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Synthesis, Characterization, and Applications of ZnO Nanowires

Synthesis, Characterization, and Applications of ZnO Nanowires

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Published by Akshay Gupta
Synthesis, Characterization, and Applications of
ZnO Nanowires
Synthesis, Characterization, and Applications of
ZnO Nanowires

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Published by: Akshay Gupta on Mar 01, 2013
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Hindawi Publishing CorporationJournal of NanomaterialsVolume 2012, Article ID 624520,22pagesdoi:10.1155/2012/624520
Review Article
Synthesis,Characterization,and Applicationsof ZnONanowires
 YangyangZhang, ManojK. Ram,EliasK. Stefanakos,and D.Yogi Goswami
Clean Energy Research Center, College of Engineering, University of South Florida, Tampa, FL 33620, USA
Correspondence should be addressed to Elias K. Stefanakos,estefana@usf.eduReceived 13 January 2012; Accepted 18 April 2012Academic Editor: Tong LinCopyright © 2012 Yangyang Zhang et al. This is an open access article distributed under the Creative Commons AttributionLicense, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.ZnO nanowires (or nanorods) have been widely studied due to their unique material properties and remarkable performancein electronics, optics, and photonics. Recently, photocatalytic applications of ZnO nanowires are of increased interest inenvironmental protection applications. This paper presents a review of the current research of ZnO nanowires (or nanorods)with special focus on photocatalysis. We have reviewed the semiconducting photocatalysts and discussed a variety of synthesismethods of ZnO nanowires and their corresponding e
ff 
ectiveness in photocatalysis. We have also presented the characterizationof ZnO nanowires from the literature and from our own measurements. Finally, a wide range of uses of ZnO nanowires in variousapplications is highlighted in this paper.
1.Introduction
Nanomaterials have attracted tremendous interest due totheir noticeable performance in electronics, optics, andphotonics. Nanomaterials are typically classified into threegroups: 0-dimensional, 1-dimensional, and 2-dimensional.0-dimensional nanostructures, referred to as quantum dotsor nanoparticles with an aspect ratio near unity, havebeen extensively used in biological applications [1,2]. 2- dimensional nanomaterials, such as thin films, have alsobeen widely used as optical coatings, corrosion protection,and semiconductor thin film devices. One-dimensional (1D)semiconductor nanostructures such as nanowires, nanorods(short nanowires), nanofibres, nanobelts, and nanotubeshave been of intense interest in both academic researchand industrial applications because of their potential asbuilding blocks for other structures [3]. 1D nanostructuresare useful materials for investigating the dependence of electrical and thermal transport or mechanical propertieson dimensionality and size reduction (or quantum con-finement) [4]. They also play an important role as bothinterconnects and functional units in the fabrication of electronic, optoelectronic, electrochemical, and electrome-chanical nanodevices [5]. Among the one-dimensional (1D)nanostructures, zinc oxide (ZnO) nanowire is one of themostimportantnanomaterialsfornanotechnologyintoday’sresearch [6].ZnO is a semiconductor material with a direct wideband gap energy (3.37eV) and a large exciton bindingenergy (60meV) at room temperature [7]. ZnO is alsobiocompatible, biodegradable, and biosafe for medical andenvironmental applications [8]. ZnO crystallizes in twomain forms, hexagonal wurtzite and cubic zinc blende.Under general conditions, ZnO exhibits a hexagonal wurtzitestructure. The crystalline nature of ZnO could be indexed toknown structures of hexagonal ZnO, with
a
=
0
.
32498nm,
b
=
0
.
32498nm, and
c
=
5
.
2066nm (JCPS card no. 36–1451) [9]. The ratio of 
c/a
of about 1.60 is close to the idealvalue for a hexagonal cell
c/a
=
1
.
633 [10]. The structureof ZnO could be described as a number of alternating planescomposedoftetrahedrallycoordinatedO
2
andZn
2+
stackedalternately along the
-axis (Figure 1(a)). The O
2
andZn
2+
form a tetrahedral unit, and the entire structure lackscentral symmetry (Figure 1(b)). Due to their remarkableperformance in electronics, optics, and photonics, ZnOnanowires are attractive candidates for many applicationssuch as UV lasers [11], light-emitting diodes [12], solar cells [13], nanogenerators [14], gas sensors [15], photodetectors
 
2 Journal of Nanomaterials
(a) (b)
Figure
1: ZnO structure: (a) the wurtzite structure model; (b) the wurtzite unit cell (fromhttp://www.wikipedia.org/).
[16], and photocatalysts [17]. Among these applications, ZnO nanowires are being increasingly used as photocatalyststo inactivate bacteria and viruses and for the degradationof environmental pollutants such as dyes, pesticides, andvolatile organic compounds under appropriate light irradi-ation [18,19]. This paper reviews recent research in ZnO nanowires(or nanorods) with an emphasis on ZnO nanowires used inphotocatalysis. In the following sections we have revieweddi
ff 
erent semiconductor photocatalysts, compared theirproperties, and discussed a variety of synthesis methods of ZnO nanowires. We have also presented the characterizationof ZnO nanowires from both the literature and our ownmeasurements. Finally, a wide range of ZnO nanowires invarious applications is highlighted in this paper.
2.Photocatalysts
Photocatalysis is a promising process for environmentalprotection because it is able to oxidize low concentrationsof organic pollutants into benign products [2026]. Photo- catalysis utilizes semiconductor photocatalysts to carry outa photo-induced oxidation process to break down organiccontaminants and inactivate bacteria and viruses [2729]. Figure 2illustrates the process of photocatalysis. Whenphotons with energies greater than the band gap energy of the photocatalyst are absorbed, the valence band (VB)electrons are excited to the conduction band to facilitatea number of possible photoreactions. The photocatalyticsurface with su
cient photo energy leads to the formationof a positive hole (h
+
) in the valence band and an electron(e
) in the conduction band (CB). The positive hole couldeither oxidize organic contaminants directly or producevery reactive hydroxyl radicals (OH
). The hydroxyl radicals(OH
) act as the primary oxidants in the photocatalyticsystem [30], which oxidize the organics. The electron in theconduction band reduces the oxygen that is adsorbed on thephotocatalyst.Thereareanumberofsemiconductorsthatcouldbeusedas photocatalysts, such as TiO
2
, ZnO, and WO
3
, Fe
2
O
3
. The
Energy UVCB
     E   x   c     i    t   a    t     i   o   n     R   e   c   o   m     b     i   n   a    t     i   o   n
VBh
+
O
2
O
−
2
e
PhotoreductionH
2
O/
OH; R 
OH; R +Photooxidation
OH + R 
intermediates
CO
2
+ H
2
O
OHe
+ H
2
O
2
OH +
OHTiO
2
Figure
2: A schematic of the principle of photocatalysis (repro-duced with permission from [30] ©2010 Elsevier).
band gap energy plays a significant role in the photocatalyticprocess.Figure 3shows the band gap energies and the bandedge positions of common semiconductor photocatalysts[3133]. It is necessary to point out that the band gap values of ZnO, reported in the literature, are not all equivalentdue to the di
ff 
erent levels of the O vacancy in ZnO [34].Although TiO
2
is the most widely investigated photocatalyst,ZnO has also been considered as a suitable alternative of TiO
2
because of its comparability with TiO
2
band gap energy and its relatively lower cost of production [18,35,36]. Moreover, ZnO has been reported to be more photoactivethan TiO
2
[3740] due to its higher e
ciency of generationand separation of photoinduced electrons and holes [18,41, 42].Since the contaminant molecules need to be adsorbedon the photocatalytic surface before the reactions take place,the surface area plays a significant role in the photocat-alytic activity. Although nanoparticles o
ff 
er a large surfacearea, they have mostly been used in water suspensions,which limit their practical use due to di
culties in their
 
Journal of Nanomaterials 3
33.5
1.5
1
0.500.511.522.5Energy (V versus NHE)
ZnO3.2 eVWO
3
2.7 eVFe
2
O
3
2.2 eVTiO
2
3.2 eVSrTiO
3
3.4 eVZnS3.6 eVZnFe
2
O
4
1.9 eVCdS2.4 eVGaAs1.4 eVCdSe1.7 eVH
+
/H
2
O
2
/H
2
O
Figure
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
ff 
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 compares di
ff 
erent ZnO nanostructures for photocatalyticapplications. There are many advantages in nanowire struc-tures that could be used as photocatalysts.
3.Synthesisof ZnONanowires
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 [45]. The growthvelocities under hydrothermal conditions along the di
ff 
erentdirections are following the pattern
(0001)
>
(1011)
>
(1010) [46]. 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 [5]. 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 [47], chemical vapor deposition (CVD)[48], metal organic chemical vapor deposition (MOCVD)[49], physical vapor deposition (PVD) [50], molecular beam epitaxy (MBE) [51], pulsed laser deposition (PLD) [52], and metal organic vapor phase epitaxy (MOVPE) [53]. 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 [54]. 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 [55]. The quality and growthbehavior of the ZnO nanowires are strongly a
ff 
ected by thechamber pressure, oxygen partial pressure, and thicknessof the catalyst layer [56,57]. Chu et al. [58] 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 [60]. 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 [5].Zeng et al. [61] 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
2
O (99.999%) were used as zinc and oxygen sources,respectively, and N
2
as the carrier gas. The base pressureof the reactor chamber and the working pressure were10
-
5
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

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