Thermodynamic Stability and Hydrogen Bonds in Mixed Halide Perovskites

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.

Figures (4)

• Figure 1: Unit cell of cubic perovskite FAPbI$_3$. Iodide anions outside unit cell are added at top left corner to show a PbI$_6$ octahedron. Green dotted lines indicate hydrogen bonds.
• Figure 2: Orientational autocorrelation functions $C(t)$ for the FA N--N axis and the MA C--N axis in pure and mixed perovskites (A-site, Y-site, and A+Y mixing). Slower decay (larger correlation time) indicates slower reorientation; correlation times are obtained from fits as described in the SI.
• Figure 3: Thermodynamic bowing curves for $\Delta G_\text{mix}^\text{tot}$ (solid lines) and $\Delta G_\text{mix}^\text{conf}$ (dashed lines) at 350 K for A-site, Y-site, and A+Y-site mixed perovskites. The vertical dashed line marks the simulated composition $x=1/8$.
• Figure 4: (a)-(h) ACFs of N$-$H$\cdots$I and N$-$H$\cdots$Br HBs calculated as continuous (continuous line) and intermittent types (dashed line) of the pure and mixed compounds.