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Understanding the interplay between the structural, chemical and physicalproperties of nanomaterials is crucial for designing new devices with enhancedperformance. In this regards, doping of metal oxides is a general strategy totune size, morphology, charge, lattice, orbital and spin degrees of freedomsand has been shown to affect nanomaterials properties for photoelectrochemicalwater splitting, batteries, catalysis, magnetic applications and optics. Herewe report the role of lattice small polaron in driving the morphologicaltransition from nearly isotropic to nanowire crystals in Si doped hematite($\alpha-Fe_2O_3$). Lattice small polaron formation is well evidenced by theincrease of hexagonal strain and degree of distortion of $FeO_6$ showing ahyperbolic trend with increasing Si content. Local analysis via pairdistribution function highlights an unreported crossover from small to largepolarons, which affects the correlation length of the polaronic distortion fromshort to average scales. Ferromagnetic double exchange interactions between$Fe^{2+}/Fe^{3+}$ species is found to be the driving force of the crossover,constraining the chaining of chemical bonds along the [110] crystallographicdirection. This promotes the increase in the reticular density of Fe atomsalong the hematite basal plane only, which boosts the anisotropic growth ofnanocrystals with more extended [110] facets. Our results show that magneticand electronic interactions drive preferential crystallographic growth in dopedmetal oxides, thus providing a new route to design their functional properties.

Lattice small polarons and magnetic interactions drive preferential nanocrystal growth in silicon doped hematite