Advanced nanoparticle based resistive-optoplasmonic solid state chemical gas sensors with high sensitivity for environment protection, healts improvement and explosive detection.

Joint research project

Project leaders: Roberto Rella, Stefan Luby
Agreement: REPUBBLICA SLOVACCA - SAS - Slovak Academy of Sciences
Call: CNR-SAS 2016-2017
Department: Physical sciences and technologies of matter
Thematic area: Physical sciences and technologies of matter
Status of the project: New

Research proposal

Metal-oxide (MO) gas and vapour sensors are used in the environmental protection, for security reasons and in health care&diagnostic techniques. Broad variety of gases are monitored. Nevertheless, NO2, CO and acetone is a triad well representing three above mentioned fields, respectively, and they were already included into the collaborative research between institutions involved in this proposal, as it follows from the sample of publications from the last years [1-3]. At present gas sensors belong to the most frequent electronic devices. Innovative sensors are built from nanostructures, like nanorods, nanoparticles and other nanostructured materials. In comparison with continuous films based devices these structures provide higher surface/volume ratio, i.e. better gas sensitivity. In spite of matured metal-oxide sensor technology there are requirements for the improvement of devices in all three basic areas - sensitivity, selectivity and stability. Apart of nanostructuring which is important in NO2 and CO monitoring, for acetone the ferroelectric µ - WO3 should be a sensitive medium because of high dipole moment of acetone 2.88 D, higher than that of NO2 (0.32 D) or CO (0.11 D) [4]. Monitoring of acetone in human breath is in the forefront of interest for non-invasive diagnostics of diabetes. Sensors are improved also using functionalization by noble metals, the basic principles of which are known longer time [5]. However, the detailed mechanisms are not clarified yet and often overlaping of various effects, like electronic orspillover phenomena, catalytic reactions or surface coarsening are reported (e.g. [6, 7]). Sensitivity of devices may be increased also by charge generating UV irradiation [8], but it is reasonable to use illumination source which could be integrated with the sensor. Here new semiconducting LED diodes have large potential. A very progressive way is also implementation of surface plasmon resonance effect, which was already studied by us, e.g. with TiO2 [9], which is another efficient sensing material. Here also our experience with nanoparticle based plasmonic solar cells might be helpful [10]. The field of metal-oxide sensors is often reviewed [11 - 13].
In the last years grahene entered this field. Schedin et al. reported on the possibility of detection of single NO2 molecule under specially controlled circumstances at surface of mechanically exfoliated graphene. The high potential of this material for gas sensing is derived from its large specific surface area of 2600 m2/g for gas adsorption, fast electron transport, structural stability, long-term durability, low Johnson and 1/f noise and possible operation at room temperature (c.f. reviews[15, 16]). The disadvantage of graphene lies in not yes completely mastered preparation techniques with big productivity and low chemical reactivity due to strong in-plane covalent sp2 bonds between carbon atoms as well as due to low defect density. To overcome this limitation the graphene gas sensors were senzitized in various ways, e.g. by functionalized of catalytic Pd particles. The sensitivity of graphene sensors step by step approaches that of metal-oxide devices in the ppm or even ppb range. It must be however emphasized that sensor research contributes also the the understanding basic properties of this strategic material.
[1] S. Luby, L. Chitu, M. Jergel, E. Majkova, P. Siffalovic, A. P. Caricato, A. Luches, M. Martino, R. Rella, M. G. Manera, Oxide nanoparticle arrays for sensors of CO and NO2 gases, Vacuum 86, 2012, 590 - 593.
[2] J. Ivanco, S. Luby, M. Jergel, P. Siffalovic, M. Benkovicova, Y. Halahovets, E. Majkova, R. Rella, M. G. Manera, Nitric oxide and acetone sensors based on iron oxide nanoparticles, Sensor Lett. 11, 2013, 2322 - 2326.
[3] S. Capone, M. G. Manera, A. Taurino, P. A. Siciliano, R. Rella, S Luby, M. Benkovicova, P. Siffalovic, E. Majkova, Fe3O4/ ³- Fe2O3 nanoparticle multilayers deposited by Langmuir Blodgett technique for gas sensing, Langmuir 30, 2014, 1190 - 1197.
[4] L. Wang, A. Teleki, S. E. Pratsinis, P. I. Gouma, Ferroelectric WO3 nanoparticles for acetone selective detection, Chem. Mater. 20, 2008, 4794 - 4796.
[5] D. Kohl, The role of noble metals in the chemistry of solid-state gas sensors, Sens. Actuators B 1, 1990, 158 - 165.
[6] S.-W. Choi, S. S. Kim, Room temerature CO sensing of selectively grown networked ZnO wires by Pd nanodot functionalization, Sens. Actuators B 168, 2012, 8 - 13.
[7] X Liu, J. Zhang, T. Yang, X. Guo, S. Wu, S. Wang, Synthesis of Pt nanoparticles functionalized WO3 nanorods and their gas sensing properties, Sens. Actuators B 156, 2011, 918 - 923.
[8] G. Lu, J. Xu, J. Sun, Y. Yu, Y. Zhang, F. Liu, UV-enhanced room temperature NO2 sensor using ZnO nanorods modified with SnO2 nanoparticles, Sens. Actuators B 162, 2012, 82 - 88.
[9] M. G. Manera, P. D. Cozzoli, G. Leo, M. L. Curri, A. Agostiano, L. Vasanelli, R. Rella, Thin films of TiO2 nanocrystals with controlled shape and surface coating for SPR alcohol vapour sensing, Sens. Actuators B 126, 2007, 562 - 572.
[10] A. Vojtko, M Jergel, V Náda?dy, P. ?iffalovi
, M. Kaiser, Y. Halahovets, M. Benkovi
ová, J. Ivan
o, E. Majkova, M. O. A. Erola, S. Suvanto, T. T. Pakkanen, towards organic solar cells without the hole transporting layer on the plasmon=enhanced ITO electrode, Phys. Stat. Sol. A 212, 2015, 867 - 876.
[11] K. Wetchakun, T. Samerjai, N. Tamaekong C. Liewhiran, CC. Siriwong, V. Kruefu, A. Wisitsiraat, A. Tuantranont, S. Phanichphant, Semiconducting metal oxides as sensors for environmentally hazardous gases, Sens. Actuators B 160, 2011, 580 - 591.
[12] A. Afzal, N. Cioffi, L. Sabatini, L. Torsi, NOx sensors based on semiconducting metal oxide nanostructures: Progress and perspective, Sens. Actuators B 171 - 172, 2012, 25 - 42.
[13] E. Comini, C. Baratto, I. Concina et al., Metal-oxide nanoscience and nanotechnology for chemical sensors, Sens. Actuators B 179

Research goals

1) Improvement of the preparation technology of Fe2O3 nanoparticles towards the size dispersion in order to achieve better regularity of nanoparticle arrays
2) Preparation by PLD deposition of TiO2 thin layers decorated by metal nanoparticles using Matrix Assisted Pulsed Layer Evaporation (MAPLE) technique. Au and Ag nanoparticles will be prepared as well.
3) Elaboration of new technology for preparation of two- or more component semiconducting metal-oxide (MO) materials or metal decorated nanoparticle arrays from the mixtures of different nanoparticle colloid solutions spread onto the water subphase in a Langmuir-Blodgett (LB) trough by modified Langmuir-Schaeffer technique patented by SAS. In parallel suitable targets containing metal and/or MO nanoparticles for MAPLE deposition techniques will be prepared.
4) Improvement of sensing parameters of sensors in term of sensitivity towards CO,NO2 and acetone detection by plasmonic activation of metal nanoparticles. Here the stimulation of sensors will be using UV radiation. AlGaN diodes with the wavelengths 240, 250 and 345 nm with colimated or focused radiation will be employed.
5)Elaboration of preparation technology of µ - WO3 ferrolectric nanoparticles with high dipole moment approriate for acetone sensing and testing of the experimental sensors.
6) Introduction of few-layered graphene and its application in NO2 sensors from pure or Pd decorated material.

Last update: 09/06/2025