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.

The polarization of PbTiO3/SrTiO3 superlattices is experimentally tuned from 0-60 mu C/cm(-2) and the transition temperature from room temperature to 1000 K while maintaining a perfect crystal structure and low leakage currents (see figure). A simple model based on Landau theory is developed as a guide for the straightforward production of samples with ferroelectric properties designed for particular applications

The dielectric response of PbTiO(3)/SrTiO(3) superlattices is studied using electrical and structural measurements. While the dielectric response of paraelectric superlattices is well accounted for by the lattice contribution, superlattices with ferroelectric compositions exhibit an enhanced permittivity. X-ray diffraction allowed the presence of ordered nanodomains in ferroelectric superlattices to be established and their displacement under an applied bias to be directly probed, demonstrating that the enhanced permittivity in these artificial materials is due to domain wall motion.

Strain relaxation and the ferroelectric critical temperature were investigated in a series of epitaxial Pb͑Zr 0.20 Ti 0.80 ͒O 3 thin films of different thicknesses grown on metallic 0.5% Nb-doped SrTiO 3 substrates. Detailed x-ray diffraction studies reveal that strain relaxation progressively occurs via misfit dislocations as the film thickness is increased from fully coherent films ͑for films below 150 Å͒ to essentially relaxed films ͑for thicknesses above typically 800 Å͒. It is found that this change in the strain state does not modify the ferroelectric critical temperature which is found for all the samples to be around 680°C, a value much higher than the bulk.

Electrochemistry and surface water redox reactions on Pb(Zr0.2,Ti0.8)O3 ferroelectric thin films as a function of polarization and external electric field, as studied by AP-XPS and KPFM.