The application of ferroelectric materials (i.e. solids that exhibit
spontaneous electric polarisation) in solar cells has a long and controversial
history. This includes the first observations of the anomalous photovoltaic
effect (APE) and the bulk photovoltaic effect (BPE). The recent successful
application of inorganic and hybrid perovskite structured materials (e.g.
BiFeO3, CsSnI3, CH3NH3PbI3) in solar cells emphasises that polar semiconductors
can be used in conventional photovoltaic architectures. We review developments
in this field, with a particular emphasis on the materials known to display the
APE/BPE (e.g. ZnS, CdTe, SbSI), and the theoretical explanation. Critical
analysis is complemented with first-principles calculation of the underlying
electronic structure. In addition to discussing the implications of a
ferroelectric absorber layer, and the solid state theory of polarisation (Berry
phase analysis), design principles and opportunities for high-efficiency
ferroelectric photovoltaics are presented