Although 10 years have passed since the initial report of ferroelectricity in hafnia (HfO2), researchers are still intensely fascinated by this material system and the promise it holds for future applications. A wide variety of deposition methods have been deployed to create ferroelectric HfO2 thin films such as atomic layer deposition, chemical solution deposition, and physical vapor deposition methods such as sputtering and pulsed laser deposition. Process and design parameters such as deposition temperature, precursor choice, target source, vacuum level, reactive gases, substrate strain, and many others are often integral in stabilizing the polar orthorhombic phase and ferroelectricity. We examine processing parameters across four main different deposition methods and their effect on film microstructure, phase evolution, defect concentration, and resultant electrical properties. The goal of this review is to integrate the process knowledge collected over the past 10 years in the field of ferroelectric HfO2 into a single comprehensive guide for the design of future HfO2-based ferroelectric materials and devices.

Ferroelectricity in fluorite-structured ferroelectrics such as HfO2 and ZrO2 has been attracting increasing interest since its first publication in 2011. Fluorite-structured ferroelectrics are considered to be promising for semiconductor devices because of their compatibility with the complementary metal–oxide–semiconductor technology and scalability for highly dense information storage. The research on fluorite-structured ferroelectrics during the first decade of their conceptualization has been mainly focused on elucidating the origin of their ferroelectricity and improving the performance of electronic devices based on such ferroelectrics. Furthermore, as is known, to achieve optimal performance, the emerging biomimicking electronic devices as well as conventional semiconductor devices based on the classical von Neumann architecture require high operating speed, sufficient reliability, and multilevel data storage. Nanoscale electronic devices with fluorite-structured ferroelectrics serve as candidates for these device systems and, thus, have been intensively studied primarily because in ferroelectric materials the switching speed, reliability, and multilevel polarizability are known to be strongly correlated with the domains and domain dynamics. Although there have been important theoretical and experimental studies related to domains and domain dynamics in fluorite-structured ferroelectrics, they are yet to be comprehensively reviewed. Therefore, to provide a strong foundation for research in this field, herein, domains, domain dynamics, and emerging applications, particularly in neuromorphic computing, of fluorite-structured ferroelectrics are comprehensively reviewed based on the existing literature.

Polymorphic (HfxZr1−x)O2 (HZO) thin films exhibit ferroelectric, dielectric, and antiferroelectric properties across a wide compositional range due to the existence of orthorhombic, monoclinic, and tetragonal phases. To better understand the phase stability across the HfO2–ZrO2 compositional range, we investigate the structural evolution of HZO thin films in situ via high-temperature x-ray diffraction (HTXRD) for five different compositions [ZrO2, (Hf0.23Zr0.77)O2, (Hf0.43Zr0.57)O2, (Hf0.67Zr0.33)O2, and HfO2]. The real-time monitoring of HZO crystallization reveals a competing driving force between the tetragonal and monoclinic phase stabilities for HfO2-rich vs ZrO2-rich compositions. Additionally, we confirm an XRD peak shift toward lower 2θ with increasing temperature in ZrO2, (Hf0.23Zr0.77)O2, and (Hf0.43Zr0.57)O2 films, which we ascribe to the appearance of a metastable orthorhombic phase during heating. A monotonic trend for the onset crystallization temperature is reported for five compositions of HZO and reveals an increase in onset crystallization temperature for HfO2-rich compositions. Relative intensity fraction calculations suggest a higher fraction of monoclinic phase with increasing annealing temperature for (Hf0.67Zr0.33)O2. This study of phase stability and onset crystallization temperatures offers insight for managing the thermal budget for HZO thin films, especially for temperature-constrained processing.

Ferroelectric materials are known to be ideal materials for nonvolatile memory devices, owing to their two electrically switchable spontaneous polarization states. However, difficulties in scaling down devices with ferroelectric materials have hindered their practical applications and research. The discovery of ferroelectricity in fluorite-structured ferroelectrics has revived research on semiconductor devices based on ferroelectrics. With their scalability and established fabrication techniques, the performance of nanoscale electronic devices with fluorite-structured ferroelectrics is being rapidly developed. However, the fundamental physics behind the superior ferroelectricity is yet to be elucidated. From this Perspective, the status of research on fluorite-structured ferroelectrics and state-of-the-art semiconductor devices based on them are comprehensively reviewed. In particular, the fundamental physics of fluorite-structured oxides is critically reviewed based on a newly developed theory as well as on the classical theory on ferroelectrics. A perspective on the establishment of emerging semiconductor devices based on fluorite-structured ferroelectrics is provided from the viewpoint of materials science and engineering.

We introduce an Atomic Layer Deposition (ALD) technique referred to here as Sequential, No-Atmosphere Processing (SNAP) to fabricate ferroelectric Hf0.5Zr0.5O2 capacitors in Metal–Ferroelectric–Metal (MFM) structures. SNAP involves the ALD of each layer sequentially while maintaining the sample under vacuum process conditions without ambient exposure during the entire sequential deposition processes. We first use plasma enhanced ALD to fabricate 002-textured TiN films and study the degree of texture and quality of the film by X-ray Diffraction (XRD), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and transmission electron microscopy. Building upon the textured TiN film, we fabricate MFM capacitors with 10-nm-thick Hf0.5Zr0.5O2 via SNAP deposition and observe an unexpectedly large remanent polarization (2Pr = 54.2 μC/cm2). We report that annealing at T <800 °C and at T = 800 °C results in different ferroelectric behaviors and phases determined by grazing incidence XRD patterns. We infer that the nonpolar tetragonal phase is dominant in films treated at T <800 °C, whereas the polar orthorhombic phase is dominant in films treated at T = 800 °C. Using ToF-SIMS and x-ray spectroscopy depth profiling on MFM capacitors, we observe an increase in the concentration of defects in the Hf0.5Zr0.5O2 layer after annealing. We believe that the absence of the native passive layer between Hf0.5Zr0.5O2 and TiN layers made via SNAP deposition is responsible for the unexpectedly large remanent polarization. In addition, we associate the 002-textured TiN as potentially playing a role in realizing the unexpectedly large remanent polarization.

Ferroelectric fluorite-structured oxide thin films have attracted increased interest from both academia and industry because of their superior scalability�in which their ferroelectric properties can be maintained even below 10 nm thickness�and excellent compatibility with current complementary metal−oxide− semiconductor technology. Regarding recent efforts to downscale the technology node of semiconductor processing, the emergence of ferroelectric properties in fluorite-structured oxide thin films at small length scales is of particular interest. As the length scale of the fluorite-structured oxide thin films reaches the atomic scale, the contribution of the interfacial layer to the properties naturally increases. In particular, the quality and type of interfacial layer, as well as the reaction chemistry in response to the electric field, play a major role in determining the properties of the devices. Consequently, understanding the chemistry of ferroelectric−electrode and ferroelectric−semiconductor interfaces is crucial for their use in industrial applications in the near future. In this context, emerging semiconductor devices based on fluorite-structured oxide ferroelectrics, including ferroelectric field-effect transistors, ferroelectric random-access memories, and ferroelectric tunnel junctions, and the impact of interface chemistry in the devices are reviewed in detail.

Hafnia–zirconia (HfO2–ZrO2) solid solution thin films have emerged as viable candidates for electronic applications due to their compatibility with Si technology and demonstrated ferroelectricity at the nanoscale. The oxygen source in atomic layer deposition (ALD) plays a crucial role in determining the impurity concentration and phase composition of HfO2–ZrO2 within metal–ferroelectric–metal devices, notably at the Hf0.5Zr0.5O2 /TiN interface. The interface characteristics of HZO/TiN are fabricated via sequential no-atmosphere processing (SNAP) with either H2O or O2-plasma to study the influence of oxygen source on buried interfaces. Time-of-flight secondary ion mass spectrometry reveals that HZO films grown via O2-plasma promote the development of an interfacial TiO x layer at the bottom HZO/TiN interface. The presence of the TiO x layer leads to the development of 111-fiber texture in HZO as confirmed by two-dimensional X-ray diffraction (2D-XRD). Structural and chemical differences between HZO films grown via H2O or O2-plasma were found to strongly affect electrical characteristics such as permittivity, leakage current density, endurance, and switching kinetics. While HZO films grown via H2O yielded a higher remanent polarization value of 25 μC/cm2, HZO films grown via O2-plasma exhibited a comparable P r of 21 μC/cm2 polarization and enhanced field cycling endurance limit by almost 2 orders of magnitude. Our study illustrates how oxygen sources (O2-plasma or H2O) in ALD can be a viable way to engineer the interface and properties in HZO thin films.

HfO2-based ferroelectric thin films have attracted significant interest for semiconductor device applications due to their compatibility with complementary metal oxide semiconductor (CMOS) technology. One of the benefits of HfO2 based ferroelectric thin films is their ability to be scaled to thicknesses as low as 10 nm while retaining their ferroelectric properties; a feat that has been difficult to accomplish with conventional perovskite-based ferroelectrics using CMOS-compatible processes. However, reducing the thickness limit of HfO2-based ferroelectric thin films below the sub-5-nm thickness regime while preserving their ferroelectric property remains a formidable challenge. This is because both the structural factors of HfO2, including polymorphism and orientation, and the electrical factors of HfO2-based devices, such as the depolarization field, are known to be highly dependent on the HfO2 thickness. Accordingly, when the thickness of HfO2 drops below 5 nm, these factors will become even more crucial. In this regard, the size effect of HfO2-based ferroelectric thin films is thoroughly discussed in the present review. The impact of thickness on the ferroelectric property of HfO2-based thin films and the electrical performance of HfO2-based ferroelectric semiconductor devices, such as ferroelectric random access memory, ferroelectric field-effect-transistor, and ferroelectric tunnel junction, is extensively discussed from the perspective of fundamental theory and experimental results. Finally, recent developments and reports on achieving ferroelectric HfO2 at sub-5 nm thickness regime and their applications are discussed.