Ultrathin ferroelectric materials could potentially enable low-power logic and nonvolatile memories1,2. As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides—the archetypal ferroelectric system3. Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes4. Here we report ferroelectricity in ultrathin doped hafnium oxide (HfO2), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems—that is, from perovskite-derived complex oxides to fluorite-structure binary oxides—in which ‘reverse’ size effects counterintuitively stabilize polar symmetry in the ultrathin regime. Enhanced switchable ferroelectric polarization is achieved in doped hafnium oxide films grown directly onto silicon using low-temperature atomic layer deposition, even at thicknesses of just one nanometre.

Enhanced ferroelectricity in ultrathin films grown directly on silicon.

Towards Oxide Electronics: a Roadmap

Hf0.5Zr0.5O2 thin films are one of the most appealing HfO2-based ferroelectric thin films, which have been researched extensively for their applications in ferroelectric memory devices. In this work, a 1 mol % La-doped Hf0.5Zr0.5O2 thin film was grown by plasma-assisted atomic layer deposition and annealed at temperatures of 450 and 500 °C to crystallize the film into the desired orthorhombic phase. Despite the use of a lower temperature than that used in previous reports, the film showed highly promising ferroelectric properties—a remnant polarization of ∼30 μC/cm2 and switching cycle endurance up to 4 × 1010. The performance was much better than that of undoped Hf0.5Zr0.5O2 thin films, demonstrating the positive influence of La doping. Such improvements were mainly attributed to the decreased coercive field (by ∼30% compared to the undoped film), which allowed for the use of a lower applied field to drive the cycling tests while maintaining a high polarization value. La doping also decreased the leakage...

Improved Ferroelectric Switching Endurance of La-Doped Hf0.5Zr0.5O2 Thin Films

Recently, ferroelectric tunnel junctions (FTJs) have attracted considerable attention for potential applications in next-generation memories, owing to attractive advantages such as high-density of data storage, nondestructive readout, fast write/read access, and low energy consumption. Herein, recent progress regarding FTJ devices is reviewed with an emphasis on the modulation of the potential barrier. Electronic and ionic approaches that modulate the ferroelectric barriers themselves and/or induce extra barriers in electrodes or at ferroelectric/electrode interfaces are discussed with the enhancement of memory performance. Emerging physics, such as nanoscale ferroelectricity, resonant tunneling, and interfacial metallization, and the applications of FTJs in nonvolatile data storage, neuromorphic synapse emulation, and electromagnetic multistate memory are summarized. Finally, challenges and perspectives of FTJ devices are underlined.

Ferroelectric Tunnel Junctions: Modulations on the Potential Barrier

Epitaxial Ferroelectric Hf0.5Zr0.5O2 Thin Films and Their Implementations in Memristors for Brain‐Inspired Computing

The critical impact of epitaxial stress on the stabilization of the ferroelectric orthorhombic phase of hafnia is proved. Epitaxial bilayers of Hf0.5Zr0.5O2 (HZO) and La0.67Sr0.33MnO3 (LSMO) electr...

/pdf/engineering-ferroelectric-hf0-5zr0-5o2-thin-films-by-17deryy1s4.pdf

Engineering Ferroelectric Hf0.5Zr0.5O2 Thin Films by Epitaxial Stress

Ferroelectric orthorhombic Hf0.5Zr0.5O2 thin films have been stabilized epitaxially on La2/3Sr1/3MnO3/SrTiO3(001) by pulsed laser deposition. The epitaxial orthorhombic films, (111)-oriented and with a very flat surface, show robust ferroelectric properties at room temperature. They present a remnant polarization around 20 μC/cm2 without the need of a wake-up process, a large coercive electric field of around 3 MV/cm, an extremely long retention extending well beyond 10 years, and an endurance up to about 108 cycles. Such outstanding properties in the nascent research on epitaxial HfO2-based ferroelectric films can pave the way for a better understanding of the effects of orientation, interfaces, strain, and defects on ferroelectricity in HfO2.

Robust ferroelectricity in epitaxial Hf1/2Zr1/2O2 thin films

The metastable orthorhombic phase of hafnia is generally obtained in polycrystalline films, whereas in epitaxial films, its formation has been much less investigated. We have grown Hf0.5Zr0.5O2 fil...

http://digital.csic.es/bitstream/10261/177249/1/Lyu_ACSApplElectrMat_2019_postprint.pdf

Growth Window of Ferroelectric Epitaxial Hf0.5Zr0.5O2 Thin Films

SrTiO3 templates have been used to integrate epitaxial bilayers of ferroelectric Hf0.5Zr0.5O2 and La2/3Sr1/3MnO3 bottom electrodes on Si(001). The Hf0.5Zr0.5O2 films show enhanced properties in comparison to equivalent films on SrTiO3(001) single crystalline substrates. The films, thinner than 10 nm, have a very high remnant polarization of 34 μC/cm2. Hf0.5Zr0.5O2 capacitors at an operating voltage of 4 V present a long retention time well beyond 10 years and high endurance against fatigue up to 109 cycles. The robust ferroelectric properties displayed by the epitaxial Hf0.5Zr0.5O2 films on Si(001) using SrTiO3 templates pave the way for the monolithic integration on silicon of emerging memory devices based on epitaxial HfO2.

/pdf/enhanced-ferroelectricity-in-epitaxial-hf0-5zr0-5o2-thin-3dh4tzylkm.pdf

Enhanced ferroelectricity in epitaxial Hf0.5Zr0.5O2 thin films integrated with Si(001) using SrTiO3 templates

Epitaxial ferroelectric Hf0.5Zr0.5O2 films have been successfully integrated in a capacitor heterostructure on Si(001). The orthorhombic Hf0.5Zr0.5O2 phase, [111] out-of-plane oriented, is stabilized in the films. The films present high remnant polarization Pr close to 20 μC/cm2, rivaling with equivalent epitaxial films on single crystalline oxide substrates. Retention time is longer than 10 years for a writing field of around 5 MV/cm, and the capacitors show endurance up to 109 cycles for a writing voltage of around 4 MV/cm. It is found that the formation of the orthorhombic ferroelectric phase depends critically on the bottom electrode, being achieved on La0.67Sr0.33MnO3 but not on LaNiO3. The demonstration of excellent ferroelectric properties in epitaxial films of Hf0.5Zr0.5O2 on Si(001) is relevant toward fabrication of devices that require homogeneity in the nanometer scale, as well as for better understanding of the intrinsic properties of this promising ferroelectric oxide.

http://digital.csic.es/bitstream/10261/177241/1/Lyu_ACSAMI_2019_postprint.pdf

Jike Lyu

Papers

Engineering Ferroelectric Hf0.5Zr0.5O2 Thin Films by Epitaxial Stress

Robust ferroelectricity in epitaxial Hf1/2Zr1/2O2 thin films

Growth Window of Ferroelectric Epitaxial Hf0.5Zr0.5O2 Thin Films

Enhanced ferroelectricity in epitaxial Hf0.5Zr0.5O2 thin films integrated with Si(001) using SrTiO3 templates

Epitaxial Integration on Si(001) of Ferroelectric Hf0.5Zr0.5O2 Capacitors with High Retention and Endurance.