Transport, magnetic, and structural properties of La0.7_{0.7}Ce0.3_{0.3}MnO3_3 thin films. Evidence for hole-doping

Cerium-doped manganite thin films were grown epitaxially by pulsed laser deposition at $720 ^\circ$C and oxygen pressure $p_{O_2}=1-25$Pa and were subjected to different annealing steps. According to x-ray diffraction (XRD) data, the formation of CeO$_2$ as a secondary phase could be avoided for $p_{O_2}\ge 8$Pa. However, transmission electron microscopy shows the presence of CeO$_2$ nanoclusters, even in those films which appear to be single phase in XRD. With O$_2$ annealing, the metal-to-insulator transition temperature increases, while the saturation magnetization decreases and stays well below the theoretical value for electron-doped La$_{0.7}$Ce$_{0.3}$MnO$_3$ with mixed Mn$^{3+}$/Mn$^{2+}$ valences. The same trend is observed with decreasing film thickness from 100 to 20 nm, indicating a higher oxygen content for thinner films. Hall measurements on a film which shows a metal-to-insulator transition clearly reveal holes as dominating charge carriers. Combining data from x-ray photoemission spectroscopy, for determination of the oxygen content, and x-ray absorption spectroscopy (XAS), for determination of the hole concentration and cation valences, we find that with increasing oxygen content the hole concentration increases and Mn valences are shifted from 2+ to 4+. The dominating Mn valences in the films are Mn$^{3+}$ and Mn$^{4+}$, and only a small amount of Mn$^{2+}$ ions can be observed by XAS. Mn$^{2+}$ and Ce$^{4+}$ XAS signals obtained in surface-sensitive total electron yield mode are strongly reduced in the bulk-sensitive fluorescence mode, which indicates hole-doping in the bulk for those films which do show a metal-to-insulator transition.Comment: 8 pages, 10 figure

Electronically coupled complementary interfaces between perovskite band insulators

Perovskite oxides exhibit a plethora of exceptional electronic properties, providing the basis for novel concepts of oxide-electronic devices. The interest in these materials is even extended by the remarkable characteristics of their interfaces. Studies on single epitaxial connections between the two wide-bandgap insulators LaAlO3 and SrTiO3 have revealed them to be either high-mobility electron conductors or insulating, depending on the atomic stacking sequences. In the latter case they are conceivably positively charged. For device applications, as well as for basic understanding of the interface conduction mechanism, it is important to investigate the electronic coupling of closely-spaced complementary interfaces. Here we report the successful realization of such electronically coupled complementary interfaces in SrTiO3 - LaAlO3 thin film multilayer structures, in which the atomic stacking sequence at the interfaces was confirmed by quantitative transmission electron microscopy. We found a critical separation distance of 6 perovskite unit cell layers, corresponding to approximately 2.3 nm, below which a decrease of the interface conductivity and carrier density occurs. Interestingly, the high carrier mobilities characterizing the separate electron doped interfaces are found to be maintained in coupled structures down to sub-nanometer interface spacing

Optimized fabrication of high quality La0.67Sr0.33MnO3 thin films considering all essential characteristics

In this article, an overview of the fabrication and properties of high quality La0.67Sr0.33MnO3 (LSMO) thin films is given. A high quality LSMO film combines a smooth surface morphology with a large magnetization and a small residual resistivity, while avoiding precipitates and surface segregation. In literature, typically only a few of these issues are adressed. We therefore present a thorough characterization of our films, which were grown by pulsed laser deposition. The films were characterized with reflection high energy electron diffraction, atomic force microscopy, x-ray diffraction, magnetization and transport measurements, x-ray photoelectron spectroscopy and scanning transmission electron microscopy. The films have a saturation magnetization of 4.0 {\mu}B/Mn, a Curie temperature of 350 K and a residual resistivity of 60 {\mu}{\Omega}cm. These results indicate that high quality films, combining both large magnetization and small residual resistivity, were realized. A comparison between different samples presented in literature shows that focussing on a single property is insufficient for the optimization of the deposition process. For high quality films, all properties have to be adressed. For LSMO devices, the thin film quality is crucial for the device performance. Therefore, this research is important for the application of LSMO in devices.Comment: Accepted for publication in Journal of Physics D - Applied Physic

Combination of HAADF-STEM and ADF-STEM Tomography for Core–Shell Hybrid Materials

Characterization of core–shell type nanoparticles in 3D by transmission electron microscopy (TEM) can be very challenging. Especially when both heavy and light elements coexist within the same nanostructure, artifacts in the 3D reconstruction are often present. A representative example would be a particle comprising an anisotropic metallic (Au) nanoparticle coated with a (mesoporous) silica shell. To obtain a reliable 3D characterization of such an object, a dose-efficient strategy is proposed to simultaneously acquire high-angle annular dark-field scanning TEM and annular dark-field tilt series for tomography. The 3D reconstruction is further improved by applying an advanced masking and interpolation approach to the acquired data. This new methodology enables us to obtain high-quality reconstructions from which also quantitative information can be extracted. This approach is broadly applicable to investigate hybrid core–shell materials

Geometric reconstruction methods for electron tomography

Electron tomography is becoming an increasingly important tool in materials science for studying the three-dimensional morphologies and chemical compositions of nanostructures. The image quality obtained by many current algorithms is seriously affected by the problems of missing wedge artefacts and nonlinear projection intensities due to diffraction effects. The former refers to the fact that data cannot be acquired over the full $180^\circ$ tilt range; the latter implies that for some orientations, crystalline structures can show strong contrast changes. To overcome these problems we introduce and discuss several algorithms from the mathematical fields of geometric and discrete tomography. The algorithms incorporate geometric prior knowledge (mainly convexity and homogeneity), which also in principle considerably reduces the number of tilt angles required. Results are discussed for the reconstruction of an InAs nanowire

Three dimensional mapping of Fe dopants in ceria nanocrystals using direct spectroscopic electron tomography

Electron tomography is a powerful technique for the 3D characterization of the morphology of nanostructures. Nevertheless, resolving the chemical composition of complex nanostructures in 3D remains challenging and the number of studies in which electron energy loss spectroscopy (EELS) is combined with tomography is limited. During the last decade, dedicated reconstruction algorithms have been developed for HAADF-STEM tomography using prior knowledge about the investigated sample. Here, we will use the prior knowledge that the experimental spectrum of each reconstructed voxel is a linear combination of a well-known set of references spectra in a so-called direct spectroscopic tomography technique. Based on a simulation experiment, it is shown that this technique provides superior results in comparison to conventional reconstruction methods for spectroscopic data, especially for spectrum images containing a relatively low signal to noise ratio. Next, this technique is used to investigate the spatial distribution of Fe dopants in Fe:Ceria nanoparticles in 3D. It is shown that the presence of the Fe2+ dopants is correlated with a reduction of the Ce atoms from Ce4+ towards Ce3+. In addition, it is demonstrated that most of the Fe dopants are located near the voids inside the nanoparticle

Interplay of Doping and Structural Modulation in Superconducting Bi2Sr2-xLaxCuO6+d thin films

We have studied the evolution of the structural modulation in epitaxial, c-axis oriented, Bi2Sr2-xLaxCuO6+d thin films when varying the La content x and for a given x as a function of oxygen content. A series of thin films with 0<x<0.8 have been prepared in-situ by rf magnetron sputtering and characterized by R(T) measurements and RBS, TEM and X-Ray diffraction techniques. The oxygen content of each individual film was varied by thermal annealing across the phase diagram. The evolution of the structural modulation has been thoroughly studied by X-Ray diffraction in determining the variation of the amplitude of satellite reflections in special 2 axes 2theta /theta-theta scans (reciprocal space scans). It is shown that the amplitude of the modulation along the c-axis decreases strongly when x increases from 0 to 0.2. It is demonstrated that this variation is essentially governed by La content x and that changing the oxygen content by thermal treatments has a much lower influence, even becoming negligible for x>0.2. Such study is important to understand the electronical properties of Bi2Sr2-xLaxCuO6+d thin films.Comment: 25 pages with 10 figures, accepted for publication in Phys.Rev.