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Abstract:

Metal halide perovskite based tandem solar cells are promising to achieve power conversion efficiency beyond the theoretical limit of their single-junction counterparts. However, overcoming the significant open-circuit voltage deficit present in wide-bandgap perovskite solar cells remains a major hurdle for realizing efficient and stable perovskite tandem cells. Here, a holistic approach to overcoming challenges in 1.8 eV perovskite solar cells is reported by engineering the perovskite crystallization pathway by means of chloride additives. In conjunction with employing a self-assembled monolayer as the hole-transport layer, an open-circuit voltage of 1.25 V and a power conversion efficiency of 17.0% are achieved. The key role of methylammonium chloride addition is elucidated in facilitating the growth of a chloride-rich intermediate phase that directs crystallization of the desired cubic perovskite phase and induces more effective halide homogenization. The as-formed 1.8 eV perovskite demonstrates suppressed halide segregation and improved optoelectronic properties.

Abstract:

Formamidinium lead trioiodide (FAPbI₃) is a promising perovskite for single-junction solar cells. However, FAPbI₃ is metastable at room temperature and can cause intrinsic quantum confinement effects apparent through a series of above-bandgap absorption peaks. Here, we explore three common solution-based film-fabrication methods, neat N,N-dimethylformamide (DMF)–dimethyl sulfoxide (DMSO) solvent, DMF-DMSO with methylammonium chloride, and a sequential deposition approach. The latter two offer enhanced nucleation and crystallization control and suppress such quantum confinement effects. We show that elimination of these absorption features yields increased power conversion efficiencies (PCEs) and short-circuit currents, suggesting that quantum confinement hinders charge extraction. A meta-analysis of literature reports, covering 244 articles and 825 photovoltaic devices incorporating FAPbI₃ films corroborates our findings, indicating that PCEs rarely exceed a 20% threshold when such absorption features are present. Accordingly, ensuring the absence of these absorption features should be the first assessment when designing fabrication approaches for high-efficiency FAPbI₃ solar cells.

Abstract:

Metal halide perovskite (MHP) semiconductors have driven a revolution in optoelectronic technologies over the last decade, in particular for high-efficiency photovoltaic applications. Low-dimensional MHPs presenting electronic confinement have promising additional prospects in light emission and quantum technologies. However, the optimisation of such applications requires a comprehensive understanding of the nature of charge carriers and their transport mechanisms. This study employs a combination of ultrafast optical and terahertz spectroscopy to investigate phonon energies, charge-carrier mobilities, and exciton formation in 2D (PEA)₂PbI₄ and (BA)₂PbI₄ (where PEA is phenylethylammonium and BA is butylammonium). Temperature-dependent measurements of free charge-carrier mobilities reveal band transport in these strongly confined semiconductors, with surprisingly high in-plane mobilities. Enhanced charge-phonon coupling is shown to reduce charge-carrier mobilities in (BA)₂PbI₄ with respect to (PEA)₂PbI₄. Exciton and free charge-carrier dynamics are disentangled by simultaneous monitoring of transient absorption and THz photoconductivity. A sustained free charge-carrier population is observed, surpassing the Saha equation predictions even at low temperature. These findings provide new insights into the temperature-dependent interplay of exciton and free-carrier populations in 2D MHPs. Furthermore, such sustained free charge-carrier population and high mobilities demonstrate the potential of these semiconductors for applications such as solar cells, transistors, and electrically driven light sources.

Abstract:

All-optical control of terahertz pulses is essential for the development of optoelectronic devices for next-generation quantum technologies. Despite substantial research in THz generation methods, polarisation control remains difficult. Here, we demonstrate that by exploiting bandstructure topology, both helicity-dependent and helicity-independent THz emission can be generated from nanowires of the topological Dirac semimetal Cd3As2. We show that narrowband THz pulses can be generated at oblique incidence by driving the system with optical (1.55 eV) pulses with circular polarisation. Varying the incident angle also provides control of the peak emission frequency, with peak frequencies spanning 0.21 – 1.40 THz as the angle is tuned from 15° - 45°. We therefore present Cd3As2 nanowires as a promising novel material platform for controllable terahertz emission.

Abstract:

Understanding the mechanism of light-induced halide segregation in mixed-halide perovskites is essential for their application in multijunction solar cells. Here, photoluminescence spectroscopy is used to uncover how both increases in temperature and light intensity can counteract the halide segregation process. It is observed that, with increasing temperature, halide segregation in CH3NH3Pb(Br0.4I0.6)3 first accelerates toward ≈290 K, before slowing down again toward higher temperatures. Such reversal is attributed to the trade-off between the temperature activation of segregation, for example through enhanced ionic migration, and its inhibition by entropic factors. High light intensities meanwhile can also reverse halide segregation; however, this is found to be only a transient process that abates on the time scale of minutes. Overall, these observations pave the way for a more complete model of halide segregation and aid the development of highly efficient and stable perovskite multijunction and concentrator photovoltaics.