Role of Ge and Si substrates in higher-k tetragonal phase formation and interfacial properties in cyclical atomic layer deposition-anneal Hf1−xZrxO2/Al2O3 thin film stacks

Using a five-step atomic layer deposition (ALD)-anneal (DADA) process, with 20 ALD cycles of metalorganic precursors followed by 40 s of rapid thermal annealing at 1073 K, we have developed highly crystalline Hf1−xZrxO2 (0 ≤ x ≤ 1) thin films (<7 nm) on ∼1 nm ALD Al2O3 passivated Ge and Si substrates for applications in higher-k dielectric metal oxide semiconductor field effect transistors below 10 nm technology node. By applying synchrotron grazing incidence x-ray d-spacing maps, x-ray photoelectron spectroscopy (XPS), and angle-resolved XPS, we have identified a monoclinic to tetragonal phase transition with increasing ZrO2 content, elucidated the role of the Ge vs Si substrates in complete tetragonal phase formation (CTPF), and determined the interfacial characteristics of these technologically relevant films. The ZrO2 concentration required for CTPF is lower on Ge than on Si substrates (x ∼ 0.5 vs. x ∼ 0.86), which we attribute as arising from the growth of an ultra-thin layer of metal germanates betw...