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The prospect of creating ferroelectric or high permittivity nanomaterials provides motivation for investigating complex transition metal oxides of the form Ba(Ti, MV)O3, where M = Nb or Ta. Solid state processing typically produces mixtures of crystalline phases, rarely beyond minimally doped Nb/Ta. Using a modified sol-gel method, we prepared single phase nanocrystals of Ba(Ti, M)O3. Compositional and elemental analysis puts the empirical formulas close to BaTi0.5Nb0.5O3−δ and BaTi0.5Ta0.5O3−δ. For both materials, a reversible temperature dependent phase transition (non-centrosymmetric to symmetric) is observed in the Raman spectrum in the region 533–583 K (260–310 °C); for Ba(Ti, Nb)O3, the onset is at 543 K (270 °C); and for Ba(Ti, Ta)O3, the onset is at 533 K (260 °C), which are comparable with 390–393 K (117–120 °C) for bulk BaTiO3. The crystal structure was resolved by examination of the powder x-ray diffraction and atomic pair distribution function (PDF) analysis of synchrotron total scattering data. It was postulated whether the structure adopted at the nanoscale was single or double perovskite. Double perovskites (A2B′B″O6) are characterized by the type and extent of cation ordering, which gives rise to higher symmetry crystal structures. PDF analysis was used to examine all likely candidate structures and to look for evidence of higher symmetry. The feasible phase space that evolves includes the ordered double perovskite structure Ba2(Ti, MV)O6 (M = Nb, Ta) Fm-3m, a disordered cubic structure, as a suitable high temperature analog, Ba(Ti, MV)O3Pm-3m, and an orthorhombic Ba(Ti, MV)O3Amm2, a room temperature structure that presents an unusually high level of lattice displacement, possibly due to octahedral tilting, and indication of a highly polarized crystal. 

The bulk photovoltaic effect (BPE) has drawn considerable attention due to its ability to generate photovoltages above the bandgap and reports of highly enhanced photovoltaic current when using nanoscale absorbers or nanoscale electrodes, which, however, do not lend themselves to practical, scalable implementation. Herein, it is shown that a strikingly high BPE photoresponse can be achieved in an ordinary thin‐film configuration merely by tuning fundamental ferroelectric properties. Nonmonotonic dependence of the responsivity (R_SC) on the ferroelectric polarization is observed and at the optimal value of the film polarization, a more than three orders of magnitude increase in theR_SCfrom the bulk BaTiO₃value is obtained, reachingR_SCclose to 10⁻² A W⁻¹, the highest value reported to date for the archetypical ferroelectric BaTiO₃films. Results challenge the applicability of standard first‐principles‐based descriptions of BPE to thin films and the inherent weakness of BPE in ferroelectric thin films. 

The quantum phenomenon of shift photovoltaic current was predicted decades ago, but this effect was never observed directly because shift and ballistic currents coexist. The atomic-scale relaxation time of shift, along with the absence of a photo-Hall behavior, has made decisive measurement of shift elusive. Here, we report a facile, direct-current, steady-state method for unambiguous determination of shift by means of the simultaneous measurements of linear and circular bulk photovoltaic currents under magnetic field, in a sillenite piezoelectric crystal. Comparison with theoretical predictions permits estimation of the signature length scale for shift. Remarkably, shift and ballistic photovoltaic currents under monochromatic illumination simultaneously flow in opposite directions. Disentangling the shift and ballistic contributions opens the way for quantitative, fundamental insight into and practical understanding of these radically different photovoltaic current mechanisms and their relationship.