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the formation of a non-centrosymmetric Pca2 1 orthorhombic phase (o-phase). [1][2][3][4][5][6][7] For increasing doping concentrations, ALD HfO 2 films undergo a phase transition from a non-ferroelectric m-phase to ferroelectric orthorhombic phase and for higher concentrations to the tetragonal phase (t-phase; space group: P4 2 /nmc) if the dopants are smaller than Hf like Si and Al, or to the cubic phase if the dopants are larger than Hf like Gd, La, Sr, and Y. [8] Besides the influence of doping, four other factors are known to promote the stabilization of the ferroelectric phase: surface or interface/grain boundary energy, film stress, and the presence of oxygen vacancies. [9][10][11][12][13] Oxygen vacancies and the related defect states play an important role in the so-called wake-up effect. [14] Wake-up describes the increase of the remanent polarization during electrical field cycling with opening of an initially pinched polarization-voltage hysteresis. [11] In Hf 1−x Zr x O 2 films, Materlik et al. suggested that the bulk and surface free energy of the o-phase is located between those of the m-phase and t-phase. As a result, the o-phase is stabilized in a specific film thickness and grain size region. This suggestion matches well Thin film metal-insulator-metal capacitors with undoped HfO 2 as the insulator are fabricated by sputtering from ceramic targets and subsequently annealed. The influence of film thickness and annealing temperature is characterized by electrical and structural methods. After annealing, the films show distinct ferroelectric properties. Grazing incidence X-ray diffraction measurements reveal a dominant ferroelectric orthorhombic phase for thicknesses in the 10-50 nm range and a negligible non-ferroelectric monoclinic phase fraction. Sputtering HfO 2 with additional oxygen during the deposition decreases the remanent polarization. Overall, the impact of oxygen vacancies and interstitials in the HfO 2 film during deposition and annealing is correlated to the phase formation process.

Although some years have passed since the discovery of the ferroelectric phase in HfO 2 and ZrO 2 and their solid solution system Hf x Zr 1−x O 2 , the details of the emergence of this phase are still under investigation. Surface energy contribution, dopant inclusion, residual stress, electric field, and oxygen vacancies have been proposed and studied as potential factors that can influence the phase stabilization. In this work, Hf x Zr 1−x O 2 layers with different Hf/Zr ratios are deposited via atomic layer deposition (ALD) and physical vapor deposition (PVD) and the amount of oxygen that is supplied during deposition is varied. Results are compared for the two deposition techniques for undoped HfO 2 layers. Electrical and structural analysis for the atomic layer-deposited films with different Zr contents and O 2 contents is then performed and the reliability of the films when integrated into capacitors is addressed. The results are correlated to the composition of the layers and a model for layer crystallization is suggested.

The defect chemistry and its effect on nanoscale polymorphism and physical/electrical properties in fluorite-structure ferroelectrics are reviewed.

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