The synthesis of (Al,Cr)2O3 coatings by PVD frequently results in metastable cubic structures next to the thermodynamically stable and mechanically favourable hexagonal corundum phase. By alloying small amounts of Fe to powder-metallurgically produced Al0.7Cr0.3 targets used to synthesise (Al,Cr)2O3 films by cathodic arc evaporation a considerable increase of the hexagonal phase fraction is observed. Detailed transmission electron microscopy studies show that the growth of hexagonal crystallites of a solid solution (Al,Cr,Fe)2O3 can be triggered by small Cr- and Fe-enriched spherical particles, so-called droplets. In contrast, larger spherical or flat-shaped Al-rich droplets induce re-nucleation of undesired cubic film growth. Extending these studies to additional (Al,Cr)2O3 coating systems revealed similar mechanisms, albeit by far less frequent than in the case of Fe-alloyed films. Modifications of the chemical composition of the target by small amounts of dopants may reduce droplet generation and contribute to controlled coating nucleation. Therefore, the cathode surface used is compared with particles, intentionally selected from the plasma stream.