Photovoltaic & Optoelectronic Device Group

Abstract:

We present a crystallographic and optoelectronic study of the double perovskite Cs2AgBi1–xInxBr6. From structural characterization we determine that the indium cation shrinks the lattice and shifts the cubic-to-tetragonal phase transition point to lower temperatures. The absorption onset is shifted to shorter wavelengths upon increasing the indium content, leading to wider band gaps, which we rationalize through first-principles band structure calculations. Despite the unfavorable band gap shift, we observe an enhancement in the steady-state photoluminescence intensity, and n-i-p photovoltaic devices present short-circuit current greater than that of neat Cs2AgBiBr6 devices. In order to evaluate the prospects of this material as a solar absorber, we combine accurate absorption measurements with thermodynamic modeling and identify the fundamental limitations of this system. Provided radiative efficiency can be increased and the choice of charge extraction layers are specifically improved, this material could prove to be a useful wide band gap solar absorber.

Abstract:

Mixed-halide perovskites offer bandgap tunability essential for multijunction solar cells; however, a detrimental halide segregation under light is often observed. Here we combine simultaneous in situ photoluminescence and X-ray diffraction measurements to demonstrate clear differences in compositional and optoelectronic changes associated with halide segregation in MAPb(Br_0.5I_0.5)₃ and FA_0.83Cs_0.17Pb(Br_0.4I_0.6)₃ films. We report evidence for low-barrier ionic pathways in MAPb(Br_0.5I_0.5)₃, which allow for the rearrangement of halide ions in localized volumes of perovskite without significant compositional changes to the bulk material. In contrast, FA_0.83Cs_0.17Pb(Br_0.4I_0.6)₃ lacks such low-barrier ionic pathways and is, consequently, more stable against halide segregation. However, under prolonged illumination, it exhibits a considerable ionic rearrangement throughout the bulk material, which may be triggered by an initial demixing of A-site cations, altering the composition of the bulk perovskite and reducing its stability against halide segregation. Our work elucidates links between composition, ionic pathways, and halide segregation, and it facilitates the future engineering of phase-stable mixed-halide perovskites.

Abstract:

Lead-based halide perovskites have received great attention in light-emitting applications due to their excellent properties, including high photoluminescence quantum yield (PLQY), tunable emission wavelength, and facile solution preparation. In spite of excellent characteristics, the presence of toxic element lead directly obstructs their further commercial development. Hence, exploiting lead-free halide perovskite materials with superior properties is urgent and necessary. In this review, the deep-seated reasons that benefit light emission for halide perovskites, which help to develop lead-free halide perovskites with excellent performance, are first emphasized. Recent advances in lead-free halide perovskite materials (single crystals, thin films, and nanocrystals with different dimensionalities) from synthesis, crystal structures, optical and optoelectronic properties to applications are then systematically summarized. In particular, phosphor-converted LEDs and electroluminescent LEDs using lead-free halide perovskites are fully examined. Ultimately, based on current development of lead-free halide perovskites, the future directions of lead-free halide perovskites in terms of materials and light-emitting devices are discussed.