Fabrication of High-κ Dielectric Metal Oxide Films on Topographically Patterned Substrates: Polymer Brush-Mediated Depositions.

Fabrication of ultrathin films of dielectric (with particular reference to materials with high dielectric constants) materials has significance in many advanced technological applications including hard protective coatings, sensors, and next-generation logic devices. Current state-of-the-art in microelectronics for fabricating these thin films is a combination of atomic layer deposition and photolithography. As feature size decreases and aspect ratios increase, conformality of the films becomes paramount. Here, we show a polymer brush template-assisted deposition of highly conformal, ultrathin (sub 5 nm) high-κ dielectric metal oxide films (hafnium oxide and zirconium oxide) on topographically patterned silicon nitride substrates. This technique, using hydroxyl terminated poly-4-vinyl pyridine (P4VP-OH) as the polymer brush, allows for conformal deposition with uniform thickness along the trenches and sidewalls of the substrate. Metal salts are infiltrated into the grafted monolayer polymer brush films via solution deposition. Tailoring specific polymer interfacial chemistries for ion infiltration combined with subsequent oxygen plasma treatment enabled the fabrication of high-quality sub 5 nm metal oxide films.

Precise Definition of a "Monolayer Point" in Polymer Brush Films for Fabricating Highly Coherent TiO2 Thin Films by Vapor-Phase Infiltration.

In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2-4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.

Photoelectrocatalytic Degradation of Methylene Blue Using ZnO Nanorods Fabricated on Silicon Substrates.

ZnO nanorods were grown on silicon (Si) substrates by two techniques: (i) Chemical Bath Deposition (CBD) and (ii) a CBD seed layer combined with Carbothermal Reduction Vapor Phase Transport (CTR-VPT). The structured ZnO nanorods were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and contact angle measurments. The photoelectrochemical property of ZnO nanorods were analyzed by linear voltammetry under UV-ABC light excitation. Using the ZnO nanorod samples as photoanodes, the removal of methylene blue (MB) as a representative organic compound was studied by the photoelectrocatalytic (PEC) technique applying a potential (E) of 0.6 V. For comparison purposes, experiments were performed under the same conditions using photocatalysis (PC), direct photolysis and using samples of pure Si (support material) as working electrodes in PEC. XRD analyses of ZnO prepared by both methods showed the expected ZnO wurtzite phase and a preferred c-axial orientation in the growth of the nanorods. The presence of ZnO was further confirmed by XPS and contact angle measurements showed that ZnO grown by CBD (ZnO/CBD) had a slightly hydrophobic behavior while ZnO grown by CTR-VPT (ZnO/CTR-VPT) is hydrophilic. Both ZnO sample types were shown to be photoactive, with ZnO/CBD showing higher resultant photocurrent compared to ZnO/CTRVPT. For the degradation of MB 53% of the compound was removed using ZnO/CBD as a working electrode, while using the ZnO/CTR-VPT electrode led to a removal of 43% of MB. However, direct photolysis alone removed 39% of the MB. The lower removal of MB using ZnO/CTR-VPT samples was related to surface dissociation during the degradation process. The results show that ZnO nanorods prepared by the CBD techique are a promising photoelectrode for PEC applications. Our data also indicate that CTR-VPT-grown nanorods produce uniform nanorod arrays, but this uniform nanostructure deposit does not lead to any increase in PEC activity.

H2O2-assisted photoelectrocatalytic degradation of Mitoxantrone using CuO nanostructured films: Identification of by-products and toxicity.

CuO nanostructured thin films supported on silicon with 6.5 cm2 area (geometric area greater than the studies reported in the literature) were synthesized by a chemical bath deposition technique. The electrodes were characterized by MEV, XRD, XPS, contact angle, cyclic voltammetry and electrochemical impedance spectroscopy analyses. To evaluate the photoelectrochemical properties of the CuO films, photocurrent-voltage measurements were performed using linear voltammetry. The catalytic activities of CuO nanostructures were evaluated by monitoring photodegradation of Mitoxantrone (MTX) under UV-A light irradiation. The method of photoelectrocatalysis (PEC), applying a voltage of 1.5 V and assisted by adding H2O2, was undertaken. To the best of our knowledge, no studies on the degradation of anticancer agents using PEC process have been found in the literature. For comparison purposes, experiments were performed under the same conditions by assisted photocatalysis (PC) with H2O2 and direct photolysis. CuO deposits consist of a needle-like morphology. The presence of CuO in the tenorite phase was evidenced by XRD and the XPS spectra showed the presence of copper(II) oxide. The increase in current under illumination shows that CuO exhibits photoactivity. The PEC system showed a 75% level of MTX degradation, while the level achieved using PC was 50%. Under UV-A light alone only 3% removal was obtained after 180 min. Up to 10 by-products were identified by chromatography-mass spectrometry (LC-MS) with m/z values ranging between 521 and 285 and a plausible degradation route has been proposed. It is worth mentioning that 9 by-products identified in this work, were not found in the literature in other studies of degradation or products generated as metabolites. The toxicity tests of MTX before and after PEC treatment with Artemia Salina and Allium cepa showed a decrease in the acute toxicity of the medium as the antineoplastic was degraded.

Enhanced Optical Properties of ZnO and CeO2-coated ZnO Nanostructures Achieved Via Spherical Nanoshells Growth On A Polystyrene Template.

In this paper, ZnO, CeO2 and CeO2-coated ZnO nanostructures were synthesised by simple and efficient low temperature wet chemical methods on Si (100) and quartz substrates. The ZnO films were prepared by a drop coating deposition method. This was then combined with a thin layer of the redox active material CeO2 to form CeO2-coated ZnO films. Spherical ZnO nanoshell structures and CeO2-coated ZnO nanoshells have been prepared using polystyrene (PS) sphere monolayer templates. The structural properties and morphologies of the nanostructures were analysed by x-ray diffraction (XRD) and scanning electron microscopy (SEM). The nanostructure compositions are studied in more detail using secondary ion mass spectroscopy (SIMS). The optical properties of the nanostructures were measured using ultraviolet-visible (UV-Vis) absorption spectroscopy in order to ascertain the effects of the nanoshell structures and the whispering gallery modes associated with these structures on the optical properties of the deposits. Our data show UV and visible light absorption was very significantly enhanced due to this nanostructuring.

A catalyst-free and facile route to periodically ordered and c-axis aligned ZnO nanorod arrays on diverse substrates.

In this work we present a method for the deposition of periodically ordered, c-axis aligned ZnO nanorod arrays. By using chemical bath deposited films in conjunction with silica templating through nanosphere monolayers, masks suitable for high temperature deposition are created. A vapour phase transport technique is then used to deposit ordered arrays, quickly and inexpensively in a manner ideal for low cost, scalable and reproducible growth on a diverse range of substrates.

Spatial inhomogeneity of donor bound exciton emission from ZnO nanostructures grown on Si.

We report low temperature cathodoluminescence spectroscopy measurements of the band edge emission from ZnO nanostructures grown by vapour phase transport on Si. A range of donor bound exciton emission lines are found and the Al-related emission at 3.3605 eV in particular shows a marked inhomogeneity in its distribution throughout the sample. Increased 3.3605 eV emission is seen at a range of locations in nanorods and nanosheets where different nanostructures cross or coalesce, suggesting aggregation of Al donors in ZnO in regions of crystal structure disruption. However, localized crystal structure disruption appears to be a necessary rather than a sufficient condition for Al aggregation, since increased 3.3605 eV emission is seen only in such regions, but not all such regions show increased emission, implying that the microscopic nature of such regions is important in determining Al aggregation. Supporting data are presented from well-aligned, non-crossing, nanorods on a-sapphire.

ZnO films grown by pulsed-laser deposition on soda lime glass substrates for the ultraviolet inactivation of Staphylococcus epidermidis biofilms.

We found that a ZnO film of 2 µm thickness which was laser-deposited at room temperature onto a plain soda lime glass substrate, exhibits notable antibacterial activity against a biofilm of Staphylococcus epidermidis when back-illuminated by a UVA light source with a peak emission wavelength of about 365 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-visible absorption spectroscopy, Raman spectroscopy and x-ray photoemission spectroscopy (XPS) were used to characterize the ZnO films before and after the interactions with the biofilm and the ultraviolet light, respectively. The as-deposited film was highly textured with the wurtzite (0002) in-plane orientation (c-axis perpendicular to ZnO surface) and had a surface rms roughness of 49.7 nm. In the as-deposited film, the Zn to O ratio was 1 to 0.95. After the UV and biofilm treatments, the ZnO film surface had become rougher (rms roughness 68.1 nm) and presented uniform micron-sized pitting randomly distributed, while the zinc to oxygen ratio had become 1 to 2.2. In this case, both the UV-visible and Raman spectra pointed to degradation of the structural quality of the material. On the strength of these data, we propose a model for the mediation of the bactericidal activity in which the photogeneration of highly oxidizing species and the presence of active surface defect sites both play an important role. This study is of particular interest for the acute problem of disinfection of pathogenic biofilms which form on medical device/implant surfaces.

The dominant role of adsorbed fluid layers on the polar surfaces of ZnO in ambient atmospheric conditions.

Polar ZnO surfaces with O- and Zn-termination were studied with atomic and lateral force microscopy and force curves. Adsorbed fluid layers on both surfaces are found to dominate their adhesion properties in air. The hydrophilic O-surface has a substantially thicker adsorbed layer and larger residual particle densities. Our data suggest that different preparation is required for the two surfaces before use in epitaxy, and may resolve some contradictions in the literature. The data also indicate that adsorbed fluid layers may be important in the growth of certain ZnO nanostructures.