Few but interesting research publications
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.
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.
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.
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.
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.
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.
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
powders with the eﬀect of substrate seeding withgold catalysts.
The nanowires crystallize in the body-centered cubic (bcc) structure and grow along the  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
structuralmonitoring. Although lately some
transmission andscanning electron microscopy (TEM and SEM, respectively)observations of the nanowires growth were presented limitedto a small number of nanowires such as silicon,
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
usingX-ray diﬀraction for the ﬁrst time,
by heating metallic zincpowder in air at 368
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
optical and photoelectron emissionmicroscopy studies of VO
nanostructures growth of usingvapor transport of V
in vacuum and in inert gas environ-ment were reported.
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
, or VO
.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.
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.
The models presented suggest that the nanowireformation in a vapor-solid growth process
is related tostress relaxation at the interface
or to competing grainboundary and lattice diﬀusion of copper ions across the
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.
One-Dimensional Metal Oxide for Gas Sensing and Light Emission