Oxidation of silicon nanowires

D. Shir, B. Z. Liu, A. M. Mohammad, K. K. Lew, and S. E. Mohney

Citation: Journal of Vacuum Science & Technology B 24, 1333 (2006); doi: 10.1116/1.2198847
View online: http://dx.doi.org/10.1116/1.2198847
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 Oxidation of silicon nanowires
D. Shir and B. Z. Liu
Department of Materials Science and Engineering, The Pennsylvania State University, University Park,
Pennsylvania 16802 and The Materials Research Institute, The Pennsylvania State University,
University Park, Pennsylvania 16802
A. M. Mohammad
Department of Electronic Chemistry, Tokyo Institute of Technology, Yokahama, Japan
K. K. Lew and S. E. Mohneya兲
Department of Materials Science and Engineering, The Pennsylvania State University, University Park,
Pennsylvania 16802 and The Materials Research Institute, The Pennsylvania State University,
University Park, Pennsylvania 16802
共Received 20 January 2006; accepted 29 March 2006; published 10 May 2006兲
Silicon nanowires have received attention for nanoscale electronic devices and chemical and
biological sensors. The thermal oxide grown on the silicon nanowires could be used in a variety of
devices, so the oxidation of the silicon nanowires is investigated in this work. Silicon nanowires
with an average radius of 37 nm were grown for these experiments using the vapor-liquid-solid
technique with Au to mediate the growth. Etching of the Au tips from the silicon nanowires was
performed prior to oxidation to avoid local accelerated oxidation at the nanowire tip. Oxidation was
performed at 700 ° C for 1 – 121 h and at 650 and 750 ° C for 4 h in O2, and the oxidized nanowires
were examined by transmission electron microscopy. Depending on the conditions for oxidation, an
oxide shell as thin as 6 nm was observed, or the entire nanowire was oxidized. The kinetics of
oxidation differ from those of a planar silicon wafer and are discussed in this work. © 2006
American Vacuum Society. 关DOI: 10.1116/1.2198847兴

I. INTRODUCTION SiNW tips. When oxidized at a temperature higher than the

Silicon nanowires 共SiNWs兲 have received considerable at-
tention in recent years as building blocks1 for nanoelectronic
devices, including field-effect transistors,2 thin-film
transistors,3 and chemical and biological sensors.4 The ther-
mal oxide on the SiNWs may provide a dielectric shell
around the nanowires for nanoscale electronic devices, sur-
face passivation, or a sacrificial spacer during the assembly
of nanowire arrays. Small diameter SiNWs may also be ob-
tained from larger diameter SiNWs by oxidizing the larger
diameter SiNWs and then removing the oxide layer. The oxi-
dation of the SiNWs should be investigated to facilitate its
use in SiNW devices and processing steps.
Researchers have previously investigated the oxidation of
etched silicon microstructures.5–8 The influence of the stress
in the oxide in the case of cylindrical oxidation has also been
discussed both qualitatively7,8 and quantitatively,6,9,10 and
models for wet oxidation of cylindrical silicon have shown
good agreement with the experimental data.6,10
Besides fabricating SiNWs using various etching tech-
niques, the vapor-liquid-solid 共VLS兲 growth mechanism can
also be used to grow SiNWs.11,12 We are interested in the
oxidation of this type of SiNW, and we have focused on dry
rather than wet oxidation since the quality of the Si/ SiO2
interface for use in electronic devices is usually higher for
dry oxidation. Westwater et al.11 have studied the dry oxida-
tion of SiNWs grown directly on a Si wafer using the VLS
approach, but they did not remove the Au catalyst from the
a兲
Electronic mail: mohney@ems.psu.edu
Au–Si eutectic 共363 ° C兲, a Au–Si liquid alloy ball formed at
the tip of the SiNWs and accelerated oxidation at the end of
the SiNWs. The SiNW became segmented and consisted of a
solid SiO2 nanowire, a gold nanoparticle, and then a Si nano-
wire with a SiO2 shell. These segmented SiNWs produced by
Westwater et al.11 do not have the structure we desire, which
is simply a SiNW with an oxide shell. Furthermore, we do
not want to oxidize our SiNWs at higher temperatures than
VLS growth was performed without first removing the Au
from the SiNWs, since the solubility of Au in Si increases at
higher temperatures. Therefore, we have investigated the dry
oxidation of VLS-grown SiNWs without Au tips.
II. EXPERIMENTAL PROCEDURE
The SiNWs used in our studies were prepared using the
VLS growth technique.12 A very thin layer of Au catalyst
was deposited on the wafer prior to SiNW growth. The Au
tip remaining on the SiNWs after growth was etched in a
KI – I2 solution prior to oxidation. 关Confirmation that the tips
were removed was provided using scanning electron micros-
copy 共SEM兲 on a separate set of samples.兴 The samples were
then rinsed in de-ionized 共DI兲 water and dried. They were
next placed into a quartz tube that was purged for 1 h before
it was placed into the furnace. The O2 flow rate was main-
tained at 100 SCCM 共SCCM denotes cubic centimeter per
minute at STP兲 at all times.
The oxidized SiNWs were released from the surface of
the substrate on which they were grown using ultrasonic agi-
tation with the sample in isopropyl alcohol 共IPA兲. The liquid,

1333 J. Vac. Sci. Technol. B 24„3…, May/Jun 2006 1071-1023/2006/24„3…/1333/4/$23.00 ©2006 American Vacuum Society 1333

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 1334 Shir et al.: Oxidation of silicon nanowires 1334

FIG. 2. Thickness of the oxide layer around the Si core for dry oxidation at
700 ° C plotted vs oxidation time. Data for the oxidation of a planar wafer
from Deal and Grove 共Ref. 13兲 are also plotted.

FIG. 1. TEM image of a SiNW oxidized at 700 ° C for 4 h.

which contained the SiNWs, was then centrifuged to concen-
trate the SiNWs into the bottom of the tube. The IPA was
next removed from the top of the tube to obtain a higher
SiNW density in the remaining liquid. Samples for transmis-
sion electron microscopy 共TEM兲 were made by transferring a
few drops of IPA, which contained the SiNWs, onto the
TEM grid. TEM was then used to measure the oxide thick-
ness and determine the growth direction of the SiNWs.
III. RESULTS AND DISCUSSION
The SiNWs were oxidized at 700 ° C for 1, 4, 9, 16, 25,
49, or 121 h; 650 ° C for 4 h; or 750 ° C for 4 h. The oxide
thickness and silicon core radii were measured using TEM. A
TEM image of a typical oxidized SiNW is shown in Fig. 1.
The contrast between the silicon core and the oxide shell
allows one to easily measure the oxide thickness and the
silicon core radius. The starting radius of the SiNW was
determined based on the increase in volume of SiO2 over that
of Si 共the molecular volume of SiO2 is 2.25 times that of the
atomic volume of Si兲:
b2 1.25 2
a 02 = + a ,
2.25 2.25
where a0 is the starting radius of SiNWs, b is the total radius
after oxidation, and a is the silicon core radius after oxida-
tion. Table I shows the oxidation temperature, oxidation
time, average starting SiNW radius, average oxide thickness,
average SiNW radius after oxidation, and average Si core
radius after oxidation. Due to limitations in how far the TEM
specimen holder could be tilted, not all of the nanowires
could be imaged in the same orientation. The data in Table I
therefore reflect nanowire diameters and oxide thicknesses
averaged over different orientations for different nanowires.
The oxidized SiNWs had an average starting radius of
37 nm. The thicknesses of the oxides grown at 700 ° C are
plotted as a function of time in Fig. 2. For comparison with
the planar geometry, the thickness of the dry thermal oxide
grown at 700 ° C on a Si wafer is also plotted using experi-
mental data from Deal and Grove’s study.13 We would not
necessarily expect the curves to overlap due to the effects
of crystallographic orientation and surface preparation on
the rate of oxidation; however, the different shapes of the
curves are due to the different geometries of the Si prior to
oxidation.
It is first important to note that the curve for the Si wafer
represents the early stages of dry oxidation—the initial
anomalous rapid oxidation followed by growth controlled by
the rate of reaction at the SiO2 / Si interface 共linear portion of
共1兲 the curve兲. At this stage of oxidation, diffusion through the
oxide 共supply of oxidant兲 does not limit the growth of the
oxide. For the convex geometry of a nanowire, we expect the
rate of interfacial reaction to continue to control the rate of

TABLE I. Oxidation temperatures and times and nanowire dimensions.

Oxidation Oxidation Avg. starting Avg. oxide Avg. Si core Number

temperature 共°C兲 time 共h兲 radius 共nm兲 thickness 共nm兲 radius 共nm兲 of NWs

650 4 44 16 36 3
700 1 33 9 29 4
700 4 37 21 26 3
700 9 38 27 24 11
700 16 36 28 21 9
700 25 37 38 15 10
700 49 34 32 16 3
700 121 35 43 8 4
750 4 34 27 20 3

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 1335 Shir et al.: Oxidation of silicon nanowires 1335

FIG. 3. Dependence of starting radii of SiNWs on the oxidation rate at

700 ° C for various times.

FIG. 4. Bright field TEM image of the cross-sectional view of a SiNW

oxidation for even greater oxide thicknesses than for planar oxidized at 700 ° C for 16 h.
oxidation, because diffusion is enhanced by geometric ef-
fects for the nanowire case. In their model of the wet oxida-
tion of Si microstructures, Kao et al.6 argue that the supply The resulting oxide thickness for 4 h of oxidation at 650,
of oxidant to the SiO2 / Si interface can be enhanced by a 700, and 750 ° C ranged from 16 to 27 nm. The temperature
convex microstructure, since the area exposed to the ambient dependence of oxidation in this temperature range is mild,
共surface of the oxide shell兲 is greater than the interfacial area although no activation energy was extracted from the limited
at the SiO2 / Si interface. Furthermore, a tangential tensile data collected as a function of oxidation temperature.
stress due to stretching of the old oxide as it expands to a In micron-sized etched nanostructures, a variation in oxi-
larger circumference leads to an increased diffusivity. We dation rates of different orientations14 causes the cross sec-
may therefore assume that during the oxidation of the SiNWs tion of both the oxidized Si core and outer SiO2 shell to vary
in our study, it is the rate of interfacial reaction that controls from its starting circular shape.6 The cross section of a SiNW
the rate of oxidation. oxidized for 16 h at 700 ° C was prepared using a focus ion
Although diffusion can be enhanced by the convex nano- beam 共FIB兲 and examined using TEM, as shown at low and
wire geometry, we instead observe a marked slowing of the high magnifications in Figs. 4 and 5 respectively. Note that
oxidation of the SiNWs as time increases. A decrease in oxi- Pt was deposited for FIB sample preparation and is seen as
dation rate can be explained by a compressive stress normal spots on the perimeter of the oxide. Figure 4 shows that the
to the Si/ SiO2 interface. As new oxide grows at the interface, oxide forms a rounded shell around the Si core, but the cross
the old oxide expands due to the increase in volume of SiO2 section of the Si core is not perfectly circular. However, we
compared to Si, resulting in a compressive stress normal to should not assume that the deviation from a circular cross
the interface that slows the interfacial reaction between the section of the Si core is due solely to a variation in the rate of
oxidant and Si at the Si/ SiO2 interface. This stress effect is oxidation of different crystallographic faces, since the cross
exacerbated by the nanowire geometry. section of the nanowires is not necessarily circular prior to
Further evidence of the effect of the convex nanowire oxidation. Li et al.15 reported that the SiNWs tend to be
geometry on the rate of oxidation is provided by examining
the influence of the starting nanowire radius. The oxide
thicknesses for 1, 16, and 25 h at 700 ° C are plotted versus
the starting radii of the SiNWs in Fig. 3. A slightly reduced
oxide thickness is observed in Fig. 3 as the starting radius of
the SiNW is reduced for sufficiently thick oxides 共16 and
25 h of oxidation兲. The compressive stress normal to the
SiO2 / Si interface, which retards oxidation, becomes more
important for smaller nanowires. For etched Si nanostruc-
tures with radii as small or smaller than 25 nm, a self-
limiting oxidation has been reported in which the rate of
oxidation plateaus before the Si core is completely
consumed.7,8 However, the smallest SiNWs observed in our
study 共starting radii from 12 to 19 nm兲 were fully oxidized
after either 49 or 121 h at 700 ° C. 共Due to the deviation of
these small nanowires from the average size of the nanowires
used in our work, these small nanowires were not included in FIG. 5. TEM image of cross section of a SiNW oxidized at 700 ° C for 16 h
Table I.兲 共shown at lower magnification in Fig. 4兲. The Si core is outlined.

JVST B - Microelectronics and Nanometer Structures

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 1336 Shir et al.: Oxidation of silicon nanowires
FIG. 6. TEM image of SiNW oxidized at 650 ° C for 4 h showing the mor-
phology of the oxide on a SiNW with an undulation in radius along the
growth direction.
bounded by 兵111其 facets, since the 兵111其 plane has the lowest
surface energy. Growth of the SiNW shown in Figs. 4 and 5
was along the 具112典 direction, and the long, flat regions at the
SiO2 / Si interface viewed in cross section are, in fact, 兵111其
planes.
Other variations from the idealized core/shell geometry
have also been observed. For example, we have seen an un-
dulation in radius along the growth direction of the nano-
wires prior to oxidation, similar to the “sawtooth faceting” of
SiNWs reported by other researchers,16 although we have
observed this effect on nanowires with a 具112典 growth direc-
tion rather than 具111典. As shown in Fig. 6, oxidation some-
times evens out lateral variations in the nanowire radius at
the outer surface of the oxide shell.
IV. CONCLUSIONS
A procedure was established for oxidizing SiNWs grown
using the VLS growth technique. The Au tips on the SiNWs
were removed prior to oxidation using a KI – I2 solution to
avoid local accelerated oxidation at the nanowire tip. Dry
oxidation of the SiNWs was performed at temperatures from
650 to 750 ° C. The resulting oxide thicknesses were mea-
sured by TEM, and the kinetics of oxidation at 700 ° C were
examined. Stress effects eventually slowed the oxidation of
the SiNWs compared to the planar case; however, it was
J. Vac. Sci. Technol. B, Vol. 24, No. 3, May/Jun 2006
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1336
possible to oxidize some of the SiNWs fully, in contrast to
the self-limiting effect reported for etched nanostructures.
The results of this work suggest that 700 ° C is a convenient
temperature for controlled formation of a thin oxide shell on
SiNWs of this size, and the weak dependence of the oxida-
tion rate on temperature should make it possible to use other
temperatures for dry oxidation should they prove more favor-
able for the electronic properties of the oxide or its interface.
ACKNOWLEDGMENTS
This work was supported by the National Science Foun-
dation through the Research for Undergraduates Program of
the Materials Science and Research Center 共MRSEC兲 on
Nanoscale Science and through the NSF NIRT Grant No.
DMR-0103068.
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