Lithium doped sodium niobate is an ecofriendly piezoelectric material that exhibits a variety of structural phase transitions with composition and temperature. We have investigated the phase stabilities of an important composition Li0.12Na0.88NbO3 (L
NN12) using a combination of powder x-ray and neutron diffraction techniques in the temperature range 300 - 1100 K. Detailed Rietveld analyses of thermo-diffractograms show a variety of structural phase transitions ranging from non-polar antiferrodistortive to ferroelectric in nature. In the temperature range of 525 K to 675 K, unambiguous experimental evidence is shown for phase coexistence of orthorhombic paraelectric O1 phase (space group Cmcm) and orthorhombic ferroelectric O2 phase (space group Pmc21). The bp primitive lattice parameter of the ferroelectric orthorhombic phase (O2 phase) decreases, while the ap and cp primitive lattice parameters show normal increase with increase in temperature. Above 675 K, in the O1 phase, all lattice parameters come close to each other and increase continuously with increase of temperature, and around 925 K, ap parameter approaches bp parameter and thus the sample undergoes an orthorhombic to tetragonal phase transition. Further as temperature increases, the cp lattice parameter decreases, and finally approaches to ap parameter, and the sample transform into the cubic phase. The continuous change in the lattice parameters reveals that the successive phase transformations from orthorhombic O1 to high temperature tetragonal phase and finally to the cubic phase are not of a strong first order type in nature. We argue that application of chemical pressure as a result of Li substitution in NaNbO3 matrix, favours the freezing of zone centre phonons over the zone boundary phonons that are known to freeze in pure NaNbO3 as function of temperature.
The layered structure of tetragonal Ni(CN)2, consisting of square-planar Ni(CN)4 units linked in the a-b plane, with no true periodicity along the c-axis, is expected to show anisotropic compression on the application of pressure. High-pressure neutr
on diffraction (elastic) and inelastic neutron scattering experiments have been performed on polycrystalline Ni(CN)2 to investigate its compressibility and stability. The intralayer a lattice parameter does not show any appreciable variation with increase of pressure up to 2.7 kbar. Above this pressure value, a decrease in a is observed. The c lattice parameter decreases slowly up to 1 kbar, then decreases sharply up to 20 kbar. It does not show any significant variation with further pressure increase up to 50 kbar. The response of the lattice parameters to the applied pressure is strongly anisotropic as the interlayer spacing (along the c-axis) shows a significantly larger contraction than the a-b plane. The experimental pressure dependence of the volume data is fitted to a bulk modulus, B0, of 1050 (20) kbar over the pressure range 0-1 kbar, and to 154 (2) kbar in the range 1-50 kbar. The change in the slope of the lattice parameters at 1 kbar is also supported by high-pressure Raman measurements, which indicate a phase transition at 1 kbar. Probably arising from a change in the CN ordering within the Ni(CN)2 layers. Raman measurements, performed up to 200 kbar, highlight the possible existence of a second phase transition taking place at about 70 kbar. Our neutron inelastic scattering measurements of the pressure dependence of the phonon spectra performed up to 2.7 kbar, also support the occurrence of a phase transition at low pressure.
The antiferrodistortive (AFD) phase transition for a pseudotetragonal composition of Pb(Zr0.530Ti0.470)O3 (PZT) doped with 6% Sr has been investigated using sound velocity (4 to 320K), high resolution synchrotron X-ray powder diffraction (100 to 800K
) and high resolution as well as high flux neutron powder diffraction measurements (4K) to settle the existing controversies about the true ground state of PZT in the morphotropic phase boundary (MPB) region. The multiplet character of the neutron diffraction profiles of (3/2 1/2 1/2)pc (pseudocubic or pc indices) and (3/2 3/2 1/2)pc superlattice peaks, appearing below the AFD transition temperature, rules out the rhombohedral R3c space group. The true ground state is confirmed to be monoclinic in the Cc space group in agreement with the predictions of the first principles calculations and earlier findings for pure PZT in the MPB region. 6% Sr2+ substitution and the use of high wavelength ({lambda}=2.44{AA}) neutrons have played key role in settling the existing controversies about the true ground state of PZT in the MPB region.
The controversies about the structure of the true ground state of pseudorhombohedral compositions of Pb(ZrxTi1-x)O3 (PZT) are addressed using a 6% Sr2+ substituted sample with x=0.550. Sound velocity measurements reveal a phase transition at Tc~279K.
The temperature dependence of FWHM of (h00)pc peaks and the unit cell volume also show anomalies around 279K even though there is no indication of any change of space group in the synchrotron X-ray powder diffraction (SXRD) patterns. The neutron powder diffraction patterns reveal appearance of superlattice peaks below Tc~279K confirming the existence of an antiferrodistortive phase transition. The Rietveld analysis of the room temperature and low temperature SXRD data below Tc shows that the structure corresponds to single monoclinic phase in the Cm space group while the analysis of neutron powder diffraction data reveals that the structure of the ground state phase below Tc corresponds to the Cc space group. Our analysis shows that the structural models for the ground state phase based on R3c space group with or without the coexistence of the room temperature monoclinic phase in the Cm space group can be rejected.
We report the observation of the skyrmion lattice in the chiral multiferroic insulator Cu2OSeO3 using Cu L3-edge resonant soft x-ray diffraction. We observe the unexpected existence of two distinct skyrmion sublattices that arise from inequivalent Cu
sites with chemically identical coordination numbers but different magnetically active orbitals. The skyrmion sublattices are rotated with respect to each other implying a long wavelength modulation of the lattice. The modulation vector could be controlled with an applied magnetic field, associating this Moire-like phase with a continuous phase transition. Our findings will open a new class of science involving manipulation of quantum topological states.
Sodium niobate (NaNbO3) exhibits most complex sequence of structural phase transitions in perovskite family and therefore provides as excellent model system for understanding the mechanism of structural phase transitions. We report temperature depend
ence of inelastic neutron scattering measurements of phonon densities of states in sodium niobate. The measurements are carried out in various crystallographic phases of this material at various temperatures from 300 K to 1048 K. The phonon spectra exhibit peaks centered around 19, 37, 51, 70 and 105 meV. Interestingly, the peak around 70 meV shifts significantly towards lower energy with increasing temperature, while the other peaks do not exhibit an appreciable change. The phonon spectra at 783 K show prominent change and become more diffusive as compared to those at 303 K. In order to better analyze these features, we have performed first principles lattice dynamics calculations based on the density functional theory. The computed phonon density of states is found to be in good agreement with the experimental data. Based on our calculation we are able to assign the characteristic Raman modes in the antiferroelectric phase to the A1g symmetry, which are due to the folding of the T (w=95 cm-1) and delta(w=129 cm-1) points of the cubic Brillouin zone.
The structural properties of the CaFe2As2 have been investigated by x-ray and neutron powder diffraction techniques as a function of temperature. Unambiguous experimental evidence is shown for coexistence of tetragonal and orthorhombic phases below 1
70 K in contrast to existing literature. Detailed Rietveld analyses of thermo-diffractograms show that the sample does not transform completely in to the orthorhombic phase at the lowest temperature even though it is the majority phase. We have found that the unit cell volume of the orthorhombic phase is higher compared to that of the tetragonal phase for all the temperatures. X-ray data on CaFe2As2 shows anomalous (at) lattice parameter contraction with increasing temperature and phase co-existence behavior below 170 K unlike other members of the 122 family of compounds like SrFe2As2 and EuFe2As2. Temperature dependent magnetization of polycrystalline CaFe2As2 sample show weak anomalies below 170 K. This behavior of the polycrystalline sample is in contrast to that of a single crystal reported earlier.
We report a detailed high-temperature powder neutron diffraction investigation of the structural behavior of the multiferroic GaFeO3 between 296 and 1368 K. Temperature dependent neutron diffraction patterns do not show any appreciable change either
in intensity or appearance/disappearance of the observed peaks upto 1368 K, ruling out any structural transition in the entire temperature range. The lattice parameters and volume exhibit normal thermal expansion behaviour, indicating the absence of any structural changes with increasing temperature. The origin of the magnetoelectric couplings and multiferroicity in GaFeO3 is known to be influenced by the site disorder from Ga/Fe atoms. Our analysis shows that this disorder remains nearly the same upon increase of temperature from 296 to 1368 K. The structural parameters as obtained from Rietveld refinement of neutron diffraction data are used to calculate the interatomic distances and distortions of the oxygen polyhedra around the Ga1, Ga2, Fe1 and Fe2 cations. Evolution of the distortion of the oxygen polyhedra around these sites suggests that the Ga1-O tetrahedron is least distorted and Fe1-O is most distorted. Structural features regarding the distortion of polyhedral units would be crucial to understand the temperature dependence of the microscopic origin of polarizations. The electric polarization has been estimated using a simple ionic model and its value is found to decrease with increasing temperature.
The presence of superlattice reflections and detailed analyses of the powder neutron and x-ray diffraction data reveal that La rich (BF$_{0.50}$-LF$_{0.50}$)$_{0.50}$-(PT)$_{0.50}$ (BF-LF-PT) has ferroelectric rhombohedral crystal structure with spac
e group textit{$R3c$} at ambient conditions. The temperature dependence of lattice parameters, tilt angle, calculated polarization $(P_{s})$, volume, and integrated intensity of superlattice and magnetic reflections show an anomaly around 170 K. Impedance spectroscopy, dielectric and ac conductivity measurements were performed in temperature range $473K leq T leq 573K$ to probe the origin of large remnant polarization and frequency dependent broad transitions with large dielectric constant near $T_c^{FE}$. Results of impedance spectroscopy measurements clearly show contributions of both grain and grain boundaries throughout the frequency range ($10^{3}$ Hz$leq fleq 10^{7} $ Hz). It could be concluded that the grain boundaries are more resistive and capacitive as compared to the grains, resulting in inhomogeneities in the sample causing broad frequency dependent dielectric anomalies. Enhancement in dielectric constant and remnant polarization values are possibly due to space charge polarization caused by piling of charges at the interface of grains and grain boundaries. The imaginary parts of dielectric constant ($epsilon^{primeprime}$) Vs frequency data were fitted using Maxwell-Wagner model at $T_c^{FE}(sim 523$K) and model fits very well with the data up to $10^{5}$ Hz. Magnetodielectric measurements prove that the sample starts exhibiting magnetoelectric coupling at $sim 170$ K, which is also validated by neutron diffraction data.
We have employed Soft and Hard X-ray Resonant Magnetic Scattering and Polarised Neutron Diffraction to study the magnetic interface and the bulk antiferromagnetic domain state of the archetypal epitaxial Ni$_{81}$Fe$_{19}$(111)/CoO(111) exchange bias
ed bilayer. The combination of these scattering tools provides unprecedented detailed insights into the still incomplete understanding of some key manifestations of the exchange bias effect. We show that the several orders of magnitude difference between the expected and measured value of exchange bias field is caused by an almost anisotropic in-plane orientation of antiferromagnetic domains. Irreversible changes of their configuration lead to a training effect. This is directly seen as a change in the magnetic half order Bragg peaks after magnetization reversal. A 30 nm size of antiferromagnetic domains is extracted from the width the (1/2 1/2 1/2) antiferromagnetic magnetic peak measured both by neutron and x-ray scattering. A reduced blocking temperature as compared to the measured antiferromagnetic ordering temperature clearly corresponds to the blocking of antiferromagnetic domains. Moreover, an excellent correlation between the size of the antiferromagnetic domains, exchange bias field and frozen-in spin ratio is found, providing a comprehensive understanding of the origin of exchange bias in epitaxial systems.
