Author's personal copy
Plasmonics (2013) 8:13–23
DOI 10.1007/s11468-012-9371-3
A Shape-Engineered Surface-Enhanced Raman Scattering
Optical Fiber Sensor Working from the Visible
to the Near-Infrared
Antonino Foti & Cristiano D’Andrea &
Francesco Bonaccorso & Maurizio Lanza &
Giuseppe Calogero & Elena Messina &
Onofrio Maria Maragò & Barbara Fazio &
Pietro Giuseppe Gucciardi
Received: 20 February 2012 / Accepted: 23 May 2012 / Published online: 24 June 2012
# Springer Science+Business Media, LLC 2012
Abstract Surface-enhanced Raman scattering (SERS) takes
advantage of the giant electromagnetic field enhancement
provided by localized surface plasmons in metal nanoparticles
to amplify the weak Raman scattering of the molecules. Op-
tical fibers coated with noble metal nanoparticles can therefore
be used as SERS-based sensors for remote detection of mo-
lecular species. In this article, we report on the development of
an optical fiber SERS sensor capable to operate on a range of
excitation wavelengths from the visible to the near-infrared.
We introduce a quasistatic chemical etching protocol to engi-
neer the tip shape and investigate the effects of the tip shape on
the sensor performances.
Keywords Surface-enhanced Raman scattering . Molecular
detection . Label free detection . Optical fiber sensors
Introduction
Surface-enhanced raman scattering (SERS) is a process that
strongly amplifies the weak Raman signal of molecules
adsorbed on metal nanostructures [1, 2]. Such a large
A. Foti : C. D’Andrea : F. Bonaccorso : M. Lanza : G. Calogero :
E. Messina : O. M. Maragò : B. Fazio : P. G. Gucciardi (*)
CNR-Istituto Processi Chimico-Fisici,
Viale F. Stagno D’Alcontres 37,
98158 Messina, Italy
e-mail: gucciardi@me.cnr.it
F. Bonaccorso
Department of Engineering, University of Cambridge,
Cambridge CB3 0FA, UK
enhancement (∼108–1014) is provided by the resonant, col-
lective excitation of free-conduction electrons in metal
nanoparticles (NPs) or colloidal aggregates, the so-called
localized surface plasmons (LSP) [3–5].
Since the nineties SERS-active nanoparticles have been
coupled with optical fibers in order to develop new concepts
of SERS optical fiber sensors (SERSORS) [6]. SERSORS
provide a safe technique to remotely analyze toxic or poten-
tially harmful molecules in hazardous environments [7–9],
allowing one to detect small quantities (µg/mL) of chemical
and biological molecules [10] without any sample prepara-
tion and with short acquisition times (tens of seconds). For
these reasons, SERSORS can be used in the medical field, in
order to detect proteins [11] and biomarkers of specific
diseases [12], or as high-sensitive control system of concen-
tration of toxic molecules in the environment or in food
products [13].
In literature, different concepts of SERSORS have been
developed, together with methodologies to improve their mo-
lecular sensitivity [6, 8, 14–17]. Reference [6] proposed the
use of two fibers, one to deliver the excitation laser beam to an
external SERS-active substrate (on which the target molecules
are adsorbed) and the other to collect the scattered radiation, in
a head-on configuration. In the so called optrode configura-
tion [16], the fiber apical part is coated with optically resonant
metal nanoparticles, acting as a SERS-active element to en-
hance the signal of the target molecules directly adsorbed on
its surface. This configuration is much more compact and
better suited for operation in microenvironments of difficult
access. SERSORS can work either in liquid or in a dip and dry
configuration [14]. In the first case, the signal is acquired
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14
during the immersion of the fiber tip in the liquid containing
the target molecules. In the second case, the fiber is immersed
in the target solution, but the signal acquisition is carried out
after removal and evaporation of the liquid in which the mol-
ecules are dispersed. The fiber geometry strongly affects the
sensitivity of the SERSORS. Shaping the fiber apex as a tip,
e.g., increases the number of SERS photons trapped into the
fiber, improving the sensitivity [17]. SERSORS with conical
tips have been produced by abrasive roughening [16], single
[17] or double-static [14, 18] chemical etching processes.
To date, SERSORS have been produced employing silver or
gold NPs evaporated directly on the fiber surface [13, 16–18],
or adsorbed on the fiber by immersion in colloidal NP disper-
sions [13–15, 19]. The adhesion of the NPs onto the fiber
surface is obtained thanks to cross-linker molecules, as alumina
[8, 16] or organic polymers [14, 15, 19]. In SERS, the signal
amplification is maximum when both the excitation and the
scattered radiation energies are close to the LSP resonance
energy of the metal nanostructures [20–23]. The LSP energies
are different for silver and gold NPs, ranging from the visible to
the near-infrared (NIR) [24]. The excitation wavelength is
therefore a crucial parameter to play with for the optimization
of the SERSORS sensitivity. Moreover, the choice of the
“right” wavelength permits to match the electronic resonances
of the target molecules in order to exploit resonant Raman
scattering effects [25] to further boost the signals (102–103).
Finally, the excitation wavelength also affects the intensity of
the intrinsic fiber background signal, one of the major obstacles
to extend the operational range of optical fiber sensors below
1,000 cm−1 [14]. Varying the laser wavelength can therefore
improve the SERS signal-to-background ratio. The develop-
ment of SERS fiber sensor operating over a wide range of
wavelengths could, therefore, open new ways towards the
optimization of the sensitivity and the minimization of the fiber
background signal. To the best of our knowledge, however, all
the sensors developed to date [10–19] have been tested with
only one excitation wavelength, and no comparative studies on
the performances at different excitation wavelengths have been
reported. In this paper, we report on the development of a
broadband optical fiber SERS sensor for molecular sensing
with excitation ranging from the visible to the NIR (515, 633,
and 785 nm), whose shape is engineered by a new quasistatic
chemical etching protocol.
Fabrication of the SERSORS
The key elements to take in consideration when designing a
SERS fiber sensor are: (1) nature, morphology, and aggregation
state of the metal NPs exploited to induce the SERS effect; (2)
the optical fibers to be used (single mode, multimode, length,
and shape); (3) the experimental configuration used to acquire
and analyze the signals (spectrometer, laser wavelength, power,
Plasmonics (2013) 8:13–23
and light-to-fiber injection configuration). In the following
paragraphs, we analyze and describe the choice of each of these
elements for a sensor capable to operate from the visible to the
NIR.
Silver Colloids: Synthesis, Morphology, and Plasmon
Resonances
Silver colloids are prepared by using a modified Lee and Meisel
procedure [14, 26]. Two hundred milligrams of silver nitrate
(99.5 %; Sigma-Aldrich) are dissolved in 500 ml of distilled
water and brought to boiling. Afterwards, 20 ml of trisodium
citrate solution (Sigma-Aldrich, 3 %) is added, and the mixture
is kept boiling for 1 h. The mixture is then placed in a closed
flask and stored in a dark environment for 1 month. During this
period, a gravitational separation occurs among the silver NPs in
the mixture. Lighter particles, floating at the top of the dispersion
as a transparent supernatant (an aliquot is shown in left vial in
Fig. 1a), are separated from the denser layer of aggregated
particles which deposits at the bottom of the flask. This is due
to the difference in sedimentation coefficients between small
and large and/or aggregated NPs. The same principle has been
exploited for the separation of nanomaterials (0D, 1D, and 2D)
in centrifugal fields [27, 28]. The layer of aggregated NPs is
transferred with a pipette to a smaller flask and undergone to a
further week of gravitational separation. We end up, again, with
a yellow transparent top supernatant (central vial of Fig. 1a) and
an ultraconcentrated silver colloidal dispersion at the bottom of
the flask (an aliquot is shown in the right vial of Fig. 1a). Due to
the presence of a large number of SERS-active silver colloidal
aggregates, this is the fraction that we extract and use for the
realization of the SERS sensors (vide infra).
Extinction spectra on the top fractions extracted from the first
and second gravitational separations have been acquired with a
standard UV-VIS setup (Perkin Elmer, Lambda-20) and display
LSP resonance peaks at 414 nm (Fig. 1b, black line) and 427 nm
(Fig. 1b, red line), respectively, indicating the abundance of
individual nanoparticles of different diameter [24, 29]. Compar-
ing the measured peak position with the specifications of com-
mercial (Sigma-Aldrich) silver nanoparticles in aqueous buffer
[30], we can estimate NPs diameters between 20 and 30 nm in
the first case, and 40 nm in the second. The bottom layer was too
dense (optically) to be analyzed by conventional in-liquid UV–
VIS techniques. A drop of NPs has been, therefore, spin cast on
a glass substrate, allowing us to use the Xenon lamp embedde in
the the Raman microspectrometer (LabRAM HR800) as light
source, and the microspectrometer itself as detector, to acquire
extinction spectra from spots ca. 100 μm in diameter. The
spectrum in Fig. 1c suggests the presence of both individual
nanoparticles (the single resonance peak at 445 nm corresponds
to NPs with diameters between 50 and 60 nm [30]) and large
colloidal aggregates yielding the broad resonance band from
530 nm to over 700 nm [24, 29, 31, 32].
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Fig. 1 a Pictures of silver colloids extracted from the top supernatant
layers after the first (left vial) and second (middle vial) gravitational
separation, and (right) from the dense bottom layer of the final disper-
sion. b Extinction spectra of the top fractions after the first (black) and
second (red) gravitational separation steps. c Extinction spectrum of a
dried drop of silver colloidal aggregates extracted from the bottom of
The extinction measurements have been correlated with
scanning electron microscopy (SEM) images in order to evalu-
ate the silver NP dimensions. SEM has been carried out on NP
dispersions droplets, deposited on a silicon substrate, after sol-
vent evaporation. As shown in Fig. 1d, top part of the dispersion
is rich in individual silver particles with a diameter below 50 nm
with some small aggregates few hundred nanometers wide,
likely formed during the evaporation of the solvent. The bottom
fraction, instead, is characterized by the presence of fractal
aggregates (Fig. 1e) tens of micrometers wide. These aggregates
feature a high density of hot spots. Hot spots in random metal-
on-dielectric films have been attributed to Anderson localization
of surface plasmon modes and yield giant fluctuations of local
electric fields at the nanometer scale [33]. At the hot spots, the
local fields are much greater than the applied one and are
assumed to be responsible for SERS amplification [24, 33–35].
Optical Fibers: Etching, Capillary Phenomena, and Shape
Engineering
Chemical Etching of Silica Fibers
To engineer the shape of the optical fiber sensor, we exploit
chemical etching methods [14, 15] already developed in our
labs for the fabrication of probes [36, 37] for scanning near-
field optical microscopy [38–41]. We use the so-called
15
the final dispersion (the red line is an interpolation of the rough data).
SEM images of silver colloids cast on a silicon substrate: d aliquot
extracted from the top supernatant fraction rich in individual silver
nanoparticles; e aliquot extracted from the bottom fraction, showing
large fractal colloidal aggregates
Turner-etching process [42]. In this method, the first step
relies in the removal of the polymeric jacket by mechanical
stripping. The nude fiber is then immersed in a hydrofluoric
acid (HF) solution covered with a layer of isooctane (Fig. 2a).
This layer is essential to prevent the corrosion of the part of the
fiber not immersed in the HF solution. HF is an acid not
completely dissociated in water ([H+][F−]/[HF] 06.85 ×
10−4 l/mol). HF is also present in dimer form H2F2 ([H2F2]/
[HF]2 02.7 l/mol), and the dimers can lose a proton yielding
HF2− ions ([HF2−]/[HF][F−]03.963 l/mol) [43]. In the etching
of SiO2, the Si–O bond is broken and exchanged with a Si–F
one. Therefore, the concentrations of all the H+, HF, and HF2−
ions are important. The reaction occurs in two steps [43]:
Si ! O ! X þ Hþ !Si ! OðHÞþ ! Xðwhere X ¼ Si or HÞ ð1Þ
Si ! OðHÞþ ! X þ HF2 ! !Si ! F þ HO ! X þ HFðwhere X ¼ Si or HÞ
ð2Þ
The group HO−X is soluble and stable in water. The
reactions 1 and 2 are pH-dependent, and each one is dom-
inant in a specific pH range [43]. The first reaction, howev-
er, determines the velocity of the overall process, which, in a
first approximation, will be proportional to [H+].
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Capillarity Phenomena and Tip Formation Mechanisms
When the fiber is immersed in the HF–isooctane, which is
an immiscible mixture, two different etching processes start
simultaneously [44, 45]: the bulk etching, taking place in the
bulk HF fluid (green zone in Fig. 2b), and the meniscus
etching, occurring at the HF–isooctane–fiber interface (cir-
cled zone in Fig. 2b). The two processes proceed on differ-
ent time scales and give rise to two different tips shapes. In
bulk, the lateral attack of HF on the fiber sidewalls, com-
bined with a slight etching rate gradient (higher at the
bottom because of the larger silica surface exposed to the
acid), leads a sharp and long tip (cone angle ∼5°, length in
the millimeter range). Conversely, tip resulting from the
meniscus etching is much shorter (hundreds of micrometers)
since its formation is driven by the lowering of the HF–
isooctane meniscus [36] generated by the capillarity forces
at the interface. The meniscus height h (inset in Fig. 2b) is
related to the radius of the fiber (r0) by [46]:
! "
4a
h ffi r0 cos θc ' log ! Γ Euler ð3Þ
r0 ð1 þ sin θc Þ
Where θc is the contact angle (inset in Fig. 2b), ΓEluer ∼
pffiffiffiffiffiffiffiffiffiffi
0.577 the Euler constant, and a ¼ σ=ρg the capillary
constant related to σ, ρ, and g being, respectively, the
surface tension, the density of the liquid, and the gravity
acceleration constant. We can figure out the tip formation
dynamics at the meniscus as follows: HF attacks the fiber in
bulk reducing its radius r(t) and, according to Eq. 3 lowering
the meniscus height h(t). As the meniscus lowers, the iso-
octane layer covers the etched part, preserving it from fur-
ther corrosion and generating the conical shape of the tip.
The meniscus etching self-terminates when the fiber in bulk
is completely etched and the conical tip is totally shaped
inside the isooctane layer.
Lateral Shaping of the SERSOR
To fabricate our sensor, we have used FOS (Fibre Ottiche
del Sud) silica–silica multimode fibers with an inner core
diameter of 50 μm and an outer cladding diameter of
125 μm. Such a large core diameter permits to easily launch
laser beams of different wavelengths with the same micro-
scope objective. On the other hand, the core is sufficiently
small (e.g. with respect to the 200-μm core fibers) to allow
us to effectively collect the backscattered light emerging
from the entire core area. For the etching process, 50 ml of
solution is prepared in a Teflon beaker using 46 ml of HF
aqueous solution (50 %) covered by 4 ml of isooctane.
Optical fiber pieces ∼1 m long are used. About 3 cm of
external polymeric jacket is mechanically removed. The
stripped part is cleaned with ethanol and immersed in HF
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[14, 15]. The fiber is initially etched for a time interval T1 ∼
24 min. After the clad has been totally removed the fiber is
moved upward of 2 mm via a micrometer screw (Fig. 2c)
and kept in this position until the complete etching of the
fiber in bulk, which occurs a few minutes later (Fig. 2d).
The fiber is then removed and washed with ethanol (96 %)
to eliminate the residual material. We end up with double-
taper fibers shown in Fig. 2e.
Best sensor performances are expected when the SERS-
active colloids are in direct contact with the fiber core (so to
be directly excited by the laser light), and when the core
lateral surface coated with the nanoparticles is maximal. In
order to fulfill such conditions, the control on the experi-
mental parameters is of key importance. The initial etching,
in fact, must be stopped just after the cladding has been
totally removed (etching time T1), hindering subsequent
attacks of the fiber core that would reduce its lateral surface.
To experimentally determine T1, we etch a single piece of
fiber, several centimeters long, retracting it by ∼1 mm every
5 min. Such a procedure yields a multi-tapered fiber, which
we use to determine the diameter Vs time dependence
plotted in Fig. 2f (black symbols). The fiber diameter is
observed to decrease linearly with time, well fitted by the
relation dðtÞ ¼ d0 ! ad ( t (red line), where d0 0125 μm is
the cladding diameter and ad 0(3.15±0.03)μm/min is the
etching rate retrieved from the fit of experimental data.
The exact etching time T1 (24 min) is thus determined by
the intercept between the linear fit curve d(t) and the core
diameter value d 0dc 050 μm (horizontal black line in
Fig. 2f).
Shaping of the SERSOR Tip by Quasistatic Etching
Equation 3 determines the height, h, of the meniscus, and
therefore, of the tip formed after the meniscus etching.
h depends on a, θc, and d0 02r0. For a liquid–fluid immiscible
binary mixture, the capillarity constant is approximated by the
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
expression a ) ðσa ! σb Þ=ðρa ! ρb Þ [47]. In our case,
σHF ∼58 dyn/cm, ρHF ∼1.155 g/cm3, σiso ∼18 dyn/cm, and
ρiso ∼0.691 g/cm3 [48, 49]. Thus, for the HF–isooctane mix-
ture, a is ∼4 mm. From Eq. 3, tip heights between 200 and
310 μm are, therefore, expected for contact angles in the 0–π/
4 range (Fig. 3a). These values are in agreement with those
observed experimentally. In the following, we show how it is
possible to extend this range in a controlled manner. This is
accomplished by a micrometric change of the fiber vertical
position during the etching process, in a quasistatic fashion,
accomplished by means of a micrometer screw. The results are
shown in Fig. 3b–d. The first two tips (Fig. 3b, c), featuring
lengths of 380 and 290 μm, have been obtained by retracting
the tip at steps of Δz010 μm every Δt05 and 10 min,
respectively. The third tip (Fig. 3d) is ca. 210 μm long and
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Plasmonics (2013) 8:13–23
Fig. 2 Experimental setup for the shaping of the optical fiber by the
Turner chemical etching method. The fiber is stripped and immersed in
a HF–isooctane mixture. The immersion depth is controlled via a
micrometer screw. b–d Etching dynamics during the etching process.
Upon the immersion of the fiber in the HF–isooctane, a meniscus forms
at their interface (circled in b) having height h and contact angle θc (inset).
The HF attacks the sidewall of the fiber reducing its diameter and
has been fabricated by pushing the fiber towards the liquid
surface at steps of Δz0−10 μm every Δt010 min. Quasistatic
etching techniques allow one to vary the length of the tip by
more than 180 %.
From a theoretical point of view, when a small fiber
is immersed in a nonviscous fluid, the meniscus rises on
pffiffiffiffiffiffiffiffiffiffiffi
time scales of the order of t ) 2:2 ' ρr03 =σ [46]. For
the HF–air interface, τ∼100 μs, i.e. the meniscus rises
almost immediately to its equilibrium position h, given
by Eq. 3. This means that we should not be able to
significantly vary the meniscus position when moving
the fiber up and down since the meniscus should im-
mediately (100 μs) relax on its equilibrium position. To
explain why we can drag up and down the meniscus
during the quasistatic etching process, i.e. on time
scales of tens of seconds, we observe that two phenom-
ena bring us far from the ideal situation assumed in
[46], during the etching process. First, the presence of
isooctane, a viscous fluid [49], on top of HF can slow
down the meniscus rise time by orders of magnitude
[46]. Second, the presence of a non-negligible surface
roughness induced by the chemical attack can induce
meniscus pinning effects [50]. The meniscus, i.e., pins
at local surface defects allowing us to drag it during the
fiber vertical movement. The combination of these two
17
lowering the meniscus height (b). After the cladding is etched away, the
fiber is retracted by ca. 2 mm (c). The etching process terminates (d) when
the fiber core is totally etched, and the final tip is formed inside the
isooctane layer. (e) Picture of the doubly tapered fiber. f Plot of the fiber
diameter Vs time during the etching in bulk. The red line is a linear fit.
The black lines indicate the core diameter value (horizontal) and the T1
etching time (vertical)
processes results in a variation of the effective meniscus
height and, consequently, of the final tip length.
Integration of the SERSORS
In order to operate in liquid environment, any detach-
ment of the metal nanoparticles from the SERSOR
surface must be avoided upon immersion in the target
molecules’ dispersion. Several methods to link silver
nanoparticles on glassy materials like silica optical
fibers have been developed [13–19]. For our purpose,
we have employed a conventional procedure capable to
maximize the surface coverage that exploits the polymer
3-aminopropyltrimethoxysilane (APTMS) [13–15, 19].
The polymer acts as a linker, sticking to the optical
fiber from one side and to silver colloids from the
other, playing the role of glue between them (see sche-
matic in Fig. 4a). To this aim, the fiber is dipped in an
APTMS solution (5 % v/v APTMS, 90 % v/v methanol,
and 5 % v/v distilled water) for 15 min, washed in
methanol, and heated at 90 °C for 30 min; then, it is
immersed in the highly concentrated silver colloidal
suspension (bottom fraction) for 48 h. In Fig. 4b is
shown an optical image of the fiber sensor, surface,
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18 Plasmonics (2013) 8:13–23

Fig. 4 Schematic (a) and optical microscopy image (b) of the SERS
fiber sensor. Silver colloids are linked to the walls of the shape-
engineered fiber by using APTMS

collected through the same objective, spectrally ana-

lyzed (600 lines/mm grating), and detected by a CCD
(JY Synapse).

Fig. 3 a Theoretical value of the meniscus height Vs contact angle for a

125-μm diameter optical fiber immersed in a HF–isooctane binary mix- Multiwavelength Operation of the SERSORS
ture. b–d Images of tips produced by quasistatic etching. By retracting
the fiber out of the HF–isooctane immiscible binary mixture at steps of
10 μm every 5 (b) and 10 min (c), we obtain tips with heights of 380 and SERS Activity of the Silver Colloids and Enhancement
290 μm, respectively. Shorter tips (210 μm) are obtained by pushing Factor Evaluation
down the fiber towards the HF–isooctane immiscible binary mixture at
steps of 10 μm every 10 min (d)
Preliminarily, we have checked the SERS activity and
evaluated the enhancement factor of the silver col-
loids. In doing this, we use Rhodamine 6G (R6G), a
and tip, covered by a layer of silver colloids and ready standard molecular probe for SERS [4, 51] featuring
to be used as SERSOR.

Experimental Configuration for SERSORS Operation

Our sensor operates in the optrode configuration. SERS

sensing is accomplished by coupling the shape-
engineered, silver NP-coated optical fiber to a Raman
spectrometer (Horiba Jobin-Yvon Labram HR800)
equipped with three different excitation laser wave-
lengths: Ar+ ions line at 514 nm, He–Ne line at
633 nm, and diode laser at 785 nm (Fig. 5). Each laser
beam is launched into the fiber by means of the same
microscope objective (Olympus 10X, N.A. 0.25). The
sample inspection camera embedded in the spectrometer Fig. 5 Schematic representation of the apparatus for the SERS optical
fiber sensor operation. The fiber is coupled to a multiwavelength
allows us to easily localize and focus the laser spot on excitation (515, 633, and 785 nm) Raman spectrometer working in
the fiber core, achieving maximum coupling efficiencies backscattering configuration. The fiber sensor is dipped in the target
>90 %. The SERS scattered light from the fiber is solution and then dried in air
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Plasmonics (2013) 8:13–23
resonant Raman excitation at 515 nm [52]. A solution
of R6G at concentration of 10−4 M in H2O has been
mixed to the ultraconcentrated silver colloidal suspen-
sion in a 1:1 v/v volume ratio. A drop of the obtained
mixture has been drop cast on a microscope slide and
dried in air, then placed under the spectrometer and
analyzed with a 100X objective. Figure 6a shows a
picture of the sample after solvent evaporation. Large
NP aggregates are visible, alternated to void regions.
At 515 and 633 nm, we measure a nonnegligible
signal IRaman even from the void regions (Fig. 6b, blue
line), suggesting the presence of R6G stuck to the
glass substrate. This signal can be used as a reference
to experimentally estimate the SERS enhancement factor
(EF) provided by the silver colloids. The EF can be
calculated [4] as the ratio between the SERS, measured
on the colloidal aggregates (Fig. 6b, red line), and the
Raman signal intensities (ISERS and IRaman), normalized
to the number of probed molecules (NSERS and NRaman),
Fig. 6 a Optical image of a R6G-colloids mixture after evaporation of
the water solvent. b Raman (blue line) and SERS (red line) spectrum of
R6G excited at 633 nm, acquired outside and inside the silver aggregates,
respectively
19
Fig. 7 Background signal of the SERSORS measured at 515 (green), 633
(red), and 785 nm (brown). Laser power, 8–10 mW; integration time, 1 s
the excitation powers (PSERS and PRaman), and integration
times (TSERS and TRaman) used in each measurement, i.e.,
ISERS =ðNSERS ' PSERS ' TSERS Þ
EF ¼ ð4Þ
IRaman =ðNRaman ' PRaman ' TRaman Þ
The number of probed molecules, N, is the product
between the laser spot area and the molecular surface
coverage (number of molecules per unit area). With
probing areas located only a few tens of microns apart
(Fig. 6a), it is reasonable to assume an almost equal
surface coverage of R6G molecules for both measure-
ments “on the aggregate” and “out of the aggregate.”
We use the same objective for both Raman and SERS
measurements, i.e., we can assume same probed areas
and, consequently, NSERS ∼NRaman. Figure 6b shows the
Raman (blue line) and SERS (red line) spectra of R6G
carried out at 633 nm, a wavelength at which R6G is
not resonantly excited. The Raman reference measure-
ment required 8 mW of power and 10 s of integration
while the SERS spectrum has been acquired with
640 nW, integrating 10 s. At 633 nm, we therefore
calculate EF 633 ∼106 for the R6G modes at 1,366,
1,513, and 1,651 cm−1. Comparable SERS intensities
are obtained at 515 nm, while at 785 nm, the SERS
signal is ca. 100 times weaker (although it is still
possible to detect a strong R6G SERS signal with
2 μW and with integration times of 10 s). At 515 and
785 nm excitation wavelengths, it has not been possible
to obtain a distinct reference Raman signal. At 515 nm,
it was due to the broad fluorescence band of R6G,
while at 785 nm, the signal was too noisy. In the latter
case, however, we can exploit the noise signal as a
reference to estimate a lower limit of the EF. Calling
INoise the noise level in the Raman spectrum of R6G
(we consider the RMS value of the signal) measured
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20
when shining a laser power PRaman and integrating for
an interval TRaman, a lower limit for the enhancement
factor can be calculated considering that IRaman ≤INoise,
thus obtaining
ISERS =ðPSERS ' TSERS Þ
EF ð5Þ
INoise =ðPRaman ' TRaman Þ
In our case at 785 nm using P Raman 011 mW and
TRaman 0300 s, we find EF785 >5×104.
Background Signal
One of the limitations in SERS optical fiber sensors is
the presence of an inaccessible spectral zone at low
Fig. 8 a SERS signal of R6G from the sensor (dark green) vs back-
ground (light green) for 515 nm excitation (spectra are offset for
clarity). b Zoom on the 1,000–1,730 cm−1 range. The SERS signal
from the fiber sensor (light green, P09.2 mW, T030 s) is compared,
after subtraction of the background, to the spectrum acquired on the
metal aggregates drop casted on glass (dark yellow, P08.2 μW, T01 s).
c SERS signal of R6G from the sensor (red line, P08 mW, T01 s) with
Plasmonics (2013) 8:13–23
energies (< 900 cm−1) in which the signal is dominated
by a strong background coming from stimulated Raman
scattering of the silica fiber [53]. Determining the spec-
tral shape of the background, however is important
since we can use this information to subtract it from
the SERS signal and retrieve the Raman scattering from
target molecules. In Fig. 7, we show the background
measured at 515 (green), 633 (red), and 785 nm
(brown), acquired on the “as fabricated” sensor, i.e.,
before immersion in the target molecules’ dispersion.
At 515 and 785 nm, we see an intense band peaked
at 425 cm−1 with a tail extending towards 900 cm−1,
vanishing from 1,300 cm−1 onward. SERS detection
with the optical fiber sensors is, therefore, hindered
for molecules having Raman-active vibrations at wave-
633 nm excitation, after background subtraction, compared to the
SERS of R6G from the colloids drop casted on glass (gray line, P0
6 μW, T01 s). d SERS signal of R6G from the sensor exciting at
785 nm, after background subtraction (hollow symbols, P010.7 mW,
T0120 s), compared to the SERS from the colloids cast on glass (black
line, P02 μW, T010 s)
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Plasmonics (2013) 8:13–23
numbers lower than 900 cm−1, while good performances
are expected in the range above 1,300 cm −1 . At
633 nm, the background extends to energies higher than
1,800 cm−1. We have checked that this additional signal
arises from the specific model of fibers used and not
from the silver nanoparticles linked to the fiber apex.
Test of the SERSORS at Different Excitation Wavelengths
The performances of our SERSORS have been checked in a
“dip and dry” configuration. The metal-coated part of the
SERSORS is dipped in a solution of R6G 10−6 M in H2O
for 4 min and then dried in air. Measurements at 515 nm have
been carried out launching 9.2 mW into the fiber and setting
an integration time of 30 s. The R6G signal (Fig. 8a, dark
green) clearly emerges from the silica background (Fig. 8a,
light green) only in the 900–1,700 cm−1 range (spectra are
offset for clarity). The detected R6G signal at 515 nm benefits
of a further resonant Raman amplification and shows SERS
peaks superimposed to an enhanced fluorescence band.
Figure 8b highlights the correspondence of the R6G vibra-
tional peaks detected through the fiber sensor (light green)
with the SERS signal measured on the silver colloids (dark
yellow), after subtraction of the silica background. Excitation
at 633 nm gives interesting results, although with the presence
of a much stronger background (Fig. 7, red line), we detect a
clear SERS signal of R6G in the 1,150–1,700 cm−1 range
(Fig. 8c, red line) with only 1 s integration time (P08 mW).
Comparison with SERS of R6G deposited on the colloids
drop casted on glass (Fig. 8c, gray line) confirms that the
signal detected with the fiber sensor is actually the vibrational
fingerprint of R6G. We remark that R6G is not resonantly
excited at 633 nm; nevertheless, a signal comparable to the
one at 515 nm is observed. The sensor has been finally tested
at 785 nm. We show in Fig. 8d (hollow symbols are the rough
data, the red line is a Savitzky–Golay smoothed curve) the
SERS spectrum of R6G probed by the fiber sensor using
10.7 mW of power and integrating 120 s. Again, the most
intense peaks are in agreement with SERS from colloidal
nanoparticles casted on glass (Fig. 8d, black line). Although
at this wavelength the sensor is ca. two orders of magnitude
less efficient than at 633 nm, our measurements show that it
can indeed be operated for molecular sensing in the NIR.
Influence of the Tip Cone Angle
We have investigated the influence of the tip geometry on the
sensor efficiency by developing SERSORS with different cone
angles. The SERSORS have been etched, functionalized, and
coated with metallic colloids in parallel processes, in order to
reduce systematic errors. In the first etching step, we pull out
the fibers from the HF–isooctane mixture by 2 mm after
24 min. During the subsequent quasistatic etching procedure,
21
a
Tip B
Tip A
k b
k
k
Fig. 9 a Signal of R6G from two different SERSORS featuring (tip A)
α015°, L075 μm and (tip B) α010°, L0118 μm at 633 nm excitation
(symbols represent the experimental data, lines result from multiple
peaks Lorentzian fitting, P0630 μW). Inset: picture of the two fiber
the SERSORS are either pushed inside the solution or pulled
out at steps of 20 μm every 2 min. Two fibers, featuring
different cone angles α and lengths L (tip A, α015°, L0
75 μm; tip B, α010°, L0118 μm), are displayed in the inset
of Fig. 9. The fibers have then been functionalized with
APTMS and coated with metal colloids following the proce-
dure described above. Measurements with the SERSORS are
carried out after immersion in R6G for 12 min, in a dip and dry
configuration, exciting at 633 nm (P00.63 mW). The resulting
spectra, after background subtraction, normalization to the laser
power actually coupled into the fiber, and normalization to the
integration times, are reported in Fig. 9a (hollow and full
symbols refer to the longer tip, A, and the shorter tip, B,
respectively, continuous lines arise from a multi-peak Lorent-
zian fit of the data). We collect a notably stronger signal from
the SERSORS featuring a longer, sharper tip, a factor ca. 2.5
more intense with respect to the signal measured on SERSORS
with a shorter cone. We interpret this finding as the indication of
a better light trapping efficiency provided by SERSORS with
longer cones. SERS photons trapped inside the fiber core, and
propagating towards the fiber end, are more efficiently retrore-
flected by sharper tips, yielding a larger number of photons
detected in the backscattering configuration we adopt. These
findings are in agreement with the general trend found by Viet
et al. [17], i.e., shaping the fiber apex as cones, instead of flat
surfaces, increases the number of SERS photons trapped into
the fiber, improving the sensitivity. We can tailor this conclu-
sion, suggesting that sharper cones accomplish the light trap-
ping function more efficiently.
Conclusions
In this work, we show that multimode optical fibers (50 μm
core–125 μm cladding) can be successfully shaped and
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22
functionalized to produce SERSORS capable to work in a
broad range of excitation wavelengths. We have tested our
SERSORS in a dip and dry configuration, detecting R6G
molecules dissolved in water at 1 μM concentration with
515, 633, and 785 nm laser wavelengths using powers of
∼10 mW. Best sensitivity is achieved at 633 nm where R6G
molecules are detected with only 1 s integration time. The
versatility of these broadband SERSORS paves the way to
remote detection of resonant biomolecules, such as hemo-
proteins, in which resonant Raman effects can be exploited
to boost the Raman signal by tuning the excitation
wavelength.
Acknowledgments We acknowledge financial support from MIUR
(PRIN 2008J858Y7), European Union Seventh Framework
Programme (FP7-HEALTH-F5-2009-241818-NANOANTENNA,
Grant Agreement No. 241818), Programma Operativo Nazionale
Ricerca e Competitività 2007–2013, PON01_01322 PANREX.
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