Plasma assisted atomic oxygen deposition was used to grow polycrystalline ferroelectric Hf1-xZrxO2 (x = 0.5–0.7) on technologically important (100) Germanium substrates showing sharp crystalline interfaces free of interfacial amorphous layers and strong evidence for the presence of a predominately orthorhombic phase. The electrical properties, evaluated using metal-ferroelectric-semiconductor (MFS) capacitors, show symmetric and robust ferroelectric hysteresis with weak or no wake-up effects. The MFS capacitors with x = 0.58 show very large remanent polarization up to 34.4 μC/cm2 or 30.6 μC/cm2 after correction for leakage and parasitics, combined with good endurance reaching 105 cycles at a cycling field of 2.3 MV/cm. The results show good prospects for the fabrication of Ge ferroelectric field effect transistors (FeFETs) for use in 1 T FeFET embedded nonvolatile memory cells with improved endurance.

Germanium Metal-Ferroelectric-Semiconductor (MFS) capacitors based on ferroelectric Hf1-xZrxO2 (HZO) with clean, oxide free Ge/HZO interfaces emerge as an interesting layer structure for the fabrication of FeFET non-volatile memory devices. It is shown that, at low temperature (<160 K), a semiconductor depletion forms in Ge near the interface resulting in an increase of coercive voltage by about 2 V, accompanied by a distortion of the ferroelectric hysteresis with subloop asymmetric behavior, which becomes more severe at higher frequencies of measurement. At higher temperatures, the Ge surface near the ferroelectric is easily inverted due to low energy gap of Ge, providing sufficient screening of the polarization charge by minority free carriers, in which case, nearly ideal, symmetric hysteresis curves are recovered. The depolarization field is experimentally extracted from the coercive voltage and the capacitance measurements and is found to be ~ 2.2 MV/cm in the low temperature range, comparable to the coercive field, then rapidly decreasing at higher temperatures and effectively diminishing at room temperature. This makes Ge MFS good candidates for FeFETs for low voltage nonvolatile memory with improved reliability.

The reliability of Hf0.5Zr0.5O2 (HZO) metal-ferroelectric-semiconductor capacitors grown by plasma assisted atomic oxygen deposition on Ge substrates is investigated with an emphasis on the influence of crystallization annealing. The capacitors show very weak wake-up and imprint effects allowing reliable operation in excess of 10 years, which is attributed partly to the clean, oxide-free Ge/HZO bottom interface. The weak temperature dependence as well as the observed asymmetries between polarization up and down states and between positive and negative coercive voltage shifts, lead to the conclusion that imprint is controlled by carrier injection at the top electrode interface. The latter mechanism is associated with trapping at interfacial oxygen-vacancy defects. On the other hand, using ultrafast (millisecond) flash annealing improves the leakage current by at least an order of magnitude and the endurance by a factor of 3 compared to conventional rapid thermal annealing, which makes them suitable for low power non-volatile memory applications where (ultra)thin HZO is an essential requirement.

As ferroelectric Hf0.5Zr0.5O2 (HZO) thickness scales below 10 nm, the switching characteristics are severely distorted typically showing an antiferroelectric-like behavior (pinched hysteresis) with reduced remanent polarization. Using Landau-Ginsburg-Devonshire (LGD) theory for the analysis of the experimental results, it is shown here that, in thin (5 nm) HZO, depolarization fields drive the system in a stable paraelectric phase coexisting with a metastable ferroelectric one, which explains the pinched hysteresis. This state of matter resembles a first order ferroelectric above the Curie temperature which is known to result in similar double-loop behavior. Here, based on the analysis of experimental data in the framework of LGD theory, it is reported that charge injection and trapping at pre-existing interface defects during field cycling (“wake-up”) screens the depolarization field stabilizing ferroelectricity. It is found in particular that a sufficiently large energy density of interface states is beneficial for the recovery of fully open ferroelectric loops.