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G. Shirane

Publications and source records attributed to G. Shirane.

At least 19 recordsLinked to original sources

Neutron and X-ray diffraction study of cubic [111] field cooled Pb(Mg1/3Nb2/3)O3

Neutron and x-ray diffraction techniques have been used to study the competing long and short-range polar order in the relaxor ferroelectric Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ (PMN) under a [111] applied electric field. Despite reports of a structural transition from a cubic phase to a rhombohedral phase for fields E $>$ 1.7 kV/cm, we find that the bulk unit cell remains cubic (within a sensitivity of 90$^{\circ}$-$α$ =0.03$^{\circ}$)for fields up to 8 kV/cm. Furthermore, we observe a structural transition confined to the near surface volume or `skin' of the crystal where the cubic cell is transformed to a rhombohedral unit cell at T$_{c}$=210 K for E $>$ 4 kV/cm, for which 90$^{\circ}$-$α$=0.08 $\pm$ 0.03$^{\circ}$ below 50 K. While the bulk unit cell remains cubic, a suppression of the diffuse scattering and concomitant enhancement of the Bragg peak intensity is observed below T$_{c}$=210 K, indicating a more ordered structure with increasing electric field yet an absence of a long-range ferroelectric ground state in the bulk. The electric field strength has little effect on the diffuse scattering above T$_{c}$, however below T$_{c}$ the diffuse scattering is reduced in intensity and adopts an asymmetric lineshape in reciprocal space. The absence of hysteresis in our neutron measurements (on the bulk) and the presence of two distinct temperature scales suggests that the ground state of PMN is not a frozen glassy phase as suggested by some theories but is better understood in terms of random fields introduced through the presence of structural disorder. Based on these results, we also suggest that PMN represents an extreme example of the two-length scale problem, and that the presence of a distinct skin maybe necessary for a relaxor ground state.

cond-mat.mtrl-sci

Dielectric properties and lattice dynamics of Ca-doped K$_{0.95}$Li$_{0.05}$TaO$_{3}$

Relaxor behavior and lattice dynamics have been studied for a single crystal of K$_{1-x}$Li$_x$TaO$_3$ $(x=0.05)$, where a small amount of a Ca impurity ($\sim 15$~ppm) was incorporated. The dielectric measurements revealed Debye-like relaxations with Arrhenius activation energies of 80 and 240 meV that are assigned to Li$^+$ dipoles and the Li$^+$-Li$^+$ dipolar pairs, respectively. In the neutron scattering results, diffuse scattering ridges appear around the nuclear Bragg peaks below $\sim 150$ K and phonon line broadening features start to appear at even higher temperatures suggesting that polar nano-regions (PNR's) start to form at these temperatures. These results are supported by the dielectric data that reveal relaxor behavior starting at $\sim 200$ K on cooling. From analyses of the diffuse intensities, the displacements include a uniform phase shift of all of the atoms in addition to the atomic displacements corresponding to a polarization vector of the transverse optic soft ferroelectric mode, a finding that is analogous to that in the prototypical relaxor material Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$.

cond-mat.mtrl-sci

Coexistence and competition of local- and long-range polar orders in a ferroelectric relaxor

We have performed a series of neutron diffuse scattering measurements on a single crystal of the solid solution Pb(Zn$_{1/3}$Nb$_{2/3}$)O$_3$ (PZN) doped with 8% PbTiO$_3$ (PT), a relaxor compound with a Curie temperature T$_C \sim 450$ K, in an effort to study the change in local polar orders from the polar nanoregions (PNR) when the material enters the ferroelectric phase. The diffuse scattering intensity increases monotonically upon cooling in zero field, while the rate of increase varies dramatically around different Bragg peaks. These results can be explained by assuming that corresponding changes occur in the ratio of the optic and acoustic components of the atomic displacements within the PNR. Cooling in the presence of a modest electric field $\vec{E}$ oriented along the [111] direction alters the shape of diffuse scattering in reciprocal space, but does not eliminate the scattering as would be expected in the case of a classic ferroelectric material. This suggests that a field-induced redistribution of the PNR has taken place.

cond-mat.mtrl-sci

Damped Soft Phonons and Diffuse Scattering in 40PMN-60PT

Using neutron elastic and inelastic scattering and high-energy x-ray diffraction, we present a comparison of 40% Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$-60% PbTiO$_{3}$ (PMN-60PT) with pure Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ (PMN) and PbTiO$_{3}$ (PT). We measure the structural properties of PMN-60PT to be identical to pure PT, however, the lattice dynamics are exactly that previously found in relaxors PMN and PZN. PMN-60PT displays a well-defined macroscopic structural transition from a cubic to tetragonal unit cell at 550 K. The diffuse scattering is shown to be weak indicating that the structural distortion is long-range in PMN-60PT and short-range polar correlations (polar nanoregions) are not present. Even though polar nanoregions are absent, the soft optic mode is short-lived for wavevectors near the zone-centre. Therefore, PMN-60PT displays the same waterfall effect as prototypical relaxors PMN and PZN. We conclude that it is random fields resulting from the intrinsic chemical disorder which is the reason for the broad transverse optic mode observed in PMN and PMN-60PT near the zone centre and not due to the formation of short-ranged polar correlations. Through our comparison of PMN, PMN-60PT, and pure PT, we interpret the dynamic and static properties of the PMN-xPT system in terms of a random field model in which the cubic anisotropy term dominates with increasing doping of PbTiO$_{3}$.

cond-mat.mtrl-sci

Inelastic neutron scattering study of phonons and magnetic excitations in LaCoO$_{3}$

We have investigated the phonon and the magnetic excitations in LaCoO3 by inelastic neutron scattering measurements. The acoustic phonon dispersions show some characteristic features of the folded Brillouin zone (BZ) for the rhombohedrally distorted perovskite structure containing two chemical formula units of LaCoO3 in the unit cell. We observed two transverse optical (TO) phonon branches along (delta, delta, delta), consistent with previously reported Raman active Eg modes which show remarkable softening associated with the spin-state transition [Ishikawa et al., (Phys. Rev. Lett. 93 (2004) 136401.)]. We found that the softening takes place in the TO mode over the whole BZ. In contrast, the acoustic phonons show no anomalous softening associated with the spin-state transition. The low-energy paramagnetic scattering at 8 K is weak, increasing towards a maximum at E > 15 meV, consistent with excitation of the nonmagnetic low-spin to magnetic intermediate-spin state of Co 3+ ions.

cond-mat.str-el

The Persistence and Memory of Polar Nano-Regions in a Ferroelectric Relaxor Under an Electric Field

The response of polar nanoregions (PNR) in the relaxor compound Pb[(Zn$_{1/3}$Nb$_{2/3}$)$_{0.92}$Ti$_{0.08}$]O$_3$ subject to a [111]-oriented electric field has been studied by neutron diffuse scattering. Contrary to classical expectations, the diffuse scattering associated with the PNR persists, and is even partially enhanced by field cooling. The effect of the external electric field is retained by the PNR after the field is removed. The ``memory'' of the applied field reappears even after heating the system above $T_C$, and cooling in zero field.

cond-mat.mtrl-sci

Low Symmetry Phase in (001) BiFeO$_3$ Epitaxial Constrained Thin Films

The lattice of (001)-oriented BiFeO$_3$ epitaxial thin film has been identified by synchrotron x-ray diffraction. By choosing proper scattering zones containing the fixed (001) reflection, we have shown that low-symmetry phases similar to a $M_A$ phase exist in the thin film at room temperature. These results demonstrate a change in phase stability from rhombohedral in bulk single crystals, to a modified monoclinic structure in epitaxial thin films.

cond-mat.mtrl-sci

Defect Structure of the High-Dielectric-Constant Perovskite Cacu3ti4o12

Using transmission electron microscopy (TEM) we studied CaCu3Ti4O12, an intriguing material that exhibits a huge dielectric response, up to kilohertz frequencies, over a wide range of temperature. Neither in single crystals, nor in polycrystalline samples, including sintered bulk- and thin-films, did we observe the twin domains suggested in the literature. Nevertheless, in the single crystals, we saw a very high density of dislocations with a Burger vector of [110], as well as regions with cation disorder and planar defects with a displacement vector 1/4[110]. In the polycrystalline samples, we observed many grain boundaries with oxygen deficiency, in comparison with the grain interior. The defect-related structural disorders and inhomogeneity, serving as an internal barrier layer capacitance (IBLC) in a semiconducting matrix, might explain the very large dielectric response of the material. Our TEM study of the structure defects in CaCu3Ti4O12 supports a recently proposed morphological model with percolating conducting regions and blocking regions.

cond-mat.mtrl-sci

Structural phase transformation and phase boundary/stability studies of field-cooled Pb(Mg1/3Nb2/3O3)-32%PbTiO3 crystals

Structural phase transformations in (001)-oriented (1-x)Pb(Mg1/3Nb2/3O3)-32%PbTiO3 (PMN-x%PT) crystals have been investigated by x-ray diffraction. A C->T->MC sequence was observed in both the field-cooled (FC) and zero-field-cooled (ZFC) conditions. Most interestingly, an anomalous increase in the C->T phase boundary with increasing field has been observed, which is seemingly a common characteristic of crystals whose compositions are in the vicinity of the MPB, irrespective of the width of the T and MC phase regions.

cond-mat.mtrl-sci

Soft phonons and structural phase transitions in La$_{1.875}$Ba$_{0.125}$CuO$_{4}$

Soft phonon behavior associated with a structural phase transition from the low-temperature-orthorhombic (LTO) phase ($Bmab$ symmetry) to the low-temperature-tetragonal (LTT) phase ($P4_{2}/ncm$ symmetry) was investigated in La$_{1.875}$Ba$_{0.125}$CuO$_{4}$ using neutron scattering. As temperature decreases, the TO-mode at $Z$-point softens and approaches to zero energy around $T_{\rm d2}=62$ K, where the LTO -- LTT transition occurs. Below $T_{\rm d2}$, the phonon hardens quite rapidly and it's energy almost saturates below 50 K. At $T_{\rm d2}$, the energy dispersion of the soft phonon along in-plane direction significantly changes while the dispersion along out-of-plane direction is almost temperature independent. Coexistence between the LTO phase and the LTT phase, seen in both the soft phonon spectra and the peak profiles of Bragg reflection, is discussed in context of the order of structural phase transitions.

cond-mat.supr-con

Low-temperature phases in Pb(Zr0.52Ti0.48)O3: A neutron powder diffraction study

A neutron powder diffraction study has been carried out on Pb(Zr0.52Ti0.48)O3 in order to resolve an ongoing controversy about the nature of the low-temperature structure of this strongly-piezoelectric and technologically-important material. The results of a detailed and systematic Rietveld analysis at 20 K are consistent with the coexistence of two monoclinic phases having space groups Cm and Ic respectively, in the approximate ratio 4:1, and thus support the findings of a recent electron diffraction study by Noheda et al. [Phys. Rev. B 66, 060103 (2002)]. The results are compared to those of two recent conflicting neutron powder diffraction studies of materials of the same nominal composition by Hatch et al. [Phys. Rev. B 65, 212101 (2002)] and Frantti et al. [Phys. Rev. B 66, 064108 (2002)].

cond-mat.mtrl-sci

Direct observation of the near-surface layer in Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ using neutron diffraction

Spatially resolved neutron diffraction as a function of crystal depth in Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ reveals the presence of a distinct near-surface region. A dramatic change in both the lattice constant and the Bragg peak intensity as a function of crystal depth is observed to occur in this region over a length scale $\sim$ 100 $μ$m. This confirms a previous assertion, based on a comparison between high-energy x-rays and neutrons, that such a near surface region exists in the relaxors. Consequences to both single crystal and powder diffraction measurements and previous bulk neutron diffraction measurements on large single crystals are discussed.

cond-mat.mtrl-sci

Structural phase transition and dielectric relaxation in Pb(Zn1/3Nb2/3)O3 single crystals

The structure and the dielectric properties of Pb(Zn1/3Nb2/3)O3 (PZN) crystal have been investigated by means of high-resolution synchrotron x-ray diffraction (with an x-ray energy of 32 keV) and dielectric spectroscopy (in the frequency range of 100 Hz - 1 MHz). At high temperatures, the PZN crystal exhibits a cubic symmetry and polar nanoregions inherent to relaxor ferroelectrics are present, as evidenced by the single (222) Bragg peak and by the noticeable tails at the basis of the peak. At low temperatures, in addition to the well-known rhombohedral phase, another low-symmetry, probably ferroelectric, phase is found. The two phases coexist in the form of mesoscopic domains. The para- to ferroelectric phase transition is diffused and observed between 325 and 390 K, where the concentration of the low-temperature phases gradually increases and the cubic phase disappears upon cooling. However, no dielectric anomalies can be detected in the temperature range of diffuse phase transition. The temperature dependence of the dielectric constant show the maximum at higher temperature (Tm = 417 - 429 K, depending on frequency) with the typical relaxor dispersion at T < Tm and the frequency dependence of Tm fitted to the Vogel-Fulcher relation. Application of an electric field upon cooling from the cubic phase or poling the crystal in the ferroelectric phase gives rise to a sharp anomaly of the dielectric constant at T 390 K and diminishes greatly the dispersion at lower temperatures, but the dielectric relaxation process around Tm remains qualitatively unchanged. The results are discussed in the framework of the present models of relaxors and in comparison with the prototypical relaxor ferroelectric Pb(Mg1/3Nb2/3)O3.

cond-mat.mtrl-sci

3-D mapping of diffuse scattering in PZN-xPT

High energy (67 keV) x-ray diffuse scattering measurements were performed on single crystals of Pb(Zn$_{1/3}$Nb$_{2/3}$)O$_3$-$x$PbTiO$_3$ (PZN-$x$PT). A novel technique was developed to map out the diffuse scattering distribution in all three dimensions around a large number of Bragg peaks simultaneously, taking advantage of the almost flat Ewald sphere of the high energy x-ray beam. For $x=0, 4.5%$, and 8%, the results are very similar, indicating same type of correlations of polarizations in these compounds. Our results show that the diffuse scattering intensity consists of six $<110>$ rod-type intensities around reciprocal lattice points. These rod-type intensities are very likely due to condensations of soft optic phonon modes, polarized in the perpendicular $<1\bar{1}0>$ directions. A simple model is suggested where these soft phonon modes condense into static \{110\} type planar or ``pancake'' shaped correlations of the in-plane $<1\bar{1}0>$ polarizations.

cond-mat.mtrl-sci

Strong Influence of the diffuse component on the lattice dynamics in Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$

The temperature and zone dependence of the lattice dynamics in Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_{3}$ is characterized using neutron inelastic scattering. A strong correlation between the diffuse and phonon scattering is measured. The lattice dynamics in Brillouin zones where the diffuse scattering is strong is observed to display qualitatively different behavior than those zones where the diffuse scattering is weak. In the (220) and (200) zones, where there is a weak diffuse component, the dynamics are well described by coupled harmonic oscillators. Compared with SrTiO$_{3}$, the coupling is weak and isotropic, resulting in only a small transfer of spectral weight from one mode to another. A comparison of the scattering in these zones to the (110) zone, where a strong diffuse component is present, reveals a strong coupling of the diffuse (or central) component to the acoustic mode. We speculate that the coupling to the central peak is the reason for several recent conflicting interpretations of the lattice dynamics based on data from zones with a strong diffuse component.

cond-mat.mtrl-sci

An Anomalous Phase in the Relaxor Ferroelectric Pb(Zn$_{1/3}$Nb$_{2/3}$)O$_3$

X-ray diffraction studies on a Pb(Zn$_{1/3}$Nb$_{2/3}$)O$_3$ (PZN) single crystal sample show the presence of two different structures. An outer-layer exists in the outer most $\sim$ 10 to 50~$μ$m of the crystal, and undergoes a structural phase transition at the Curie temperature $T_C\approx410$ K. The inside phase is however, very different. The lattice inside the crystal maintains a cubic unit cell, while ferroelectric polarization develops below $T_C$. The lattice parameter of the cubic unit cell remains virtually a constant, i.e., much less variations compared to that of a typical relaxor ferroelectric, in a wide temperature range of 15 K to 750 K. On the other hand, broadening of Bragg peaks and change of Bragg profile line-shapes in both longitudinal and transverse directions at $T_C$ clearly indicate a structural phase transition occurring.

cond-mat.mtrl-sci

Cold neutron scattering study on diffuse and phonon excitations in the relaxor PbMg(1/3)Nb(2/3)O3

Cold neutron scattering experiments have been performed to explore the energy, temperature, and wave-vector dependence of the diffuse scattering and the transverse acoustic (TA) phonons in the relaxor PbMg(1/3)Nb(2/3)O3. We have observed a weak, but definitive, diffuse scattering cross section above the Burns temperature T_d ~ 600 K. This cross section, which is most likely caused by chemical short-range order, persists down to 100 K, and coexists with the much stronger diffuse scattering that is attributed to the polar nanoregions. A systematic study of the TA phonon around (1, 1, 0) has also been carried out. The phonon is well defined for small wave vectors q, but broadens markedly around q = (0.1, -0.1, 0).

cond-mat.mtrl-sci

X-ray and Neutron Diffraction Investigations of the Structural Phase Transformation Sequence under Electric Field in 0.7Pb(Mg1/3Nb2/3)-0.3PbTiO3 Crystals

The structural phase transformations of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-30%PT) have been studied using x-ray diffraction (XRD) and neutron scattering as a function of temperature and electric field. We observe the phase transformational sequence (i) cubic (C)-> tetragonal (T)-> rhombohedral (R) in the zero-field-cooled (or ZFC) condition; (ii) C->T-> monoclinic (MC)-> monoclinic (MA) in the field-cooled (or FC) condition; and (iii) R->MA->MC->T with increasing field at fixed temperature beginning from the ZFC condition. Upon removal of the field, the MA phase is stable at room temperature in the FC condition, and also in the ZFC condition with increasing field. Several subtleties of our findings are discussed based on results from thermal expansion and dielectric measurements, including (i) the stability of the MA phase; (ii) a difference in lattice parameters between inside bulk and outside layer regions; and (iii) the diffuse nature of the MA and MC phase transition.

cond-mat.mtrl-sci