Phase segregation in mixed-halide perovskites affects charge-carrier dynamics while preserving mobility
Nature Communications Springer Nature 12 (2021) 6955
Abstract:
Mixed halide perovskites can provide optimal bandgaps for tandem solar cells which are key to improved cost-efficiencies, but can still suffer from detrimental illumination-induced phase segregation. Here we employ optical-pump terahertz-probe spectroscopy to investigate the impact of halide segregation on the charge-carrier dynamics and transport properties of mixed halide perovskite films. We reveal that, surprisingly, halide segregation results in negligible impact to the THz charge-carrier mobilities, and that charge carriers within the I-rich phase are not strongly localised. We further demonstrate enhanced lattice anharmonicity in the segregated I-rich domains, which is likely to support ionic migration. These phonon anharmonicity effects also serve as evidence of a remarkably fast, picosecond charge funnelling into the narrow-bandgap I-rich domains. Our analysis demonstrates how minimal structural transformations during phase segregation have a dramatic effect on the charge-carrier dynamics as a result of charge funnelling. We suggest that because such enhanced recombination is radiative, performance losses may be mitigated by deployment of careful light management strategies in solar cells.Ultrafast photo-induced phonon hardening due to Pauli blocking in MAPbI3 single-crystal and polycrystalline perovskites
Journal of Physics: Materials IOP Publishing 4:4 (2021) 044017
Abstract:
Metal-halide perovskite semiconductors have attracted intensive interest in the last decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb—I stretching in both MAPbI3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz (THz) conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI3. First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI3, phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI3. We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI3. Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI3.In-Operando Characterization of P-I-N Perovskite Solar Cells Under Reverse Bias
Institute of Electrical and Electronics Engineers (IEEE) 00 (2021) 1365-1367
Temperature Coefficients of Perovskite Photovoltaics for Energy Yield Calculations.
ACS energy letters 6:5 (2021) 2038-2047
Abstract:
Temperature coefficients for maximum power (T PCE), open circuit voltage (V OC), and short circuit current (J SC) are standard specifications included in data sheets for any commercially available photovoltaic module. To date, there has been little work on determining the T PCE for perovskite photovoltaics (PV). We fabricate perovskite solar cells with a T PCE of -0.08 rel %/°C and then disentangle the temperature-dependent effects of the perovskite absorber, contact layers, and interfaces by comparing different device architectures and using drift-diffusion modeling. A main factor contributing to the small T PCE of perovskites is their low intrinsic carrier concentrations with respect to Si and GaAs, which can be explained by its wider band gap. We demonstrate that the unique increase in E g with increasing temperatures seen for perovskites results in a reduction in J SC but positively influences V OC. The current limiting factors for the T PCE in perovskite PV are identified to originate from interfacial effects.Limits to electrical mobility in lead-halide perovskite semiconductors
Journal of Physical Chemistry Letters American Chemical Society 12:14 (2021) 3607-3617