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J ournal J. Am. Ceram. Soc., 95 [3] 831–850 (2012) DOI: 10.1111/j.1551-2916.2011.05056.x © 2012 The

J ournal

J. Am. Ceram. Soc., 95 [3] 831–850 (2012) DOI: 10.1111/j.1551-2916.2011.05056.x © 2012 The American Ceramic Society

Metal Oxides Mono-Dimensional Nanostructures for Gas Sensing and Light Emission

Caterina Soldano, Elisabetta Comini, Camilla Baratto, Matteo Ferroni, Guido Faglia, and Giorgio Sberveglieri

CNR-IDASC and Dipartimento di Chimica e Fisica per l’Ingegneria e i Materiali, Universita` degli Studi di Brescia, 25131 Brescia, Italy

The present Review opens with an overview of metal oxides and the description of their material properties. The first part mainly deals with various preparation techniques and growth mechanisms, which have been largely developed in the last few decades to fabricate different types of metal oxide nanostruc- tures. The second part, on the other hand, will provide the Reader with an up-to-date summary of different applications in which metal oxides nanostructures have been successfully implemented and/or suggested. In particular, great attention will be dedicated to the implementation of metal oxide nano- structures for gas sensing as well as light emission applications, for which both working principles and integration, as well as the latest reported cutting edge results are herein reported. Finally, we emphasize on the current potentials of metal oxide nanostructured materials and future challenges that this field in continuous expansion is currently facing.

I . Introduction II. Preparation techniques and growth mechanisms

1.

Doping of quasi-one-dimensional metal oxide

nanostructures

2.

Preparation of quasi-one-dimensional metal oxide heterostructures

III.

Applications of metal oxide nanostructures

IV.

Metal oxide gas sensors

a.

Working principle

b.

Nanowires integration

c.

Functional devices i. Conductometric chemical sensors ii. Optical chemical sensors

V. Light emission

a. Working principle

b. Nanowires integration

c. Light emitting diodes

D. J. Green—contributing editor

Manuscript No. 30088. Received July 29, 2011; approved December 07, 2011. Author to whom correspondence should be addressed. e-mail: caterina.soldano@ ing.unibs.it

VI. Conclusions

VII. Acknowledgments VIII. References

I.

Introduction

M ETAL oxides (MOxs) represent a vast class of materials of interest for various scientific communities, ranging

from physics to chemistry, from material science to engineer-

ing. 1 4

There exist a large variety of metal oxides com-

pounds, mostly depending on the type of metals used along with oxygen. To the latter, most of the properties character-

izing those types of materials, are related. A number of very different properties have been observed so far, ranging from metallic, semiconducting as well as insu- lating behavior, mainly depending on the specific electronic structure of the particular oxides. This broad range of mate- rials properties has opened up the way to numerous and ver- satile applications, often very different one from each other

such as microelectronic circuits, 5 sensors, 6

piezoelectric

devices, 7 fuel cells, 8 anti-corrosive coatings, 9 catalysts, more.

For decades now, metal oxides have been successfully used in various forms in the field of gas sensing, where the con- ductometric properties of those materials are exploited based principally on the induced variation of the electrical resis- tance upon interaction (absorption, chemisorption or physi- sorption) of a gas molecule on the oxide surface. MOxs catalytic properties are also very well known and exploited in the chemical and petrochemical industries, where a large number of processes implicate the usage of these materials. Further, catalysts- and absorbents-oxides-based are fre- quently used to remove species such as CO, NO x , and SO x , common by-products of fuel-based combustion processes, and, at the same time, to monitor and control environmental pollution. 11 Microelectronics and semiconductor industries represent further additional and predominant fields for metal oxides applications; in fact, most commercially available chips nowadays contain at least one metal oxide element. However, there are still a number of not yet very much investigated and unexplored fields in which those materials

and

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can be successfully employed, such as lighting 12 14 [in partic- ular for light emitting diodes (LEDs) and lasers], solar

cells, 15 field emitters

In the continuous quest for novel applications, new func- tionalities have been introduced by simply reducing the size of the material of interest toward the nanoscale world, as in the case of nanoparticles, nanowires, carbon nanotubes, 18 fullerenes, 19 and graphene. 20 In the particular field of metal oxides, quasi one-dimensional (1-D) structures 21 have shown several advantages with respect to their traditional thin- and thick-film counterpart such as very large surface-to-volume ratio, dimensions comparable to the extension of surface

charge region, greater stability as a result of the high degree

of crystalline order,

tion methods, 10 possibility of different chemical surface func- tionalization 23 with selective species, modulation of their operating temperature to select the specific reactions, catalyst deposition over the surface for promotion or inhibition of specific reactions. Moreover, there is also the possibility of field-effect transistors (FETs) configuration, which probes the gate-modulated transport characteristics to tailor sensitivity and selectivity. Novel synthesis approaches, physical as well as chemical, have been developed to fabricate metal oxides nanostructures (nanoparticles, nanowires, nanotubes, whiskers, and a variety of more exotic nanoscale objects). Both “top-down” and “bottom-up” fabrication techniques are used: the former, involving the micro-fabrication techniques to reduce the lat- eral dimension of a bulk material, the latter based on the assembly of molecular building blocks from the bottom by various synthesis methods which envision an “atom-by- atom” or “molecule-by-molecule” growth. In this Review, the Reader will be provided with “state- of-the-art” overview of the different preparation techniques currently used to grow metal oxides nanostructures and architectures, as well as various methods to dope one-dimen- sional nanostructures to tune their electronic properties. Among a large numbers of possible applications (which will be herein only briefly summarized), most of the attention will be dedicated to the use of metal oxide nanostructures to fab- ricate devices for gas sensing as well as light emission. Details will be given for both fields in terms of their working princi- ples, as well as the integration of those nanostructures in working or existing architectures, together with the most recent results reported in literature. When needed, the Reader will be referred to more specific and detailed literature.

16

as well as high-capacity batteries. 17

22

relatively simple and low-cost prepara-

24

II. Preparation Techniques and Growth Mechanisms

One-dimensional structures can be prepared following two different approaches: “bottom-up” and “top-down technolo- gies.” Top-down technology is based on standard micro- fabrication equipment with deposition and etching on planar structures to reduce the lateral dimensions of films down to the nanoscale level. To selectively remove the material the

following techniques can be used: electron-beam, focused ion beam, X-ray lithography, nano-imprinting, and others. Draw- backs of top-down reside in the extremely elevated costs and long preparation times, although advantages are the great knowledge and control for the well developed technology coming from the semiconductor industry; furthermore, the device is directly prepared on planar surfaces which allows for easier subsequent contacting approaches. Top-down approaches have been so far used to fabricate highly ordered nanowire, 25 28 however, the 1-D nanostructures produced with these techniques are in general not single crystal. The “bottom-up” approach instead is based on the assem- bly of molecular building blocks or chemical synthesis directly in the nanosized morphology. This approach pre- sents many advantages such as the high purity and crystallin- ity of the produced materials, the easy achievement of reduced dimensions, the low cost of the experimental set-ups and the possibility to easily dope and form junctions. On the other hand, the integration on planar substrates, necessary for the full exploitation of their useful properties, can be troublesome. In addition, the alignment and patterning of the nanostructures could be more challenging when using the bottom-up approach. 29 The combination of the bottom-up approach (for the production of high quality nanostructures) with top-down approach (that can lead to large scale fabrica- tion) represents at the moment the most promising strategy to fabricate highly functional devices. In literature, depending on the creativity and imagination of the authors, a lot of different names have been used, such as whiskers, nanowires, nanotubes, nanocastles, fibers, fibrils, nanotubules, nanocables, etc., as shown in Fig. 1. Some of these manifold morphologies have indeed potential applica- tions as functional devices. The preparation of films or small particles can be obtained with an early stop of the growth process; whereas for the achievement of one-dimensional morphologies with an iso- tropic atomic bonding it is necessary to induce a break in the symmetry during the growth. There must be a preferential growth direction characterized by a much faster growth rate. The number of synthesis techniques is growing very rapidly; we can distinguish between catalyst-free and catalyst-assisted methods and between vapor- and solution-phase growth. Vapor-phase preparation techniques are very popular in liter- ature, although solution-phase ones provide flexible synthesis procedures with cheaper equipment. Depending on the pres- ence of the catalyst during the growth, different mechanisms have been proposed, i.e., vapor-liquid-solid (VLS), solution- liquid-solid (SLS) or vapor-solid process (VS) (Fig. 2). Wagner and Ellis in 1964 30 discovered the controlled cata- lytic growth of whiskers and named the VLS mechanism for the three phases involved: the Vapor-phase precursor, the “Liquid” catalyst droplet, and the “Solid” crystalline prod- uct. Silicon whiskers could be grown by heating a Si sub- strate covered with Au particles in a mixture of SiCl 4 and

H 2 .

with Au particles in a mixture of SiCl 4 and H 2 . Fig. 1. heterostructure,

Fig. 1.

heterostructure, (e,f) nanobelts, and (g) hierarchical structure.

Different morphologies for sensing and lighting applications: (a) nanowire, (b) longitudinal heterostructure, (c) nanotube, (d) core-shell

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Metal Oxide for Gas Sensing and Light Emission 833 Fig. 2. Vapor-Liquid-Solid (VLS) growth of nanowires.

Fig. 2. Vapor-Liquid-Solid (VLS) growth of nanowires. The catalyst is in the liquid phase and precursors in the vapor phase can adsorb and condense to form the nanowire. In the Solution-Liquid- Solid (SLS) growth of nanowires the precursors in the liquid phase react to form the nanowire.

Few but interesting research publications 31,32 present a shape diagram of nanostructures as a function of selected parameters such as source and substrate temperature as well

as type of catalyst; even if there is no clear explanation of the different results obtained, it is indeed useful for an even- tual confirmation and/or confutation of subsequent theoreti- cal studies. The presence of the catalyst particle at the top of the nanowire is the result of a VLS growth mechanism; however, this does not define the catalyst phase and role during the growth. It has been shown that for all the vapor phase pro- cesses there is a “dead time” before the nanowires growth begins. 33 Different methods can be used for the preparation

of the catalytic nanoparticles, including thermal evaporation,

sputtering, colloidal solutions; nevertheless, the focus has to remain on the agglomeration of the nanoparticles because the dimension of the clusters strongly influences the diameter of the growing nanowire. Since the nanowire deposition is performed at elevated temperatures, even if the metal forms

a thin layer covering the entire substrate, clusters will be formed due to the Ostwald ripening. 34 When the nanowires

have a uniform cross-section along their entire length, the condensation happens mainly at the catalyst surface, and then it diffuses and segregates at the interface with the nano- wire. In this case, a uniform catalyst dimension on the sub- strate should result in a uniform nanowire diameter, if nanoparticles coalescence effect is negligible. 35,36 Whereas, if the catalyst is consumed or evaporated during the growth process, the diameter of the nanowire will decrease, resulting

in conical shape nanowires.

Growth temperature is one of the key parameters to con- trol the critical phases during the nanowires elongation, defining the adsorption, diffusion (surface and bulk), and sol- ubility. Temperature, pressure, and gas composition must be well controlled to obtain reproducible and reliable nanowires growth. Furthermore, the selection of the catalyst is crucial since it has to lower the activation energy of nucleation at the nanowire-catalyst interface to ensure the preferential one- dimensional growth.

During a VS growth, instead, the nanowire crystallization originates from the direct condensation from the vapor phase. First, it was attributed to the presence of lattice defects, but defect-free nanowires obtained by VS are also frequently reported in literature. Very little is still known, even if a number of experimental and theoretical works have been presented. At high temperatures, the source material is evaporated and then condensed on the substrate at lower temperatures. The initially condensed molecules form seed crystals that serve as the nucleation sites; as a result of which, they facilitate directional growth to minimize the sur- face energy. This self-catalytic growth associated with many thermodynamic parameters is a rather complicated process that often needs quantitative modeling. 38

37

Recently, some investigations on the nanowires growth have been presented in literature, according to which differ- ent growth mechanisms have to be taken into account all together with a large number of parameters involved which makes a systematic study more difficult. 39 A quantitative investigation on the nucleation and growth of indium oxide nanowires on single crystal substrate, with catalytically active gold particles, was studied through thermal evaporation of pure In 2 O 3 powders with the effect of substrate seeding with

gold catalysts.

The nanowires crystallize in the body-

centered cubic (bcc) structure and grow along the [100] vec-

tor of the cubic crystalline cell without any preferential growth direction. The measured growth rate can be satisfac- torily explained taking into account a concurrent direct VS and catalyst-mediated VLS mechanism during nanowire

growth, with the formation of high-index lateral faces which regulates longitudinal elongation at high temperature, according to the periodic bond chain theory. Most of the combined theoretical and experimental investi- gations first perform the synthesis and afterward the struc- ture analysis. There is lack of detailed in situ structural monitoring. Although lately some in situ transmission and scanning electron microscopy (TEM and SEM, respectively) observations of the nanowires growth were presented limited

to a small number of nanowires such as silicon,

nium, 42 44 gallium arsenide, 45,46 bismuth, 47 CdTe 48 a com-

plete picture is still missing. The application at elevated temperatures and in a controlled gas environment for elec- tron microscopy still remains an experimental challenge, like other structural characterization methods such as SPM (Scanning Probe Microscopy) or X-ray diffraction tech- niques. The growth of ZnO nanobelts was monitored in situ using X-ray diffraction for the first time, 49 by heating metallic zinc powder in air at 368 °C 568° C. A morphology diagram for the synthesized products was generated after systematic study of the experimental parameters. Higher temperatures and faster heating rates favor one-dimensional growth. Fas- ter growth was observed for samples with higher growth temperatures, lower heating rates, and one-dimensional growth. Recently, direct in situ optical and photoelectron emission microscopy studies of VO 2 nanostructures growth of using vapor transport of V 2 O 5 in vacuum and in inert gas environ- ment were reported. 50 The formation, coexistence, and trans- formation of the intermediate oxide phases and morphologies were structurally and compositionally charac- terized. Both kinetic and thermodynamic factors seem to play a role in the composition, structure, and morphology during multiple phase transformations. The key factors governing the growth emerged from this study were:

germa-

40

41

1. abundance of the precursor on the surface and its temper- ature;

2. liquid droplets affinity to the substrate;

3. competition between oxygen loss (if in vacuum or a reduc- tive atmosphere) and heating rate.

Controlling these parameters carefully, the chemical com- position, morphology, and size of the final structures may be tailored. Using a heating rate lower than the vanadia reduc-

tion rate allowed the interruption of the growth at an inter- mediate step obtaining V 2 O 5 , V 6 O 13 , or VO 2 . Lately, a lot of research has also been performed on nano- wire preparation by oxidation in controlled environment of the metal composing the metal oxide, especially in the case

of copper oxide.

tion of nanowires by thermal oxidation is still under debate,

but the most interesting thing is that the wires are single crystals. 54 The models presented suggest that the nanowire formation in a vapor-solid growth process 55 is related to stress relaxation at the interface 56 or to competing grain boundary and lattice diffusion of copper ions across the

The growth mechanism for the forma-

51 53

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Cu 2 O layer. 49,57 Nevertheless, this technique offers many advantages such as an easy patterning of the nanowires using conventional patterning techniques on the metal film, large area, and catalyst-free nanowire production, and the inexpen- sive equipment. Finally, another possible mechanism for the preparation of nanowires is solution-based catalyzed-growth (SLS), which is similar to the VLS: a metallic nanoparticle catalyzes the pre- cursors decomposition and crystalline nanowire growth. 58,59 There are many experimental procedures for the preparation of nanowires from the liquid phase, but in general VLS pro- duce nanowires with better crystalline properties. Large research effort has been devoted to the template-free methods for the deposition of one-dimensional nanostruc- tures in liquid environment exploring surfactant-assisted, sonochemical, hydrothermal, electrochemical and electrospin- ning deposition techniques. Surfactant-assisted deposition is a trial-and-error proce- dure, where the surfactant is used to promote the anisotropic crystal growth and confine it as in a micrometer-size reactor. Different surfactants have been proposed such as oleic acid, hexylphosphonic acid (HPA), tetradecylphosphonic acid, tri- octylphosphine oxide, and trioctylphosphine 60 ; different con- ditions and surfactants must be used for different materials. In addition, sonochemical method instead uses ultrasonic waves to modify the crystal growth; in fact, bubbles, formed in the aqueous solution, tend to grow and subsequently col- lapse leading to extreme reaction conditions needed to form

nanowires. Nevertheless, both hydrothermal and electrochemical pro- cesses are well-known procedures for material synthesis. In the first, a solution of an aqueous mixture of soluble precur- sors metal salt (metal and/or metal-organic) is placed in an autoclave at high temperature (between 100° C and 300° C) and relatively high pressure ( > 1 atm) conditions. 63,64 Electrochemical deposition instead, is obtained using an electrolytic cell with the substrate acting as cathode and where the metal ions in the solution are moved by an electric field to coat the substrate. Nanowires may be formed directly or by using a template. 65 Electrospinning is known since 1994 and exploits an elec- trical charge to force the formation of mats of fine fibers. A solid fiber is produced as the electrified jet is continuously stretched due to the electro-static repulsions between the sur- face charges and the evaporation of solvent. 66 68

61,62

(1) Doping of Quasi 1-D Metal Oxide Nanostructures

The doping issue is extremely important for both electrical and optical properties of nanowires and, of course, it does also influence the morphology as well. The formation of pre- cipitates, the segregation, and nucleation of second phases must be carefully avoided such as in single crystals, dopant atoms may produce defects and distortions in the lattice, thanks to the confined dimension of nanowires much more tensile stress can be managed. Furthermore, unintentional defect formation may result in a decrease in the charge car-

rier mobility and cause defect emission in the optical spec-

The dopant has to change the electrical and optical

69

tra. 70,71

properties avoiding any structural and chemical stability deterioration. Doping during the growth can be very easy, but there is still lack in control necessary for a reliable preparation. Fur- thermore, a quantitative study of the doping density and profile along the nanowire is challenging, due to the reduced dimensionality, and a high spatial and compositional resolu-

tion is necessary. 72 Different methods have been proposed

for nanowires doping

73 : the dopant can be added in the

vapor- or liquid-phase during the growth process 74 or intro- duced in the nanostructure after the growth. By modifying the composition of the precursor in the evaporation-conden- sation process, the dopant may be easily added in the lattice

of the growing nanowire, but a fine control in the amount of dopant remains challenging. There is of course a significant difference between the composition of the precursor and the composition of the obtained nanowires due to differences in the evaporation rate and in the condensation within the nanowire lattice. 75 Another interesting technique to intro- duce doping into nanowires is the use of low temperature electrochemical process as reviewed in reference. 76 In this scenario, ZnO nanowires have been doped with Co and Ni. 77 In 2008, the monolayer doping technique (MLD) 78 has been proposed, which consists in the formation of self-assem- bled monolayers of dopant-containing molecules on the nanostructure surface followed by a thermal diffusion of dopant atoms by rapid thermal annealing. The dose can be tuned by the molecular footprint of the precursor (i.e., smal- ler molecules allow for higher doses), whereas the annealing temperature and time, allow for the control of the junction depth. Furthermore, more conventional doping techniques such as ion implantation and diffusion may be used, with atten- tion to side effects such as modification in the structure and morphology due to ion bombardment and also amorphiza- tion at higher doses. 79

For particular metal oxides, oxygen stoichiometry can modify the electrical properties, changing the carrier concen- tration, the mobility, and the overall electrical resistivity. 80 The oxygen vacancies concentration may be controlled through variation of the oxygen content in the gas carrier during the nanowires growth, or by post-synthesis treatment in reducing or oxidizing atmospheres. 75 The most studied metal oxide for doping is by far zinc oxide, especially for optical and optoelectronic applications; it has a wideband gap (~ 3.37 eV), it is transparent to visible light and it has a room temperature and high temperature luminesce (e-h binding energy ~ 60 meV). ZnO is naturally n-type doped although achieving reliable and stable p-type doping is still challenging and the key factors leading to reproducible and stable p-type doping have not yet been identified. To grow p-type ZnO, the acceptor concentration has to be higher than the unintentional donor concentration. Different authors have reported the effect of doping with V-group elements such as As, P, N, 81 85 and effect of doping also with Tm, Yb, and Eu using ion implantation and post annealing was reported in the literature. 86 Recently, also Sb has been proposed as acceptor doping. 87 Currently, the challenge is the formation of homojunctions exploiting the natural n-type behavior of ZnO and control- ling the acceptor dopant introduction selectively during the nanowires growth process. Few reports on ZnO nanowires homojunctions have been reported in literature. In Ref. [88] arsenic atoms, used as acceptors, were introduced into ZnO lattice by diffusion from the GaAs substrate using thermal

annealing after ZnO nanowire array were grown by chemical vapor deposition. While in Ref. [89] As atoms were added by ion implantation along the direction perpendicular to the ver- tically aligned ZnO nanowires, the nanowires section was intentionally increased with their length to avoid ion implan- tation into the sidewalls. Dopant activation was obtained by annealing of the As-implanted ZnO nanowires in vacuum. Another acceptor dopant used for the preparation of homo- junctions is phosphorus that has been introduced either dur-

ing the nanowire

growth 90 (using a P 2 O 5 powder as a

precursor in the chemical vapor deposition process 91 or add- ing NH 4 H 2 PO 4 during the hydrothermal growth process 92 ) or by ion implantation and successive annealing treatment to activate the acceptors, as shown in Fig. 3. 93 A lot of effort has been devoted to possibly control nanowires doping and, although there is still the need of further research, interesting results have been presented and the real integration into reli- able electrical and electro-optical devices will surely be soon available.

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Metal Oxide for Gas Sensing and Light Emission 835 Fig. 3. Low-magnification TEM image of an

Fig. 3.

Low-magnification TEM image of an annealed ZnO:P rod. (Inset) Change in lattice spacing along the a- and c-axis along the ZnO rod. [(d)(f)] High-resolution TEM images from different parts of the rod as indicated in (c). The arrows indicate the growth direction. (g) SAED pattern of

region labeled “d” (Reprinted with permission from Appl. Phys. Lett., 95, 133124 (2009). Copyright 2009, American Institute of Physics).

(a) Top and (inset) side view of the as-grown ZnO rods. (b) Top and (inset) 45° tilted view of ZnO:P rods embedded in SOG layer. (c)

(2) Preparation of Quasi One-Dimensional Metal Oxide Heterostructures

The preparation of well controlled heterostructures has an intrinsic complexity, especially when radial or longitudinal heterostructures are concerned. The preparation of metal oxi-

des heterostructures in particular, is more difficult with respect to III V semiconductors. 94 Several examples have been reported in literature for radial, longitudinal, and differ- ent morphologies of heterostructures. They can be prepared in a single crystalline fashion with a change in precursors or vapor phase during the deposition process or with a 2-step growth of catalysts particles onto the nanowires’ surface. By periodically controlling the growth condition during the syn- thesis process, longitudinal heterojunctions can be created along the length of the nanowires. On the other hand, differ- ent heterostructures can be easily formed just decorating with a secondary phase the nanowires to create new metal oxide and oxide oxide interfaces. The VLS and VS growth mechanisms can be combined for heterostructures production. A 2-step VLS growth with the deposition of catalyst particles on the nanowires obtained from the first VLS process leads to formation of dendritic structures, as previously shown in Fig. 1(f). A 2-step VLS and VS growth may lead to the formation of core-shell struc-

tures, 95 97

or the decoration of nanowires with small crys-

tals. 17,98 Epitaxial relationship is typically found between the crys- tal lattice of the nanowire acting as the backbone in

branched heterostructures or in the core-shell geometry and the second phase. Various mechanisms have been proposed for production of core-shell heterojunctions. For example, vertically aligned n-GaN/ZnO coaxial heterostructures were prepared on p-GaN substrates by using metal organic vapor phase epitaxy to grow GaN layers onto ZnO nanoneedles. ZnCdO/ZnO core-shell heterostructures were fabricated in the form of vertically aligned arrays by combining a chemical vapor deposition and pulsed laser deposition method. 100 Using two steps, BiFeO 3 /ZnO coreshell heterostructures were prepared: first a ZnO core by hydrothermal method then a BiFeO 3 shell was deposited by sputtering and the end product annealed in an oxygen atmosphere. Moreover, the synthesis of the low density core-shell ZnO/ ZnMgO heterostructures was reported in Ref. [102] using successively two pulsed laser deposition chambers: a high- pressure quartz glass pulsed laser deposition chamber for the nanowire growth and a conventional (low pressure) pulsed laser deposition chamber for the initial buffer layer growth and for the shell growth. The introduction of a ZnO buffer layer enables the fabrication of individual nanowires with low areal density, suppressing any shadowing effect by neigh- boring nanowires during subsequent growth. Both radial and longitudinal nanosized In 2 O 3 SnO 2 heterostructures were prepared by sequential VLS and VS steps, as shown in Fig. 4. Radial heterostructures were obtained by two subsequent VS condensations, whereas longitudinal heterostructures were obtained with two VLS

101

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American Ceramic Society—Soldano et al. Vol. 95, No. 3 Fig. 4. Structural characterization of longitudinal

Fig. 4. Structural characterization of longitudinal heterostructures. (Main panel) TEM image (panoramic view) of an In 2 O 3 nanowire, with the SnO 2 nanowire extending along the length. The black arrow marks the termination of the SnO 2 nanowire and the catalytic Au nanoparticle, which assisted the VLS growth. (1) SAED pattern showing the cubic single crystal arrangement for the indium oxide nanowire. (2a) CBED pattern and (2b) high-resolution image from the tin oxide nanowire, demonstrating its single crystalline tetragonal (cassiterite) arrangement. (34) High magnification TEM image and corresponding SAED pattern of the heterojunction, where superimposition of both indium and tin oxides has been recorded (Reprinted with permission from Nano Lett., 7, 35538 (2007). Copyright 2007, American Chemical Society).

deposition steps, exploiting the same catalytic gold cluster during both VLS steps. In the first one, there was an epitax- ial growth of crystalline tin oxide on the In 2 O 3 single crystal at first, but due to the lattice mismatch between the cubic In 2 O 3 and the tetragonal SnO 2 lattices, it resulted in poly- crystalline shell. In the latter heterostructure instead, both metal oxides are single crystals. The synthesis of highly ordered ultra-dense hetero-epitaxial Si/ZnO hierarchical nanostructures has been recently pro- posed. 103 The first step is the deposition of silicon nanowires by chemical vapor deposition, followed by deposition of ZnO seeds on the nanowires itself by atomic layer deposition (ALD); then the nanowires are dispersed on a new substrate and the ZnO nanorods growth is performed in aqueous media. Particle-nanowire heterostructures have been prepared using different techniques for the dispersion or growth of nanostructures over the oxide nanowires. For example, het- erostructures of ZnO/Fe 3 O 4 and ZnO/Fe 2 O 3 were prepared by depositing magnetic nanoparticles on ZnO microrod tem- plates by a low-temperature hydrothermal procedure. 104 Quantum dots of PbS were freshly deposited by atomic layer deposition on silicon nanowires. 105

III. Applications of Metal Oxide Nanostructures

This part of the Review is dedicated to the multiple applica- tions of metal oxide nanostructures in different fields. For some of those applications, which do not represent a compre- hensive collection of all possible applications, we will briefly summarize herein the main aspects and characteristics, for others such as gas sensing (Section IV) and light emission (Section V) we will provide dedicated sections with further and more deep detailed description.

(1) As Catalyst

Catalysts are species capable of favoring, from a thermody- namic point of view, reactions (chemical or not) while remaining unaltered at the end of the reaction itself. 11,106 The effectiveness of a catalytic material is often measured in terms of its influence and effects on the reaction kinetics. It has been shown that gold nanoparticles, traditionally known for being catalytically inactive in the bulk form, when sup- ported by a metal oxides substrate become very active cata- lysts. 107,108 As a matter of fact, the catalytic activity of nanostructured gold catalysts depends on the size of the gold particles (inactive for diameter larger than ~ 8 nm). 109,110

Metal oxides such as ZrO 2 , Al 2 O 3 , TiO 2 , and SiO 2 are fur- ther widely used as catalyst supports. Oxides-supported gold catalysts are active towards many reactions, including oxida- tion of CO, selective oxidation (alkenes, alcohols, and even alkanes), water-gas shift, and removal of atmosphere pollu- tants, such as NO x . These properties open up the way to numerous applications, especially in chemistry, where those materials can be used in reactions such as selective oxidation of alcohols, oxidation of CO, reduction of selective reduction of nitro groups. 111,112

(2) As Absorbents

Metal oxides nanostructures have been recently proposed as efficient adsorbents in case of environmental contaminations, ranging from radioactive residues, by-products of nuclear fission reaction and leakage of the nuclear reactors to air and water purification. It is indeed of vital importance to have materials capable of absorbing those contaminants in an irreversible and selective fashion while remaining stable at the same time. Due to their large high surface areas and elevated concentration of reactive edges, corners, and defect sites, MOx nanostructures represent very flexible and prom- ising candidates for a new generation of absorbent materi- als, which could lead to safe disposal of undesired species. Compared to currently used technology as in the case of zeolites, activated alumina or activated carbon, metal oxide nanostructures are in general more efficient and have a broader range of sensitive materials. For example, a com- posite material based on nanostructured SiO 2 and TiO 2 has been shown to be effective for the removal of elemental mercury vapor 113 under UV exposure, which has clearly a great impact both from an environmental as well as health point of view. Volatile organic compounds as well as acid gases cause great concerns for the quality of the air; those compounds are commonly removed by using activated car- bon, which, however, is not capable of efficiently removing SO 2 [Ref. 114] or destructively remove (no desorption over time) organic molecules, as for example copper oxide does.

115

(3) As Field Emission Devices

As for other types of one-dimensional nanostructures such as carbon nanotubes, 116 characterized by sharp ends and large aspect ratio, metal oxide one-dimensional nanostructures exhibit impressive field-induced electron emission properties,

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indicating their potential as future electron sources and dis-

plays. Nanowires, 16 needles shape, 117 nanopyramids, 118 and oth- ers have been widely investigated and studied in terms of their field emission features; Bhise et al. have for example extensively demonstrated efficient field emission properties

for SnO 2

RuO 2, 120 Fe, 121 In 122 ), both in terms of emission from a sin- gle structure as well as from ordered arrays.

nanotube

arrays 123 have been shown to be efficient and stable electron

field emitters even at room temperature with rather low turn- on fields ( 280 V per electrode distance of 100 l m).

nanowires with different types of doping (Sb,

conductive

vertically

aligned

TiO 2

119

Further,

In this specific field, crystallinity 15 plays a crucial role due

to the increased diffusion length in the anode. Further, the possibility of tailoring the electronic properties of nanowires allows for a consequent tuning of the absorption spectrum with the solar spectrum. Zinc oxide nanowires have been widely applied in dye- synthetized solar cells (DSSC); the nanowire nature provides a direct path for charge collection, thus reducing the recom- bination processes that are mainly responsible for reduction of the overall cell efficiency. Innovative photoanodes have been proposed by using ZnO and SnO 2 single crystalline nanowires and TiO 2 nanotu-

bes, 135

as well as nanowires-based hybrid structures in con-

junction with quantum dots acting as light absorbers. 136

(4) As BioSensing Devices

Nanostructured metal oxides have recently gathered great

interest also in the field of biosensing,

compatibility, non-toxicity, and enhanced electron-transfer kinetics and strong adsorption capability; these features pro- vide a suitable microenvironment for the immobilization of biomolecules and result in enhanced electron transfer and in improved biosensing characteristics. 126

A biosensor is an integrated miniaturized device that

employs a biological element (antibody, enzyme, receptor protein, nucleic acid, entire cell or tissue section) as a sensing element coupled to a transducer for signal detection. A bio- sensor combines the molecule selectivity with the progress of microelectronics, hence providing a powerful analytical tool with applications in medical diagnostics and other areas.

124,125

due to their bio-

In this perspective, metal oxide nanostructures are able to

selectively immobilize species (enzymes, 114 cholesterol, 127 antibody, 128 DNA, 129 ) hence reaching a high degree of selec- tivity and stability. Very recently metal oxide nanostructures materials [ZnO, Cu(I)/(II) oxides, MnO 2 , TiO 2 , CeO 2 , SiO 2 ,

ZrO 2 ] have been proposed and investigated as glucose bio- sensors. 130 We here refer the Reader to more specific litera- ture 114 and references therein for a detailed description of this topic, which is of great interest for the medicine commu- nity. Due to their specificity, portability, rapid response time and low cost, biosensors are expected to play a critical role in both clinical and non-clinical applications.

(5) As Battery

Owing to their reduced lateral size and large surface area, nanomaterials represent potential candidates for batteries fabrication, in particular for lithium-based ones. Single hybrid nanostructures (SnO 2 In 2 O 3 ) 131 have been shown to possibly enhance the electrochemical performances of a bat- tery, due to a large increase of the electronic conductivity as compared to single material nanostructure (SnO 2 ) as a result

of the doping-like effect of the In 2 O 3 lattice during the nucle- ation and growth of the shell structure. In addition, array or complex structures based on metal oxide nanowires are of large importance in the implementation and performance enhancement of the anode.

In this scenario, Wan et al. 132 have investigated the syn-

thesis of massive SnO 2 nanowires by the thermal evaporation method on button-type electrode for Li-ion batteries. Direct

of one-dimensional SnO 2 nanowires on the current

growth

collector 133 [Si (100) or stainless steel foil] via a VLS method

at 600 °C have also been suggested.

(6) As Solar Cells

The MOx nanowires have been recently applied in the field of solar cells. CdSe nanorods-polymer structure 134 was sug- gested, where tailoring the CdSe diameter allowed optimizing the overlap between the absorption spectrum of the cell and the solar emission spectrum.

IV. Metal Oxide Gas Sensors

(1) Working Principle

Deviation of stoichiometry is responsible for high gap MOxs semiconducting properties 137 ; in SnO 2 for example shallow states made up of oxygen vacancies are double n-type donors

donating electrons to the conduction band. 138

are generally operated in air in the temperature range between 500 and 800 K where conduction is electronic and oxygen vacancies are doubly ionized and fixed. The gas sens- ing properties arise from surface chemisorption of oxygen, which acts as a surface state capturing an electron or a hole 139 from the conduction band: charge transfer between bulk and surface takes place producing a non-neutral region (with a non-zero electric field) in the semiconductor bulk, usually referred to as the surface space-charge region (SCR) and semiconductor bands are bent upward near the surface. The implementation of MOx nanowires in the field of gas

sensing has had a major impact on conductometric-based devices; in fact the high crystalline nature, the regular shape of the crystal and the large length-to-width ratio render the nanowires a model system to investigate the effect of gas adsorption on the electrical properties. The variation in pho- toluminescence emission of MOx nanowires upon gas expo- sure have been also used as working principle for gas detection and will be later discussed, in more details. On the other hand, electrochemical sensors present advantages in using nanowires whereas other architectures such as micro- balance and surface-acoustic-waves devices are still in the early stage of development. The process of gas detection is intimately related to the oxidation reactions between the species to be detected and

the chemisorbed surface oxygen,

from surface states to the conduction band and decrease the height of the surface barrier. Other target species, such as the

strongly electronegative NO 2 , directly chemisorb over the oxide surface decreasing sensor conductance by trapping electrons. Electrons can also be injected as an effect of chemisorption, as in the case of water adsorption, 119 which forms a “hydroxylated surface,” where the OH ion is bounded to the cation and the H + ion to the oxide anion. As regards the overall electrical properties, by contacting the two opposite bases of a single crystal quasi 1-D NW, after placing it on a thermally oxidized highly doped Si sub- strate, and depositing a gate back contact, one obtains a Sin- gle Nanowire Transistor (SNT) structure, as shown in Fig. 5(b). The current flows along the cylindrical axes and parallel to the surface where electrons are trapped: when the nanowire section is thin enough, almost all available elec- trons are trapped and only the ones thermally activated from surface states are responsible for conduction. Besides if a gate bias is applied, the position of the electrochemical potential and the availability of electrons for surface reac- tions can be modulated (electroadsorbitive effect 141 ); a major- ity carrier channel in accumulation mode is indeed created upon application of a positive gate bias as in n-channel Thin Film Transistors (TFT). 142,143

Metal oxides

140

which release electrons

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American Ceramic Society—Soldano et al. Vol. 95, No. 3 Fig. 5. 5 [4 – 5], 450

Fig. 5.

5 [45], 45074 (2008). Copyright 2008, Inderscience).

Current transport in nanowire bundles (a) and in a single nanowire transistor (b) (Reprinted with permission from Int. J. Nanotechnol. ,

Instead when contacting nanowire bundles the conduction mechanism is dominated by the SCR created at the inter- crystalline boundaries between NWs: the carriers must over- come the energy barrier to cross from one nanowire to the

neighbor as reported in Fig. 5(a). In this case, the conduc- tance of the bundle (as for polycrystalline gas sensor) can

therefore be expressed as: G ¼ G 0 e qV s =kT ¼ G 0 e q 2

where V s is the bulk to surface potential barrier, T the tem- perature, N d is the donor density (oxygen vacancies), N t the density of charged surface states and G 0 is a pre-exponential term, independent in first approximation from the surface adsorption and temperature. The metal semiconductor junction that forms at the inter- face between the nanowires and the contacts can play a role in gas detection: the contact resistance is more important for a single NW since it is in series to the semiconductor resis- tance than that for bundles where it is connected to a large number of resistances. Addition of a small amount of noble metals over the MOx surface such as Au, Pd, Pt, and Ag can speed up surface reactions and improve selectivity toward target gas species.

From the energetic point of view, the effect of catalysis is to provide a more favorable reaction path. Catalyst should be dispersed as small crystallites over the surface of the oxide to be active near the grain boundaries where carrier transport takes place. As for signal transduction, the easiest measurable physical quantity is the sensor conductance in DC conditions. The sensor response toward a target gas concentration is defined as the (relative) change of conductance (resistance in presence of NO 2 or other oxidizing species). Starting from the sensor response it is possible to derive the sensor response curve, which is the representation of the steady state output as a

function of the input concentration.

The sensor response

curve is frequently erroneously called sensitivity, which is

instead the derivative of the sensor response curve.

ð

N

t

Þ 2 =2e N d kT ,

144

(2) Nanowires Integration

For fabrication of devices, nanostructures should be grown or transferred on a suitable substrate and provided with elec- trical contacts. A proper design of the transducer including electrical contacts, bonding, and packaging should be made to assure correct device behavior. Silicon and alumina are the most used substrates, since they are commonly available and not very expensive. Sap- phire can be used if transparency is required, but high cost limits its application to commercial devices. Plastic and paper

substrates are being employed recently for portable and flexi- ble devices. In this case the use of low temperature growth process is required, or a transfer technique such as drop

coating or roll-transfer printing 145

damage of the substrate; room temperature operation is also

needed in this case.

For higher temperature operation, a metallic meander is used as a heater to maintain the NWs at the working temper- ature: this feature can be integrated into micromachined sili- con substrate or deposited on the backside of the alumina/ sapphire substrate. The working temperature of the metal oxide gas sensors is maintained applying a constant voltage to the heating meander. Electrical contacts are deposited in two- or four-terminal configuration to measure the nanowire resistivity. The con- tact must provide as low contact resistance as possible to minimize the voltage drops along the interconnections and should be ohmic. Platinum is one of the most used metalliza- tion source since it has a good ohmic contact with most of the metal oxides, it does not oxidize at high temperatures, it has a low diffusivity and it is resistive to corrosive gases. In the case of bundles of nanowires either two contacts are deposited on top of the mesh after the growth or nano- wires are transferred to micromachined “substrate”. Then, nanowires are removed from the growth substrate, dispersed in a solvent and using drop coating. To realize single nanowire device, a conveniently placed nanowire is selected. If needed, it can be aligned between specific contacts with nanomanipulation or dielectrophoresis (DEP). Most of the manipulations are performed in associa- tion with high-resolution imaging techniques such as scan- ning probe microscopy (SPM and SEM). DEP technique utilizes the dielectrophoretic force acting on particles to induce spatial movement when exposed to a non-uniform electric field in the suspension medium. DEP has been shown to be capable of aligning tin oxide nanobelts, 146 zinc oxide

must be used to avoid

nanobelts, 147,148 and nanoparticles 149 and GaN nanowires. 150 After the nanowires were placed between contacts, plati- num or gold stripes are deposited using Focused Ion Beam

(FIB) 151

or electron-beam lithography (EBL) to fabricate

nanoscale contacts between pre-deposited contacts and NW

or to improve existing electrical contacts.

(3) Functional Devices (A) Conductometric Chemical Sensors: In the basic

layout, a sensor device is made of a sensing layer with two conducting electrodes for the two-probe measurement of the

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One-Dimensional Metal Oxide for Gas Sensing and Light Emission

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electrical resistance, which is the principal figure of merit for the characterization of the sensing performance. Several works have been done for implementation of nanowires in a dedicated layout: from a technological point of view, bundled nanowire devices are much simpler to prepare than single nanowire devices, as it does not require the manipulation of individual nanostructures. In 1996, Yumoto et al. 152 first reported on the gas sensing properties of indium-tin-oxide 1-D structures known as whis- kers grown by VLS mechanism. Comini et al. reported a sig- nificant response to CO, ethanol and NO 2 in pure SnO 2 nanowire bundles prepared by thermal evaporation, and sub- sequently transferred. 153 The device was operated at 400°C.

A number of publications have been reported since, address-

ing the enhancement of the sensor fabrication and perfor-

mance. Wang et al. 154

tional substrates. Vomiero et al. 155 combined two consoli-

dated techniques (vapor transport and condensation and wet etching of a sacrificial layer) for the patterned fabrication of metal oxide nanowires directly over the functional substrate. Three-dimensional (3-D) architectures of tungsten oxide prepared by evaporation-condensation method have been used to develop conductometric gas sensors highly sensitive

to

in

ture with a large number of nanowire-nanowire interfaces. The measured high sensitivity has been associated to this peculiar hierarchical three-dimensional network. The expo- sure to 50 ppb of NO 2 increased the electrical conductance

by a factor of 5. In addition, the nanowire network featured

a sensitivity to gases such as ammonia or CO lower than the

one observed with WO 3 thin films. 157 Reducing the crystallite size allows one to increase the sen-

sitivity. 158 Accordingly, Polleux and co-workers adopted this

approach to detect sub-ppm concentrations of NO 2.

In this

work, a significant temperature effect was reported for nano-

wires (about 1 nm in diameter) bundles prepared by soft- chemistry route. The response decreased by about one order of magnitude by increasing the temperature from 150°C to 225° C. The low temperature range (down to room temperature)

was investigated by Kim et al. working with sub-stoichiomet-

ric tungsten oxide (WO

ter. 160 As shown in Fig. 6, the normalized resistance decreases upon exposure to ammonia at 200° C operating temperature, although it decreases unexpectedly at lower temperature. As the nanowire diameter is comparable with the mean free path of electrons, it has been supposed that adsorbed molecules may act as scattering centers, thus increasing the overall resistance. The addition of dopants or catalysts to sensitize nanowires has been also exploited. Wan et al. reported the use of Sb

doping to tune the resistivity of SnO 2 nanowires trough to the formation of shallow donor levels by introduction of

Sb +5 into SnO 2. 161 Authors also recorded an increase in sen-

sor kinetics, attributed to Sb doping, which would favor and accelerate the absorption of oxygen molecules and the forma- tion of oxygen ions on the surface. Kolmakov et al. report the effect of Pd nanoparticles over

a single SnO 2 nanowire. 162 The improved sensing performance

to oxygen and hydrogen was attributed to the combined effect

of spillover of atomic oxygen catalytically formed and the back spillover effect in which molecular oxygen migrates to the Pd nanoparticles and is catalytically dissociated. Sysoev et al. comparatively investigated long-time stability

of SnO 2 nanoparticles and nanowires. 163 As shown in Fig. 7,

nanoparticles show higher response than nanowires during the first few days of operation. Monitoring the variation along time, the authors concluded that the time-dependence

of the response could be due to coarsening effect in nanopar-

ticles.

grew SnO 2

nanowires directly over func-

NO 2.

156

Nanowires from tens to hundreds of nanometers

width were assembled in a three-dimensional open struc-

159

2.72 ) nanowires, few nm in diame-

open struc- 159 2.72 ) nanowires, few nm in diame- Fig. 6. Normalized resistance ( R

Fig. 6. Normalized resistance (R gas / R air ) at different operating temperatures for a tungsten oxide nanowire-based sensor (Reprinted with permission from Appl. Phys. Lett., 86, 213105 (2005). Copyright 2005, American Institute of Physics).

Single nanowire devices offer the opportunity to exploit the peculiar nanoscaled size and high crystalline quality, without effects arising from nanowire-nanowire interfaces. The high crystalline quality of nanowires immediately sug- gested their potentialities as suitable materials to develop

field-effect transistor. 164 Zhang et al. 165 investigated the pos- sibility to use the gate voltage to modulate the performance of FET gas-sensors. In addition, considering that the high electrical conductiv- ity flowing in a nanowire connected by two electrodes, allows increasing the wire temperature, extremely low power con-

sumption can be obtained.

heating devices revealed very promising even with respect to

thin suspended micromachined substrates, both in terms of power consumption and thermal dynamics.

(B) Optical Chemical Sensors: In MOx nanostructures

the use of transduction mechanism different from electrical one is desirable to overcome difficulties in contacting nano- structures. One possible solution is to use the bright room temperature photoluminescence (PL) signal shown by nano- wires of SnO 2 and ZnO to realize all-optical gas sensors for low concentrations of pollutants such as NO 2 . The SnO 2 nanostructures typically exhibit strong visible PL emission at room temperature with a broad emission band peaked at about 2 eV, 168 170 commonly attributed to radiative defective states within the bandgap (oxygen vacan-

cies). 15 On the other hand, ZnO nanostructures show room temperature PL spectra composed by an UV peak due to excitonic recombination at about 3.26 eV, 171 and broad emis- sion band in the range from green to yellow depending on

deep defect states lying inside the bandgap,

position of this band is determined by growth condi-

where the

166,167

This approach toward self-

172,173

tions. 174,175

Faglia et al. 176 showed that PL in SnO 2 is quenched in a reversible way by NO 2 at a temperature of 120°C: the gas adsorbs over the surface creating competitive non-radiative recombination paths. Lettieri et al. 177 demonstrated that lar- ger PL quenching by NO 2 absorption is observed at room temperature with Continuous Wave (CW). Similarly, photo- luminescence of ZnO is quenched by interaction with NO 2 room temperature. 178,179 Differently from SnO 2 , either UV or visible peaks can be investigated showing that they are quenched in the same fashion without any peak shift. Detec-

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American Ceramic Society—Soldano et al. Vol. 95, No. 3 Sensor baseline of SnO 2 mesoporous layer

Sensor baseline of SnO 2 mesoporous layer and nanowire bundle versus time (a). Experiments have been first carried out in dry air, then

(since day 26) in humidified air. (b) Open and filled circles correspond to nanoparticles and nanowires (Reprinted with permission from Sensors Actuat. B, 139, 699703 (2009). Copyright 2009, Elsevier).

Fig. 7.

tion of very low concentration of NO 2 as low as 0.1 ppm has also been shown by Baratto et al. 180 (as shown in Fig. 8). By trapping an electron from the conduction band, NO 2 adsorbs over the metal oxide surface as NO 2 . At room tem- perature, reversibility of chemisorption is guaranteed by UV excitation that supplies the energy needed for desorption. Both for SnO 2 168 and ZnO, 171 time-resolved photolumines- cence (TRPL) measurements in presence of NO 2 showed small modification of recombination rates and lifetimes upon introduction of the gas. The results support a surface static quenching model, according to which the gas molecules sup- press a fraction of radiative transitions instead of simply reducing their probabilities. At higher NO 2 concentration, a saturation effect has been observed by Valerini et al. , 181 sug- gesting limitation in usage of optical gas sensor at concentra- tions higher than 20 ppm. The same authors have also shown the effect of the ZnO nanostructure morphology: rela- tive response to NO 2 is higher for sample constituted by “pencil-like” rods well separated one from each other, char- acterized by larger surface available for gas-surface interac- tion. Literature available on this subject shows that all- optical gas sensor based on nanowires is feasible for NO 2 detection, even if stability and reproducibility issue were not addressed. Concerning cross interference issue, humidity and ethanol caused an increase in PL signal thus demonstrating that cross interference effect must be taken into account.

171

cross interference effect must be taken into account. 171 Fig. 8. Dynamic photoluminescence quenching of the

Fig. 8. Dynamic photoluminescence quenching of the signal coming from ZnO nanowires by sub-ppm concentration of NO 2 (Reprinted with permission from Sensors Actuat. B Chem. , 140 [2] 461 6 (2009). Copyright 2009, Wiley).

V. Light Emission

(1) Working Principle

Light emitting diodes are different from traditional light sources in the way the light is produced; in fact, light emission is achieved by filament heating (incandescent lamp) or an elec- tric arc exciting mercury atoms (fluorescent lamp). An LED, in contrast, is basically a semiconductor diode, based on a p-n junction, where current flows from the p-side to the n-side, but not in the reverse direction, when an external bias is applied to the junction itself. Charges (both electrons and holes) pass then through the junction and when an electron meets a hole, it falls into a lower energy level, and releases photons (light). The emission wavelength (or equivalently the color) in this case mainly depends on the constituent material. Metal oxides are usually high band gap semiconductors not feasible to develop light emitting diodes. Some of them, such as SnO 2 , have shown emission in the visible region, which is indeed due to defects or impurities, which are in general difficult to control during the growth process. Zinc oxide, with a bandgap of 3.37 eV, represents an exception due its large exciton binding which lead to an effective radia- tive recombination at room temperature, allowing for efficient LEDs in the short-wavelength range (UV). The simplest type of LED based on ZnO is made from a p-type and n-type homojunction diode forward biased as shown in Fig. 9: when a current passes through the diode,

as shown in Fig. 9: when a current passes through the diode, Fig. 9. Working principle

Fig. 9.

Working principle of a LED based on a p-n homojunction.

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Metal Oxide for Gas Sensing and Light Emission 841 Fig. 10. Band offsets of GaN, NiO,

Fig. 10.

Band offsets of GaN, NiO, Si and CuAlO 2 semiconductors respect to ZnO.

electrons in the conduction band flow across the junction from the n-doped side, and holes in the valence band flow from the p-doped side. The result is that a significant number of electrons and holes recombine at the junction where both their densities are quite high, emitting light with energy equal to the exciton recombination energy. Due to difficulties to p-type dope ZnO, a possible alterna- tive is to prepare heterojunctions with an easily p- dopable materials. Further, to provide an efficient holes injection in the n-ZnO regions, one has to select materials with lower (or negative) valence band offsets as compared to ZnO. Fig- ure 10 shows band approximate offsets of GaN, 182 Cu- AlO 2, 183 Si, and NiO 184 p- type semiconductors with respect to ZnO; it is clear that the most suitable candidate is p-type GaN, whereas other materials valence band offsets are too large to provide effective hole injection. Thus, LED efficien- cies reported in literature for CuAlO 2 , Si, and NiO are quite low. On the contrary, GaN is a wurtzite-type material (similarly ZnO) with a lattice constant similar to that of ZnO (mis- match is about 1.9%). In accordance with the Anderson model, a simplified picture of bands at equilibrium for the p- GaN/ n-ZnO heterojunction, which disregards polarization charge at interfaces, is reported in Fig. 11. As long as forward bias is applied to the junction, effective minority carrier injection takes place [see Fig. 11(b)] and satisfactory luminescence can be obtained from radiative recombination in the ZnO region. Unfortunately, emission from the p-GaN region is detected as well. Therefore, this simple heterostructure can be further improved by introduc- ing blocking (i.e., MgO) layers with the objective to confine carriers in the ZnO regions, as shown in Fig. 12, where elec- trons experience a much higher energy barrier than the holes

(which can easily tunnel through the barrier) and carrier den- sities are effective for recombination only in the ZnO region. It is possible to induce electroluminescence even in a n- GaN/ n-ZnO heterojunction by applying a considerably high voltage; holes are created by defect assisted tunneling or impact ionization. This effect is briefly shown in Fig. 13, where indeed the emission is induced in the GaN applying a positive voltage to the ZnO side. As for commercial diodes, higher internal quantum effi- ciency can be obtained only by preparing double heterostruc- tures (DHs) through band gap engineering, with the introduction of ternary compounds as MgZnO, CdZnO, and BeZnO. A DH is made by an active region, a quantum well (QW), in which recombination occurs, and two confinement layers cladding the active region. The two cladding or confinement layers have a larger bandgap than the active region. Band configuration is beneficial also from the point of view of pho- tons reabsorption, which cannot take place in the higher bandgap claddings. The resulting radiation is better defined due to carrier confinement and the optical power generated per unit volume is much larger as well. Figure 14 shows a typical DH configuration. For a more realistic view, considering the polar nature of both ZnO and GaN, the piezoelectric and spontaneous polarizations need to be incorporated into the band model, appearing as positive or negative energy steps depending on sign as in Fig. 15. Although polarization is usually detrimen- tal because the electric field moves away electrons and holes, in some configurations it can be exploited to improve charge confinement in the active regions. Discussions so far reported in terms of ZnO bands, are generally valid both for thin films and for nanowires, consid- ering that the nanoscale objects are usually considerably

ering that the nanoscale objects are usually considerably Fig. 11. Energy band diagram of the n

Fig. 11.

Energy band diagram of the n-ZnO/p-GaN heterojunction at (a) equilibrium and (b) forward bias.

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American Ceramic Society—Soldano et al. Vol. 95, No. 3 Fig. 12. MgO layer. Energy band structure

Fig. 12.

MgO layer.

Energy band structure of a p-GaN/n-ZnO diode with a

larger than the ZnO Bohr radius (2.34 nm) and quantum confinement effects can be neglected. Indeed nanowires growth produces grain-boundary free and a much less strained and defective interface, which are sources of non- radiative recombination, compared to thin films. In addition, nanowires can act as direct waveguides and favor directional light extraction without use of lenses and reflectors.

(2) Nanowires Integration

The LED structure-based nanowires reported in literature so far mainly deals with ZnO homojunctions and heterojunc- tions, with some rather limited and preliminary investigations for SnO 2 [Ref. 185] and In 2 O 3 . For homojunctions based on a nanowires/nanowires junc- tion, the introduction of a doping element during the growth process can lead to the synthesis of p- and n-type segments in ZnO NWs, hence forming the junction, where the p- and n- part are naturally aligned due to the continuity of the growth process itself. 186 In some cases, ZnO layer is present at the base of ZnO nanowires, thus preventing use of nanojunctions effects. On the other end, heterojunction-based devices are mostly realized by growing n-type ZnO nanowires on p-type sub- strate, mainly thin film. Since it was reported that the carrier

injection rate significantly increases for nanoscale contacts in

Schottky diodes,

could benefit from increased carrier injection efficiency due to nanosized junctions. In general, it is necessary to achieve high quality interface between the heterojunctions to get high-efficiency LEDs, since the interface states generally act as non-radiative cen- ters that annihilate free electrons and holes. Vertically aligned nanowires are usually employed in these types of devices to take advantage of the waveguiding effect in nano- wires, even if the emission from non-aligned mesh of nano- wires is reported. 188

Electroluminescence in these junctions is investigated in a typical two-terminal device, fabricated by depositing appro- priate film as the conducting electrode on top of the ZnO NW arrays. The metal used should ensure ohmic contact with ZnO: ITO was used for p-ZnO, Au for p-GaN while Ti/ Au, In, and Al were used for n-ZnO. To prevent the short circuit of connection between the top and the bottom elec- trodes in the two-terminal devices, an insulating layer made of a polymer matrix [i.e., poly(methyl methacrylate) (PMMA) or spin-on-glass (SOG)] is spin-coated on the NW arrays, followed by oxygen plasma treatment to remove the excess PMMA on top of NWs. A scheme of the heterojunc- tion device with vertical nanowires is reported in Fig. 16.

nanowires grown directly on p-type film

187

(3) Light Emitting Diodes

In this scenario, metal oxides, and in particular ZnO, have been proposed as possible materials for light emission and optoelectronic applications. As previously mentioned, due to

the high excitonic binding energy and the wide room temper- ature energy gap, zinc oxide is suitable for emission in the near-UV ( 370 nm). Further, the value of the energy gap can be selectively tuned by introducing a very small amount

Cd 191,192 ), which could shift

the emission toward the visible region. In addition, ZnO is piezoelectric, 193 biocompatible and bio-safe. 194 The growth of ZnO in various nanostructured forms can be achieved using different high- as well as low-temperature ( < 100° C) growth methods. 195

Nowadays, one major and fundamental limitation to the full exploitation of zinc oxide in light emission applications, is represented by the fabrication of stable and reliable p-type ZnO, for which so far the possibility of doping ZnO homo- junction has been demonstrated, however, achieving light emission from those ZnO heterostructures still represent some limiting aspects. Recently, Chen et al. 166 have demonstrated the synthesis of the catalyst-free epitaxial p-n homojunction ZnO NW

of doping atoms (i.e., Mg,

189,190

p-n homojunction ZnO NW of doping atoms (i.e., Mg, 189,190 Fig. 13. (a) The equilibrium condition

Fig. 13. (a) The equilibrium condition n-GaN/n-ZnO heterojunction. (b) n-GaN/i -MgO/n-ZnO heterojunction LED under positive bias at n-ZnO side (Reprinted with permission from Appl. Phys. Lett. , 96, 201111 (2010). Copyright 2010, American Institute of Physics).

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Metal Oxide for Gas Sensing and Light Emission 843 Fig. 14. (a) Band diagram and distributions

Fig. 14. (a) Band diagram and distributions of carrier concentrations for a QW based ZnO LED and (b) wave functions of electrons and holes near the QW and principal optical transitions (Reprinted with permission from J. Appl. Phys., 104, 093107 (2008). Copyright 2008, American Institute of Physics).

(2008). Copyright 2008, American Institute of Physics). Fig. 15. (a) Charge distribution and (b) band diagram

Fig. 15. (a) Charge distribution and (b) band diagram of a ZnO/ AlGaN heterostructures incorporating polarization effects ( r ZnO ) (Reprinted with permission from Appl. Phys. Lett. , 85, 4272 (2004). Copyright 2004, American Institute of Physics).

arrays in which phosphorus (P) and zinc (Zn) are used to dope different segments of the same ZnO nanowire to each behave as p- and n-type nanowires, respectively. The as-fab- ricated p-ZnO/ n-ZnO array structure shows a cathodolumi- nescence (CL) emission peak at 340 nm, for which the electron concentration is expected to be as high as 10 20 cm 3 and which can be tuned with different cycles of

cm 3 and which can be tuned with different cycles of Fig. 16. Schematics of LED

Fig. 16. Schematics of LED architecture based on heterojunction between p-type film (GaN) and n-type nanowires (ZnO). PMMA or SOG is used to electrically insulate top electrode from bottom of nanowires to prevent short circuit. PMMA surface removal is needed to expose tips of nanowires for deposition of electrical contact.

annealing in oxygen environment, 196 as shown in Fig. 17. In addition, electroluminescence (EL) measurements show emission at 325 nm when a large external bias is applied (50 V), which can further be selectively blue-shifted by reducing the applied bias. Nevertheless, a lot still has to be done to obtain reliable and stable p-n junction based on solely zinc oxide, due to the lack of high conductivity and carrier concentration. To over- come this current limitation, the use of single or multiple het- erojunction(s) has been proposed, where a single (or more) metal oxide(s) are combined with other materials to obtain the diode behavior. Further, functional devices will definitely require a large number (10 10 3 ) of individual building blocks and the entire device requires overall stability, reproducibility and a suffi- ciently long life. The nanostructures need to be highly orga- nized and placed selectively in a specific location to perform particular tasks. Vertically aligned ordered array are often grown using chemical vapor deposition (CVD) methods and subsequently filled with insulating material (frequently a polymer matrix 197 ) to isolate each nanotube from its neigh- bor and to reduce the inter-tube interaction. It has been shown that the growth of a crystalline two-dimensional ZnO layer on the previously grown NWs makes these structures promising candidates for LED applications. 198 Gallium nitride (GaN) has soon become a very promising and highly compatible junction material (to combine with ZnO) because of its very small lattice mismatch respect to ZnO and its tendency of spontaneous electric polarization, 199 which allows for the formation of an efficient heterojunction. GaN can be used both as a p-type as well as n-type, however, due to the current limitation in obtaining stable and reliable p-doped ZnO; the p-n junction is more often based on n- ZnO/p-GaN as compared to p-ZnO/ n- GaN. The ZnO nanowires have been grown with various tech-

(metal organic chemical

niques, including MOCVD 200 204

vapor deposition), MOVPE 177 (metal organic vapor phase epitaxy), as well as others based on ZnO solutions. Jeong et al. 182 have shown that an array based on n-ZnO nanowires grown by MOCVD on p -GaN and covered by a ZnO polycrystalline top film exhibits EL emission in the UV-violet (386 nm) spectral range under forward bias. Thermal treatment (180 ° C for 1 h) has been shown to fur-

ther improve the overall efficiency of the diode, as a result of the enhanced desorption of oxygen species on the oxide surface and favored electron transport (from the film to the nanowires), which promotes the radiative e-h recombination

rate.

205

206,207

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American Ceramic Society—Soldano et al. Vol. 95, No. 3 Fig. 17. (a) Low-magnification TEM image of

Fig. 17. (a) Low-magnification TEM image of a single ZnO NW, including both the n - and p-type segments. (Zoom) High-resolution TEM image of the interface region between p-type ZnO (top)/n-type ZnO (bottom) interface showing the high quality epitaxial growth without any transition phase. (b) Normalized CL spectra of the as-grown n-type and p-type ZnO NW arrays (top) and as a function of annealing time intervals in the oxygen ambient (bottom). Inset shows the relative spectra in the range [300410 nm] (Reprinted with permission from Nano Lett. , 10, 43879 (2010). Copyright 2010, American Chemical Society).

Zhang et al. 180 have prepared ZnO nanowires/ p-GaN het- erojunction by physical vapor deposition methods; those junctions show a marked bluelight emission, which becomes more and more visible by the naked eye when the bias volt- age exceeded 10 V, with its intensity rapidly increasing above the threshold voltage. Electroluminescence spectrum showed broad emission peaks from UV to blue, with emissions at around 370 nm as well as strong and broad peak centered at 400440 nm. Increasing the applied forward bias (from 10 to 35 V), a significant enhancement of the emission peak was observed, together with a shift of the main emission peak (from 440 to 400 nm), as shown in Fig. 18. There exist alternative methods to grow nanostructures (and in particular nanowires) such as electrochemistry-based

methods; in fact, electrodeposition 208,209

low-cost, catalyst- and seed-layer-free growth technique to fabricate high quality ZnO nanowire arrays. The method uses zinc ions and molecular oxygen as the growth precursor dissolved in an aqueous bath. 210 Lupan et al. have fabricated

epitaxial heterojunction between electrodeposited free-stand- ing vertically aligned ZnO NWs and p-type GaN(0001) thin film substrate supported on sapphire. The so-fabricated device presents a stable emission in the UV centered at 397 nm for a low forward-voltage emission threshold of 4.4 V, where the intensity of the emission increases (0.5 1.5 mA) very rapidly for larger voltages (for biases larger than 6 V, the violet-blue emission is observable by the naked eye). The significantly low emission threshold and strong emission at low voltage reveal the high quality nature and the low level of defects of the p-Gan/ZnO nanowires inter- face. Other types of tubular nanostructures have been also pro- posed as building blocks for a new class of LEDs (see Fig. 1); in fact, electrochemically grown ZnO nanotubes show an EL spectrum with strong visible luminescence from 400 to 600 nm at relatively high forward biases, in agreement with PL measurements. I V characteristics for ZnO nanotu- bes show a Schottky-barrier type contact, as reported in the case of ZnO nanowire 212 ; however, as a result of the large

represents an easy,

211

; however, as a result of the large represents an easy, 211 Fig. 18. The electroluminescence

Fig. 18. The electroluminescence spectrum of the (n-ZnO NWs)/ ( p-GaN film) LED device under various forward bias voltages (10, 15, 20, 25,30, 35 V), showing broad emission peaks from UV to blue and blue shift with increasing of bias voltage. Inset is a band structure diagram of the LED for explaining the observed EL blue shifting (Reprinted with permission from Adv. Mater., 21 [27] 276770 (2009). Copyright 2009, WILEY-VCH Verlag GmbH).

surface area in the case of the tube, a lower turn-on voltage is found, together with a higher current growth rate, offering overall a total electric current much higher than the nanowire counterpart (10 mA for nanowires as compared to 150 mA for nanotubes at 10 V of applied external bias). Light emis- sion has been also shown for various zinc oxide-based com- posites, in which the introduction of ZnO induces light emission in the composites material. Tu et al. 213 have shown that the addition of ZnO nanorods in poly(N -vinylcarbazole) (PVK) induces a violet electroluminescence of the composite, with a main peak centered at around 440 nm (singlet exci- mer) and a second peak at 607 nm (triplet excimer). Further,

have shown that polymer-based light

emitting devices fabricated with ZnO nanoparticles dispersed

Madhava Rao et al.

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into a 2,3-dibutoxy-1,4-poly(phenylenevinylene) (DBPPV) polymer matrix present enhanced current density, brightness, and luminance efficiency upon addition of ZnO nanoparti- cles, as a result of the enhancement of both charge injection and charge transport. These properties have also been dem-

onstrated to be further improved upon annealing cycles, cre- ating the potential condition for the practical application to flat panel displays. Other polymer matrices have been proposed as well as various types of oxide structures. ZnO nanofibers in polyvi- nyl alcohol (PVA) 215 hybrid composites prepared by electros- pinning technique, show that, when successfully embedded, PVA/ZnO nanofibers have an intense white-light emission, which originates from the simultaneous emission of three bands covering from the UV to visible range.

It is also very important to note that in PLED (polymer-

based LED), different MOx nanostructures can lead to reliable and efficient light emission diodes; in addition to this properties, functionalities as the transparency as well as the flexibility of the polymer could become key successful points in the development of a new class of transparent and flexible displays.

VI.

Conclusions

This Review article has presented an overview on various metal oxide nanostructures used in particular in fields such as gas sensing and light emission.

A great effort has been devoted to understand and, at the

same time, control the growth process for the production of 1-D nanostructures. In addition to standard VLS growth mechanisms, a number of novel techniques have been pro- posed for the fabrication of high quality nanowires and to control the alignment of these structures in light of device integration. Solution-based techniques represent a viable and promising alternative approach for mass production of metal oxide nanostructures with good control of shape, composi- tion and reproducibility; however, single crystal nature is not yet entirely confirmed as well as their growth mechanisms still lack of a complete understanding. In the field of gas sensing, MOx nanowires have demon- strated improved sensitivity to numerous gas species, enhanced stability due to high crystalline degree, even if selec- tivity remains still a concern. Differentiating NWs response represent the key challenge to broaden the range of applica- bility of those nanostructures: surface coating and/or by spe- cific functional groups, or multi-component sensing elements coupled with signal processing functions to discriminate very low concentration could represent possible avenues to explore in this perspective. On the other hand, reliable and stable electrical contacts still represent an important issue, which, once properly addressed, would lead to the full exploitation of metal oxide nanostructures in the gas sensing field. For the implementation of metal oxide nanostructures for the light emission applications, the key challenge is represented by the growth of p-type metal oxide nanowires (i.e., ZnO), which is of crucial importance for the fabrication of p-n junctions. Efforts have been devoted to the fabrication of homojunctions, while introducing n- and p-type doping during the growth process; although feasibility has been dem- onstrated, nevertheless poor carrier confinement at the junc- tion and the imbalance between the currents created in two sides still represent fundamental limitations. Hence, hetero- structures are more favorable and successful for the fabrica- tion of efficient p-n junction. Depending on the metal oxide material, a proper substrate (with minimal lattice mismatch) can be used to fabricate the junction itself and favor the carrier injection. Electrochemis- try-based methods can surely provide an easy and low-cost method to fabricate such heterostructures; however, high quality requirements are lost. Light emission in metal oxides nanostructures presents still a lot of new avenues that will be surely explored in the years to come.

Acknowledgments

This work was partially supported by the EC FP7 Small Project no. NMP- 2009-1.2-3 247768 (Russian Federation Government State Contract 02.527.11.0008) “S3 - Surface ionization and novel concepts in nano-MOX gas sensors with increased Selectivity, Sensitivity and Stability for detection of low concentrations of toxic and explosive agents”, the EC Large Project FP7 NMP-2009-2.2-1 246334: “ORAMA - Oxide Materials for Electronics Applica- tions” and FIRB “Rete Nazionale di Ricerca sulle Nanoscienze ItalNanoNet”, Protocollo: RBPR05JH2P, 2009-2013.

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h

Caterina Soldano received her B.Sc. degree in physics from University of Bari, Italy in 2002 where she worked on the design and development of a THz spectrometer. In 2004, she earned her M.Sc. in physics at Rensselaer Poly- technic Institute in Troy, NY with a project on the detection of explosive materials in the THz region. She con- tinued her education in physics at Rensselaer Polytechnic Institute, where in 2007 she earned her Ph.D. while studying the low-temperature charge and magneto-transport in hybrid carbon nanotube-based struc- tures. In the period 2008–2010, she worked as post-doctoral research associate at the Centre d’Elaboration de Mate´riaux et d’Etudes Structurales in Toulouse, France where she developed a resist-free technique to contact graphene and hence investigate its electrical properties. At the SENSOR Lab, Caterina is working on spectroscopic characterization of nanostructures for light emission application and the implementation of the e-beam lithography set-up and char- acterization of nanostructures. Her expertise includes low- temperature charge and magneto-transport in nanostructures, Focus Ion Beam (FIB), nanofabrication and standard clean room processes.

(FIB), nanofabrication and standard clean room processes. Elisabetta Comini was born in 1972 in Brescia, Italy.

Elisabetta Comini was born in 1972 in Brescia, Italy. She received her degree in Physics at the University of Pisa in 1996. Then she started her Ph.D. on chemical sensors, focusing on the deposition of thin films by PVD techni- que and electrical characterisation of MOX thin films. She received her Ph.D. degree in material science at the Uni- versity of Brescia. In 2001 she has been appointed Assistant Professor of physics of matter at Brescia University. She has been organizer of several symposia in the sensing field for MRS and E-MRS. She has filed four Italian patents. She has a high productivity confirmed by the numer- ous publications in international journals (more than 154) and the high number of invited presentations at conferences together with the plenary talk given during the International Symposium on Advanced Materials and Processing, 6–8 December, 2004. Furthermore she is responsible of the

6–8 December, 2004. Furthermore she is responsible of the research line on “Metal oxide nanocrystalline quasi

research line on “Metal oxide nanocrystalline quasi 1D struc- ture preparation” at the SENSOR laboratory (CNR- IDASC). Hirsch index (h-index) of Elisabetta Comini is 30 (ISI Web of Knowledge), with a sum of times cited of 3594 and a total number of published articles in peer review jour- nals equal to 154.

Camilla Baratto was born in Brescia in 1972. She graduated in Physics with hon- ours at the University of Parma in 1997. In 2002 she received her Ph.D. degree in material science at the University of Bres- cia. Since 2000 she has worked as a Research Assistant at the Sensor Lab at the University of Brescia. Research topics are: optical characterization of gas sensors based on quenching of photoluminescence of MOX nanowires; optical properties of metal oxides; electrical characterization of nanosized gas sensors; thin film deposition by magnetron sputtering; development of label-free MOX based biosensors; study of optical properties of dye sensitized solar cells. Camilla Baratto is coauthor of 41 publications in peer reviewed journals. h-index: 15.

of 41 publications in peer reviewed journals. h-index: 15. Matteo Ferroni was born in 1970, and

Matteo Ferroni was born in 1970, and received his B.Sc. degree in physics at the University of Ferrara in 1994, with a thesis on the CHORUS experiment on neutrino oscillations (CERN – Ge`neve). He pursued the Ph.D. degree in physics in 1998 at the same University, and con- tinued his activity as research fellow at the EMAT center of electron micro- scopy for materials research (Antwerp) and as researcher for the INFM. He eventually became researcher at the Department of Chemistry and Physics in the University of Brescia in 2004. Matteo Ferroni published about 80 papers in peer-reviewed journals and is referee of several international journals. His main research activity con- cerns the characterization of nanostructured metal oxides by means of transmission and scanning electron microscopy. Presently, Matteo Ferroni is in charge of the high-resolution scanning electron microscopy facility at the SENSOR CNR laboratory in Brescia.

Ferroni is in charge of the high-resolution scanning electron microscopy facility at the SENSOR CNR laboratory

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Guido Faglia was born in 1965 and received in 1991 the M.S. degree from the Polytechnic of Milan in electronics. In 1993 he was appointed Assistant Pro- fessor at the Gas Sensor Lab by the University of Brescia. In 1996 he received the Ph.D. degree in semi- conductor gas sensors. Since 2000 he is Associate Professor in Experimental Physics at University of Brescia. He is involved in the study of preparation of metal oxide semi- conductors MOX as thin films and quasi-monodimensional nanostructures, the interactions between gases and MOX surfaces and their functional characterization. He has been involved in European Commission Projects since 1992 in basic and applied physics research on semiconductors and their application in an interdisciplinary field as biochemical sensing. He has a relevant working experience with many international institutions like EC, NATO, European Space Agency (ESA), the International Association for the Promo- tion of Co-operation with Scientists from the New Indepen- dent States (NIS) of the Former Soviet Union INTAS. During his career, Guido Faglia has published more than 135 articles in referred international journals and has a Hirsch factor of 32.

international journals and has a Hirsch factor of 32. Prof. Giorgio Sberveglieri was born on July

Prof. Giorgio Sberveglieri was born on July 17, 1947 and received his degree in Physics cum laude from the University of Parma (Italy), where he started in 1971 his research activities on the preparation of semiconducting thin film solar cells. He is now the Director of the CNR– INFM and Brescia University Sensor Laboratory (http://sensor.ing.unibs.it) at Brescia University where are working more than 20 researchers. In 1988 he established the Sensor Lab, mainly devoted to the preparation and characterization of chemical sensors based on nanostrucured metal oxide semi- conductors either in size of thin film or more recently as nano- wires and nanobelts of metal oxides. Other activity in his Lab, is since the mid 90s, the area of Electronic Noses for security, food and environmental applications. In 1994, he was appoin- ted full Professor in Experimental Physics. He is referee of many international journals and Associate Editor of IEEE Sensor Journal and has acted as Chairman in several Con- ferences on Materials Science and on Sensors. During 35 years of scientific activity, he has published more than 250 papers in international journals; he has presented more than 250 Oral Communications to international congresses.

than 250 papers in international journals; he has presented more than 250 Oral Communications to international