Microstructural evolution of ZrO2-HfO2 nanolaminate structures grown by atomic layer deposition

Zirconia-hafnia (ZrO2-HfO2) nanolaminate structures were grown using the atomic layer deposition (ALD) technique with different stacking sequences and layer thickness layer thicknesses. The microstructural evolution and surface roughness were compared with those of single-layer ZrO2 or HfO2 films using transmission electron microscopy and atomic force microscopy. Thin single-layer ALD-ZrO2 films were polycrystalline and composed of the tetragonal ZrO2 phase as-deposited, whereas thicker (>14 nm) films were composed mainly of the monoclinic phase. HfO2 films were amorphous as-deposited and crystallized into primarily monoclinic during subsequent anneals at temperatures over 500 degreesC. All the nanolaminate structures having individual layer thicknesses greater than approximately 2 nm were crystalline (mixture of tetragonal and monoclinic phases) independent of layer sequence and also exhibited a layer-to-layer epitaxy relationship within each grain. However, the identity of the starting layer determined the final grain size and surface roughness of the nanolaminates. A qualitative model for the observed microstructure evolution of the laminate films is proposed.