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Abstract As the demand for photovoltaic technologies continues to grow, the quest for efficient and sustainable transparent conducting electrodes (TCEs) rapidly rises. Traditional solutions, such as indium tin oxide (ITO), face challenges related to indium scarcity and environmental impact. To tackle these issues, a novel metal mesh rear TCE consisting of gold micro‐meshes is developed as ITO replacement in perovskite solar cells (PSCs). This study reveals that optimized Au meshes can guarantee 75% of the extracted photocurrent compared to reference devices with ITO and a promising power conversion efficiency (PCE) of 8.65%. By utilizing hybrid mesh structures with a 10‐nm ITO layer, the PCE further improves to 12.1%, with the extracted current exceeding 80% of the reference. Metal meshes can even serve to replace the opaque metal contact of PSCs, amplifying their functionality and efficiency through bifacial and multi‐junction applications. Here, aerosol jet‐printed silver meshes serve as front electrodes, combined with either 5–10 nm of Au, achieving efficient semi‐transparent devices (PCE 16.8%), or with 5–10 nm of ITO, providing enhanced bifacial properties while maintaining competitive efficiency. Overall, this work highlights remarkable features of metal meshes, making them promising alternatives to commonly used TCEs in optoelectronic applications.

Abstract In influencing fundamental properties—and ultimately device performance—of lead halide perovskites, interfacial interactions play a major role, notably with regard to carrier diffusion and recombination. Here anodized porous Si (pSi) as well as porous silica particles are employed as templates for formation of methylammonium lead trihalide nanostructures. This allows synthesis of relatively small perovskite domains and comparison of associated interfacial chemistry between as‐prepared hydrophobic hydrideterminated functionalities and hydrophilic oxide‐terminated surfaces. While physical confinement of MAPbBr3 has a uniform effect on carrier lifetime, pore size (7–18 nm) of the silicon‐containing template has a sensitive influence on perovskite photoluminescence (PL) wavelength maximum. Furthermore, identity of the surface functionality of the template significantly alters the PL quantum efficiency, with lowest PL intensity associated with the H‐terminated pSi and the most intense PL affiliated with the oxideterminated pSi surface. These effects are explored for green‐emitting MAPbBr3 as well as infrared‐emitting MAPbI3. In addition, the role of silicon surface chemistry on the time‐dependent stability of these perovskites packaged within a given mesoporous template is also evaluated, specifically, a lack of miscibility between MAPbI3 and the H‐terminated pSi template results in a diffusion of this specific perovskite composition eluting from this porous matrix over time.