Thermodynamic Stability and Hydrogen Bonds in Mixed Halide Perovskites

TL;DR

This study develops a thermodynamic framework using ab initio molecular dynamics to understand the stability of mixed halide perovskites, revealing that configurational entropy stabilizes these materials against phase separation despite positive mixing enthalpy.

Contribution

The paper introduces a comprehensive thermodynamic model that decomposes free energy contributions, showing configurational entropy dominates stability in mixed halide perovskites, challenging the role of hydrogen bonds.

Findings

Configurational entropy stabilizes mixed halide perovskites.

Hydrogen bonding does not significantly influence thermodynamic stability.

Cs-containing mixtures are stable without hydrogen bonds.

Abstract

The stability of mixed halide perovskites against phase separation is crucial for their optoelectronic applications, yet difficult to rationalize due to the interplay of enthalpic, configurational, and dynamical effects. Here we present a simple thermodynamic framework for multicomponent halide perovskites of composition FA$_{1-x}$MA$_{x-y}$Cs$_y$Pb(I$_{1-z}$Br$_z$)$_3$, based on \textit{ab initio} molecular dynamics. By decomposing the free energy of mixing into enthalpic, configurational, and rotational entropic contributions, we show that although the enthalpy of mixing is generally positive, the solid solutions are thermodynamically stable against phase separation due to the large configurational entropy associated with random substitution on cation and halide sublattices. Mixing reduces the rotational entropy of the organic cations, partially offsetting the configurational stabilization. However, within our model, this rotational penalty is not sufficient to overcome the configurational driving force, and a curvature analysis within a regular-solution model does not predict a miscibility gap for any of the mixing channels considered. Analysis of hydrogen-bond dynamics shows that MA--Y (Y = I, Br) interactions are more persistent than FA--Y interactions, while the dominant FA-donated N$-$H$\cdots$I hydrogen bonds remain nearly composition-invariant. Cs-containing mixtures, in which Cs$^{+}$ forms no hydrogen bonds, can nevertheless be thermodynamically stable. These results demonstrate that hydrogen bonding does not control thermodynamic stability in mixed halide perovskites. Instead, phase stability is governed by the balance between strong configurational entropy and a smaller, systematically destabilizing rotational-entropy correction.