Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Photoconductive hybrid films via directional self-assembly of C 60 on aligned carbon nanotubes

Hybrid nanostructured materials can exhibit different properties than their constituent components, and can enable decoupled engineering of energy conversion and transport functions. Novel means of building hybrid assemblies of crystalline C 60 and carbon nanotubes (CNTs) are presented, wherein aligned CNT films direct the crystallization and orientation of C 60 rods from solution. In these hybrid films, the C 60 rods are oriented parallel to the direction of the CNTs throughout the thickness of the film. High-resolution imaging shows that the crystals incorporate CNTs during growth, yet grazing-incidence X-ray diffraction (GIXD) shows that the crystal structure of the C 60 rods is not perturbed by the CNTs. Growth kinetics of the C 60 rods are enhanced 8-fold on CNTs compared to bare Si, emphasizing the importance of the aligned, porous morphology of the CNT films as well as the selective surface interactions between C 60 and CNTs. Finally, it is shown how hybrid C 60-CNT films can be integrated electrically and employed as UV detectors with a high photoconductive gain and a responsivity of 10 5 A W -1 at low biases (± 0.5 V). The finding that CNTs can induce rapid, directional crystallization of molecules from solution may have broader implications to the science and applications of crystal growth, such as for inorganic nanocrystals, proteins, and synthetic polymers. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of process parameters on the morphology and nanostructure of roll-to-roll printed P3HT:PCBM thin films for organic photovoltaics

Roll-to-roll (R2R) gravure exhibits significant advantages such as high precision and throughput for the printing of photoactive and conductive materials and the fabrication of flexible organic electronics such as organic photovoltaics (OPVs). Since the photoactive layer is the core of the OPV, it is important to investigate and finally control the process parameters and mechanisms that define the film morphology in a R2R process. The scope of this work is to study the effect of the R2R gravure printing and drying process on the nanomorphology and nanostructure of the photoactive P3HT:PCBM thin films printed on PEDOT:PSS electrodes towards the fabrication of indium tin oxide (ITO)-free flexible OPVs. In order to achieve this, P3HT:PCBM blends of different concentration were R2R printed under various speeds on the PEDOT:PSS layers. Due to the limited drying time during the rolling, an amount of solvent remains in the P3HT:PCBM films and the slow-drying process takes place which leads to the vertical and lateral phase separation, according to the Spectroscopic Ellipsometry and Atomic Force Microscopy analysis. The enhanced slow-drying leads to stronger phase separation, larger P3HT crystallites according to the Grazing Incidence X-Ray Diffraction data and to weaker mechanical response as it was shown by the nanoindentation creep. However, in the surface of the films the P3HT crystallization is controlled by the impinged hot air during the drying, where the more the drying time the larger the surface P3HT crystallites. The integration of the printed P3HT:PCBM and PEDOT:PSS layers in an OPV device underlined the feasibility of fabricating ITO-free flexible OPVs by R2R gravure processes. © 2013 Elsevier B.V.

The absorption of sound by helmholtz resonators with and without flow

Helmholtz resonators are commonly used as absorbers of incident acoustic power. Theoretical and experimental investigations have been performed in the four cases of no mean flow, grazing mean flow, bias mean flow and a combination of grazing and bias mean flows. In the absence of a mean flow, the absorption coefficient (deflned as the proportion of incident energy absorbed) is a non-linear function of the acoustic pressure and high incident acoustic pressures are required before the absorption becomes signiflcant. In contrast, when there is a mean flow present, either grazing or bias, the absorption is linear and thus absorption coefficient is independent of the magnitude of the acoustic pressure, and absorption is obtained over a wider range of frequencies. Non-linear effects are only discernible very close to resonance and at very-high amplitude. With grazing mean flow, there is the undesirable effect that sound can be generated over a range of frequencies due to the interaction between the unsteadily shed vorticity waves and the downstream edge of the aperture. This production is not observed when there is a bias flow because here the vorticity is shed all around the rim of the aperture and swept away by the mean flow. When there is both a grazing mean flow and a mean bias flow, we flnd that only a small amount of bias mean flow, compared with grazing mean flow, is required to destroy the production of acoustic energy. © 2002 by the author(s). Published by the American Institute of Aeronautics and Astronautics, Inc.