The low solubility of Mn (equilibrium limit of 13 %) and precipitation of Mn oxides at slightly higher Mn doping (> 4 %) have remained major obstacles in the growth of Mn doped ZnO (ZnO:Mn) thin films for potential spintronic applications. In this work, epitaxial ZnO:Mn thin films were deposited on c-cut Al₂O₃ (0001) substrates, with increasing Mn concentrations from 2 to 12 %, using the dual-laser ablation process. In this process, an excimer (KrF) laser and a CO₂ laser pulses are spatially and temporally overlapped onto the target surface. Initially the target is heated by the CO₂ laser to produce a transient molten layer, from which the slightly time-delayed KrF laser initiates the ablation. Ablation for a momentary liquid target not only results in a drastic reduction of particulates in the deposited films but also overcomes the problem of non-congruent ablation of the ZnO:Mn target, leading to stoichiometric film deposition. Moreover, the optimum coupling of the laser energies produces an ablation plume that has a broader angular distribution, compared to the plume generated by KrF pulse alone, as observed from the intensified-charge-coupled-detector (ICCD) images of the ablated plumes. This allows the deposition of uniform films over larger area. Further, the higher ionization of the ablated species as seen in the optical emission spectra (OES) of the dual-laser ablated plumes leads to enhanced gas phase reaction and better film morphology and crystallinity. X-ray diffraction studies revealed that the dual-laser deposited ZnO:Mn films were single crystalline with no secondary phase formation even at 12 % doping while single-laser deposited ZnO:Mn films showed secondary Mn oxide phases. Room temperature magnetic measurements showed ferromagnetism (FM) with enhanced saturation magnetization (M_s) values from 1.3 emu/cm³ for 2 % ZnO:Mn films to 2.9 emu/cm³ for 12 % ZnO:Mn films. In- and out-of-plane magnetization revealed absence of magnetic anisotropy. Further, temperature dependent Hall measurements showed a strong correlation between the effective carrier densities and the observed FM. All these measurements suggested a carrier mediated mechanism of FM in ZnO:Mn thin films. Using both the experimental data and theoretical analysis the FM in less conducting ZnO:Mn films was described by a bound magnetic polaron model whereas that in highly conducting films was consistent with a carrier mediated interaction via RKKY exchange mechanism.

Transition metal oxides (TMO) offer various functionalities ranging from electronic devices to environmental catalysts [1, 2]. Often, the central part of such devices is the interface between different materials. In order to improve their device performance, control of charge transport across these interfaces is essential. Originally developed in semiconductor heterostructures, interface band alignment control is based on the interface electrostatic boundary conditions and is one of the most fundamental methods to tune the carrier transport across interfaces [3]. Given their strongly ionic nature and their accessibility to multiple valence states, the TMO interface should be more suitable than covalent semiconductors for manipulating interface band alignments. Here we focus on epitaxial metal-semiconductor Schottky interfaces between perovskite oxides to demonstrate the effectiveness of this technique. I will present two SrTiO₃ based perovskite Schottky junctions in which the interface energy barriers were modulated by interface dipoles controlled on the atomic scale [4]. Further, I will present the application of this technique in the form of an all-oxide hot electron transistor [5].

2. J. Suntivich et al., Science 334, 1383 (2011).

3. F. Capasso et al., Appl. Phys. Lett. 46, 664 (1985).

5. T. Yajima et al., Nature Mater. 10, 198 (2011).

The design of surfaces with controlled stiffness is attractive for a variety of applications ranging from controlling cell growth to mechanical and electrical engineering design. Here, the creation of layered composites with tunable surface stiffness has been achieved by coating a soft PDMS polymer with a stiff film of amorphous titanium oxide with thickness varying from 2 to 50 nm. The oxide layer is smooth (6 nm rms roughness at 2 µm² image size), and crack-free. Air plasma treatment was used to form a silica surface layer on the soft polymer base to promote of adhesion of the titania overlayer. To gain insight into the mechanics of the layered structure, nanomechanical quantification has been performed using different experimental approaches, as well as modeling studies. The surface mechanical properties of the samples have been probed using both instrumented nanoindentation and atomic force microscopy—based nanomechanical characterization. These results have been compared to finite element analysis (FEA) simulations.

By fitting the FEA simulations with experimental curves it is shown that the hard titania film and softer PDMS substrate individually maintain their characteristic elastic moduli, while the stiffness of the vertical nanocomposite can be controllably modified by changing the thickness of the stiff layer. Liquid phase deposition of the oxide allows control of its thickness at the nm level. During an indentation cycle, the stiff layer transmits the stress to the underlying PDMS base by deformation of its overall shape, but only negligible compression of the film thickness.

This synthetic approach can be quite versatile, and can, in principle, be extended to different oxides and a wide range of thicknesses. It allows control of surface properties while maintaining bulk material properties. This exploratory work is a first step towards defining the range of surface stiffnesses that can be achieved in this way, as well as developing general methodologies for their characterization.