Designed Giant Room‐Temperature Electrocaloric Effects in Metal‐Free Organic Perovskite [MDABCO](NH₄)I₃ by Phase–Field Simulations

Abstract Achieving a colossal room‐temperature electrocaloric effect is essential for practical solid‐state refrigeration applications with low‐cost and high‐efficiency. Here, through the design of applying external stimuli (hydrostatic pressure and misfit strain), giant room‐temperature electrocaloric effects in the bulk and thin film of metal‐free organic perovskite [MDABCO](NH₄)I₃ are obtained by using a combination of thermodynamic calculations and phase–field simulations. Under the hydrostatic pressure of 1 GPa, there emerges excellent room‐temperature (300 K) electrocaloric performance with the temperature change (ΔT) of 8.41 K at 30 MV m⁻¹ and electrocaloric strength (ΔT/ΔE) of 0.63 K m MV⁻¹ at 10 MV m⁻¹, respectively. The prominent electrocaloric effects of MDABCO(NH₄)I₃ may be related to its rapid change rates of free energy barrier height. Additionally, it can be found that some stripe domains and non‐180° domain walls form in the [MDABCO](NH₄)I₃ bulk, which is consistent with the experimental results. This work not only provides new insights into organic perovskite [MDABCO](NH₄)I₃, but also guides for further developing to realize remarkable room‐temperature electrocaloric cooling.