The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions. Metal-ferroelectric-metal capacitors containing Gd:HfO2 showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants. A qualitative model describing the influence of basic process parameters on the crystal structure of HfO2 was proposed. The influence of different structural parameters on the field cycling behavior was examined. This revealed the wake-up effect in doped HfO2 to be dominated by interface induced effects, rather than a field induced phase transition. TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO2 compared to TiN electrodes, yielding a P-r of up to 35 mu C/cm(2). This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:HfO2 films. Ab initio simulations confirmed the influence of oxygen vacancies on the phase stability of ferroelectric HfO2

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Recently simulation groups have reported the lanthanide series elements as the dopants that have the strongest effect on the stabilization of the ferroelectric non-centrosymmetric orthorhombic phase in hafnium oxide. This finding confirms experimental results for lanthanum and gadolinium showing the highest remanent polarization values of all hafnia-based ferroelectric films until now. However, no comprehensive overview that links structural properties to the electrical performance of the films in detail is available for lanthanide-doped hafnia. La:HfO appears to be a material with a broad window of process parameters, and accordingly, by optimization of the La content in the layer, it is possible to improve the performance of the material significantly. Variations of the La concentration leads to changes in the crystallographic structure in the bulk of the films and at the interfaces to the electrode materials, which impacts the spontaneous polarization, internal bias fields, and with this the field cycling behavior of the capacitor structure. Characterization results are compared to other dopants like Si, Al, and Gd to validate the advantages of the material in applications such as semiconductor memory devices.

For the rather new hafnia- and zirconia-based ferroelectrics, a lot of questions are still unsettled. Among them is the electric field cycling behavior consisting of (1) wake-up, (2) fatigue, and (3) the recently discovered subcycling-induced split-up/merging effect of transient current peaks in a hysteresis measurement. In the present work, first-order reversal curves (FORCs) are applied to study the evolution of the switching and backswitching field distribution within the frame of the Preisach model for three different phenomena: (1) The pristine film contains two oppositely biased regions. These internal bias fields vanish during the wake-up cycling. (2) Fatigue as a decrease in the number of switchable domains is accompanied by a slight increase in the mean absolute value of the switching field. (3) The split-up effect is shown to also be related to local bias fields in a complex situation resulting from both the field cycling treatment and the measurement procedure. Moreover, the role of the wake-up phenomenon is discussed with respect to optimizing low-voltage operation conditions of ferroelectric memories toward reasonably high and stable remanent polarization and highest possible endurance.

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