The current best performing p-type transparent conducting oxides are typically highly crystalline materials, deposited at high temperatures, and hence incompatible with the drive to low cost flexible electronics. We investigated a nanocrystalline, copper deficient CuxCrO2, deposited at low temperatures upon a flexible polyimide substrate. The as-deposited film without post annealing has an electrical conductivity of 6Scm−1. We demonstrate that this p-type transparent oxide retains its excellent electrical conductivity under tensile strain, withstanding more than one thousand bending cycles without visible cracks or degradation in electrical properties. In contrast, compressive strain is shown to lead to an immediate reduction in conductivity which we attribute to a de-lamination of the thin film from the substrate.
The delafossite structured CuCrO2 system is well known as p-type transparent conducting oxide. We have synthesized a Cu deficient form at low process temperature maintaining its good conductive properties.
The valence band structure of p-type transparent oxides-crystalline MgxCr2-xO3 and nanocrystalline CuxCrOy-is analyzed as a function of incoming photon energy. The valence band of both p-type transparent conducting oxides shows striking similarities to measurements on crystalline CuCrO2:Mg with all films showing that chromium states compose the top of the valence band, suggesting that the valence-band structure is dominated by the presence of the Cr-O-6 octahedra. A comparison of the valence band between the best performing p-type, crystalline CuCrO2:Mg, with crystalline MgxCr2-xO3 and nanocrystalline CuxCrOy shows that the chromium 3d states are fixed irrespective of changes in long-range crystallographic order. This indicates little spatial overlap between adjacent Cr 3d states. This further confirms the conduction mechanism via hopping for chromium based p-type TCOs as the Cr 3d states are localized within the Cr-O-6 octahedra.
We demonstrate an alternative approach to tuning the refractive index of materials. Current methodologies for tuning the refractive index of a material often result in undesirable changes to the structural or optoelectronic properties. By artificially layering a transparent conducting oxide with a lower refractive index material the overall film retains a desirable conductivity and mobility while acting optically as an effective medium with a modified refractive index. Calculations indicate that, with our refractive index change of 0.2, a significant reduction of reflective losses could be obtained by the utilisation of these structures in optoelectronic devices. Beyond this, periodic superlattice structures present a solution to decouple physical properties where the underlying electronic interaction is governed by different length scales.
In this letter, we demonstrate a low temperature (≈345 °C) growth method for Cu deficient CuCrO2 performed by spray pyrolysis using metal-organic precursors and a simple air blast nozzle. Smooth films were grown on glass substrates with a highest conductivity of 12 S/cm. The most conductive samples retain transparencies above 55% resulting in a figure of merit as high as 350 μS, which is the best performing p-type transparent conducting material grown by solution methods to date. Remarkably, despite the nano-crystallinity of the films, properties comparable with crystalline CuCrO2 are observed. No postannealing of the films is required in contrast to previous reports on crystalline material. The low processing temperature of this method means that the material can be deposited on flexible substrates. As this is a solution based technique, it is more attractive to industry as physical vapour deposition methods are slow and costly in comparison.
We present an analysis of the Raman spectra of p-type transparent conducting Cr2O3:Mg grown by various techniques including spray pyrolysis, pulsed laser deposition, molecular beam epitaxy and reactive magnetron sputtering. The best performing films show a distinct broad range Raman signature related to defect-induced vibrational modes not seen in stoichiometric, undoped material. Our comparative study demonstrates that Raman spectroscopy can quantify unwanted dopant clustering in the material at high Mg concentrations, while also being sensitive to the Mg incorporation site. By correlating the Raman signature to the electrical properties of the films, growth processes can be optimised to give the best conducting films and the local defect structure for effective p-type doping can be studied.
Epitaxial p-type transparent conducting oxide (TCO) Cr2O3:Mg was grown by electron-beam evaporation in a molecular beam epitaxy system on c-plane sapphire. The influence of Mg dopants and the oxygen partial pressure were investigated by thermoelectric and electrical measurements. The conduction mechanism is analyzed using the small-polaron hopping model, and hopping activation energies have been determined, which vary with doping concentration in the range of 210-300 +/- 5 meV. Films with better conductivity were obtained by postannealing. The effect of postannealing is discussed in terms of a crystallographic reordering of the Mg dopant. The highest Seebeck mobilities obtained from thermoelectric measurements are of the order of 10(-4) cm(2)V(-1)s(-1). We investigate the fundamental properties of a Mg dopant in a high crystalline quality epitaxial film of a binary oxide, helping us understand the role of short range crystallographic order in a p-type TCO in detail.
Recently, significant attention has been paid to the resistance switching (RS) behaviour in Fe3O4 and it was explained through the analogy of the electrically driven metal-insulator transition based on the quantum tunneling theory. Here, we propose a method to experimentally support this explanation and provide a way to tune the critical switching parameter by introducing self-aligned localized impurities through the growth of Fe3O4 thin films on stepped SrTiO3 substrates. Anisotropic behavior in the RS was observed, where a lower switching voltage in the range of 10(4) V cm(-1) is required to switch Fe3O4 from a high conducting state to a low conducting state when the electrical field is applied along the steps. The anisotropic RS behavior is attributed to a high density array of anti-phase boundaries (APBs) formed at the step edges and thus are aligned along the same direction in the film which act as a train of hotspot forming conduits for resonant tunneling. Our experimental studies open an interesting window to tune the electrical-field-driven metal-insulator transition in strongly correlated systems.
We present a comparative study of the anomalous Nernst effect (ANE), measured at room temperature for magnetite thin films deposited on different substrates in order to study the effects induced by the substrate, compressive or tensile strain and structural defects as anti-phase boundaries (APB), on the observed ANE. From our preliminary results we have observed an increase of the measured ANE in the case of compressive strain compared with the tensile one. Moreover our results also suggest that the density of APBs also play an important role in the ANE values.
Reflectance anisotropy spectroscopy (RAS) has been used to measure the optical anisotropies of bulk and thin-film Fe3O4(110) surfaces. The spectra indicate that small shifts in energy of the optical transitions, associated with anisotropic strain or electric field gradients caused by the (110) surface termination or a native oxide layer, are responsible for the strong signal observed. The RAS response was then measured as a function of temperature. A distinct change in the RAS line-shape amplitude was observed in the spectral range from 0.8 to 1.6 eV for temperatures below the Verwey transition of the crystal. Finally, thin-film magnetite was grown by molecular beam epitaxy on MgO(110) substrates. Changes in the RAS spectra were found for different film thickness, suggesting that RAS can be used to monitor the growth of magnetite (110) films in situ. The thickness dependence of the RAS is discussed in terms of various models for the origin of the RAS signal.
Atomic layer deposition is a promising technique to deposit conformal, nm-thin metal barriers in high-aspect-ratio trenches. However, exactly because of its excellent conformality, the deposition can also occur inside the nanopores of the most advanced low-k materials. In this work, the mechanisms of atomic layer deposition on and in low-k, porous dielectric films were studied, using HfO2 as a test material. Exhaustive analyses showed firstly that the HfCl4 precursor penetrated uniformly in the pores throughout a 44 nm thick low-k film. Secondly, it was shown that the pores were sealed as function of precursor size, i.e. there are conditions where the pores became inaccessible for HfCl4, while the - smaller - H2O molecules could still penetrate the pores. From these analyses, a deposition model was proposed. (C) 2013 Elsevier B.V. All rights reserved.
Nanoporous low-kappa films were manufactured by using a 3-step process: co-deposition of a skeleton and porogens by PECVD, porogen removal by remote plasma and UV cure. In this study, the influence of both the variation of the porogen load and the different types of UV-cures on several film characteristics were investigated. Improved kappa-values were observed for increased porogen to skeleton ratios and a broad band cure, where the wavelength of the photons is always higher than 200 nm. However the Young's modulus and hardness decreased correspondingly. These variations can be attributed to the changing density and chemical composition of the different films. A wide range of low-kappa films was obtained by tuning the porogen load and applying different types of UV cures.
Atomic layer deposition is a promising technique to deposit conformal, nm-thin metal barriers in high aspect ratio trenches. However, exactly because of its excellent conformality, the deposition can also occur inside the nanopores of the most advanced low-k materials. In this work, the mechanisms of atomic layer deposition on and in low-k, porous dielectric films were studied, using HfO2 as a test material. Exhaustive analyses showed firstly that the HfCl4 precursor penetrated uniformly in the pores throughout a 44 nm low-k film. Secondly it is shown that the pores were sealed as function of precursor size, i.e. there are conditions where the pores became inaccessible for HfCl4, while the - smaller - H2O molecules could still penetrate the pores. From these analyses a deposition model was proposed.