Thermal stability of amorphous phases in various high-k layers (Al2O3, ZrO2, HfO2, ZrAlOx, HfAlOx and HfSiOx) and the phase transformation of crystalline ZrO2 and HfO2 were studied experimentally, as functions of surface preparation, deposition conditions, material composition and post deposition thermal treatment. It is found that pure ZrO2 and HfO2 show relatively low crystallization onset temperatures. The crystalline ZrO2 or HfO2 phases are tetragonal or monoclinic, depending on the layer thickness. The phase transformation of metastable t-phase into stable m-phase has been observed in ZrO2 and HfO2. Crystallization behavior of Al2O3 depends on the surface preparation of the substrate. ALCVD grown Al2O3 layers on an oxide-based surface remain amorphous after 1100°C spike annealing, while those on HF-last surface crystallize at temperatures around 800°C. Alloying Al2O3 into ZrO2 and HfO2 can improve their resistance to crystallization under thermal exposure. The kinetics of the crystallization in the alloys can be described by linear TTT curves. Hf-aluminates show better thermal stability than Zr-aluminates. A defect model relative to the phase transformation is discussed, based on the above observations.