Oxides employed in halide perovskite solar cells (PSCs) have already demonstrated to deliver enhanced stability, low cost, and the ease of fabrication required for the commercialization of the technology. The most stable PSCs configuration, the carbon‐based hole transport layer‐free PSC (HTL‐free PSC), has demonstrated a stability of more than one year of continuous operation partially due to the dual presence of insulating oxide scaffolds and conductive oxides. Despite these advances, the stability of PSCs is still a concern and a strong limiting factor for their industrial implementation. The engineering of oxide interfaces functionalized with molecules (like self‐assembly monolayers) or polymers results in the passivation of defects (traps), providing numerous advantages such as the elimination of hysteresis and the enhancement of solar cell efficiency. But most important is the beneficial effect of interfacial engineering on the lifetime and stability of PSCs. In this work, the authors provide a brief insight into the recent developments reported on the surface functionalization of oxide interfaces in PSCs with emphasis on the effect of device stability. This paper also discusses the different binding modes, their effect on defect passivation, band alignment or dipole formation, and how these parameters influence device lifetime.
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