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S
. The resulting (equilibrium) surface oxygen coverage, , depends on
the oxygen partial pressure and the system temperature through the temperature-
dependent adsorption/desorption rate constants, k
ads/des
, on the concentration of
A
n
n
u
.
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NANOWIRES, SENSORS, AND CATALYSTS 159
itinerant electrons, n, andthe concentrationof unoccupiedchemisorption(vacancy)
sites, N
s
.
2
O
gas
2
+ e
+ N
s
s
k
ads
N
s
n p
/2
O
2
= k
des
[where , = {1,2} accounts for the charge and molecular or atomic nature of the
chemisorbed oxygen (44)]. In forming ionosorbed oxygen, electrons become lo-
calized on the adsorbate, creating a 30100-nm-thick, electron-decient surface
layer corresponding approximately to the Debye length for SnO
2
(in the temper-
ature range 300500 K), which results in band bending in the surface region of
bulk samples. For 10100 nm diameter nanowires, the charge-depletion layer en-
compasses the entire nanowire, resulting in so-called at-band conditions wherein
the relative position of the Fermi level shifts away from the conduction band edge
not only at the surface but throughout the nanowire (Figure 5d). Ultimately, a new
kinetic equilibrium among the free electrons and the neutral and ionized vacancies
is re-established. Under these nearly at-band conditions at moderate tempera-
tures and for electron momenta directed radially, electrons can reach the surface
of the nanowire with essentially no interference from the low electrostatic barrier.
As a result, the electrons become distributed homogeneously throughout the entire
volume of the nanowire. Accordingly, the charge conservation condition simplies
to
N
s
=
R
2
(n n
m
),
where n
m
is the density of itinerant electrons remaining in the nanowire after
exposure to the adsorbate. The accompanying electron depletion n = 2N
s
/R
results in a signicant drop in conductance:
G =
R
2
e
L
2N
s
R
,
and the corresponding depopulation of the shallow donor states results in an in-
crease in activation energy (39). [We neglect the dependence of the mobility on
the surface coverage, a reasonable approximation at small bias voltages and when
the electron diffusion length (1 nm) is much smaller than the diameter of the
nanowire (50 nm) (45)].
Upon adsorbing a reducing gas such as CO, the following surface reaction takes
place with the ionoadsorbed oxygen
CO
gas
+ O
S
CO
gas
2
+ e
,
which results in the reformation of the adsorption (defect) sites and the redonation
of electrons to the SnO
2
(Figure 5b). It can be shown that under at-band condi-
tions the increase in electron concentration, n
CO
p
+1
CO
, and therefore in the
A
n
n
u
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160 KOLMAKOV
MOSKOVITS
conductivity of the nanowire, G
CO
e n
CO
(T) (T), increases mono-
tonically with CO partial pressure (44). This was conrmed experimentally on
nanowires assuming O
S
to be the
dominant chemisorbed species, although both single atom and diatomic species are
known to exist on the surface under appropriate conditions. Bottom: The calculated
equilibrium relative oxygen coverage as a function of gate potential before (squares)
and after (triangles) CO gas is admitted (51).
as a CO oxidation catalyst). Because the rst channel depends directly on the
ionosorbed oxygen coverage, increasing this coverage by applying a large positive
potential on the gate results in increased sensitivity toward CO. At low (nega-
tive) gate potentials, the reaction mechanism is independent of the ionosorbed
oxygen, causing the CO-sensing mechanism to switch to another mode. This il-
lustrates the prospect of a highly gate-tunable sensor (or nano-catalyst) whose
sensitivity (reactivity) and selectivity is tunable using the gate potential as a
A
n
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168 KOLMAKOV
MOSKOVITS
surface-chemistry determining parameter. The nanowire FET then becomes, in
essence, a sensor (nano-reactor) with electronically controllable selectivity and
sensitivity (reactivity).
PHOTOCHEMICAL PROPERTIES OF INDIVIDUAL
METAL-OXIDE NANOWIRES
The photochemical and photophysical properties of metal-oxide nanoparticles
and materials fabricated from them have been studied extensively, especially
in the context of solar energy conversion. In a similar vein, small diameter,
quasi-one-dimensional oxide nanostructures are promising photocatalysts on ac-
count of the efcient migration of electrons and holes to the nanostructure surface
where they can participate in chemical reactions before recombining. Although
these sorts of applications of oxide quasi-one-dimensional nanostructures are in
their infancy, a few compelling studies have already appeared. Dai and coworkers
recently reported molecular photodesorption fromsingle-walled carbon nanotubes
and its dramatic inuence on the electronic properties of a FET fabricated from
it (58). Yang and coworkers observed a record six-order-of-magnitude increase
in conductance when ZnO nanowires were exposed to 0.3 mWcm
2
of 365 nm
UV light (whose photon energy just exceeds the materials bandgap cut off) (59).
Similar results were reported for SnO
2
nanoribbons (33) whose sensing properties
were investigated under the inuence of photoexcitation. The photoresponse of
the nanowire and its associated time constants were found to depend sensitively
on the nature of the gas environment. On the basis of this observation, the au-
thors suggested that the photoresponse of nanoribbons and nanowires depended
on two contributions: (a) direct excitation of electron-hole pairs, which produce
a photocurrent that is inuenced by the bias, and (b) photoinduced desorption of
ionosorbed species through a photochemical reaction of the form h
+
+ A
A
0
(A
= O
, O
2
, NO
2
etc.), which eliminates the adsorbate-induced gating of the
nanoribbon thereby increasing the conductance of the nanowire. These effects are
exploitable in low-temperature sensing where many molecules stick irreversibly
to oxide surfaces. For example, room temperature detection of NO
2
at concentra-
tions as low as 3 ppm and with response/recovery times of the order of seconds
was reported with concurrent UV illumination. Although comparable sensitivity
was reported for thin lm semiconducting oxide sensors at room temperature (and
under UV illumination) (60, 61), their recovery times are of the order of hours.
Avouris and coworkers reported similar observations on ZnO nanobelt FETs
(36). On shutting off the 350 nm excitation, the current decay kinetics showed
two characteristic time constants: a fast process, which was likely due to electron
recombination, and a slow decay process, which was ascribed to the readsorption
of the (electron acceptor) molecules.
On illuminating an In
2
O
3
NW in air at room temperature with 3 mW/cm
2
of
254 nm UV, Zhou et al. (62) observed a 10
4
-fold increase in conductance
(Figure 11, top). The negative shift of the threshold voltage of the nanowire
A
n
n
u
.
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v
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NANOWIRES, SENSORS, AND CATALYSTS 169
Figure 11 Top: Photoresponse of the current through an In
2
O
3
nanowire to photoex-
citation, in turn, with 365 and 254 nm radiation. Bottom: Two NO
2
-sensing cycles:
(a) 254 nm light is ON; (b) light is OFF and Ar ux is ON; (c) 0.1% NO
2
is ON;
(d) NO
2
is OFF; (e) Ar is OFF; ( f ) 254 nm light is ON followed with send cycle (from
Zhang et al. 62).
congured as a FET upon UV exposure suggested an release of electrons into its
conduction band with electron concentration increases 1.8 nm
1
and 7.7 nm
1
of nanowire length for 365 nm and 254 nm light, respectively. The measured
transconductance of the FET indicated not only an increased electron
density but also 7-fold and 80-fold respective increases in mobility for the two
A
n
n
u
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170 KOLMAKOV
MOSKOVITS
wavelengths used. (The increased electron mobilities might be due to photon-
assisted electron excitation out of traps.) Because all measurements were per-
formedinair, the results were explainedinterms of the conventional model wherein
increases in conductance are linked to photoinduced quenching of O
2
and OH
C toward H
2
(after Varghese et al. 77).
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NANOWIRES, SENSORS, AND CATALYSTS 175
and length of the nanotubules was achieved by varying the anodization voltage
and time. The stoichiometry and crystallinity were improved by postannealing
at high temperatures in oxygen. Impedance measurements were carried out by
depositing two platinum electrodes, as shown in Figure 14 (top right). Record
values for hydrogen sensitivity with TiO
2
were reported for this nanotubule ar-
ray sensor (Figure 14, bottom). The superior sensitivity was explained in terms
Figure 15 Silica helices: (a) pillars, (b) zig-zag/chevron structures (d) grown using
ballistic glancing angle deposition (GLAD) (79). (c) Top view of the pillar structure
grown on a lithographically preseeded support (80). (e) The response of a humidity
sensor determined by SiO
2
pillars fabricated in this manner (84).
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176 KOLMAKOV
MOSKOVITS
of a combination of effects, including enhanced hydrogen dissociation on tita-
nia defects and on the Pt electrodes (followed by hydrogen spill-over from the
Pt) and hydrogen-induced modication of the Schottky barriers formed between
percolating nanotubules.
High-quality metal-oxide nanostructures have also been fabricated using a thin
lm deposition technique that couples glancing-angle, collimated, ballistic vapor
deposition (GLAD) with substrate rotation (78). In this fashion, arrays of colum-
nar nanostructures, complex structures consisting of arrays of helices, pillars, and
zig-zag/chevron structures with submicron (1001000 nm) diameters, microns in
length (Figure 15), were successfully grown (79, 80). Signicant morphological
differences, for example between helices (Figure 15a) and pillars (Figure 15b), are
possible by selecting the substrate rotation speed and the deposition rate appro-
priately. At higher sample rotation rates, for example, helical structures become
transformed into simple pillars, whereas zig-zag structures (Figure 15d) are ob-
tained by changing the angular orientation of the sample with respect to the depo-
sition direction. Two-dimensional periodicity was achieved by prepatterning the
surface with crystalline nuclei before lm deposition is carried out (Figure 15c).
Materials with potentially interesting magnetic, thermal, and chemical properties
were produced in this fashion, including materials showing a photonic bandgap
(81) and periodic arrays of SiO
2
nano-columns that functioned as humidity sen-
sors (8284). The pillared structure was sandwiched between two metal electrodes
(one of which was a percolating porous metal layer). The capacitance of the de-
vice was used to measure relative humidity (Figure 15e) on the basis of changes
in the dielectric constant and interfacial conductivity of the material. Because of
its open structure, the sensors response was found to be unusually fast (30 ms).
By modifying this vapor deposition method to allow for reactive ballistic deposi-
tion, a high-surface-area surface consisting of feather-like MgOlaments could be
grown (85).
CONCLUDING REMARKS
This review is a status report. Progress in the synthesis of quasi-one-dimensional
nanostructuresnanowires and nanotubulesis currently in active ferment. The
range of materials and the scope for their applications as sensors and in other elec-
tronic and photonic devices is expanding at a rapid rate. The foregoing emphasizes
structures based on metal-oxide semiconductors. Although the choice was not ar-
bitrary, much of what was reported for those materials carries over to structures
created in or potentially achievable with the broad range of available (and new)
compound semiconductors and through the new materials properties that arise in
them as their dimensions drop below certain physical correlation lengths. Hopes
are high that signicant practical devices will soon arise from the integration of
these structures with conventional microelectronics.
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NANOWIRES, SENSORS, AND CATALYSTS 177
ACKNOWLEDGMENTS
We thank Drs. Y. Zhang, G. Cheng, and Y. Lilach for their crucial contribution to
this work and Profs. H. Metiu and E. McFarland for helpful discussions and for
loaning us some equipment. This work was supported by a DURINT grant from
AFOSR. Extensive use of the MRL Central Facilities at UCSB was supported by
the National Science Foundation under award No. DMR96-32,716.
The Annual Review of Materials Research is online at
http://matsci.annualreviews.org
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P1: FRK
June 5, 2004 0:1 Annual Reviews AR218-FM
Annual Review of Materials Research
Volume 34, 2004
CONTENTS
QUANTUM DOT OPTO-ELECTRONIC DEVICES, P. Bhattacharya, S. Ghosh,
and A.D. Stiff-Roberts 1
SYNTHESIS ROUTES FOR LARGE VOLUMES OF NANOPARTICLES,
Ombretta Masala and Ram Seshadri 41
SEMICONDUCTOR NANOWIRES AND NANOTUBES, Matt Law,
Joshua Goldberger, and Peidong Yang 83
SIMULATIONS OF DNA-NANOTUBE INTERACTIONS, Huajian Gao
and Yong Kong 123
CHEMICAL SENSING AND CATALYSIS BY ONE-DIMENSIONAL
METAL-OXIDE NANOSTRUCTURES, Andrei Kolmakov
and Martin Moskovits 151
SELF-ASSEMBLED SEMICONDUCTOR QUANTUM DOTS: FUNDAMENTAL
PHYSICS AND DEVICE APPLICATIONS, M.S. Skolnick
and D.J. Mowbray 181
THERMAL TRANSPORT IN NANOFLUIDS, J.A. Eastman, S.R. Phillpot,
S.U.S. Choi, and P. Keblinski 219
UNUSUAL PROPERTIES AND STRUCTURE OF CARBON NANOTUBES,
M.S. Dresselhaus, G. Dresselhaus, and A. Jorio 247
MODELING AND SIMULATION OF BIOMATERIALS, Antonio Redondo
and Richard LeSar 279
BIONANOMECHANICAL SYSTEMS, Jacob J. Schmidt
and Carlo D. Montemagno 315
UNCONVENTIONAL NANOFABRICATION, Byron D. Gates, Qiaobing Xu,
J. Christopher Love, Daniel B. Wolfe, and George M. Whitesides 339
MATERIALS ASSEMBLY AND FORMATION USING ENGINEERED
POLYPEPTIDES, Mehmet Sarikaya, Candan Tamerler,
Daniel T. Schwartz, and Francois Baneyx 373
vii
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P1: FRK
June 5, 2004 0:1 Annual Reviews AR218-FM
viii CONTENTS
INDEXES
Subject Index 409
Cumulative Index of Contributing Authors, Volumes 3034 443
Cumulative Index of Chapter Titles, Volumes 3034 445
ERRATA
An online log of corrections to Annual Review of Materials Research
chapters may be found at http://matsci.annualreviews.org/errata.shtml
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