Single‐Step Deposition of Au‐ and Pt‐Nanoparticle‐Functionalized Tungsten Oxide Nanoneedles Synthesized Via Aerosol‐Assisted CVD, and Used for Fabrication of Selective Gas Microsensor Arrays

Tungsten oxide nanostructures functionalized with gold or platinum NPs are synthesized and integrated, using a single-step method via aerosol-assisted chemical vapour deposition, onto micro-electromechanical system (MEMS)-based gas-sensor platforms. This co-deposition method is demonstrated to be an effective route to incorporate metal nanoparticles (NP) or combinations of metal NPs into nanostructured materials, resulting in an attractive way of tuning functionality in metal oxides (MOX). The results show variations in electronic and sensing properties of tungsten oxide according to the metal NPs introduced, which are used to discriminate effectively analytes (C2H5OH, H2, and CO) that are present in proton-exchange fuel cells. Improved sensing characteristics, in particular to H2, are observed at 250 °C with Pt-functionalized tungsten oxide films, whereas non-functionalized tungsten oxide films show responses to low concentrations of CO at low temperatures. Differences in the sensing characteristics of these films are attributed to the different reactivities of metal NPs (Au and Pt), and to the degree of electronic interaction at the MOX/metal NP interface. The method presented in this work has advantages over other methods of integrating nanomaterials and devices, of having fewer processing steps, relatively low processing temperature, and no requirement for substrate pre-treatment.

[1]  Harold H. Kung,et al.  Selective Catalytic Oxidation of CO: Effect of Chloride on Supported Au Catalysts , 2002 .

[2]  Ralf Srama,et al.  Low-charge detector for the monitoring of hyper-velocity micron-sized dust particles , 2008 .

[3]  Khalifa Aguir,et al.  Ethanol and ozone sensing characteristics of WO3 based sensors activated by Au and Pd , 2006 .

[4]  Xianguo Li,et al.  Effect of contaminants on polymer electrolyte membrane fuel cells , 2011 .

[5]  A. Gurlo,et al.  Nanosensors: does crystal shape matter? , 2010, Small.

[6]  N. Xu,et al.  Study of Physical and Chemical Processes of H2 Sensing of Pt-Coated WO3 Nanowire Films , 2010 .

[7]  Andreas Hierlemann,et al.  CMOS-based chemical microsensors. , 2003, The Analyst.

[8]  Malcolm L. H. Green,et al.  CCVD Synthesis and Characterization of Cobalt-Encapsulated Nanoparticles , 2002 .

[9]  Nicolae Barsan,et al.  Sensing low concentrations of CO using flame-spray-made Pt/SnO2 nanoparticles , 2006 .

[10]  Yongming Zhang,et al.  Au Nanoparticle Modified WO3 Nanorods with Their Enhanced Properties for Photocatalysis and Gas Sensing , 2010 .

[11]  Ulrich Simon,et al.  Metal and metal oxide nanoparticles in chemiresistors: does the nanoscale matter? , 2006, Small.

[12]  P. Umek,et al.  Aerosol assisted chemical vapour deposition control parameters for selective deposition of tungsten oxide nanostructures. , 2011, Journal of nanoscience and nanotechnology.

[13]  C. Bittencourt,et al.  Platinum-carbon nanotube interaction , 2008 .

[14]  Jun Zhang,et al.  Pt clusters supported on WO3 for ethanol detection , 2010 .

[15]  Sotiris E. Pratsinis,et al.  Aerosol flame synthesis of catalysts , 2006 .

[16]  N. Bârsan,et al.  Micromachined metal oxide gas sensors: opportunities to improve sensor performance , 2001 .

[17]  N. Bârsan,et al.  Operando X-ray absorption spectroscopy studies on Pd-SnO2 based sensors. , 2009, Physical chemistry chemical physics : PCCP.

[18]  C. Bittencourt,et al.  Gold clusters on WO3 nanoneedles grown via AACVD: XPS and TEM studies , 2012 .

[19]  Ivan P. Parkin,et al.  The gas-sensing properties of WO3-x thin films deposited via the atmospheric pressure chemical vapour deposition (APCVD) of WCl6 with ethanol , 2008 .

[20]  N. Bârsan,et al.  Conduction Model of Metal Oxide Gas Sensors , 2001 .

[21]  Chao Zhang,et al.  Highly sensitive hydrogen sensors based on co-sputtered platinum-activated tungsten oxide films , 2011 .

[22]  D. Goodman,et al.  Oxidation Catalysis by Supported Gold Nano-Clusters , 2002 .

[23]  Nicolae Barsan,et al.  The structure and behavior of platinum in SnO2-based sensors under working conditions. , 2011, Angewandte Chemie.

[24]  R. S. Falconer,et al.  Stability, sensitivity and selectivity of tungsten trioxide films for sensing applications , 1993 .

[25]  M. Bäumer,et al.  Rational design of functional oxide thin films with embedded magnetic or plasmonic metallic nanoparticles. , 2011, Angewandte Chemie.

[26]  Warren B. Cross,et al.  Tungsten Oxide Coatings from the Aerosol-Assisted Chemical Vapor Deposition of W(OAr)6 (Ar = C6H5, C6H4F-4, C6H3F2-3,4); Photocatalytically Active γ-WO3 Films , 2003 .

[27]  Stella Vallejos,et al.  Important considerations for effective gas sensors based on metal oxide nanoneedles films , 2012 .

[28]  Carles Cané,et al.  Micro-machined WO3-based sensors selective to oxidizing gases , 2008 .

[29]  Carles Cané,et al.  Sensitivity and selectivity improvement of rf sputtered WO3 microhotplate gas sensors , 2006 .

[30]  E. Comini Metal oxide nano-crystals for gas sensing. , 2006, Analytica chimica acta.

[31]  G. Korotcenkov The role of morphology and crystallographic structure of metal oxides in response of conductometric-type gas sensors , 2008 .

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

[33]  Jun Chen,et al.  Self-heated hydrogen gas sensors based on Pt-coated W18O49 nanowire networks with high sensitivity, good selectivity and low power consumption , 2011 .

[34]  B. Cuenya Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects , 2010 .

[35]  Matteo Ferroni,et al.  Quasi-one dimensional metal oxide semiconductors: Preparation, characterization and application as chemical sensors , 2009 .

[36]  José Luz Silveira,et al.  The benefits of ethanol use for hydrogen production in urban transportation , 2009 .

[37]  Eduard Llobet,et al.  Au nanoparticle-functionalised WO3 nanoneedles and their application in high sensitivity gas sensor devices. , 2011, Chemical communications.

[38]  A. Martucci,et al.  Gold nanoparticles to boost the gas sensing performance of porous sol–gel thin films , 2011 .

[39]  Carles Cané,et al.  Ozone monitoring by micro-machined sensors with WO3 sensing films , 2007 .

[40]  K. Schierbaum,et al.  THE VALENCE-BAND ELECTRONIC STRUCTURE OF CLEAN AND PT-COVERED TIO2(110) SURFACES STUDIED WITH PHOTOEMISSION SPECTROSCOPY , 1997 .

[41]  Ying Liu,et al.  Growth of Aligned Square‐Shaped SnO2 Tube Arrays , 2005 .

[42]  Han‐Ik Joh,et al.  Preparation and characterization of Pt nanowire by electrospinning method for methanol oxidation , 2010 .

[43]  Kengo Shimanoe,et al.  Theory of power laws for semiconductor gas sensors , 2008 .

[44]  M. H. Yeung,et al.  Shape‐ and Orientation‐Controlled Gold Nanoparticles Formed within Mesoporous Silica Nanofibers , 2006 .

[45]  I. Parkin,et al.  Aerosol assisted chemical vapor deposition using nanoparticle precursors: a route to nanocomposite thin films. , 2006, Journal of the American Chemical Society.

[46]  H. Abdi,et al.  Principal component analysis , 2010 .

[47]  Gregorio Bottaro,et al.  Recent trends on nanocomposites based on Cu, Ag and Au clusters: A closer look , 2006 .