The high-bias stability of monatomic chains

For the metals Au, Pt and Ir it is possible to form freely suspended monatomic chains between bulk electrodes. The atomic chains sustain very large current densities, but finally fail at high bias. We investigate the breaking mechanism, that involves current-induced heating of the atomic wires and electromigration forces. We find good agreement of the observations for Au based on models due to Todorov and co-workers. The high-bias breaking of atomic chains for Pt can also be described by the models, although here the parameters have not been obtained independently. In the limit of long chains the breaking voltage decreases inversely proportional to the length.

RF plasma MOCVD of Y2O3 thin films: Effect of RF self-bias on the substrates during deposition

Yttrium oxide (Y203) thin films have been deposited by radio frequency plasma assisted metal organic chemical vapor deposition (MOCVD) process using (2,2,6,6-tetramethy1-3,5-heptanedionate) yttrium (commonly known as Y(thd)3) precursor in a plasma of argon and oxygen gases at a substrate temperature of 350 C. The films have been deposited under influence of varying RF self-bias (-50 V to 175 V) on silicon, quartz, stainless steel and tantalum substrates. The deposited coatings are characterized by glancing angle X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry and scanning electron microscopy (SEM). GIXRD and FTIR results indicate deposition of Y2 03 (BCC structure) in all cases. However, XPS results indicate nonstoichiometric cubic phase deposition on the surface of deposited films. The degree of nonstoichiometry varies with bias during deposition. Ellipsometry results indicate that the refractive index for the deposited films is varying from 1.70 to 1.83 that is typical for Y203. All films are transparent in the investigated wavelength range 300-1200 nm. SEM results indicate that the microstructure of the films is changing with applied bias. Results indicate that it is possible to deposit single phase cubic Y203 thin films at low substrate temperature by RF plasma MOCVD process. RF self-bias that decides about the energy of impinging ions on the substrates plays an important role in controlling the texture of deposited Y203 films on the substrates. Results indicate that to control the structure of films and its texture, it is important to control the bias on the substrate during deposition. The films deposited at high bias level show degradation in the crystallinity and reduction of thickness. (C) 2013 Elsevier B.V. All rights reserved.

Investigation of responsivity decreasing with rising bias voltage in a GaN Schottky barrier photodetector

The unexpected decrease in measured responsivity observed in a specific GaN Schottky barrier photodetector (PD) at high reverse bias voltage was investigated and explained. Device equivalent transforms and small signal analysis were performed to analyse the test circuit. On this basis, a model was built which explained the responsivity decrease quantitatively. After being revised by this model, responsivity curves varying with bias voltage turned out to be reasonable. It is proved that the decrease is related to the dynamic parallel resistance of the photodiode. The results indicate that with a GaN Schottky PD, the choice of load resistance is restricted according to the dynamic parallel resistance of the device to avoid responsivity decay at high bias voltage.

Simplified theory of carrier back-scattering in semiconducting carbon nanotubes: A Kane's model approach

We present a simplified yet analytical formulation of the carrier backscattering coefficient for zig-zag semiconducting single walled carbon nanotubes under diffusive regime. The electron-phonon scattering rate for longitudinal acoustic, optical, and zone-boundary phonon emissions for both inter- and intrasubband transition rates have been derived using Kane's nonparabolic energy subband model.The expressions for the mean free path and diffusive resistance have been formulated incorporating the aforementioned phonon scattering. Appropriate overlap function in Fermi's golden rule has been incorporated for a more general approach. The effect of energy subbands on low and high bias zones for the onset of longitudinal acoustic, optical, and zone-boundary phonon emissions and absorption have been analytically addressed. 90% transmission of the carriers from the source to the drain at 400 K for a 5 mu m long nanotube at 105 V m(-1) has been exhibited. The analytical results are in good agreement with the available experimental data. (c) 2010 American Institute of Physics.

Probing the location of displayed cytochrome b562 on amyloid by scanning tunnelling microscopy.

Amyloid fibres displaying cytochrome b562 were probed using scanning tunnelling microscopy (STM) in vacuo. The cytochromes are electron transfer proteins containing a haem cofactor and could, in principle, mediate electron transfer between the tip and the gold substrate. If the core fibres were insulating and electron transfer within the 3D haem network was detected, then the electron transport properties of the fibre could be controlled by genetic engineering. Three kinds of STM images were obtained. At a low bias (<1.5 V) the fibres appeared as regions of low conductivity with no evidence of cytochrome mediated electron transfer. At a high bias, stable peaks in tunnelling current were observed for all three fibre species containing haem and one species of fibre that did not contain haem. In images of this kind, some of the current peaks were collinear and spaced around 10 nm apart over ranges longer than 100 nm, but background monomers complicate interpretation. Images of the third kind were rare (1 in 150 fibres); in these, fully conducting structures with the approximate dimensions of fibres were observed, suggesting the possibility of an intermittent conduction mechanism, for which a precedent exists in DNA. To test the conductivity, some fibres were immobilized with sputtered gold, and no evidence of conduction between the grains of gold was seen. In control experiments, a variation of monomeric cytochrome b562 was not detected by STM, which was attributed to low adhesion, whereas a monomeric multi-haem protein, GSU1996, was readily imaged. We conclude that the fibre superstructure may be intermittently conducting, that the cytochromes have been seen within the fibres and that they are too far apart for detectable current flow between sites to occur. We predict that GSU1996, being 10 nm long, is more likely to mediate successful electron transfer along the fibre as well as being more readily detectable when displayed from amyloid.

Control circuits for avalanche photodiodes

Avalanche Photodiodes (APDs) have been used in a wide range of low light sensing applications such as DNA sequencing, quantum key distribution, LIDAR and medical imaging. To operate the APDs, control circuits are required to achieve the desired performance characteristics. This thesis presents the work on development of three control circuits including a bias circuit, an active quench and reset circuit and a gain control circuit all of which are used for control and performance enhancement of the APDs. The bias circuit designed is used to bias planar APDs for operation in both linear and Geiger modes. The circuit is based on a dual charge pumps configuration and operates from a 5 V supply. It is capable of providing milliamp load currents for shallow-junction planar APDs that operate up to 40 V. With novel voltage regulators, the bias voltage provided by the circuit can be accurately controlled and easily adjusted by the end user. The circuit is highly integrable and provides an attractive solution for applications requiring a compact integrated APD device. The active quench and reset circuit is designed for APDs that operate in Geiger-mode and are required for photon counting. The circuit enables linear changes in the hold-off time of the Geiger-mode APD (GM-APD) from several nanoseconds to microseconds with a stable setting step of 6.5 ns. This facilitates setting the optimal `afterpulse-free' hold-off time for any GM-APD via user-controlled digital inputs. In addition this circuit doesn’t require an additional monostable or pulse generator to reset the detector, thus simplifying the circuit. Compared to existing solutions, this circuit provides more accurate and simpler control of the hold-off time while maintaining a comparable maximum count-rate of 35.2 Mcounts/s. The third circuit designed is a gain control circuit. This circuit is based on the idea of using two matched APDs to set and stabilize the gain. The circuit can provide high bias voltage for operating the planar APD, precisely set the APD’s gain (with the errors of less than 3%) and compensate for the changes in the temperature to maintain a more stable gain. The circuit operates without the need for external temperature sensing and control electronics thus lowering the system cost and complexity. It also provides a simpler and more compact solution compared to previous designs. The three circuits designed in this project were developed independently of each other and are used for improving different performance characteristics of the APD. Further research on the combination of the three circuits will produce a more compact APD-based solution for a wide range of applications.

Current-induced transition in atomic-sized contacts of metallic alloys

We have measured conductance histograms of atomic point contacts made from the noble-transition-metal alloys CuNi, AgPd, and AuPt for a concentration ratio of 1:1. For all alloys these histograms at low-bias voltage (below 300 mV) resemble those of the noble metals, whereas at high bias (above 300 mV) they resemble those of the transition metals. We interpret this effect as a change in the composition of the point contact with bias voltage. We discuss possible explanations in terms of electromigration and differential diffusion induced by current heating.

Water-mediated electrochemical nano-writing on thin ceria films

Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing.

Transport électrique dans les nanotubes de carbone et leurs dérivés fonctionnalisés

Les nanotubes de carbone forment une structure quasi-unidimensionnelle de diamètre nanométrique, dont les propriétés mécaniques et électroniques, en particulier leur remarquable conductivité électrique, présentent un grand potentiel pour la conception de dispositifs électroniques. Les nanotubes fonctionnalisés, c’est-à-dire dont la paroi a été chimiquement modifiée, présentent aussi un intérêt majeur pour leur mise en œuvre facilitée et pour la formation d’une interface active entre le nanotube et l’environnement, cette dernière étant essentielle pour la conception de nanocapteurs chimiques et biologiques. La présente thèse porte sur l’étude des mécanismes gouvernant le transport électrique dans les nanotubes de carbone et leurs dérivés fonctionnalisés. Les travaux, de nature expérimentale, ont été réalisés sur des dispositifs électroniques constitués d’un nanotube individuel monoparoi ou biparoi, additionné de groupes fonctionnels au besoin. En première partie, on s’intéresse à l’effet de la dimensionnalité sur les mécanismes d’injection des porteurs de charge au niveau des contacts électriques avec le nanotube. En seconde partie, on étudie l’effet de la fonctionnalisation covalente sur les propriétés de transport électrique des nanotubes, et on montre notamment que l’impact de l’addition des greffons varie fortement selon leur valence et qu’il est possible d’obtenir des nanotubes fonctionnalisés avec une bonne conductance. En troisième partie, on explore les phénomènes de saturation du courant et de claquage électrique survenant à haut voltage. Enfin, on discute de l’impact des résultats obtenus sur l’avancement de la compréhension des mécanismes de transport électrique dans les systèmes hautement confinés, ainsi que des perspectives fondamentales et technologiques ouvertes par ces travaux.

Eficacia y seguridad de los agentes estimulantes de la eritropoyesis para los síndromes mielodisplásicos: Revisión sistemática de la literatura

Los síndromes mielodisplásicos son un grupo heterogéneo de desórdenes clonales de las células madre hematopoyéticas caracterizadas por displasia y producción inefectiva de células sanguíneas. Los agentes estimulantes de la eritropoyesis (AEE) constituyen una alternativa terapéutica para un grupo de pacientes con síndromes mielodisplásicos. Se realizó una revisión sistemática de la literatura de estudios aleatorizados controlados, que evaluaron la eficacia y seguridad de los AEE en adultos con diagnóstico de síndrome mielodisplásico hasta febrero de 2014. A partir de la búsqueda se encontraron 1071 referencias, se obtuvieron 12 referencias, correspondiente a 9 estudios que cumplieron criterios de selección. Todos evaluaron algún AEE pero el grupo comparador difirió entre ellos; De los estudios seleccionados, ninguno evaluó el desenlace de supervivencia según brazos de tratamiento. 3 de los estudios evaluaron el desenlace de calidad de vida en grupos comparativos diferentes, reportando mejorías no estadísticamente significativas. 7 de los estudios evaluaron la respuesta hematológica reportando resultados divergentes según diversas definiciones de la variable de interés. Los desenlaces de seguridad fueron reportaron en 3 de los estudios, ocurriendo en baja proporción y con incidencia similar entre los grupos comparadores y el tratamiento con AEE. Las evaluaciones de riesgo de sesgo consideraron un estudio con bajo riesgo de sesgo, 4 estudios con riesgo incierto y 4 estudios con riesgo alto de sesgo. Los estudios evaluados fueron considerados en su mayoría con riesgo de sesgo incierto o alto. Se sugiere evaluar dichos desenlaces de interés de manera estandarizada en investigaciones futuras en el tema.

Statistical inference of OH concentrations and air mass dilution rates from successive observations of non-methane hydrocarbons in single air masses

Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations () and air mass dilution rates (K) averaged following air masses between linked observations of nonmethane hydrocarbons (NMHCs) spanning the North Atlantic during the Intercontinental Transport and Chemical Transformation (ITCT)-Lagrangian-2K4 experiment. The Bayesian technique obtains a refined (posterior) distribution of a parameter given data related to the parameter through a model and prior beliefs about the parameter distribution. Here, the model describes hydrocarbon loss through OH reaction and mixing with a background concentration at rate K. The Lagrangian experiment provides direct observations of hydrocarbons at two time points, removing assumptions regarding composition or sources upstream of a single observation. The estimates are sharpened by using many hydrocarbons with different reactivities and accounting for their variability and measurement uncertainty. A novel technique is used to construct prior background distributions of many species, described by variation of a single parameter . This exploits the high correlation of species, related by the first principal component of many NMHC samples. The Bayesian method obtains posterior estimates of , K and following each air mass. Median values are typically between 0.5 and 2.0 × 106 molecules cm−3, but are elevated to between 2.5 and 3.5 × 106 molecules cm−3, in low-level pollution. A comparison of estimates from absolute NMHC concentrations and NMHC ratios assuming zero background (the “photochemical clock” method) shows similar distributions but reveals systematic high bias in the estimates from ratios. Estimates of K are ∼0.1 day−1 but show more sensitivity to the prior distribution assumed.

Assimilation of stratospheric ozone from MIPAS into a global general-circulation model: The September 2002 vortex split

Ozone and temperature profiles from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) have been assimilated, using three-dimensional variational assimilation, into a stratosphere troposphere version of the Met Office numerical weather-prediction system. Analyses are made for the month of September 2002, when there was an unprecedented split in the southern hemisphere polar vortex. The analyses are validated against independent ozone observations from sondes, limb-occultation and total column ozone satellite instruments. Through most of the stratosphere, precision varies from 5 to 15%, and biases are 15% or less of the analysed field. Problems remain in the vortex and below the 60 hPa. level, especially at the tropopause where the analyses have too much ozone and poor agreement with independent data. Analysis problems are largely a result of the model rather than the data, giving confidence in the MIPAS ozone retrievals, though there may be a small high bias in MIPAS ozone in the lower stratosphere. Model issues include an excessive Brewer-Dobson circulation, which results both from known problems with the tracer transport scheme and from the data assimilation of dynamical variables. The extreme conditions of the vortex split reveal large differences between existing linear ozone photochemistry schemes. Despite these issues, the ozone analyses are able to successfully describe the ozone hole split and compare well to other studies of this event. Recommendations are made for the further development of the ozone assimilation system.

Validation of ACE-FTS satellite data in the upper troposphere/lower stratosphere (UTLS) using non-coincident measurements

CO, O3, and H2O data in the upper troposphere/lower stratosphere (UTLS) measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer(ACE-FTS) on Canada’s SCISAT-1 satellite are validated using aircraft and ozonesonde measurements. In the UTLS, validation of chemical trace gas measurements is a challenging task due to small-scale variability in the tracer fields, strong gradients of the tracers across the tropopause, and scarcity of measurements suitable for validation purposes. Validation based on coincidences therefore suffers from geophysical noise. Two alternative methods for the validation of satellite data are introduced, which avoid the usual need for coincident measurements: tracer-tracer correlations, and vertical tracer profiles relative to tropopause height. Both are increasingly being used for model validation as they strongly suppress geophysical variability and thereby provide an “instantaneous climatology”. This allows comparison of measurements between non-coincident data sets which yields information about the precision and a statistically meaningful error-assessment of the ACE-FTS satellite data in the UTLS. By defining a trade-off factor, we show that the measurement errors can be reduced by including more measurements obtained over a wider longitude range into the comparison, despite the increased geophysical variability. Applying the methods then yields the following upper bounds to the relative differences in the mean found between the ACE-FTS and SPURT aircraft measurements in the upper troposphere (UT) and lower stratosphere (LS), respectively: for CO ±9% and ±12%, for H2O ±30% and ±18%, and for O3 ±25% and ±19%. The relative differences for O3 can be narrowed down by using a larger dataset obtained from ozonesondes, yielding a high bias in the ACEFTS measurements of 18% in the UT and relative differences of ±8% for measurements in the LS. When taking into account the smearing effect of the vertically limited spacing between measurements of the ACE-FTS instrument, the relative differences decrease by 5–15% around the tropopause, suggesting a vertical resolution of the ACE-FTS in the UTLS of around 1 km. The ACE-FTS hence offers unprecedented precision and vertical resolution for a satellite instrument, which will allow a new global perspective on UTLS tracer distributions.

Experimental and modeled UV erthemal irradiance under overcast conditions: the role of cloud optical depth

This paper evaluates the relationship between the cloud modification factor (CMF) in the ultraviolet erythe- mal range and the cloud optical depth (COD) retrieved from the Aerosol Robotic Network (AERONET) "cloud mode" algorithm under overcast cloudy conditions (confirmed with sky images) at Granada, Spain, mainly for non-precipitating, overcast and relatively homogenous water clouds. Empirical CMF showed a clear exponential dependence on experimental COD values, decreasing approximately from 0.7 for COD=10 to 0.25 for COD=50. In addition, these COD measurements were used as input in the LibRadtran radia tive transfer code allowing the simulation of CMF values for the selected overcast cases. The modeled CMF exhibited a dependence on COD similar to the empirical CMF, but modeled values present a strong underestimation with respect to the empirical factors (mean bias of 22 %). To explain this high bias, an exhaustive comparison between modeled and experimental UV erythemal irradiance (UVER) data was performed. The comparison revealed that the radiative transfer simulations were 8 % higher than the observations for clear-sky conditions. The rest of the bias (~14 %) may be attributed to the substantial underestimation of modeled UVER with respect to experimental UVER under overcast conditions, although the correlation between both dataset was high (R2 ~ 0.93). A sensitive test showed that the main reason responsible for that underestimation is the experimental AERONET COD used as input in the simulations, which has been retrieved from zenith radiances in the visible range. In this sense, effective COD in the erythemal interval were derived from an iteration procedure based on searching the best match between modeled and experimental UVER values for each selected overcast case. These effective COD values were smaller than AERONET COD data in about 80 % of the overcast cases with a mean relative difference of 22 %.

Chemistry‐climate model simulations of spring Antarctic ozone

Coupled chemistry‐climate model simulations covering the recent past and continuing throughout the 21st century have been completed with a range of different models. Common forcings are used for the halogen amounts and greenhouse gas concentrations, as expected under the Montreal Protocol (with amendments) and Intergovernmental Panel on Climate Change A1b Scenario. The simulations of the Antarctic ozone hole are compared using commonly used diagnostics: the minimum ozone, the maximum area of ozone below 220 DU, and the ozone mass deficit below 220 DU. Despite the fact that the processes responsible for ozone depletion are reasonably well understood, a wide range of results is obtained. Comparisons with observations indicate that one of the reasons for the model underprediction in ozone hole area is the tendency for models to underpredict, by up to 35%, the area of low temperatures responsible for polar stratospheric cloud formation. Models also typically have species gradients that are too weak at the edge of the polar vortex, suggesting that there is too much mixing of air across the vortex edge. Other models show a high bias in total column ozone which restricts the size of the ozone hole (defined by a 220 DU threshold). The results of those models which agree best with observations are examined in more detail. For several models the ozone hole does not disappear this century but a small ozone hole of up to three million square kilometers continues to occur in most springs even after 2070.