摘要： While 2D/3D layered perovskites have been the object of comprehensive research principally focused on increasing the long-term stability observed in 3D perovskites, significant opportunities still exist concerning the application of different kinds of cations outside the sphere of primary amines, which are the cations most usually applied. Our results demonstrate that the materials and the solar cells prepared with dipropylammonium iodide (DipI), a bulky secondary ammonium cation of small size, lead to obtaining materials that are not only efficient and thermodynamically stable but also robust toward heat stress. Time-resolved studies indicate longer carrier lifetime for 2D/3D layered perovskites fabricated with this bulky cation than for systems based on bulky primary ammonium cations, which allowed us to obtain PCE = 12.51% (n = 10), 15.78% (n = 50), and 17.90% (n = 90). We determine that the concentration of perovskite material after 240 min at 100 °C is up to 575% greater in the 2D/3D perovskite (n = 10) than that observed in 3D perovskite films. The material stability also improves the thermal stability of the photovoltaic devices, presenting an efficiency drop of just 4% for n = 50 and n = 10 after thermal annealing while the performance drop for reference 3D samples in the same conditions was greater than 80%.