Dr Alan Bowman

Abstract:

Reliable predictions of long-term stability are essential as halide perovskite solar cells approach widespread commercial deployment. However, extrapolation from aging tests requires knowledge of material degradation dynamics, which remain unclear for halide perovskites. Here, we reveal the structural and optoelectronic evolution of formamidinium-caesium lead-halide perovskite films under heat and/or light using in situ X-ray diffraction and photoluminescence. Heat and light combined induce much faster degradation than either stressor alone, with 1 sun illumination degrading material 53 times faster at 85 °C than room temperature. For all compositions investigated the degradation rate is highly nonlinear in time and follows a sigmoidal decay, suggestive of interface-driven dynamics. Degradation proceeds in three steps: halide segregation (for mixed-halide perovskites), A-site cation diffusion triggered by heterogeneity and strain, and finally iodine and formamidinium loss. Our findings provide a quantitative framework for lifetime predictions and highlight the necessity of combined heat and light ageing tests.

Abstract:

Halide perovskite solar cells have demonstrated a rapid increase in power conversion efficiencies. Understanding and mitigating remaining carrier losses in halide perovskites is now crucial to enable further increases to approach their practical efficiency limits. Recent observations in halide perovskites have revealed processes such as shallow carrier trapping, which give rise to an apparent non-radiative bimolecular channel that is difficult to distinguish from intrinsic radiative recombination. Here, we quantify this shallow-trap manifestation by jointly analyzing time-resolved photoluminescence and quantum efficiency to separate the total second-order term into radiative (ηesck2r) and shallow-trap-mediated non-radiative contributions (k2non), and evaluate their device impact. We show that k2non is strongly modulated by temperature and surface chemistry and thus depends on extrinsic factors and its origin is independent from deep traps, whereas the intrinsic radiative coefficient and intrinsic second-order recombination follow detailed-balance expectations and align with theoretical evaluations through van Roosbroeck–Shockley relations. Based on density functional theory simulations and Quasi-Fermi level calculations, we propose that surface states are the primary origin of this shallow-trap-related second-order component, contributing up to ∼80 mV of the overall reduction in Voc at room temperature. This work reveals that the origin of carrier losses from two non-radiative recombination types (first and second order) are not linked, emphasizing the need for distinctive mitigation strategies targeting each type to unlock the full efficiency potential of perovskite solar cells.

Abstract:

Thermo-optical nonlinearities (TONL) in metasurfaces enable dynamic control of optical properties—such as transmitted power, phase, and polarization—through external stimuli like laser irradiation or temperature. Due to the inherently slow thermal dynamics of extended systems, research has primarily focused on steady-state effects, as rapid modulation is typically considered challenging. In this study, photo-driven TONL is investigated in amorphous silicon (a-Si) metasurfaces under both steady-state and, more importantly, dynamic conditions using a modulated 488 nm continuous-wave pump laser. First, a non-monotonic change is observed in transmission as a function of irradiation intensity at a wavelength red-shifted by 15 nm from the electric-dipole resonance. Specifically, transmission initially decreases by 30% before increasing by 30% as the laser intensity reaches 5 mW/ (Formula presented.). Next, it is demonstrated that TONL decouple thermal and optical response times, with the optical response being up to seven times faster than the thermal response under tested conditions ((Formula presented.) (Formula presented.) vs. (Formula presented.) (Formula presented.)). Most remarkably, it is experimentally shown that the interplay of these effects enables optical modulation at twice (100 kHz) the excitation laser's modulation frequency (50 kHz). Finally, it is shown that exploiting these unique conditions allow thermo-optical metasurfaces to intrinsically encode multiple optical states within a single modulation cycle, realizing a self-modulating photonic platform. TONL thus open new avenues for engineering active metasurfaces that combine fast, high-amplitude modulation with self-modulating optical dynamics, making them promising for next-generation optical switching, dynamic holography, optical information processing, and neuromorphic computing.

Abstract:

Second-harmonic generation (SHG) is a powerful surface-specific probe for centrosymmetric materials, with broad relevance to energy and biological interfaces. Plasmonic nanomaterials have been extensively utilized to amplify this nonlinear response. Yet, material instability has constrained most studies to gold, despite the significance of plasmonic metals such as copper for catalysis. Here, we demonstrate stable and anisotropic SHG from monocrystalline copper, overcoming long-standing challenges associated with surface degradation. By leveraging an on-substrate synthesis approach that yields atomically flat and oxidation-resistant Cu microflakes, we enable reliable SHG measurements and reveal a strong cross-polarized response with C 3v surface symmetry. The SHG signal remains stable over 3 h of continuous femtosecond excitation, highlighting the remarkable optical robustness of the Cu microflakes. These results reinforce the viability of monocrystalline Cu as a robust platform for nonlinear nanophotonics and surface-sensitive spectroscopy, expanding the range of copper-based optical applications.

Abstract:

Copper is one of the most extensively studied materials for energy conversion and catalytic systems, with a wide range of other applications, from nanophotonics to biotechnology. However, existing synthesis methods are limited with many undesirable byproducts and poorly defined morphologies. Here, we report an on-substrate wet synthesis approach that yields purely metallic and monocrystalline Cu microflakes with an exposed (111) crystalline surface. By systematically studying the growth mechanism, we achieve unprecedented sizes of more than 130 mu m, which is 2 orders of magnitude larger than reported in most previous studies, along with high aspect ratios of over 400. Furthermore, we show significantly higher stability against oxidation provided by the halide adlayer, which also eliminates the need for any organic surfactants in the synthesis. Overall, our facile synthesis approach delivers an exciting avenue for the emerging fields of catalysis and nanophotonics.LNE