Double perovskites (DP, A2BB’O6) exhibit a breadth of multifunctional properties with a huge potential range of applications, including magneto-optic and spintronic devices. However, spontaneous cation ordering is limited by the similar size and charge of B and B’ cations. We introduce a route to stimulate B-site rock-salt ordering. By growing thin films on (111)-oriented substrates, ‘in-plane’ strain acts on the intrinsically tilted oxygen octahedra of the DP and produces two different B-site cages (in size and shape), stimulating spontaneous cation ordering. For the ferromagnetic insulator La2CoMnO6, clear Co/Mn ordering was achieved by growing on (111)-oriented substrates. The difference in B-site cages was further enhanced when grown under minor (111) in-plane compressive strain, resulting in long-range ordering with a saturation magnetization of 5.8 μB/formula unit (f.u.), close to the theoretical 6 μB/f.u., without antiferromagnetic behavior. Our approach enables the study of many new ordered DPs which have never been made before.This work was supported by the European Research Council (ERC) (Advanced Investigator grant ERC-2009-AdG-247276-NOVOX), the EPSRC (Equipment Account Grant EP/K035282/1) and the Isaac Newton Trust (Minute 13.38(k)). LJ thank the support of the European Union Seventh Framework Programme under Grant Agreement 312483—ESTEEM2 (Integrated Infrastructure Initiative-I3). SuperSTEM is the UK National Facility for Aberration Corrected STEM funded by EPSRC
