Ab-initio study of oxygen vacancies in alpha-quartz

Extrinsic levels, formation energies, and relaxation geometries are calculated ab initio for oxygen vacancies in alpha-quartz SiO2. The vacancy is found to be thermodynamically stable in the charge states Q=+3, Q=0, Q=--2, and Q=-3. The charged states are stabilized by large and asymmetric distortions near the vacancy site. Concurrently, Franck-Condon shifts for absorption and recombination related to these states are found to be strongly asymmetric. In undoped quartz, the ground state of the vacancy is the neutral charge state, while for moderate p-type and n-type doping, the +3 and -3 states are favored, respectively, over a wide Fermi level window. Optical transitions related to the vacancy are predicted at around 3 eV and 6.5 eV (absorption) and 2.5 to 3.0 eV (emission), depending on the charge state of the ground state.Comment: 6 figures included, but only Fig.1 actually change

Stability of E' centers induced by 4.7eV laser radiation in SiO2

The kinetics of E' centers (silicon dangling bonds) induced by 4.7eV pulsed laser irradiation in dry fused silica was investigated by in situ optical absorption spectroscopy. The stability of the defects, conditioned by reaction with mobile hydrogen of radiolytic origin, is discussed and compared to results of similar experiments performed on wet fused silica. A portion of E' and hydrogen are most likely generated by laser-induced breaking of Si-H precursors, while an additional fraction of the paramagnetic centers arise from another formation mechanism. Both typologies of E' participate to the reaction with H_2 leading to the post-irradiation decay of the defects. This annealing process is slowed down on decreasing temperature and is frozen at T=200K, consistently with the diffusion properties of H_2 in silica.Comment: 12 pages, 3 figures, in press on J. Non cryst. solids (2007

29Si Hyperfine Structure of the E'_\alpha Center in Amorphous Silicon Dioxide

We report a study by electron paramagnetic resonance (EPR) on the E'_\alpha point defect in amorphous silicon dioxide (a-SiO2). Our experiments were performed on gamma-ray irradiated oxygen-deficient materials and pointed out that the 29Si hyperfine structure of the E'_alpha consists in a pair of lines split by 49 mT. On the basis of the experimental results a microscopic model is proposed for the E'_alpha center, consisting in a hole trapped in an oxygen vacancy with the unpaired electron sp3 orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO2 matrix.Comment: 4 page

Online fabrication and characterization of capsule populations with a flow-focusing microfluidic system

This paper was presented at the 3rd Micro and Nano Flows Conference (MNF2011), which was held at the Makedonia Palace Hotel, Thessaloniki in Greece. The conference was organised by Brunel University and supported by the Italian Union of Thermofluiddynamics, Aristotle University of Thessaloniki, University of Thessaly, IPEM, the Process Intensification Network, the Institution of Mechanical Engineers, the Heat Transfer Society, HEXAG - the Heat Exchange Action Group, and the Energy Institute.We have designed a microfluidic system that combines a double flow-focusing setup for calibrated capsule fabrication with a microchannel for the characterization of their mechanical properties. The double flow-focusing system consists of a first Y junction to create the microdroplets and of a second Y junction to introduce the cross-linking agent allowing the membrane formation. The human serum albumin (HSA) aqueous solution for the dispersed solution, hydrophobic phase for the continuous solution and cross-linking agent solution are introduced by means of syringe pumps. A wavy channel after the second junction allows to control the reticulation time. A cylindrical microchannel then enables to deform and characterize the capsules formed. The mechanical properties of the capsule membrane are obtained by inverse analysis (Chu et al. 2011). The results show that the drop size increases with the flow rate ratio between the central and lateral channels and does not change much regardless of the flow rate of the reticulation phase. The mean shear modulus of the capsules fabricated after 23 s of reticulation is of the order of the surface tension of HSA solution with Dragoxat indicating that the reticulation time is too short to form an elastic membrane around the droplet. When the reticulation time is increased to 60 s, the membrane shear modulus is multiplied by a factor of 3 confirming that a solid membrane has formed around the drop

Structural relaxation of E' gamma centers in amorphous silica

We report experimental evidence of the existence of two variants of the E' gamma centers induced in silica by gamma rays at room temperature. The two variants are distinguishable by the fine features of their line shapes in paramagnetic resonance spectra. These features suggest that the two E' gamma differ for their topology. We find a thermally induced interconversion between the centers with an activation energy of about 34 meV. Hints are also found for the existence of a structural configuration of minimum energy and of a metastable state.Comment: 4 pages, 2 figures, submitted to Phys. Rev. Let

H(II) centers in natural silica under repeated UV laser irradiations

We investigated the kinetics of H(II) centers (=Ge'-H) in natural silica under repeated 266nm UV irradiations performed by a Nd:YAG pulsed laser. UV photons temporarily destroy these paramagnetic defects, their reduction being complete within 250 pulses. After re-irradiation, H(II) centers grow again, and the observed recovery kinetics depends on the irradiation dose; multiple 2000 pulses re-irradiations induce the same post-irradiation kinetics of H(II) centers after each exposure cycle. The analysis of these effects allows us to achieve a deeper understanding of the dynamics of the centers during and after laser irradiation.Comment: Submitted to Journal of Non Crystalline Solid

Manipulation and Optical Detection of Colloidal Functional Plasmonic Nanostructures in Microfluidic Systems

The very strong optical resonances of plasmonic nanostructures can be harnessed for sensitive detection of chemical and biomolecular analytes in small volumes. Here we describe an approach towards optical biosensing in microfluidic systems using plasmonic structures (functionalized gold nanoparticles) in colloidal suspension. The plasmonic nanoparticles provide the optical signal, in the form of resonant light scattering or absorption, and the microfluidic environment provides means for selectively manipulating the nanoparticles through fluid dynamics and electric fields. In the first part we discuss recent literature on functionalized colloidal particles and the methods for handling them in microfluidic systems. Then we experimentally address aspects of nanoparticle functionalization, detection through plasmonic resonant light scattering under dark-field illumination and the electrokinetic behavior of the particles under the action of an alternating electric field

Quantitative full-colour transmitted light microscopy and dyes for concentration mapping and measurement of diffusion coefficients in microfluidic architectures

International audienceA simple and versatile methodology has been developed for the simultaneous measurement of multiple concentration profiles of colourants in transparent microfluidic systems, using a conventional transmitted light microscope, a digital colour (RGB) camera and numerical image processing combined with multicomponent analysis. Rigorous application of the Beer-Lambert law would require monochromatic probe conditions, but in spite of the broad spectral bandwidths of the three colour channels of the camera, a linear relation between the measured optical density and dye concentration is established under certain conditions. An optimised collection of dye solutions for the quantitative optical microscopic characterisation of microfluidic devices is proposed. Using the methodology for optical concentration measurement we then implement and validate a simplified and robust method for the microfluidic measurement of diffusion coefficients using an H-filter architecture. It consists of measuring the ratio of the concentrations of the two output channels of the H-filter. It enables facile determination of the diffusion coefficient, even for non-fluorescent molecules and nanoparticles, and is compatible with non-optical detection of the analyte

Reconciling timber extraction with biodiversity conservation in tropical forests using reduced-impact logging

Over 20% of the world's tropical forests have been selectively logged, and large expanses are allocated for future timber extraction. Reduced-impact logging (RIL) is being promoted as best practice forestry that increases sustainability and lowers CO2 emissions from logging, by reducing collateral damage associated with timber extraction. RIL is also expected to minimize the impacts of selective logging on biodiversity, although this is yet to be thoroughly tested. We undertake the most comprehensive study to date to investigate the biodiversity impacts of RIL across multiple taxonomic groups. We quantified birds, bats and large mammal assemblage structures, using a before-after control-impact (BACI) design across 20 sample sites over a 5-year period. Faunal surveys utilized point counts, mist nets and line transects and yielded >250 species. We examined assemblage responses to logging, as well as partitions of feeding guild and strata (understorey vs. canopy), and then tested for relationships with logging intensity to assess the primary determinants of community composition. Community analysis revealed little effect of RIL on overall assemblages, as structure and composition were similar before and after logging, and between logging and control sites. Variation in bird assemblages was explained by natural rates of change over time, and not logging intensity. However, when partitioned by feeding guild and strata, the frugivorous and canopy bird ensembles changed as a result of RIL, although the latter was also associated with change over time. Bats exhibited variable changes post-logging that were not related to logging, whereas large mammals showed no change at all. Indicator species analysis and correlations with logging intensities revealed that some species exhibited idiosyncratic responses to RIL, whilst abundance change of most others was associated with time. Synthesis and applications. Our study demonstrates the relatively benign effect of reduced-impact logging (RIL) on birds, bats and large mammals in a neotropical forest context, and therefore, we propose that forest managers should improve timber extraction techniques more widely. If RIL is extensively adopted, forestry concessions could represent sizeable and important additions to the global conservation estate – over 4 million km2