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We report the first systematic assessment of intrinsic photothermal stability of a large panel of complex lead halides APbX3 incorporating different univalent cations (A = CH3NH3 +, [NH2CHNH2]+, Cs+) and halogen anions (X = Br, I) using a series of analytical techniques such as UV–vis and X-ray photoelectron spectroscopy, X-ray diffraction, EDX analysis, atomic force and scanning electron microscopy, ESR spectroscopy, and mass spectrometry. We show that heat stress and light soaking induce a severe degradation of perovskite films even in the absence of oxygen and moisture. The stability of complex lead halides increases in the order MAPbBr3 < MAPbI3 < FAPbI3 < FAPbBr3 < CsPbI3 < CsPbBr3, thus featuring all-inorganic perovskites as the most promising absorbers for stable perovskite solar cells. An important correlation was found between the stability of the complex lead halides and the volatility of univalent cation halides incorporated in their structure. The established relationship provides useful guidelines for designing new complex metal halides with immensely improved stability.

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