Bismuth ferrite layers, ∼200-nm-thick, are deposited on SrRuO3-coated DyScO3(110)o substrates in a step-flow growth regime via adsorption-controlled molecular-beam epitaxy. Structural characterization shows the films to be phase pure with substrate-limited mosaicity (0.012° x-ray diffraction ω-rocking curve widths). The film surfaces are atomically smooth (0.2 nm root-mean-square height fluctuations) and consist of 260-nm-wide [11¯1]o-oriented terraces and unit-cell-tall (0.4 nm) step edges. The combination of electrostatic and symmetry boundary conditions promotes two monoclinically distorted BiFeO3 ferroelectric variants, which self-assemble into a pattern with unprecedentedly coherent periodicity, consisting of 145 ± 2-nm-wide stripe domains separated by [001]o-oriented 71° domain walls. The walls exhibit electrical rectification and enhanced conductivity.
