An in Situ Study of Precursor Decomposition via Refractive Index Sensing in p-Type Transparent Copper Chromium Oxide

Oxide semiconductors are penetrating into a wide range of energy, environmental, and electronic applications, possessing a potential to outrun currently employed semiconductors. However, an insufficient development of p-type oxides is a major obstacle against complete oxide electronics. Quite often oxide deposition is performed by the spray pyrolysis method, inexpensive to implement and therefore accessible to a large number of laboratories. Although, the complex growth chemistry and a lack of in situ monitoring during the synthesis process can complicate the growth optimization of multicomponent oxides. Here we present a concept of plasmonic, optical sensing that has been applied to spray pyrolysis oxide film growth monitoring for the first time. The proposed method utilizes a polarization based refractive index sensing platform using Au nanodimers as transducing elements. As a proof of concept, the changes in the refractive index of the grown film were extracted from individual Cu(acac)2 and Cr(acac)3 precursors in real time to reveal their thermal decomposition processes. Obtained activation energies give insight into the physical origin of the narrow temperature window for the synthesis of high performing p-type transparent conducting copper chromium oxide CuxCrO2. The versatility of the proposed method makes it effective in the growth rate monitoring of various oxides, exploring new candidate materials and optimizing the synthesis conditions for acquisition of high performing oxides synthesized by a high throughput cost-effective method

Reconciling the theoretical and experimental electronic structure of NbO2

Metal-insulator transition materials such as NbO2 have generated much excitement in recent years for their potential applications in computing and sensing. NbO2 has generated considerable debate over the nature of the phase transition, and the values for the band gap/band widths in the insulating phase. We present a combined theoretical and experimental study of the band gap and electronic structure of the insulating phase of NbO2. We carry out ab-initio density functional theory plus U calculations, directly determining U and J parameters for both the Nb 4d and O 2p subspaces through the recently introduced minimum-tracking linear response method. We find a fundamental bulk band gap of 0.80 eV for the full DFT+U+J theory. We also perform calculations and measurements for a (100) oriented thin film. Scanning tunnelling spectroscopy measurements show that the surface band gap varies from 0.75 eV to 1.35 eV due to an excess of oxygen in and near the surface region of the film. Slab calculations indicate metallicity localised at the surface region caused by an energy level shift consistent with a reduction in Coulomb repulsion. We demonstrate that this effect in combination with the simple, low cost DFT+U+J method can account for the band widths and p-d gap observed in X-ray photoelectron spectroscopy experiments. Overall, our results indicate the possible presence of a 2D anisotropic metallic layer at the (100) surface of NbO2.Comment: 11 pages, 5 figures, plus 3 pages of Supporting Informatio

Unravelling the atomic and electronic structure of nanocrystals on superconducting Nb(110): Impact of the oxygen monolayer

The Niobium surface is almost always covered by a native oxide layer which greatly influences the performance of superconducting devices. Here we investigate the highly stable Niobium oxide overlayer of Nb(110), which is characterised by its distinctive nanocrystal structure as observed by scanning tunnelling microscopy (STM). Our ab-initio density functional theory (DFT) calculations show that a subtle reconstruction in the surface Niobium atoms gives rise to rows of 4-fold coordinated oxygen separated by regions of 3-fold coordinated oxygen. The 4-fold oxygen rows are determined to be the source of the nanocrystal pattern observed in STM, and the two chemical states of oxygen observed in core-level X-ray photoelectron spectroscopy (XPS) are ascribed to the 3-fold and 4-fold oxygens. Furthermore, we find excellent agreement between the DFT calculated electronic structure with scanning tunnelling spectroscopy and valence XPS measurements.Comment: 8 pages, 4 figures, plus 3 pages of Supporting Informatio

Oxidation of Nb(110): atomic structure of the NbO layer and its influence on further oxidation.

NbO terminated Nb(110) and its oxidation are examined by scanning tunneling microscopy and spectroscopy (STS). The oxide structures are strongly influenced by the structural and electronic properties of the underlying NbO substrate. The NbO is terminated by one-dimensional few-nanometer nanocrystals, which form an ordered pattern. High-resolution STS measurements reveal that the nanocrystals and the regions between the nanocrystals exhibit different electronic characters. Low-dosage oxidation, sufficient for sub-monolayer coverage of the NbO, with subsequent UHV annealing results in the formation of resolved sub-nanometer clusters, positioned in-between the nanocrystals. Higher dosage oxidation results in the formation of a closed Nb2O5-y layer, which is confirmed by X-ray photoelectron spectroscopy measurements. The pentoxide is amorphous at the atomic-scale. However, large scale (tens of nanometers) structures are observed with their symmetry matching that of the underlying nanocrystals

Optical Anisotropy of SrTiO3(110) for Different Surface Terminations

In this work we investigate the SrTiO3(110) surface by reflectance anisotropy spectroscopy (RAS) at varying preparation steps including ex situ wet etching, high temperature oxygen annealing, as well as in situ vacuum annealing. Different surface terminations show distinctly different RAS spectra which are correlated to an altered surface stoichiometry measured by X?ray photoelectron spectroscopy (XPS) and an altered valence band structure measured by UV?photoelectron spectroscopy (UPS) in cases of conductive samples. We link the changes in the observed RAS spectra to various surface reconstructions, with particular focus of the signature of (3???1) and (1???4) reconstructed surfaces, and a metallic surface state observed in vacuum annealed SrTiO3

Low-Cost, High-Performance Spray Pyrolysis-Grown Amorphous Zinc Tin Oxide: The Challenge of a Complex Growth Process

Transparent conductive oxides (TCOs) are important materials for a wide range of optoelectronic devices. Amorphous zinc tin oxide (a-ZTO) is a TCO and one of the best nontoxic, low-cost replacements for more expensive amorphous indium-gallium-zinc oxide. Here, we employ spray pyrolysis (SP), an inexpensive and versatile chemical vapor deposition-based technique, to synthesize a-ZTO with an as-deposited conductivity of ?300 S/cm?the highest value hitherto among the reported solution-processed films. Compositional analysis via X-ray photoelectron spectroscopy reveals a nonstoichiometric transfer of Zn and Sn from the dissolved precursors into the film, with the best electrical properties achieved at a film composition of xfilm = 0.38 ? 0.04 ((ZnO)x(SnO2)1?x (0 < x < 1)). The morphology of these films is compared to films synthesized by physical vapor deposition (PVD), and a strong correlation between morphology and electrical properties is revealed. The granular nature of the SP-grown films, which seems like a drawback at first glance, brings about the prospect of using a-ZTO in ink-jet-printed films from a nanoparticle suspension for the room-temperature deposition. Brief post-anneal cycles in N2 gas improve the conductivity of the films by means of grain boundary (GB) passivation

SOLUTION-BASED DEPOSITION OF TRANSPARENT EU-DOPED TITANIUM OXIDE THIN FILMS FOR POTENTIAL SECURITY LABELING AND UV SCREENING

Transparent titanium oxide thin films attract enormous attention from the scientific community because of their prominent properties, such as low-cost, chemical stability, and optical transparency in the visible region. In this study, we developed an easy and scalable solution-based process for the deposition of transparent TiOx thin films on glass substrates. We showed that the proposed method is also suitable for the fabrication of metal-doped TiOx thin films. As proof-of-the-concept, europium Eu(III) ions were introduced into TiOx film. A photoluminescence (PL) study revealed that Eu-doped TiOx thin films showed strong red luminescence associated with 5D0→7Fj relaxation transitions in Eu (III). We found that prepared TiOx thin films significantly reduce the transmittance of destructive UV radiation; a feature that can be useful for the protection of photovoltaic devices. In addition, transparent and luminescent TiOx thin films can be utilized for potential security labeling

VOx Phase Mixture of Reduced Single Crystalline V2O5: VO2 Resistive Switching

The strongly correlated electron material, vanadium dioxide (VO2), has seen considerable attention and research application in metal-oxide electronics due to its metal-to-insulator transition close to room temperature. Vacuum annealing a V2O5(010) single crystal results in Wadsley phases (VnO2n+1, n &gt; 1) and VO2. The resistance changes by a factor of 20 at 342 K, corresponding to the metal-to-insulator phase transition of VO2. Macroscopic voltage-current measurements with a probe separation on the millimetre scale result in Joule heating-induced resistive switching at extremely low voltages of under a volt. This can reduce the hysteresis and facilitate low temperature operation of VO2 devices, of potential benefit for switching speed and device stability. This is correlated to the low resistance of the system at temperatures below the transition. High-resolution transmission electron microscopy measurements reveal a complex structural relationship between V2O5, VO2 and V6O13 crystallites. Percolation paths incorporating both VO2 and metallic V6O13 are revealed, which can reduce the resistance below the transition and result in exceptionally low voltage resistive switching