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Germanium combined with high-κ dielectrics has recently been put forth by the semiconductor industry as potential replacement for planar silicon transistors, which are unlikely to accommodate the severe scaling requirements for sub-45-nm generations. Therefore, we have studied the atomic layer deposition (ALD) of HfO2 high-κ dielectric layers on HF-cleaned Ge substrates. In this contribution, we describe the HfO2 growth characteristics, HfO2 bulk properties, and Ge interface. Substrate-enhanced HfO2 growth occurs: the growth per cycle is larger in the first reaction cycles than the steady growth per cycle of 0.04 nm. The enhanced growth goes together with island growth, indicating that more than a monolayer coverage of HfO2 is required for a closed film. A closed HfO2 layer is achieved after depositing 4–5 HfO2 monolayers, corresponding to about 25 ALD reaction cycles. Cross-sectional transmission electron microscopy images show that HfO2 layers thinner than 3 nm are amorphous as deposited, while local epitaxial crystallization has occurred in thicker HfO2 films. Other HfO2 bulk properties are similar for Ge and Si substrates. According to this physical characterization study, HfO2 can be used in Ge-based devices as a gate oxide with physical thickness scaled down to 1.6 nm. [ABSTRACT FROM AUTHOR]