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

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 Added by Feiming Bai
 Publication date 2004
  fields Physics
and research's language is English




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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.



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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$^{circ}$-$alpha$ =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$^{circ}$-$alpha$=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.
247 - Hu Cao , Feiming Bai , Jiefang Li 2004
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.
Ferroelectric photovoltaic materials are an alternative to semiconductor-based photovoltaics and offer the advantage of above bandgap photovoltage generation. However, there are few known compounds, and photovoltaic efficiencies remain low. Here, we report the discovery of a photovoltaic effect in undoped lead magnesium niobate-lead titanate crystal and a significant improvement in the photovoltaic response under suitable electric fields and temperatures. The photovoltaic effect is maximum near the electric-field-driven ferroelectric dipole reorientation, and increases threefold near the Curie temperature. Moreover, at ferroelectric saturation, the photovoltaic response exhibits clear remanent and transient effects. The transient-remanent combinations together with electric and thermal tuning possibilities indicate photoferroelectric crystals as emerging elements for photovoltaics and optoelectronics, relevant to all-optical information storage and beyond.
Single crystals of Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) poled along [001] were investigated by dielectric, x-ray, and polarized light (PLM) and piezo-force microscopy (PFM) methods. PLM revealed {100} macro-domain plates that formed after poling, whose size increased on heating between room temperature and a rhombohedral rightarrow tetragonal phase transition, above which point a break-up of the macro-domain plates was observed. Corresponding PFM studies demonstrated that poling reduced the size of stripe-like domains that were internal to the macro-domain plates, whose size also increased on heating to TR-T. The temperature dependence of both the size of the macro-domain plates and internal sub-domains followed the Arrhenius relation with the activation energy of 0.4-0.5eV. The coercive field displays an abnormal increase on heating below TR-T, different than that for PMN-PT. The anomalously increased coercive field can be ascribed to the Arrhenius-type domain growth, indicating a simple thermally activated process and an important role of hierarchial domains in the improved performance of PIN-PMN-PT.
The temperature dependence of elastic, dielectric, and piezoelectric properties of (65-x)Pb(Mg1/3Nb2/3)O3-xBaTiO335-PbTiO3 ceramics with x=0, 1, 2, 3, and 4 was investigated. Compound with x=2 was found to exhibit a large piezoelectric response (d31=-170 pC/N, d33=530 pC/N at 300 K). Particularly, its d31 value was nearly a constant over a temperature range from 185 to 360 K. A broad ferroelectric phase transition tuned by BaTiO3 doping was deduced from the dielectric constant, elastic compliance constant and Raman spectra. The temperature-stable piezoelectric response was attributed to the counter-balance of contributions from the dielectric and elastic responses.
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