Publication date: 15th December 2025
Guanidinium salts are emerging as powerful chaotropic agents for next-generation perovskite solar cells, simultaneously boosting device efficiency and stability across different architectures. In inverted lead-halide perovskites, partial A-site substitution with guanidinium enhances short-circuit current and fill factor by accelerating charge transport and suppressing ion migration, delivering stable performance improvements distinct from conventional devices. In mixed tin–lead (Sn–Pb) perovskites, guanidinium thiocyanate plays a mechanistic role in crystallization, slowing crystal growth and enabling homogeneous films with suppressed nonradiative recombination. Using hyperspectral and real-time in situ photoluminescence imaging, we reveal that perovskite crystallization continues during cooldown, a previously overlooked regime that critically determines film quality. Together, these findings establish guanidinium as a versatile additive for tailoring charge dynamics and crystal growth, advancing perovskite photovoltaics towards higher efficiency and stability, while providing design principles for additive engineering across diverse material systems, processing windows, and device architectures relevant to scalable manufacturing and long-term operational reliability.
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