Equilibrium Thermochemistry and Crystallographic Morphology of Manganese Sulfide Nanocrystals

Abstract

Manganese sulfide (MnS) is a p-type magnetic semiconductor whose physicochemical properties are sensitive to nanocrystal (NC) morphology, yet the thermodynamic driving forces governing morphology across MnS polymorphs remain poorly understood. Here, we use density functional theory (DFT) to predict the equilibrium morphologies of rock salt (RS), zinc blende (ZB), and wurtzite (WZ) MnS NCs as a function of the relative chemical potential of sulfur, $\Delta \mu_{S}$. Benchmarking against Heyd$\unicode{x2013}$Scuseria$\unicode{x2013}$Ernzerhof (HSE06) hybrid functional calculations reveals that the r$^2$SCAN meta-generalized gradient approximation reproduces experimental lattice constants and thermochemical reaction energies but underestimates S-terminated polar surface energies by up to a factor of five; applying a Hubbard $U$ correction (r$^2$SCAN+$U$, $U = 2.7$ eV) to the Mn 3d states brings the results into close agreement with HSE06. Using the validated r$^2$SCAN+$U$ framework with the Gibbs$\unicode{x2013}$Wulff theorem, we predict that RS-MnS NCs favor nanocubes across nearly the entire stability window, ZB-MnS NCs transform from rhombic dodecahedra (Mn-rich) to polyhedra with 16 triangular faces (S-rich), and WZ-MnS NCs adopt rod-like morphologies with $\Delta \mu_{S}$-sensitive base truncation. Synthesized RS-MnS NCs confirm the predicted cubic morphology, and high-temperature oxidative solution calorimetry yields an apparent surface energy of 1.15 $\pm$ 0.38 J$\cdot$m$^{-2}$, higher than the theoretical equilibrium value (0.42$\unicode{x2013}$0.43 J$\cdot$m$^{-2}$) due to high-index facet exposure, surface area uncertainty, and non-ideal surface configurations in real samples. This work establishes a framework for predicting the equilibrium morphologies of metal chalcogenide NCs.