Room temperature ferroelectricity in pulsed laser deposited rare-earth doped hafnium oxide (HfO 2 ) thin films is discussed. Maximum values of remnant polarizations (P r ) ∼13.5 and 12 μC/cm 2 along with coercive fields (E C ) ∼334 and 384 kV/cm are observed in 6 mol. % of rare-earth (Sm or Gd) doped-HfO 2 thin films (Sm:HfO 2 and Gd:HfO 2 ), respectively. Piezoresponse force microscopy measurements confirmed ferroelectric nature of films by showing phase hysteresis and butterfly amplitude loops. It is noticed that wake-up cycles improved the remnant polarization and found to be necessary for the forming of well saturated hysteresis loops. Our results showed potential toward realization of future highly scaled non-volatile ferroelectric memories. Ferroelectric materials are engendering considerable interest because of a variety of emerging applications including ferroelectric memories which have promising potentials for next generation high integration density and low power nonvolatile memory technology. 1,2The most studied material for ferroelectric memories, Pb[Zr x Ti 1-x ]O 3 (PZT), 1 is facing severe scaling limitations due to its complicated crystal structure which in turn hinders its applicability toward dense integration in the complementary metal oxide semiconductor (CMOS) technology. The lead (Pb) toxicity in PZT is also a snag due to ecological concerns.Recently, experimental as well as theoretical studies showed ferroelectricity in doped hafnia (HfO 2 ) thin films which are compatible with existing CMOS technology.3-10 Ferroelectric phenomenon in these doped-HfO 2 films deposited by various deposition techniques such as atomic layer deposition, 5-10 chemical solution deposition, 11 and sputtering 12 was mainly explained by the existence of noncentrosymmetric orthorhombic phase (space group of Pca2 1 ). 5,6,12 The dopant incorporation into monoclinic HfO 2 matrix results in a transformation to tetragonal/cubic phase with the appearance of an intermediate metastable orthorhombic (Pca2 1 ) phase. On the other hand, in some of the reports, ferroelectric nature in doped-HfO 2 films was attributed to the influence of "wake-up" effect. [11][12][13] In this paper, we report on the ferroelectric properties of rare earth doped Sm:HfO 2 (SHO) and Gd:HfO 2 (GHO) thin films fabricated by the sequential pulsed laser deposition (SPLD) technique. [14][15][16] The deposition was performed by periodic depositions from HfO 2 and Sm 2 O 3 /Gd 2 O 3 ceramic targets. The dopant concentration was obtained by controlling number of Sm 2 O 3 /Gd 2 O 3 ablation pulses relative to that of HfO 2 . To study the ferroelectric properties of the deposited samples, polarization-voltage (P-V), capacitance-voltage (C-V), and piezoresponse force microscopy (PFM) measurements were performed. ExperimentalPolycrystalline thin films of SHO and GHO of ∼60 nm thickness were fabricated on Pt/TiO 2 /SiO 2 /Si substrates by SPLD technique at a fixed temperature of 650• C and in an oxygen ambient partial pressure of ∼0.5 Pa. The KrF excimer laser...
Electric-field-dependent in situ Raman studies have been carried out on chemically prepared graphene oxide. The Raman spectra show significant changes with increase in the applied electric field; in particular, the intensity of the G peak decreases with electric field. This behavior is typical for chemically or thermally reduced graphene oxide. To understand the nature of reduction, we compared the temperature-dependent and electric-field-dependent Raman spectra of graphene oxide and found that the evolutions of Raman spectra are not in agreement with each other, except the intensity of the G peak that decreases in both cases. The D peak broadens significantly with increase in temperature, whereas it sharpens in the case of applied electric field. The electron-field-emission properties of the electrically reduced graphene oxide were also carried out, and the turn-on field was found to be 9.1 V/μm.
We demonstrate the room temperature polar switching and tunneling in PbZr0.52Ti0.48O3 (PZT) ultra-thin films of thickness 3-7 nm, sandwiched between platinum metal and ferromagnetic La0.67Sr0.33MnO3 (LSMO) layers, which also shows magnetic field dependent tunnel current switching in Pt/PbZr0.52Ti0.48O3/La0.67Sr0.33MnO3 heterostructures. The epitaxial nature, surface quality and ferroelectric switching of heterostructured films were examined with the help of x-ray diffraction patterns, atomic force microscopy, and piezo force microscopy, respectively. The capacitance versus voltage graphs show butterfly loops above the coercive field (> ±3 V) of PZT for small probe area (∼16 μm(2)). The effect of ferroelectric switching was observed in current density versus voltage curves with a large variation in high-resistance/low-resistance (HRS/LRS) ratio (2:1 to 100:1), however, these effects were more prominent in the presence of in-plane external magnetic field. The conductance is fitted with Brinkman's model, and the parabolic conductance upon bias voltage implies electron tunneling governs the transport.
The ultra thin ferroelectric PbZr0.52Ti0.48O3 (PZT) films with various thicknesses ranging from 100 (P100) to 10 (P10) nm were grown on La0.67Sr0.33MnO3/(LaAlO3)0.3(Sr2AlTaO6)0.7 (LSMO/LSAT) (001) substrates deposited by pulsed laser deposition technique. The x-ray diffraction patterns of the heterostructures show only (00l) (l = 1 and/or 2) reflections corresponding to the LSAT substrate, PZT, and LSMO layers. The atomic force microscopy studies show that the root mean square surface roughnesses of P100 and P10 films are 2.39 and 0.99 nm, respectively. An increase of both real (ε′) and imaginary (ε″) permittivities was observed when thickness of PZT increases from 10 nm to 100 nm. Temperature dependent ε′ presents an anomaly, related to ferromagnetic-metal to paramagnetic-insulator transition of the LSMO, in the range of 350–500 K. The dielectric anomalies and magnetic phase transition temperature shifted to the lower temperature values with decrease in the PZT films thicknesses. The values of the remanent polarization (Pr) and coercive field (Ec) of the heterostructures were in the range of 24–42 μC/cm2–170–1300 kV/cm. An appreciable increase of saturated magnetization (Ms) was observed with increase of PZT layer thickness. The average Ms values of PZT/LSMO heterostructure were 170, 150, 100, and 45 emu/cm3 for 100, 50, 25, and 10 nm at 300 K, respectively. Enhancement in magnetization with increase in PZT thickness may be due to the interface effect between PZT/LSMO layers.
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