Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Kinetics of interface state-limited hole injection in alpha-naphthylphenylbiphenyl diamine (alpha-NPD) thin layers

Injection-limited operation is identified in thin-film, alpha-NPD-based diodes. A detailed model for the impedance of the injection process is provided which considers the kinetics of filling/releasing of interface states as the key factor behind the injection mechanism. The injection model is able to simultaneously account for the steady-state, current-voltage (J-V) characteristics and impedance response. and is based on the sequential injection of holes mediated by energetically distributed surface states at the metal-organic interface. The model takes into account the vacuum level offset caused by the interface dipole, along with the partial shift of the interface level distribution with bias voltage. This approach connects the low-frequency (similar to 1 Hz) capacitance spectra, which exhibits a transition between positive to negative values, to the change in the occupancy of interface states with voltage. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 5 x 10(12) cm(-2)), which exhibit a Gaussian-like distribution. A kinetically determined hole barrier is calculated at levels located similar to 0.4 eV below the contact work function. (C) 2008 Elsevier B.V. All rights reserved.

Impedance of carrier injection at the metal-organic interface mediated by surface states in electron-only tris(8-hydroxyquinoline) aluminium (Alq(3)) thin layers

Capacitance spectra of thin (< 200 nm) Alq(3) electron-only devices have been measured as a function of bias voltage. Capacitance spectra exhibit a flat response at high frequencies (> 10(3) Hz) and no feature related to the carrier transit time is observed. Toward low frequencies the spectra reach a maximum and develop a negative excess capacitance. Capacitance response along with current-voltage (J-V) characteristics are interpreted in terms of the injection of electrons mediated by surface states at the metal organic interface. A detailed model for the impedance of the injection process is provided that highlights the role of the filling/releasing kinetics of energetically distributed interface states. This approach connects the whole capacitance spectra to the occupancy of interface states, with no additional information about bulk trap levels. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 1.5 x 10(12) cm (2)). (C) 2008 Elsevier B.V. All rights reserved.

Surface protection of fluoroindate glasses by sol-gel dip-coated SnO2 thin layers

SnO2 coatings were deposited by a sol-gel dip-coating process to shield fluoroindate glasses (40In-F-3:16BaF(2):20SrF(2):20ZnF(2):2NaF:2GaF(3)) against corrosion in aqueous environments. The effect of the number of coating applications and of the withdrawal speed on the thickness, density and roughness of tin oxide films was investigated by X-ray reflectivity. Film thickness increases both with the number of coating applications and the withdrawal speed. The aqueous leaching of uncoated and SnO2-coated fluoroindate glasses was studied by scanning electron microscopy (SEM) and infrared spectroscopy (FTIR), showing that the glass surface was protected against hydrolytic attack. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Nano-scale morphological and electrical characterization of nc-SiOxNy thin layers for photovoltaic applications

Il presente lavoro di tesi propone uno studio approfondito di proprietà morfologiche e di trasporto di carica di film sottili di SiOxNy amorfi (a-SiOxNy) e nanocristallini (nc-SiOxNy), che trovano importanti applicazioni in celle fotovoltaiche ad eterogiunzione in silicio, ad alta efficienza. Lo studio è condotto mediante caratterizzazione elettrica e morfologica attraverso tecniche di microscopia a forza atomica (AFM). Sono stati studiati campioni di a-SiOxNy cresciuti con tecnica PECVD (Plasma Enhanced Chemical Vapor Deposition), in cui è stata variata unicamente la distanza tra gli elettrodi durante la deposizione. Sono stati inoltre studiati campioni di nc-SiOxNy, cresciuti con PECVD con una differente percentuale di N2O come gas precursore e un differente tempo di annealing. In entrambi i casi si tratta di un materiale innovativo, le cui proprietà fisiche di base, nonostante le numerose applicazioni, sono ancora poco studiate. L'analisi morfologica, condotta mediante AFM e successiva analisi statistica delle immagini, ha permesso di determinare alcune proprietà morfologiche dei campioni. L’analisi statistica delle immagini è stata validata, dimostrandosi stabile e consistente per lo studio di queste strutture. Lo studio delle proprietà di trasporto è stato condotto mediante acquisizione di mappe di corrente con tecnica conductive-AFM. In questo modo si è ottenuta una mappa di conducibilità locale nanometrica, che permette di comprendere come avviene il trasporto nel materiale. L'analisi di questo materiale mediante tecniche AFM ha permesso di evidenziare che l'annealing produce nei materiali nanocristallini sia un clustering della struttura, sia un significativo aumento della conducibilità locale del materiale. Inoltre la distanza tra gli elettrodi in fase di deposizione ha un leggero effetto sulle dimensioni dei grani. È da notare inoltre che su questi campioni si sono osservate variazioni locali della conducibilità alla nanoscala. L’analisi delle proprietà dei materiali alla nanoscala ha contribuito alla comprensione più approfondita della morfologia e dei meccanismi di trasporto elettronico.

Characteristics, Distribution and Persistence of Thin Layers Over a 48 Hour Period

The biological and physical processes contributing to planktonic thin layer dynamics were examined in a multidisciplinary study conducted in East Sound, Washington, USA between June 10 and June 25, 1998. The temporal and spatial scales characteristic of thin layers were determined using a nested sampling strategy utilizing 4 major types of platforms: (1) an array of 3 moored acoustical instrument packages and 2 moored optical instrument packages that recorded distributions and intensities of thin layers; (2) additional stationary instrumentation deployed outside the array comprised of meteorological stations, wave-tide gauges, and thermistor chains; (3) a research vessel anchored 150 m outside the western edge of the array; (4) 2 mobile vessels performing basin-wide surveys to define the spatial extent of thin layers and the physical hydrography of the Sound. We observed numerous occurrences of thin layers that contained locally enhanced concentrations of material; many of the layers persisted for intervals of several hours to a few days. More than one persistent thin layer may be present at any one time, and these spatially distinct thin layers often contain distinct plankton assemblages. The results suggest that the species or populations comprising each distinct thin layer have responded to different sets of biological and/or physical processes. The existence and persistence of planktonic thin layers generates extensive biological heterogeneity in the water column and may be important in maintaining species diversity and overall community structure.

Optimization of AlN thin layers on diamond substrates for high frequency SAW resonators

AlN/diamond heterostructures are very promising for high frequency surface acoustic wave (SAW) resonators. In their design, the thickness of the piezoelectric film is one of the key parameters. On the other hand, the film material quality and, hence, the device performance, also depend on that thickness. In this work, polished microcrystalline diamond substrates have been used to deposit AlN films by reactive sputtering, from 150 nm up to 3 μm thick. A high degree of the c-axis orientation has been obtained in all cases. SAW one port resonators at high frequency have been fabricated on these films with a proper combination of the film thickness and transducer size.

An investigation on the preparation and properties of some transparent conducting oxides and lead selenide thin films”

The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology

Isolating single primary rat hippocampal neurons & astrocytes on ultra-thin patterned parylene-C/silicon dioxide substrates

We report here the patterning of primary rat neurons and astrocytes from the postnatal hippocampus on ultra-thin parylene-C deposited on a silicon dioxide substrate, following observations of neuronal, astrocytic and nuclear coverage on strips of different lengths, widths and thicknesses. Neuronal and glial growth was characterized ‘on’, ‘adjacent to’ and ‘away from’ the parylene strips. In addition, the article reports how the same material combination can be used to isolate single cells along thin tracks of parylene-C. This is demonstrated with a series of high magnification images of the experimental observations for varying parylene strip widths and thicknesses. Thus, the findings demonstrate the possibility to culture cells on ultra-thin layers of parylene-C and localize single cells on thin strips. Such work is of interest and significance to the Neuroengineering and Multi-Electrode Array (MEA) communities, as it provides an alternative insulating material in the fabrication of embedded micro-electrodes, which can be used to facilitate single cell stimulation and recording in capacitive coupling mode.

Geochemistry of glass shards in the volcanic ash layers of the Izu-Bonin Arc

To examine the processes and histories of arc volcanism and of volcanism associated with backarc rifting. 130 samples containing igneous glass shards were taken from the Plioccne-Quatemai^ succession on the rift Hank (Site 788) and the Quaternary fill in the basin fill of the Sumisu Rift (Sites 790 and 791). These samples were subsequently analyzed at the University of Illinois at Chicago and Shizuoka University. The oxides determined by electron probe do not account for the total weight of the material; differences between summed oxides and 100% arise from the water contents, probably augmented by minor losses thai result from alkali vaporization during analysis. Weight losses in colorless glasses are up to 9%; those in brown glasses (dacitcs to basalts) arc no more than 4.5%; shards from the rift-flank (possibly caused by prolonged proximity to ihc scafloor) generally have higher values than those from the rift-basin fill How much of the lost water is magmatic, and how much is hydrated is uncertain; however, although the shards absorb potassium, calcium, and magnesium during hydration in the deep sea, they do so only to a minor extent that does not significantly alter their major element compositions. Therefore, the electron-probe results are useful in evaluating the magmatism recorded by the shards. Pre- and syn-rift Izu-Bonin volcanism were overwhelmingly dominated by rhyolile explosions, demonstrating that island arcs may experience significant silicic volcanism in addition to the extensive basaltic and basaltic andestic activity, documented in many arcs since the 1970s, that occurs in conjunction with the andesitic volcanism formerly thought to be dominant. Andesitic eruptions also occurred before rifting, but the andesitic component in our samples is minor. All the pre- and syn-rift rhyolites and andesites belong to the low-alkali island-arc tholeiitic suite, and contrast markedly with the alkali products of Holocene volcanism on the northernmost Mariana Arc that have been attributed to nascent rifting. The Quaternary dacites and andesites atop the rift flank and in the rift-basin fill are more potassic than those of Pliocene age, as a result of assimilation from the upper arc crust, or from variations in degrees of partial melting of the source magmas, or from metasomatic fluids. All the glass layers from the rift-flank samples belong to low-K arc-tholeiitic suites. Half of those in the Pliocene succession are exclusively rhyolitic: the others contain minor admixtures of dacite and andesite, or andesite and either basaltic andesite or basalt. In Contrast, the Quaternary (syn-rift) volcaniclastics atop the rift-flank lack basalt and basaltic andesite shards. These youngest sediments of the rift flank show close compositional affinities with five thick layers of coarse, rhyolitic pumice deposits in the basin fill, the two oldest more silicic than the younger ones. The coarse layers, and most thin ash layers that occur in hemipelagites below and intercalated between them, are low-K rhyolites and therefore probably came from sources in the arc. However, several thin rhyolitic ash beds in the hemipelagites are abnormally enriched in potassium and must have been provided by more distal sources, most likely to the west in Japan. Remarkably, the Pliocene-Pleistocene geochemistry of the volcanic front does not appear to have been influenced by the syn-rift basaltic volcanism only a few kilometers away. Rare, thin layers of basaltic ash near the bases of the rift-basin successions are not derived from the arc. They deviate strongly from trends that the arc-derived glasses display on oxide-oxide plots, and show close affinities to the basalts empted all over the Sumisu Rift during rifting. These basalts, and the basaltic ashes in the basal rift-basin fill, arc compositionally similar to those erupted from mature backarc basins elsewhere.

Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.

Bottom-up growth of fully transparent contact layers of indium tin oxide nanowires for light-emitting devices

Thin layers of indium tin oxide are widely used as transparent coatings and electrodes in solar energy cells, flat-panel displays, antireflection coatings, radiation protection and lithium-ion battery materials, because they have the characteristics of low resistivity, strong absorption at ultraviolet wavelengths, high transmission in the visible, high reflectivity in the far-infrared and strong attenuation in the microwave region. However, there is often a trade-off between electrical conductivity and transparency at visible wavelengths for indium tin oxide and other transparent conducting oxides. Here, we report the growth of layers of indium tin oxide nanowires that show optimum electronic and photonic properties and demonstrate their use as fully transparent top contacts in the visible to near-infrared region for light-emitting devices.

Change in the rate of shell deposition and shell microstructure in response to shell borers in the abalone Haliotis rubra

Gastropod shells consist of two crystal types of calcium carbonate, an outer, prismatic calcite layer and an inner nacreous layer made of aragonite. In cross-section, the nacre of the nacreous layer appears to have a regular brick-like microstructure composed of thin laminae of aragonite crystals, separated by very thin sheets of protein (Lutz and Rhoads, 1980; Nakahara, 1983). In abalone (Genus, Haliotis) and other gastropods, thin layers of non-lamellar pigmented material occur within the nacre and have been termed alternatively, fine lines, growth rings or growth lines (Shepherd et al., 1995). It has been suggested that these pigmented layers are small, prismatic, calcite layers (Shepherd and Avalos-Borja, 1997; Zaremba et al., 1996) but investigations using a Raman laser in Haliotis rubra show that they contain aragonite rather than calcite (Hawkes et al, 1996). Day and Fleming (1992) suggest that the occurrence of pigmented layers is correlated with regular exogenous cues such as reproduction or temperature changes and indeed in some species, pigmented layers in the shell can be used to age abalone (review: Shepherd and Triantafillos, 1997). However, McShane and Smith (1992) suggest that pigmented layers can occur irregularly and therefore may be unreliable indicators of age.