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Metal Oxide Nanoparticles

Metal Oxide Nanoparticles

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Metal Oxides Mono-Dimensional Nanostructures forGas 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 oxidesand the description of their material properties. The first partmainly deals with various preparation techniques and growthmechanisms, which have been largely developed in the last fewdecades to fabricate different types of metal oxide nanostruc-tures. The second part, on the other hand, will provide theReader with an up-to-date summary of different applications inwhich metal oxides nanostructures have been successfullyimplemented and/or suggested. In particular, great attentionwill 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 asthe latest reported cutting edge results are herein reported.Finally, we emphasize on the current potentials of metal oxidenanostructured materials and future challenges that this field incontinuous expansion is currently facing.
I . IntroductionII. Preparation techniques and growth mechanisms1. Doping of quasi-one-dimensional metal oxidenanostructures2. Preparation of quasi-one-dimensional metal oxideheterostructuresIII. Applications of metal oxide nanostructuresIV. Metal oxide gas sensorsa. Working principleb. Nanowires integrationc. Functional devicesi. Conductometric chemical sensorsii. Optical chemical sensorsV. Light emissiona. Working principleb. Nanowires integrationc. Light emitting diodesVI. ConclusionsVII. AcknowledgmentsVIII. References
I. Introduction
M
ETAL
oxides (MOxs) represent a vast class of materialsof interest for various scientific communities, rangingfrom 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 alongwith oxygen. To the latter, most of the properties character-izing those types of materials, are related.A number of very different properties have been observedso far, ranging from metallic, semiconducting as well as insu-lating behavior, mainly depending on the specific electronicstructure 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 othersuch as microelectronic circuits,
5
sensors,
6
piezoelectricdevices,
7
fuel cells,
8
anti-corrosive coatings,
9
catalysts,
10
andmore.For decades now, metal oxides have been successfully usedin various forms in the field of gas sensing, where the con-ductometric properties of those materials are exploited basedprincipally on the induced variation of the electrical resis-tance upon interaction (absorption, chemisorption or physi-sorption) of a gas molecule on the oxide surface. MOxscatalytic properties are also very well known and exploited inthe chemical and petrochemical industries, where a largenumber 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 environmentalpollution.
11
Microelectronics and semiconductor industriesrepresent further additional and predominant fields for metaloxides applications; in fact, most commercially availablechips nowadays contain at least one metal oxide element.However, there are still a number of not yet very muchinvestigated and unexplored fields in which those materials
D. J. Green—contributing editorManuscript No. 30088. Received July 29, 2011; approved December 07, 2011.
Author to whom correspondence should be addressed. e-mail: caterina.soldano@ing.unibs.it
J. Am. Ceram. Soc.,
95
[3] 831–850 (2012)DOI: 10.1111/j.1551-2916.2011.05056.x
©
2012 The American Ceramic Society
 Journal
Feature 
 
can be successfully employed, such as lighting
12
 – 
14
[in partic-ular for light emitting diodes (LEDs) and lasers], solarcells,
15
field emitters
16
as well as high-capacity batteries.
17
In the continuous quest for novel applications, new func-tionalities have been introduced by simply reducing the sizeof the material of interest toward the nanoscale world, as inthe case of nanoparticles, nanowires, carbon nanotubes,
18
fullerenes,
19
and graphene.
20
In the particular field of metaloxides, quasi one-dimensional (1-D) structures
21
have shownseveral advantages with respect to their traditional thin- andthick-film counterpart such as very large surface-to-volumeratio, dimensions comparable to the extension of surfacecharge region, greater stability as a result of the high degreeof crystalline order,
22
relatively simple and low-cost prepara-tion methods,
10
possibility of different chemical surface func-tionalization
23
with selective species, modulation of theiroperating temperature to select the specific reactions, catalystdeposition over the surface for promotion or inhibition of specific reactions. Moreover, there is also the possibility of field-effect transistors (FETs) configuration, which probes thegate-modulated transport characteristics to tailor sensitivityand selectivity.
24
Novel synthesis approaches, physical as well as chemical,have been developed to fabricate metal oxides nanostructures(nanoparticles, nanowires, nanotubes, whiskers, and a varietyof more exotic nanoscale objects). Both “top-downand“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 theassembly of molecular building blocks from the bottom byvarious 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 techniquescurrently used to grow metal oxides nanostructures andarchitectures, as well as various methods to dope one-dimen-sional nanostructures to tune their electronic properties.Among a large numbers of possible applications (which willbe herein only briefly summarized), most of the attention willbe dedicated to the use of metal oxide nanostructures to fab-ricate devices for gas sensing as well as light emission. Detailswill be given for both fields in terms of their working princi-ples, as well as the integration of those nanostructures inworking or existing architectures, together with the mostrecent results reported in literature. When needed, the Readerwill be referred to more specific and detailed literature.
II. Preparation Techniques and Growth Mechanisms
One-dimensional structures can be prepared following twodifferent approaches: “bottom-up” and “top-down technolo-gies.” Top-down technology is based on standard micro-fabrication equipment with deposition and etching on planarstructures to reduce the lateral dimensions of films down tothe nanoscale level. To selectively remove the material thefollowing techniques can be used: electron-beam, focused ionbeam, X-ray lithography, nano-imprinting, and others. Draw-backs of top-down reside in the extremely elevated costs andlong preparation times, although advantages are the greatknowledge and control for the well developed technologycoming from the semiconductor industry; furthermore, thedevice is directly prepared on planar surfaces which allowsfor easier subsequent contacting approaches. Top-downapproaches have been so far used to fabricate highly orderednanowire,
25
 – 
28
however, the 1-D nanostructures produced withthese techniques are in general not single crystal.The “bottom-up” approach instead is based on the assem-bly of molecular building blocks or chemical synthesisdirectly 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-upsand the possibility to easily dope and form junctions. On theother hand, the integration on planar substrates, necessaryfor the full exploitation of their useful properties, can betroublesome. In addition, the alignment and patterning of the nanostructures could be more challenging when using thebottom-up approach.
29
The combination of the bottom-upapproach (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 strategyto fabricate highly functional devices.In literature, depending on the creativity and imaginationof the authors, a lot of different names have been used, suchas 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 obtainedwith an early stop of the growth process; whereas for theachievement of one-dimensional morphologies with an iso-tropic atomic bonding it is necessary to induce a break in thesymmetry during the growth. There must be a preferentialgrowth 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-assistedmethods and between vapor- and solution-phase growth.Vapor-phase preparation techniques are very popular in liter-ature, although solution-phase ones provide flexible synthesisprocedures with cheaper equipment. Depending on the pres-ence of the catalyst during the growth, different mechanismshave 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 forthe 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
andH
2
.
Fig. 1.
Different morphologies for sensing and lighting applications: (a) nanowire, (b) longitudinal heterostructure, (c) nanotube, (d) core-shellheterostructure, (e,f) nanobelts, and (g) hierarchical structure.
832
Journal of the American Ceramic Society—Soldano et al.
Vol. 95, No. 3
 
Few but interesting research publications
31,32
present ashape diagram of nanostructures as a function of selectedparameters such as source and substrate temperature as wellas 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 thenanowire is the result of a VLS growth mechanism; however,this does not define the catalyst phase and role during thegrowth. It has been shown that for all the vapor phase pro-cesses there is a “dead time” before the nanowires growthbegins.
33
Different methods can be used for the preparationof the catalytic nanoparticles, including thermal evaporation,sputtering, colloidal solutions; nevertheless, the focus has toremain on the agglomeration of the nanoparticles becausethe dimension of the clusters strongly influences the diameterof the growing nanowire. Since the nanowire deposition isperformed at elevated temperatures, even if the metal formsa thin layer covering the entire substrate, clusters will beformed due to the Ostwald ripening.
34
When the nanowireshave a uniform cross-section along their entire length, thecondensation happens mainly at the catalyst surface, andthen 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 growthprocess, the diameter of the nanowire will decrease, resultingin 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 bewell controlled to obtain reproducible and reliable nanowiresgrowth. Furthermore, the selection of the catalyst is crucialsince it has to lower the activation energy of nucleation atthe nanowire-catalyst interface to ensure the preferential one-dimensional growth.
37
During a VS growth, instead, the nanowire crystallizationoriginates from the direct condensation from the vaporphase. First, it was attributed to the presence of latticedefects, but defect-free nanowires obtained by VS are alsofrequently reported in literature. Very little is still known,even if a number of experimental and theoretical works havebeen presented. At high temperatures, the source material isevaporated and then condensed on the substrate at lowertemperatures. The initially condensed molecules form seedcrystals 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 manythermodynamic parameters is a rather complicated processthat often needs quantitative modeling.
38
Recently, some investigations on the nanowires growthhave been presented in literature, according to which differ-ent growth mechanisms have to be taken into account alltogether with a large number of parameters involved whichmakes a systematic study more difficult.
39
A quantitativeinvestigation on the nucleation and growth of indium oxidenanowires on single crystal substrate, with catalytically activegold particles, was studied through thermal evaporation of pure In
2
O
3
powders with the effect of substrate seeding withgold catalysts.
40
The nanowires crystallize in the body-centered cubic (bcc) structure and grow along the [100] vec-tor of the cubic crystalline cell without any preferentialgrowth direction. The measured growth rate can be satisfac-torily explained taking into account a concurrent direct VSand catalyst-mediated VLS mechanism during nanowiregrowth, with the formation of high-index lateral faces whichregulates 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
structuralmonitoring. Although lately some
in situ
transmission andscanning electron microscopy (TEM and SEM, respectively)observations of the nanowires growth were presented limitedto a small number of nanowires such as silicon,
41
germa-nium,
42
 – 
44
gallium arsenide,
45,46
bismuth,
47
CdTe
48
a com-plete picture is still missing. The application at elevatedtemperatures and in a controlled gas environment for elec-tron microscopy still remains an experimental challenge, likeother structural characterization methods such as SPM(Scanning Probe Microscopy) or X-ray diffraction tech-niques.The growth of ZnO nanobelts was monitored
in situ
usingX-ray diffraction for the first time,
49
by heating metallic zincpowder in air at 368
°
C
 – 
568
°
C. A morphology diagram forthe synthesized products was generated after systematicstudy of the experimental parameters. Higher temperaturesand faster heating rates favor one-dimensional growth. Fas-ter growth was observed for samples with higher growthtemperatures, lower heating rates, and one-dimensionalgrowth.Recently, direct
in situ
optical and photoelectron emissionmicroscopy studies of VO
2
nanostructures growth of usingvapor 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 andmorphologies were structurally and compositionally charac-terized. Both kinetic and thermodynamic factors seem to playa role in the composition, structure, and morphology duringmultiple phase transformations. The key factors governingthe growth emerged from this study were: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 betailored. 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 caseof copper oxide.
51
 – 
53
The growth mechanism for the forma-tion of nanowires by thermal oxidation is still under debate,but the most interesting thing is that the wires are singlecrystals.
54
The models presented suggest that the nanowireformation in a vapor-solid growth process
55
is related tostress relaxation at the interface
56
or to competing grainboundary and lattice diffusion of copper ions across the
Fig. 2.
Vapor-Liquid-Solid (VLS) growth of nanowires. Thecatalyst is in the liquid phase and precursors in the vapor phase canadsorb and condense to form the nanowire. In the Solution-Liquid-Solid (SLS) growth of nanowires the precursors in the liquid phasereact to form the nanowire.
March 2012
One-Dimensional Metal Oxide for Gas Sensing and Light Emission
833

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