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Silver iodide (AgI) is used for a wide range of applications from photocatalysis and antimicrobial coatings to photography and ice nucleation. By fitting powder X-ray diffraction patterns with DIFFaX, we show that AgI displays a strong tendency to form stacking-disordered materials. Its polytypism is determined by the silver cation to iodide molar ratio upon precipitation. Under iodide-rich conditions, fully hexagonal β-AgI is obtained, whereas a maximal percentage of cubic stacking of 81% is obtained at a 2:1 molar ratio in the silver cation-rich regime. These findings are explained on the basis of a concentration-dependent competition between kinetically and thermodynamically favored adsorption processes. Furthermore, the previously reported memory effects, observed upon transforming hexagonal and cubic AgI to the high-temperature superionic phase and back, are now followed quantitatively. We propose that the memory effects originate from excess ions at the surfaces of AgI crystals that stabilize the py...

Stacking Disorder by Design: Factors Governing the Polytypism of Silver Iodide upon Precipitation and Formation from the Superionic Phase