In situ monitoring of atomic layer epitaxy via optical ellipsometry

We report on the use of time-resolved optical ellipsometry to monitor the deposition of single atomic layers with subatomic sensitivity. Ruddlesden–Popper thin films of SrO(SrTiO3) n=4 were grown by means of metalorganic aerosol deposition in the atomic layer epitaxy mode on SrTiO3(1 0 0), LSAT(1 0 0) and DyScO3(1 1 0) substrates. The measured time dependences of ellipsometric angles, Δ(t) and Ψ(t), were described by using a simple optical model, considering the sequence of atomic layers SrO and TiO2 with corresponding bulk refractive indices. As a result, valuable online information on the atomic layer epitaxy process was obtained. Ex situ characterization techniques, i.e. transmission electron microscopy, x-ray diffraction and x-ray reflectometry verify the crystal structure and confirm the predictions of optical ellipsometry

Strain-Driven Structure-Ferroelectricity Relationship in hexagonal TbMnO3_3 Films

Thin films and heterostructures of hexagonal manganites as promising multiferroic materials have attracted a considerable interest recently. We report structural transformations of high quality epitaxial h-TMO/YSZ(111) films, analyzed by means of various characterization techniques. A phase transition from P63mc to P63mcm structure at TC~800 K was observed by temperature dependent Raman spectroscopy and optical ellipsometry. The latter probing directly electronic system, indicates its modification at the structural phase transition likely due to charge transfer from oxygen to Mn. In situ transmission electron microscopy (TEM) of the lamella samples displayed an irreversible P63mc-P63mcm transformation and vanishing of ferroelectric domains already at 410 K. After the temperature cycling (300K-1300K-300K) the room temperature TEM of h-TMO films revealed an inhomogeneous microstructure, containing ferroelectric and paraelectric nanodomains with P63mc and P63mcm structure, respectively. We point out a strong influence of stress relaxation, induced by temperature and by constrained sample geometry onto the structure and ferroelectricity in strain-stabilized h-TMO thin films.Comment: 24 pages, 10 figure

Probing the bulk ionic conductivity by thin film hetero-epitaxial engineering

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO3 and SrTiO3 grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO2 and 8 mol% Y2O3 stabilized ZrO2 are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity. © 2015 National Institute for Materials Science

The structure of thin zirconia films obtained by self-assembled monolayer mediated deposition: TEM and HREM study

Transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS) and energy dispersive X-ray analysis (EDX) have been performed on thin zirconia films produced by means of self-assembled monolayer (SAM) mediated deposition from aqueous zirconium sulphate dispersion at 50°C. As-grown films were found to be amorphous. Electron beam irradiation can induce the crystallization of as-grown amorphous zirconia films to tetragonal polycrystalline ZrO2 films. EELS revealed changes in the oxygen K-edge peak caused by the beam-induced structural transition of the amorphous phase to tetragonal ZrO2