Alloyed lead-free double perovskites display intense photoluminescence, are environmentally friendly, and their devices show long-term operation. Thanks to these properties, which make them excellent warm white-emitting materials, they have recently received great attention in lighting applications. An important factor to tune the optical properties of alloyed lead-free double perovskites is the presence of self-trapped excitons. Here, it is demonstrated that in leadfree double perovskites, the strong electron-phonon coupling plays a crucial role in the generation of self-trapped excitons. The strong electron-phonon coupling is confirmed by a large Huang-Rhys factor and by the presence of multiphonon transitions. In particular, sharp emission lines superimposed on the broad photoluminescence emission band of one of these samples (Cs 2 Ag 0.6 Na 0.4 InCl 6 0.5%Bi) are observed; these are due to the strong coupling of longitudinal-optical phonons with excited electronic states caused by the tetragonally distorted AgCl 6 octahedrons. Such a strong coupling of longitudinal-optical phonons to electrons can effectively modulate the photophysical properties of alloyed double perovskites, and its understanding is, thus, of paramount importance for the design of future optoelectronic devices.

No abstract

No abstract

The presence of Ge during the synthesis of thin film kesterite Cu2ZnSnSe4 (CZTSe) solar cell absorbers boosts their power conversion efficiency, especially due to an improved open circuit voltage. The mechanism underlying this beneficial effect of Ge is still under debate. We gained deep insights into the role of Ge by applying advanced synchrotron nanoprobe-based X-ray fluorescence spectroscopy and X-ray absorption near-edge structure spectroscopy to cross-sectional lamellas taken from high efficiency devices. We observe that Ge remains in the CZTSe absorber layer after the synthesis process with a specific heterogeneous distribution. Different grains contain different Ge concentrations. Moreover, Ge depletion exists at random grain boundaries but not at symmetric Σ3-boundaries, leading to different band alignments. The incorporated Ge occupies Sn lattice sites in the CZTSe crystal structure; however, the concentration is only 0.1 to 0.5 at %. Also Ge aggregates in nanoscale inclusions, which we could identify to be GeO2 that likely lessen the beneficial effect of Ge on the photovoltaic performance.

No abstract