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Abstract:

Bulk formamidinium lead triiodide (FAPbI3) films host spontaneously formed quantum-confined (QC) domains, but their structural origin remains unclear. Using controlled material degradation in humid air as a dynamic lattice perturbation, we track the evolution of QC features in thin-film absorption of FAPbI3. With aging, above-bandgap QC features redshift and diminish, indicating weakened electronic confinement. Concurrently, X-ray diffraction reveals that breakdown of α-phase connectivity coincides with the loss of short-range higher-order hexagonal (nH, n > 2) polytypes as the material converts to the 2H δ-phase. Such polytypic nanodomains may generate peaked absorption features by forming higher-energy barriers confining charge carriers within α-FAPbI3 or by introducing distinct electronic states associated with mixed octahedral connectivity. Progressive degradation dismantles this framework, causing the disappearance of the QC features. Our results identify the structural motifs underpinning QC effects and propose that controlling higher-order (n > 2) hexagonal polytypes offers a route to tuning quantum confinement in FAPbI3 films.

Abstract:

Two-dimensional perovskites have emerged as promising materials for optoelectronic applications owing to their excellent environmental stability and tunable quantum confinement. Such 2D perovskites can incorporate a particularly versatile range of organic cations of different size, chemical nature, and optoelectronic character. However, understanding and controlling thin-film transport for this vast family of materials remains a key challenge to their successful application in devices. Here, we systematically investigate odd-even effects in thin films of Ruddlesden-Popper-type (RP) lead-iodide 2D perovskites based on nonconjugated alkylammonium spacer cations with chain lengths ranging from three to eight carbon atoms. A pronounced odd-even dependence on the carbon number is observed in both optical and transport properties, including absorption coefficients, photoluminescence energies and lifetimes, and excitation diffusion dynamics. Notably, the coefficients for charge-carrier diffusion out of the film plane─extracted via a dynamic photon reabsorption approach─display an opposite odd-even trend to the in-plane charge-carrier mobility obtained from optical pump-terahertz probe measurements, causing a pronounced odd-even modulation of the thin-film mobility anisotropy. Grazing-incidence wide-angle X-ray scattering measurements reveal that this behavior is related to cation-controlled nanostructural orientation: even-numbered alkyl spacer cations induce lead-iodide planes lying highly oriented within the film plane, while odd-numbered ones cause more disordered stacking. Furthermore, the observed 1/d²-dependence on interplane distance d in ordered films demonstrates that Förster resonance energy transfer underpins diffusion of excitations between lead-iodide layers. Our findings establish a direct structure-transport correlation in 2D perovskite films and provide valuable guidelines for the design of optoelectronic devices.

Abstract:

Mixed-halide perovskites exhibit ideal band gaps for use in perovskite-based multijunction photovoltaics, but stable performance is compromised by light-induced halide segregation. Photoluminescence (PL) tracking is universally used to monitor such photoinstability; however, here we reveal that such data do not accurately quantify halide segregation. We utilize a combination of simultaneously recorded PL and X-ray diffraction (XRD) measurements to explore CH3NH3Pb­(I1–x Br x )3 films across 18 different halide ratios. While PL data suggests that segregation rates increase exponentially with bromide fraction x, XRD patterns reveal that they are actually unchanged. We demonstrate that PL cannot accurately reflect the rate and extent of halide segregation because it is governed by charge funneling to iodide-rich minority domains, which is strongly influenced by additional factors, including luminescence efficiency, band energetics, and charge extraction. To assess the efficacy of treatments to suppress such photoinstabilities, it is therefore essential to probe changes across the full material volume, e.g. by monitoring XRD or absorption spectra.

Abstract:

We explore multiple-cation chalco–halide phase fields evaluated by their synthetic accessibility using machine learning models. Exploratory synthesis guided by computational tools leads to the discovery of two new compounds; CuSn₂SI₃ and Cu_0.35Sn_5.29S₂I₇, their structures, and electronic and optical properties are reported herein. This is the first report of a stable quaternary compound in the Cu–Sn–S–I phase field. The two new compounds show related crystal structures where Sn₄S₂I₄ layers are a common structural motif in both. These Sn₄S₂I₄ layers are connected by Cu₂I₂ layers and disordered Cu–Sn–I layers, forming the three-dimensional structures of CuSn₂SI₃ and Cu_0.35Sn_5.29S₂I₇ respectively. Electronic band structure calculations using density functional theory show the presence of a direct band gap in CuSn₂SI₃ and suggest anisotropic transport, in line with the layered structure of the compound. A mixture of the two compounds with ∼86% CuSn₂SI₃, shows a band gap in the visible region, close to 2.1 eV and a significant photo-induced charge carrier mobility of ∼1.3 cm² V^−1 s^−1. This demonstrates Cu–Sn chalco–halides can form a promising phase space to explore for solar absorber materials, with further design and tuning of band gap.

Abstract:

Mixed-halide perovskites offer ideal bandgaps for tandem solar cells, but they suffer from light-induced halide segregation, which compromises their operational stability. Here, we directly probe the impact of halide segregation on charge-carrier dynamics at the interface between a mixed-halide perovskite and charge transport layers by using a free-space synchronous multimodal spectroscopy approach, combining time-resolved microwave conductivity, time-resolved photoluminescence (PL) and steady-state PL. We present a method to distinguish directly between charge-carrier dynamics dominated by either majority or minority carriers, enabling us to isolate effects arising from charge-selective extraction from the perovskite to commonly used hole- or electron transport layers, i.e. poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) and SnO2, respectively. We show that halide segregation creates iodide-rich phases that capture charge carriers within sub-nanoseconds, which slightly reduces their mobilities at microwave frequencies. We reveal that charge extraction from such iodide-rich domains is still surprisingly feasible, but competes with enhanced radiative recombination resulting from higher charge concentrations caused by funnelling into these minority phases. We demonstrate that together such effects reduce charge diffusion lengths and can account for the widely observed reduction in open-circuit voltages and short-circuit currents in solar cells under operational conditions. Our findings unravel the causes underpinning the adverse impact of halide segregation and provide guidelines to improve device performance.