Amorphous BaTiO3 layers deposited on SrTiO3 (001) substrates at room temperature were subsequently crystallized using solid phase epitaxy (SPE). Heating an initially amorphous BaTiO3 layer in air at 650 °C for 3 h resulted in crystallization with components in two distinct crystallographic orientation relationships with respect to the substrate. Part of the volume of the BaTiO3 layer crystallized in a cube-on-cube relationship with the substrate. Other volumes crystallized in four variants of a 70.5° rotation about ⟨110⟩, resulting in a ⟨221⟩ surface normal in each case. Each of these four variants forms a Σ = 3 coincident site lattice with respect to the SrTiO3 substrate and the cube-on-cube oriented BaTiO3. Heating for the same duration and temperature in a reducing gas atmosphere resulted in the formation of polycrystalline BaTiO3 with no preferred crystallographic orientation. The dependence on the gas atmosphere indicates that it may be possible to tune the annealing time, temperature, and atmosphere to produce a single crystalline BTO on STO by SPE or produce a desired distribution of orientations.
Abstract The structure, magnetic, and magnetocaloric (MC) properties of orthorhombic nanocrystalline GdCrO 3 with six particle sizes: ⟨ d ⟩ = 87, 103, 145, 224, 318, and 352 nm are reported. The particle size was tailored by annealing under different temperatures and estimated by scanning electron microscopy. With increase in ⟨ d ⟩, Goldschmidt tolerance factor t , orthorhombic strain s , and out-of-plane Cr–O 1 –Cr bond angle first decrease, reaching minimum values for ⟨ d ⟩ = 224 nm, and then increase for sample with ⟨ d ⟩ = 318 nm and 352 nm, thus showing a V-shaped variation. Temperature dependence of the magnetization ( M ) reveals an antiferromagnetic transition at TNCr∼168 K for ⟨ d ⟩ ⩾ 224 nm and TNCr∼167 K for ⟨ d ⟩ < 224 nm and an essentially d -independent spin-reorientation at T SR = 9 K. M measured at 5 K and 7 T first increases with increase in ⟨ d ⟩, reaching maximum value for sample with ⟨ d ⟩ = 224 nm, and then decreases for samples with ⟨ d ⟩ = 318 nm and 352 nm, showing an inverted-V variation with ⟨ d ⟩. Similar ⟨ d ⟩-dependence is observed for the magnetic entropy change (MEC) and relative cooling power (RCP) showing a close relationship between the structural and magnetic properties of GdCrO 3 nanoparticles investigated here. The 224 nm sample with the minimum values of t , s , and Cr–O 1 –Cr bond angle exhibits the maximum value of MEC (−Δ S ) = 37.8 J kg −1 K −1 at 5 K under a field variation (Δ H ) of 7 T and its large estimated RCP of 623.6 J Kg −1 is comparable with those of typical MC materials. Both (−Δ S ) and RCP are shown to scale with the saturation magnetization M S , suggesting that M S is the crucial factor controlling their magnitudes. Assuming (−Δ S ) ∼ (Δ H ) n , the temperature dependence of n for the six samples are determined, n varying between 1.3 at 5 K to n = 2.2 at 130 K in line with its expected magnitudes based on mean-field theory. These results on structure-property correlations and scaling in GdCrO 3 suggest that its MC properties are tunable for potential low-temperature magnetic refrigeration applications.
In the perovskite oxide SrCrO$_{3}$ the interplay between crystal structure, strain and orbital ordering enables a transition from a metallic to an insulating electronic structure under certain conditions. We identified a narrow window of oxygen partial pressure in which highly strained SrCrO$_{3}$ thin films can be grown using radio-frequency (RF) off-axis magnetron sputtering on three different substrates, (LaAlO$_{3}$)$_{0.3}$-(Sr$_{2}$TaAlO$_{6}$)$_{0.7}$ (LSAT), SrTiO$_{3}$ (STO) and DyScO$_{3}$ (DSO). X-ray diffraction and atomic force microscopy confirmed the quality of the films and a metal-insulator transition driven by the substrate induced strain was demonstrated.
The magnetoelectric effect (ME) is an important strain mediated-phenomenon in a ferromagnetic-piezoelectric composite for a variety of sensors and signal processing devices. A bias magnetic field, in general, is essential to realize a strong ME coupling in most composites. Magnetic phases with (i) high magnetostriction for strong piezomagnetic coupling and (ii) large anisotropy field that acts as a built-in bias field are preferred so that miniature, ME composite-based devices can operate without the need for an external magnetic field. We are able to realize such a magnetic phase with a composite of (i) barium hexaferrite (BaM) with high magnetocrystalline anisotropy field and (ii) nickel ferrite (NFO) with high magnetostriction. The BNx composites, with (100 - x) wt.% of BaM and x wt.% NFO, for x = 0-100, were prepared. X-ray diffraction analysis shows that the composites did not contain any impurity phases. Scanning electron microscopy images revealed that, with an increase in NFO content, hexagonal BaM grains become prominent, leading to a large anisotropy field. The room temperature saturation magnetization showed a general increase with increasing BaM content in the composites. NFO rich composites with x ≥ 60 were found to have a large magnetostriction value of around -23 ppm, comparable to pure NFO. The anisotropy field HA of the composites, determined from magnetization and ferromagnetic resonance (FMR) measurements, increased with increasing NFO content and reached a maximum of 7.77 kOe for x = 75. The BNx composite was cut into rectangular platelets and bonded with PZT to form the bilayers. ME voltage coefficient (MEVC) measurements at low frequencies and at mechanical resonance showed strong coupling at zero bias for samples with x ≥ 33. This large in-plane HA acted as a built-in field for strong ME effects under zero external bias in the bilayers. The highest zero-bias MEVC of ~22 mV/cm Oe was obtained for BN75-PZT bilayers wherein BN75 also has the highest HA. The Bilayer of BN95-PZT showed a maximum MEVC ~992 mV/cm Oe at electromechanical resonance at 59 kHz. The use of hexaferrite-spinel ferrite composite to achieve strong zero-bias ME coupling in bilayers with PZT is significant for applications related to energy harvesting, sensors, and high frequency devices.
Magnetic and magneto-caloric properties of polycrystalline powder samples of HoCrO3 with four different particle sizes are reported here. The samples were prepared by citrate method and were annealed at 700, 900, 1100, and 1300 °C to yield average particle sizes of 60 nm, 190 nm, 320 nm, and 425 nm, respectively, as determined by the analysis of X-ray diffraction patterns and images obtained by scanning electron microscopy. Additional structural characterization was done using Raman spectroscopy. Measurements of the magnetization of the samples were done from 5 K to 300 K in magnetic fields up to 70 kOe. Analysis of the temperature dependence of the paramagnetic susceptibility in terms of the modified Curie-Weiss law, including the Dzyaloshinsky-Moriya (DM) interaction, show small but systematic changes in the Néel temperature TNCr of Cr3+ ions, exchange constant J, and the DM interaction with variation in particle size. However, below TNCr the largest size-dependent effects are observed at 5 K, and the measured magnitudes of coercivity field HC are 1930, 2500, 4660, and 7790 Oe for the 60 nm, 190 nm, 320 nm, and 425 nm size particles, respectively, which can be interpreted by a single domain model. Enhancement of the particle size gives about a fourfold increase in the magnitude of the energy product, HC * MS, where MS is the saturation magnetization. However, as the particle size rises, an opposite trend is observed in the max magnetic entropy (ΔSM = 8.73, 7.22, 7.77, and 6.70 J/kg K) and the refrigerant capacity (RC = 388, 354, 330, and 310 J/kg) for the 60 nm, 190 nm, 320 nm, and 425 nm size particles, respectively. These results suggest ways to optimize the properties of HoCrO3 for applications in magnetic storage and magnetic refrigeration.
An important feature in ultrathin ferroelectric films is the spontaneous formation of nanoscale polarization domain patterns. Epitaxial strain can greatly increase the ferroelectric transition temperature such that films can be in the ferroelectric state during growth. On the other hand, depolarization fields compete with ferroelectricity in ultrathin films, and, consequently, the optimal domain configuration during growth is a moving target. Under these conditions it is readily possible for a grown film to be in a nonequilibrium domain configuration. As the energy landscape in the system is quite complex, the relaxation dynamics by which a system can evolve towards the true equilibrium configuration are also quite interesting. To capture the details of this process we used Bragg-geometry x-ray photon correlation spectroscopy (XPCS), in which x-ray scattering speckle patterns contain the information from the domain arrangements inside the film. With modest heating (∼150 °C) domain relaxation from T (tetragonal) to M_{C} (monoclinic) was observed in BaTiO_{3} films grown on ultrathin ferroelectric PbTiO_{3} layers. Two-time correlation analysis reveals fascinating details associated with sticking points and reversals in the process.
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