Optical and Chemical Characterization of Uranium Dioxide (UO2) and Uraninite Mineral: Calculation of the Fundamental Optical Constants.

Uranium dioxide (UO2) is a material with historical and emerging applications in numerous areas such as photonics, nuclear energy, and aerospace electronics. While often grown synthetically as single-crystal UO2, the mineralogical form of UO2 called uraninite is of interest as a precursor to various chemical processes involving uranium-bearing chemicals. Here, we investigate the optical and chemical properties of a series of three UO2 specimens: synthetic single-crystal UO2, uraninite ore of relatively high purity, and massive uraninite mineral containing numerous impurities. An optical technique called single-angle reflectance spectroscopy was used to derive the optical constants n and k of these uranium specimens by measuring the specular reflectance spectra of a polished surface across the mid- and far-infrared spectral domains (ca. 7000-50 cm-1). X-ray diffractometry, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were further used to analyze the surface composition of the mineralogical forms of UO2. Most notably, the massive uraninite mineral was observed to contain significant deposits of calcite and quartz in addition to UO2 (as well as other metal oxides and radioactive decay products). Knowledge of the infrared optical constants for this series of uranium chemicals facilitates nondestructive, noncontact detection of UO2 under a variety of conditions.

Single-angle reflectance spectroscopy to determine the optical constants n and k: considerations in the far-infrared domain.

Single-angle infrared (IR) reflectance spectroscopy is a proven and effective method for determining the complex optical constants n and k of condensed matter. The modern method uses a Fourier transform IR spectrometer to record the quantitative reflectance R(ν) spectra followed by application of the Kramers-Kronig transform (KKT) to obtain the complex optical constants. In order to carry out the KKT, it is essential to measure the reflectance spectra to as high and low a frequency (wavenumber) as possible. Traditionally, the reflectance spectra of solid specimens consist of large (typically>10 mm diameter) polished single-crystal faces free of defects or voids. The requirement of a large polished face, however, is not a realistic expectation for many synthetic, geologic, or rare specimens where the size is usually small and the morphology can vary. In this paper we discuss several improvements and considerations to both the hardware and far-IR measurement protocols that lead to more accurate R(ν) values and thus to more accurate n/k values, especially for small (millimeter-sized) specimens where the R(ν) spectrum is concatenated from multiple independent R(ν) spectra from overlapping hardware/spectral domains. Specifically, the improved hardware and analyses introduced here include the following: (1) providing a set of far-IR calibration standards; (2) custom-designing and manufacturing low reflectivity, stray-light reducing sample masks for small specimens; (3) minimizing stray light interaction between the sample mask, the interferometer Jacquinot stop, and the detector; (4) optimizing the methods to "splice" together the spectra from independent domains; (5) discussing what methods one can use to obtain or calculate the important R(0 cm-1) value; (6) using a quartic relationship to extrapolate from the measured R data to R(0); and (7) accounting for the limiting effects of diffraction for the spot size at the sample mask and detector for millimeter-sized specimens, especially at the very long wavelengths. These seven considerations are all highly interconnected and are discussed in turn, as well as their strong interdependencies. This paper presents a holistic approach for determining reliable n/k values of millimeter-sized samples using single-angle reflectance in the mid- and far-IR.

Shock Wave Mediated Plume Chemistry for Molecular Formation in Laser Ablation Plasmas.

Although it is relatively straightforward to measure the ionic, atomic, molecular, and particle emission features from laser ablation plumes, the associated kinetic and thermodynamic development leading to molecular and nanocluster formation remain one of the most important topics of analytical chemistry and material science. Very little is known, for instance, about the evolutionary paths of molecular and nanocluster formation and its relation to laser plume hydrodynamics. This is, to a large extent; due to the complexity of numerous physical processes that coexist in a transient laser-plasma system. Here, we report the formation mechanisms of molecules during complex interactions of a laser-produced plasma plume expanding from a high purity aluminum metal target into ambient air. It is found that the plume hydrodynamics plays a great role in redefining the plasma thermodynamics and molecular formation. Early in the plasma expansion, the generated shock wave at the plume edge acts as a barrier for the combustion process and molecular formation is prevalent after the shock wave collapse. The temporally and spatially resolved contour mapping of atoms and molecules in laser ablation plumes highlight the formation routes and persistence of species in the plasma and their relation to plume hydrodynamics.

Precision control of multiple quantum cascade lasers for calibration systems.

We present a precision, 1-A, digitally interfaced current controller for quantum cascade lasers, with demonstrated temperature coefficients for continuous and 40-kHz full-depth square-wave modulated operation, of 1-2 ppm/ °C and 15 ppm/ °C, respectively. High precision digital to analog converters (DACs) together with an ultra-precision voltage reference produce highly stable, precision voltages, which are selected by a multiplexer (MUX) chip to set output currents via a linear current regulator. The controller is operated in conjunction with a power multiplexing unit, allowing one of three lasers to be driven by the controller, while ensuring protection of controller and all lasers during operation, standby, and switching. Simple ASCII commands sent over a USB connection to a microprocessor located in the current controller operate both the controller (via the DACs and MUX chip) and the power multiplexer.

Real-time trace gas sensing of fluorocarbons using a swept-wavelength external cavity quantum cascade laser.

We present results demonstrating real-time sensing of four different fluorocarbons at low part-per billion (ppb) concentrations using an external cavity quantum cascade laser (ECQCL) designed for infrared vibrational spectroscopy of molecules with broad absorption features. The ECQCL was repeatedly swept at 20 Hz over its full tuning range of 1145-1265 cm(-1) providing a scan rate of 3535 cm(-1) s(-1), and a detailed characterization of the ECQCL scan stability and repeatability is presented. The ECQCL was combined with a 100 meter path length multi-pass cell for direct absorption spectroscopy. A portable sensor system is described, which was deployed on a mobile automotive platform to provide spatially-resolved detection of fluorocarbons in outdoor experiments. Noise-equivalent detection limits of 800-1000 parts-per-trillion (ppt) are demonstrated for 1 s integration times.

External cavity quantum cascade laser for quartz tuning fork photoacoustic spectroscopy of broad absorption features.

We demonstrate mid-infrared spectroscopy of large molecules with broad absorption features using a tunable external cavity quantum cascade laser. Absorption spectra for two different Freons are measured over the range 1130-1185 cm(-1) with 0.2 cm(-1) resolution via laser photoacoustic spectroscopy with quartz tuning forks as acoustic transducers. The measured spectra are in excellent agreement with published reference absorption spectra.

Stabilization, injection and control of quantum cascade lasers, and their application to chemical sensing in the infrared.

Quantum cascade lasers (QCLs) are a relatively new type of semiconductor laser operating in the mid- to long-wave infrared. These monopolar multilayered quantum well structures can be fabricated to operate anywhere between 3.5 and 20 microm, which includes the molecular fingerprint region of the infrared. This makes them an ideal choice for infrared chemical sensing, a topic of great interest at present. Frequency stabilization and injection locking increase the utility of QCLs. We present results of locking QCLs to optical cavities, achieving relative linewidths down to 5.6 Hz. We report injection locking of one distributed feedback grating QCL with light from a similar QCL, demonstrating capture ranges of up to +/-500 MHz, and suppression of amplitude modulation by up to 49 dB. We also present various cavity-enhanced chemical sensors employing the frequency stabilization techniques developed, including the resonant sideband technique known as NICE-OHMS. Sensitivities of 9.7 x 10(-11) cm(-1) Hz(-1/2) have been achieved in pure nitrous oxide.

Frequency stabilization of quantum-cascade lasers by use of optical cavities.

We report a heterodyne beat with a linewidth of 5.6+/-0.6 Hz between two cavity-stabilized quantum-cascade lasers operating at 8.5 microm . We also present a technique for measuring this beat that avoids the need for extreme isolation of the optical cavities from the environment, that of employing a third servo loop with low bandwidth to force one cavity to track the slow drifts and low-frequency fluctuations of the other. Although it is not fully independent, this technique greatly facilitates heterodyne beat measurements for evaluating the performance of cavity-locked lasers above the bandwidth of the third loop.