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We have studied zirconia films on a Rh(111) substrate with thicknesses in therange of 2-10 monolayers (ML) using scanning tunneling microscopy (STM) andlow-energy electron diffraction (LEED). Zirconia was deposited using aUHV-compatible sputter source, resulting in layer-by-layer growth and gooduniformity of the films. For thicknesses of 2-4 ML, a layer-dependent influenceof the substrate on the structure of the thin films is observed. Beyond thisthickness, films show a (2 $\times$ 1) or a distorted (2 $\times$ 2) surfacestructure with respect to cubic ZrO$_2$(111); these structures correspond totetragonal and monoclinic zirconia, respectively. The tetragonal phase occursfor annealing temperatures of up to 730 {\deg}C; transformation to thethermodynamically stable monoclinic phase occurs after annealing at 850 {\deg}Cor above. High-temperature annealing also breaks up the films and exposes theRh(111) substrate. We argue that the tetragonal films are stabilized by oxygendeficiency, while the monoclinic films are only weakly defective and show bandbending at defects and grain boundaries. This observation is in agreement withpositive charge being responsible for the grain-boundary blocking effect inzirconia-based solid electrolytes. Our work introduces the tetragonal andmonoclinic 5 ML-thick ZrO$_2$ films on Rh(111) as well-suited model system forsurface-science studies on ZrO$_2$ as they do not exhibit the charging problemsof thicker films or the bulk material and show better homogeneity and stabilitythan the previously-studied ZrO$_2$/Pt(111) system.

Surface structures of ZrO$_2$ films on Rh(111): From two layers to bulk termination