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Copyright 2012 American Scientic Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoelectronics and Optoelectronics
Vol. 7, 15, 2012
Growth, Structure and Optical Properties of Silicon
Nanowires Formed by Metal-Assisted Chemical Etching
K. A. Gonchar
1
, L. A. Osminkina
1
, R. A. Galkin
1
, M. B. Gongalsky
1
,
V. S. Marshov
1
, V. Yu. Timoshenko
1
, M. N. Kulmas
3
, V. V. Solovyev
2
,
A. A. Kudryavtsev
2
, and V. A. Sivakov
3
1
Physics Department, Lomonosov Moscow State University, Leninskie Gory 1, 119991 Moscow, Russia
2
Institute of Theoretical and Experimental Biophysics of RAS, Puschino, 142290 Moscow Region, Russia
3
Institute of Photonic Technology, Albert Einstein Street 9, D-07745 Jena, Germany
Silicon nanowires SiNWs formed by metalsilver-assisted chemical etching of lowly boron-doped
100-oriented single crystalline silicon substrates in hydrouoric acid solutions are investigated
by means of the electron microscopy and optical spectroscopy absorption and reection mea-
surements, photoluminescence spectroscopy and imaging. The growth rate of SiNWs is found to
depend nonlinearly on the time of etching. The formed SiNW arrays demonstrate a strong decrease
of the total reectance below 1% in the full visible and near infrared region between 300 and
1000 nm and the samples show the similar optical properties as Black Silicon, which can be used
as antireection coating in photovoltaic applications. The prepared SiNWs exhibit efcient photolu-
minescence in the spectral region of 6001000 nm and it is explained by the radiative recombination
of excitons conned within nanostructured sidewall of SiNWs. The excitons luminescence is also
observed in aqueous suspensions of SiNWs, whose application in bio-imaging is demonstrated
in vitro.
Keywords: Silicon, Nanowires, Black Silicon, Photoluminescence, Bio-Imaging.
1. INTRODUCTION
Nowadays one dimensional (1D) silicon nanostructures,
i.e., silicon nanowires (SiNWs), are of great interest
because of their potential applications in various elds
as microelectronics, optoelectronics, photonics, photo-
voltaics, bio- and chemical sensing.
19
SiNWs can exhibit
room temperature photoluminescence (PL),
10
enhanced
Raman scattering,
11
low reectance in the visible spectral
range and a strong broadband optical absorption.
6
There
are several ways to form SiNWs, and the rst method was
based on the bottom-up or well-known vaporliquidsolid
(VLS) growth catalyzed by noble metal as proposed by
Wagner and Ellis in 1964.
12
Then it was demonstrated that
SiNWs can be formed by top-down approachlike reactive
ion etching, electrochemical etching, aor metal-assisted
chemical etching (MACE).
6, 10, 1318
The latter is rather
simple, high efcient and relatively cheap method. Since
the electronic and optical properties of nanostructures
are strongly dependent on their formation, it is of great
importance to control the growth and structure of SiNWs
formed by MACE.

Author to whom correspondence should be addressed.

In the present paper we study the growth process, struc-
ture and optical properties of SiNWs obtained by MACE
of wafers of lowly-boron doped (100)-oriented crystalline
silicon (c-Si) in hydrouoric acid solution. In particu-
lar, it is shown that the formed SiNWs, which look like
quasi-ordered silicon nanograss, exhibit very low total
reectance and efcient room temperature photolumines-
cence (PL) in the visible spectral range as well they can
penetrate into living cells, saving their PL properties.
2. EXPERIMENTAL DETAILS
SiNWs were prepared by MACE of -type double-side pol-
ished (100)-oriented boron-doped c-Si wafers with specic
resistivity of 1 Dcm. Prior the etching, the c-Si surfaces
were rinsed in 49% HF solution for 1 min to remove native
oxide layer. Then, in the rst step, silver (Ag) nanoparti-
cles were deposited on surfaces of the wafers by immers-
ing them in aqueous solution of 0.02 M of silver nitrate
(AgNO
3
) and 5 M of HF in the volume ratio of 1:1 for
3060 sec. In the second step, the c-Si surfaces covered
with Ag nanoparticles were immersed in a 50 ml of the
solution containing 5 M of HF and 30% H
2
O
2
in the
J. Nanoelectron. Optoelectron. 2012, Vol. 7, No. 6 1555-130X/2012/7/001/005 doi:10.1166/jno.2012.1401 1
Vol.7, 602-606, 2012
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Growth, Structure and Optical Properties of Silicon Nanowires Formed by Metal-Assisted Chemical Etching Gonchar et al.
volume ratio 10:1 in a teon vessel for time varied from
1 to 120 min. Finally, the samples were rinsed several
times in de-ionized water and dried at room temperature.
A part of the formed SiNW samples could be also washed
in a solution of the concentrated (65%) nitric acid (HNO
3
)
for 15 min to remove residual Ag nanoparticles from the
SiNWs. Figure 1(a) represents schematically step-by-step
the procedure of SiNWs formation.
The morphology and microstructure of SiNWs were
investigated by using a scanning electron microscope
(SEM) of Lyra Tescan and a transmission electron micro-
scope (TEM) of LEO 912 AB OMEGA. The reectance
spectra and composition of SiNW surfaces were measured
by a Fourier-transform infrared (FTIR) spectrometer of
Bruker IFS 66 v/S. The total reectance FTIR spectra were
detected by a Perkin Elmer Lambda 35 spectrophotometer
with an integrating sphere. PL of the SiNWs arrays was
measured in the spectral region of 4001000 nm under
excitation with ultraviolet (UV) radiation of an Ar
+
laser
(wavelength 364 nm, excitation intensity 0.1 W/cm
2
). The
PL was detected by using a grating spectrometer (MS 750,
SOLAR TII) equipped with a CCD unit.
In-vitro experiments were carried out with CF2Th (dog
thymus) cells infected with green uorescent protein
(GFP) gene. Before introducing into the cells, SiNWs were
removed from the c-Si substrate by ultrasound irradiation
(37 kHz, 90 W) and then sterilized by UV lamp irradiation
for 1 h. Prior the bioimaging analysis an inducer RSL-1
was added to the CF2Th culture to cause the synthesis
of GFP. The luminescence wavelength of GFP was near
515 nm (green light). Aqueous suspensions of SiNWs were
introduced into CF2Th culture with 5 hours delay after the
inducer injection. The bioimaging registration was carried
out after the lapse of 25 hours from the SiNW suspension
introduction. Cell nuclei were imbued with 5 jg Hoechst
30 min before the experiment. The luminescence wave-
length of Hoechst is near 460 nm (blue light). Images of
cells containing SiNWs were reordered by using a confo-
cal laser microscope Leica TCS SP5.
3. RESULTS AND DISCUSSION
Figure 1(b) shows typical large-scale cross-sectional SEM
micrograph of a sample with SiNWs. One can see that
SiNWs look like quasi-ordered nano-grass with preferential
orientation along the [100] crystallographic direction. This
fact, which is in agreement with results of Refs. [10, 11],
indicates that the MACE of c-Si in HF-solution is strongly
crystallographic oriented. While the thickness (diameter
size) of SiNWs in their array demonstrates a broad diameter
distribution from about 20 upto 200 nm, for each individual
SiNW the diameter does not vary signicantly along the
nanowire (see Figs. 1(b) and (c)).
The length of SiNW is controlled by duration of the
etching catalyzed by Ag nanoparticles. The latter nanopar-
ticles are clearly visible as shown in Figure 1(c) at the
SiNW/c-Si interface for as-prepared samples. Ag nanopar-
ticles are also present on sidewalls of SiNWs as it can be
seen in the TEM image (Fig. 1(e)). Nevertheless, the silver
contamination in the MACE-grown samples is well known
and it can be even used for long-term antimicrobial prop-
erties of SiNWs,
19
Ag nanoparticles are easily removed
from the SiNW array by washing the samples in HNO
3
as
shown in Figure 1(d).
The inset of Figure 1(e) shows the electron diffrac-
tion pattern measured for the SiNW with Ag nanoparti-
cles shown in TEM micrographin Figure 1(e). The pattern
indicates both the crystalline structure of Ag nanoparti-
cles (bright spots) and partially disordered porous struc-
ture of SiNWs (white diffuse rings). The SiNW sidewall
roughness in nanoscale was early reported in Ref. [10].
Based on our observations the SiNW sidewall nanorough-
ness strongly depends on the doping level of c-Si sub-
strate and on the etching time during MACE. Furthermore,
the additional etching of SiNWS in nitric acid, which is
used to remove Ag nanoparticles, can also increase the
nanoroughness of SiNWs.
Figure 2(a) shows dependence of the SiNW length
measured by SEM on the MACE time. The dependence
demonstrates a power low and it can be tted by the fol-
lowing expression:
L =Ct
o
(1)
where L the SiNW lengths, t is the MACE time, and C
and o are constant coefcients. The coefcient o was cal-
culated from the data presented in Figure 2(a) and it is
accounted 0.75.
The growth rate of SiNWs, V, is found to decrease with
the etching time (Fig. 2(b)). The value of V can be easily
calculated from Eq. (1) as the rst derivative of L:
V =
JL
Jt
=oCt
o1
(2)
The exponent of V(t) dependence is about 0.25 that is
agreement with Eq. (2). The growth rate decrease with
etching time can be explained by diffusion-controlled
transport of uorine ions from the solution to the SiNW/c-
Si interface through the SiNW array. The similar growth
rate lowering is usually observed in electrochemically pre-
pared porous silicon layers.
20
Figures 2(c), (d) shows SEM images of the samples
of SiNWs, which were grown simultaneously from the
both sides on a double-polished c-Si substrates by keep-
ing intentionally two different spatial orientation of c-Si
substrates. In particular, the Earths gravity was along
(Fig. 2(c)) and perpendicular (Fig. 2(d)) to the c-Si surface.
The etching time was 60 min and 80 min, respectively. The
thickness of the SiNWs layer was found almost to be the
same for the both sides of substrates. Therefore, the force
of the Earths gravity doesnt inuence the process of c-Si
MACE and also on the growth rate of SiNWs. This latter
seems to be controlled by diffusive transport of uorine
ions and red-ox processes at Ag/c-Si interface.
6, 18
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Vol. 7, No. 6, 602-606, 2012
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Gonchar et al. Growth, Structure and Optical Properties of Silicon Nanowires Formed by Metal-Assisted Chemical Etching
(a)
(b)
Ag
(c) (d) (e)
Fig. 1. Schematic step-by-step representation of the SiNWs preparation method (a), typical cross sectional SEM images of a sample with SiNW
length of 20 jm (b) and 2 jm with (c) and without (d) Ag nanoparticles, respectively; TEM image of an individual SiNW with Ag nanoparticles
marked by arrows (e). Inset in the panel (e) shows the corresponding electron diffraction patterns.
Fig. 2. Thickness (a) and growth rate (b) of SiNWs versus etching time. SEM micrographs of SiNWs obtained when the force of the Earths gravity
was directed along (c) and perpendicular (d) to the c-Si substrate, respectively.
J. Nanoelectron. Optoelectron. 7, 15, 2012 3
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Growth, Structure and Optical Properties of Silicon Nanowires Formed by Metal-Assisted Chemical Etching Gonchar et al.
0 2000 4000 6000 8000 10000 12000
0
10
20
30
40
50
60
-- 5000 2500 1667 1250 1000 833
Wavelength (nm)
SiNWs/c-Si
Si-Si
R
e
f
l
e
c
t
a
n
c
e

(
%
)
Wavenumber (cm
1
)
Si-O-Si
c-Si
200 400 600 800 1000 1200
1
10
100
SiNWs/c-Si
T
o
t
a
l

R
e
f
l
e
c
t
a
n
c
e

(
%
)
Wavelength (nm)
c-Si
c-Si SiNWs
(a)
(b)
(c)
Fig. 3. Mirror reectance at normal incidence (a) and total reectance spectra (b) of SiNW with L =2 jm (red curves) of double-side polished c-Si
substrate (black curves) as well as a photograph of the corresponding SiNW/c-Si sample together with a centimeter scale (yellow).
Figure 3(a) shows typical optical reectance spectra
of SiNWs (L = 2 jm) and c-Si substrate measured at
normal incidence. The reectance of c-Si substrate demon-
strates the well-known behavior of the double-side pol-
ished wafer, the reection value 40% for the range
500 600 700 800 900 1000
0.0
0.2
0.4
0.6
0.8
1.0
(a) (b)
SiNWs
P
L

I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
.
)
Wavelength (nm)
c-Si
25 m
Fig. 4. (a) PL spectra of a sample of SiNWs (red curve) and c-Si substrate as well as typical image of the SiNW sample under UV laser excitation
(red spot in the center) in inset. (b) Luminescence image of living CF2Th cells with SiNWs. Green, blue, and red colors correspond to the PL of cell
membrane, cell nucleus, and SiNWs, respectively.
of the strong absorption, and for the transparency region
\ >1 jm the reection value increases because of both
side contribution. The reectance of SiNWs decreases
strongly in the high frequency range because of the strong
scattering.
4 J. Nanoelectron. Optoelectron. 7, 15, 2012
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Gonchar et al. Growth, Structure and Optical Properties of Silicon Nanowires Formed by Metal-Assisted Chemical Etching
The spectrum of SiNWs in the infrared region the
absorption peaks of SiOSi stretching vibrations at
1118 cm
1
and impurity-related stretching vibrations at
624 cm
1
.
20
So, the prepared SiNWs are characterized by
mostly silicon oxide termination of the sidewalls. The oxide
surface of SiNWs can obviously ensure their hydrophilic
properties.
Figure 3(b) shows the total reectance spectra of
double-side polished c-Si and SiNWs (L = 2 jm). The
total reectance of c-Si is near 40% for the visible spec-
trum region, opposite to the SiNW sample, which show a
strong decrease of the total reectance below 1%. So, the
light either absorbed in the SiNWs layer or/and transmitted
into the c-Si substrate. A typical photograph of the sample
of SiNW/c-Si with L>2 jm is shown in Figure 3(c). It is
seen that SiNWs surface looks similar to Black silicon.
Note, MACE SiNWs can be easily produced in a large
scale in comparison to the physical approach for the black
silicon formation and it can be used as antireection coat-
ing for solar cells.
The PL spectra of SiNWs consist of a broad band in the
visible range with maximum at 740 nm (photon energy of
1.7 eV) as it is shown in Figure 4. This PL emission is
well explained by the radiative recombination of excitons
conned in small Si nanocrystals at nanowire sidewalls.
10
The nanocrystal size estimated from the spectral position
of the PL peak by using a quantum connement model
21
is 3 0.3 nm. It should be mentioned, that the external
quantum yield of the PL of SiNWs was estimated to be
about 5% and the PL spot under UV excitation could be
easily observed with a naked eye (see inset in Fig. 4).
Figure 4(b) shows a luminescence image of living
CF2Th cells with introduced SiNWs suspension. The red
PL of SiNWs is visible in nearest vicinity of both cells
membranes (stained in green) and nuclei (stained in blue).
This fact indicates that SiNWs could penetrate into the
cells via an endocytosis mechanism.
21
Therefore, SiNWs
can be used as luminescent labels for living cells.
4. CONCLUSIONS
The obtained experimental data on the growth, structure
and optical properties of silicon nanowires prepared by
the Ag-nanoparticle-assisted etching of (100) c-Si wafer
in hydrouoric acid solutions could be used to produce
Si-based nanostructures with desired properties for pho-
tonic and biomedical applications. The growth rate of
SiNWs was found to decrease and the thickness of the
sample depends nonlinearly on the time of etching. The
formed SiNW arrays demonstrate a strong decrease of
the total reectance below 1% in the spectral region of
3001000 nm and the samples look like Black Silicon,
which can be used as anti-reective layer in photonics and
photovoltaics. The prepared SiNWs exhibit efcient PL in
the spectral region of 6001000 nm, which is related to
the radiative recombination of excitons conned in small
Si nanocrystals on SiNW surfaces. SiNWs dispersed in
aqueous solution could penetrate into the living cells and
acted as luminescent labels for bioimaging applications.
Acknowledgments: The work was partially performed
at User Facilities Center of Lomonosov Moscow State
University and supported by the Russian Foundation for
Basic Research (projects Nos. 11-02-90506 and 11-02-
01342) and the Ministry of Education and Science of the
Russian Federation (contracts Nos. 11.519.11.3017 and
16.513.12.3010). Authors thank A. S. Abramchuk and
D. V. Petrov for their help in TEM and SEM measure-
ments, respectively.
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