Electron temperature versus laser intensity times wavelength squared: a comparison of theory and experiments

The peak temperature in the corona of plasma ejected by a laser-irradiated slab is discussed in terms of a one-electron-temperature model. Both heat-flux saturation and pulse rise-time effects are considered;the intensity in the rising half of the pulse is approximated by a linear function of time, I(t) = Iot/r. The temperature is found to be proportional to (IQX2)273 and a function of I0X4/r. Above a certain value of I0X4/T, the plasma presents two characteristic temperatures (at saturation and at the critical surface) which can be identified with experimentally observed cold- and hot-electron temperatures. The results are compared with extensive experimental data available for both nd and CO2 lasers, I0(W'cnf2) X2 (/um) starting around 1012. The agreement is good if substantial flux inhibition is assumed (flux-limit factor f = 0.03), and fails for I0X2 above 1O1S. Results for both ablation pressure and mass ablation rate are also given.

Optical absorption analysis of quaternary molybdate- and tungstate-ordered double perovskites

Quaternary-ordered double perovskite A2MM’O6 (M=Mo,W) semiconductors are a group of materials with a variety of photocatalytic and optoelectronic applications. An analysis focused on the optoelectronic properties is carried out using first-principles density-functional theory with several U orbital-dependent one-electron potentials applied to different orbital subspaces. The structural non-equivalence of the atoms resulting from the symmetry has been taken in account. In order to analyze optical absorption in these materials deeply, the absorption coefficients have been split into inter- and intra-non-equivalent species contributions. The results indicate that the effect of the A and M’ atoms on the optical properties are minimal whereas the largest contribution comes from the non-equivalent O atoms to M transitions.

Optical absorption and applications of the ABO4 (A=Ca, Pb and B= Mo, W) semiconductors

Ternary molybdates and tungstates ABO4 (A=Ca, Pb and B= Mo, W) are a group of materials that could be used for a variety of optoelectronic applications. We present a study of the optoelectronic properties based on first-principles using several orbitaldependent one-electron potentials applied to several orbital subspaces. The optical properties are split into chemical-species contributions in order to quantify the microscopic contributions. Furthermore, the effect of using several one-electron potentials and orbital subspaces is analyzed. From the results, the larger contribution to the optical absorption comes from the B-O transitions. The possible use as multi-gap solar cell absorbents is analyzed.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Direct Vlasov simulations of electron-attracting cylindrical Langmuir probes in flowing plasmas

Current collection by positively polarized cylindrical Langmuir probes immersed in flowing plasmas is analyzed using a non-stationary direct Vlasov-Poisson code. A detailed description of plasma density spatial structure as a function of the probe-to-plasma relative velocity U is presented. Within the considered parametric domain, the well-known electron density maximum close to the probe is weakly affected by U. However, in the probe wake side, the electron density minimum becomes deeper as U increases and a rarified plasma region appears. Sheath radius is larger at the wake than at the front side. Electron and ion distribution functions show specific features that are the signature of probe motion. In particular, the ion distribution function at the probe front side exhibits a filament with positive radial velocity. It corresponds to a population of rammed ions that were reflected by the electric field close to the positively biased probe. Numerical simulations reveal that two populations of trapped electrons exist: one orbiting around the probe and the other with trajectories confined at the probe front side. The latter helps to neutralize the reflected ions, thus explaining a paradox in past probe theory.

Electron transport and azimuthal oscillations in hall thrusters

The Hall Effect Thruster (HET) is a type of satellite electric propulsion device initially developed in the 1960’s independently by USA and the former USSR. The development continued in the shadow during the 1970’s in the Soviet Union to reach a mature status from the technological point of view in the 1980’s. In the 1990’s the advanced state of this Russian technology became known in western countries, which rapidly restarted the analysis and development of modern Hall thrusters. Currently, there are several companies in USA, Russia and Europe manufacturing Hall thrusters for operational use. The main applications of these thrusters are low-thrust propulsion of interplanetary probes, orbital raising of satellites and stationkeeping of geostationary satellites. However, despite the well proven in-flight experience, the physics of the Hall Thruster are not completely understood yet. Over the last two decades large efforts have been dedicated to the understanding of the physics of Hall Effect thrusters. However, the so-called anomalous diffusion, short name for an excessive electron conductivity along the thruster, is not yet fully understood as it cannot be explained with classical collisional theories. One commonly accepted explanation is the existence of azimuthal oscillations with correlated plasma density and electric field fluctuations. In fact, there is experimental evidence of the presence of an azimuthal oscillation in the low frequency range (a few kHz). This oscillation, usually called spoke, was first detected empirically by Janes and Lowder in the 1960s. More recently several experiments have shown the existence of this type of oscillation in various modern Hall thrusters. Given the frequency range, it is likely that the ionization is the cause of the spoke oscillation, like for the breathing mode oscillation. In the high frequency range (a few MHz), electron-drift azimuthal oscillations have been detected in recent experiments, in line with the oscillations measured by Esipchuk and Tilinin in the 1970’s. Even though these low and high frequency azimuthal oscillations have been known for quite some time already, the physics behind them are not yet clear and their possible relation with the anomalous diffusion process remains an unknown. This work aims at analysing from a theoretical point of view and via computer simulations the possible relation between the azimuthal oscillations and the anomalous electron transport in HET. In order to achieve this main objective, two approaches are considered: local linear stability analyses and global linear stability analyses. The use of local linear stability analyses shall allow identifying the dominant terms in the promotion of the oscillations. However, these analyses do not take into account properly the axial variation of the plasma properties along the thruster. On the other hand, global linear stability analyses do account for these axial variations and shall allow determining how the azimuthal oscillations are promoted and their possible relation with the electron transport.