Multiferroic bismuth ferrite, BiFeO3, offers a vast landscape to study the interplay between different ferrroic orders. Another aspect which is equally exciting, and yet underutilized, is the possibility of large-scale ordering of domains. Along with symmetry-driven bulk photovoltaic effect, BiFeO3 presents opportunities to conceptualize novel light-based devices. In this work, we investigate the evolution of the bulk photovoltaic effect in BiFeO3 thin films with stripe-domain pattern as the polarization of light is modulated from linear to elliptical to circular. The open-circuit voltages under circularly polarized light exceed ± 25 V. The anomalous character of the effect arises from the contradiction with the analytical assessment involving tensorial analysis. The assessment highlights the need for a domain-specific interaction of light which is further analyzed with spatially-resolved Raman measurements. Appropriate positioning of electrodes allows observation of a switch-like photovoltaic effect, i.e., ON and OFF state, by changing the helicity of circularly polarized light.

Ever since the first observation of a photovoltaic effect in ferroelectric BaTiO3, studies have been devoted to analyze this effect, but only a few attempted to engineer an enhancement. In conjunction, the steep progress in thin-film fabrication has opened up a plethora of previously unexplored avenues to tune and enhance material properties via growth in the form of superlattices. In this work, we present a strategy wherein sandwiching a ferroelectric BaTiO3 in between paraelectric SrTiO3 and CaTiO3 in a superlattice form results in a strong and tunable enhancement in photocurrent. Comparison with BaTiO3 of similar thickness shows the photocurrent in the superlattice is 103 times higher, despite a nearly two-thirds reduction in the volume of BaTiO3. The enhancement can be tuned by the periodicity of the superlattice, and persists under 1.5 AM irradiation. Systematic investigations highlight the critical role of large dielectric permittivity and lowered bandgap.

Absence of inversion symmetry is the underlying origin of ferroelectricity, piezoelectricity, and the bulk photovoltaic (BPV) effect, as a result of which they are inextricably linked. However, till now, only the piezoelectric effects (inverse) have been commonly utilized for probing ferroelectric characteristics such as domain arrangements and resultant polarization orientation. The bulk photovoltaic effect, despite sharing same relation with the symmetry as piezoelectricity, has been mostly perceived as an outcome of ferroelectricity and not as a possible analytical method. In this work, we investigate the development of BPV characteristics, i.e. amplitude and angular dependency of short-circuit current, as the ferroelastic domain arrangement is varied by applying electric fields in planar devices of BiFeO3 films. A rather sensitive co-dependency was observed from measurements on sample with ordered and disordered domain arrangements. Analysis of the photovoltaic response manifested in a mathematical model to estimate the proportion of switched and un-switched regions. The results unravel the potential utility of BPV effect to trace the orientation of the polarization vectors (direction and amplitude) in areas much larger than that can be accommodated in probe-based techniques.

Photovoltaic effect in ferroelectrics can be considered as a sum of two dominant contributions, that is, arising from the ferroelectric/metal junctions and from the bulk of the ferroelectrics. In the case of Pb­(Zr0.2Ti0.8)­O3, several studies have been devoted to analyze the contributions from the junctions and associated aspects such as barrier height. In this work, we elaborate on the contribution from the bulk, and the role of an inherent nano-sized entity, that is, domain walls. Systematic investigations were conducted with samples of different thicknesses (75–700 nm), which evidently also assisted in varying the proportion of domain walls. The open-circuit voltages scaled up with thickness in accordance with the bulk-driven photovoltaics phenomenology. Temperature-resolved measurements highlighted the influence of domain walls on the overall transport characteristics under light and dark conditions. Analysis of the spectral photoresponse unraveled the sub-band gap character of the domain walls and the prospective role in the overall photovoltaic effect.

We demonstrate the synthesis of self-assembled threedimensional nanocomposite thin films consisting of NiO nanocolumns in an layered Aurivillius phase matrix. The structures were grown on single-crystal SrTiO 3 substrates via pulsed laser deposition (PLD) with single ceramic (PbTiO 3 ) x (BiNi 2/3 Nb 1/3 O 3 ) 1−x targets. The nanocolumns, which are about 10 nm in diameter each, extend over the entire film thickness of up to 225 nm. We reveal the difference in electrical conduction properties of the nanocolumns and the surrounding matrix on the nanoscale via conductive atomic force microscopy. The nanocomposite thin films exhibit improved photovoltaic performance compared to both pure PbTiO 3 and homogeneous Aurivillius phase thin films.