Plasmonics-based detection of H(2) and CO: discrimination between reducing gases facilitated by material control.

Monitoring emissions in high-temperature-combustion applications is very important for regulating the discharge of gases such as NO(2) and CO as well as unburnt fuel into the environment. This work reports the detection of H(2) and CO gases by employing a metal-metal oxide nanocomposite (gold-yttria stabilized zirconia (Au-YSZ)) film fabricated through layer-by-layer physical vapor deposition (PVD). The change in the peak position of the localized surface plasmon resonance (LSPR) was monitored as a function of time and gas concentration. The responses of the films were preferential towards H(2), as observed from the results of exposing the films to the gases at temperatures of 500 °C in a background of dry air. Characterization of the samples by XRD and SEM enabled the correlation of material properties with the differences in the CO- and H(2)-induced LSPR peak shifts, including the relative desensitization towards NO(2). Sensing characteristics of films with varying support thicknesses and metal-particle diameters have been studied, and the results are presented. A comparison has been made to films fabricated through co-sputtered PVD, and the calibration curves of the sensing response show a preferential response towards H(2). The distinction between H(2) and CO responses is also seen through the use of principal-component analysis (PCA). Such material arrangements, which can be tuned for their selectivity by changing certain parameters such as particle size, support thickness, etc., have direct applications within optical chemical sensors for turbine engines, solid-oxide fuel cells, and other high-temperature applications.

Plasmonic-based sensing using an array of Au-metal oxide thin films.

An optical plasmonic-based sensing array has been developed and tested for the selective and sensitive detection of H(2), CO, and NO(2) at a temperature of 500 °C in an oxygen-containing background. The three-element sensing array used Au nanoparticles embedded in separate thin films of yttria-stabilized zirconia (YSZ), CeO(2), and TiO(2). A peak in the absorbance spectrum due to a localized surface plasmon resonance (LSPR) on the Au nanoparticles was monitored for each film during gas exposures and showed a blue shift in the peak positions for the reducing gases, H(2) and CO, and a red shift for the oxidizing gas, NO(2). A more in-depth look at the sensing response was performed using the multivariate methods of principal component analysis (PCA) and linear discriminant analysis (LDA) on data from across the entire absorbance spectrum range. Qualitative results from both methods showed good separation between the three analytes for both the full array and the Au-TiO(2) sample. Quantification of LDA cluster separation using the Mahalanobis distance showed better cluster separation for the array, but there were some instances with the lowest concentrations where the single Au-TiO(2) film had separation better than that of the array. A second method to quantify cluster separation in LDA space was developed using multidimensional volume analysis of the individual cluster volume, overlapped cluster volume, and empty volume between clusters. Compared to the individual sensing elements, the array showed less cluster overlap, smaller cluster volumes, and more space between clusters, all of which were expected for improved separability between the analytes.

Selective plasmonic gas sensing: H2, NO2, and CO spectral discrimination by a single Au-CeO2 nanocomposite film.

A Au-CeO(2) nanocomposite film has been investigated as a potential sensing element for high-temperature plasmonic sensing of H(2), CO, and NO(2) in an oxygen containing environment. The CeO(2) thin film was deposited by molecular beam epitaxy (MBE), and Au was implanted into the as-grown film at an elevated temperature followed by high temperature annealing to form well-defined Au nanoclusters. The Au-CeO(2) nanocomposite film was characterized by X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). For the gas sensing experiments, separate exposures to varying concentrations of H(2), CO, and NO(2) were performed at a temperature of 500 °C in oxygen backgrounds of 5.0, 10, and ∼21% O(2). Changes in the localized surface plasmon resonance (LSPR) absorption peak were monitored during gas exposures and are believed to be the result of oxidation-reduction processes that fill or create oxygen vacancies in the CeO(2). This process affects the LSPR peak position either by charge exchange with the Au nanoparticles (AuNPs) or by changes in the dielectric constant surrounding the particles. Spectral multivariate analysis was used to gauge the inherent selectivity of the film between the separate analytes. From principal component analysis (PCA), unique and identifiable responses were seen for each of the analytes. Linear discriminant analysis (LDA) was also used and showed separation between analytes as well as trends in gas concentration. Results indicate that the Au-CeO(2) thin film is selective to O(2), H(2), CO, and NO(2) in separate exposures. This, combined with the observed stability over long exposure periods, shows the Au-CeO(2) film has good potential as an optical sensing element for harsh environmental conditions.