Selective detection of naphthalene with nanostructured WO 3 gas sensors prepared by pulsed laser deposition

Abstract. Pulsed laser deposition (PLD) at room temperature with a nanosecond laser was used to prepare WO3 layers on both MEMS microheater platforms and Si/SiO2 substrates. Structural characterization showed that the layers are formed of nanoparticles and nanoparticle agglomerates. Two types of layers were prepared, one at an oxygen partial pressure of 0.08 mbar and one at 0.2 mbar. The layer structure and the related gas sensing properties were shown to be highly dependent on this deposition parameter. At an oxygen pressure of 0.2 mbar, formation of e-phase WO3 was found, which is possibly contributing to the observed increase in sensitivity of the sensor material. The gas sensing performance of the two sensor layers prepared via PLD was tested for detection of volatile organic compounds (benzene, formaldehyde and naphthalene) at ppb level concentrations, with various ethanol backgrounds (0.5 and 2 ppm) and gas humidities (30, 50 and 70 % RH). The gas sensors were operated in temperature cycled operation. For signal processing, linear discriminant analysis was performed using features extracted from the conductance signals during temperature variations as input data. Both WO3 sensor layers showed high sensitivity and selectivity to naphthalene compared to the other target gases. Of the two layers, the one prepared at higher oxygen partial pressure showed higher sensitivity and stability resulting in better discrimination of the gases and of different naphthalene concentrations. Naphthalene at concentrations down to 1 ppb could be detected with high reliability, even in an ethanol background of up to 2 ppm. The sensors show only low response to ethanol, which can be compensated reliably during the signal processing. Quantification of ppb level naphthalene concentrations was also possible with a high success rate of more than 99 % as shown by leave-one-out cross validation.

[1]  Takehiko Kitamori,et al.  Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency , 2015, Scientific Reports.

[2]  L. Meda,et al.  Quasi-1D hyperbranched WO3 nanostructures for low-voltage photoelectrochemical water splitting , 2015 .

[3]  Andreas Schütze,et al.  Optimierung des temperaturzyklischen Betriebs von Halbleitergassensoren , 2015 .

[4]  A. Spetz,et al.  Pulsed Laser Deposition of Metal Oxide Nanoparticles, Agglomerates, and Nanotrees for Chemical Sensors , 2015 .

[5]  W. Reimringer,et al.  Selective detection of hazardous VOCs for indoor air quality applications using a virtual gas sensor array , 2014 .

[6]  Andreas Schütze,et al.  Gas mixing apparatus for automated gas sensor characterization , 2014 .

[7]  Anita Lloyd Spetz,et al.  Selectivity enhancement of SiC-FET gas sensors by combining temperature and gate bias cycled operation using multivariate statistics , 2014 .

[8]  S. Schütz,et al.  The olfaction of a fire beetle leads to new concepts for early fire warning systems , 2013 .

[9]  P. Gouma,et al.  Polymorphism in nanocrystalline binary metal oxides , 2013 .

[10]  G. Niklasson,et al.  Structural and optical properties of visible active photocatalytic WO_3 thin films prepared by reactive dc magnetron sputtering , 2012 .

[11]  Andreas Schütze,et al.  Fire detection in coal mines based on semiconductor gas sensors , 2012 .

[12]  A. Schutze,et al.  Increasing the Selectivity of Pt-Gate SiC Field Effect Gas Sensors by Dynamic Temperature Modulation , 2010, IEEE Sensors Journal.

[13]  Arnan Mitchell,et al.  Nanostructured Tungsten Oxide – Properties, Synthesis, and Applications , 2011 .

[14]  Increasing the selectivity of Pt-gate SiC field effect gas sensors by dynamic temperature modulation , 2012, 2010 IEEE Sensors.

[15]  Sotiris E Pratsinis,et al.  Si:WO(3) Sensors for highly selective detection of acetone for easy diagnosis of diabetes by breath analysis. , 2010, Analytical chemistry.

[16]  Anna Paola Caricato,et al.  Nanoparticle Thin Films for Gas Sensors Prepared by Matrix Assisted Pulsed Laser Evaporation , 2009, Sensors.

[17]  Pelagia-Irene Gouma,et al.  Ferroelectric WO3 Nanoparticles for Acetone Selective Detection , 2008 .

[18]  S. Kirchner,et al.  The INDEX project: executive summary of a European Union project on indoor air pollutants , 2008, Allergy.

[19]  S. Tarlo,et al.  The health effects of non-industrial indoor air pollution. , 2008, The Journal of allergy and clinical immunology.

[20]  L. Gauckler,et al.  Microstructures of CGO and YSZ Thin Films by Pulsed Laser Deposition , 2008 .

[21]  Imre Miklós Szilágyi,et al.  Nanosize hexagonal tungsten oxide for gas sensing applications , 2008 .

[22]  Kurt D. Benkstein,et al.  The potential for and challenges of detecting chemical hazards with temperature-programmed microsensors , 2007 .

[23]  N. Koshizaki,et al.  Optical CO gas sensor using a cobalt oxide thin film prepared by pulsed laser deposition under various argon pressures. , 2006, The journal of physical chemistry. B.

[24]  R. Pinto,et al.  Structure and morphology of laser-ablated WO3 thin films , 2005 .

[25]  Chien-Hou Wu,et al.  Determination of volatile organic compounds in workplace air by multisorbent adsorption/thermal desorption-GC/MS. , 2004, Chemosphere.

[26]  W. M. Li,et al.  Risk assessment of exposure to volatile organic compounds in different indoor environments. , 2004, Environmental research.

[27]  Andreas Schütze,et al.  High performance solvent vapor identification with a two sensor array using temperature cycling and pattern classification , 2003 .

[28]  A. C. Gaeris,et al.  Internal structure and expansion dynamics of laser ablation plumes into ambient gases , 2003 .

[29]  Ricardo Gutierrez-Osuna,et al.  Pattern analysis for machine olfaction: a review , 2002 .

[30]  B. Marinkovic,et al.  A comparison between the Warren-Averbach method and alternate methods for X-ray diffraction microstructure analysis of polycrystalline specimens , 2001 .

[31]  D. Kohl,et al.  Systematic studies on responses of metal-oxide sensor surfaces to straight chain alkanes, alcohols, aldehydes, ketones, acids and esters using the SOMMSA approach , 2000 .

[32]  A. G. S. Filho,et al.  Pressure effects in the Raman spectrum of WO 3 microcrystals , 2000 .

[33]  Andrew P. Jones,et al.  Indoor air quality and health , 1999 .

[34]  B. Reedy,et al.  Temperature modulation in semiconductor gas sensing , 1999 .

[35]  Udo Weimar,et al.  Gas identification by modulating temperatures of SnO2-based thick film sensors , 1997 .

[36]  Graham K. Rand,et al.  Quantitative Applications in the Social Sciences , 1983 .