Journal
J. Am. Ceram. Soc., 95 [3] 831850 (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 EmissionCaterina Soldano, Elisabetta Comini, Camilla Baratto,
Matteo Ferroni, Guido Faglia, and Giorgio SberveglieriCNR-IDASC and
Dipartimento di Chimica e Fisica per lIngegneria 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 rst part mainly
deals with various preparation techniques and growth mechanisms,
which have been largely developed in the last few decades to
fabricate dierent types of metal oxide nanostructures. The second
part, on the other hand, will provide the Reader with an up-to-date
summary of dierent 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 nanostructures 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 eld 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
VI. Conclusions VII. Acknowledgments VIII. References
I.
Introduction
D. J. Greencontributing 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
oxides (MOxs) represent a vast class of materials of interest
for various scientic communities, ranging from physics to
chemistry, from material science to engineering.14 There exist a
large variety of metal oxides compounds, mostly depending on the
type of metals used along with oxygen. To the latter, most of the
properties characterizing those types of materials, are related. A
number of very dierent properties have been observed so far,
ranging from metallic, semiconducting as well as insulating
behavior, mainly depending on the specic electronic structure of
the particular oxides. This broad range of materials properties has
opened up the way to numerous and versatile applications, often
very dierent one from each other such as microelectronic circuits,5
sensors,6 piezoelectric devices,7 fuel cells,8 anti-corrosive
coatings,9 catalysts,10 and more. For decades now, metal oxides
have been successfully used in various forms in the eld of gas
sensing, where the conductometric properties of those materials are
exploited based principally on the induced variation of the
electrical resistance upon interaction (absorption, chemisorption
or physisorption) 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 frequently used to
remove species such as CO, NOx, and SOx, 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 elds 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 elds in which those
materialsETAL
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can be successfully employed, such as lighting1214 [in
particular for light emitting diodes (LEDs) and lasers], solar
cells,15 eld emitters16 as well as high-capacity batteries.17 In
the continuous quest for novel applications, new functionalities
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 eld of metal oxides, quasi
one-dimensional (1-D) structures21 have shown several advantages
with respect to their traditional thin- and thick-lm 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,22 relatively simple
and low-cost preparation methods,10 possibility of dierent chemical
surface functionalization23 with selective species, modulation of
their operating temperature to select the specic reactions,
catalyst deposition over the surface for promotion or inhibition of
specic reactions. Moreover, there is also the possibility of
eld-eect transistors (FETs) conguration, which probes the
gate-modulated transport characteristics to tailor sensitivity and
selectivity.24 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 lateral 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-byatom or molecule-by-molecule growth. In this
Review, the Reader will be provided with stateof-the-art overview
of the dierent preparation techniques currently used to grow metal
oxides nanostructures and architectures, as well as various methods
to dope one-dimensional nanostructures to tune their electronic
properties. Among a large numbers of possible applications (which
will be herein only briey summarized), most of the attention will
be dedicated to the use of metal oxide nanostructures to fabricate
devices for gas sensing as well as light emission. Details will be
given for both elds in terms of their working principles, 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 specic
and detailed literature.
II.
Preparation Techniques and Growth Mechanisms
One-dimensional structures can be prepared following two dierent
approaches: bottom-up and top-down technologies. Top-down
technology is based on standard microfabrication equipment with
deposition and etching on planar structures to reduce the lateral
dimensions of lms 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. Drawbacks 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,2528 however, the 1-D
nanostructures produced with these techniques are in general not
single crystal. The bottom-up approach instead is based on the
assembly of molecular building blocks or chemical synthesis
directly in the nanosized morphology. This approach presents many
advantages such as the high purity and crystallinity 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 fabrication)
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 dierent names
have been used, such as whiskers, nanowires, nanotubes,
nanocastles, bers, brils, nanotubules, nanocables, etc., as shown
in Fig. 1. Some of these manifold morphologies have indeed
potential applications as functional devices. The preparation of
lms or small particles can be obtained with an early stop of the
growth process; whereas for the achievement of one-dimensional
morphologies with an isotropic 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 literature, although
solution-phase ones provide exible synthesis procedures with
cheaper equipment. Depending on the presence of the catalyst during
the growth, dierent mechanisms have been proposed, i.e.,
vapor-liquid-solid (VLS), solutionliquid-solid (SLS) or vapor-solid
process (VS) (Fig. 2). Wagner and Ellis in 196430 discovered the
controlled catalytic 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 product. Silicon
whiskers could be grown by heating a Si substrate covered with Au
particles in a mixture of SiCl4 and H2 .
Fig. 1. Dierent morphologies for sensing and lighting
applications: (a) nanowire, (b) longitudinal heterostructure, (c)
nanotube, (d) core-shell heterostructure, (e,f) nanobelts, and (g)
hierarchical structure.
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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-LiquidSolid (SLS) growth of nanowires the precursors in
the liquid phase react to form the nanowire.
Few but interesting research publications31,32 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 dierent results
obtained, it is indeed useful for an eventual conrmation and/or
confutation of subsequent theoretical 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 dene the catalyst phase
and role during the growth. It has been shown that for all the
vapor phase processes there is a dead time before the nanowires
growth begins.33 Dierent 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 inuences 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 diuses and segregates at the
interface with the nanowire. In this case, a uniform catalyst
dimension on the substrate should result in a uniform nanowire
diameter, if nanoparticles coalescence eect 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 control the critical phases during the
nanowires elongation, dening the adsorption, diusion (surface and
bulk), and solubility. 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
onedimensional growth.37 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 surface energy. This self-catalytic growth
associated with many thermodynamic parameters is a rather
complicated process that often needs quantitative modeling.38
Recently, some investigations on the nanowires growth have been
presented in literature, according to which dierent growth
mechanisms have to be taken into account all together with a large
number of parameters involved which makes a systematic study more
dicult.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 In2O3 powders with the eect of substrate
seeding with gold catalysts.40 The nanowires crystallize in the
bodycentered cubic (bcc) structure and grow along the [100] vector
of the cubic crystalline cell without any preferential growth
direction. The measured growth rate can be satisfactorily 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 investigations rst
perform the synthesis and afterward the structure 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,41
germanium,4244 gallium arsenide,45,46 bismuth,47 CdTe48 a complete
picture is still missing. The application at elevated temperatures
and in a controlled gas environment for electron microscopy still
remains an experimental challenge, like other structural
characterization methods such as SPM (Scanning Probe Microscopy) or
X-ray diraction techniques. The growth of ZnO nanobelts was
monitored in situ using X-ray diraction for the rst time,49 by
heating metallic zinc powder in air at 368C568C. 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. Faster 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 VO2
nanostructures growth of using vapor transport of V2O5 in vacuum
and in inert gas environment were reported.50 The formation,
coexistence, and transformation of the intermediate oxide phases
and morphologies were structurally and compositionally
characterized. 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: 1. abundance of the precursor
on the surface and its temperature; 2. liquid droplets anity to the
substrate; 3. competition between oxygen loss (if in vacuum or a
reductive atmosphere) and heating rate. Controlling these
parameters carefully, the chemical composition, morphology, and
size of the nal structures may be tailored. Using a heating rate
lower than the vanadia reduction rate allowed the interruption of
the growth at an intermediate step obtaining V2O5, V6O13, or VO2.
Lately, a lot of research has also been performed on nanowire
preparation by oxidation in controlled environment of the metal
composing the metal oxide, especially in the case of copper
oxide.5153 The growth mechanism for the formation 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
process55 is related to stress relaxation at the interface56 or to
competing grain boundary and lattice diusion of copper ions across
the
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Cu2O layer.49,57 Nevertheless, this technique oers many
advantages such as an easy patterning of the nanowires using
conventional patterning techniques on the metal lm, large area, and
catalyst-free nanowire production, and the inexpensive 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
precursors 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 produce
nanowires with better crystalline properties. Large research eort
has been devoted to the template-free methods for the deposition of
one-dimensional nanostructures in liquid environment exploring
surfactant-assisted, sonochemical, hydrothermal, electrochemical
and electrospinning deposition techniques. Surfactant-assisted
deposition is a trial-and-error procedure, where the surfactant is
used to promote the anisotropic crystal growth and conne it as in a
micrometer-size reactor. Dierent surfactants have been proposed
such as oleic acid, hexylphosphonic acid (HPA),
tetradecylphosphonic acid, trioctylphosphine oxide, and
trioctylphosphine60; dierent conditions and surfactants must be
used for dierent 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 collapse leading to extreme reaction conditions needed
to form nanowires.61,62 Nevertheless, both hydrothermal and
electrochemical processes are well-known procedures for material
synthesis. In the rst, a solution of an aqueous mixture of soluble
precursors metal salt (metal and/or metal-organic) is placed in an
autoclave at high temperature (between 100C and 300C) 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 eld to coat
the substrate. Nanowires may be formed directly or by using a
template.65 Electrospinning is known since 1994 and exploits an
electrical charge to force the formation of mats of ne bers. A
solid ber is produced as the electried jet is continuously
stretched due to the electro-static repulsions between the surface
charges and the evaporation of solvent.6668
(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 inuence the
morphology as well. The formation of precipitates, 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,69 thanks to the conned dimension of
nanowires much more tensile stress can be managed. Furthermore,
unintentional defect formation may result in a decrease in the
charge carrier mobility and cause defect emission in the optical
spectra.70,71 The dopant has to change the electrical and optical
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.
Furthermore, a quantitative study of the doping density and prole
along the nanowire is challenging, due to the reduced
dimensionality, and a high spatial and compositional resolution is
necessary.72 Dierent methods have been proposed for nanowires
doping73: the dopant can be added in the vapor- or liquid-phase
during the growth process74 or introduced in the nanostructure
after the growth. By modifying the composition of the precursor in
the evaporation-condensation process, the dopant may be easily
added in the lattice
of the growing nanowire, but a ne control in the amount of
dopant remains challenging. There is of course a signicant dierence
between the composition of the precursor and the composition of the
obtained nanowires due to dierences in the evaporation rate and in
the condensation within the nanowire lattice.75 Another interesting
technique to introduce 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-assembled monolayers of
dopant-containing molecules on the nanostructure surface followed
by a thermal diusion of dopant atoms by rapid thermal annealing.
The dose can be tuned by the molecular footprint of the precursor
(i.e., smaller 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 diusion may be used, with attention to
side eects such as modication in the structure and morphology due
to ion bombardment and also amorphization at higher doses.79 For
particular metal oxides, oxygen stoichiometry can modify the
electrical properties, changing the carrier concentration, 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 identied. To grow p-type ZnO, the acceptor concentration
has to be higher than the unintentional donor concentration.
Dierent authors have reported the eect of doping with V-group
elements such as As, P, N,8185 and eect 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
controlling 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 diusion 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 vertically aligned ZnO nanowires,
the nanowires section was intentionally increased with their length
to avoid ion implantation 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 homojunctions
is phosphorus that has been introduced either during the nanowire
growth90 (using a P2O5 powder as a precursor in the chemical vapor
deposition process91 or adding NH4H2PO4 during the hydrothermal
growth process92) or by ion implantation and successive annealing
treatment to activate the acceptors, as shown in Fig. 3.93 A lot of
eort 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 reliable
electrical and electro-optical devices will surely be soon
available.
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Fig. 3. (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) Low-magnication 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 dierent 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).
(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 oxides heterostructures in particular, is more
dicult with respect to IIIV semiconductors.94 Several examples have
been reported in literature for radial, longitudinal, and dierent
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 synthesis process, longitudinal
heterojunctions can be created along the length of the nanowires.
On the other hand, dierent heterostructures can be easily formed
just decorating with a secondary phase the nanowires to create new
metaloxide and oxideoxide 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 rst 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
structures,9597 or the decoration of nanowires with small
crystals.17,98 Epitaxial relationship is typically found between
the crystal 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.99 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, BiFeO3/ZnO coreshell
heterostructures were prepared: rst a ZnO core by hydrothermal
method then a BiFeO3 shell was deposited by sputtering and the end
product annealed in an oxygen atmosphere.101 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 highpressure quartz glass pulsed laser
deposition chamber for the nanowire growth and a conventional (low
pressure) pulsed laser deposition chamber for the initial buer
layer growth and for the shell growth. The introduction of a ZnO
buer layer enables the fabrication of individual nanowires with low
areal density, suppressing any shadowing eect by neighboring
nanowires during subsequent growth. Both radial and longitudinal
nanosized In2O3SnO2 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
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Fig. 4. Structural characterization of longitudinal
heterostructures. (Main panel) TEM image (panoramic view) of an
In2O3 nanowire, with the SnO2 nanowire extending along the length.
The black arrow marks the termination of the SnO2 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 magnication 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 rst one, there was an epitaxial
growth of crystalline tin oxide on the In2O3 single crystal at rst,
but due to the lattice mismatch between the cubic In2O3 and the
tetragonal SnO2 lattices, it resulted in polycrystalline 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 proposed.103 The rst 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 dierent techniques for
the dispersion or growth of nanostructures over the oxide
nanowires. For example, heterostructures of ZnO/Fe3O4 and ZnO/Fe2O3
were prepared by depositing magnetic nanoparticles on ZnO microrod
templates by a low-temperature hydrothermal procedure.104 Quantum
dots of PbS were freshly deposited by atomic layer deposition on
silicon nanowires.105
Metal oxides such as ZrO2, Al2O3, TiO2, and SiO2 are further
widely used as catalyst supports. Oxides-supported gold catalysts
are active towards many reactions, including oxidation of CO,
selective oxidation (alkenes, alcohols, and even alkanes),
water-gas shift, and removal of atmosphere pollutants, such as NOx.
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
III.
Applications of Metal Oxide Nanostructures
This part of the Review is dedicated to the multiple
applications of metal oxide nanostructures in dierent elds. For
some of those applications, which do not represent a comprehensive
collection of all possible applications, we will briey 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 thermodynamic point of view, reactions (chemical or not) while
remaining unaltered at the end of the reaction itself.11,106 The
eectiveness of a catalytic material is often measured in terms of
its inuence and eects on the reaction kinetics. It has been shown
that gold nanoparticles, traditionally known for being
catalytically inactive in the bulk form, when supported by a metal
oxides substrate become very active catalysts.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
(2) As Absorbents Metal oxides nanostructures have been recently
proposed as ecient adsorbents in case of environmental
contaminations, ranging from radioactive residues, by-products of
nuclear ssion reaction and leakage of the nuclear reactors to air
and water purication. 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 exible and promising candidates for a
new generation of absorbent materials, 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
ecient and have a broader range of sensitive materials. For
example, a composite material based on nanostructured SiO2 and TiO2
has been shown to be eective for the removal of elemental mercury
vapor113 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 carbon, which, however, is not capable of eciently
removing SO2 [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 eld-induced electron emission
properties,
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indicating their potential as future electron sources and
displays. Nanowires,16 needles shape,117 nanopyramids,118 and
others have been widely investigated and studied in terms of their
eld emission features; Bhise et al. have for example extensively
demonstrated ecient eld emission properties for SnO2 nanowires with
dierent types of doping (Sb,119 RuO2,120 Fe,121 In122), both in
terms of emission from a single structure as well as from ordered
arrays. Further, conductive vertically aligned TiO2 nanotube
arrays123 have been shown to be ecient and stable electron eld
emitters even at room temperature with rather low turnon elds ( $
280 V per electrode distance of 100 lm).
In this specic eld, crystallinity15 plays a crucial role due to
the increased diusion 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
dyesynthetized solar cells (DSSC); the nanowire nature provides a
direct path for charge collection, thus reducing the recombination
processes that are mainly responsible for reduction of the overall
cell eciency. Innovative photoanodes have been proposed by using
ZnO and SnO2 single crystalline nanowires and TiO2 nanotubes,135 as
well as nanowires-based hybrid structures in conjunction with
quantum dots acting as light absorbers.136
(4) As BioSensing Devices Nanostructured metal oxides have
recently gathered great interest also in the eld of
biosensing,124,125 due to their biocompatibility, non-toxicity, and
enhanced electron-transfer kinetics and strong adsorption
capability; these features provide 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 biosensor combines the molecule
selectivity with the progress of microelectronics, hence providing
a powerful analytical tool with applications in medical diagnostics
and other areas. 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 selectivity and stability. Very recently metal oxide
nanostructures materials [ZnO, Cu(I)/(II) oxides, MnO2, TiO2, CeO2,
SiO2, ZrO2] have been proposed and investigated as glucose
biosensors.130 We here refer the Reader to more specic
literature114 and references therein for a detailed description of
this topic, which is of great interest for the medicine community.
Due to their specicity, 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
(SnO2In2O3)131 have been shown to possibly enhance the
electrochemical performances of a battery, due to a large increase
of the electronic conductivity as compared to single material
nanostructure (SnO2) as a result of the doping-like eect of the
In2O3 lattice during the nucleation 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 synthesis of massive SnO2 nanowires by
the thermal evaporation method on button-type electrode for Li-ion
batteries. Direct growth of one-dimensional SnO2 nanowires on the
current collector133 [Si (100) or stainless steel foil] via a VLS
method at 600C have also been suggested. (6) As Solar Cells The MOx
nanowires have been recently applied in the eld of solar cells.
CdSe nanorods-polymer structure134 was suggested, 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 properties137; in SnO2 for example
shallow states made up of oxygen vacancies are double n-type donors
donating electrons to the conduction band.138 Metal oxides 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 xed. The gas sensing properties arise from
surface chemisorption of oxygen, which acts as a surface state
capturing an electron or a hole139 from the conduction band: charge
transfer between bulk and surface takes place producing a
non-neutral region (with a non-zero electric eld) 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 eld 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 eect of gas adsorption on the electrical
properties. The variation in photoluminescence emission of MOx
nanowires upon gas exposure 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
microbalance 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,140 which release
electrons from surface states to the conduction band and decrease
the height of the surface barrier. Other target species, such as
the strongly electronegative NO2, directly chemisorb over the oxide
surface decreasing sensor conductance by trapping electrons.
Electrons can also be injected as an eect 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
substrate, and depositing a gate back contact, one obtains a Single
Nanowire Transistor (SNT) structure, as shown in Fig. 5(b). The
current ows along the cylindrical axes and parallel to the surface
where electrons are trapped: when the nanowire section is thin
enough, almost all available electrons 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 reactions can be modulated (electroadsorbitive eect141); a
majority 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
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Fig. 5. Current transport in nanowire bundles (a) and in a
single nanowire transistor (b) (Reprinted with permission from Int.
J. Nanotechnol., 5 [45], 45074 (2008). Copyright 2008,
Inderscience).
Instead when contacting nanowire bundles the conduction
mechanism is dominated by the SCR created at the intercrystalline
boundaries between NWs: the carriers must overcome the energy
barrier to cross from one nanowire to the neighbor as reported in
Fig. 5(a). In this case, the conductance of the bundle (as for
polycrystalline gas sensor) can 2 2 therefore be expressed as: G G0
eqVs =kT G0 eq Nt =2eNd kT , where Vs is the bulk to surface
potential barrier, T the temperature, Nd is the donor density
(oxygen vacancies), Nt the density of charged surface states and G0
is a pre-exponential term, independent in rst approximation from
the surface adsorption and temperature. The metal semiconductor
junction that forms at the interface 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 resistance 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 eect 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 dened as the (relative) change of conductance (resistance in
presence of NO2 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.144 The sensor response curve
is frequently erroneously called sensitivity, which is instead the
derivative of the sensor response curve.
(2) Nanowires Integration For fabrication of devices,
nanostructures should be grown or transferred on a suitable
substrate and provided with electrical 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. Sapphire 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 exible
devices. In this case the use of low temperature growth process is
required, or a transfer technique such as drop coating or
roll-transfer printing145 must be used to avoid 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 temperature: this feature
can be integrated into micromachined silicon 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 conguration to measure the
nanowire resistivity. The contact 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 metallization 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 diusivity 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 nanowires 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 specic contacts with
nanomanipulation or dielectrophoresis (DEP). Most of the
manipulations are performed in association with high-resolution
imaging techniques such as scanning 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 eld in the suspension medium. DEP has been shown to be
capable of aligning tin oxide nanobelts,146 zinc oxide
nanobelts,147,148 and nanoparticles149 and GaN nanowires.150 After
the nanowires were placed between contacts, platinum 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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electrical resistance, which is the principal gure 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 rst reported on the gas sensing properties of
indium-tin-oxide 1-D structures known as whiskers grown by VLS
mechanism. Comini et al. reported a signicant response to CO,
ethanol and NO2 in pure SnO2 nanowire bundles prepared by thermal
evaporation, and subsequently transferred.153 The device was
operated at 400C. A number of publications have been reported
since, addressing the enhancement of the sensor fabrication and
performance. Wang et al.154 grew SnO2 nanowires directly over
functional substrates. Vomiero et al.155 combined two consolidated
techniques (vapor transport and condensation and wet etching of a
sacricial 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 NO2.156 Nanowires
from tens to hundreds of nanometers in width were assembled in a
three-dimensional open structure with a large number of
nanowire-nanowire interfaces. The measured high sensitivity has
been associated to this peculiar hierarchical three-dimensional
network. The exposure to 50 ppb of NO2 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 WO3 thin lms.157 Reducing the crystallite
size allows one to increase the sensitivity.158 Accordingly,
Polleux and co-workers adopted this approach to detect sub-ppm
concentrations of NO2.159 In this work, a signicant temperature
eect was reported for nanowires (about 1 nm in diameter) bundles
prepared by softchemistry route. The response decreased by about
one order of magnitude by increasing the temperature from 150C to
225C. The low temperature range (down to room temperature) was
investigated by Kim et al. working with sub-stoichiometric tungsten
oxide (WO2.72) nanowires, few nm in diameter.160 As shown in Fig.
6, the normalized resistance decreases upon exposure to ammonia at
200C 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 SnO2 nanowires
trough to the formation of shallow donor levels by introduction of
Sb+5 into SnO2.161 Authors also recorded an increase in sensor
kinetics, attributed to Sb doping, which would favor and accelerate
the absorption of oxygen molecules and the formation of oxygen ions
on the surface. Kolmakov et al. report the eect of Pd nanoparticles
over a single SnO2 nanowire.162 The improved sensing performance to
oxygen and hydrogen was attributed to the combined eect of
spillover of atomic oxygen catalytically formed and the back
spillover eect in which molecular oxygen migrates to the Pd
nanoparticles and is catalytically dissociated. Sysoev et al.
comparatively investigated long-time stability of SnO2
nanoparticles and nanowires.163 As shown in Fig. 7, nanoparticles
show higher response than nanowires during the rst few days of
operation. Monitoring the variation along time, the authors
concluded that the time-dependence of the response could be due to
coarsening eect in nanoparticles.
Fig. 6. Normalized resistance (Rgas/Rair) at dierent 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 oer the opportunity to exploit the
peculiar nanoscaled size and high crystalline quality, without
eects arising from nanowire-nanowire interfaces. The high
crystalline quality of nanowires immediately suggested their
potentialities as suitable materials to develop eld-eect
transistor.164 Zhang et al.165 investigated the possibility to use
the gate voltage to modulate the performance of FET gas-sensors. In
addition, considering that the high electrical conductivity owing
in a nanowire connected by two electrodes, allows increasing the
wire temperature, extremely low power consumption can be
obtained.166,167 This approach toward selfheating 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 dierent from electrical one is
desirable to overcome diculties in contacting nanostructures. One
possible solution is to use the bright room temperature
photoluminescence (PL) signal shown by nanowires of SnO2 and ZnO to
realize all-optical gas sensors for low concentrations of
pollutants such as NO2. The SnO2 nanostructures typically exhibit
strong visible PL emission at room temperature with a broad
emission band peaked at about 2 eV,168170 commonly attributed to
radiative defective states within the bandgap (oxygen vacancies).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 emission band in the range from green
to yellow depending on deep defect states lying inside the
bandgap,172,173 where the position of this band is determined by
growth conditions.174,175 Faglia et al.176 showed that PL in SnO2
is quenched in a reversible way by NO2 at a temperature of 120C:
the gas adsorbs over the surface creating competitive non-radiative
recombination paths. Lettieri et al.177 demonstrated that larger PL
quenching by NO2 absorption is observed at room temperature with
Continuous Wave (CW). Similarly, photoluminescence of ZnO is
quenched by interaction with NO2 room temperature.178,179 Dierently
from SnO2, 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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Vol. 95, No. 3
Fig. 7. Sensor baseline of SnO2 mesoporous layer and nanowire
bundle versus time (a). Experiments have been rst carried out in
dry air, then (since day 26) in humidied air. (b) Open and lled
circles correspond to nanoparticles and nanowires (Reprinted with
permission from Sensors Actuat. B, 139, 699703 (2009). Copyright
2009, Elsevier).
tion of very low concentration of NO2 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, NO2 adsorbs over the metal
oxide surface as NO2. At room temperature, reversibility of
chemisorption is guaranteed by UV excitation that supplies the
energy needed for desorption. Both for SnO2168 and ZnO,171
time-resolved photoluminescence (TRPL) measurements in presence of
NO2 showed small modication of recombination rates and lifetimes
upon introduction of the gas. The results support a surface static
quenching model, according to which the gas molecules suppress a
fraction of radiative transitions instead of simply reducing their
probabilities. At higher NO2 concentration, a saturation eect has
been observed by Valerini et al.,181 suggesting limitation in usage
of optical gas sensor at concentrations higher than 20 ppm. The
same authors have also shown the eect of the ZnO nanostructure
morphology: relative response to NO2 is higher for sample
constituted by pencil-like rods well separated one from each other,
characterized by larger surface available for gas-surface
interaction. Literature available on this subject shows that
alloptical gas sensor based on nanowires is feasible for NO2
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 eect must be taken into account.171
V.
Light Emission
(1) Working Principle Light emitting diodes are dierent from
traditional light sources in the way the light is produced; in
fact, light emission is achieved by lament heating (incandescent
lamp) or an electric arc exciting mercury atoms (uorescent lamp).
An LED, in contrast, is basically a semiconductor diode, based on a
p-n junction, where current ows 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 SnO2, have shown emission in the
visible region, which is indeed due to defects or impurities, which
are in general dicult 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 eective radiative
recombination at room temperature, allowing for ecient 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,
Fig. 8. Dynamic photoluminescence quenching of the signal coming
from ZnO nanowires by sub-ppm concentration of NO2 (Reprinted with
permission from Sensors Actuat. B Chem., 140 [2] 4616 (2009).
Copyright 2009, Wiley).
Fig. 9. Working principle of a LED based on a p-n
homojunction.
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Fig. 10. Band osets of GaN, NiO, Si and CuAlO2 semiconductors
respect to ZnO.
electrons in the conduction band ow across the junction from the
n-doped side, and holes in the valence band ow from the p-doped
side. The result is that a signicant 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 diculties to p-type dope ZnO, a possible alternative
is to prepare heterojunctions with an easily p-dopable materials.
Further, to provide an ecient holes injection in the n-ZnO regions,
one has to select materials with lower (or negative) valence band
osets as compared to ZnO. Figure 10 shows band approximate osets of
GaN,182 CuAlO2,183 Si, and NiO184 p-type semiconductors with
respect to ZnO; it is clear that the most suitable candidate is
p-type GaN, whereas other materials valence band osets are too
large to provide eective hole injection. Thus, LED eciencies
reported in literature for CuAlO2, 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 (mismatch is about 1.9%).
In accordance with the Anderson model, a simplied picture of bands
at equilibrium for the pGaN/n-ZnO heterojunction, which disregards
polarization charge at interfaces, is reported in Fig. 11. As long
as forward bias is applied to the junction, eective 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 introducing blocking (i.e., MgO) layers with
the objective to conne carriers in the ZnO regions, as shown in
Fig. 12, where electrons experience a much higher energy barrier
than the holes
(which can easily tunnel through the barrier) and carrier
densities are eective for recombination only in the ZnO region. It
is possible to induce electroluminescence even in a nGaN/n-ZnO
heterojunction by applying a considerably high voltage; holes are
created by defect assisted tunneling or impact ionization. This
eect is briey 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 eciency can be
obtained only by preparing double heterostructures (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 connement
layers cladding the active region. The two cladding or connement
layers have a larger bandgap than the active region. Band
conguration is benecial also from the point of view of photons
reabsorption, which cannot take place in the higher bandgap
claddings. The resulting radiation is better dened due to carrier
connement and the optical power generated per unit volume is much
larger as well. Figure 14 shows a typical DH conguration. 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 detrimental because the electric eld moves away
electrons and holes, in some congurations it can be exploited to
improve charge connement in the active regions. Discussions so far
reported in terms of ZnO bands, are generally valid both for thin
lms and for nanowires, considering that the nanoscale objects are
usually considerably
Fig. 11. Energy band diagram of the n-ZnO/p-GaN heterojunction
at (a) equilibrium and (b) forward bias.
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Fig. 12. Energy band structure of a p-GaN/n-ZnO diode with a MgO
layer.
injection rate signicantly increases for nanoscale contacts in
Schottky diodes,187 nanowires grown directly on p-type lm could
benet from increased carrier injection eciency due to nanosized
junctions. In general, it is necessary to achieve high quality
interface between the heterojunctions to get high-eciency LEDs,
since the interface states generally act as non-radiative centers
that annihilate free electrons and holes. Vertically aligned
nanowires are usually employed in these types of devices to take
advantage of the waveguiding eect in nanowires, even if the
emission from non-aligned mesh of nanowires is reported.188
Electroluminescence in these junctions is investigated in a typical
two-terminal device, fabricated by depositing appropriate lm 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
electrodes 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 heterojunction device with vertical nanowires is
reported in Fig. 16.
larger than the ZnO Bohr radius (2.34 nm) and quantum connement
eects can be neglected. Indeed nanowires growth produces
grain-boundary free and a much less strained and defective
interface, which are sources of nonradiative recombination,
compared to thin lms. In addition, nanowires can act as direct
waveguides and favor directional light extraction without use of
lenses and reectors.
(2) Nanowires Integration The LED structure-based nanowires
reported in literature so far mainly deals with ZnO homojunctions
and heterojunctions, with some rather limited and preliminary
investigations for SnO2 [Ref. 185] and In2O3. For homojunctions
based on a nanowires/nanowires junction, 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 npart 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 eects. On the other end, heterojunction-based devices
are mostly realized by growing n-type ZnO nanowires on p-type
substrate, mainly thin lm. Since it was reported that the
carrier
(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
temperature 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 of doping
atoms (i.e., Mg,189,190 Cd191,192), 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 dierent high- as well as
low-temperature (