The present work is a final dissemination of activities carried out and main results obtained in the national founded project Firb "Square". The project is leaded by Centro Ricerche Fiat and it involves the most qualified national public Research Institutes and Universities active in the fields of nanomaterials synthesis, nanotechnology and gas sensors development

Bonavita, Anna

Callone, Emanuela

Cao, Giacomo

Capone, Simonetta

Carturan, Giovanni

Coppede, Nicola

Debenedetti, Bruno

Deorsola, Fabio

Di Natale, Corrado

Forleo, Angiola

Iannotta, Salvatore

Lattore, M.

Licheri, Roberta

Martinelli, Eugenio

Marzorati, Diego

Merlone Borla, Edoardo

Micali, Giuseppe

Neri, Giovanni

Orru, Roberto

Paolesse, Roberto

Pennazza, Giorgio

Roncari, Edoardo

Sanson, Alessandra

Siciliano, Pietro

Taurino, Antonella

Toccoli, Tullio

PUblication MAnagement

1 
FIRB “SQUARE” PROJECT: NANO-STRUCTURED SENSORS 
FOR THE DETECTION OF THE POLLUTING IC ENGINE 
EXHAUST GASES AND FOR INDOOR AIR QUALITY 
MONITORING 
 
D. MARZORATI1, E. MERLONE BORLA1, M. LATTORE1, G. CARTURAN2, E. 
CALLONE2, G. NERI3, G. MICALI3, A. BONAVITA3, E. RONCARI4, A. SANSON4, 
C. DI NATALE5, E. MARTINELLI5, G. PENNAZZA5, R. PAOLESSE5, P. 
SICILIANO6, A. FORLEO6, S. CAPONE6, A.M. TAURINO6, B. DEBENEDETTI7,  
F. DEORSOLA7, S. IANNOTTA8, T. TOCCOLI8, N. COPPEDÈ8, R. LICHERI9,        
R ORRÙ9, G. CAO9,  
1)Mat. Eng. Dept., Adv. Manuf. & Materials, Centro Ricerche Fiat, Strada Torino, 50, 
10043 Orbassano (TO); 2)Dip. Ingegneria dei Materiali e Tecnologie Industriali, 
Università di Trento, Via Mesiano 77, 38100 Trento; 3)Dip. Chimica Ind. e Ing. dei 
Materiali, Università di Messina, Contrada di Dio, S. Agata, 98166 Messina; 4)Istituto 
di Scienza e Tecnologia dei materiali Ceramici, CNR, Via Granarolo, 64, 48018 Faenza 
(RA); 5)Dip.Ing.Elettronica e Scienze e Tecn. Chim, Università di "Tor Vergata", Via del 
Politecnico,1, 00133 Roma; 6)Istituto per la Microelettronica e Microsistemi, CNR, Via 
Monteroni c/o Campus Ekotecne, 73100 Lecce; 7)Dip. Scienza dei Materiali e Ing. 
Chimica, Politecnico di Torino, C.so Duca degli Abruzzi, 24, 10129 Torino; 8)Istituto di 
Fotonica e Nanotecnologie, CNR, Via Sommarive, 18, 38050 Povo (Trento); 9)Dip. 
Ingegneria Chimica e Materiali, Università di Cagliari e INSTM, Piazza d’Armi, 09123 
Cagliari 
abstract. 
 The present work is a final dissemination of activities carried out and main 
results obtained in the national founded project Firb “Square”. The project is 
leaded by Centro Ricerche Fiat and it involves the most qualified national 
public Research Institutes and Universities active in the fields of 
nanomaterials synthesis, nanotechnology and gas sensors development. 
1.   Introduction 
The project aims are to develop the technologies necessary to realise micro-
sensors with nanometric structure to detect the emissions of internal combustion 
engines and to monitor the indoor air quality. These sensors, by means of 
benefits given by the nanometric structure and thanks to the innovative 
nanotechnologies developed, offer several important advantages: 
 
 High sensitivity and selectivity to the chemical pollutants 
 Fast response time 
 Low dimensions 
 Low raw material costs 
XIII Convegno Associazione Italiana Sensori e Microsistemi, XIII AISEM, Roma, 19-21 febbraio 2008
 2 
 
Main technical objectives of the project are: 
 Synthesis of nano-materials for sensing element: SHS, Gel 
Combustion, Sol Gel and Spry Coating technologies; 
 Film deposition technologies: PMCS, Spin coating and Spry/drop 
coating (thin film); Screen Printing (thick film); 
 Micro-injection moulding technology of ceramic nano-powders for 
sensor holder production; 
 Development of specific gas sensors prototypes for automotive 
application (exhaust gas monitoring, indoor air quality, olfactory 
perception). 
2.   Experimental 
The technical activities are organized in four main line: 
1. Synthesis of nano-materials:  
the most promising materials obtained were SrFexTi1-xO3 (SHS) and SnO2 + CuO 
(GC) for exhaust application; In2O3 (Sol Gel), ZnPc-TiO2 (PMCS) for indoor air 
quality application; cluster of Me TPP (Cu, Co, Zn, Mn, Fe, Sn Ru, Cr) for 
indoor olfactory perception. Figures 2-4 show three different sensitized 
materials.                                             
  
  
 
5 m 
 
Figure 2 – Sol gel In2O3 Figure 3 – SHS SrFexTi1-xO3 
Figure 4 – Gel combustion 
SnO2 
    
2. Thick and thin film deposition:  
the processes used in the final prototypes production were: screen printing for 
both exhaust and IAQ application; plasma & supersonic beam for IAQ; spry 
coating for olfactory application. Figures 5-7 show the three different deposition 
process prototypes. 
 
 3 
   
Figure 5 – Screen printing  Figure 6 – PMCS deposition Figure 7 – Spry coating 
 
1. Sensor prototypes manufacturing:  
several kind of materials and deposition technologies have been characterized in 
order to select the most promising solution for the different applications. 
 
2. Sensors validation:  
the selected sensors have been tested in two specific bench capable to reproduce 
the working automotive condition (exhaust & indoor applications). The most 
promising prototypes for both applications have been implement in two Fiat 
Auto cars for an extensive road test campaign.  
3.   Results & Discussion 
SrFexTi1-xO3 oxygen sensor vehicle tests: 
to verify its performance in real operating conditions, the SrFexTi1-xO3 sensor 
was installed in an exhaust pipe of a diesel car together with a commercial Bosch 
probe (Figure 8).  
 
 
 
 
Figure 8: SrFe0.6Ti0.4O3 sensor prototype equipped on a Fiat Croma exhaust line. 
 
With respect to laboratory measurements, in road tests the sensor is exposed to 
an harsh ambient. Therefore an adequate protection is necessary to preserve the 
sensor life and stability. The probe for car testing was then fabricated by 
mounting the housing of a commercial lambda probe on the SrFexTi1-xO3 sensor, 
in order to protect and eliminate turbulence near the sensing film due to high 
spatial velocity of the gases. Another problem to solve is the wide temperature 
fluctuation of the exhaust gases. A temperature control has been achieved by 
means of a Proportional Integrated Derivative (PID) controller that finely adjusts 
 4 
the power delivered to the sensor by the heater. Fig. 9 shows the output 
responses of the resistive SrFexTi1-xO3 sensor and Bosch commercial probe 
acquired at the exhaust pipe during a time period of the road test, in response to 
wide variations of oxygen concentration (in the range 4-20 vol. %). It should be 
note that the sensors output are opposites. The resistive sensor increases its 
resistance with the increase of O2 concentration, whereas the voltage of the 
Bosch oxygen sensor decreases correspondingly.  
 
 
Figure 9: SrFe0.6Ti0.4O3 sensor experimental results. 
 
During road test the concentration of exhaust gases changes very quickly. Then, 
an essential requirement of the oxygen probe is, a prompt response. The strict 
signal overlapping between sensor response and lambda sensor signal indicate 
that the SrFexTi1-xO3 sensor responds quickly to oxygen concentration variations 
as the Bosch probe.  
These promising results demonstrate the feasibility of resistive oxygen sensor 
based on cost effective raw materials and with good performances; anyhow 
furter investigation on the sensor behaviour during long-term operation are 
required in order to verify the stability, reproducibility and life-time of the 
SrFexTi1-xO3 sensor in real operating conditions. 
 
AQS sensors: 
 
The laboratory screening on AQS sensors of two types (thin and thick film) 
allowed to select the ones with best performances. The next step has been a test 
on board in order to check their sensibility to air pollutant (CO and NO2) in 
actual conditions (see Fig. 10). 
 5 
 
 
Figure 10: In2O3 sensor prototype equipped on a Fiat Idea cabin inlet air duct 
 
The location and casing in the inlet air duct were adapted from those of 
commercial sensors. 
Figure 11 show the good results obtained: sensibility and selectivity to the air 
pollutants and besides a low response time. All that confirms the maturity of 
these technologies for the automotive field. 
 
 
 
Figure 11: In2O3 sensor Experimental results 
 
 
Olfactive sensors: 
 
This type of sensors were tested in laboratory with a prototype Electronic Nose 
supplied by the “Tor Vergata” Rome University (see Fig. 12). 
The metalloporfirine cavity, hosting the suitable metal ion, are able to produce a 
frequency variation in the quartz assembly. 
The aim of this research is to collect these signal and create a sensorial map, in 
order to discriminate among the various gases influencing the air quality. 
Advanced mathematical techniques, such as Principal Component Analysis 
(PCA), were used to show this behaviour. 
 
 6 
 
 
 
Figure 12: Kit of MeTPP sensor prototype on bench test 
 
 
The overall results showed in Fig. 13 are promising, but the great spread caused 
by the varying operating condition (umidity, temperature) suggests further 
development and research study.  
 
 
 
Figure 13: Experimental results 
 
References 
1.  T. Toccoli, A. Pallaoro, M. Tonezzer, N. Coppedè, and S. Iannotta, OFET 
for sensing based on SuMBE grown pentacene films, Solid State 
Electronics, 52, (2008), 417 
2.  P. Piseri, H. Vahedi Tafreshi, P. Milani, Manipulation of nanoparticles in 
supersonic beams for the production of nanostructured materials, Current 
Opinion in Solid State & Materials Science 8, (2004), 195 
3.  F. Siviero, N. Coppedè, A.M. Taurino, T. Toccoli, P. Siciliano, S. Iannotta, 
Hybrid titania - zincphthalocyanine nanostructured multilayers with novel 
gas sensing properties Sensors & Actuators: B. Chemical, 130, (2008), 405 
4.  M. Taurino, S. Capone, A. Boschetti, T. Toccoli, R. Verucchi, A. Pallaoro, 
P. Siciliano, S. Iannotta, Titanium dioxide thin films prepared by seeded 
supersonic beams for gas sensing applications, Sensor and Actuators B: 
Chemical 100, (2004), 177-184 
Time (s) 
F (Hz) 
 7 
5.  Neri G., Bonavita A., Micali G., Donato N., Deorsola F.A., Mossino P., 
Amato I., DeBenedetti B., “Ethanol sensors based on Pt-doped tin oxide 
powders synthesised by gel-combustion”, Sensors and Actuators B 117 
(2006), 196-204. 
6.  Siviero, N. Coppedè, A. Pallaoro, A. M. Taurino, T. Toccoli, P. Siciliano, 
S. Iannotta, Hybrid n-TiO2-CuPc Gas Sensors Sensitive to Reducing 
Species, Synthetized By Cluster and Supersonic Molecular Beam 
Deposition, Sensors and Actuator B: Chemical, 126, (2007), 214 
7.  Y. Wu, T. Toccoli, N. Koch, E. Iacob, A. Pallaoro, P. Rudolf, S. Iannotta, 
Control on the early stages of Pentacene growth by supersonic molecular 
beam deposition, Physical Review Letters, 98, (2007) 076601 (selected for 
February, 26, 2007 issue of Virtual Journal of Nanoscale Science and 
Technology http://www.vjnano.org) 
8.  T. Toccoli, A. Pallaoro, N. Coppedè, and S. Iannotta, F. De Angelis, L. 
Mariucci, G. Fortunato, Controlling Field Effect Mobility in Pentacene 
Based Transistors by Supersonic Molecular Beam Deposition, Applied 
Physics Letters 88, (2006) 132106 1-3 (selected for April, 10, 2006 issue of 
Virtual Journal of Nanoscale Science and Technology 
http://www.vjnano.org) 
9.  T. Mazza, E. Barborini, I. N. Kholmanov, P. Piseri, G. Bongiorno, S. 
Vinati, and P. Milani, C.Ducati, D.Cattaneo, A. Li Bassi, and C. Bottani, 
A.M.Taurino and P.Siciliano, Libraries of cluster-assembled titania films for 
chemical sensing, Applied Physics Letters 87, (2005), 103108 
10.  Walzer, T. Toccoli, A. Pallaoro, S. Iannotta, C. Wagner, T. Fritz and K. 
Leo, Comparison of organic thin films deposited by supersonic molecular-
beam epitaxy and organic molecular-beam epitaxy: The case of titanyl 
phthalocyanine, Surface Science, 600, (2006) 2064-2069 
11.  E.Barborini, A.M.Conti, I.Kholmanov, P.Piseri, A.Podestà, P.Milani, 
C.Cepek, O.Sakho, R.Macovez, and M.Sancrotti, Nanostructured TiO2 
Films with 2 eV Optical Gaps, Advanced Materials 17, (2005) 1842 
12.  Walzer, T. Fritz and K. Leo, T. Toccoli, A. Pallaoro, R. Verucchi, A. 
Boschetti and S. Iannotta, Structural and optical properties of titanyl 
phthalocyanine films deposited by supersonic molecular beam epitaxy 
(SuMBE), Surface Science, 573, (2004), 346-358 
13.  F. De Angelis, T. Toccoli, A. Pallaoro, N. Coppedè, L. Mariucci, G. 
Fortunato, S. Iannotta, SuMBE Based Thin Film Transistors, Synthetic 
Metals 146, (2004), 291–295 
14.  R. Ruiz, D. Choudhary, B. Nickel, T. Toccoli, K. C. Chang, A. C. Mayer, P. 
Clancy, J. M. Blakely, R. L. Headrick, S. Iannotta, G. G. Malliaras, 
Pentacene Thin Film Growth, Chemistry of Materials 16, (2004), 4497-4508 
15.  Sanson, D. Gardini, G. Montanari, C. Galassi, E. Roncari “The key role of 
milling in the optimization of TiO2 nanoinks”, J. Mater. res. 21 (6) (2006) 
1561 
 8 
16.  F.A. Deorsola, P. Mossino, I. Amato, B. DeBenedetti, A. Bonavita, G. 
Micali, G. Neri, “Gas Sensing Properties of TiO2 and SnO2 Nanopowders 
Obtained through Gel Combustion”, Advances in Science and Technology, 
Vol. 45 (2006), pp. 1828-1833. 
17.  G. Neri, A. Bonavita, G. Micali, G. Rizzo, R. Licheri, R. Orrù, G. Cao, 
“Resistive λ-sensors based on ball milled Fe doped-SrTiO3 nanopowders 
obtained by self-propagating high-temperature synthesis (SHS)”, Sensors 
and Actuators B: Chem., (2006), doi.10.1016/J.snb.2006.12.008. 
18.  Licheri, S. Fadda, R. Orrù, G. Cao, V. Buscaglia, “Self-propagating High-
temperature Synthesis of Barium Titanate and subsequent densification by 
Spark Plasma Sintering (SPS)”, J. Europ. Ceram. Soc., 27 (2007), 2245-
2253. 
19.  G. Neri, A. Bonavita, G. Micali, N. Donato, F. Deorsola, I. Amato, P. 
Mossino, B. De Benedetti, “Gas-sensing properties of SnO2 nanopowders 
synthesised by gel-combustion”    Proc. 1th Workshop on Advances in 
Sensors and Interfaces, pp. 193-198 (2005) 
20.  G. Neri, A. Bonavita, G. Micali, F. Deorsola, P. Mossino, I. Amato, B. De 
Benedetti, “Ethanol sensors based on Pt-doped tin oxide nanopowders 
synthesised by gel-combustion”,Sensors and Actuators B 117, 196-204 
(2006) 
21.  G. Neri, A. Bonavita, G. Rizzo, S. Galvagno, S. Capone, P. Siciliano, M. 
Niederberger, N. Pinna,“Towards enhanced performances in gas sensing: 
SnO2 based nanocrystalline oxides application”, Sensors and Actuators B 
122, 564-571 (2007) 
22.  G. Neri, A. Bonavita, G. Micali, G. Rizzo, S. Galvagno, N. Pinna, M. 
Niederberger, J. Ba, “Effect of the chemical composition on the sensing 
properties of In2O3-SnO2 nanoparticles synthesized by a nonaqueous 
method”, Sensors and Actuators (submitted) 
23.  G. Neri, A. Bonavita, G. Micali, G. Rizzo, E. Callone, G. Carturan, 
“Resistive CO gas sensors based on In2O3 and InSnOx nanopowders 
synthesized via starch-aided sol-gel process”, Sens. Actuators B (Submitted) 
24.  S. Nardis, D. Monti, C. Di Natale, A. D’Amico, P. Siciliano, A. Forleo, M. 
Epifani, A. Taurino, R. Rella, R. Paolesse, Preparation and characterization 
of Cobalt Porphyrin modified Tin Dioxide films for sensor applications, in 
Sensors and Actuators B, 103 (2004), 339-343. 
25.  Di Natale, R. Paolesse, A. D’Amico; Metalloporphyrins based artificial 
olfactory receptors, Sensors and Actuators B 121 2007 238-246 
26.  Falconi, E. Martinelli, C. Di Natale, A. D’Amico, F. Maloberti, P. 
Malcovati, A. Baschirotto, V. Stornelli, G. Ferri; Electronic interfaces, 
Sensors and Actuators B 121 2007 295-329 
27.  M. Mascini, A. Macagnano, G. Scortichini, M. Del Carlo, G. Diletti, A. 
D’Amico, C. Di Natale, D. Compagnone; Biomimetic sensors for dioxine 
detection in food samples, Sensors and Actuators B 111 2005 102-105 
 9 
28.  S. Nardis, D. Monti, C. Di Natale, A. D’Amico, P. Siciliano, A. Forleo, M. 
Epifani, A. Taurino, R. Rella, R. Paolesse; Preparation and characterization 
of cobalt porphyrin modified tin dioxide films for sensor applications, 
Sensors and Actuators B 103 2004 339-343 
29.  Falconi C., D’Amico A., Di Natale C., Faccio M.; Low cost curvature 
correction of bandgap references for integrated sensors, Sensors and 
Actuators A 117 2005 127-136 
30.  Bonavita, G. Micali, G. Rizzo G. Neri, “Alternative sol-gel routes for 
synthesizing gas sensing nanostructured materials”, ECS Transaction 3, 221 
(2006) 
31.  G. Neri, A. Bonavita, G. Micali, G. Rizzo, N. Pinna, M. Niederberger, J. 
Ba, “A study on the microstructure and gas sensing properties of ITO 
nanocrystals”, Thin Sol. Films (submitted) 
32.  G. Neri, A. Bonavita, G. Rizzo, S. Galvagno, N. Pinna, M. Niederberger, S. 
Capone, P., Siciliano, “Enhancement of sensor performance by using metal 
oxide nanocrystals”, Sensors and Microsystems 10, (in press) 
33.  F. Deorsola, I. Amato, B. De Benedetti, A. Bonavita, G. Micali, G. Neri, 
“Oxygen sensing properties of TiO2 nanopowders prepared by gel-
combustion”, Sensors and Microsystems 10, (in press) 
34.  E.Callone, G.Carturan, A.Sicurelli, J. Mater. Res., “Size stabilization of 
nanoparticles by polysaccharides: effectiveness in the wet and curing steps”, 
2007, 0, 000 
35.  E.Callone, G.Carturan, M.Ischia, A.Sicurelli, “Nanometric oxides from 
molecular precursors in the presence of starch. Coatings of glass with these 
oxides in silica sols”, J. Mat. Res., 2006, v. 21, n. 7, p. 1726-1737; 
36.  E.Callone, G.Carturan, M.Ischia, M.Epifani, S.Capone, P. Siciliano, Inorg. 
Chim. Acta, “The hydrolytic route to Co-porphyrin-doped SnO2 gas sensing 
materials Chemical study of Co-  porphyrin vs. Sn(IV) oxide interactions”, 
2007,  DOI http://dx.doi.org/10.1016/j.ica.2007.06.030  
37.  Callone, G. Carturan, Y. Jestin, M. Ferrari, “Synthesis improvement of 
Yb3+-activated SnO2 nanocrystals”, Solid State Phenom., 2007, 128, 31-
39; 
38.  R.Dela Pena, A.Sicurelli, E.Callone, G.Carturan, R.Raj, "A picoscale 
catalyst for hydrogen generation from NaBH4 for fuel-cells". J. Power 
Sources, 2007, v. 165, p. 315-323; 
39.  E.Callone, G.Carturan, A.Sicurelli, “Nanopowders of metallic oxides by the 
hydrolytic route with starch stabilization and biological abetment”, J. 
Nanosci. Nanotech., 2006, 6, 254-257 
40.  D.Cattaneo, A. Li Bassi, and C. Bottani, A.M.Taurino and P.Siciliano, 
Libraries of cluster-assembled titania films for chemical sensing, Applied 
Physics Letters 87, (2005), 103108 
 10 
41.  Monti, M. Venanzi, M. Stefanelli, A- Sorrenti, G. Mancini, C. Di Natale, R. 
Paolesse; Chiral amplification of chiral porphyrin derivatives by templeated 
heteroaggregation, Journal of American Chemical Society (in press) 
42.  L. Dolci, E. Marzocchi, M. Montalti, L. Prodi, D. Monti, C. Di Natale, A. 
D’Amico, R. Paolesse; Amphiphilic porphyrin film on glass as a simple and 
selective solid-state chemosensor for acqueous Hg2+, Biosensors and 
Bioelectronics 22 2006 399-404 
43.  R. Fortezza, G. Pontetti, E. Martinelli, F. Lo Castro, C. Di Natale, A. 
D’Amico; Soyuz missions and taxi flights: new opportunities for technology 
development. an example: the ENEIDE mission, Acta Astronautica 59 2006 
351-357 
44.  D. Monti, M. Venanzi,G. Mancini, C. Di Natale, R. Paolesse; 
Supramolecular chirality control by solvent changes. Solvodichroic effect on 
chiral porphyrin aggregation, Chemical Communication 2005 2005 2471-
2473 
45.  H. Willers, P. de Gijsel, N. Ogink, A. D’Amico, E. Martinelli, C. Di Natale, 
N. Van Ras, J. Van der Waarde; Monitoring of biological odour filtration in 
closed environments with olfactometry and an electronic nose, Water 
Science and Technology 50 2004 93-100 
46.  Monti D., Venanzi M., Russo M., Bussetti G., Goletti C., Montalti M., 
Zaccheroni N., Prodi L., Rella R., Manera M.G., Mancini G., Di Natale C., 
Paolesse R.; Spontaneous deposition of amphiphilic porphyrin films on 
glass, New Journal of Chemistry 9 2004 1123-1128I.Stoev, D.Kohl, Sensors 
and Actuators B, 2 (1990) , 233  
 


FIRB "SQUARE" project: nano-structured sensors for the detection of the polluting in engine exhaust gases and for indoor air quality monitoring

http://puma.isti.cnr.it/rmydownload.php?filename=cnr.istec/cnr.istec/2008-A3-002/2008-A3-002_0.pdf

FIRB "SQUARE" project: nano-structured sensors for the detection of the polluting in engine exhaust gases and for indoor air quality monitoring

Abstract

Similar works

Full text

Available Versions

PUblication MAnagement