The recent progress in ferroelectricity and antiferroelectricity in HfO2-based thin films is reported. Most ferroelectric thin film research focuses on perovskite structure materials, such as Pb(Zr,Ti)O3, BaTiO3, and SrBi2Ta2O9, which are considered to be feasible candidate materials for non-volatile semiconductor memory devices. However, these conventional ferroelectrics suffer from various problems including poor Si-compatibility, environmental issues related to Pb, large physical thickness, low resistance to hydrogen, and small bandgap. In 2011, ferroelectricity in Si-doped HfO2 thin films was first reported. Various dopants, such as Si, Zr, Al, Y, Gd, Sr, and La can induce ferro-electricity or antiferroelectricity in thin HfO2 films. They have large remanent polarization of up to 45 μC cm(-2), and their coercive field (≈1-2 MV cm(-1)) is larger than conventional ferroelectric films by approximately one order of magnitude. Furthermore, they can be extremely thin ( 5 eV). These differences are believed to overcome the barriers of conventional ferroelectrics in memory applications, including ferroelectric field-effect-transistors and three-dimensional capacitors. Moreover, the coupling of electric and thermal properties of the antiferroelectric thin films is expected to be useful for various applications, including energy harvesting/storage, solid-state-cooling, and infrared sensors.

Ferroelectricity and Antiferroelectricity of Doped Thin HfO2‐Based Films

Here, we present a structural study on the origin of ferroelectricity in Gd doped HfO2 thin films. We apply aberration corrected high-angle annular dark-field scanning transmission electron microscopy to directly determine the underlying lattice type using projected atom positions and measured lattice parameters. Furthermore, we apply nanoscale electron diffraction methods to visualize the crystal symmetry elements. Combined, the experimental results provide unambiguous evidence for the existence of a non-centrosymmetric orthorhombic phase that can support spontaneous polarization, resolving the origin of ferroelectricity in HfO2 thin films.

On the structural origins of ferroelectricity in HfO2 thin films

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 Pr of up to 35 μC/cm2 This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:Hf

Stabilizing the ferroelectric phase in doped hafnium oxide

The ferroelectricity in fluorite-structure oxides such as hafnia and zirconia has attracted increasing interest since 2011 They have various advantages such as Si-based complementary metal oxide semiconductor-compatibility, matured deposition techniques, a low dielectric constant and the resulting decreased depolarization field, and stronger resistance to hydrogen annealing However, the wake-up effect, imprint, and insufficient endurance are remaining reliability issues Therefore, this paper reviews two major aspects: the advantages of fluorite-structure ferroelectrics for memory applications are reviewed from a material’s point of view, and the critical issues of wake-up effect and insufficient endurance are examined, and potential solutions are subsequently discussed

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/3DB31D1931EA9955AF5E300BC33891D6/S2159685918001751a.pdf/div-class-title-review-and-perspective-on-ferroelectric-hfo-span-class-sub-2-span-based-thin-films-for-memory-applications-div.pdf

Review and perspective on ferroelectric HfO2-based thin films for memory applications

Since 2011, ferroelectric HfO2 has attracted growing interest in both fundamental and application oriented groups. In this material, noteworthy wake-up and fatigue effects alter the shape of the polarization hysteresis loop during field cycling. Such changes are problematic for application of HfO2 to ferroelectric memories, which require stable polarization hystereses. Herein, electrical and structural techniques are implemented to unveil how cyclic switching changes nanoscale film structure, which modifies the polarization hysteresis. Impedance spectroscopy and scanning transmission electron microscopy identify regions with different dielectric and conductive properties in films at different cycling stages, enabling development of a structural model to explain the wake-up and fatigue phenomena. The wake-up regime arises due to changes in bulk and interfacial structuring: the bulk undergoes a phase transformation from monoclinic to orthorhombic grains, and the interfaces show changes in and diminishment of a nonuniform, defect rich, tetragonal HfO2 layer near the electrodes. The evolution of these aspects of structuring contributes to the increase in Pr and the opening of the constricted P–V hysteresis that are known to occur with wake-up. The onset of the fatigue regime is correlated to an increasing concentration of bulk defects, which are proposed to pin domain walls.

Structural Changes Underlying Field-Cycling Phenomena in Ferroelectric HfO2 Thin Films

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, whic...

TaN interface properties and electric field cycling effects on ferroelectric Si-doped HfO2 thin films

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.

Ferroelectric phenomena in Si-doped HfO2 thin films with TiN and Ir electrodes

Ferroelectric Si-doped HfO2 thin films are integrated into three different device stacks with a p+ Ge substrate, a p+ Si substrate, and a TaN bottom metal gate. The ferroelectric behavior of the Si-doped HfO2 thin films is strongly dependent on the bottom interfaces. The Si-doped HfO2 thin films have favorably improved ferroelectric properties on the p+ Ge substrate due to the lack of a dielectric interfacial layer between HfO2 and Ge. The low-voltage operation and cycling stability of Si-doped HfO2 ferroelectric thin films on Ge can lead to the realization of high performance, robust Ge ferroelectric field-effect transistors for nonvolatile memory applications.

Ferroelectric Si-Doped HfO 2 Device Properties on Highly Doped Germanium

Atomic layer deposited Si-doped HfO2 thin films approximately 10 nm thick are deposited with various Si-dopant concentrations and distributions. The ferroelectric behavior of the HfO2 thin films are shown to be dependent on both the Si mol. % and the distribution of Si-dopants. Metal-ferroelectric-insulator-semiconductor capacitors are shown to exhibit a tunable remanent polarization through the adjustment of the Si-dopant distribution at a constant Si concentration. Inhomogeneous layering of Si-dopants within the thin films effectively lowers the remanent polarization. A pinched hysteresis loop is observed for higher Si-dopant concentrations and found to be dependent on the Si layering distribution.

Qanit Takmeel

Papers

TaN interface properties and electric field cycling effects on ferroelectric Si-doped HfO2 thin films

Ferroelectric phenomena in Si-doped HfO2 thin films with TiN and Ir electrodes

Ferroelectric Si-Doped HfO 2 Device Properties on Highly Doped Germanium

The effects of layering in ferroelectric Si-doped HfO2 thin films

Annealing behavior of ferroelectric Si-doped HfO2 thin films