The amorphous precursors of the ZrO₂-SnO₂ system on the ZrO₂-rich side of the concentration range were prepared by co-precipitation from aqueous solutions of the corresponding salts. The Zr/Sn molar ratio in the obtained products was determined by the results of energy-dispersive X-ray spectrometry (EDS). The thermal behaviour of the amorphous precursors was monitored using differential thermal analysis (DTA), X-ray powder diffraction (XRD), Raman spectroscopy and field emission scanning electron microscopy (FE-SEM). Crystallization temperature of the amorphous precursors rose with an increase in the SnO₂ content, from 405 °C (0 mol% SnO₂) to 500 °C (40 mol% SnO₂). The results of phase analysis show that the incorporation of Sn⁴⁺ ions has very small influence on the stabilization of high-temperature polymorphs of ZrO₂. A phase structurally closely related to monoclinic (m-) ZrO₂ is dominant in all crystallization products. Metastable products obtained upon crystallization of amorphous precursors also contain a phase structurally closely related to tetragonal (t-) ZrO₂, which disappears with further thermal treatment (up to 1100 °C). The first sign of a phase structurally closely related to cassiterite (t-SnO₂) appeared in the crystallization products with 30 mol% of SnO₂. A rise in calcination temperature leads to a decrease in the solid solubility of Sn⁴⁺ ions. The results of precise lattice parameter measurements show that the incorporation of Sn⁴⁺ ions causes an asymmetric local distortion of the m-ZrO₂-type crystal lattice.

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