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Raman spectra and cross sections of ammonia, chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400-1400 cm-1

Published in:
AIP Advances, Vol. 6, No. 2, February 2016, 025310, doi: 10.1063/1.4942109.

Summary

Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint region 400-1400 cm-1. A relatively compact (< 2'x2'x2'), sensitive, 532 nm 10 W CW Raman system with double-pass laser and double-sided collection was used for these measurements. Two Raman modes are observed at 934 and 967 cm-1 in NH3. Three Raman modes are observed in Cl2 at 554, 547, and 539 cm-1, which are due to the 35/35 35/37, and 37/37 Cl isotopes, respectively. Raman modes are observed at 870, 570, and 1151 cm-1 in H2S, COCl2, and SO2, respectively. Values of 3.68 ± 0.26x10-32 cm2/sr (3.68 ± 0.26x10-36 m2/sr), 1.37 ± 0.10x10-30 cm2/sr (1.37 ± 0.10x10-34 m2/sr), 3.25 ± 0.23x10-31 cm2/sr (3.25 ± 0.23x10-35 m2/sr), 1.63 ± 0.14x10-30 cm2/sr (1.63 ± 0.14x10-34 m2/sr), and 3.08 ± 0.22x10-30 cm2/sr (and 3.08 ± 0.22x10-34 m2/sr) were determined for the differential Raman cross section of the 967 cm-1 mode of NH3, sum of the 554, 547, and 539 cm-1 modes of Cl2, 870 cm-1 mode of H2S, 570 cm-1 mode of COCl2, and 1151 cm-1 mode of SO2, respectively, using the differential Raman cross section of 3.56 ± 0.14x10-31 cm2/sr (3.56 ± 0.14x10-35 m2/sr) for the 1285 cm-1 mode of CO2 as the reference.
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Summary

Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint region 400-1400 cm-1. A relatively compact ( 2'x2'x2'), sensitive, 532 nm 10 W CW Raman system with double-pass laser and double-sided collection was used for these...

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Reagent approaches for improved detection of chlorate and perchlorate salts via thermal desorption and ionization

Published in:
Rapid Commun. Mass Spectrom., Vol. 30, No. 1, 15 January 2016, pp. 191-8, DOI: 10.1002/rcm.7427.

Summary

RATIONALE: Techniques for improving the detectability of chlorate and perchlorate salts with thermal desorption based ionizers (i.e. radioactive, corona discharge and photoionization-based) are desired. This work employs acidic reagents to chemically transform chlorate and perchlorate anions into traces of chloric and perchloric acid. These high vapor pressure acids are easier to detect than the originating salts. METHODS: The efficacy of the reagent chemistry was quantified with a triple-quadrupole mass spectrometer interfaced with a custom-built thermal-desorption atmospheric-pressure chemical ionization (TD-APCI) source. Additional experiments were conducted using tandem IMS/MS instrumentation. Reagent pKa and pH values were varied in order to gain a better understanding of how those parameters affect the degree of observed signal enhancement. RESULTS: Samples of chlorates and perchlorates treated with liquid acidic reagents exhibit signal enhancement of up to six orders of magnitude compared with signals from untreated analytes. Three orders of magnitude of signal enhancement are demonstrated using solid-state reagents, such as weakly acidic salts and polymeric acids. Data is presented that demonstrates the compatibility of the solid-state approach with both MS and IMS/MS platforms. CONCLUSIONS: Several methods of acidification were demonstrated for enhanced vaporization and detection of chlorates and perchlorates. For applications where rapid surface collection and analysis for chlorates and perchlorates are desired, the solid-state approaches offer the simplest means to integrate the reagent chemistry into MS or IMS detection.
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Summary

RATIONALE: Techniques for improving the detectability of chlorate and perchlorate salts with thermal desorption based ionizers (i.e. radioactive, corona discharge and photoionization-based) are desired. This work employs acidic reagents to chemically transform chlorate and perchlorate anions into traces of chloric and perchloric acid. These high vapor pressure acids are easier...

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Photothermal speckle modulation for noncontact materials characterization

Summary

We have developed a noncontact, photothermal materials characterization method based on visible-light speckle imaging. This technique is applied to remotely measure the infrared absorption spectra of materials and to discriminate materials based on their thermal conductivities. A wavelength-tunable (7.5-8.7 um), intensity-modulated, quantum cascade pump laser and a continuous-wave 532 nm probe laser illuminate a sample surface such that the two laser spots overlap. Surface absorption of the intensity-modulated pump laser induces a time-varying thermoelastic surface deformation, resulting in a time-varying 532 nm scattering speckle field from the surface. The speckle modulation amplitude, derived from a series of visible camera images, is found to correlate with the amplitude of the surface motion. By tuning the pump laser's wavelength over a molecular absorption feature, the amplitude spectrum of the speckle modulation is found to correlate to the IR absorption spectrum. As an example, we demonstrate this technique for spectroscopic identification of thin polymeric films. Furthermore, by adjusting the rate of modulation of the pump beam and measuring the associated modulation transfer to the visible speckle pattern, information about the thermal time constants of surface and sub-surface features can be revealed. Using this approach, we demonstrate the ability to distinguish between different materials (including metals, semiconductors, and insulators) based on differences in their thermal conductivities.
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Summary

We have developed a noncontact, photothermal materials characterization method based on visible-light speckle imaging. This technique is applied to remotely measure the infrared absorption spectra of materials and to discriminate materials based on their thermal conductivities. A wavelength-tunable (7.5-8.7 um), intensity-modulated, quantum cascade pump laser and a continuous-wave 532 nm...

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Super-resolution microscopy by movable thin-films with embedded microspheres: resolution analysis

Summary

Microsphere-assisted imaging has emerged as an extraordinary simple technique of obtaining optical super-resolution. This work addresses two central problems in developing this technology: i) methodology of the resolution measurements and ii) limited field-of-view provided by each sphere. It is suggested that a standard method of resolution analysis in far-field microscopy based on convolution with the point-spread function can be extended into the superresolution area. This allows developing a unified approach to resolution measurements, which can be used for comparing results obtained by different techniques. To develop the surface scanning functionality, the high-index (n ~ 2) barium titanate glass microspheres were embedded in polydimethylsiloxane (PDMS) thin-films. It is shown that such films adhere to the surface of nanoplasmonic structures so that the tips of embedded spheres experience the objects' optical near-fields. Based on rigorous criteria, the resolution ~lambda/6-lambda/7 (where lambda is the illumination wavelength) is demonstrated for arrays of Au dimers and bowties. Such films can be translated along the surface of investigated samples after liquid lubrication. It is shown that just after lubrication the resolution is diffraction limited, however the super-resolution gradually recovers as the lubricant evaporates.
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Summary

Microsphere-assisted imaging has emerged as an extraordinary simple technique of obtaining optical super-resolution. This work addresses two central problems in developing this technology: i) methodology of the resolution measurements and ii) limited field-of-view provided by each sphere. It is suggested that a standard method of resolution analysis in far-field microscopy...

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Versatile alignment layer method for new types of liquid crystal photonic devices

Summary

Liquid crystal photonic devices are becoming increasingly popular. These devices often present a challenge when it comes to creating a robust alignment layer in pre-assembled cells. In this paper, we describe a method of infusing a dye into a microcavity to produce an effective photo-definable alignment layer. However, previous research on such alignment layers has shown that they have limited stability, particularly against subsequent light exposure. As such, we further describe a method of utilizing a pre-polymer, infused into the microcavity along with the liquid crystal, to provide photostability. We demonstrate that the polymer layer, formed under ultraviolet irradiation of liquid crystal cells, has been effectively localized to a thin region near the substrate surface and provides a significant improvement in the photostability of the liquid crystal alignment. This versatile alignment layer method, capable of being utilized in devices from the described microcavities to displays, offers significant promise for new photonics applications.
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Summary

Liquid crystal photonic devices are becoming increasingly popular. These devices often present a challenge when it comes to creating a robust alignment layer in pre-assembled cells. In this paper, we describe a method of infusing a dye into a microcavity to produce an effective photo-definable alignment layer. However, previous research...

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Sensitive detection and identification of isovanillin aerosol particles at the pg/cm^3 mass concentration level using Raman spectroscopy

Published in:
Aerosol Sci. Technol., Vol. 49, No. 9, 2015, pp. 753-6.

Summary

A compact Raman spectroscopy system with high sensitivity to chemical aerosols has been developed. This system has been used to detect isovanillin aerosols with mass concentration of 12 pg/cm3 in a 15 s signal integration period with a signal-to-noise ratio of 32. We believe this represents the lowest chemical aerosol concentration and signal integration period product ever reported for a Raman spectroscopy system. The Raman system includes (i) a 10 W, 532-nm cw laser, (ii) an aerosol flow cell, (iii) a 60x aerosol concentrator, (iv) an f/1.8 Raman spectrometer with a spectral range of 400-1400 cm^-1 and a resolution of 4 cm^-1, and (v) a low-noise CCD camera (1340 x 400 pixels). The collection efficiency of the Raman system has been determined to be 2.8%. Except for the laser cooling subsystem, the Raman system fits in a 0.61 m x 0.61 m x 0.61 m box.
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Summary

A compact Raman spectroscopy system with high sensitivity to chemical aerosols has been developed. This system has been used to detect isovanillin aerosols with mass concentration of 12 pg/cm3 in a 15 s signal integration period with a signal-to-noise ratio of 32. We believe this represents the lowest chemical aerosol...

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In situ microfluidic SERS assay for monitoring enzymatic breakdown of organophosphates

Summary

In this paper, we report on a method to probe the breakdown of the organophosphate (OP) simulants o, s-diethyl methyl phosphonothioate (OSDMP) and demeton S by the enzyme organophosphorous hydrolase (OPH) in a microfluidic device by surface enhanced Raman spectroscopy (SERS). SERS hotspots were formed on-demand inside the microfluidic device by laser-induced aggregation of injected Ag NPs suspensions. The Ag NP clusters, covering micron-sized areas, were formed within minutes using a conventional confocal Raman laser microscope. These Ag NP clusters were used to enhance the Raman spectra of the thiol products of OP breakdown in the microfluidic device: ethanethiol (EtSH) and (ethylsulfanyl) ethane-1-thiol (2-EET). When the OPH enzyme and its substrates OSDMP and demeton S were introduced, the thiolated breakdown products were generated, resulting in changes in the SERS spectra. With the ability to analyze reaction volumes as low as 20 nL, our approach demonstrates great potential for miniaturization of SERS analytical protocols.
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Summary

In this paper, we report on a method to probe the breakdown of the organophosphate (OP) simulants o, s-diethyl methyl phosphonothioate (OSDMP) and demeton S by the enzyme organophosphorous hydrolase (OPH) in a microfluidic device by surface enhanced Raman spectroscopy (SERS). SERS hotspots were formed on-demand inside the microfluidic device...

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Coherent beam-combining of quantum cascade amplifier arrays

Summary

We present design, packaging and coherent beam combining of quantum cascade amplifier (QCA) arrays, measurements of QCA phase noise, the drive-current-to-optical-phase transfer function, and the small signal gain for QCAs.
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Summary

We present design, packaging and coherent beam combining of quantum cascade amplifier (QCA) arrays, measurements of QCA phase noise, the drive-current-to-optical-phase transfer function, and the small signal gain for QCAs.

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Permittivity evaluation of multilayered hyperbolic metamaterials: ellipsometry vs. reflectometry

Published in:
J. Appl. Phys., Vol. 117, No. 10, 14 March 2015, 103104.

Summary

Metal-dielectric nanolaminates represent a class of hyperbolic metamaterials with uniaxial permittivity tensor. In this study, we critically compare permittivity extraction of nanolaminate samples using two techniques: polarized reflectrometry vs. spectroscopic anisotropic ellipsometry. Both Au/MgF2 and Ag/MgF2 metal-dielectric stacks are examined. We demonstrate the applicability of the treatment of the multilayered material as a uniaxial medium and compare the derived optical parameters to those expected from the effective medium approximation. We also experimentally compare the effect of varying the material outer layer on the homogenization of the composite. Additionally, we introduce a simple empirical method of extracting the epsilon-near-zero point of the nanolaminates from normal incidence reflectance. The results of this study are useful in accurate determination of the hyperbolic material permittivity and in the ability to tune its optical properties.
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Summary

Metal-dielectric nanolaminates represent a class of hyperbolic metamaterials with uniaxial permittivity tensor. In this study, we critically compare permittivity extraction of nanolaminate samples using two techniques: polarized reflectrometry vs. spectroscopic anisotropic ellipsometry. Both Au/MgF2 and Ag/MgF2 metal-dielectric stacks are examined. We demonstrate the applicability of the treatment of the multilayered...

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Nanochannel fabrication based on double patterning with hydrogen silsesquioxane

Published in:
J. Vac. Sci. Technol. B, Microelectron. Process. Phenon., Vol. 33, No. 2, March 2015, 020601.

Summary

A double patterning process is presented to pattern sub-35 nm wide channels in hydrogen silsesquioxane with near 100% pattern densities. Using aligned electron beam lithography, each side of the nanochannel structure is patterned as a separate layer. A 50000 uC/cm^2 high-dose anneal is applied to the first layer after exposure. Channels with widths below ~60 nm are shown to exhibit footing with standard tetramethyl ammonium hydroxide developers. This problem is resolved by adding surfectant during the development of the final channel structure. The resulting process produced channels
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Summary

A double patterning process is presented to pattern sub-35 nm wide channels in hydrogen silsesquioxane with near 100% pattern densities. Using aligned electron beam lithography, each side of the nanochannel structure is patterned as a separate layer. A 50000 uC/cm^2 high-dose anneal is applied to the first layer after exposure...

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