Analytica Chimica Acta 568 (2006) 28–40

Review

Metal oxide nano-crystals for gas sensing
Elisabetta Comini ∗
SENSOR Lab, CNR-INFM, Brescia University, via valotti 9, 25133 Brescia, Italy Received 8 August 2005; received in revised form 21 October 2005; accepted 25 October 2005 Available online 1 December 2005

Abstract This review article is focused on the description of metal oxide single crystalline nanostructures used for gas sensing. Metal oxide nanowires are crystalline structures with precise chemical composition, surface terminations, and dislocation-defect free. Their nanosized dimension generate properties that can be significantly different from their coarse-grained polycrystalline counterpart. Surface effects appear because of the magnification in the specific surface of nanostructures, leading to an enhancement of the properties related to that, such as catalytic activity or surface adsorption. Properties that are basic phenomenon underlying solid-state gas sensors. Their use as gas-sensing materials should reduce instabilities, suffered from their polycrystalline counterpart, associated with grain coalescence and drift in electrical properties. High degree of crystallinity and atomic sharp terminations make them very promising for better understanding of sensing principles and for development of a new generation of gas sensors. These sensing nano-crystals can be used as resistors, in FET based or optical based gas sensors. The gas experiments presented confirm good sensing properties, the possibility to use dopants and catalyser such in thin film gas sensors and the real integration in low power consumption transducers of single crystalline nanobelts prove the feasibility of large scale manufacturing of well-organized sensor arrays based on different nanostructures. Nevertheless, a greater control in the growth is required for an application in commercial systems, together with a thorough understanding of the growth mechanism that can lead to a control in nano-wires size and size distributions, shape, crystal structure and atomic termination. © 2005 Elsevier B.V. All rights reserved.
Keywords: Nano crystals; Gas sensors; FET; PL; Nanowires

Contents
1. 2. 3. 4. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Deposition techniques and growth mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Working principle of metal oxide gas sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Measurements methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. DC conductimetric gas sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.1. Tin oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.2. Zinc oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.3. Other metal oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. FET based gas sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1. Indium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.2. Tin oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.3. Zinc oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. PL based gas sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other fields of application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 29 31 32 32 33 34 34 35 36 36 37 37 38

5.

Tel.: +390303715706; fax: +390302091271. E-mail address: comini@tflab.ing.unibs.it.

0003-2670/$ – see front matter © 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.aca.2005.10.069

. Some of these structures could not have been created easily or economically using top-down technologies. . ZnO. . . . . . domestic safety. . . . . . . . . . . . Their crystallinity assures improved stability and the nanosized lateral dimension the good sensing properties. . . . . . addition of a foreign element [2] or phase [3]. . has a great effect on sensor conductance. The evaporation method will be extensively described since it is one of the promising and most explored in the recent papers and also one of the cheapest for single crystal production. . . Gas sensors have a great influence in many areas such as environmental monitoring. . . . . . . . . . . . . In the literature a lot of different names has been used. . . . . . sensors networks. . . . . nanotubules. . Ag. The sensing properties of semiconductor metal oxide in form of thin or thick films other than SnO2 . . . Due to this huge application range the need of cheap. . . nano-wires or nano-ribbons) by simply evaporating the desired commercial metal oxide powders at high temperatures [4. . . . . mono dimensional for nano-wires and two dimensional for films. . . . . . . . . . . . . several solutions have been put forward to stabilize the nanostructure. . . . . . . like whiskers. spacecrafts and houses. . . rods. 2. . . . . . . . air conditioning in airplanes. . . . fibrils. In this configuration the transition from activated to strongly not activated carrier density. . . . . . . Introduction Metal oxides represent an assorted and appealing class of materials which properties cover the entire range from metals to semiconductors and insulators and almost all aspects of material science and physics in areas including superconductivity and magnetism. . The geometrical shapes can be tubes. . Pt. . 39 39 39 1. 1. In 1991 Yamazoe [1] showed that reduction of crystallite size caused a huge improvement in sensor performance. Since sensor performance depends on percolation path of electrons through intergranular regions. . public security. . . . . . . . . . . . . . . Fe2 O3 and In2 O3 . automotive applications. A few classes of these new nanostructures with potential as sensing devices are summarized schematically in Fig. . . . . . . . . . . . for more than five decades it has been known that the electrical conductivity of semiconductors varies with the composition of the gas atmosphere surrounding them. . . . e. . . In a low grain size metal oxide almost all the carriers are trapped in surface states and only a few thermal activated carriers are available for conduction. . . . . . . . . cages. . nanocable etc. . .5]. . has grown over the years and triggered a huge research worldwide to overcome metal oxide sensors drawbacks. . . . Conclusions . . fibers. a possible classification is zero dimensional for clusters. . . In the past years the number of synthesis techniques has grown exponentially. . . . . . . . have been studied as well as the benefits from the addition of noble metals: Pd. . . . . . compositions. sheets and even more complex morphologies. . cables. . . . . . . . . . . . . . . . . cylindrical wires. . . . . The challenge became to prepare materials with small crystallize size which were stable when operated at high temperature for long periods. . low power consuming and reliable solid state gas sensors. produced by target gases species. . Their peculiar characteristics and size effects make them interesting both for fundamental studies and for potential nano-device applications. . uniformity and crystalline properties. by physical and chemical vapour deposition. From the preparation side. Selectivity and Stability. . . . . . . . . . . like TiO2 . . . Deposition techniques and growth mechanisms Nanocrystalline materials can be classified into different categories depending on the number of dimensions that are nanosized (with dimensions lower than 100 nm). . . . . . . . . Subject treatment will start with presenting the preparation techniques and their development and improvements. . Thus. . . . . . . . pointing out the steps critical for applications in real environments. . . the technological improvement went along with a reduction of sensing performances due to a lower porosity of the prepared devices. . and morphologies have recently been fabricated using so-called bottom-up synthetic routes. . . . . . . . . . The source material has to be evaporated and then transported and condensed on a substrate. . A nomenclature for these peculiar structures has not been well established. belts. Au. Acknowledgments . . . . . Furthermore an outlook on other possible intriguing and new applications of metal oxide single crystals will be presented. by varying small details in the preparation process. . Numerous one-dimensional oxide nanostructures with useful properties. . . . . An unexpected step forward has been the successful preparation of stable single crystal quasi-one-dimensional semiconducting oxides nanostructures (so called nano-belts. . . . . WO3 . . . . . . . . . . .g. . . . . . . a more automated production method that offers higher reproducibility and compatibility with Si technology. . In the field of chemical sensing. . nails. . . . A . This review article is focused on the description of metal oxide single crystalline nanostructure used for gas sensing. . . . . . . .E. . . . . small. . first generation devices were prepared by thick film technology starting from powders. In order to obtain onedimensional structures the growth must have a preferential direction with a faster growth rate. . . . . . When developing 1D nanocrystals the most important requirements are dimensions and morphology control. . . . . . leading to a third generation of metal oxide gas sensors. . . each sensor differed slightly in its initial characteristics. . Comini / Analytica Chimica Acta 568 (2006) 28–40 29 6. . . Therefore the materials fabrication processes have been improved towards thin film technology. porosity modification and grain-boundary alteration. . . . . . . . . . . . . . . . These effects become more critical because the metal oxide layers must be kept at a relatively high temperature in order to guarantee the reversibility of chemical reactions at surface. . . . . . . summed up in improving the well known “3S”: Sensitivity. Both thin and thick films electrical properties drift due to grain coalescence. . The main advantage of the vapour phase process is the possibility to produce different type of materials in an easy way and with cheap deposition systems [7]. in improving selectivity and stability. . . . . . . . . . . References . However. . . . . . .

The growth chamber has to be designed in order to obtain the proper temperature gradient necessary for 1D nanostructures preparation. In VLS both liquid and solid phase contribute to the process. The liquid drop of the catalyser is a preferential growth site because all the adsorbed atoms are captured and are not able to desorb. This induces a higher growth rate of the VLS with respect to the VS growth process. This method is similar to VLS. In order to obtain this process there are some requirements to fulfil. the limiting factor is the surface growth step. when the concentration in the drop is too high the growth species precipitate and form the nano-wire. such as: catalyser has to allow the formation of a liquid solution with the material that has to be deposited. the catalyser vapour pressure must be low. At the beginnings the growth was attributed to the presence of lattice defects. The dimensions of the 1D structures can be controlled varying parameters such as pressure. where α is the accommodation coefficient and sigma is the super-saturation of the growth species in the gas phase. adsorption/desorption mechanism of molecules on substrate surface. with an additional window that allows laser incidence on source material. nanotubule. nanorod. but when defectsfree nano-wires were observed this explanation cannot be any longer accepted. but a drawback is the possible presence of the catalyser at the top of the grown structure. The growth process can be summarize in some steps: diffusion of growth species towards substrate surface. Another peculiar effect registered was a nanowire growth rate higher than the calculated condensation rate from the vapour phase.30 E. In the vapour phase deposition. inlet for gas carriers (Ar. furthermore the substrate temperature can be varied independently from the source one. while at high super-saturation powders are formed by homogeneous nucleation in the vapour phase. alumina). If the concentration of the growth species is low then the limiting Fig. the source can be evaporated using pulsed laser ablation. source material (metal. core-shell structure. vacuum sealed tube (quartz. The uses of laser to produce evaporation of the oxide source allows lower operation temperatures. The metal oxide powder is placed in the higher temperature region and the gas carrier transports the evaporated oxide towards the substrates where it condenses. acts as a favourite site for crystallization. dendrite. A possible explanation proposed is that all non-wire faces adsorb the molecules that then diffuse on the principal growth surface of the wire. . vapor–liquid–solid (VLS) and solution–liquid–solid (SLS). Some of these growth steps can limit the crystal growth rate. 2. nanobelt. For metal oxide nano-wires the metal itself can act as a catalyzer. Indeed the produced nano-wires are in general polycrystalline and for this reason are not so valuable for gas sensing applications. As the vapour pressure increases the defect formation probability increases and furthermore possible secondary nucleation site occur losing the mono-crystallinity. which is proportional to the vapour pressure of the growth species: J=√ ασP0 2πmkT (1) Fig. nanocomb. typical experimental set-up consists of a vacuum-sealed tubular furnace with an inlet for the carrier gas and an output connected to a vacuum pump as reported in Fig. but the source material is a solution. H2 ). Experimental set-up for vapour phase deposition of 1D structures with an heating furnace. Different 1D metal oxide nanostructures. the control of super saturation condition is the key factor to control the morphology of the deposition products. aggregation of adsorbed species to form the crystal and diffusion and evacuation of possible by products [8]. Growth mechanism can be classified as: vapor–solid (VS). from top right: nanowire. The drawback is the higher cost of such deposition system. This is an old growth mechanism proposed in 1964 by Wagner. The VS growth takes place when the nano-wire crystallization originates from direct condensation from vapour phase without the use of a catalyser. O2 . Other than direct heating for the formation of 1D nanostructure. 2. Comini / Analytica Chimica Acta 568 (2006) 28–40 step is the adsorption mechanism. A low super-saturation is required for 1D nanostructure. An advantage is an enhanced control in nano-wire diameter induced by the control in catalyser dispersion and dimension. metal oxide). nanoring. the growth rate is controlled by the condensation rate. The growth species in the vapour phase diffuses in the liquid drop of catalyser. valves and vacuum pump. when the super saturation is reached. in general the liquid phase is a liquid metal cluster or catalyser that acts as a favourite site for adsorption of the vapour phase and. the catalyser has to be chemical inert. 2. an alternative method is the SLS. SLS can operate at lower temperatures than VLS. 1. hierarchical nanostructure. This kind of deposition set-up is quite similar to the one reported in Fig. diffusion of adsorbed species on substrate surface since a growth site is reached. In general high temperatures are required for VLS growth of nano-wires. When the growth species concentration is high. a medium super-saturation for bulk crystals.

and also this junction can play a role in the sensing mechanism. Some works drew the attention on the VLS (vapour–liquid–solid) mechanism. that has a cubic structure.E. This technique provides a good control of the uniformity and on the dimension (owing a good control on pores dimensions and distribution). At the present. The direct flux is used during the deposition process while the reversed flux is used during the temperature gradient in order to avoid the formation of uncontrolled nanostructures. oxygen vacancies mobility become appreciable and the mechanism of conduction become mixed ionic-electronic. low vacuum pumping system has to be used (see Fig. to avoid long term changes. In single crystal-based gas sensors the current flows parallel to the surface and is modulated by the surface reactions like the channel of a Field Effect Transistor by the gate voltage. In the case of single crystalline layers the . the flux and the gases have to be optimized. The evaporation temperatures of these oxides are quite high then a tubular furnace with maximum heating temperatures higher than thousands degree centigrade. the nanostructure grows within or around it. nano-wires can be prepared as reported in Fig. 3. A key point is that the local variations of the thermo-dynamic variable such as pressure temperature and concentrations are not known along the furnace. to obtain 1D and not 3D structures. through which thermal evaporation techniques can favour a fast growth below 1000 ◦ C (crystal growth by thermal evaporation of SnO2 powders usually occurs at temperatures higher than 1300 ◦ C). The high degree of crystallinity is confirmed by HRTEM. The normal operation temperature of metal oxide gas sensors is in general within the range between 200 and 500 ◦ C where conduction is electronic and oxygen vacancies are doubly ionized. 3. In the particular case of indium oxide. As it has been already pointed out the high degree of crystallinity and the control in the surface termination is a key factor for producing and understanding stable and reliable gas sensors. 3D crystalline structures. Secondary electron images of different Inidium oxide structures obtained by a vapour phase deposition depending on substrates temperature: from 1100 to 800 ◦ C wires with lateral dimensions of the order of microns. Vapor phase deposition is not the only technique used for the preparation of 1D structures. several investigations have been devoted to tin and zinc oxide nano-wires/nanobelts and different approaches to their synthesis have been developed [9–13]. for each different apparatus and are not directly transferable form one to others apparatus. substrates and source holders. however the number of nano-wires that can be produced are limited by the template and the template removal can cause damage to 1D structures. The set-up can be designed to allow a direct (from source material to substrates) or reversed (from substrates to. The template can serve as a container. When the channel is fully depleted. temperature and substrates. Cleanness of all the alumina parts used during the deposition is a key factor for the deposition of reproducible structures. When a metal oxide is operated in the semiconducting temperature range. Clearly when dealing with single crystals synthesised at temperatures higher than the operating temperatures of the sensors there should not be instability problems caused by structural changes or coalescence. This problem is more important in depositions from evaporation of oxides powders since the high temperature requires the use of alumina and there is no easy wet cleaning process for oxide removal over alumina. We report in detail an example of vapour phase deposition procedure for the preparation of indium oxide nano-wires/nanobelts. Among the studies on 1D nanostructures. source) flux. the pressure. the charge transfer process induced by surface reactions determines its resistance. Different morphologies can be obtained depending on the temperature of the substrates. Working principle of metal oxide gas sensors Conductimetric metal oxide gas sensors rely on changes of electrical conductivity due to the interaction with the surrounding atmosphere. should be operated at temperatures low enough so that appreciable bulk variation never occurs and high enough so that gas reactions occur in a time on the order of the desired response time. nano-wires. due to their simplicity and low costs. 3. At the interface between metal and metal oxide. Comini / Analytica Chimica Acta 568 (2006) 28–40 31 Fig. At higher temperatures. from 1100 to 800 ◦ C wires with lateral dimensions of the order of microns. for this reason strict procedures before every deposition have to be followed. For example 1D nanostructures synthesis can be obtained also by templates. the shape of 1D nanostructure is complementary to the one of the chosen template. together with alumina tube. Special kind of boats for source and for substrates in alumina can be used in order to obtain a quite selective deposition. 3D crystalline structures. a possible way is the use of higher temperatures to induce evaporation of the oxide deposited over tubes. the nanowire section is constant through all its length without any defect and with atomically sharp terminations. 2). Metal oxide gas sensors. vapour phase processes seem to be the most promising ones. The temperature of the furnace. the deposition condition are more critical due to the difficulties in producing anisotropic growth from such a symmetric structure. The effective value of super saturation is a difficult number to evaluate in the deposition chamber without studies of all the thermodynamics variables inside the deposition chamber. carriers thermally activated from surface states are responsible for conduction. metal semiconductor junction will appear. necessary to connect the nanowire to the outside world.

After selective removal. The overall effect is a change of the density of ionosorbed oxygen that is detected as an increase of sensor conductance. at higher temperature the O− form dominates. The mobility dependence on surface coverage can be neglected because electron diffusion length (about 1 nm) is much shorter than the diameter (tens of nanometres). since O2 − has a lower activation energy it is dominating up to about 200 ◦ C. there will be an ensemble of nano-wires on all the substrate surface and a selective removal have to be performed if a single wire sensor is desired. Measurements methods Metal oxide 1D structures can be configured. which are much deeper in the band-gap than oxygen’s. for example. Obviously not all the transducers are suited for depositions at high temperatures and the presence of metals can cause a catalytic growth.ads NO− 2. In single nano-wire configurations a nano-manipulator can be used for transferring nano-wire in the desired position on the transducer.gas + e− (2) (3) 4. in a molecular (O2 − ) and atomic form (O− ) [14]. In the temperature range between 100 and 500 ◦ C oxygen ionosorbs over metal oxide. 4. Of course some of these procedures described are not ready for an implementation for large-scale production. In the case of a one-dimensional wire along the main axis the treatment can be done using the Poisson equation in cylindrical coordinates. large variations of carrier concentrations. the nano-wire can be dispersed in a solvent and transferred by drop-coating on the complete transducer (with metallization pads). Density of carriers is thermally activated from surface states into the conduction band. gas detection is related to the reactions between the species to be detected and ionosorbed surface oxygen. that is very weak compared to the case of polycrystalline materials. Contacting issue remains still one of the biggest open problems when dealing with 1D nanostructures. The most important ionosorbed species when operating in ambient air are oxygen and water. are produced by the transition from strongly activated to not activated carrier density [58]. . When charge density is reduced due to surface reactions with ionosorbed oxygen. thin metallizations can be deposited by focused ion beam (FIB) or electron beam deposition (EBD) between the nano-wires and the pre-existing pads.ads The occupation of surface states. the conducting channel thickness is reduced. As it has been already pointed out only some of the manifold metal oxide nanocrystals produced were tested with particular regard to their electrical properties in controlled atmosphere for These consume ionosorbed oxygen and in turn change the electrical conductance of metal oxide. in such case there is no problem relating with contacts or manipulation. Direct adsorption is also proposed for the gaseous species—like strongly electronegative NO2 —whose effect is to decrease sensor conductance: NO2. the following reactions may take place: COgas → COads COads + Oads − → CO2.e. Comini / Analytica Chimica Acta 568 (2006) 28–40 contact resistance is more important since it is in series to the semiconductor resistance while for polycrystalline material it is connected to a large number of resistances. If the deposition is performed on substrates other than the transducer. the metal contacts have to be deposited on the nano-wires. The bands shape can be parabolic or flat as for small grain polycrystalline materials. Then in order to improve the mechanical stability and electrical contacts.gas NO2. with the difference that current flows parallel instead that perpendicular to the surface like in a pinched-off FET channel. The transducer has to provide at least two electrical contacts on the metal oxide to measure conductance changes and a heating system in order to maintain the metal oxide at the suitable operation temperature that in general is of the order of hundreds degrees centigrade. In both configurations 1D structures can be grown directly on transducer or transferred to it after the deposition process on a more suitable substrate. When a reducing gas like CO comes into contact with the surface. increases the surface potential and reduces the overall sensor conductance.32 E. The dependence of the conductance on the density of occupied surface states is linear. For some reducing gases. but the final device cannot be as cheap as the one based on electrical properties monitoring and the sensing mechanism is not yet completely understood. A different possibility to measure a gas sensing activity is monitoring the optical luminescence properties instead of the electrical ones. If the growth is made on the final device transducer. the space charge region extends through all the wire cross section and all electrons are trapped in surface states. this is also related to the difficulties that we have just exposed like the contacting problems for electrical measurements. The articles recently published will be reported following the measurement method used. Electrical transport changes when the thickness of the wire is small like in nano-wires with lateral dimensions low compared to the debye lenght. DC conductimetric gas sensors The easiest way to transduce the gas sensor is by simply measuring the DC resistance of the sensing element as a function of the surrounding atmosphere.ads (4) (5) e− + NO2. The research on gas sensing properties of nano-crystals is still not as developed as the one on the preparation of 1D nanostructure. in FET devices or in normal resistor configuration with single or multiple nano-wires in one device.1. This is of course not an easy task when dealing with metal oxide structures due to their resistance to corrosive environments. FET or optical gas sensors (Table 1). and therefore of conductivity. The simplest transducer is a bulk insulating substrate with electrical contacts on one side of the substrate and a heater on the backside. gas adsorption creates a surface depletion layer. DC conductimetric. The sensing mechanism in metal oxide gas sensors is related to ionosorption of species over their surfaces. When dealing with wire with lateral dimensions of the order of hundreds of nanometer. to produce conductimetric gas sensors. i.

1. due to its better performances in terms of sensitivity and stability compared to other oxides. Then. for breath analyser and food quality control. propanol Lipo protein O2 CO. measurement method and target species studied Year 2002 2003 Metal oxide SnO2 SnO2 TiO2 In2 O3 In2 O3 Cd:ZnO ZnO In2 O3 SnO2 ZnO In2 O3 ZnO ZnO ZnO V 2 O5 In2 O3 SnO2 + Pd SnO2 Ru:SnO2 SnO2 + CuO ZnO SnO2 SnO2 MoO3 WO3 Measurements method DC. Table 1 reports a list of the metal oxide nano-crystal gas sensors that have been found in the literature together with the target gas chosen. M DC.1. NH3 NO2 . M FET. In the field of metal oxide conductimetric gas sensors tin oxide is by far one of the most studied and also one of the few that has been commercialized. 4. towards ethanol and NO2 at 300 ◦ C with 50% RH using synthetic air as a carrier gas in order to reproduce a real environment. M FET. NO2 ethanol NO2 H2 . HCHO. CO. CO and ethanol were found to increase the conductivity. S DC. CO DMMP CO. M DC. . M DC. 5 reports an example of variation of the current flowing through the nanobelts configured in a DC resistor configuration. Kinetic response of a SnO2 nanowires based sensor conductance produced by steps in ethanol and NO2 concentrations with 50% RH and at a working temperature of 300 ◦ C. M FET. Comini / Analytica Chimica Acta 568 (2006) 28–40 33 Fig. M FET. FET: FET based gas sensors. M DC. that is common for an n-type semiconductor such as tin oxide. the gases tested were CO. Fig. M Target species CO. NH3 . M FET. NO2 and ethanol that are important for environmental applications. 5. The conductance value in air was stable during all the operation time and there was no poisoning of the Table 1 List of published studies on gas sensing properties of 1D nanostructures. O2 O2 Ethanol RH CO. M DC. and furthermore to the biocompatibility of this oxide that make it promising also for medical and in vivo applications. as depicted in Fig. together with publication year metal oxide analysed. in form of thick films. M DC. M FET. a bunch of nanobelts was transferred onto the electrodes for electric conductance measurements. PL: PL based gas sensors. H2 S. S DC. a platinum interdigitated electrode structure. as explained in the previous section. while the opposite behaviour was registered for NO2 . S DC. ethanol H2 S NO2 . toluene. gas sensing applications. 4. S DC. M DC. S FET. DC: DC resistive configuration. NH3 H2 1-Butylamine. S DC. M DC. Tin oxide Tin oxide nanobelts based gas sensor was the first one with a simple DC-resistive measurement presented in 2002 [5].E. NO2 . this is due to the easiness in preparing nano-wires and multiple intriguing nanostructure. S. ethanol NO2 Reference [5] [34] [26] [29] [31] [21] [22] [32] [36] [38] [19] [20] [23] [24] [25] [33] [37] [15] [16] [17] [40] [44] [18] [54] [55] 2004 2005 M: multiple nanowire. S: single nanowire. S FET. S FET. Layout of two terminal resistive measurements with interdigitated contacts on the bottom of metal oxide nanowires in a single wire and multiple wires configuration. 4. S PL. M DC. N2 . NO2 NH3 RH Ethanol NO2 CO. NH3 . was made using sputtering technique with shadow masking on alumina substrate. In the nano- crystals case instead Zinc oxide is one of the most studied. O2 NH3 . Fig. The transducer fabrication.

response and recovery times were quite fast. but the concentration. the detection limit was estimated to be equal to . ZnO nanorods showed a predominant sensitivity to alcohols compared to other gases tested such as CO. Of course the addition of a polycrystalline material reduces the advantages of the use of single crystalline metal oxide as sensing layer. This study reported the response of bare ZnO and Pd coated ZnO nanorods. Zang et al. molybdenum. used (50 ppm) was very high compared to the threshold for environmental monitoring. A mixture of In2 O3 nanowire and polyvinyl alcohol solution was coated on alumina tubes with two gold contacts at the end. ethanol and RH. The nanorods resulted covered for the 70% with a rms roughness of 8 nm and a catalytic effect was obtained. Furthermore no response to oxygen variations have been registered at room temperature. The resistance of the nanobelt increased of 5% when 78 ppb of dimethyl methylphosphonate (DMMP) a nerve agent simulant (Fig. Furthermore the sensor poisoning. Another work published on tin oxide nanowires in this DC configuration is reporting the effect on Ru doping obtained by simultaneous evaporation of oxides [16]. The sensor dynamics were limited by the filling time of the chamber. H2 S. [23]. The resistance of 1D ZnO nanostructures decreased as RH value was increased. The integration of top down and bottom up approaches prove the feasibility of large scale manufacturing of well organized sensor arrays based on different nanostructures. In the same year this group reported about ethanol sensing properties of ZnO nanowires [22]. no saturation effect was registered for concentration till 200 ppm. Other tests on humidity resistance variation have been reported in [21] for Cd doped ZnO nanowires. ZnO nanorods were characterized towards hydrogen at room temperature. and Pd deposition was performed with sputtering. this is of course an encouraging result. This catalyst was chosen since it is known in thick and thin film to enhance the sensing properties towards H2 S of SnO2 (an effect ascribed to the p–n junction formation). especially at low concentration levels. Nanobelts and nanowires were mixed with a CuO 4% mol solution. such as indium. ethanol and other gases. The final sensor showed good ethanol sensing properties and the detection limit was lower than 1ppm of ethanol. Other metal oxides Other than tin and zinc oxide also other oxides were investigated in DC resistor configuration. recently published a contribution on tin oxide nanobelts proving their integration with micro-machined substrate. of the orders of seconds. the detection limit reached was lower than 3 ppm. Zinc oxide As far as zinc oxide nano-crystals are concerned. Concentrations of ethanol as small as 10 ppm were detected at 330 ◦ C with response and recovery times lower than 10 s. The increase in H2 S response was confirmed in 1D nanostructure. H2 S. H2 . The gas test measurements were repeated at 25 ◦ C every 5 days for 1 month and the variations in the resistance were less than 3% for the entire RH range tested. reported variations in the electrical properties due to humidity changes at room temperature [20]. which is crucial if a real application is envisaged.3. present in some measurements. suggested application of nanorods as hydrogen sensors in [24]. A more complete gas characterization on the sensing properties of ZnO nanorods was reported by Jiaquiang et al. The resistance of the nanowires was monitored in presence of air. SnO2 single nanobelt have been transferred on a silicon microsystem device fabricated with the top-down approach. The response of nanorods based sensor was lower and the authors ascribed this difference to more homogeneous nanowires morphology and to smaller lateral nanowires dimen- sions that increased their higher specific surface area. HCHO. for a room temperature working sensor. A strong increase in the response to hydrogen was measured. an application of increasing interest for security reasons [18]. The detection limit is lower than the limit needed for breath analyser and the fast dynamics are compatible with a real application also if response to possible interfering gases still have to be investigated. The highest response was obtained with ethanol. and showing their sensitivity to nerve agent. The gas tested was nitrogen dioxide. Wang et al. Nanorods and nanowires have been deposited on a Si oxidized substrate with interdigitated Pt electrods on the top and their electrical properties have been tested at room temperature in presence of different relative humidity values. with a total variation of about 4 orders of magnitude. but only sporadic works were reported. gas sensing properties have been studied towards CO. a heating wire was inserted in the tube to operate in the temperature range 100–500 ◦ C. the change of resistance of nanowires were relatively linear with RH from 12 to 97%. HCHO. the detection limit was not estimated but also in this case it should be compatible with the afore mentioned application. The authors performed also measurements as a function of the nanobelts-nanowires densities and reported a dependency of the gas sensing properties on the densities of the meshes. 4. was attributed to the contacts failure and eliminated with the deposition of good ohmic electrical contacts on the nanobelt. tungsten and titanium oxide. suggesting that in a DC configuration with multiple wires also the potential barriers.34 E. This work is interesting because nanowires were dispersed on a micromachined substrate complete with Pt interdigitated contacts and heater. Comini / Analytica Chimica Acta 568 (2006) 28–40 sensor due to gas exposures. NH3 . [19]. The nanorods were deposited on alumina tubes with two gold contacts at the end. that can appear due to wire to wire contact. Indium oxide nanowires have been tested towards ethanol by Xiangfeng et al. The results showed a variation of 3 orders of magnitude to 95% RH that is a worse performance compared to the one reported in [20]. 7).1. Yu et al. the deposition was performed over a glass substrate with pre-existing Au contacts. but still it is interesting to see how the Ru doping could increase NO2 response. vanadium.2. recovery time transients were faster than 20 s upon removal of H2 . could be important for sensing mechanism [15].1. a heating wire was inserted in the tube to operate in the temperature range 100–500 ◦ C. NH3 . 4. Another work on SnO2 1D nanostructure reports the effect of catalysts on nanowires sensing properties [17].

The nanorods were deposited on alumina substrates and then equipped with Pt heater and IDC contacts in order to investigate their gas sensing properties. Layout of three terminal FET with a metal oxide single nanowire or multiple metal oxide nanowires acting as channel. Response of the as-assembled nanobelt sensor to 78 and 53 ppb DMMP balanced with air when the nanobelt temperature was 500 ◦ C. Phys. [25] report about a V2 O5 nanofiber based sensor. In such way the Fermi level within the band gap of the nanowire can be varied and used to control surface process electronically. Lett. but the good response to amines is promising for the development of sensors for healthcare applications like diagnosis of uremia. compared Fig. cancer. These results were attributed to the increase in the surface area of these structures. but showed a high response to oxygen. to the large amount of literature on gas sensing properties of carbon nanotubes. or for food freshness analyses. Copyright 2005. The estimated detection limit was 30 ppb and the same sensor resulted less sensitive to ammonia and quite insensitive to vapour of toluene and 1-propanol. Sawicka et al. The nanowire acts as a conductive channel that joins source and drain electrode. Reprinted with permission from Appl. or lower than 100 ppm and response and recovery times were in the second range. The response and recovery times were quite long due to the low operation temperature. Vanadia nanofibers were deposited on silicon substrate and the resistance of the nanofibers was measured at room temperature in presence of different concentration of 1-butylamine.5 V. The effect of processing parameters variation was studied and a comparison with thin films prepared by sol–gel was presented.2. In 2005. nanorods or nanobelts. 86 (2005) 063101. As the diameter of the pore decreased the sensing performance increased. 6. [26] studied the hydrogen sensing properties of titania nano-tubes prepared by anodization. 6. Raible et al. The response to 1-butylamine increased linearly with relative humidity and also the type of contacting changed the response characteristics. Comini / Analytica Chimica Acta 568 (2006) 28–40 35 Fig. only little attention was put in the studies of gas sensing properties of tubular structures. while. faster response and lower gas detection limit that the sol–gel based elements. Tuning of the metal oxide properties in a FET . M 81.E. MoO3 nanorods were characterized by high response to ethanol and CO at temperatures in the range of hundreds degrees centigrade. All these examples reported were related to single crystals in form of nanowire. The sensors showed high selectivity compared to CO and NH3 . a work on molybdenum oxide nanorods gas sensing properties has been published [54]. the response increased with temperature and the response time was 2–3 min. American Institute of Physics. For example Varghese et al. presented in 2005 [55] nitrogen dioxide sensing properties of tungsten oxide nanowires prepared with electrospinning. Nanowires exhibit improved gas sensitivity. The authors ascribed this peculiarity to the high surface to volume ratio due to the intrinsic morphology of nanorods and to the very reduced lateral dimensions of these nanorods. FET based gas sensors Nanowires can be configured in a FET structure with a 3 terminal configuration as represented in Fig. 4. 7. The voltage applied to the nanobelt was 1. The response of thin films with the same structure was comparatively studied and nanorods based sensors resulted one order of magnitude more sensitive of their 3D counterpart. WO3 nanowires showed better NO2 gas sensing performances compared to sol–gel processed films. The tests were performed in nitrogen atmosphere and 1% H2 produced a variation of 3 orders of magnitude in the resistance of the array of titania nanotubes.

NO2 chemisorb strongly on SnO2 surface. high sensitivity down to ppb range. Other experiments have been presented by Zhang et al. Furthermore a big influence was found on nanowires pre-treatment. Investigations on SnO2 and ZnO have been performed while operating in air. The adsorption of lipoproteins on these two different surfaces revealed a tenfold higher adsorption on carbon nanotubes than on In2 O3 nanowires because of hydrophobic/hydrophilic interactions. the atmospheres tested were pure nitrogen. [34] analysed room temperature sensing properties of a single crystalline tin oxide nanowire sensor towards nitrogen dioxide. while upon UV exposure photo-generated holes migrate to the surface and recombine with electrons releasing oxygen ions. the device can be tested in a single wire or a multiple wire FET as depicted in Fig. [36] on tin oxide single nanowire sensor in a FET structure. but it has been reported also in thin films in [30] the key factor that distinguish 1D structures from thin films is the effect that small variation in surface coverage can cause in the conducting properties. and the results were promising for a possible control on the sensitivity towards gases in a FET structure. Two methods were used to produce the FET structure. In 2005. The detection limit suggested was 2–10 ppm of nitrogen dioxide that is not suited for environmental application for example.36 E. and an easier fabrication.1. shifting the threshold potential to more positive values. Tang et al. with a depletion layer decrease and an increase in conductance. The response and recovery were quite fast also if working at room temperature. of course. A strong dependence on the channel length of the switching ratio was found and for lengths higher than 100 nm no valuable switching was recorded. oxygen and CO. the presence of oxygen of course caused oxygen ionosorption and depletion of electrons on the nano-wire surface. Comini / Analytica Chimica Acta 568 (2006) 28–40 configuration has been reported in references [27. pointing out that a strict control in the deposition process and post-treatment procedures has to be achieved to produce reliable sensors. In the dark oxygen adsorbs on the surface capturing electrons form the semiconductor and creates a depletion layer. In2 O3 nanowire transistors exhibited higher conductance accompanied by a negative shift of the threshold voltage. A pinch off effect was reported. the first one consisted in nanowires dispersion in ethanol by ultrasonication and drying on a silicon dioxide-silicon substrate. the nanotube transistors showed lower conductance after the exposure. the advantages of these sensors are the low power consumption due to room temperature operation and potential stability due to the single crystalline nature of these structures. Of course operating at room temperature reaction dynamics are very slow and in the time cycle used the steady state value was not reached. Indium oxide Li et al. Specific works devoted to the gas sensing properties of metal oxides nanowires in a FET configuration were performed on tin. furthermore to recover the initial conductance value UV light exposure was used to desorb nitrogen dioxide molecules previously adsorbed on the metal oxide surface. the authors ascribed this effect to a redistribution of the electron density in the conduction channel closer to the nanowire surface due to the bias. was used on this single nanowire and led to a positive effect on both adsorption and desorption process. in vacuum and in presence of low oxygen and nitrogen concentration in vacuum [27]. This latter approach led to very resistive contacts. In the same reference a study of the influence on the sensing properties of the gate voltage was performed. nitrogen. published interesting results on the response to low density lipoprotein of metal oxide nanowires and carbon nanotubes [33]. indium and zinc oxide (Table 1). but the measurements showed a huge variation that can foresee good results also in normal environment as reported by other groups. and also a negative resistance effect. In 2004 the same authors reported the detection of NO2 down to ppb levels for the first time with metal oxide nano-wire transistors [32].2. and at room temperature desorption is not complete when the NO2 is removed. but the response could be increased with the use of dopants or catalysers. Furthermore a change of conductance in opposite directions was observed with different nanowire sensors and the authors suggest that this response is caused by various doping concentrations in the semiconducting In2 O3 nano-wires. This is attributed to the complementary doping type of In2 O3 nanowires (n type) and carbon nanotubes (p type). In2 O3 nanowire and carbon nanotube transistors were used to study the chemical gating effect of low-density lipoproteins. and then in electrodes deposition by electron beam lithography. Tin oxide Law et al. is not only related to 1D structure.2. The second procedure consisted in deposition of dispersed nano-wires on predefined electrode arrays. The use of UV light to activate this process. The experimental observations suggest that oxygen adsorption–desorption rate and CO oxidation can be changed by varying the electron density in the nano- . sensors based on multiple In2 O3 nano-wires displayed numerous advantages in terms of greater reliability. These experiments are important since they open up new possibility for developing sensors also for biological quantities. 4. 4. The same group reported in [31] the gate-screening effect at high NH3 concentrations and ascribed it to adsorbed NH3 molecules working as charge traps. The concentration used were very high compared to the range interesting for environmental applications and the use of argon instead of air of course does not match in general with a real application. nitrogen and oxygen. [29] reports an electrical characterization of a single indium oxide nanowire with dimensions of the order of ten nanometers towards ammonia and nitrogen dioxide in presence of argon at room temperature. Two types of devices were studied one based on single and one on multiple In2 O3 nano-wires operating at room temperature. that has proven to be effective with thin films [35]. These FET devices showed good switching rations between ON and OFF states. 6.26]. While single In2 O3 nano-wire devices exhibited strong gate dependence and nice transistor behaviour.2. if an annealing in vacuum was performed the nano-wire showed a very high electron density. The channel conductance and the threshold were sensitive to the gaseous surrounding atmospheres. This electro-absoption effect.

8). Peculiar effects are attributed to the decrease in the lateral dimensions of these single crystals structures. but still a response to CO was recorded and this was attributed to the interaction with lattice oxygen.2. gas-sensing properties of ZnO single nanowire FET were tested towards NO2 and NH3 at room temperature [40]. The same group in [39] characterized the electrical properties of ZnO nanowire field effect transistors with scanning probe microscopy. 4. air has to be used as a carrier gas and the effect of interfering gases and humidity have to be taken into account in the right concentration range. Most of the works are related to ZnO due to its manifold optical properties that can be exploited in different application such as lasing. the negative voltage pulse produced a complete recovery of the conductance value to the initial level before NO2 exposure. more realistic condition have to be explored. A strong field was used to refresh the sensor after molecules adsorption at room temperature. The sensing capabilities of SnO2 single nano-wires and nano-belts in a FET configuration before and after functionalization with Pd catalyst were reported. The integration of top down and bottom up approaches prove the feasibility of large scale manufacturing of well-organized sensor arrays based on different nanostructures. In 2005. at −6 V no oxygen adsorption was registered. It was shown a considerable variation of electrical properties of the single crystal ZnO nanowire upon oxygen introduction. Zinc oxide Further works in a FET configuration have been reported on zinc oxide nanostructures. Kolmakov et al. The potential drop at Schottky barrier contact was analysed. It is well known that these 1D metal oxide nanostructure such as zinc oxide. Some of the electrical measurement on nanowires gas sensors were carried out in ideal atmospheres. Copyright 2005 [37]. PL based gas sensors A new and yet not well-explored possible detection method is based on photo-luminescence quenching. for example the onset of visible PL spectra of high energy gap metal oxides and a progressive increase of the green light Fig. 4. It is interesting to note how oxygen coverage was controlled by gate voltage. The catalyst deposition was performed in the same chamber used for gas tests in order to have a direct comparison on the same sensor structure.E. indium oxide and tin oxide show a visible emission when excited in the UV range. Furthermore if a dipole moment is associated with the adsorbed molecule the gate field can induce a repulsive field weakening the bonding. Comini / Analytica Chimica Acta 568 (2006) 28–40 37 All these studies on single wire structures are important for the intrinsic results and also for the possibilities to correlate the experiments with theoretical studies performed on the interaction of specific surface termination with simple molecules like CO or NO2 [57]. if a gas sensing device has to be produced. As in the previous reported investigations. A change in the conductance was recorded in the early stage of Pd deposition indicating the formation of barrier type junction. Fan et al. (a) Schematic view of the formation of electron depleted regions beneath and in the immediate vicinity of two Pd nanoparticles. This tunability due to the electro absorptive effect is easy obtainable in a FET structure. Such a tuneable sensor can ease the application of gas sensor in real environment where more than one gas species are present simultaneously. Furthermore an interesting study of the response to oxygen as a function of the nanowire dimensions was reported. while above a threshold value the CO sensing properties are not related to gate potential. The improvement in the sensing performance after catalysation was ascribed to a combined effect of spill-over of atomic oxygen formed catalytically on Pd clusters and migrating on SnO2 surface and to the back spillover effect in which weakly bound molecular oxygen migrates to Pd clusters and are catalytically dissociated (Fig. but clearly. evidencing an increase in the response as the nanowire radius decreases. [37] studied the effect of catalysts in tin oxide single wire FET structures. The negative gate potential depleted electron in nano-wire and reduced the number of electrons available at the vacancy sites. the hole migration to the surface instead led to a discharge of gas molecules. (b) Response of a pristine (dashed line) and Pd-functionalized (solid line) nanostructure to sequential oxygen and hydrogen pulses at 473 K (top pane) and 543 K (bottom). Nevertheless the presented experiments show good sensing properties. Gate potential increase can enhance CO sensing properties. the electrical field applied to the back gate electrode influenced the sensitivity. the possibility to use dopants and catalyser such in the thin film gas sensors and the real integration in low power consumption transducers of single crystalline nanobelts.3. wire through the change in potential.3. [38] reported oxygen adsorption on the nanowire surface. . 8. the conductive SPM tip was used as a movable local gate in order to change the electrical properties of FET device. Finally. Reprinted with permission from Nanoletters (2005) 5 (4) 667–673.

38 E. the cut-off for ZnO was about 385 nm. The nano-size perturbations on the nano-needle tips were assumed to cause such excellent field-emission performance. The response was highly selective towards humidity and other polluting species like CO and NH3 . novel probe microscopy. Needle tips diameters were in a range of 20–50 nm. The extremely high photoconductivity effect makes 1D nanowires also good candidates for highly sensitive electrical switching. Photonic crystals can be produced with an array of catalyst patterned with electron beam lithography used as a template for the growth of ordered nanowires structures by VLS growth mechanism. sapphire and air nanorods ends can serve as mirrors for the optical cavity without cleavage and etching. Park et al. just 1–3 nm in dimension. since the photons cannot be absorbed. Only Faglia et al. reporting broad PL optical bands from tin oxide nanobelts in the visible range from 400 to 600 nm.e. etc [46]. Electronic circuit built with nanowires or nanotubes can be a possible way to maintain the miniaturization trend that has now featured a slow down due to intrinsic limit in lithographic processes. Non volatile electric polarization was reproducibly induced and manipulated on nano-wires. NH3 (50 ppm) and CO (10–1000 ppm) in dry and humid synthetic air and normal ambient pressure conditions. the light induced transition between insulator to semiconductor allows them to reversibly switch the nanowire between ON and OFF state rapidly.5 and 4. once the power exceeded the treshold value of 40 kW cm−2 a sharp . Some of these manifold possibilities will be describe hereafter. Li et al. using light emitting nano-junctions. The nanoneedles were single crystals growing along the [0 0 1] direction and exhibiting multiple tip surface perturbations. Field-emission measurements on the prepared nanostructures showed fairly low turn-on and threshold fields of 2. the electrons needed for cathode ray guns within televisions screen can be pulled from tips of nanowires and the sharp ends of these structures allow the use of lower level electric fields. Huang et al. the time scale was supposed to be reduced to the microsecond scale with proper optimisations. p–n junctions. Prototype devices have been prepared with bottom-up approach trough self-assembly such as FET. These properties of ZnO have already been reported in thin films and disordered particles [51]. The pump used was Ng:YAG laser. that create surface states. The examined species were NO2 (300 ppb–10 ppm). Nanowires might also be the basis of high definition TV. Nanowires can also be used for lasing and as guide of light in the same way as optical fibers. respectively. but also the optical properties can change with gas exposure. The authors believed that adsorbed gaseous species. The sensing mechanism underneath a photoluminescense based gas sensor is not completely understood. Due to the difference of refractive index of ZnO. Also if realization and feasibility of electronic circuits and non volatile memories with single crystal metal oxide nanostructure is a big step towards nano-electronics of course there is still much work on this topic to get closer to large-scale fabrication. Many studies reported the onset of visible photoluminescense in nanocrystals but only few reported the photoluminescense as a function of the surrounding atmosphere. For example Kind et al. functional nano-structured materials. High performance MESFETs and logic gate devices have been produced using electron beam deposition and metal evaporation to produce ohmic contacts on ZnO nanorods. However single crystalline oxide nanostructures seem to solve part of these limits. 5. Another possible application that has been demonstrated is information storage. there is no photo-response with wavelengths outside the UV range. The application of metal oxide in real electronic circuits was limited by the ability to produce epitaxial or crystalline films and also by difficulties in controlling metal oxide junction characteristics. i. The optical and electrical properties can be tailored with the catalyst template characteristics. 1D nanostructure will however require an understanding of fundamental chemistry and physics undergoing preparation and materials properties. The onset of visible PL in tin oxide fishbone like nanoribbons has been recently showed [42] and luminescence properties of SnO2 nanoparticles studied [43]. [49] report about the possibility in electron emitter and flat panel display applications with ZnO nano-needles. could quench PL by creating competitive non-radiative paths. [48] with ferroelectric BaTiO3 nano-wires. The ones with faceted flat ends can serve as intrinsic optical resonant cavities to generate coherent light.0 V/mm. rich in oxygen vacancies. The switch was also wavelength selective. [50] observed room temperature UV lasing with ZnO nanorods array deposited on sapphire substrate with VLS technique. [47] report that the conductance of single ZnO nano-wire was extremely sensitive to UV light exposure. To realize these and other proposed use. to volume ratio influence the electrical properties of the metal oxide as the studies presented in the previous sections prove. Quantum size effects and increase of surface. Furthermore nano-wire can be used also in nano-electronic in order to go beyond fabrication limit determined by top-down approaches. obtained by Yun et al. [45] prove the ability of single crystal to be used in logic circuits. Comini / Analytica Chimica Acta 568 (2006) 28–40 emission intensity was registered as the wires diameter decreases [41]. these 10 nm nano-wires retained ferro-electricity with a coercive field for reversal polarization of about 7 kV/cm and with a retention time for the induced polarization exceeding 5 days. nevertheless it proves the possibility to produce a sensing device based on simultaneous monitoring of both resistance and luminescence in order to exploit all the different informations obtained from metal oxide nanowires interaction with gases. A comparison between conductimetric and PL response suggests that the two responses are attributed to different adsorption processes [56]. [44] published on the quenching in the visible photoluminescence (PL) of tin oxide nanobelts due to the introduction of nitrogen dioxide at ppm level in a fast (time scale order of seconds) and reversible way. Other fields of application There are also many other applications where these nanocrystals could be exploited including: nano-electronics.

Still a greater control in the growth is required for an application in commercial systems. which reduce instability associated with hopping and coalescence. J. [3] E. Z. shape. Considerable efforts and progress have been made in aspects of the development and testing of 1D metal oxides gas sensors. Sens. and furthermore the European Commission that funded her research in the nanostructures field with the project NMP4-CT-2003001528 “Nanostructured solid-state gas sensors with superior performance” (NANOS4). This may be improved by fabricating sensor arrays using several different nanobelts. Comini. Bonini.E. i. Lett. C. due to the crystallographic structure of the substrate. Sberveglieri. G. Comini. [5] E. Frigeri. Mater. G. Wang. . Z. Guidi. peak was registered in the emission spectrum. for example a nanocomb can be viewed as an array of nanocantilever and with dip pen each cantilever can be coated with different catalysers or polymers (Fig. Paglialonga. the better stoichiometry and greater level of crystallinity compared to polycrystalline oxides. L. Actuators B 68 (2000) 274. C. Wang. Z. [53]. to the confinement obtained by a template. but at least some of them. M. The greater surface to volume ratio. [4] Z. make newly developed quasi mono-dimensional semiconducting oxide very promising for better understanding of sensing principles and development of a new generation of sensors. The future developments will be improving quickly and in an unpredictable way. Sacerdoti. Dai. G. Ferroni. Sberveglieri. Boscarino. Sens.L. which she belong to. D. Malagu. controlling the supersaturation and other parameters. Phys. with width 50 times smaller than the spontaneous emission. Martinelli. The anisotropic growth required by the 1D nanocrystals can be achieved in different conditions. Acknowledgments The author wants to thank first of all the member of the SENSOR lab group in Brescia. or by functionaliztion of their surfaces. 81 (2002) 1869. 9) producing an array of microns dimensions. together with a thorough understanding of the growth mechanism that can lead to a control in nano-wires size and size distributions. physical and chemical properties. The discovery of gas sensing properties of single crystal nanostructure comparable or even better than their thin film counterpart triggered the attention of the gas sensor research community. vapour phase process. 6. Schematic drawing of a possible array of cantilevers coated with different materials and SEM image of a ZnO nanocomb. Progress both in synthesis and manipulation of 1D nanostructures is growing fast and with it the range of materials prepared and the applications foreseen. We have focused our attention to the techniques used for the preparation of most of single crystalline gas sensor. Faglia.L. A great attention has to be paid to problems like the electrical contacts and nano-manipulation that allow production and integration of sensors. The use of a single crystalline structure with lateral dimensions of less than hundreds nanometers allows the fabrication of an array of sensors in a chip with lateral dimensions of the order of microns. Z. Conclusions A survey of preparation techniques. The reduced dimensions of nanobelts increase the cantilever sensitivity. 16 (2001) 1559. carbon nanotubes have been used at the end of Si tips [52]. V. Yamazoe. Appl. Science 291 (2001) 1947. M. G. Pan. M. 9. The selectivity of course still remains a concern for metal oxide based gas sensor. Finally 1D nanostructures can be used also as novel probes for SPM.C. Actuators B 5 (1991) 7. Carotta. the resolution of AFM is determined by size and shape of the probe tip used for imaging. Of course not all the problems of metal oxide gas sensor can be solved with the use of single crystalline materials. [2] N.e. Pan. Res. and performances of 1D nanocrystals metal oxide gas sensors has been presented. V. Guidi. Comini / Analytica Chimica Acta 568 (2006) 28–40 39 Fig. crystal structure and atomic termination. References [1] N. but of course also metal oxide 1D structure can be used as tips in order to enhance the resolution of the lateral information acquired as reported in ref. Furthermore metal oxides are ideal candidates for cantilever applications due to their defect free crystallinity and to their excellent mechanical properties.R.W.

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