Intermediate structural state in Bi1−xPrxFeO3 ceramics at the rhombohedral–orthorhombic phase boundary

Crystal structure of the Bi1−xPrxFeO3 ceramics of the compositions corresponding to the threshold concentrations separating the polar rhombohedral (R3c) and anti-polar orthorhombic (Pbam) phases has been investigated with X-ray diffraction, transmission electron microscopy and differential scanning calorimetry measurements performed in a broad temperature range. The structural study specifies the peculiarities of the temperature-driven transition into the non-polar orthorhombic (Pnma) phase depending on the structural state of the compounds at room temperature. The crystal structure analysis reveals the revival of the anti-polar orthorhombic phase upon the temperature-induced transition, thus assuming that it can be considered as the bridge phase between the polar rhombohedral and the non-polar orthorhombic phases.publishe

High pressure route to generate magnetic monopole dimers in spin ice

The gas of magnetic monopoles in spin ice is governed by one key parameter: the monopole chemical potential. A significant variation of this parameter could access hitherto undiscovered magnetic phenomena arising from monopole correlations, as observed in the analogous electrical Coulomb gas, like monopole dimerization, critical phase separation, or charge ordering. However, all known spin ices have values of chemical potential imposed by their structure and chemistry that place them deeply within the weakly correlated regime, where none of these interesting phenomena occur. Here we use high-pressure synthesis to create a new monopole host, Dy2Ge2O7, with a radically altered chemical potential that stabilizes a large fraction of monopole dimers. The system is found to be ideally described by the classic Debye–Huckel–Bjerrum theory of charge correlations. We thus show how to tune the monopole chemical potential in spin ice and how to access the diverse collective properties of magnetic monopoles

Magnetic and Electrical Properties of Ordered 112-type Perovskite LnBaCoMnO5+\delta (Ln = Nd, Eu)

Investigation of the oxygen-deficient 112-type ordered oxides of the type LnBaCoMnO5+\delta (Ln = Nd, Eu) evidences certain unusual magnetic behavior at low temperatures, compared to the LnBaCo2O5+\delta cobaltites. One observes that the substitution of manganese for cobalt suppresses the ferromagnetic state and induces strong antiferromagnetic interactions. Importantly, NdBaCoMnO5.9 depicts a clear paramagnetic to antiferromagnetic type transition around 220 K, whereas for EuBaCoMnO5.7 one observes an unusual magnetic behavior below 177 K which consists of ferromagnetic regions embedded in an antiferromagnetic matrix. The existence of two sorts of crystallographic sites for Co/Mn and their mixed valence states favor the ferromagnetic interaction whereas antiferromagnetism originates from the Co3+-O-Co3+ and Mn4+-O-Mn4+ interactions. Unlike the parent compounds, the present Mn-substituted phases do not exhibit prominent magnetoresistance effects in the temperature range 75-400K.Comment: 23 pages including figure

Anomalous behavior of displacement correlation function and strain in lanthanum cobalt oxide analyzed both from X-ray powder diffraction and EXAFS data

A combined X-ray powder diffraction (XPD) and high-resolution extended X-ray absorption fine structure (EXAFS) at the Co and Ga K-edges study has been performed for LaCoO3 and LaGaO3 ceramics, the latter sample was used as a reference without spin transitions. Based on the X-ray diffraction data, we have found that isotropic atomic displacement parameters (ADP) or mean-squared displacement of the Co–O bond exhibit gradual growth below ~50 K, wherein the strain dependencies testify rapid increase below 150 K for the LaCoO3 having rhombohedral structure. No similar features could be observed for LaGaO3 sample. Above ~100 K the isotropic ADP of the Co–O bond indicate a gradual growth, whereas strain curves show distinct bend near the spin-state transition temperature at about 150 K. According to the EXAFS data, the correlated parallel mean squared relative displacement (MSRD||) of Co–O and Ga–O bonds exhibit a gradual growth above 150 K; however, in the LaCoO3 this parameter is notably bigger. It is supposed that at low temperature the cobalt ions are dominantly in low-spin (LS) state, while certain amount of Co3+ ions located within the surface layer of the crystallines have high-spin state (HS). Temperature growth leads to a gradual transformation of the HS state of the cobalt ions into the highly-hybridized intermediate-spin (IS) state, while the cobalt ions located in the inner part of the crystallines remain LS configuration up to 150 K. Further temperature increase leads to a spin transition of the Co3+ ions located within the crystallines from the LS state into the IS one

Anomalous behavior of displacement correlation function and strain in lanthanum cobalt oxide analyzed both from X-ray powder diffraction and EXAFS data

A combined X-ray powder diffraction (XPD) and high-resolution extended X-ray absorption fine structure (EXAFS) at the Co and Ga K-edges study has been performed for LaCoO3 and LaGaO3 ceramics, the latter sample was used as a reference without spin transitions. Based on the X-ray diffraction data, we have found that isotropic atomic displacement parameters (ADP) or mean-squared displacement of the Co–O bond exhibit gradual growth below ~50 K, wherein the strain dependencies testify rapid increase below 150 K for the LaCoO3 having rhombohedral structure. No similar features could be observed for LaGaO3 sample. Above ~100 K the isotropic ADP of the Co–O bond indicate a gradual growth, whereas strain curves show distinct bend near the spin-state transition temperature at about 150 K. According to the EXAFS data, the correlated parallel mean squared relative displacement (MSRD||) of Co–O and Ga–O bonds exhibit a gradual growth above 150 K; however, in the LaCoO3 this parameter is notably bigger. It is supposed that at low temperature the cobalt ions are dominantly in low-spin (LS) state, while certain amount of Co3+ ions located within the surface layer of the crystallines have high-spin state (HS). Temperature growth leads to a gradual transformation of the HS state of the cobalt ions into the highly-hybridized intermediate-spin (IS) state, while the cobalt ions located in the inner part of the crystallines remain LS configuration up to 150 K. Further temperature increase leads to a spin transition of the Co3+ ions located within the crystallines from the LS state into the IS one

Investigation of a spin transition in a LaCoO3 single crystal by the method of X-ray magnetic circular dichroism at the cobalt K- and L2,3-edges

Spin transitions of cobalt ions in LaCoO3 single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L2,3-edges of Co3+ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/S from 0.48 to 0.53 in the temperature range from 60 K to 120 K

Investigation of a spin transition in a LaCoO3 single crystal by the method of X-ray magnetic circular dichroism at the cobalt K- and L2,3-edges

Spin transitions of cobalt ions in LaCoO3 single crystals have been studied by the method of X-ray magnetic circular dichroism (XMCD) at the K- and L2,3-edges of Co3+ ions. The orbital momentum of cobalt ions obtained for the K-edge at the 3d level in the region of the spin transition in the temperature range from 25 to 120 K increases by a factor of approximately 1.6, whereas the slope of the magnetization curve value in the same temperature range and magnetic field increases by a factor of more than 10. XMCD experiments at the cobalt L2,3-edges demonstrate gradual growth of the ratio of the orbital momentum to the spin one L/S from 0.48 to 0.53 in the temperature range from 60 K to 120 K

Phase coexistence in Bi1-xPrxFeO3 ceramics

Bi1-x Pr (x) FeO3 ceramics across the rhombohedral-orthorhombic phase boundary have been studied by X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The structural phase transitions in Bi1-x Pr (x) FeO3 driven by doping concentration and temperature are significantly different from those in BiFeO3 compounds doped with other rare-earth elements. The features of the structural transformations have been discussed based on the specific character of the chemical bonds associated with praseodymium ions. The detailed study of the crystal structure evolution clarified the ranges of both single-phase and phase coexistence regions at different temperatures and dopant concentrations. For x = 0.125, compound extraordinary three-phase coexistence state has been observed in a narrow temperature range at about 400 A degrees C. The results explicate driving forces of the structural transitions and elucidate the origin of the remarkable physical properties of BiFeO3-based compounds near the morphotropic phase boundary