The unexpected ferroelectric properties of nanoscale hafnia-zirconia are considered to be promising for a wealth of applications including ferroelectric memory, field effect transistors, and energy-related applications. However, the reason why the unexpected ferroelectric Pca2 phase can be stabilized has not been clearly understood although numerous extensive theoretical and experimental results have been reported recently. The ferroelectric orthorhombic phase is not a stable phase under processing conditions from the viewpoint of bulk free energy. Although the possibility of stabilization of the ferroelectric phase due to the surface energy effect has been theoretically suggested, such a theoretical model has not been systematically compared with actual experimental results. In this study, the experimental observations on polymorphism in nanoscale HfO-ZrO solid solution thin films of a wide range of film compositions and thicknesses are comprehensively related to the theoretical predictions based on a thermodynamic surface energy model. The theoretical model can semi-quantitatively explain the experimental results on the phase-evolution, but there were non-negligible discrepancies between the two results. To understand these discrepancies, various factors such as the film stress, the role of a TiN capping layer, and the kinetics of crystallization are systematically studied. This work also reports on the evolution of electrical properties of the film, i.e. dielectric, ferroelectric, anti-ferroelectric, and morphotropic phase changes, as a function of the film composition and thickness. The in-depth analyses of the phase change are expected to provide an important guideline for subsequent studies.

The effects of annealing temperature (Tanneal) and film thickness (tf) on the crystal structure and ferroelectric properties of Hf0.5Zr0.5O2 films were examined. The Hf0.5Zr0.5O2 films consist of tetragonal, orthorhombic, and monoclinic phases. The orthorhombic phase content, which is responsible for the ferroelectricity in this material, is almost independent of Tanneal, but decreases with increasing tf. In contrast, increasing Tanneal and tf monotonically increases (decreases) the amount of monoclinic (tetragonal) phase, which coincides with the variations in the dielectric constant. The remanant polarization was determined by the content of orthorhombic phase as well as the spatial distribution of other phases.

The ever-shrinking dimensions of dynamic random access memory (DRAM) require a high quality dielectric film for capacitors with a sufficiently high growth-per-cycle (GPC) by atomic layer deposition (ALD). SrTiO 3 (STO) films are considered to be the appropriate dielectric films for DRAMs with the design rule of ∼20 nm, and previous studies showed that STO films grown by ALD have promising electrical performance. However, the ALD of STO films still suffers from much too slow GPC to be used in mass-production. Here, we accomplished a mass-production compatible ALD process of STO films using Ti(O-i Pr) 2 -(tmhd) 2 as a Ti-precursor for TiO 2 layers and Sr( i Pr 3 Cp) 2 as a Sr-precursor for SrO layers. O 3 and H 2 O were used as the oxygen sources for the TiO 2 and SrO layers, respectively. A highly improved GPC of 0.107 nm/unit-cycle (0.428 nm/supercycle) for stoichiometric STO films was obtained at a deposition temperature of 370 °C, which is ∼7 times higher than previously reported. The origin of such high GPC values in this STO films could be explained by the partial decomposition of the precursors used and the strong tendency of water adsorption onto the SrO layer in comparison to the TiO 2 layer. The STO film grown in this study also showed an excellent step coverage (∼95%) when deposited inside a deep capacitor hole with an aspect ratio of 10. Owing to the high bulk dielectric constant (∼ 146) of the STO film, an equivalent oxide thickness of 0.57 nm was achieved with a STO film of 10 nm. In addition, the leakage current density was sufficiently low (3 Â 10 À8 Acm À2 at þ0.8 V). This process is extremely promising for fabrication of the next generation DRAMs.

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The characteristics of the atomic layer deposition (ALD) of SrTiO3 (STO) films were examined for metal–insulator–metal capacitors, with Cp-based precursors Sr(iPr3Cp)2 and Cp*Ti(OMe)3 [Cp* = C5(CH3)5] employed as the Sr and Ti precursors, respectively. While the Sr precursor has a higher reactivity toward oxygen on the Ru substrate compared with another Ti precursor, with a 2,2,6,6-tetramethyl-3,5-heptanedionato ligand, which results in the highly Sr excessive STO film, the enhanced reactivity of the present Ti precursor suppressed the unwanted excessive incorporation of Sr into the film. A possible mechanism for the Sr overgrowth and retardation is suggested in detail. By controlling the subcycle ratio of SrO and TiO2 layers, stoichiometric STO could be obtained, even without employing a deleterious reaction barrier layer. This improved the attainable minimum equivalent oxide thickness of the Pt/STO/RuO2 capacitor to 0.43 nm, with acceptable leakage current density (∼8 × 10–8 A/cm2). This indicates an improvement of ∼25% in the capacitance density compared with previous work.

Phase change random access memory appears to be the strongest candidate for next-generation high density nonvolatile memory. The fabrication of ultrahigh density phase change memory (≫1 Gb) depends heavily on the thin film growth technique for the phase changing chalcogenide material, most typically containing Ge, Sb and Te (Ge–Sb–Te). Atomic layer deposition (ALD) at low temperatures is the most preferred growth method for depositing such complex materials over surfaces possessing extreme topology. In this study, [(CH3)3Si]2Te and stable alkoxy-Ge (Ge(OCH3)4) and alkoxy-Sb (Sb(OC2H5)3) metal–organic precursors were used to deposit various layers with compositions lying on the GeTe2–Sb2Te3 tie lines at a substrate temperature as low as 70 °C using a thermal ALD process. The adsorption of Ge precursor was proven to be a physisorption type while other precursors showed a chemisorption behavior. However, the adsorption of Ge precursor was still self-regulated, and the facile ALD of the pseudobinary solid solutions with composition (GeTe2)(1‑x)(Sb2Te3) x were achieved. This chemistry-specific ALD process was quite robust against process variations, allowing highly conformal, smooth, and reproducible film growth over a contact hole structure with an extreme geometry. The detailed ALD behavior of binary compounds and incorporation behaviors of the binary compounds in pseudobinary solid solutions were studied in detail. This new composition material showed reliable phase change and accompanying resistance switching behavior, which were slightly better than the standard Ge2Sb2Te5 material in the nanoscale. The local chemical environment was similar to that of conventional Ge2Sb2Te5 materials.

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The dielectric constant, equivalent oxide thickness (tox), and leakage current properties of Pt/(Al-doped)TiO2/RuO2 capacitors were examined in comparison with Pt/(Al-doped)TiO2/Ru capacitors. The Al-doped TiO2 and undoped TiO2 films grown on RuO2 showed high dielectric constants of 60 and 102, respectively. The minimum tox of these films were 0.46 nm and 0.56 nm, respectively, while still satisfying the dynamic random access memory leakage current density specification (< 1 × 10−7 Acm−2 at capacitor voltage of 0.8 V). These excellent electrical properties of (Al-doped) TiO2 on RuO2 were attributed to the high work function and the reduced interfacial effect on RuO2.