Interests in nanoscale integrated ferroelectric devices using doped HfO2-based thin films are actively reviving in academia and industry. The main driving force for the formation of the metastable non-centrosymmetric ferroelectric phase is considered to be the interface/grain boundary energy effect of the small grains in polycrystalline configuration. These small grains, however, can invoke unfavorable material properties, such as nonuniform switching performance. This study provides an in-depth understanding of such aspects of this material through careful measurement and modeling of the ferroelectric switching kinetics. Various previous switching models developed for conventional ferroelectric thin-film capacitors cannot fully account for the observed time- and voltage-dependent switching current evolution. The accurate fitting of the experimental results required careful consideration of the inhomogeneous field distribution across the electrode area, which could be acquired by an appropriate mathematical formulation of polarization as a function of electric field and time. Compared with the conventional polycrystalline Pb­(Zr,Ti)­O3 film, the statistical distribution of the local field was found to be three times wider. The activation field and characteristic time for domain switching were larger by more than 1 order of magnitude. It indicates that doped HfO2 is inhomogeneous and “hard” ferroelectric material compared with conventional perovskite-based ferroelectrics.

Various possibilities have been proposed as the cause of the doped‐ or undoped‐HfO2 thin film materials showing unusual ferroelectricity. These assumptions are based on empirical results, yet finding the origin of the unprecedented ferroelectricity within HfO2 has suffered from a serious gap between its theoretical calculation, mostly based on thermodynamic approach and the actual experimental results. To fill the gap, this study proposes to consider the kinetic energy, providing the evidence of the kinetic energy barrier upon a phase transformation from the tetragonal phase to the monoclinic phase affected by the TiN top electrode (capping layer). 10 nm thick Hf0.5Zr0.5O2 thin films are deposited and annealed with or without the TiN capping layer with subsequent annealing at different time and temperature. Arrhenius plot is constructed to obtain the activation energy for the tetragonal‐to‐monoclinic phase transformation by calculating the amount of the transformed phase using X‐ray diffraction pattern. Johnson–Mehl–Avrami and nucleation‐limited transformation models are utilized to describe the characteristic nucleation and growth time and calculate the activation energy for the monoclinic phase transformation of the Hf0.5Zr0.5O2 thin film. Both models demonstrate that the TiN capping layer provides a kinetic energy barrier for tetragonal‐to‐monoclinic phase transformation and enhances the ferroelectric property.

The negative capacitance (NC) effect is now attracting a great deal of attention in work towards low-power operation of field effect transistors and extremely large capacitance density in dynamic random access memory. However, to date, observation of the NC effect in dielectric/ferroelectric bilayer capacitors has been limited to the use of epitaxial ferroelectric thin films based on perovskite crystal structures, such as Pb(Zr,Ti)O 3 and BaTiO 3 , which is not compatible with current complementary metal oxide semiconductor technology. This work, therefore, reports on the transient NC effect in amorphous-Al 2 O 3 /polycrystalline-Hf 0.3 Zr 0.7 O 2 bilayer systems prepared using atomic layer deposition. The thin film processing conditions are carefully tuned to achieve the appropriate ferroelectric performances that are a prerequisite for the examination of the transient NC effect. Capacitance enhancement is observed in a wide voltage range in 5-10 nm thick Al 2 O 3 /Hf 0.3 Zr 0.7 O 2 bilayer thin films. It is found that the capacitance of the dielectric layer plays a critical role in the determination of additional charge density induced by the NC effect. In addition, inhibition of the leakage current is important for stabilization of nonhysteretic charge-discharge behavior of the bilayers. The mean-field approximation combined with classical Landau formalism precisely reproduces the experimental results.

The chemical, physical, and electrical properties of the atomic layer deposited Hf 0.5 Zr 0.5 O 2 thin films using tetrakis(ethylmethylamino) (TEMA) and tetrakis(dimethylamino) (TDMA) precursors are compared. The ligand of the metal-organic precursors strongly affects the residual C concentration, grain size, and the resulting ferroelectric properties. Depositing Hf 0.5 Zr 0.5 O 2 films with the TDMA precursors results in lower C concentration and slightly larger grain size. These findings are beneficial to grow more ferroelectric-phase-dominant film, which mitigates its wake-up effect. From the wake-up test of the TDMA-Hf 0.5 Zr 0.5 O 2 film with a 2.8 MV/cm cycling field, the adverse wake-up effect was well suppressed up to 10 5 cycles, with a reasonably high double remanent polarization value of 40 μC/cm 2. The film also showed reliable switching up to 10 9 cycles with the 2.5 MV/cm cycling field without involving the wake-up effect but with the typical fatigue behavior.

Ferroelectric Hf0.5Zr0.5O2 (HZO) films were grown by the atomic layer deposition (ALD) technique on an ALD or physical-vapor-deposited (PVD, sputtering) TiN bottom electrode (BE). The PVD TiN film showed small grains with flat surface morphology, mainly consisting of the (111) crystallographic plane. In contrast, the ALD TiN film exhibited a larger diameter and faceted grain shapes, with the (200) crystallographic surface planes. The 10-nm-thick HZO film on the ALD TiN BE showed a lower internal field, enhanced endurance (>1 × 1010 cycle at 2.5 MV/cm), and decreased leakage current than identical HZO films on the PVD TiN BE. Lower interfacial oxidation of the ALD TiN BE as a result of the smaller grain boundary area of the ALD TiN induced a lower defect density in the HZO film. The higher work function of the ALD TiN film also contributed to the lowering of the leakage current.