).