Enhanced surface-enhanced Raman

scattering performance by folding silver

nanorods
Cite as: Appl. Phys. Lett. 100, 113101 (2012); https://doi.org/10.1063/1.3694056
Submitted: 10 February 2012 . Accepted: 23 February 2012 . Published Online: 12 March 2012

Qin Zhou, Xian Zhang, Yu Huang, Zhengcao Li, Yiping Zhao, and Zhengjun Zhang

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Appl. Phys. Lett. 100, 113101 (2012); https://doi.org/10.1063/1.3694056 100, 113101

© 2012 American Institute of Physics.

 APPLIED PHYSICS LETTERS 100, 113101 (2012)

Enhanced surface-enhanced Raman scattering performance by folding silver

nanorods
Qin Zhou,1,2 Xian Zhang,1 Yu Huang,1 Zhengcao Li,1 Yiping Zhao,3,a) and Zhengjun Zhang1,a)
1
Advanced Materials Laboratory, Department of Materials Science and Engineering, Tsinghua University,
Beijing 100084, People’s Republic of China
2
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084,
People’s Republic of China
3
Department of Physics and Astronomy, Nanoscale Science and Engineering Center,
The University of Georgia, Athens, Georgia 30602, USA

(Received 10 February 2012; accepted 23 February 2012; published online 12 March 2012)
Folding straight Ag nanorods into zig-zag structures could generate corners or bends that become
potential hot spots for surface-enhanced Raman scattering (SERS). Using a dynamic shadowing
growth method, zig-zag silver nanorod arrays of different bending number N with a fixed total rod
length are fabricated, and their SERS performance are measured and compared using the Raman
probe Rhodamine 6G. The SERS intensity increases with N when N < 4 and decreases when
N > 4. The results suggest that folding silver nanorods into three-dimensional structures is a
promising way to design highly sensitive SERS substrates. V C 2012 American Institute of Physics.

[http://dx.doi.org/10.1063/1.3694056]

Recently, silver nanorod (AgNR) arrays have attracted
considerable attentions due to their high performance surface
enhanced Raman scattering (SERS).1–7 In particular, the
aligned AgNR arrays prepared by a simple physical vapor
deposition method, specifically oblique angle deposition
(OAD), have found many applications in chemical and bio-
logical sensing.3,8–12 These AgNR arrays have SERS
enhancement factors greater than 108 with uniform response
across large area4 and can be fabricated into other sensing
devices when combined with other microfabrication techni-
ques.10,13 The main SERS enhancement mechanism for these
AgNR arrays is believed to be the electromagnetic (EM)
mechanism, where the local electric fields between the adja-
cent nanorods, on the tip of the nanorods and in the corner
between the nanorods and Ag film, have been enhanced sig-
nificantly due to the geometry of the nanorod arrays when
excited by incident laser beam.14–16 Clearly, further
improvement of this enhancement through improved nano-
structure engineering is desirable to augment the sensitivity.
The EM enhancement strongly depends on the shape, size,
separation, arrangement of nanostructures, as well as the sur-
rounding dielectric environment; the enormous EM enhance-
ment is believed to originate from the surface locations with
specific nanoscale topologies called “hot spots.” The “hot
spots” are usually topologically singularities on metal surfa-
ces, such as small gaps between two adjacent nano-objects,
corners, or bends. Therefore, it is expected that when the
SERS performance could be tuned when the straight Ag
nanorods are bent. We have recently fabricated two kinds of
bent Ag nanorod arrays, the square helical and L-shaped
nanorod arrays, using the dynamic shadowing growth
method.16,17 For the helical nanorod arrays with fixed arm
length, the SERS intensity was found to increase with the
number of bending,17 while for the L-shaped nanorod array
a)
Authors to whom correspondence should be addressed. Electronic
addresses: zhaoy@physast.uga.edu and zjzhang@tsinghua.edu.cn.
(with only one bend), the SERS intensity increased with arm
length.18 In those studies, the total length of the nanorods
was changed due to the variation of the aforementioned
structuring parameters, which results in two possible side
effects: (1) the surface area of AgNRs is not fixed; it
increases with the arm number for helical structure and with
arm length for L-shaped nanorods. Such a change makes it
hard to predict the surface coverage of the Raman probes;
and (2) the thickness of the nanostructured film also varies;
such a change in film thickness makes one to consider the
role of film thickness plays in the observed SERS change, as
demonstrated by our previous works.19–21 Therefore, a direct
comparison of the SERS intensity could not accurately reveal
the effect of the structure design on SERS performance. A
better comparison is to fix the total length of the nanorods,
and change the number N of bendings along the nanorods. In
this Letter, we have fabricated zig-zag AgNR arrays with dif-
ferent numbers of bendings but fixed the total length of the
nanorods. Their SERS performance has been characterized
by Rhodamine 6G under the same sampling and measure-
ment conditions. We observe that the SERS intensity
increases with N when N  4 and decreases when N > 4.
The zig-zag AgNRs are fabricated by the dynamic shad-
owing growth (DSG) method.16,17,22 DSG is a physical vapor
deposition method that can produce metal nanostructured
films by simply manipulating the deposition angle and thick-
ness during deposition. In an electron-beam evaporation sys-
tem, glass substrates pre-cleaned with acetone and ethanol
were mounted on a substrate holder controlled by two step-
per motors, with the substrate surface normal forming an
angle h ¼ 85 with respect to the vapor incident direction.
After the background pressure of the chamber reached
1  105 Pa, Ag (99.99%, purchased from Institute of Non-
ferrous Metals of China) was evaporated at a rate of 0.5 nm/
s. The thickness and deposition rate of Ag were monitored
by a quartz crystal microbalance (QCM) directly facing the
vapor source. To realize zig-zag structures, we programmed

0003-6951/2012/100(11)/113101/3/$30.00 100, 113101-1 C 2012 American Institute of Physics

V
113101-2 Zhou et al. Appl. Phys. Lett. 100, 113101 (2012)

the azimuthal rotation of the substrate and the deposition

thickness repeatedly with the following two steps: step#1—
depositing AgNRs with a fixed QCM reading value t;
step#2—stopping deposition, letting the substrates cool
down, and then rotating the substrates 180 azimuthally.
Repeating above two steps N þ 1 times, one can obtain N-
bending zig-zag AgNR arrays. In our experiments, the total
QCM thickness T was fixed to be 2160 nm; thus, for each
deposition cycle, t ¼ T/(N þ 1), and N varied from 0 to 7.
The larger N leads to shorter arm length. The actual thick-
ness and arm length of AgNRs are different from the QCM
reading due to the geometric shadowing effect.
The morphologies of the AgNR arrays were character-
ized by a scanning electron microscope (FEI QUANTA
200FEG). The SERS spectra were measured with a FIG. 2. (Color online) The log-log plots of the arm length l, total length L,
Renishaw Raman 100 spectrometer using a 633 nm Arþ and arm aspect ratio c of zigzag Ag nanostructures versus bending number
N þ 1. The linear curves give the best fitting.
laser, 3 mW power, and 30 s integration time. The zig-zag
AgNR samples were dipped in a 1  106 M solution of shows almost a constant relationship with L ¼ 655 6 50 nm,
R6G in distilled water for 30 min and dried with a continuous while both l and c decrease monotonically with N þ 1. In Fig. 2,
gentle nitrogen blow before SERS measurements were both l and c has a linear relationship with N þ 1 in log-log
acquired. scale, i.e., l ! (N þ 1)a and c ! (N þ 1)b. The fitting gives
The typical SEM images of zig-zag AgNRs are shown a ¼ 0.96 6 0.02, and b ¼ 0.92 6 0.05. Since L can be approxi-
in Fig. 1. All the zig-zag shaped nanorods with different N mated as a constant, one can roughly obtain l ¼ L0/(N þ 1)
are well separated, and the thickness of all samples is very
similar. From Fig. 1, we can obtain the arm length l, the total
rod length L (¼ (N þ 1)*l), and aspect ratio of the arm
c (¼ l/D, where D is the diameter of the nanorods), and plot
them in log-log scale against N þ 1 in Fig. 2. The L versus N

FIG. 1. SEM images of zigzag Ag nanostructures with different bending
number: (a) N ¼ 0; (b) N ¼ 1; (c) N ¼ 2; (d) N ¼ 3; (e) N ¼ 4; (f) N ¼ 5; (g)
N ¼ 6; and (h) N ¼ 7, respectively.
FIG. 3. (Color online) (a) R6G SERS spectra obtained from zigzag shaped
Ag nanostructures with different bending number N; (b) The plot of experi-
mental Raman intensity as a function of bending number N at Raman shift
Dv ¼ 611 cm1. The spectra in (a) are artificially offset to better demonstrate
the intensity change.
113101-3 Zhou et al. Appl. Phys. Lett. 100, 113101 (2012)

FIG. 4. (Color online) Folding nanorod into

zigzag shape to increase the amount of “hot
spots.”

and c ¼ c0/(N þ 1), which are consistent with the fitted strates that bending the Ag nanorods appropriately can
results. greatly enhance their SERS performance.
Figure 3(a) shows the representative R6G SERS spec-
tra obtained from the zig-zag Ag nanorods with different Q.Z., X.Z., Y.H., Z.C.L., and Z.J.Z. are grateful to the fi-
N. Each spectrum is an average of at least 5 different nancial support by China Scholarship Council and the
spectra taken at different spots on the substrates. All the National Natural Science Foundation of China (50931002).
spectra show the characteristic peaks of R6G at Dv ¼ 612, Y.P.Z. is supported by National Science Foundation (Grant
774, 1180, 1311, 1361, 1511, 1575, and 1648 cm1, No. ECCS-1029609). The authors also thank Justin Abell for
respectively.23 To quantitatively compare the SERS proof reading the manuscript.
response of these substrates, the Raman peak intensity I611 1
E. A. Wachter, A. K. Moore, and J. W. Haas, Vib. Spectrosc. 3(1), 73
at Dv ¼ 611 cm1 is plotted versus N in Figure 3(b), and (1992).
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13
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16
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19
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20
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22
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24
spots” contribute to SERS intensity. This result also demon- Z. Y. Zhang, Ph. D. dissertation, University of Georgia, 2009.