Journal of Nanomaterials 3
0.500.511.522.5Energy (V versus NHE)
3.4 eVZnS3.6 eVZnFe
1.9 eVCdS2.4 eVGaAs1.4 eVCdSe1.7 eVH
3: Band edge positions of common semiconductor photo-catalysts (data from [32,33,43]).
separation and recovery. Moreover, additional equipment isneeded for catalyst nanoparticle separation. Photocatalystsupportedonasteadysubstratecaneliminatethisissue.One-dimensional nanostructures, such as nanowires grown ona substrate, o
er enhanced photocatalytic e
ciency due totheir extremely large surface-to-volume ratio as comparedto a catalyst deposition on a ﬂat surface [28,44].Table 1
erent ZnO nanostructures for photocatalyticapplications. There are many advantages in nanowire struc-tures that could be used as photocatalysts.
ZnO nanowires can be either grown independently or grownoncertainsubstrates.However,averticalalignedgrowthonasubstratehasmoreadvantagesinphotocatalyticapplications.The anisotropy of the ZnO crystal structure assists thegrowth of nanowires. The most common polar surface is thebasal plane (0 0 1) with one end of the basal polar planeterminating in partially positive Zn lattice points and theother end terminating in partially negative oxygen latticepoints. The anisotropic growth of the nanowires takes placealong the
-axis in the [0 0 0 2] direction . The growthvelocities under hydrothermal conditions along the di
erentdirections are following the pattern
(1010) . The relative growth rate of these crystal faceswill determine the ﬁnal shape and aspect ratio of the ZnOnanostructures.The synthesis methods of ZnO nanowires could mainly be classiﬁed as vapor phase and solution phase synthesis.
3.1. The Vapor Phase Synthesis.
Vapor phase synthesis isprobably the most extensively explored approach in theformation of 1D nanostructures . A typical vapor phasesynthesis method takes place in a closed chamber witha gaseous environment. Vapor species are ﬁrst producedby evaporation, chemical reduction, and gaseous reaction.After that, the species are transferred and condensed ontothe surface of a solid substrate. Generally, the vapor phasesynthesis process is carried out at higher temperatures from500
C to 1500
C and produces high-quality nanowires. Thetypical vapor phase synthesis method includes vapor liquidsolid (VLS) growth , chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), physical vapor deposition (PVD) , molecular beam
epitaxy (MBE) , pulsed laser deposition (PLD) , and
metal organic vapor phase epitaxy (MOVPE) . Amongthe vapor phase synthesis methods, VLS and MOCVD aretwo of the most important methods for the ZnO nanowiressynthesis.Compared to other vapor phase techniques, VLS methodis a simpler and cheaper process, and is advantageous forgrowing ZnO on large wafers . The VLS process has beenwidely used for the growth of 1D nanowires and nanorods.A typical VLS process is used with nanosized liquid metaldroplets as catalysts. The gaseous reactants interact withthe nanosized liquid facilitating nucleation and growth of single crystalline rods and wires under the metal catalyst.Typical metal catalysts in the VLS process are Au, Cu, Ni,Sn, and so forth. ZnO nanowires have been successfully grown on sapphire, GaN, AlGaN, and ALN substratesthrough the VLS process . The quality and growthbehavior of the ZnO nanowires are strongly a
ected by thechamber pressure, oxygen partial pressure, and thicknessof the catalyst layer [56,57]. Chu et al.  synthesized
well-aligned ZnO nanowires using VLS mechanism on Sisubstrate with chamber temperature varying from 600 to950
C and pressure from 0.75 to 3torr. They showed thatZnO nanowires with high aspect ratio grew vertically onthe substrate at 700 to 750
C, the density of nanowiresdecreased when the temperature was higher than 800
C, andthe growth rate and length of nanowires were decreased withincreasing total chamber pressure.Catalyst-free metal-organic chemical vapor deposition(MOCVD) is another important synthesis method for ZnOnanowires [49,59]. The catalyst-free method eliminates the
possible incorporation of catalytic impurities and produceshigh-purity ZnO nanowires. Moreover, the growth temper-ature of catalyst-free MOCVD is lower than a typical VLSgrowth temperature . The ability to grow high-purity ZnO nanowires at low temperatures is expected to greatly increase the versatility and power of these building blocks fornanoscale photonic and electronic device applications .Zeng et al.  reported that well-aligned ZnO nanowireswere prepared by MOCVD on Si substrate without catalysts.In their grown process, high-purity diethyl zinc (99.999%)and N
O (99.999%) were used as zinc and oxygen sources,respectively, and N
as the carrier gas. The base pressureof the reactor chamber and the working pressure were10
and 50torr, respectively. A thin nucleation layer of ZnO was grown at a low substrate temperature of 400
Cat the beginning. After annealing the nucleation layer,ZnO nanowires were grown on the nucleation layer at thesubstrate temperature of 650
C.Physical vapor deposition (PVD) technique has also beenused to fabricate ZnO nanowires. The advantages of PVDtechnique are the following: (1) composition of productscan be controlled, (2) there is no pollution such as drain