Somdutta Mukherjee

Room temperature nanoscale ferroelectricity in magnetoelectric GaFeO3 epitaxial thin films.

We demonstrate room temperature ferroelectricity in the epitaxial thin films of magnetoelectric gallium ferrite. Piezoforce measurements show a 180° phase shift of piezoresponse upon switching the electric field indicating nanoscale ferroelectricity in the thin films. Further, temperature-dependent impedance analysis with and without the presence of an external magnetic field clearly reveals a pronounced magnetodielectric effect across the magnetic transition temperature. In addition, our first principles calculations show that Fe ions are not only responsible for ferrimagnetism as observed earlier but also give rise to the observed ferroelectricity, making gallium ferrite a unique single phase multiferroic.

Influence of Zr doping on the structure and ferroelectric properties of BiFeO3 thin films

We have prepared thin films of BiFe1−xZrxO3 (x=0.0–0.15) by chemical solution deposition on Pt/Si substrates. Structural characterization of the films using x-ray diffraction and Raman spectroscopy suggests lattice distortion upon doping for x<0.15. This also appears to be the limit for pure phase formation. Ferroelectric measurements reveal that Zr doping leads to reduction in the remnant polarization and an increase in the coercive field, attributed to lattice distortion. Dielectric measurements indicate that the doped compositions exhibit absence of low frequency relaxation, usually associated with defects and grain boundaries. Absence of Fe2+ in our films was verified using x-ray photoelectron spectroscopy. Role of Zr in controlling the film’s properties has been explained in terms of changes in the bond strength.

Electronic structure, Born effective charges and spontaneous polarization in magnetoelectric gallium ferrite.

We present a theoretical study of the structure-property correlation in gallium ferrite, based on first-principles calculations followed by a subsequent comparison with experiments. The local spin density approximation (LSDA + U) of the density functional theory has been used to calculate the ground state structure, electronic band structure, density of states and Born effective charges. The calculations reveal that the ground state structure is orthorhombic Pc 2(1)n having A-type antiferromagnetic spin configuration, with lattice parameters matching well with those obtained experimentally. Plots of the partial density of states of constituent ions exhibit noticeable hybridization of Fe 3d, Ga 4s, Ga 4p and O 2p states. However, the calculated charge density and electron localization function show a largely ionic character of the Ga/Fe-O bonds which is also supported by a lack of any significant anomaly in the calculated Born effective charges with respect to the corresponding nominal ionic charges. The calculations show a spontaneous polarization of ∼ 59 µC cm( - 2) along the b-axis which is largely due to asymmetrically placed Ga1, Fe1, O1, O2 and O6 ions.

Probing magnetoelastic coupling and structural changes in magnetoelectric gallium ferrite

Temperature dependent x-ray diffraction and Raman spectroscopic studies were carried out on flux-grown single crystals of gallium ferrite with a Ga:Fe ratio of 0.9:1.1. Site occupancy calculations from the Rietveld refinement of the x-ray data led to an estimated magnetic moment of ~0.60 μ(B)/f.u. which was in good agreement with the experimental data. A combination of these two measurements indicates that there is no structural phase transition in the material between 18 and 700 K. A detailed line shape analysis of the Raman mode at ~374 cm(-1) revealed a discontinuity in the peak position data indicating the presence of spin-phonon coupling in gallium ferrite. A correlation of the peak frequency with the magnetization data led to two distinct regions across a temperature ~180 K with appreciable change in the spin-phonon coupling strength from ~0.9 (T < 180 K) to 0.12 cm(-1) (180 K < T < T(c)). This abrupt change in the coupling strength at ~180 K strongly suggests an altered spin dynamics across this temperature.

Compositional dependence of structural parameters, polyhedral distortion and magnetic properties of gallium ferrite

Abstract We show the effect of composition on the structure, polyhedral distortion and magnetic characteristics of pure phase polycrystalline Ga 2− x Fe x O 3 (GFO) for compositions between 0.8≤ x ≤1.3. X-ray analysis reveals that lattice parameters of GFO exhibit a linear dependence on Fe content in single phase region indicating manifestation of Vegards law. Upon changing the composition, a rather small change in the overall unit cell volume (∼1%) appears to be an outcome of a competition between changing trends of various polyhedra. Increasing Fe content of the samples also leads to stretching of the bonds as indicated by the Raman peak shifts. Further, low temperature magnetic measurements show that the coercivity of the samples is maximum for Ga:Fe ratio of 1:1 driven by a competition between decreasing crystallite size and increasing magnetic anisotropy.

Phonons and magnetic excitation correlations in weak ferromagnetic YCrO3

Here, we report the temperature dependent Raman spectroscopic studies on orthorhombically distorted perovskite YCrO3 over a temperature range of 20–300 K. Temperature dependence of DC-magnetization measurements under field cooled and zero field cooled protocols confirmed a Neel transition at TN ∼ 142 K. Magnetization isotherms recorded at 125 K show a clear loop opening without any magnetization saturation up to 20 kOe, indicating a coexistence of antiferromagnetic (AFM) and weak ferromagnetic (WFM) phases. Estimation of exchange constants using mean-field approximation further confirm the presence of a complex magnetic phase below TN. Temperature evolution of Raman line-shape parameters of the selected modes (associated with the octahedral rotation and A(Y)-shift in the unit-cell) reveal an anomalous phonon shift near TN. An additional phonon anomaly was identified at T* ∼ 60 K, which could possibly be attributed to the change in the spin dynamics. Moreover, the positive and negative shifts in Raman freq...

Dielectric response and magnetoelectric coupling in single crystal gallium ferrite

Here we report the dielectric response and electric conduction behavior of magnetoelectric gallium ferrite single crystals studied using impedance analysis in time and temperature domain. The material exhibits two distinct relaxation processes: a high frequency bulk response and a low frequency interfacial boundary layer response. Calculated bulk capacitance as a function of temperature showed an anomaly at ferri- to paramagnetic transition temperature (∼ 300 K), suggestive of magneto-dielectric coupling in the material. Interestingly, we also witness an abrupt change in the activation energy at ∼ 220 K, in the vicinity of spin-glass transition temperature in GaFeO3.

Effects of site disorder, off-stoichiometry and epitaxial strain on the optical properties of magnetoelectric gallium ferrite.

We present a combined experimental-theoretical study demonstrating the role of site disorder, off-stoichiometry and strain on the optical properties of magnetoelectric gallium ferrite. Optical properties (bandgap, refractive indices and dielectric constants) were experimentally obtained by performing ellipsometric studies over the energy range 0.8-4.2 eV on pulsed laser deposited epitaxial thin films of stoichiometric gallium ferrite with b-axis orientation and the data were compared with theoretical results. Calculations on the ground state structure show that the optical activity in GaFeO(3) arises primarily from O 2p-Fe 3d transitions. Further, inclusion of site disorder and epitaxial strain in the ground state structure significantly improves the agreement between the theory and the room temperature experimental data substantiating the presence of site disorder in the experimentally derived strained GaFeO(3) films at room temperature. We attribute the modification of the ground state optical behavior upon inclusion of site disorder to the corresponding changes in the electronic band structure, especially in Fe 3d states leading to a lowered bandgap of the material.

Suppression of grain boundary relaxation in Zr-doped BiFeO3 thin films

Here, we present the results of temperature dependent dielectric studies on chemical solution processed Zr-doped BiFeO3 (BFO) thin films deposited on Pt/Si substrates. We find that in contrast to the undoped BFO films, Zr doping at Fe-site suppresses the low frequency dielectric relaxation originating from the grain boundaries, attributed to the increased dipolar rigidity due to stronger Zr-O bonds. Temperature dependent dc conductivity obtained from impedance and modulus analyses shows two distinct conduction processes occurring inside the grains. At temperature below ∼ 423 K, conductivity is nearly temperature independent, while in the high temperature regime (above ∼ 423 K), conduction is governed by the long range movement of oxygen vacancies with an activation energy of ∼1 eV.

Structure and Properties of Magnetoelectric Gallium Ferrite: A Brief Review

Here, we review the advances in understanding the structure and properties of magnetoelectric gallium ferrite (GaFeO3 or GFO). Special significance of GFO lies in its compositional tunability over a large range of Ga:Fe ratio without forming a second phase which also renders prospective room temperature magnetoelectricity in the material. Detailed structural studies show noncentrosymmetric orthorhombic Pc21n symmetry without any structural phase transition between 4 K and 700 K. The material shows a ferrimagnetic behavior driven by cation site disorder, corroborated both experimentally as well as theoretically, with transition temperature dependent upon Ga:Fe ratio. GFO exhibits magnetostructural and magnetoelectric coupling indicating coupling among the structural, magnetic and electrical degrees of freedom which could possibly be utilized to strain engineer electrical and magnetic properties in the thin film structures. However, the biggest challenge remains to reduce the leakage in the material in both thin film and bulk form which hinders its potential as a device material.