The water vapour self- and water-nitrogen continuum absorption in the 1000 and 2500 cm(-1) atmospheric windows

The pure water vapour and water-nitrogen continuum absorption in the 1000 and 2500?cm(-1) atmospheric windows has been studied using a 2?m base-length White-type multi-pass cell coupled with a BOMEM DA3-002 Fourier transform infrared spectrometer. The measurements were carried out at the National Institute of Standards and Technology (NIST, Gaithersburg, MD) over the course of several years (2004, 2006-2007, 2009). New data on the H(2)O:N(2) continuum in the 1000?cm(-1) window are presented and summarized along with the other experimental results and the continuum model. The experimental data reported on the water vapour continuum in these atmospheric windows basically agree with the most reliable laboratory data from the other sources. The MT_CKD (Mlawer-Tobin-Clough-Kneizys-Davies) continuum model significantly departs from the experimental data in both windows. The deviation observed includes the continuum magnitude, spectral behaviour and temperature dependence. In the 2500?cm(-1) region, the model does not allow for the nitrogen fundamental collision-induced absorption (CIA) band intensity enhancement caused by H(2)O:N(2) collisions and underestimates the actual absorption by over two orders of magnitude. The water vapour continuum interpretation as a typical CIA spectrum is reviewed and discussed.     

Investigation of cation (Sn2+) and anion (N3-) substitution in favor of visible light photocatalytic activity in the layered perovskite K2La2Ti3O10

Noticeable lowering of the energy gaps have been achieved for the layered perovskite K(2)La(2)Ti(3)O(10) as a result of the attempts made to incorporate Sn(2+) and N(3-) ions. Incorporation of Sn(2+) ions was carried out by the ion-exchange reaction of K(2)La(2)Ti(3)O(10) with aqueous tin(II) chloride solution. Nitrogen incorporation was attempted by the solid state reaction of the parent oxide with urea around 400 °C in air. The resultant oxides have been characterized by power X-ray diffraction, UV-visible diffuse reflectance spectroscopy, and Fourier transform infrared spectroscopy. Room temperature ion-exchange was sufficient to introduce Sn(2+) ions with the resulting product of composition (Sn(0.45)K(0.2)H(0.9))La(2)Ti(3)O(10) · H(2)O. Visible light absorption was observed with the absorption edge red shift of ～ 100 nm from that of the parent K(2)La(2)Ti(3)O(10). The lowering of the band gap was as expected by the contribution of Sn 5s orbitals to the O 2p orbitals in the formation of the valence band. Nitridation using urea resulted not only in nitrogen doping but with the additional sensitization by the presence of carbon nitride (CN) polymers, which again resulted in visible light absorption. The product oxides obtained as a result of cation and anion intended substitutional studies have been found to be useful for the visible light photocatalytic decomposition of organic dyes such as rhodamine B.     

Infrared collision-induced absorption by N(2) near 4.3 μm for atmospheric applications: measurements and empirical modeling

Accurate measurements of collision-induced absorption by pure nitrogen in the fundamental band near 4.3 μm have been made in the 0-10 atm and 230-300 K pressure and temperature ranges, respectively. A Fourier-transform spectrometer was used with a resolution of 0.5 cm(-1). The current measurements, which agree well with previous ones but are more precise, reveal that weak features are superimposed on the broad N(2) continuum. These features have negligible temperature dependence, and their origin is not clear at the present time. Available experimental data in the 190-300 K temperature range have been used to build a simple empirical model that is suitable for use to compute atmospheric N(2) absorption. Tests indicate that this model is accurate unlike the estimates produced by widely used atmospheric transmission codes.     

Comparison of Gas Temperatures Measured by Coherent Anti-Stokes Raman Spectroscopy (CARS) of O(2) and N(2)

We investigate the accuracy of temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) of O(2) and use measurements taken with N(2) CARS and a thermocouple for comparison. Scanning vibrational CARS spectra of O(2) and N(2) were recorded over a broad range of temperatures: between 294 K and 1900 K in air that was heated in a tube furnace and at approximately 2450 K in a fuel-lean CH(4)-O(2)-N(2) flame. Temperatures were derived from least-squares fits of simulated and experimental spectra. Both the fundamental vibrational band and the first hot vibrational band were included in fitting. In the case of the tube furnace, the N(2) and the O(2) CARS temperature measurements agreed to within 3%, and results were similar with the thermocouple; in the flame the agreement was to within 1%. We conclude that, for cases in which O(2) is present in sufficient concentrations ( approximately 10% or greater), the accuracy of O(2) thermometry is comparable with that of N(2).     

Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called 'windows') was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H(2)O--H(2)O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H(2)O--N(2) bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430?K in four near-infrared windows between 1.1 and 5?μm (9000-2000?cm(-1)). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46?W?m(-2) (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer-Tobin-Clough-Kneizys-Davies) foreign-continuum model.     

Infrared collision-induced absorption by O2 near 6.4 microm for atmospheric applications: measurements and empirical modeling

Accurate measurements of collision-induced absorption by O(2) and O(2)-N(2) mixtures in the fundamental band near 6.4 mum have been made. A Fourier-transform spectrometer was used with a resolution of 0.5 cm(-1). Absorption has been investigated in the 0-20-atm and 193-293 K pressure and temperature ranges, respectively. The current measurements confirm that the broad O(2) continuum carries small features whose attribution is not yet clear. Available experimental data in the 190-360 K temperature range have been used to build a simple, low cost computer, empirical model that is well adapted for computation of atmospheric O(2) absorption. Tests show that it is accurate, contrary to predictions of widely used atmospheric transmission codes.     

Enhanced surface-excitonic emission in ZnO/Al(2)O(3) core-shell nanowires

We report the influence of an Al(2)O(3) shell on the photoluminescence emission of ZnO nanowires. At room temperature, the spectrum of the core-shell nanowires shows a strong reduction of the relative intensity of the green defect emission with respect to the near-band-edge emission. At 5?K an increase of the relative intensity of the surface exciton band with respect to the donor-bound exciton emission is observed. Annealing the core-shell nanowires at 500?°C does not increase the green defect luminescence at 5?K. We propose a model explaining the spectral changes.     

Multiphoton excitation ionization of N(2) following collisional energy transfer with H(2)O: a potential measure of molecular mixing

A multiphoton ionization excitation of N(2) following collisional energy exchange with optically excited H(2) O was demonstrated, and its potential for measuring H(2) O-N(2) mixing at the molecular level was evaluated. In this process, N(2) is sensitized by a collisional energy exchange with H(2)O molecules excited by a tunable KrF laser. The sensitized N(2) molecules are further excited and ionized by two additional photons of the same laser pulse. Independent images of sensitized N2(+) emission at 391.4 nm and by OH at 308 nm formed by the dissociation of excited H(2)O were obtained along a laser beam traversing slow dry-air and N(2) jets entering room air. Although effects of O(2) and N(2) collisional quenching were noted, such images can potentially be used to measure H(2)O-N(2) molecular mixing and the concentration of H(2)O independently. The detection of H(2)O nucleation by this technique suggests that imaging of H(2)O droplet evaporation or visualizing and monitoring H(2)O condensation may also be possible.     

Optical evidence for reactive processes when embedding Cu nanoparticles in Al(2)O(3) by pulsed laser deposition

The optical response of nanocomposite thin films formed by Cu nanoparticles (NPs) embedded in amorphous aluminium oxide (Al(2)O(3)) prepared by pulsed laser deposition (PLD) in vacuum is studied in order to investigate the possible existence of reactive processes on the Cu NPs during their covering with Al(2)O(3). The study is performed as a function of the laser fluence on the Al(2)O(3) target (0.6-4.6?J?cm(-2)), while the laser fluence for Cu ablation is kept constant (1.8?J?cm(-2)). The structural analysis of the films shows that they are formed by a high density of NPs with average dimensions in the 4.9-5.9?nm range. The optical response of the films has been followed in situ by real-time reflectivity measurements at 633?nm and after deposition by transmission measurements as a function of wavelength around the surface plasmon resonance (SPR). For low laser fluences on the Al(2)O(3) target, the absorption spectrum is dominated by a well-defined SPR absorption band at 1.9?eV. As the laser fluence is increased, the intensity of the absorption band associated with the SPR decreases and shifts to 2.1?eV. The films deposited at low fluences contain metallic Cu NPs and, as the laser fluence increases sputtering of Cu from the NPs and mixing of the species from the Al(2)O(3) deposition with the Cu from the NPs surface takes place. The latter process leads to the formation of an Al-Cu oxide cover on the Cu NPs. The present results provide evidence for mixing of species from the host and Cu at the surface of the NPs, and it is shown how the degree of mixing depends on the laser fluence used to ablate the Al(2)O(3) host target.     

Synthesis of fluorescent and photovoltaic Cu(2)O nanocubes

Hollow and filled Cu(2)O nanocubes of about 28 ± 5?nm in edge length with a band gap ～2.42?eV have been prepared from cupric nitrate in alkaline aqueous solutions containing fructose and ascorbic acid at room temperature. To the best of our knowledge, this simple strategy demonstrates the first example of preparing high-quality Cu(2)O nanocubes (yield>95%) with sizes smaller than 30?nm. By controlling several important experimental parameters such as pH, concentrations of fructose, and molar ratios of fructose/copper (II), different Cu(2)O nanostructures were prepared. The cubic nanostructures were evidenced by the metal shadowing and transmission electron microscope (TEM) images. We confirmed that the Cu(2)O nanocubes were formed from hollow to filled structures by conducting time-evolution TEM measurements. The thus-prepared Cu(2)O nanocubes possess size-dependence absorption and luminescence characteristics; they absorb light at wavelengths 360 and 454?nm and fluoresce at 493?nm (quantum yield 6.6 × 10(-2)%) when excited at 360?nm. A film of Cu(2)O nanocubes provided a photocurrent density of ～80?mA?m(-2) at a biased voltage 3?V under sunlight illumination (100?mW?cm(-2)).     

Absorption line shift with temperature and pressure: impact on laser-diode-based H2O sensing at 1.393 microm

High-resolution absorption measurements of the H2O line in the v1 + v3 band at 1.3928 microm were made in the temperature range of 296-1100 K by use of an InGaAsP distributed-feedback laser diode operating at 1.39 microm. Spectral line shift, line strength, and N2 broadening on the water-vapor line and their impact on the accuracy of optical-absorption-based gas sensing have been investigated. The results obtained were compared with values obtained from the HITRAN database and values reported in the literature, facilitating H2O sensing in a nonstandard temperature and pressure environment.     

Temperature and pressure dependence of dielectric properties of ceramic Pb(Fe(1/2)Ta(1/2))O(3)

Dielectric properties such as the real epsilon" and imaginary epsilon" parts of the complex permittivity and the spontaneous polarization P(N) of ceramic Pb(Fe(1/2)Ta(1/2))O(3) with the diffuse phase transition (DPT) were measured under pressures up to 6 kbar. The value of epsilon" shows a broad maximum at a temperature T(m) (mean Curie temperature). As the pressure increases, T(m) of the maximum epsilon" (epsilon"(max)) and the value of epsilon"(max) decrease, and the shape of the maximum in epsilon" around T(m) becomes broader. The pressure coefficient of T(m) is about -3.4 K/kbar. The small heat effect associated with the DPT was observed around T(m). The temperature and pressure dependence of epsilon" and P(s ) is explained in terms of a phenomenological theory using statistical treatments based on a Gaussian distribution of the local Curie temperature. The value of the standard deviation sigma describing the intensity of the DPT is 25 K and increases with increasing pressure.     

Optical characterization of MBE-grown GaNAs

We report on low-temperature (T=2 K) optical studies of GaNAs epi-layers with different nitrogen concentrations grown by molecular beam epitaxy (MBE). The content of N in the layers was analyzed by X-ray diffraction (XRD) and secondary-ion mass spectrometry (SIMS). Using absorption data we have determined the fundamental band gap energy and the bowing parameter as a function of nitrogen concentration in the GaN_xAs_1-x alloy up to x=4%.     

Temperature measurements from first-negative N(2)(+) spectra produced by laser-induced multiphoton ionization and optical breakdown of nitrogen

A 248-nm excimer laser was used to produce ionized nitrogen by the process of multiphoton excitation in gaseous nitrogen at room temperature. First-negative N(2)(+) emission spectra were analyzed to yield rotational temperatures of typically 600 to 1200 K. Rotational Raman scattering of H(2) in gaseous mixtures of N(2) and H(2) was used to determine if laser heating of the gas produced the observed increase in temperature, but the room temperature value of 295 K was inferred from the H(2) Raman data. Therefore the use of N(2)(+) spectra produced by multiphoton excitation at 248 nm does not appear to be acceptable for air-temperature diagnostics. N(2)(+) emission spectra were also recorded subsequent to optical breakdown in air induced by Nd:YAG 1064-nm radiation, and temperatures were determined to be greater than 5000 K in the decaying plasma.     

Experimental investigation of the self- and N(2)-broadened continuum within the ν(2) band of water vapor

We present an experimental study of the self- and N(2)-broadened H(2) O continuum in microwindows within the ν(2) fundamental centered at ~1600 cm(-1). The continuum is derived from transmission spectra recorded at room temperature with a BOMEM Fourier transform spectrometer at a resolution of ~0.040 cm(-1). Although we find general agreement with previous studies, our results suggest that there is significant near-wing super-Lorentzian behavior that produces a highly wave-number-dependent structure in the continuum as it is currently defined.     

Spray-deposited CuInS(2) solar cells

Spray deposition of CuInS(2) offers an attractive route towards industrial production of thin-film solar cells. With spray deposition it is possible to make nanocomposites of n-type TiO(2) and p-type CuInS(2). Upon application of an In(2)S(3) buffer layer, solar cells can be made with efficiencies of ～7%, being comparable to that of amorphous silicon. Rapid thermal annealing is not involved in the production of these solar cells. In order to further improve the performance, the concentration of electronic defect states in the bandgap must be reduced. Towards this end a detailed study has been undertaken to elucidate the role of associated point defects in the recombination of electron-hole pairs. Especially with transient absorption spectroscopy it is possible to make an accurate assessment of the fundamental electronic processes that are involved. We find electronic states in the bandgap related to the presence of anti-site defects. In addition, indium vacancies are also involved. State-to-state recombination occurs, indicating that the involved defects are associated. An electronic state located at 1.1?eV above the valence band, which is related to indium on a copper position, has a lifetime of about 20?μs at room temperature. The lower lying states related to copper on indium positions, and indium vacancies, are populated from this 1.1?eV state.     

Synthesis of carbon nanotube-TiO(2) nanotubular material for reversible hydrogen storage

A material consisting of multi-walled carbon nanotubes (MWCNTs) and larger titania (TiO(2)) nanotube arrays has been produced and found to be efficient for reversible hydrogen (H(2)) storage. The TiO(2) nanotube arrays (diameter ～60?nm and length ～2-3?μm) are grown on a Ti substrate, and?MWCNTs a few μm in length and ～30-60?nm in diameter are grown inside these TiO(2) nanotubes using chemical vapor deposition with cobalt as a catalyst. The resulting material has been used in H(2) storage experiments based on a volumetric method using the pressure, composition, and temperature relationship of the storage media. This material can store up to 2.5?wt% of H(2) at 77?K under 25?bar with more than 90% reversibility.     

Time-resolved wavelength modulation spectroscopy measurements of HO 2 kinetics

High-frequency wavelength modulation spectroscopy (WMS) has been applied to the detection of the hydroperoxyl radical (HO2 ) in a laser photolysis and long-path absorption pump-probe kinetics reactor with a near-infrared distributed feedback diode laser. The HO2 is formed by the 355-nm photolysis of Cl2 in the presence of CH3 OH and O2 and monitored by a phase-sensitive detection of the second-harmonic (2f ) signal in the 2?1 band with a 1.5- ?m diode laser directly modulated at 5 MHz. The measured 2f WMS signal is calibrated by direct absorption and converted to an absolute number density with the known absorption line strength of the HO2 line at 6625.80cm-1 . The utility of time-resolved WMS as a second-order kinetics probe is demonstrated through the measurement of the HO2 self-reaction rate constant at 295 K.     

Preparation and characterization of SiO2-pillared H2Ti4O9 and its photocatalytic activity for methylene blue degradation

SiO(2) pillared layered titanate (SiO(2)-H(2)Ti(4)O(9)) was prepared via intercalating organosilanes into the interlayers of the layered K(2)Ti(4)O(9) followed by calcination at 500 degrees C. The resulting materials were characterized using XRD, N(2) adsorption-desorption isotherms, UV-vis spectra, IR spectroscopy and Raman spectroscopy. The photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was evaluated by photocatalytic degradation of aqueous methylene blue dye (MB). XRD and specific surface area results showed that SiO(2)-H(2)Ti(4)O(9) had an interlayer distance of 1.45 nm and a specific surface area of 148 m(2)g(-1). UV-vis absorption spectrum of SiO(2)-H(2)Ti(4)O(9) showed a red shift, indicative of a narrower band gap compared to K(2)Ti(4)O(9). In addition, SiO(2)-H(2)Ti(4)O(9) showed higher MB adsorption capacity compared to H(2)Ti(4)O(9) and K(2)Ti(4)O(9). MB photodegradation over H(2)Ti(4)O(9), K(2)Ti(4)O(9) and SiO(2)-K(2)Ti(4)O(9) followed zero-order kinetics under our experimental conditions, and the photocatalytic activity of SiO(2)-H(2)Ti(4)O(9) was found to be three times higher than that of K(2)Ti(4)O(9), which could be attributed to the increase of interlayer space and specific surface area of SiO(2)-pillared layered titanate.