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We have investigated magnetic, structural and dielectric properties of Bi 5 FeTi 3 O 15 (BFTO) in the temperature range 5K-300 K. Using diffraction, Raman spectroscopy and x-ray absorption fine structure measurements, iso-structural modifications are observed at low temperatures (≈100 K). The analysis of dielectric constant data revealed signatures of dielectric relaxation, concomitant with these structural modifications in BFTO at the same temperatures. Further, employing complementary experimental methods, it is shown that the distribution of Fe/Ti ions in BFTO is random. With the help of techniques that probe magnetism at various length and time scales, it is shown that the phase-pure BFTO is non-magnetic down to the lowest temperatures., (© 2021 IOP Publishing Ltd.)

The double perovskite compound Tb 2 CoMnO 6 has been investigated using x-ray absorption spectroscopy (XAS), Raman spectroscopy, magnetic measurements and ab initio band structure calculations. It is observed that both anti-ferromagnetic (AFM) and ferromagnetic (FM) phase coexist in this material. The presence of anti-site disorder (ASD) has been established from the analysis of neutron diffraction data. Moreover, a prominent metamagnetic transition is observed in the M ( H ) behavior that has been explained with the drastic reorientation of the pinned domain which are aligned antiparallel by the antiphase boundaries (APBs) at zero field. The ASD further gives rise to spin frustration at low temperature which leads to the re-entrant cluster glass ∼33 K. The coupling between phononic degree of freedom and spin in the system has also been demonstrated. It is observed that the theoretical calculation is consistent with that of the experimentally observed behavior., (© 2021 IOP Publishing Ltd.)

Recently, CuO has been proposed as a potential multiferroic material with high transition temperature. Competing models based on spin current and ionic displacements are invoked to explain ferroelectricity in CuO. The theoretical model based on ionic displacement predicted very small displacement (∼10 -5 Å) along the b axis. Experimentally detecting displacements of such a small amplitude in a particular direction is extremely challenging. Through our detailed angle resolved polarized Raman spectroscopy study on single crystal of CuO, we have validated the theoretical study and provided direct evidence of displacement along the b axis. Our study provides important contribution in the high temperature multiferroic compounds and showed for the first time, the use of the polarized Raman scattering in detecting ionic displacements at the femtometer scale., (© 2021 IOP Publishing Ltd.)

Enhanced magnetic moment and coercivity in SrRuO 3 thin films are significant issues for advanced technological usages and hence are researched extensively in recent times. Most of the previous reports on thin films with enhanced magnetic moment attributed it to the high spin state. Our magnetization results show high magnetic moment of 3.3 μ B /Ru ion in the epitaxial thin films grown on LSAT substrate against 1.2 μ B /Ru ion observed in bulk compound. Contrary to the previous reports the Ru ions are found to be in low spin state and the orbital moment is shown to be contributing significantly in the enhancement of magnetic moment. We employed x-ray absorption spectroscopy and resonant valance band spectroscopy to probe the spin state and orbital contributions in these films. The existence of strong spin-orbit coupling responsible for the de-quenching of the 4d orbitals is confirmed by the observation of the non-statistical large branching ratio at the Ru M 2,3 absorption edges. X-ray magnetic circular dichroism studies performed at the Ru M 2,3 edges provided direct evidence of significant contribution of orbital moment in the film grown on LSAT. The relaxation of orbital quenching by strain engineering provides a new tool for enhancing magnetic moment and strain disorder is shown to be an efficient mean to control the spin-orbit coupling.

The present work reports magnetic, magnetoelastic and magnetoelectric (ME) response of scandium (Sc) doped barium hexaferrite, BaFe 10 Sc 2 O 19 . DC magnetization shows that partial substitution of non-magnetic Sc for Fe in barium hexaferrite results in a reduction of Curie temperature (T C ) from 730 K known for the parent compound BaFe 12 O 19 to 430 K. Magnetization measurements show that, in BaFe 10 Sc 2 O 19 , in addition to the magnetic transition at 250 K corresponding to longitudinal conical magnetic structure, another magnetic anomaly occurs in the vicinity of 50 K (T max ). Ac susceptibility and magnetic relaxation show that the magnetic transition at T max is associated with spin glass like dynamics. Field dependence of this glassy transition temperature follows the Almeida-Thouless (A-T) line expected for spin glass-like behaviour. Unit cell volume obtained from the neutron diffraction (ND) measurements shows deviation from the Debye-Gruneisen behaviour below 50 K, revealing the magnetoelastic coupling. Existence of magnetoelastic coupling is also confirmed by Raman spectra as Raman modes show anomalous changes around 50 K and also indicates presence of lattice modulation. Further, the magnetic structure obtained from ND data shows that incommensurate longitudinal conical ferrimagnetic structure persists from 210 K to 3 K. The integrated intensity of (0 0 2) peak and magnetic moments undergoes a subtle change below 50 K that seems to favour coexistence of long range magnetic ordering and spin glass-like dynamics. Significant magneto-dielectric effect was observed around 50 K. Temperature dependent studies of dielectric constant and pyroelectric current indicate the presence of ferroelectricity even in zero magnetic field. Further, existence of ME coupling below 50 K is confirmed by temperature dependence of pyroelectric current under magnetic fields up to 70 kOe. In short, this work identifies a new magnetic anomaly around 50 K, which is spin-glass-like inducing magnetoelastic and ME anomalies, even in the absence of external magnetic fields.

The competition and cooperation between ferroelectric and anti-ferro-distortion (AFD) instabilities are studied using pressure dependent Raman spectroscopy on polycrystalline powder samples of Sr 1-x Ca x TiO 3 (x  =  0.0, 0.06, 0.25, 0.35). For x  =  0.0 composition, a broad polar mode is detected in the Raman spectra above 6 GPa, while for x  =  0.06 composition, the polar modes appear well above 9 GPa where the AFD modes showed strong suppression. In x  =  0.25 and 0.35 composition, the application of small pressure resulted in the appearance of strong AFD modes suppressing the polar modes. At elevated pressures, re-entrant polar modes are observed along with the broad AFD modes and some new peaks are also observed, signifying the lowering of local symmetry. The reappearance of polar modes is found to be related to pressure induced symmetry disorder at local level, suggesting its electronic origin. The re-entrant polar modes observed at higher pressure values are found to be significantly broad and asymmetric in nature, signifying the development of ferroelectric micro regions/nano domains coexisting with AFD. The lower symmetry at local length scale provides a conducive atmosphere for coexisting AFD and FE instabilities.

Our study shows that extrinsic disorder plays a decisive role in shaping inhomogeneities at large length scales in phase separated systems. Epitaxial La5/8-yPryCa3/8MnO3 (y = 0.45) thin films grown on SrTiO3, LaAlO3 and NdGaO3 substrates exhibited comparable biaxial strain while showing markedly dissimilar extrinsic disorder. Compressively strained film on LaAlO3 is found to be free from extrinsic disorder and has a robust insulating phase with small phase separation while film grown on SrTiO3 shows huge extrinsic disorder due to the strain relaxation process which invokes phase separation at a large length scale that is sufficient to cross the percolation threshold and cause a metal-insulator transition.

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

The local domain structure of a strain free, 150 nm thick, epitaxially grown single crystalline thin film of CaCu(3)Ti(4)O(12) is probed by polarized Raman spectroscopy. The polarization dependence of the Raman intensities of the observed bands as a function of varying angle between the domain axes and the polarization vector of the scattered laser photon is measured. Theoretical formulations involving the Raman tensor are presented, which enable determination of the domain structure from the observed polarized Raman spectra, and a single-crystal-like domain structure is found. The Raman tensor elements and domain orientation direction were determined by fitting the observed Raman intensities with theoretical calculations and by carrying out Raman mapping of the film. Our data show an absence of twin domain structure and twin domain boundaries in the single-crystal-like epitaxial thin films of CaCu(3)Ti(4)O(12).

Phononic excitations have been investigated using Raman scattering studies on CaCu(3)Ti(4)O(12) and SrCu(3)Ti(4)O(12) compounds as a function of temperature down to 10 K. Evidence of the Fano resonance effect is found in the A(g)(1) mode with an asymmetric phonon line shape that occurs because of composite electron-phonon scattering due to the onset of metallic fractions in the system. The evolution of the Fano line shape with temperature affirms the existence of nanoscale phase separation and the prominence of orbitally disrupted metallic regions above 100 K. Anomalies in the evolution of the line width of the A(g)(1) Raman mode with temperature are observed around 100 K where these compounds show an orbital order/disorder transition. These anomalies manifest mutual coupling of orbital degrees of freedom to lattice degrees of freedom.

Raman scattering studies on CaCu(3)Ti(4)O(12) and SrCu(3)Ti(4)O(12) compounds provide evidence of the physics underlying the giant dielectric effect in the CaCu(3)Ti(4)O(12) compound. The temperature, polarization, and photon energy dependence of a broad Raman mode observed at high wavenumbers below ∼130 K indicates its origin from orbital excitations. The orbital order disorder transition observed around 100 K may be responsible for the conductivity changes required in the internal barrier layer capacitance model, hitherto used to explain the huge dielectric constant above 100 K in these compounds., (© 2011 IOP Publishing Ltd)

Inspection of multiferroicity in BiMn(2 - x)Ti(x)O(5) (0 ≤ x ≤ 0.30) (BMTO) ceramics is performed through specific heat and Raman spectroscopic studies. Thermal variation of specific heat (C) (in the absence and presence of fixed magnetic fields up to 14 T) and Raman spectra of BMTO are presented. In the temperature variation of C, a remarkable anomaly at the antiferromagnetic (AFM) ordering temperature (T(N) ∼ 39 K) is observed in all samples. Pure BiMn(2)O(5) (for x = 0.0) exhibits a larger specific heat anomaly at T(N) compared to that of Ti substituted samples, both in the presence and absence of external magnetic fields. The excess specific heat (ΔC) versus T clearly illustrates appreciable anomalies at ∼ 86 and ∼ 120 K in Ti doped samples related to the magnetic and dielectric transitions, respectively. The low temperature specific heat (LTSH) data indicate a considerably improved ferromagnetic contribution in samples with higher Ti concentration (x > 0.15). The Raman spectra of the doped samples at different fixed temperatures validate the strong electron-phonon coupling corresponding to the observed magnetism and increased harmonicity at dielectric transitions.

We present our study of the effect of substrate induced strain on La(5/8-y)Pr(y)Ca(3/8)MnO(3) (y = 0.45) thin films grown on LaAlO(3), NdGaO(3) and SrTiO(3) substrates that show large scale phase separation. It is observed that unstrained films grown on NdGaO(3) behave quite similarly to bulk material but the strained films grown on SrTiO(3) show melting of the insulating phase to the metallic phase at low temperatures. However, the large scale phase separation and metastable glass-like state is observed in all the films despite differences in substrate induced strain. The measurements of resistivity as a function of temperature under a cooling and heating in unequal field (CHUF) protocol elucidate the presence of a glass-like metastable phase generated due to kinetic arrest of the first order transformation in all the films. Like structural glasses, these magnetic glass-like phases show evidence of devitrification of the arrested charge order antiferromagnetic insulator (CO-AFI) phase to the equilibrium ferromagnetic metallic (FMM) phase with isothermal increase of magnetic field and/or iso-field warming. These measurements also clearly show the equilibrium ground state of this system to be FMM and the metastable glass-like phase to be AFI phase.

The magnetic and phonon properties of polycrystalline magnetoelectric/multiferroic GaFeO(3) are studied. Using high field (57)Fe Mossbauer spectroscopy, occupation of Fe is observed at four cation sites. A Fe population of about 6% is observed at the tetrahedral Ga1 site, which explains the observed pinched-like M-H curve and initial sharp increase of the magnetization. The calculated net magnetization value from Mossbauer data suggests that the Fe moment at the Ga1 site is parallel to Fe1 and opposite to that of Fe2 and Ga2 sites, resulting in ferrimagnetism. From low temperature Raman data, anomalous temperature variation in frequency at T(C) is observed for the mode at ∼700 cm(-1)., (© 2010 IOP Publishing Ltd)

Strongly correlated electron systems give an opportunity to manipulate charge, orbital, magnetic and structural phases of matter. Here we show that the insulating phase where charges are localized can be delocalized through photo-excitation which, in turn changes the structure locally, inducing an orthorhombic to rhombohedral phase transition. The I-M transition was witnessed for La(1-x)Sr(x)MnO(3) compounds in Raman spectra and photo-induced conduction simultaneously. A simple continuous argon ion laser source was used for optical excitation. The photon energy was 2.53 eV and the power can be chosen anywhere between 5 and 45 mW. Our studies clearly bring out the role of local disorder in the form of Jahn-Teller distortion in the localization of electrons.