The origin of the unexpected ferroelectricity in doped HfO₂ thin films is now considered to be the formation of a non-centrosymmetric Pca2₁ orthorhombic phase. Due to the polycrystalline nature of the films as well as their extremely small thickness (∼10 nm) and mixed orientation and phase composition, structural analysis of doped HfO₂ thin films remains a challenging task. As a further complication, the structural similarities of the orthorhombic and tetragonal phase are difficult to distinguish by typical structural analysis techniques such as X-ray diffraction. To resolve this issue, the changes in the grazing incidence X-ray diffraction (GIXRD) patterns of HfO₂ films doped with Si, Al, and Gd are systematically examined. For all dopants, the shift of o111/t101 diffraction peak is observed with increasing atomic layer deposition (ALD) cycle ratio, and this shift is thought to originate from the orthorhombic to P4₂/nmc tetragonal phase transition with decreasing aspect ratio (2a/(b + c) for orthorhombic and c/a for the tetragonal phase). For quantitative phase analysis, Rietveld refinement is applied to the GIXRD patterns. A progressive phase transition from P2₁/c monoclinic to orthorhombic to tetragonal is confirmed for all dopants, and a strong relationship between orthorhombic phase fraction and remanent polarization value is uniquely demonstrated. The concentration range for the ferroelectric properties was the narrowest for the Si-doped HfO₂ films. The dopant size is believed to strongly affect the concentration range for the ferroelectric phase stabilization, since small dopants can strongly decrease the free energy of the tetragonal phase due to their shorter metal–oxygen bonds.

Ferroelectric HfO₂-based thin films, which can exhibit ferroelectric properties down to sub-10 nm thicknesses, are a promising candidate for emerging high density memory technologies. As the ferroelectric thickness continues to shrink, the electrode-ferroelectric interface properties play an increasingly important role. We investigate the TaN interface properties on 10 nm thick Si-doped HfO₂ thin films fabricated in a TaN metal-ferroelectric-metal stack which exhibit highly asymmetric ferroelectric characteristics. To understand the asymmetric behavior of the ferroelectric characteristics of the Si-doped HfO₂ thin films, the chemical interface properties of sputtered TaN bottom and top electrodes are probed with x-ray photoelectron spectroscopy. Ta-O bonds at the bottom electrode interface and a significant presence of Hf-N bonds at both electrode interfaces are identified. It is shown that the chemical heterogeneity of the bottom and top electrode interfaces gives rise to an internal electric field, which causes the as-grown ferroelectric domains to preferentially polarize to screen positively charged oxygen vacancies aggregated at the oxidized bottom electrode interface. Electric field cycling is shown to reduce the internal electric field with a concomitant increase in remanent polarization and decrease in relative permittivity. Through an analysis of pulsed transient switching currents, back-switching is observed in Si-doped HfO₂ thin films with pinched hysteresis loops and is shown to be influenced by the internal electric field.

Ferroelectric HfO2 is an attractive candidate for future ferroelectric random access memory devices due to its compatibility with the complementary metal-oxide-semiconductor process, conformal deposition, and scaling ability. Crystallization of HfO2 with different dopants and annealing conditions can produce the stabilization of the monoclinic, tetragonal, cubic, or orthorhombic crystal phases. In this work, the authors observe ferroelectric behavior in Si-doped hafnium oxide with TiN and Ir electrodes. Atomic layer deposited 10 nm HfO2 capacitors doped with varying concentrations of SiO2 have been fabricated in the metal–ferroelectric–insulator–semiconductor (MFIS) structure. The ferroelectric characteristics of thin film HfO2 are compared in the MFIS and metal–ferroelectric–metal configurations. Post-metallization anneals were applied to all thin film ferroelectric HfO2 capacitors, resulting in a remanent polarization of up to 22 μC/cm2 and a range of observed coercive voltages, emphasizing the importance of the annealing conditions, electrode materials, and device structure on the ferroelectric properties of thin film HfO2.