The critical size limit of electric polarization remains a fundamental question in nanoscale ferroelectric research 1 . As such, the viability of ultrathin ferroelectricity greatly impacts emerging low-power logic and nonvolatile memories 2 . Size effects in ferroelectrics have been thoroughly investigated for perovskite oxides -the archetypal ferroelectric system 3 . Perovskites, however, have so far proved unsuitable for thickness-scaling and integration with modern semiconductor processes 4 . Here, we report ultrathin ferroelectricity in doped-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 1 nm. Our results indicate not only the absence of a ferroelectric critical thickness, but also enhanced polar distortions as film thickness is reduced, contradictory to perovskite ferroelectrics. This work shifts the focus on the fundamental limits of ferroelectricity to simpler transition metal oxide systems -from perovskite-derived complex oxides to fluoritestructure binary oxides -in which 'reverse' size effects counter-intuitively stabilize polar symmetry in the ultrathin regime.Ferroelectric materials exhibit stable states of collectively ordered electrical dipoles whose polarization can be reversed under an applied electric field 5 . Consequently, ultrathin ferroelectrics are of great technological interest for high-density electronics, particularly field-effect transistors and nonvolatile memories 2 . However, ferroelectricity is typically suppressed at the few nanometer scale in the ubiquitous perovskite oxides 6 . First-principles calculations predict six unit cells as the critical thickness in perovskite ferroelectrics 1 due to incomplete screening of depolarization fields 3 . Atomic-scale ferroelectricity in perovskites often fail to demonstrate polarization switching 7,8 , a crucial ingredient for application. Furthermore, attempts to synthesize ferroelectric perovskite films on silicon 9,10 are plagued by chemical incompatibility 4,11 and high temperatures required for epitaxial growth. Since the discovery of ferroelectricity in HfO2-based thin films in 2011 12 , fluorite-structure binary oxides (fluorites) have attracted considerable interest 13 as they enable lowtemperature synthesis and conformal growth in three-dimensional (3D) structures on silicon 14,15 , thereby overcoming many of the issues that restrict its perovskite counterparts in terms of complementary metal-oxide-semiconductor (CMOS) compatibility and thickness scaling 16 .

Resistive switching (RS) of (001) epitaxial multiferroic BiFeO3/La0.67Sr0.33MnO3/SrTiO3 heterostructures is investigated for varying lengths scales in both the thickness and lateral directions. Macroscale current–voltage analyses in conjunction with local conduction atomic force microscopy (CAFM) reveal that whilst both the local and global resistive states are strongly driven by polarization direction, the type of conduction mechanism is different for each distinct thickness regime. Electrode‐area dependent studies confirm the RS is dominated by an interface mechanism and not by filamentary formation. Furthermore, CAFM maps allow deconvolution of the roles played by domains and domain walls during the RS process. It is shown that the net polarization direction, and not domain walls, controls the conduction process. An interface mechanism based on barrier height and width alteration due to polarization reversal is proposed, and the role of electronic reconstruction at the interface is further investigated.

Results of switching behavior of the improper ferroelectric LuFeO3 are presented. Using a model set of films prepared under controlled chemical and growth‐rate conditions, it is shown that defects can reduce the quasi‐static switching voltage by up to 40% in qualitative agreement with first‐principles calculations. Switching studies show that the coercive field has a stronger frequency dispersion for the improper ferroelectrics compared to a proper ferroelectric such as PbTiO3. It is concluded that the primary structural order parameter controls the switching dynamics of such improper ferroelectrics.

We evidence field-electron emission (FE) studies on the large-area array of one-dimensional (1D) brookite (b) TiO 2 nanorods. The pure 1D b-TiO 2 nanorods of 10 nm width and 760 nm long were synthesized on Si substrate utilizing hot-filament metal vapor deposition technique. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis evidenced the b-TiO 2 nanorods to be composed of orthorhombic crystals in brookite (b) phase. X-ray photoemission spectroscopy (XPS) revealed the formation of pure stoichiometric (i.e. 1 : 1.98) 1D TiO 2 nanorods. The values of turn-on field, required to draw current density of 10 mA cm À2 , was observed 3.9 V mm À1 for pristine 1D b-TiO 2 nanorods emitters, which were found significantly lower than doped/undoped 1D TiO 2 nanostructures (i.e. nanotubes, nanowires, nanorods) based field emitters. The enhanced FE behavior of the TiO 2 /Si emitter can be attributed to modulation of electronic properties due to the high aspect ratio of vertically aligned TiO 2 nanorods. Furthermore, the orthodox emission situation of pristine TiO 2 /Si emitters exhibit good emission stability and reveal their potentials as promising FE material.