Ge-Sb-Te Chalcogenide Thin Films Deposited by Nanosecond, Picosecond, and Femtosecond Laser Ablation.

Ge-Sb-Te thin films were obtained by ns-, ps-, and fs-pulsed laser deposition (PLD) in various experimental conditions. The thickness of the samples was influenced by the Nd-YAG laser wavelength, fluence, target-to-substrate distance, and deposition time. The topography and chemical analysis results showed that the films deposited by ns-PLD revealed droplets on the surface together with a decreased Te concentration and Sb over-stoichiometry. Thin films with improved surface roughness and chemical compositions close to nominal values were deposited by ps- and fs-PLD. The X-ray diffraction and Raman spectroscopy results showed that the samples obtained with ns pulses were partially crystallized while the lower fluences used in ps- and fs-PLD led to amorphous depositions. The optical parameters of the ns-PLD samples were correlated to their structural properties.

CO2 capture using semi-clathrates of quaternary ammonium salt: structure change induced by CO2 and N2 enclathration.

Semi-clathrates of tetrabutylammonium bromide (TBAB) are investigated for their potential application in the CO2 capture context based on hydrate technology. The three-phase lines of semi-clathrates of CO2-TBAB-H2O and N2-TBAB-H2O are established simultaneously with their structure using in situ Raman scattering performed at high pressure. The preferred crystal phase obtained at ambient pressure from solutions of 5 and 40 wt % TBAB initial concentrations is shown to change upon enclathration of CO2 or N2, or by applying a higher pressure on the system. Deep in the stability field, metastable hydrate phases are occurring at the onset of the formation and correspond to the ones expected under ambient pressure conditions. Depending on the pressure, they progressively transformed into the most stable ones when approaching equilibrium and dissociation points. Besides, it is shown that a 5 wt % TBAB original solution forms preferentially a mixed structure of both type B and type A at low gas pressure with CO2 as the guest gas. A new structure is spectroscopically characterized at pressures higher than ∼2 MPa CO2. Type A is demonstrated to be stable at 5 wt % initial TBAB concentration with N2 as the guest molecule and pressure between 8 and 12 MPa. These structural data address new insights on the relationship between the hydrophilic-anion and hydrophobic-cation intercalation with a guest gas producing hydrophobic interaction in a distorted water lattice.

Ice particle crystallization in the presence of ethanol: an in situ study by Raman and X-ray diffraction.

Two distinct ethanol aqueous solution droplets ((X(EtOH))L = 8.7 wt % and 46.5 wt %) are investigated by in situ Raman spectroscopy and X-ray diffraction between 253 and 88 K. Structural changes are identified by modifications in the O-H and C-H stretching modes (2800-3800 cm(-1) spectral region) during freezing and annealing events. They are attributed to the formation of ice and/or different hydrate structures in the EtOH-water system. At high initial ethanol concentration, the particle is found to be composed of a modified clathrate I (cubic structure) at 211 K on cooling and transformed into an ethanol hydrate II (monoclinic structure) on annealing between ∼143 and 173 K. This latter decomposes at ∼200 K and leaves an aqueous solution and ice Ih which further dissociates above ∼230 K. At low initial concentration, ice first forms on cooling and the particle consists of a crystalline ice core embedded in a liquid layer of high ethanol content at ~200 K (or an amorphous layer at lower T). A new hydrate (IV) of distinct structure (orthorhombic) is observed on annealing (from 100 K) between ∼123 K and ∼142 K (depending on initial composition), which transforms into the ethanol hydrate II at ∼160 K. The hydrate II decomposes at ∼200 K, and ice Ih remains (and dissociate above ∼220 K) in coexistence with the liquid layer of high ethanol content. It is proposed that the complex crystalline ice particles formed may have the potential to impact several atmospherical processes differently in comparison to the pure ice case.

Environmental effects on vibrational properties of carotenoids: experiments and calculations on peridinin.

Carotenoids are employed in light-harvesting complexes of dinoflagellates with the two-fold aim to extend the spectral range of the antenna and to protect it from radiation damage. We have studied the effect of the environment on the vibrational properties of the carotenoid peridinin in different solvents by means of vibrational spectroscopies and QM/MM molecular dynamics simulations. Three prototypical solvents were considered: cyclohexane (an apolar/aprotic solvent), deuterated acetonitrile (a polar/aprotic solvent) and methanol (a polar/protic solvent). Thanks to effective normal mode analysis, we were able to assign the experimental Raman and IR bands and to clarify the effect of the solvent on band shifts. In the 1500-1650 cm(-1) region, seven vibrational modes of the polyene chain were identified and assigned to specific molecular vibrations. In the 1700-1800 cm(-1) region a strong progressive down-shift of the lactonic carbonyl frequency is observed passing from cyclohexane to methanol solutions. This has been rationalized here in terms of solvent polarity and solute-solvent hydrogen bond interactions. On the basis of our data we propose a classification of non-equivalent peridinins in the Peridinin-Chlorophyll-Proteins, light-harvesting complexes of dinoflagellates.

Ethanol hydrates and solid solution formed by gas condensation: an in situ study by micro-Raman scattering and X-ray diffraction.

Thin films of ethanol-water solid mixtures formed by gas co-condensation are investigated in situ by micro-Raman scattering in the 800-1600 and 2800-3800 cm(-1) spectral regions. Information at the molecular level on the structure is derived from accompanying changes observed in band shapes and vibrational mode frequencies. Depending on the ethanol content, the formation of two distinct ethanol hydrates is spectroscopically characterized, and their structures are independently confirmed by X-ray diffraction measurements. The attribution of the different phases is made in comparison with literature data and in relation with the ethanol phase diagram. Raman characteristic spectral features of ethanol extremely diluted in ice and corresponding to a solid solution regime are reported.

Cross determination of the vapor liquid equilibrium of formaldehyde aqueous solutions by quadrupole mass spectrometry and infrared diode laser spectroscopy.

Quantitative measurements of the partial vapor pressure of formaldehyde are performed above aqueous H2CO solutions of different concentrations (from 10(-5) to 0.3 molar fraction) using mass spectrometry and IR diode laser spectroscopy. Both experimental techniques allow direct probing of the gas phase concentration collected at equilibrium above the aqueous solutions. A correlation is observed between the polymerization processes occurring in the solution and the partial pressure of H2CO measured at vapor liquid equilibrium (VLE). A similar correlation is observed from total pressure measurements for which the equilibrium vapor pressure decreases as [VLE XH2CO]liq is increased. A saturation regime of the H2CO partial pressure is reached as the dissolved fraction of formaldehyde increases above approximately 0.15 mol frac. Henry's law constants are derived at 295K for the diluted solutions.

Ice mixtures formed by simultaneous condensation of formaldehyde and water: an in situ study by micro-Raman scattering.

Thin films of formaldehyde-water mixtures are co-deposited at 88 K and 10(-1) Torr from gas collected above formaldehyde aqueous solutions of different concentrations (5, 10, 15, 20, 30 mol%). They are analyzed in situ by micro-Raman scattering in the 2700-3800 cm(-1) spectral range. The spectral characteristic of H2CO distributed molecularly in amorphous solid water is obtained under vacuum conditions. As temperature is increased formaldehyde is released during the crystallization of ice between 118 and 138 K. On the other hand, under controlled nitrogen atmosphere, the deposits crystallize in hydrate phases (or solid H2CO(s)) during annealing. A new phase (metastable FOR-A) of H2CO(s) (or a low hydrate after rejection by crystallizing ice) can be spectroscopically identified at 138 K before transformation into a hydrate (with molecular H2CO distributed within the cages of the clathrate FOR-B) takes place at 148 K. This latter phase decomposes between ca. 180 and 200 K. The significant spectral differences between these hydrates and those formed in frozen formaldehyde aqueous solutions reflect the existence of H2CO-clusters of distinctive structural nature relative to those resulting from important oligomerization process in the liquid. Moreover, the structure, the gas distribution and relative gas population in the formaldehyde clathrate cages are influenced by the relative amount of trapped nitrogen at the surface, which moreover depends on the ice film morphology. The dependence on the crystallization temperature of the deposits is explained by the relative amounts of occluded H2CO/N2 and the external pressure conditions. The distinct behavior observed between vacuum and N2-atmosphere conditions certainly reflects a complex mechanism of surface mediated nucleation in which the transport of the reactants to the hydrate reaction zone is facilitated by the presence of a polar dopant.

Micro-Raman investigations of the formaldehyde-ice system.

Rapidly frozen aqueous solutions containing variable amounts of dissolved formaldehyde (0.1, 5, 7, 10, 15, and 20 mol %) have been analyzed by micro-Raman spectroscopy at ambient pressure and low temperature. The importance of the formladehyde-ice system has been repeatedly quoted in various contexts, such as atmospheric and snowpack chemistry and interstellar and cometary ices. Understanding and characterizing the effects of freezing and the interactions of formaldehyde with ice are therefore of relevant interest. In this study, the distinct vibrational signatures of the oligomers present in the solution and in the frozen ice mixtures have been identified in the 120-4000 cm(-1) spectral range. From the subtle changes of the bands assigned to the CO and CH group frequencies, at least two distinct crystalline phases (pI and pII) are found to coexist with ice at different temperatures. Depending on the cooling-rewarming protocol, pI is found to crystallize in the 163-213 K temperature range. Above approximately 213 K, pI gets transformed irreversibly into pII which is stable up to approximately 234 K. pII is found to interact more strongly with ice than pI, as revealed, for example, by the drop in frequency of the bands assigned to the O-H stretching as pI transforms into pII. It is suggested that pII consists of a hydrogen-bonded network of oligomers and water molecules. On the other hand, it is suggested that the oligomers mainly present in pI interact through weak forces with the surrounding water molecules.