Organic light emitting diods (OLEDs) are revolutionizing display applications. In this aspect luminescent complexes of precious metals such as iridium, platinum, or ruthenium play a significant role. Emissive compounds of earth-abundant copper with equivalent performance are desired for practical, large-scale applications such as solid-state lighting and displays. Copper(I)-based emitters are well-known to suffer from weak spin-orbit coupling and a high reorganization energy upon photoexcitation. Here we report a cationic organo-copper cluster [Cu 4 (PCP) 3 ] + (PCP = 2,6-(PPh 2) 2 C 6 H 3) that features suppressed non-radiative decays, giving rise to a robust narrow-band green luminophore with a photoluminescent (PL) efficiency up to 93%. PL decay kinetics corroborated by DFT calculations reveal a complex emission mechanism involving contributions of both thermally activated delayed fluorescence (TADF) and phosphorescence. This robust compound was solution-processed into a thinfilm in prototype OLEDs with external quantum efficiency up to 11% and a narrow emission bandwidth (65 nm FWHM).
To obtain luminescent lanthanide complexes with a low energy LMCT state the 2-(2'-mercaptophenyl)benzothiazolates, Ln(SSN), and 2-(2'-mercaptophenyl)benzoxazolates, Ln(OSN) (Ln = Gd, Yb), were synthesized by the reaction of amides Ln[N(SiMe)] with respective thiophenols. Ytterbium complexes were structurally characterized by X-ray diffraction analysis. Cyclic voltammetry revealed that the deprotonated mercaptophenyl ligands have significantly lower oxidation potentials than their phenoxy analogues and some β-diketones. The photophysical properties of Gd and Yb compounds were studied both in solution and in the solid state. The fluorescence spectra of the compounds in solution display the bands of the keto and enol forms of the ligands. No energy transfer from the organic part to Yb has been detected in solutions of both Yb complexes, whereas in solids an intense metal-centered emission in the near infrared region was observed. The solid Gd compounds exhibited room temperature phosphorescence caused by unusually efficient intersystem crossing facilitated by the essentially reducing properties of OSN and SSN ligands. To explain the sensitization process occurring in solids Yb(OSN) and Yb(SSN) a specific non-resonant energy transfer mechanism via a ligand to metal charge transfer state has been proposed. Based on the Yb derivatives, NIR-emitting OLEDs with 860 μW cm maximal irradiance were obtained. Their Gd counterparts showed bright electrophosphorescence (up to 1350 cd m) in the devices containing doped emission layers.
The observation of a stimulated emission at interband transitions in monocrystalline n-InN layers under optical pumping is reported. The spectral position of the stimulated emission changes over a range of 1.64 to 1.9 μm with variations of free electron concentration in InN layers from 2·1019 cm−3 to 3·1017 cm−3. The main necessary conditions for achieving the stimulated emission from epitaxial InN layers are defined. In the best quality samples, a threshold excitation power density is obtained to be as low as 400 W/cm2 at T = 8 K and the stimulated emission is observed up to 215 K. In this way, the feasibility of InN-based lasers as well as the potentials of crystalline indium nitride as a promising photonic material are demonstrated.
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