Infrared Microspectroscopy: A Molecular Probe with Micron Resolution

The 4^th International Workshop on Infrared Microscopy and Spectroscopy with Accelerator Based Sources (WIRMS 2007) was held from September 25 to 29, 2007, at the Awaji Yumebutai International Conference Center in Japan. This was the first WIRMS workshop to be held in Asia, following the highly fruitful workshops at Porquerolles (France, 2001), Lake Tahoe (USA, 2003) and Rathen (Germany, 2005). As such, it showcased some exemplary science from that region, as well as highlights from the rest of the world. The growth of the field and increased sophistication of the facilities and applications were very evident.     

Effects of pressure on flame propagation in a premixture containing fine fuel droplets

Combustion experiments on fuel droplet–vapor–air mixtures have been performed with a rapid expansion apparatus which generates monodispersed droplet clouds with narrow diameter distribution using the condensation method. The effects of fine fuel droplets on flame propagation were investigated for ethanol droplet–vapor–air mixtures at various pressures from 0.2 to 1.0 MPa. A stagnant fuel droplet–vapor–air mixture, generated in a rapid expansion chamber, was ignited at the center of the chamber using an ignition wire. Spherical flame propagation under constant-pressure conditions was observed with a high-speed video camera and flame speed was measured. Total equivalence ratio, and the ratio of liquid fuel mass to total fuel mass, was varied from 0.6 to 1.4 and from zero to 56%, respectively. The mean droplet diameter of fuel droplet–vapor–air mixtures was set at 8.5 and 11 μm. It was found that the flame speed of droplet–vapor–air mixtures less than 0.9 in the total equivalence ratio exceeds that of premixed gases of the same total equivalence ratio at all pressures. The flame speed of fuel droplet–vapor–air mixtures decreases as the pressure increases in all total equivalence ratios. At large ratios of liquid fuel mass to total fuel mass, the normalized flame speed (the flame speed of droplet–vapor–air mixtures divided by the flame speed of the premixed gas with the same total equivalence ratio), increases with the increase in pressure for fuel-lean mixtures, and it decreases for fuel-rich mixtures. The outcome is reversed at small ratios of liquid fuel mass to total fuel mass; the normalized flame speed decreases with the increase in pressure for fuel-lean mixtures, and increases for fuel-rich mixtures. The results suggest that the increase in pressure promotes droplet evaporation in the preheat zone.     

Tyrosyl Fluorescence Decays and Rotational Dynamics in Tyrosine Monomers and in Dipeptides

Picosecond time-correlated single-photon counting was used to measure fluorescence lifetimes and fluorescence anisotropy decays of tyrosine and the tyrosine–alanine and tyrosine–leucine dipeptides. After excitation of tyrosine at 287 nm two emitting species were observed, one at 303 nm with a lifetime of 3.3 ns and another at 340 nm with a lifetime of 360 ps. The rotational correlation time of tyrosine at 303 nm is 38 ps in water at pH 7 and depends linearly on viscosity with a slope of 44 ps/cP, consistent with Stokes–Einstein–Debye theory. We calculated a value of 45 ns for the radiative lifetime of tyrosine, yielding a fluorescence quantum yield of 0.07. The dipeptides Tyr–Ala and Tyr–Leu exhibit two- or three-exponential decays. The amplitudes of the decay components for three-exponential fits correlate closely with the populations of rotamers in these peptides as determined by NMR. The quenching of dipeptide fluorescence is shown to depend on the solvent polarity, strongly supporting the hypothesis that tyrosyl fluorescence in peptides is quenched by charge transfer. The rotational correlation times of tyrosine, Tyr–Ala, and Tyr–Leu increase linearly with the van der Waals volumes. However, rotational relaxation is somewhat faster than expected from Stokes–Einstein–Debye theory with stick boundary conditions.     

Alloy formation at the Ni–Al interface for nickel films deposited on Al(110) surfaces

Alloy formation at the Ni–Al interface for thin nickel films deposited on Al(110) surfaces has been studied using high-energy ion scattering/channeling (HEIS) and X-ray photoelectron spectroscopy (XPS). For nickel atoms deposited at room temperature on Al(110), a large amount of nickel–aluminum intermixing occurs at the interface. For the first two monolayers (ML) of deposited nickel, an NiAl-like compound is formed. The intermixing continues with a different rate, forming an Ni₃Al-like compound for nickel coverages from 2 to 8 ML, at which point a nickel metal film begins to grow on the surface. Nickel atoms deposited at 250°C on the Al(110) surface exhibit no surface compound formation, but diffuse up to 400 Å into the aluminum substrate. Interatomic potentials based on the embedded-atom method (EAM) are used in a Monte Carlo approach to simulate the evolution of the Ni–Al(110) interface as a function of the nickel coverage. The calculated ion-scattering yields and X-ray photoelectron intensities from nickel and aluminum atoms in these simulated interfaces are in good quantitative agreement with the experimental results. The simulations show a high-density Ni–Al alloy forming at the Al(110) surface which apparently inhibits outward diffusion of aluminum, leading to the more nickel-rich alloy and finally nickel film growth. The ion-scattering simulations show an unusually large amount of backscattering occurring below the Ni–Al(110) interface, apparently associated with defocusing of the incident ion beam.     

A microwave absorption study in the thermochromic SrMnO3

We report electron paramagnetic resonance (EPR) and magnetically modulated microwave absorption spectroscopy (MAMMAS) studies at X-band (8.8–9.6 GHz) on powdered SrMnO₃ in the 90–400 K temperature range. EPR spectrum shows one broad single-line at room temperature, which is observed only above 280.5 K, being compatible with an antiferromagnetic order. The onset of the para–antiferromagnetic transition has been determined from the temperature dependence of three main parameters extracted from the EPR spectra: resonant field (H_res), peak-to-peak linewidth (ΔH_pp) and integrated intensity (I_EPR). The MAMMAS response shows a change in the region 276–283 K, compatible with the para–antiferromagnetic transition, without presenting any significant change in the region of thermochromism.     

Effects of precursors on nucleation in atomic layer deposition of HfO2

Atomic layer deposition of hafnium dioxide (HfO₂) on silicon substrates was studied. It was revealed that due to low adsorption probability of HfCl₄ on silicon substrates at higher temperatures (450–600 °C) the growth was non-uniform and markedly hindered in the initial stage of the HfCl₄–H₂O process. In the HfI₄–H₂O and HfI₄–O₂ processes, uniform growth with acceptable rate was obtained from the beginning of deposition. As a result, the HfI₄–H₂O and HfI₄–O₂ processes allowed deposition of smoother, more homogeneous and denser films than the HfCl₄–H₂O process did. The crystal structure developed, however, faster at the beginning of the HfCl₄–H₂O process.     

Performance improvements of ultraviolet/infrared dual-band detectors

Results are reported on dual-band detectors based on a GaN/AlGaN structure operating in both the ultraviolet–midinfrared (UV–MIR) and ultraviolet–farinfrared (UV–FIR) regions. The UV detection is due to an interband process, while the MIR/FIR detection is from free carrier absorption in the emitter/contact followed by internal photoemission over the barrier at the GaN/AlGaN interface. The UV detection, which was observed from 300 K to 4.2 K, has a threshold of 360 nm with a peak responsivity of 0.6 mA/W at 300 K. The detector shows a free carrier IR response in the 3–7 μm range up to 120 K, and an impurity response around 54 μm up to 30 K. A response in the range 7–13 μm, which is tentatively assigned to transitions from C impurities and N vacancies in the barrier region, was also observed. It should also be possible to develop a detector operating in the UV–visible–IR regions by choosing the appropriate material system. A dual-band detector design, which allows not only to measure the two components of the photocurrent generated by UV and IR radiation simultaneously but also to optimize the UV and IR responses independently, is proposed.     

Absorption of subpicosecond ultraviolet laser pulses in high-density plasma

The absorption of 250 fs KrF laser pulses incident on solid targets of aluminum, copper and gold has been measured for normal incidence as a function of laser intensity in the range of 10¹²–10¹⁴ W cm^–2 and as a function of polarization and angle of incidence for the intensity range of 10¹⁴–2.5×10¹⁵ W cm^–2. As the intensity increases from 10¹² W cm^–2 the reflectivity at normal incidence changes from the low-intensity mirror reflectivity value to values in the range of 0.5–0.61 at 10¹⁴ W cm^–2. For this intensity maximum absorption of 63–80% has been observed for p-polarized radiation at angles of incidence in the range of 54°–57°, increasing with atomic number. The results are compared with the expected Fresnel reflectivity from a sharp vacuum-plasma interface with the refractive index given by the Drude model and also to numerical calculations of reflectivity for various scale length density profiles. Qualitative agreement is found with the Fresnel/Drude model and quantitative agreement is noticed with the numerical calculations of absorption on a steep density profile with normalized collision frequencies, v/, in the range of 0.13–0.15 at critical density and normalized density gradient scale lengths, L/₀, in the range of 0.018–0.053 for a laser intensity of 10¹⁴ W cm^–2.At 2.5×10¹⁵ W cm^–2 a small amount of preplasma is present and maximum absorption of 64–76% has been observed for p-polarized radiation at angles of incidence in the range of 45°–50°.Dedicated to Prof. Dr. Rudolf Wienecke on the occasion of his 65^th birthdayOn leave from: Department of Electrical Engineering, University of Alberta, Edmonton, T6G 2G7, Canada     

Electrodischarge Ultraviolet Xenon/Iodine Lamp

The emission characteristics of the low-pressure electrodischarge UV lamp based on a mixture of xenon with iodine vapors have been investigated. The lamp was pumped in a dc longitudinal flow discharge with an interelectrode spacing of 50 cm at an electric power of discharge of 50–250 W. We investigated the volt-ampere characteristics, the plasma radiation spectra, and the dependences of the radiation power and efficiency of the lamp on the discharge electric power and the partial pressure of xenon in the mixture. The total radiation power of the electrodischarge lamp in the 206– 350-nm range reaches 22 W at an efficiency of ≤11%.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 247–250, March–April, 2005.     

Novel mid-IR laser based on hybrid AlGaAsSb/InAs/CdMgSe heterostructure

We report on the development of a novel design of a mid-IR laser combining III–V and II–VI compounds in a “hybrid” double heterostructure. It possesses large (1.5 eV) potential barriers both for injected electrons and holes, suppressing their leakage from the active region, and provides strong optical confinement. An AlGaAsSb/InAs/CdMgSe laser diode with a III–V/II–VI heterovalent interface at the 0.6 μm-InAs active region has been grown by molecular beam epitaxy on an InAs substrate. Despite a far from optimal defect density at the CdMgSe/InAs interface and high losses inherent for bulk active region of the laser, the structure demonstrates lasing at 2.8 μm (up to 100 K) in the pulsed regime with a threshold current density of 3–4 kA/cm². Type II InSb monolayer insertions into an InAs layer show bright photoluminescence at 3.8 μm (77 K), confirming the great potential of the InAs-based nanostructure active region for longer wavelength applications.     

Decomposition mechanism of triethylindium (TEI) on a GaP(0 0 1)-(2×1) surface studied by LEED, AES, TPD and HREELS

Adsorption and decomposition of triethylindium (TEI: (C₂H₅)₃In) on a GaP(0 0 1)-(2×1) surface have been studied by low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). It is found from the TPD result that ethyl radical and ethylene are evolved at about 300–400 and 450–550 K, respectively, as decomposition products of TEI on the surface. This result is quite different from that on the GaP(0 0 1)-(2×4) surface. The activation energy of desorption of ethyl radical is estimated to be about 93 kJ/mol. It is suggested that TEI is adsorbed molecularly on the surface at 100 K and that some of TEI molecules are dissociated into C₂H₅ to form P–C₂H₅ bonds at 300 K. The vibration modes related to ethyl group are decreased in intensity at about 300–400 and 450–550 K, which is consistent with the TPD result. The TEI molecules (including mono- and di-ethylindium) are not evolved from the surface. Based on the TPD and HREELS results, the decomposition mechanism of TEI on the GaP(0 0 1)-(2×1) surface is discussed and compared with that on the (2×4) surface.     

Asymmetric double-barrier S–I1–N–I2–S Josephson heterojunctions: experiment and theory

Double-barrier highly asymmetric Nb–Al oxide–Al–Nb oxide–Nb structures with reproducible characteristics were fabricated. The heterocontacts with the middle Al layer thickness ranging from 4 to 6 nm exhibited a well-defined d.c. Josephson supercurrent I_c at 4.2 K and characteristic voltages V_c=I_cR_N (R_N is the normal resistance, V_c defines the response time of the junction) from 0.3 to 0.4 mV. Two prominent features in the quasiparticle current–voltage curves have been observed: a so-called ‘knee' in the energy-gap region and an additional (to the linear voltage dependence) current at higher biases. They are discussed within a simple Landauer–Büttiker scattering approach to the phase-coherent quasiparticle transport in a quasiballistic S–I₁–N–I₂–S heterostructure with an extremely great difference between the barrier transparencies.     

Analysis of diffuse reflection and absorption spectra of ZnO in the near-IR region

It is established that the absorption of ZnO in the near-IR region of the spectrum is determined by free electrons and chemisorbed gases. The free-electron absorption spectrum is approximated by a power function with an exponent which varies within the range 2–3, depending on the defectiveness of the specimen. Chemisorbed gases yield absorption bands at 1.37; 1.18; 1.08–1.03; 0.95–0.93; 0.85; 0.75–0.73; and 0.65–0.63 eV. The bands at 1.18 and 0.85 eV are due to chemisorbed oxygen in the states O^– and O₂ ^–, while the other bands can be attributed mainly to atomic hydrogen and OH-groups.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 86–90, July, 1988.We thank E. V. Komarov for his help in conducting the experiments.     

Thermodynamic modeling of the ZrO2–YO1.5 system

In the present work, an optimized set of Gibbs energy functions is proposed for the Y–Zr–O ternary system. We focus on the ZrO₂–YO_1.5 quasi-binary system, but reoptimizations of the Zr–O and Y–O binary systems are included as well. The parameters for the Y–Zr binary system were taken from a previous assessment.

The ZrO₂–YO_1.5 system was treated as a quasi-binary section of the Y–Zr–O ternary system. The existing experimental data on the ZrO₂–YO_1.5 system were carefully reviewed. The related parameters were optimized using both thermodynamic data and phase diagram data. A calculated phase diagram of the ZrO₂–YO_1.5 system is presented. Our optimization agrees well with most experimental data. Two calculated isothermal sections of the Y–Zr–O system at 1500 and 2000 K are also included.     

Dislocation structure of kcl crystals grown with vibration of the melt

Summary The amplitude at all frequencies was 0.04 mm. Three crystals were grown at each frequency, with seeds of dislocation density D = 6 × 10⁴ cm^–2. Figure 1 shows the frequency dependence of the final D. Each point in Figs. 1 and 2 is the mean from 50 measurements (50 fields of view). At all frequencies except 180 Hz, D was 2–4 times less than that without vibration, while at 100 and 160 Hz it was less by nearly an order of magnitude.The effects of amplitude (0.02 to 0.2 mm) were examined at 100 Hz, the minimum D occurring at 0.1 mm (Fig. 2). At 0.04–0.08 mm, D was less by a factor 3–4 than for crystals grown without vibration, while at 0.1 mm it was less by an order of magnitude, being 2 × 10^–4 cm^–2. The size of the etch pits on crystals grown at amplitudes up to 0.1 mm did not differ from that for crystals grown at rest, but above 0.1 mm the size increased, by more than a factor 3 at 0.2 mm. Figure 3 illustrates these effects.Optimal vibration reduces D by improving the growth conditions (reduction of temperature gradients by mixing, more uniform impurity distribution).     

Low-temperature internal friction of modified Ti50Ni42Co8 alloy

In this work we have investigated the internal friction of the alloy Ti₅₀Ni₄₂Co₈ with Hf (0.5–0.8 at. %) and Y (0.1 at. %) additives in the temperature range 4.2–293 K at frequencies of 200–600 Hz. We see two peaks on the temperature dependence of the internal friction for the alloy oxidized in an air atmosphere at 1100 K: the first peak at T=40 K is connected with movement of interphase boundaries during the thermoelastic phase transformation occurring according to the scheme B2 R B19'; and the second peak at 220–240 K is mainly connected with diffusion under the pressure of hydrogen adsorbed on the oxide particles. The hydrogen penetrates the alloy during sample preparation upon etching and electropolishing in acid solution. Support for the latter hypothesis comes from internal friction vs temperature data for the alloy hydrogen-charged at 1073 K in a gaseous atmosphere and then subjected to vacuum annealing at the same temperature, as well as the results of x-ray diffraction analysis.Voronezh Polytechnical Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 14–20, December, 1992.     

Test-based thermal explosion model for HMX

We present a thermal explosion (cookoff) model for an HMX-based plastic bonded explosive (LX-10). The thermal–chemical–mechanical response of LX-10 is modeled based on the measurements from the scaled thermal explosion experiment (STEX) at the Lawrence Livermore National Laboratory. Confined LX-10 is heated at a rate of 1 °C/h until an explosion is observed. The modeled cookoff problem is simulated by the Arbitrarily Lagrangian–Eulerian hydrocode (ALE3D) that can handle a wide spectrum of time scales that vary from a structural to a high speed shock physics time scale. In addition to a comprehensive model for energetic material, the confinement material namely an AerMet 100 steel is modeled as a Steinberg–Guinan material with a Johnson–Cook failure model with a statistical failure distribution. By using the size distribution data from the fragmentation experiment, the metal fracture and fragmentation due to an explosion are modeled. The explosion temperature is predicted to within 1°. Calculated wall strain provides violence associated with the thermal explosion process and agrees favorably with the measured STEX data.     

Recent advances in linear and nonlinear Raman spectroscopy. Part VII

The aim of this paper is to provide an overview of advances in the field of Raman spectroscopy as reflected in articles published each year in the Journal of Raman Spectroscopy as well as in trends across related journals publishing in this research area. The context for this review is derived from statistical data on article counts obtained from Thomson Reuters ISI Web of Knowledge by year and by subfield of Raman spectroscopy. Additional information is gleaned from presentations featuring Raman spectroscopy presented at the International Conference on Advanced Vibrational Spectroscopy in Kobe Japan in August 2013 and at SCIX 2013 sponsored by the Federation of Analytical Chemistry and Spectroscopy Societies in Milwaukee, Wisconsin, USA, October 2013. Papers published in the Journal of Raman Spectroscopy in 2012 are highlighted in this review and reflect topics and advances at the frontier of Raman spectroscopy, a field that is expanding rapidly as a sensitive photonic probe of matter at the molecular level in an ever widening sphere of novel applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Properties of MgO at high pressures: Shell-model molecular dynamics simulation

Shell-model molecular dynamics (MD) simulation has been performed to investigate the melting of the major Earth-forming mineral: periclase (MgO), at elevated temperatures and high pressures, based on the thermal instability analysis. The interatomic potential is taken to be the sum of pair-wise additive Coulomb, van der Waals attraction, and repulsive interactions. The MD simulation with selected Lewis–Catlow (LC) potential parameters is found to be very successful in describing the melting behavior for MgO, by taking account of the overheating of a crystalline solid at ambient pressure. The thermodynamic melting curve is estimated on the basis of the thermal instability MD simulations and compared with the available experimental data and other theoretical results in the pressure ranges 0–150 GPa. Our simulated melting curve of MgO is consistent with results obtained from Lindemann melting equation and two-phase simulated data at constant pressure by Belonoshko and Dubrovinsky, in the pressure below 20 GPa. The extrapolated melting temperatures in the lower mantle are in good agreement with the results obtained from Wang's empirical model up to 100 GPa. Compared with experimental measurements, our results are substantially higher than that determined by Zerr and Boehler, and the discrepancy between DAC and MD melting temperatures may be well explained with different melting mechanisms. Meanwhile, the radial distribution functions (RDFs) of Mg–Mg, O–Mg, and O–O ion pairs near the melting temperature have been investigated.