Photoacoustic spectrometer for accurate,continuous measurements of atmospheric carbon dioxide concentration

We have developed a portable photoacoustic spectrometer that offers routine, precise and accurate measurements of the molar concentration of atmospheric carbon. The temperature-controlled spectrometer continuously samples dried atmospheric air and employs an intensity-modulated distributed feedback laser and fiber amplifier operating near 1.57 µm. For measurements of carbon dioxide in air, we demonstrate a measurement precision (60-s averaging time) of 0.15 µmol mol^?1 and achieve a standard uncertainty of 0.8 µmol mol^?1 by calibrating the analyzer response in terms of certified gas mixtures. We also investigate how water vapor affects the photoacoustic signal by promoting collisional relaxation of the carbon dioxide.     

Point focusing with flat and wedged crossed multilayer Laue lenses

Point focusing measurements using pairs of directly bonded crossed multilayer Laue lenses (MLLs) are reported. Several flat and wedged MLLs have been fabricated out of a single deposition and assembled to realise point focusing devices. The wedged lenses have been manufactured by adding a stress layer onto flat lenses. Subsequent bending of the structure changes the relative orientation of the layer interfaces towards the stress‐wedged geometry. The characterization at ESRF beamline ID13 at a photon energy of 10.5 keV demonstrated a nearly diffraction‐limited focusing to a clean spot of 43 nm × 44 nm without significant side lobes with two wedged crossed MLLs using an illuminated aperture of approximately 17 µm × 17 µm to eliminate aberrations originating from layer placement errors in the full 52.7 µm × 52.7 µm aperture. These MLLs have an average individual diffraction efficiency of 44.5%. Scanning transmission X‐ray microscopy measurements with convenient working distances were performed to demonstrate that the lenses are suitable for user experiments. Also discussed are the diffraction and focusing properties of crossed flat lenses made from the same deposition, which have been used as a reference. Here a focal spot size of 28 nm × 33 nm was achieved and significant side lobes were noticed at an illuminated aperture of approximately 23 µm × 23 µm.     

High resolution laser-based detection of ammonia

In the present paper we compare the response of two types of photoacoustic cells (resonant and nonresonant) to determine the amount of ammonia volatilized from biological liquid samples at constant temperature, pressure and pH. The home made detector was a photoacoustic spectroscopy apparatus developed by Molecular Spectroscopy Laboratory staff at ENEA Frascati Research Centre in Italy. The sensor makes use of photo-acoustic cells equipped with commercially available high sensitivity miniaturized microphones. The radiation source was a line-tunable stabilized 10 W CW CO₂ laser. Ammonia measurements were performed by tuning the laser source on the 9R30 laser line (9.2197 µm radiation wavelength). Ammonium chloride standard solutions were prepared by us in laboratory, to serve as reproducible ideal samples. The photoacoustic response of the two type of photoacoustic cells was determined and compared. The feasibility study was reported.     

Enhanced photoacoustic imaging in tissue-mimicking phantoms using polydopamine-shelled perfluorocarbon emulsion droplets

The current work features process parameters for the ultrasound (25 kHz)-assisted fabrication of polydopamine-shelled perfluorocarbon (PDA/PFC) emulsion droplets with bimodal (modes at 100–600 nm and 1–6 µm) and unimodal (200–600 nm) size distributions. Initial screening of these materials revealed that only PDA/PFC emulsion droplets with bimodal distributions showed photoacoustic signal enhancement due to large size of their optically absorbing PDA shells. Performance of this particular type of emulsion droplets as photoacoustic agents were evaluated in Intralipid®–India ink media, mimicking the optical scattering and absorbance of various tissue types. From these measurements, it was observed that PDA/PFC droplets with bimodal size distributions can enhance the photoacoustic signal of blood-mimicking phantom by up to five folds in various tissue-mimicking phantoms with absorption coefficients from 0.1 to 1.0 cm⁻¹. Furthermore, using the information from enhanced photoacoustic images at 750 nm, the ultimate imaging depth was explored for polydopamine-shelled, perfluorohexane (PDA/PFH) emulsion droplets by photon trajectory simulations in 3D using a Monte Carlo approach. Based on these simulations, maximal tissue imaging depths for PDA/PFH emulsion droplets range from 10 to 40 mm, depending on the tissue type. These results demonstrate for the first time that ultrasonically fabricated PDA/PFC emulsion droplets have great potential as photoacoustic imaging agents that can be complemented with other reported characteristics of PDA/PFC emulsion droplets for extended applications in theranostics and other imaging modalities.     

Microfocusing options for the inelastic X‐ray scattering beamline at sector 3 of the Advanced Photon Source

Synchrotron radiation from third‐generation high‐brilliance storage rings is an ideal source for X‐ray microbeams. The aim of this paper is to describe a microfocusing scheme that combines both a toroidal mirror and Kirkpatrick–Baez (KB) mirrors for upgrading the existing optical system for inelastic X‐ray scattering experiments at sector 3 of the Advanced Photon Source. SHADOW ray‐tracing simulations without considering slope errors of both the toroidal mirror and KB mirrors show that this combination can provide a beam size of 4.5 µm (H) × 0.6 µm (V) (FWHM) at the end of the existing D‐station (66 m from the source) with use of full beam transmission of up to 59%, and a beam size of 3.7 µm (H) × 0.46 µm (V) (FWHM) at the front‐end of the proposed E‐station (68 m from the source) with a transmission of up to 52%. A beam size of about 5 µm (H) × 1 µm (V) can be obtained, which is close to the ideal case, by using high‐quality mirrors (with slope errors of less than 0.5 µrad r.m.s.). Considering the slope errors of the existing toroidal and KB mirrors (5 and 2.9 µrad r.m.s., respectively), the beam size grows to about 13.5 µm (H) × 6.3 µm (V) at the end of the D‐station and to 12.0 µm (H) × 6.0 µm (V) at the front‐end of the proposed E‐station. The simulations presented here are compared with the experimental measurements that are significantly larger than the theoretical values even when slope error is included in the simulations. This is because of the experimental set‐up that could not yet be optimized.     

Semiconducting properties of CoO thin films

This paper reports electrical properties of CoO thin films of different thickness in the range 0.375 – 7.95 μm. Both electrical conductivity and thermopower were measured at elevated temperatures (1223 – 1423 K) and under controlled oxygen partial pressure (5 − 2.1x10⁴ Pa). It was found that at low p(O₂) the electrical conductivity decreases with film thickness. The activation energy of the electrical conductivity (E_a) in air decreases with the oxide thickness from 0.56 eV at 0.375 μm to 0.52 eV for massive CoO while at low p(O₂)=5 Pa the E_a is independent of the thickness (E_a = 0.46 eV). The reciprocal of the p(O₂) exponent of the electrical conductivity (n_δ) in the range 1223 K – 1373 K is close to four for the 7,95 μm film and is about 3.5–3.7 for the 0.375 μm film. The electrical properties of the CoO thin films are considered assuming different defect structures in the bulk phase and the surface layer.     

Infrared-laser photoacoustic spectroscopy

This paper reviews the applications of IR-laser photoacoustics to trace-gas monitoring as well as to spectroscopic studies on absorbing liquids.In the first part we present a stationary, dual-beam CO-laser and a mobile CO₂-laser photoacoustic system which have both been applied to the monitoring of various gaseous pollutants. Emphasis is put on selectivity, sensitivity and on temporal resolution. Novel cell designs and experimental techniques and an iterative procedure for the analysis of photoacoustic spectra of multicomponent mixtures are introduced. New results are presented for measurements on car and industrial exhausts as well as on ambient air.The second part is devoted to theoretical and experimental photoacoustic studies on strongly absorbing liquids, in particular on the investigation of different boundary conditions. A characteristic enhancement of the photoacoustic signal in the liquid is obtained if a liquid or solid surface layer is present. This new phenomenon permits the analysis of surface films with a thickness of ⩾ 1 μm. Furthermore, the photoacoustic in-situ monitoring of the polymerization process on a liquid surface is presented for the first time.     

Integral and temporal characteristics of soft X-rays of the PF-4 plasma focus setup

Soft X-rays of a setup with a power from 1.5 to 5 kJ, operating with argon, were measured using X-ray pinhole cameras and SPPD 11-04 detectors. Integral measurements of X-rays in energy ranges above 1.2, 1.5, 1.8, and 2.5 keV were performed using a 4-frame pinhole camera with hole sizes of ～250 µm. Simultaneously, the X-ray yield was measured with time resolution in the energy region of > 1.8 keV using a semiconductor detector. X-ray characteristics were experimentally studied at a capacitor bank voltage of 8–14 kV and argon pressures from 1.2 to 3 Torr. The size of hot points was estimated using the pinhole camera with a hole size of ～20 µm as less than 13–25 µm.     

Effect of bismuth nanolayers on the oriented growth of fullerene C<Subscript>60</Subscript> on an amorphous substrate

The effect of a bismuth sublayer with an effective thickness of 0.5 to 4 nm on the structure of C₆₀ fullerene films grown on amorphous substrates (silicon covered with a natural oxide layer; glass) using the quasi-closed-volume method is studied. An x-ray diffraction study of fullerene films showed that the intensity ratio between the (220) and (111) peaks depends nonmonotonically on the sublayer thickness. In the bismuth sublayer thickness range 0.5–2.0 nm, fullerene films are found to exhibit a growth texture with the 〈110〉 axis; the average crystallite size was ～20 µm. The quality of the texture can be improved by varying the fullerene growth temperature.     

Dynamics of phase formation in multilayer Ti-Al nanofilms upon heating

Structural transformations in multilayer Ti-Al films (layer thickness from 4 to 500 nm, number of layers up to 4440, total foil thickness ∼18 μm) upon slow heating have been studied by time-resolved synchrotron radiation diffraction. Some specific features of heterogeneous reactions and the sequence of phase formation in multilayer samples during the interaction of interaction between layer components have been determined as functions of the single layer thickness. Original Russian Text ? I.Yu. Yagubova, A.E. Grigoryan, A.S. Rogachev, M.R. Sharafutdinov, B.P. Tolochko, P.A. Tsygankov, A.N. Nosyrev, 2007, published in Izvestiya Rossiiskoi Akademii Nauk. Seriya Fizicheskaya, 2007, Vol. 71, No. 2, pp. 278–279.     

Optical properties of a thermocapillary depression

An axisymmetrical thermocapillary depression is induced by a He-Ne laser beam in a plane-parallel layer of a transparent liquid on an absorbing substrate. The focal length of the central part of this depression in the form of a concave mirror is studied as a function of thickness of the benzyl-alcohol layer and beam power. At a laser power of 3.5–16.5 mW, the focal length increases almost linearly with the layer thickness changing from 200 to 1000 μm. In this range of thicknesses, an increase in the beam power leads to a decrease in the focal length following a power law with an exponent close to −0.8. __________ Translated from Optika i Spektroskopiya, Vol. 92, No. 4, 2002, pp. 665–670. Original Russian Text Copyright ? 2002 by Bezuglyĭ, Tarasov.     

Induced formation of corundum crystals in supercritical water fluid

The formation of fine-crystalline corundum (α-Al₂O₃) from hydrargillite in supercritical water fluid (SCWF) at 400°C and 26.8 MPa in the presence of corundum particles was studied. It was found that the α-Al₂O₃ particles added to the reaction medium accelerated the formation of fine-crystalline corundum due to an increase in the rate of nucleation. In this case, both the buildup of added corundum grains, and the generation of new corundum crystals from boehmite were observed. The formation of new crystals depended on distance between the grains of the additive. Depending on this distance, the newly formed crystals consisted of two or three fractions with different average particle sizes. It was concluded that the buildup of the fused corundum particles in SCWF occurred due to the uptake of corundum nuclei formed in a surrounding layer of boehmite. For the added particles of fused corundum with an average size of 2.82 µm, the thickness of a layer from which the buildup occurred was 17.47 µm. The corundum nuclei formed at large distances from the growing particles became the centers of growth for new corundum crystals of the smallest sizes. The role of SCWF consisted in increasing the spatial and structural mobility of the reactants.     

Optoheterodyne Doppler measurements of the ballistic expansion of the products of the shock wave-induced surface destruction: Experiment and theory

The results of optoheterodyne Doppler measurements of the ballistic expansion of the products of surface destruction under shock-wave loading are presented. The possibility of determining the physical characteristics of a rapidly flying dust cloud, including the microparticle velocities, the microparticle sizes, and the areal density of the dust cloud, is shown. A compact stand for performing experiments on shock-wave loading of metallic samples is described. Shock-wave loading is performed by a 100-µm-thick tantalum flyer plate accelerated to a velocity of 2.8 km/s. As the samples, lead plates having various thicknesses and the same surface roughness are used. At a shock-wave pressure of 31.5 GPa, the destruction products are solid microparticles about 50 µm in size. At a pressure of 42 and 88 GPa, a liquid-drop dust cloud with a particle size of 10–15 µm is formed. To interpret the spectral data on the optoheterodyne Doppler measurements of the expansion of the surface destruction products (spalled fragments, dust microparticles), a transport equation for the function of mutual coherence of a multiply scattered field is used. The Doppler spectra of a backscattered signal are calculated with the model developed for the dust cloud that appears when a shock wave reaches the sample surface at the parameters that are typical of an experimental situation. Qualitative changes are found in the spectra, depending on the optical thickness of the dust cloud. The obtained theoretical results are in agreement with the experimental data.     

Phase measurements of surface electromagnetic waves on silver with excitation through the substrate

Surface electromagnetic waves are excited in the visible and near-IR regions of the spectrum, and interference measurements are performed. Their excitation is effected by a helium-neon laser (3.39, 1.15, and 0.63 μm) on the interface between air and a silver film of thickness 100 μm deposited on a substrate in the form of a prism of fused quartz. The exciting radiation is supplied from the substrate side in a regime of total internal reflection in the prism on the edge of the silver film. The wave vector of the surface electromagnetic wave investigated is determined from the results of phase measurements. The dependence of the efficiency of the excitation of surface electromagnetic waves on the angle of incidence of the exciting radiation onto the substrate is investigated. The real part of the dielectric function of the silver film is calculated. Zh. Tekh. Fiz. 68, 64–68 (March 1998)     

A new method of creating minibeam patterns for synchrotron radiation therapy: a feasibility study

Several synchrotrons around the world are currently developing innovative radiotherapy techniques with the aim of palliating and possibly curing human brain tumors. Amongst them, microbeam radiation therapy (MRT) and, more recently, minibeam radiation therapy (MBRT) have shown promising results. In MBRT the beam thickness ranges from 500 to 700 µm with a separation between two adjacent minibeams of the same value, whilst in MRT the thickness is of the order of 25–50 µm with a distance between adjacent microbeams of the order of 200 µm. An original method has been developed and tested at the ESRF ID17 biomedical beamline to produce the minibeam patterns. It utilizes a specially developed high‐energy white‐beam chopper whose action is synchronized with the vertical motion of the target moving at constant speed. Each opening of the chopper generates a horizontal beam print. The method described here has the advantage of being simple and reliable, and it allows for an easy control of the patient safety in future clinical trials. To study the feasibility of the method, dosimetric measurements have been performed using Gafchromic HD‐810 films and compared with Monte Carlo simulations. The results of this comparison are discussed.     

Effect of primary filter using theoretical intensity of fluorescent X‐rays and scattered X‐rays

A primary filter is often used for low‐concentration analysis by energy‐dispersive X‐ray fluorescence spectrometer. We determined the material and thickness of the primary filter and calculated the theoretical intensities of the fluorescent X‐rays and scattered X‐rays using lead in brass, for which the concentration is known. The filter materials were zirconium, nickel, titanium, aluminum, and molybdenum with a thickness between 20 and 125 µm. For verification, we calculated the lower limits of detection using theoretical intensities for several filters and compared them with values calculated using the measured intensities. For example, both values were similar for a 125 µm zirconium filter: 128.0 ppm using theoretical intensities and 147.7 ppm using measured intensities. The theoretical intensity values are obtained by measurements and calculations, but require no primary filters for the measurements. This method is extremely effective for selecting the optimal filter for multiple samples and elements. Copyright © 2010 John Wiley & Sons, Ltd.     

Improved performance of silicon‐nanoparticle film‐coated dye‐sensitized solar cells

Silicon (Si) nanoparticles with average size of 13 nm and orange–red luminescence under UV absorption were synthesized using electrochemical etching of silicon wafers. A film of Si nanoparticles with thickness of 0.75 µm to 2.6 µm was coated on the glass (TiO₂ side) of a dye‐sensitized solar cell (DSSC). The cell exhibited nearly 9% enhancement in power conversion efficiency (η) at film thickness of ～2.4 µm under solar irradiation of 100 mW/cm² (AM 1.5) with improved fill factor and short‐circuit current density. This study revealed for the first time that the Si‐nanoparticle film converting UV into visible light and helping in homogeneous irradiation, can be utilized for improving the efficiency of the DSSCs. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ultra‐thin optical grade scCVD diamond as X‐ray beam position monitor

Results of measurements made at the SIRIUS beamline of the SOLEIL synchrotron for a new X‐ray beam position monitor based on a super‐thin single crystal of diamond grown by chemical vapor deposition (CVD) are presented. This detector is a quadrant electrode design processed on a 3 µm‐thick membrane obtained by argon–oxygen plasma etching the central area of a CVD‐grown diamond plate of 60 µm thickness. The membrane transmits more than 50% of the incident 1.3 keV energy X‐ray beam. The diamond plate was of moderate purity (～1 p.p.m. nitrogen), but the X‐ray beam induced current (XBIC) measurements nevertheless showed a photo‐charge collection efficiency approaching 100% for an electric field of 2 V µm^?1, corresponding to an applied bias voltage of only 6 V. XBIC mapping of the membrane showed an inhomogeneity of more than 10% across the membrane, corresponding to the measured variation in the thickness of the diamond plate before the plasma etching process. The measured XBIC signal‐to‐dark‐current ratio of the device was greater than 10⁵, and the X‐ray beam position resolution of the device was better than a micrometer for a 1 kHz sampling rate.     

Hexagonal (wurtzite) GaN inclusions as a defect in cubic (zinc-blende) GaN

The dependence of the hexagonal fraction with thickness in MBE-grown bulk cubic (c-) GaN epilayer is presented in this paper. A number of c-GaN epilayers with different thicknesses were characterized via PL and XRD measurements. From the PL spectra, the signal due to h-GaN inclusions increases as the thickness of the c-GaN increases. On the contrary, in the XRD diffractogram, c-GaN shows a dominant signal at all thicknesses, and only a weak peak at ∼35° is observed in the diffractogram, implying the existence of a small amount of h-GaN in the c-GaN layer. The best quality of c-GaN is observed in the first 10 μm of GaN on the top of GaAs substrate. Even though the hexagonal content increases with the thickness, the average content remains below 20% in c-GaN layers up to 50 μm thick. The surface morphology of thick c-GaN is also presented.     

Indentation fracture and indentation delamination in ZnO film/Si substrate systems

ZnO films with thicknesses ranging from 0.202 to 1.535?µm were deposited by using the magnetron sputtering technique on Si (100) substrates 525?µm thick. Then, Vickers indentation tests were carried out on the ZnO/Si systems at room temperature, in which the applied load varied from 10?mN to 2.0?N. The experimental results show that only indentation-induced radial cracking occurred in the systems with film thicknesses equal to and thinner than 0.554?µm, from which the residual stress in the films was extracted to be 387?MPa in compression. For the systems with film thicknesses equal to and thicker than 0.832?µm, only indentation-induced delamination occurred when indentation loads were low. Under high indentation loads, radial cracking concurrently occurred with delamination. The radial cracks were invisible at the film surfaces because the crack length was smaller than the delamination size. The critical film thickness for indentation-induced delamination was found to be around 0.7?µm for the ZnO/Si systems. Combining the composite hardness models with the indentation-induced delamination model, we developed a method to determine the interfacial fracture energy between a film and its substrate. The novel method is particularly useful for indentation equipment without any displacement measurement devices. Using the new method, we extracted the interfacial fracture energy to be about 12.2?J?m^?2 and from 9.2 to 11.7?J?m^?2 for the cases without and with buckling respectively of delaminated films. Consequently, the pure mode I interfacial fracture energy was calculated to be 10.4?J?m^?2 for the ZnO/Si systems.