Snaith group

Abstract:

The origin of the low densities of electrically active defects in Pb halide perovskite (HaP), a crucial factor for their use in photovoltaics, light emission, and radiation detection, remains a matter of discussion, in part because of the difficulty in determining these densities. Here, we present a powerful approach to assess the defect densities, based on electric field mapping in working HaP-based solar cells. The minority carrier diffusion lengths were deduced from the electric field profile, measured by electron beam-induced current (EBIC). The EBIC method was used earlier to get the first direct evidence for the n-i-p junction structure, at the heart of efficient HaP-based PV cells, and later by us and others for further HaP studies. This manuscript includes EBIC results on illuminated cell cross sections (in operando) at several light intensities to compare optoelectronic characteristics of different cells made by different groups in several laboratories. We then apply a simple, effective single-level defect model that allows deriving the densities (N_r) of the defect acting as recombination center. We find N_r ≈ 1 × 10¹³ cm^-3 for mixed A cation lead bromide-based HaP films and ∼1 × 10¹⁴ cm^-3 for MAPbBr₃(Cl). As EBIC photocurrents are similar at the grain bulk and boundaries, we suggest that the defects are at the interfaces with selective contacts rather than in the HaP film. These results are relevant for photovoltaic devices as the EBIC responses distinguish clearly between high- and low-efficiency devices. The most efficient devices have n-i-p structures with a close-to-intrinsic HaP film, and the selective contacts then dictate the electric field strength throughout the HaP absorber.

Abstract:

Efficient and stable perovskite solar cells rely on the use of Pb species potentially challenging the technologies' commercialisation. In this study, the fate of Pb derived from two common perovskite precursors is compared to cationic lead in soil-water microcosm experiments under various biogeochemical conditions. The rapid and efficient removal of Pb from the aqueous phase is demonstrated by inductively coupled plasma mass spectrometry. Sequential soil extraction results reveal that a substantial amount of Pb is associated with immobile fractions, whereas a minor proportion of Pb may become available again in the long term, when oxygen is depleted (e.g. during water logging). X-ray absorption spectroscopy results reveal that the sorption of Pb on mineral phases represents the most likely sequestration mechanism. The obtained results suggest that the availability of leached Pb from perovskite solar cells is naturally limited in soils and that its adverse effects on soil biota are possibly negligible in oxic soils. All three Pb sources used behaved very similar in the experiments, wherefore we conclude that perovskite derived Pb will have a similar fate compared to cationic Pb, so that established risk assessment considerations for Pb remain legitimate.

Abstract:

Charge carrier mobility is a fundamental property of semiconductor materials that governs many electronic device characteristics. For metal halide perovskites, a wide range of charge carrier mobilities have been reported using different techniques. Mobilities are often estimated via transient methods assuming an initial charge carrier population after pulsed photoexcitation and measurement of photoconductivity via non-contact or contact techniques. For nanosecond to millisecond transient methods, early-time recombination and exciton-to-free-carrier ratio hinder accurate determination of free-carrier population after photoexcitation. By considering both effects, we estimate long-range charge carrier mobilities over a wide range of photoexcitation densities via transient photoconductivity measurements. We determine long-range mobilities for FA0.83Cs0.17Pb(I0.9Br0.1)3, (FA0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 and CH3NH3PbI3-xClx polycrystalline films in the range of 0.3 to 6.7 cm2 V−1 s−1. We demonstrate how our data-processing technique can also reveal more precise mobility estimates from non-contact time-resolved microwave conductivity measurements. Importantly, our results indicate that the processing of polycrystalline films significantly affects their long-range mobility.