Improvement in real time detection and selectivity of phthalocyanine gas sensors dedicated to oxidizing pollutants evaluation

A sensor microsystem prototype, using copper phthalocyanine thin film as sensitive layer, and dedicated to ozone evaluation, was developed. The methodology implemented is based on cyclic sensor recalibrations by thermal cleaning of the sensitive membrane, and on pollutant concentration quantification according to the kinetics of sensor response. Results of laboratory experiments for various NO2 and O3 concentrations, in the range of 10–200 ppb, illustrate the selectivity of CuPc sensors towards ozone, obtained by our methodology. We have shown that ozone selectivity is especially improved for short time of exposure (few minutes) and for phthalocyanine layer maintained at low temperature (80 °C). For optimal conditions, our microsystem exhibits a threshold lower than 10 ppb, a resolution lower than 10 ppb, and good reproducibility of measurements. Performances obtained in real urban atmosphere are satisfying to ensure real time evaluation of ozone during several days. Long-term stability and the detection of NO2 by associating chemical filters to our microsystem will be also discussed.

[1]  John F. Currie,et al.  Micromachined thin film solid state electrochemical CO2, NO2 and SO2 gas sensors , 1999 .

[2]  Karel Štulík,et al.  An amperometric solid-state NO2 sensor with a solid polymer electrolyte and a reticulated vitreous carbon indicator electrode , 2000 .

[3]  S. N. Malchenko,et al.  In2O3-based gas sensors , 1993 .

[4]  Theodor Doll,et al.  Conductivity and work function ozone sensors based on indium oxide , 1998 .

[5]  Michele Penza,et al.  NOX GAS SENSING CHARACTERISTICS OF WO3 THIN FILMS ACTIVATED BY NOBLE METALS (PD, PT, AU) LAYERS , 1998 .

[6]  J. Souto,et al.  Lutetium bisphthalocyanine thin films as sensors for volatile organic components (VOCs) of aromas , 1999 .

[7]  Juntao Lu,et al.  A Solid‐State Ozone Sensor Based on Solid Polymer Electrolyte , 1998 .

[8]  Y. Park,et al.  Enhancement of the NO2-sensing capability of copper phthalocyanine by measuring the realtive resistance change , 1996 .

[9]  Y. Nishioka,et al.  A novel semiconductor NO gas sensor operating at room temperature , 1998 .

[10]  V. Lantto,et al.  NO2 monitoring as an air pollutant using lead phthalocyanine thin film sensors , 1992 .

[11]  Andreas Schütze,et al.  Quantitative ozone measurement using a phthalocyanine thin-film sensor and dynamic signal evaluation , 1995 .

[12]  Gian Carlo Cardinali,et al.  Gas sensors for air quality monitoring: realisation and characterisation of undoped and noble metal-doped SnO2 thin sensing films deposited by the pulsed laser ablation , 1999 .

[13]  Kenneth West,et al.  I S T I , 2003 .

[14]  Giorgio Sberveglieri,et al.  Investigation on the O3 sensitivity properties of WO3 thin films prepared by sol–gel, thermal evaporation and r.f. sputtering techniques , 2000 .

[15]  René Lalauze,et al.  Gas detection for automotive pollution control , 1999 .

[16]  T. K. Starke,et al.  NO2 detection at room temperature with copper phthalocyanine thin film devices , 2000 .

[17]  A. Pauly,et al.  Interaction of NO2 with copper phthalocyanine thin films. II: Application to gas sensing , 1992 .

[18]  Norio Miura,et al.  Potentiometric NOx sensor based on stabilized zirconia and NiCr2O4 sensing electrode operating at high temperatures , 2001 .

[19]  Yuh‐Lang Lee,et al.  Effects of heat annealing on the film characteristics and gas sensing properties of substituted and un-substituted copper phthalocyanine films , 2001 .

[20]  R. Stoyanova,et al.  Ozone decomposition and CO oxidation on CeO2 , 1995 .

[21]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[22]  K. Maeda,et al.  Solid electrolyte NOx sensor using pyrochlore-type oxide electrode 1 Devoted to the late Dr Tetsuro , 1998 .

[23]  H. Meixner,et al.  Selective gas detection with high-temperature operated metal oxides using catalytic filters , 2000 .

[24]  Peter C. Hauser,et al.  Sensitive electrochemical detection of ozone , 2002 .

[25]  J. Simon,et al.  Detection and titration of ozone using metallophthalocyanine based field effect transistors , 2001 .

[26]  Norio Miura,et al.  HIGH-TEMPERATURE POTENTIOMETRIC/AMPEROMETRIC NOX SENSORS COMBINING STABILIZED ZIRCONIA WITH MIXED-METAL OXIDE ELECTRODE , 1998 .

[27]  Norio Miura,et al.  A COMPACT SOLID-STATE AMPEROMETRIC SENSOR FOR DETECTION OF NO2 IN PPB RANGE , 1998 .

[28]  T. A. Jones,et al.  Gas-induced electrical conductivity changes in metal phthalocyanines☆ , 1986 .

[29]  M. Ivanovskaya,et al.  Mechanism of O3 and NO2 detection and selectivity of In2O3 sensors , 2001 .

[30]  G. Martinelli,et al.  Preparation and micro-structural characterization of nanosized thin film of TiO2WO3 as a novel material with high sensitivity towards NO2 , 1996 .

[31]  Giorgio Sberveglieri,et al.  Ozone detection using low-power-consumption metal–oxide gas sensors , 1999 .

[32]  T. Wada,et al.  Gas sensitive properties of copperphthalocyanine thin films , 1996 .

[33]  Maria Luisa Grilli,et al.  The NO2 response of solid electrolyte sensors made using nano-sized LaFeO3 electrodes , 2001 .

[34]  Miss A.O. Penney.  (b) , 1974, The New Yale Book of Quotations.

[35]  A. Pauly,et al.  Doping mechanisms of phthalocyanines by oxidizing gases: Application to gas sensors , 1994 .

[36]  Yung Kwon Sung,et al.  Ozone sensing properties of In2O3-based semiconductor thick films , 2000 .

[37]  N. Bârsan,et al.  In2O3 and MoO3–In2O3 thin film semiconductor sensors: interaction with NO2 and O3 , 1998 .