Photovoltaic & Optoelectronic Device Group

Abstract:

Mixed lead-tin triiodide perovskites are promising absorber materials for low band-gap bottom cells in all-perovskite tandem photovoltaic devices. Key structural and electronic properties of the FAPb1-xSnxI3 perovskite are presented here as a function of lead:tin content across the alloy series. Temperature-dependent photoluminescence and optical absorption measurements are used to identify changes in the band-gap and phase transition temperature. The large band-gap bowing parameter, a crucial element for the attainment of low band-gaps in this system, is shown to depend on the structural phase, reaching a value of 0.84 eV in the low-temperature phase and 0.73 eV at room temperature. The parabolic nature of the bowing at all temperatures is compatible with a mechanism arising from bond bending to accommodate the random placement of unevenly sized lead and tin ions. Charge-carrier recombination dynamics are shown to fall into two regimes. Tin-rich compositions exhibit fast, mono-exponential recombination that is almost temperature independent, in accordance with high levels of electrical doping. Lead-rich compositions show slower, stretched-exponential charge-carrier recombination that is strongly temperature-dependent, in accordance with a multi-phonon assisted process. These results highlight the importance of structure and composition for control of band-gap bowing and charge-carrier recombination mechanisms in low band-gap absorbers for all-perovskite tandem solar cells.

Abstract:

The synthesis of epitaxial CdSe/PbS core/shell quantum dots (QDs) is reported. The PbS shell grows in a rock salt structure on the zinc blende CdSe core, thereby creating a crystal structure mismatch through additive growth. Absorption and photoluminescence (PL) band edge features shift to lower energies with increasing shell thickness, but remain above the CdSe bulk band gap. Nevertheless, the profiles of the absorption spectra vary with shell growth, indicating that the overlap of the electron and hole wave functions is changing significantly. This leads to over an order of magnitude reduction of absorption near the band gap and a large, tunable energy shift, of up to 550 meV, between the onset of strong absorption and the band edge PL. While the bulk valence and conduction bands adopt an inverse type-I alignment, the observed spectroscopic behavior is consistent with a transition between quasi-type-I and quasi-type-II behavior depending on shell thickness. Three effective mass approximation models support this hypothesis and suggest that the large difference in effective masses between the core and shell results in hole localization in the CdSe core and a delocalization of the electron across the entire QD. These results show the tuning of wave functions and transition energies in CdSe/PbS nanoheterostructures with prospects for use in optoelectronic devices for luminescent solar concentration or multiexciton generation.