Hybrid silicon/polymer solar cells promise to be an economically feasible alternative energy solution for various applications if ultrathin flexible crystalline silicon (c-Si) substrates are used. However, utilization of ultrathin c-Si encounters problems in light harvesting and electronic losses at surfaces, which severely degrade the performance of solar cells. Here, we developed a metal-assisted chemical etching method to deliver front-side surface texturing of hierarchically bowl-like nanopores on 20 μm c-Si, enabling an omnidirectional light harvesting over the entire solar spectrum as well as an enlarged contact area with the polymer. In addition, a back surface field was introduced on the back side of the thin c-Si to minimize the series resistance losses as well as to suppress the surface recombination by the built high-low junction. Through these improvements, a power conversion efficiency (PCE) up to 13.6% was achieved under an air mass 1.5 G irradiation for silicon/organic hybrid solar cells with the c-Si thickness of only about 20 μm. This PCE is as high as the record currently reported in hybrid solar cells constructed from bulk c-Si, suggesting a design rule for efficient silicon/organic solar cells with thinner absorbers.

Self‐assembled monolayers (SAMs) have emerged as effective carrier transport layers in perovskite (PVK) solar cells because of their unique ability to manipulate interfacial property, as well as simple processing and scalable fabrication. However, the defects and pinholes derived from their sensitive adsorption process inevitably deteriorate the final device performance. Herein, a sputtered nickel oxide (NiOx) interlayer is used as a seed layer to promote the adsorption of the [2‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)ethyl]phosphonic acid (MeO‐2PACz) SAM on the indium tin oxide (ITO) substrate. The promoted adsorption is attributed to the enhanced tridentate binding between MeO‐2PACz and NiOx relative to the conventional bidentate binding between MeO‐2PACz and ITO. In addition, the NiOx modification can simultaneously improve the passivation ability and hole‐selectivity of the MeO‐2PACz, provide a favorable energy‐level alignment at the ITO/PVK interface, and prevent a direct contact between PVK and ITO. As a consequence, this NiOx‐seeded MeO‐2PACz hole transport layer enables a significantly enhanced power conversion efficiency of 19.9% in comparison with 18.4% of the control device. This work provides an effective strategy to improve the performance of the SAM‐based photoelectric device.

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