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The integration of ferroelectric oxide films into microelectronic devices, combined with the size reduction constraints imposed by the semiconductor industry, have revived interest in the old question concerning the possible existence of a critical thickness for ferroelectricity. Current experimental techniques have allowed the detection of ferroelectricity in perovskite films down to a thickness of 40 A (ten unit cells), ref. 3. Recent atomistic simulations have confirmed the possibility of retaining the ferroelectric ground state at ultralow thicknesses, and suggest the absence of a critical size. Here we report first-principles calculations on a realistic ferroelectric-electrode interface. We show that, contrary to current thought, BaTiO3 thin films between two metallic SrRuO3 electrodes in short circuit lose their ferroelectric properties below a critical thickness of about six unit cells (approximately 24 A). A depolarizing electrostatic field, caused by dipoles at the ferroelectric-metal interfaces, is the reason for the disappearance of the ferroelectric instability. Our results suggest the existence of a lower limit for the thickness of useful ferroelectric layers in electronic devices.

Complex transition metal oxides span a wide range of crystalline structures and play host to an incredible variety of physical phenomena. High dielectric permittivities, piezo-, pyro-, and ferroelectricity are just a few of the functionalities offered by this class of materials, while the potential for applications of the more exotic properties like high temperature superconductivity and colossal magnetoresistance is still waiting to be fully exploited. With recent advances in deposition techniques, the structural quality of oxide heterostructures now rivals that of the best conventional semiconductors, taking oxide electronics to a new level. Such heterostructures have enabled the fabrication of artificial multifunctional materials. At the same time they have exposed a wealth of phenomena at the boundaries where compounds with different structural instabilities and electronic properties meet, giving unprecedented access to new physics emerging at oxide interfaces. Here we highlight some of these exciting new interface phenomena.

Ferroelectric thin films and superlattices are currently the subject of intensive research because of the interest they raise for technological applications and also because their properties are of fundamental scientific importance. Ferroelectric superlattices allow the tuning of the ferroelectric properties while maintaining perfect crystal structure and a coherent strain, even throughout relatively thick samples. This tuning is achieved in practice by adjusting both the strain, to enhance the polarization, and the composition, to interpolate between the properties of the combined compounds. Here we show that superlattices with very short periods possess a new form of interface coupling, based on rotational distortions, which gives rise to 'improper' ferroelectricity. These observations suggest an approach, based on interface engineering, to produce artificial materials with unique properties. By considering ferroelectric/paraelectric PbTiO3/SrTiO3 multilayers, we first show from first principles that the ground-state of the system is not purely ferroelectric but also primarily involves antiferrodistortive rotations of the oxygen atoms in a way compatible with improper ferroelectricity. We then demonstrate experimentally that, in contrast to pure PbTiO3 and SrTiO3 compounds, the multilayer system indeed behaves like a prototypical improper ferroelectric and exhibits a very large dielectric constant of epsilon(r) approximately 600, which is also fairly temperature-independent. This behaviour, of practical interest for technological applications, is distinct from that of normal ferroelectrics, for which the dielectric constant is typically large but strongly evolves around the phase transition temperature and also differs from that of previously known improper ferroelectrics that exhibit a temperature-independent but small dielectric constant only.