For exploring the prospect of higher-k dielectric phase engineering on a high mobility substrate, films of Hf1-xZrxO2 with varying x-values (0 ≤ x ≤ 1) were deposited on Al2O3 passivated Ge substrates using atomic layer deposition (ALD) with a cyclic deposit-anneal-deposit-anneal (DADA) scheme. The evolution of monoclinic to higher-k tetragonal structure with increasing ZrO2 concentration was probed by grazing incident x-ray diffraction and partial reciprocal space maps using the highly brilliant synchrotron x-ray source at the Cornell High Energy Synchrotron Source (CHESS). A primarily amorphous/nano-crystalline matrix of the asdeposited films changed to randomly aligned grains of nanocrystalline MO2 (M=Hf, Zr) after post deposition annealing at 800 °C for 200 seconds. In contrast, the DADA films annealed for same thermal budget showed high degree of preferred orientation along certain crystallographic directions. With increasing ZrO2 content, the structure of the films changed from a monoclinic to a tetragonal phase. A lower amount of ZrO2 (x = 0.33) was required for stabilizing the tetragonal phase in films grown on Al2O3 passivated Ge substrate as compared to similar films grown on a Si substrate via the same DADA process (x ≥ 0.50).