REPORTS
drop in the Tg of the PVP phase (Tg 11. D. Stauffer, Introduction to Percolation Theory (Tay-
17C for 0.3:0.7 PANI-PSA:PVP), as
measured by differential scanning calorim-
etry in PANI-PSA:PVP binary blends.
The advantages of this self-organization
are manifest when we compare the morphol-
ogies obtained for the same PANI-PSA con-
centrations in the case of the binary blend
(Fig. 1B) and the ternary blend (Fig. 3B). As
the overall PANI-PSA volume fraction was
increased from 0.01 to 0.03 (Fig. 3C), the
concentration of dark-stained PANI-PSA
confined between the PS colloids increased
markedly, so that the hypothesis of percola-
tion of PANI-PSA within a percolating PVP
phase (double percolation) appears plausible.
Compared to the binary PANI-PSA:PVP
blends, confining the doped pi-conjugated
polymer within a lowvolume fraction chap-
erone phase reduced the concentration of the
conductive component at percolation onset
by a factor of 10. However, in principle, p
could be reduced further if block copolymers
with shorter blocks of the chaperone phase
were used. Eventually, solubility of the doped
pi-conjugated polymer in the chaperone
phase could be exploited in ternary blends to
design a single, continuous conducting phase.
Through the use of miscible dopedpi-
conjugated/chaperone polymer pairs such as
those reported in (2123) and the same pro-
cedures in self-assembly of doped-colloidal/
block-copolymer systems, semiconducting
organic-blend systems could be obtained in
which the percolation threshold in the contin-
uous phase is zero.
The method described here remains ad-
vantageous whether a double percolating
structure or a soluble single phase is de-
sired. Our approach can be applied to any
host/doped pi-conjugated polymer pair,
provided that a block copolymer can be
synthesized in which one block is compat-
ible with the surface of the colloidal system
and the other can host the doped pi-conju-
gated macromolecule. Because the solvent
options are greater when cross-linked col-
loids are used, this route offers an appeal-
ing strategy to improve many of the avail-
able semiconducting binary polymer blends.
References and Notes
1. Y. Yang, A. J. Heeger, Nature 372, 344 (1994).
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3. P. K. H. Ho, D. S. Thomas, R. H. Friend, N. Tessler,
Science 285, 233 (1999).
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6. S. L. Li, C. W. Macosko, H. S. White, Science 259, 957
(1993).
7. T. Vikki et al., Macromolecules 30, 4064 (1997).
8. E. T. Kang, K. G. Neoh, Y. Q. Dong, Z. H. Ma, K. L. Tan,
Synth. Methods 101, 696 (1999).
9. T. E. Olinga, J. Frayasse, J. P. Travers, A. Dufresne, A.
Pron, Macromolecules 33, 2107 (2000).
10. J. Frayasse, J. Planes, A. Dufresne, A. Guermache,
Macromolecules 34, 8143 (2001).
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21. S. H. Goh, H. S. O. Chan, C. H. Ong, Polymer 37, 2675
lor and Francis, Philadelphia, 1985). (1996).
12. C. Y. Yang, Y. Cao, P. Smith, A. J. Heeger, Synth. 22. , J. Appl. Polym. Sci. 68, 1839 (1998).
Methods 53, 293 (1993). 23. C. H. Ong, S. H. Goh, H. S. O. Chan, Polymer 38, 1065
13. M. Reghu et al., Macromolecules 26, 7245 (1993). (1997).
14. J. Frayasse, J. Planes, A. Dufresne, Mol. Cryst. Liq. 24. This work was partially supported by the Materials
Cryst. 354, 1099 (2000). Research Science and Engineering Centers program of
the NSF under award DMR00-80034 as well as by
15. F. Gubbels et al., Macromolecules 27, 1972 (1994).
PolyE Inc.
16. G. Yu, Q. Zhang, H. M. Zeng, Y. H. Hou, H. B. Zhang,
Polym. Eng. Sci. 39, 1678 (1999). Supporting Online Material
17. W. Thongruang, R. J. Spontak, C. M. Balik, Polymer 43, www.sciencemag.org/cgi/content/full/299/5614/1872/
3717 (2002). DC1
18. Materials and methods are available as supporting Materials and Methods
material on Science Online. Fig. S1
19. M. A. Rutgers, J. H. Dunsmuir, J. Z. Xue, W. B. Russel, Table S1
P. M. Chaikin, Phys. Rev. B. 53, 5043 (1996). References and Notes
20. K. Levon, A. Margolina, A. Z. Patashinsky, Macromol-
ecules 26, 4061 (1993). 9 December 2002; accepted 5 February 2003
Small-Diameter Silicon
Downloaded from http://science.sciencemag.org/ on March 7, 2017
Nanowire Surfaces
D. D. D. Ma, C. S. Lee, F. C. K. Au, S. Y. Tong, S. T. Lee*
Small-diameter (1 to 7 nanometers) silicon nanowires (SiNWs) were prepared,
and their surfaces were removed of oxide and terminated with hydrogen by a
hydrouoric acid dip. Scanning tunneling microscopy (STM) of these SiNWs,
performed both in air and in ultrahigh vacuum, revealed atomically resolved
images that can be interpreted as hydrogen-terminated Si (111)-(1 1) and
Si (001)-(1 1) surfaces corresponding to SiH3 on Si (111) and SiH2 on Si (001),
respectively. These hydrogen-terminated SiNW surfaces seem to be more
oxidation-resistant than regular silicon wafer surfaces, because atomically re-
solved STM images of SiNWs were obtained in air after several days exposure
to the ambient environment. Scanning tunneling spectroscopy measurements
were performed on the oxide-removed SiNWs and were used to evaluate the
electronic energy gaps. The energy gaps were found to increase with decreasing
SiNW diameter from 1.1 electron volts for 7 nanometers to 3.5 electron volts
for 1.3 nanometers, in agreement with previous theoretical predictions.
One-dimensional nanomaterials are expected to crucial issue in Si wafer technology is the re-
play a key role in future nanotechnology as well moval of the oxide layer and the formation of a
as to provide model systems to demonstrate stable, low-defect, passivated Si surface, and
quantum size effects. Silicon nanowires there is a similar need for small-diameter
(SiNWs) in particular are potentially very at- SiNWs with high-quality, passivated surfaces.
tractive, given the central role of Si in the We report the fabrication of SiNWs with
semiconductor industry and hence the existing diameters of 1.3 to 7 nm, from which the oxide
set of known fabrication technologies. Different sheath was removed and whose surfaces were
methods have been developed for SiNW fabri- terminated with H. This enabled us to achieve
cation (18), some in bulk quantities: the laser atomically resolved scanning tunneling micro-
ablation metal-catalytic vapor-liquid-solid scope (STM) images of the SiNW surfaces that
method (13), the oxide-assisted catalyst-free seem to be substantially more stable against
method (57), and solution techniques (8). All oxidation in air than the similarly H-terminated
yield wires with different orientations and di- Si wafer surfaces (1317). We also performed
ameters covered by an oxide sheath with a scanning tunneling spectroscopy (STS) mea-
minimum thickness of 1 to 3 nm. The smallest surements of the same SiNWs, showing an
SiNW diameter reported so far is 3 to 5 nm (3, increase in the electronic band gap from 1.1 to
4), although theoretical calculations indicate 3.5 eV as the wire diameter shrank from 7 to 1.3
that substantial quantum size effects require a nm. These data, which are in accord with the
SiNW diameter of 3 nm and below (912). A results of previously reported theoretical calcu-
lations (912), provide experimental evidence
Center of Super-Diamond and Advanced Films and
for the quantum size effect on the electronic
Department of Physics and Materials Science, City density of states (DOS) in SiNWs.
University of Hong Kong, Hong Kong SAR, China. SiNWs were prepared by an oxide-assisted
*To whom correspondence should be addressed. E- growth method (5, 6), in which SiO powders
mail: apannale@cityu.edu.hk were heated to 1200C in an alumina tube

under a flowing gas of 4% H2 mixed in Ar at
100 standard cm3 per min and 200 torr. The
SiNWs were produced downstream at about
900C on the inside tube wall. The wires had
diameters in the range of a few to tens of
nanometers and were composed primarily of a
single crystalline Si core and an oxide sheath
about one-third of the diameter (2, 5, 6). HF
solution was used to remove this surface oxide
[as routinely applied for Si wafers (14)], and
the SiNWs were subsequently dispersed on a
highly ordered pyrolytic graphite (HOPG) sub-
strate. Because HF treatment removes the oxide
layer and leads to H-terminated Si surfaces
(1417), we expected the HF-treated SiNWs to
also be H-terminated, as supported by our Fou-
rier transform infrared spectroscopy measure-
ments (18) on an ensemble of SiNWs (with a
large distribution of diameters from 3 to 20
nm). STM and STS measurements were per-
formed with an ultrahigh vacuum (UHV) STM
at 1 1010 torr. The atomically resolved
images were independently confirmed in an
STM operated in air. STS measurements were
made on atomically resolved SiNWs. Current
(I) versus voltage (V ) was measured at more
than 20 points on each wire, and the data were
differentiated and normalized [(dI/dV )/(I/V )] to
yield the conductance. The wire diameters were
determined by constant-current line scan and
deconvolution of the tip radius from the ob-
served wire profile and were consistent with
diameters estimated directly from the atomical-
ly resolved images. Additional details on the
STM/STS measurements are given in (19).
Atomically resolved STM images for
three nanowires of different diameters are
displayed in Figs. 1A, 2A, and 3A. The ac-
quisition of data for an individual wire is a
time-consuming process requiring hours to
days to locate the wires and obtain good
atomic resolution. The quality of the images
was not affected either by the long duration
of the experiment in which the samples were
exposed to air or by the exposure of the wires
to ambient air for several days before mea-
surement. This indicates that the oxide-
removed, H-terminated SiNW structures are
relatively resistant to oxidation in air. The
STS I-V measurements were performed in
UHV only. The axis of most of the imaged
SiNWs was along the [112] direction, with
only a few along the [110] direction, which is
consistent with our previous reports (5, 6).
Figure 1A is a high-resolution empty-state
STM image of an oxide-removed SiNW. The
corresponding filled-state image is similar and
therefore is not shown here. The atomic-like dot
arrangement of its top facet shows a threefold
symmetry. For clarity, the arrangement of the
dots is highlighted by the parallelograms in Fig.
1B: Each consists of four dots forming two
symmetrical triangles joined on one side. The
closest distance (i.e., the side length of a paral-
lelogram) between the atomic-like dots is mea-
www.sciencemag.org SCIENCE VOL 299 21 MARCH 2003
REPORTS
sured to be 0.23 nm. This distance is consider- STM image (Fig. 1A). Therefore, we ascribe
ably smaller than the distance of 0.38 nm be- the origin of the dots to the H atoms of the
tween Si atoms in a Si (111) plane. The mea- trihydride phase on the missing-top-layer Si
sured interatomic distance of 0.23 nm agrees (111) surface. The axis of the nanowire in Fig.
well with that observed on Si (111) wafers with 1A is along the [112] direction.
a 1 1 SiH3 surface obtained by similar HF Figure 2A shows an STM image of another
treatment (14). A structural model for the tri- SiNW, revealing a structure that can be inter-
hydride Si (111) surface is shown in Fig. 1B. In preted as a different H-terminated surface from
this model, atoms in the top Si plane are re- that in Fig. 1. On the topmost facet of the
moved. Each Si atom in the plane below is nanowire, one can identify regular atomic-like
bonded to three H atoms (20). The distance dots that form a rectangular lattice. Again for
between H atoms of the same SiH3 species is clarity, the dots are highlighted by the rectangles
0.24 nm and the length of the Si-H bond is 0.15 in Fig. 2B. The unit cell has dimensions of 0.38
nm, whereas the H-H distance on the neighbor- nm by 0.2 nm. As in Fig. 1, the lattices cannot
ing Si atoms is 0.21 nm (14). Consequently, the be matched to any pure Si surface but are in
arrangement of the H atoms exhibits threefold agreement with a 1 1 Si (001) dihydride
symmetry, as highlighted by the parallelo- surface. This symmetric dihydride phase on the
grams, with the average distance between H Si (001) surface has been shown to be the most
Downloaded from http://science.sciencemag.org/ on March 7, 2017
atoms about 0.22 to 0.23 nm. These values are probable structure from both experimental and
in good agreement with those obtained from the theoretical standpoints (21). Figure 2B shows a
Fig. 1. STM image and schematic view of a SiNW with a Si (111) facet. Crystallographic directions
are shown. (A) Constant-current STM image of a SiNW on a HOPG substrate. The wires axis is
along the [112] direction. (B) Schematic view of SiH3 on Si (111) viewed along the [111] direction.
Red and large blue circles represent the H atoms and Si atoms in the SiH3 radical, respectively.
Small blue circles represent Si (111) atoms in the layer below.
Fig. 2. STM image and schematic view
of a SiNW with a Si (001) facet. Crys-
tallographic directions are shown. (A)
Constant-current STM image of a
SiNW on a HOPG substrate. The
wires axis is along the [110] direction.
(B) Schematic view of the dihydride
phase on Si (001). Red and large blue
circles represent H and Si atoms in the
dihydride phase, respectively. Small
blue circles correspond to Si atoms on
the layers below. (C) Schematic view
of a Si nanowire bounded by four
(1 11)-type facets and two (001)-type
facets. The wires axis is along the
[110] direction.
1875
 REPORTS
schematic diagram of the symmetric dihydride
species on the Si (001) surface. Each Si atom on
the topmost layer is bonded to two H atoms,
which are 0.23 nm apart. The closest distance
between two H atoms bonded to two neighbor-
ing Si atoms is 0.15 nm. Thus, the H atoms on
the surface form two types of rectangular lattic-
es, 0.23 nm by 0.38 nm and 0.15 nm by 0.38 nm
(Fig. 2B). The lattice array of 0.20 nm by 0.38
nm observed in the STM image (Fig. 2A) cor-
responds to the arrangement of H atoms in the
symmetric dihydride phase on Si (001) within
the lateral resolution limit of STM of about 0.1
nm. The dots 0.38 nm apart are along the [110]
direction and the dots 0.2 nm apart are in the
[11 0] direction. The axis of the wire is along the
[110] direction. The Si-H bonds are oriented
perpendicularly to the axis of the wire. In Fig.
2C, we schematically show a SiNW with a
hexagonal cross section, bounded by four (1 11)-
type facets and two {001}-type facets. The an-
gle between two {1 11}-type facets is 109.5,
Fig. 3. Electronic properties of the SiNW surfac-
es. (A) I-V curves obtained by STS on six indi-
vidual SiNWs; the diameters of wires 1 to 6 are
7, 5, 3, 2.5, 2, and 1.3 nm, respectively. The inset
shows the atomically resolved STM image of
wire 6. (B) The corresponding normalized tun-
neling conductances, (dI/dV )/(I/V ); the curves
are offset vertically for clarity. (C) Experimental
band gap versus diameter for SiNWs of wires 1
to 6 and an additional two wires not shown in (A) and (B). Also shown are the calculated
diameter-dependent band gaps of (circles) Read et al. (9) and (triangles) Delley and Steigmeier (11).
1876 21 MARCH 2003 VOL 299 SCIENCE www.sciencemag.org
whereas that between {1 11} and {001} facets is
125.25. The schematic in Fig. 2C is consistent
with the image shown in Fig. 2A, indicating the
presence of three facets.
The formation of both the dihydride (SiH2 )
and trihydride (SiH3) phases on the facets of
SiNWs differs from that found on flat Si wafer
surfaces. For the SiH2 phase formed on a flat Si
(001) wafer, two equivalent domains with Si-H
bonds orthogonal to each other are generally
found. On the (001) facet of SiNWs, on the
other hand, we found only a single domain with
Si-H bonds perpendicular to the axis of the
wire. This can be explained by the existence of
a bending stress on the surface of a small-
diameter wire. The rebonding of dangling
bonds at the edge of two adjoining facets of a
SiNW introduces a strain, and hence possibly a
curvature, on the facet. We suggest that the
bending stress preferentially favors the forma-
tion of the domain with Si-H bonds perpendic-
ular to the wires axis. This is because for this
domain, the Si-Si back bonds on the surface are
parallel to the axis of the wire and hence are
indifferent to the bending stress. For the other
domain, the Si-Si back bonds are stretched by
the bending stress, causing the domain to be
less stable. The occurrence of the SiH3 phase on
the (111) facet of SiNWs also differs from that
found on a flat Si (111) wafer. On a flat Si (111)
wafer, the SiH3 phase is found only in certain
areas of the surface (14), unlike its predomi-
nance on the (111) facet of SiNWs. The differ-
ence again can be explained by the bending
stress on the wires surface. The curvature of
the (111) surface stretches and hence weakens
the back bonds of the top-layer Si atoms, mak-
ing it easier to form the missing-top-layer struc-
ture. We suggest that the robustness of the
SiNWs hydride structures is a consequence of
Downloaded from http://science.sciencemag.org/ on March 7, 2017
the bending stress. Although STM images with
atomic resolution of as-prepared wafer surfaces
have been observed to be stable for only up to
a few hours of exposure to air (1417, 21), the
hydride structures on SiNWs are stable in air
for several days.
STS measurements were performed on the
oxide-removed, H-terminated SiNWs (substan-
tiated by the atomically resolved STM images).
Figure 3A shows a selection of I-V curves
obtained by UHV STS measurements of differ-
ent SiNWs with diameters ranging from 1.3 to
7 nm. The corresponding (dI/dV )/(I/V ) curves
(i.e., normalized tunneling conductances) are
displayed in Fig. 3B. All the I-V curves but one
were recorded from a (111) facet on (112)-
oriented wires with images similar to that in
Fig. 1A. [Curve 3 was taken from a (100) facet
on a (110)-oriented wire and imaged in Fig.
2B.] The normalized tunneling conductance
can be considered to be proportional to the
electronic local density of states (LDOS) of the
SiNW examined (2224). Because the bias
voltage is limited to 2 V, only a small fraction
of the LDOS can be accessed (wire 6, shown by
the STM image, required extending the bias to
2.5 V because of its larger band gap). All
conductance curves show similar profiles (Fig.
3B), consisting of two distinct peaks near the
gap and two weak peaks below the valence
band (wires 1 to 5) and above the conduction
band (wires 1 and 2), respectively. The weak
peaks can move out of the bias voltage range as
the gap becomes larger (wires 3 to 6). The gaps
in Fig. 3B are not symmetrically positioned
around zero bias voltage. This shows that the
wires are doped during growth and/or by charge
transfer from the HOPG substrate. Wires 1 to 5
were from one batch of growth, whereas wire 6
was from a different batch. This may account
for the different doping characteristics of the
two batches of wires (i.e., the apparent relative
shift of the curve of wire 6 with respect to those
of wires 1 to 5). The clear separation between
the two peaks near zero bias in Fig. 3B enables
a straightforward and reliable determination of
the band gaps, which are plotted against the

wire diameter in Fig. 3C. The band gap at 7 nm
(wire 1) is close to Si bulk value at 1.1 eV, and
it increases first gradually and then steeply to a
much larger value of 3.5 eV as the diameter
decreases to 1.3 nm. The band-gap increase
with decreasing diameter provides clear evi-
dence of the quantum confinement effect. The
present results constitute an experimental test of
several theoretical works that calculate the elec-
tronic DOS of Si nanostructures (912). Figure
3C shows that our data are in good accord with
the theoretical predictions of Read et al. (9) and
Delley and Steigmeier (11). The relatively large
difference between the measured and calculated
band gap for 1.3-nm diameter SiNWs can be
attributed to the wire diameter being smaller
than the estimated value. For diameters larger
than 3 nm, the band-gap shift is relatively small
11. B. Delley, E. F. Steigmeier, Appl. Phys. Lett. 67, 2370
(1995).
12. J. B. Xia, K. W. Cheah, Phys. Rev. B 55, 15688 (1997).
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2468 (2001).
14. Y. Morita, K. Miki, H. Tokumoto, Appl. Phys. Lett. 59,
1347 (1991).
15. G. S. Higashi, Y. J. Chabal, G. W. Trucks, K. Raghava-
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Takashani, J. Appl. Phys. 76, 2157 (1994).
18. X. H. Sun et al., Inorg. Chem., in press.
19. STM and STS measurements were performed with an
Omicron UHV STM operated at 1 1010 torr and an
air STM (Park Scientic Instruments Autoprobe VP). We
obtained all images at room temperature by recording
the tip height in real time at a constant tunneling
current of 0.3 nA and a bias voltage of 2 V. Electro-
chemically polished tungsten tips were used. We cali-
brated the xy piezos for tip scanning within a few
percentage points by measuring the atomic image of
REPORTS
has different dimensions along different directions. This
is also true for a wire with the faceted cross section
shown in Fig. 2, for which the diameter presumably lies
between the diameters of an internal cylinder lying
within the at surfaces and an external one touching
the edges of the facet boundaries. The STM line scans of
SiNWs indicated near hemispherical proles with no
substantial diameter variation along different direc-
tions, in accord with our TEM images showing that the
cross section of SiNWs smaller than 20 nm in diameter
is more or less round. This is why we estimated the
diameter of SiNWs by assuming a circular wire cross
section (which in the case of the hexagonal cross sec-
tion of Fig. 2C would yield an uncertainty of 13%).
20. K. C. Pandey, T. Sakurai, H. D. Hagstrum, Phys. Rev.
Lett. 35, 1728 (1975).
21. J. E. Northrup, Phys. Rev. B 44, 1419 (1991).
22. J. A. Stroscio, R. M. Feenstra, A. P. Fein, Phys. Rev. Lett.
57, 2579 (1986).
23. N. D. Lang, Phys. Rev. B 34, R5947 (1986).
24. R. J. Hamers, Scanning Tunneling Microscopy and
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1993), pp. 51103.

Downloaded from http://science.sciencemag.org/ on March 7, 2017

and can be evaluated by a 1/diameter2 depen-
dence as given by the effective-mass theory (9).
For 2.5- and 3-nm diameter SiNWs, the mea-
sured band gaps are similar at 1.5 eV for both
(112)- (wire 3) and (110)- (wire 4) oriented
SiNWs. Indeed, the insensitivity of the band
gaps to wire orientation for diameters of 3 nm
or larger has been predicted by theory (11, 25).
In summary, we have produced SiNWs with
diameters approaching 1 nm. Oxide removal
and H termination resulted in stable, faceted
SiNW surfaces, enabling atomically resolved
STM imaging as well as STS measurement of
the electronic DOS of the SiNWs and the cor-
responding band gaps. The experimental band
gaps, in accord with previous theoretical pre-
dictions, increased with decreasing wire diam-
eters, demonstrating the quantum size effect in
SiNWs. Among the possible applications of our
findings are ultraviolet light-emitting diodes
and lasers from SiNWs (26), which may be-
come feasible if the wide band gap is a direct
one, as predicted for small-diameter SiNWs
(12). The ability to achieve atomically resolved
STM images of the oxide-removed, H-termi-
nated SiNW surfaces after long air exposure
indicates that H-terminated SiNW surfaces are
substantially more stable than similarly treated
Si wafer surfaces. The stability of H-terminated
SiNW surfaces and the consequential ability to
perform STM and STS at atomic resolution
open up opportunities for further exploration of
the structural, chemical, optical, and electronic
properties of single SiNWs.
References and Notes
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the HOPG substrate immediately before and after mea- 25. R. Q. Zhang et al., unpublished data.
suring the SiNW. All images presented here have not 26. L. Pavesi, L. Dal Negro, G. Mazzoleni, G. Franzo, F.
been processed in any way. Before and after the STS Priolo, Nature, 408, 440 (2000).
measurement on a wire, measurements were made on 27. We thank Y. Lifshitz, D. M. Chen, M. Dresselhaus, and
the HOPG substrate as references to ensure the reli- G. Dresselhaus for advice, and X. Q. Dai and C. T.
ability of I-V curves. The scanned voltages of all samples Chan for assistance with the graphics. This work is
except that with the smallest diameter of 1.3 nm (Fig. partially supported by a Central Allocation Grant
3A) were held at less than 2 V. The I-V curves of SiNWs (Project No. CityU 3/01C) and a Competitive Ear-
of various diameters were measured at the tip height marked Research Grant (Project No. CityU 1063/01P)
(about 0.8 nm) where atomically resolved STM images of the Research Grants Council of Hong Kong SAR
and by a grant from the Chinese Academy of Scienc-
were obtained. A series of I-V curves performed at
various tip-to-surface distances centering at 0.8 nm es, China.
showed that the dI/dV curves and normalized tunneling
conductances [(dI/dV )/(I/V )] were relatively insensitive 11 November 2002; accepted 10 February 2003
to the tip height, when the tip was set at or close to 0.8 Published online 20 February 2003;
nm. The diameter estimate may be inaccurate because 10.1126/science.1080313
of the uncertain shape of the wire cross section, which Include this information when citing this paper.
Plugging into Enzymes:
Nanowiring of Redox Enzymes by
a Gold Nanoparticle
Yi Xiao,1 Fernando Patolsky,1 Eugenii Katz,1 James F. Hainfeld,2
Itamar Willner1*
The reconstitution of an apo-avoenzyme, apo glucose oxidase, on a 1.4-
nanometer gold nanocrystal functionalized with the cofactor avin adenine
dinucleotide and integrated into a conductive lm yields a bioelectrocatalytic
system with exceptional electrical contact with the electrode support. The
electron transfer turnover rate of the reconstituted bioelectrocatalyst is 5000
per second, compared with the rate at which molecular oxygen, the natural
cosubstrate of the enzyme, accepts electrons (700 per second). The gold
nanoparticle acts as an electron relay or electrical nanoplug for the alignment
of the enzyme on the conductive support and for the electrical wiring of its
redox-active center.
The routing of electrons from redox proteins, redox-relay groups (57) or the immobiliza-
particularly redox enzymes, to electrodes has tion of enzymes in redox-active polymers
been a subject of extensive research (14). (811) has been used to establish electrical
The chemical modification of enzymes with communication between the biocatalysts and
electrodes. Nonetheless, the electron transfer
rate constants in electrode-contacted enzymes
1
Institute of Chemistry, The Hebrew University of
Jerusalem, Jerusalem 91904, Israel. 2Brookhaven Na-
are far lower than are those between the
tional Laboratory, Biology Department, Building 463, enzymes and their natural electron acceptor
Upton, NY 11873, USA. (O2 ) (12). This decrease has been attributed
*To whom correspondence should be addressed. E- to the tethering of the relay units in nonopti-
mail: willnea@vms.huji.ac.il mal positions and to the lack of alignment of

www.sciencemag.org SCIENCE VOL 299 21 MARCH 2003 1877

 Small-Diameter Silicon Nanowire Surfaces
D. D. D. Ma, C. S. Lee, F. C. K. Au, S. Y. Tong and S. T. Lee (February
20, 2003)
Science 299 (5614), 1874-1877. [doi: 10.1126/science.1080313]
originally published online February 20, 2003

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