Lanthanide-Induced Photoluminescence in Lead-Free Cs2AgBiBr6Bulk Perovskite: Insights from Optical and Theoretical Investigations

Emphasis was recently placed on the Cs2AgBiBr6 double perovskite as a possible candidate to substitute toxic lead in metal halide perovskites. However, its poor light-emissive features currently make it unsuitable for solid-state lighting. Lanthanide doping is an established strategy to implement luminescence in poorly emissive materials, with the additional advantage of fine-tuning the emission wavelength. We discuss here the impact of Eu and Yb doping on the optical properties of Cs2AgBiBr6 thin films, obtained from the solution processing of hydrothermally synthesized bulk crystalline powders, by combining experiments and density functional theory calculations. Eu(III) incorporation does not lead to the characteristic 5D0 → 7F2 emission feature at 2 eV, while only a weak trap-assisted sub-band gap radiative emission is reported. Oppositely, we demonstrate that incorporated Yb(III) leads to an intense and exclusive photoluminescence emission in the near-infrared as a result of the efficient sensitization of the lanthanide 2F5/2 → 2F7/2 transition

Lanthanide Induced Photoluminescence in Lead-Free Cs₂AgBiBr₆ Bulk Perovskite: Insights From Optical and Theoretical Investigations

The search for materials substituting toxic lead in metal halide perovskites has recently placed emphasis on the Cs2AgBiBr6 double perovskite as a possible candidate. The poor light-emissive features of this species, mainly associated to the indirect nature of the band gap and the strongly bound exciton, however, currently make it unsuitable for solid-state lighting applications. Doping with lanthanides is an established strategy to implement luminescence in poorly emissive materials, with the additional advantage of tuning the wavelength of emission independently from the host band structure. We discuss here the impact of Eu- and Yb-doping on the absorption and emission properties of Cs2AgBiBr6 polycrystalline thin films, obtained from solution-processing of hydrothermally synthesized bulk crystalline powders, by combining experiments and density functional theory calculations. Eu(III) incorporation does not lead to the characteristic 5D0→7F2 emission feature at 2 eV, while only a weak sub band-gap radiative emission ascribed to a trap-assisted recombination process is reported. On the other hand, we demonstrate that Yb(III) incorporated in the bulk double perovskite leads to an intense and exclusive photoluminescence emission in the near-infrared (NIR) from thin films, as a result of the efficient sensitization of the lanthanide centered 2F5/2→2F7/2 transition, with favorable mid-gap energetic position. Yb-doping may be thus exploited for the future development of stable and sustainable perovskite NIR-light emitters

Effect of fluorosubstitution on the structure of single crystals, Effect of fluorosubstitution on the structure of single crystals,thin films and spectral properties of palladium phthalocyanines

In this work, the crystalline structure of single crystals grown by vacuum sublimation of unsubstituted palladium phthalocyanines (PdPc), its tetrafluorinated (PdPcF4) and hexadecafluorinated (PdPcF16) derivatives have been investigated using X-ray diffraction measurements. Two crystalline phases have been identified for PdPc; the molecules in both phases crystallize in stacks with herringbone arrangement in the monoclinic space groups (C2/c for -PdPc; P21/n for -PdPc). Both PdPcF4 and PdPcF16 crystallize in the triclinic P-1 space group, forming stacks of molecules in columnar arrangement with molecules in adjacent columns are aligned parallel to one another. X-ray diffraction measurements have also been used to elucidate the structural features and molecular orientation of thin films of PdPc, PdPcF4 and PdPcF16, grown by organic molecular beam deposition at different substrate temperatures. The effect of fluorosubstitution on UV-visible optical absorption and vibrational spectra of palladium phthalocyanine derivatives is also discussed