Search for: All records

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. 

Ferroelectric materials, which exhibit switchable polarization, are potential candidates for photovoltaic applications owing to their intriguing charge carrier separation mechanism associated with polarization and breaking of inversion symmetry. To overcome the low photocurrent of ferroelectrics, extensive efforts have focused on reducing their bandgaps to increase the optical absorption of the solar spectrum and thus the power conversion efficiency. Here, a new avenue of enhancing photovoltaic performance via engineering the polarization across a morphotropic phase boundary (MPB) is reported. Tetragonal compositions in the vicinity of the MPB in a PbTiO₃‐Bi(Ni_1/2Ti_1/2)O₃solid solution are shown to generate up to 3.6 kV cm⁻¹photoinduced electric field and 6.2 µA cm⁻²short‐circuit photocurrent, multiple times higher than its pseudocubic counterpart under the same illumination conditions with excellent polarization retention. This enhancement allows the investigation of the correlation between the polarization switching and photovoltaic switching, which enables a controllable multistate photocurrent. Combined with a bandgap of 2.2 eV, this material exhibits a sizable photoresponse over a broad spectral range. These findings provide a new approach to improve the photovoltaic performance of ferroelectric materials and can expand their potential applications in optoelectronic devices.

 

Domain walls separating regions of ferroelectric material with polarization oriented in different directions are crucial for applications of ferroelectrics. Rational design of ferroelectric materials requires the development of a theory describing how compositional and environmental changes affect domain walls. To model domain wall systems, a discrete microscopic Landau–Ginzburg–Devonshire (dmLGD) approach with A‐ and B‐site cation displacements serving as order parameters is developed. Application of dmLGD to the classic BaTiO₃, KNbO_3,and PbTiO₃ferroelectrics shows that A–B cation repulsion is the key interaction that couples the polarization in neighboring unit cells of the material. dmLGD decomposition of the total energy of the system into the contributions of the individual cations and their interactions enables the prediction of different properties for a wide range of ferroelectric perovskites based on the results obtained for BaTiO₃, KNbO_3,and PbTiO₃only. It is found that the information necessary to estimate the structure and energy of domain‐wall “defects” can be extracted from single‐domain 5‐atom first‐principles calculations, and that “defect‐like” domain walls offer a simple model system that sheds light on the relative stabilities of the ferroelectric, antiferroelectric, and paraelectric bulk phases. The dmLGD approach provides a general theoretical framework for understanding and designing ferroelectric perovskite oxides.