Determination of Antimony by Surface-Enhanced Raman

Spectroscopy
Andrei Yu. Panarin,a Inna A. Khodasevich,a Olga L. Gladkova,b Sergei N. Terekhova,*
a
b

B.I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, Nezalezhnasti Ave., 68, 220072, Minsk, Belarus
Belarusian State University of Informatics and Radioelectronics, P. Brovka Str. 6, 220013 Minsk, Belarus

A highly sensitive method for the detection and quantitative

evaluation of antimony(III) using the surface-enhanced Raman
scattering (SERS) technique is demonstrated. The method is based
on the analysis of SERS spectra intensity of antimony bound to
phenyluorone (Sb-PhF). Phenyluorone is widely used as an
organic reagent for the spectrophotometric determination of some
heavy metals. For the SERS experiment a Sb-PhF complex was
adsorbed onto the silvered porous silicon substrate. The signicant
degradation of the SERS signal was observed during measurements in the air. The time evolution of SERS spectra at ambient and
degassed conditions was investigated to nd an optimal regime for
SERS measurements. The limit of Sb detection in degassed
samples was determined to be near 1 ng/mL, which is one order
of magnitude less than that attainable by the photometric approach.
The linear range of the method to Sb(III) was found to a mass
concentration range of 110 ng/mL. This approach permits an
absolute quantity of Sb(III) to be detected at the picogram level (50
pg). It is remarkable that a very small sample volume (50 lL) is
required for SERS analysis. Moreover this technique offers high
selectivity owing to the distinctive vibrational features for the
metallorganic complex and to the resonance character of Raman
spectra. The proposed SERS-based detection of Sb is a fast and
highly sensitive method for use in environmental and industrial
waste monitoring as well as for forensic science to determine
gunshot residue. We expect that the approach reported herein can
be further extended to develop new detection techniques for other
heavy metals.
Index Headings: Surface-enhanced Raman spectroscopy; SERS;
Antimony; Phenyluorone; Silvered porous silicon; Photobleaching.

INTRODUCTION
Heavy metals are ubiquitously present in the environment as a result of natural processes and human activity.
It is known that they have a tendency to accumulate in
living organisms and are considered to be hazardous
substances. Among them, antimony is a toxic element that
exists mainly as Sb(III) and Sb(V) in environmental,
biological, and geochemical samples.14 Antimony derived from increasing anthropogenic emissions is an
environmental pollutant because Sb and its compounds
are industrially important. They are used in manufacturing
paper, plastics, textiles, glass, semiconductor compounds, alloys, rubber, and in the pharmaceutical
industry. The United States Environmental Protection
Agency considers antimony and its compounds to be
Received 1 February 2013; accepted 18 October 2013.
* Author to whom correspondence should be sent. E-mail: terekhov@
imaph.bas-net.by.
DOI: 10.1366/13-07034

Volume 68, Number 3, 2014

pollutants of priority interest.5 Micro-amounts of Sb are

known to cause harmful effects to human health;6 e.g.,
exposure to it can stimulate disorders of the respiratory
tract, the mucous membranes of the alimentary canal,
skin, etc. The toxicity and metabolic activity of antimony
depend on its oxidation state. Sb(III) is generally accepted
to exert a 103 higher toxicity than Sb(V) compounds.7,8
Therefore, the development of methods for the sensitive
determination of Sb (III) is very important.
Until now, a variety of techniques for the analysis of
trace amounts of antimony have been established, such
as spectrophotometry,914 hydride generation atomic
absorption spectrometry (HG-AAS),1518 hydride generation-atomic uorescence spectrometry (HG-AFS),1923
inductively coupled plasma optical emission spectrometry (ICP-OES),23,24 inductively coupled plasma mass
spectrometry (ICP-MS),24,25 neutron activation analysis,26 etc. Methodologies for analysis of antimony have
been reviewed by Nash et al.4 and more recently by
Smichowski.27 A variety of electrochemical methods
have been reported for the determination of antimony
by differential pulse anodic and adsorptive stripping
voltammetry,28,29 anodic and cathodic stripping voltammetry,30,31 etc.
Most of the above methods are characterized by high
efciency, improved selectivity, low sample volume, and
low reagent consumption. However, all these techniques
are costly, require trained personnel, and are not
applicable for the rapid detection of antimony in the
sample. Compared to other methods, the spectrophotometric method has been very popular for a long time due
to its simple operation and low cost. It is based on the
formation of colored metallorganic complexes in the
course of specic reactions, which then can be assessed
from the absorption spectra of studied solutions.
However, spectrophotometric methods (in particular Sb
analysis) have poor selectivity and reproducibility and
suffer from interference with foreign species; they do not
ensure a sufciently low detection limit.
Here we report a new approach for antimony
determination based on the analysis of metallorganic
complexes by surface-enhanced Raman spectroscopy
(SERS). To our knowledge, so far there have been no
reports on the detection of antimony using a Raman
technique. SERS is a method of choice for ultra-sensitive
environmental monitoring and detecting trace amounts
of chemical and biological substances3236 even down to
the single-molecule level.3638 The high sensitivity of
SERS is due to enormous enhancement of the Raman
signal (more than six orders of magnitude) for the
molecules adsorbed on special metallic surfaces with
nanoscale roughness, so-called SERS-active sub-

0003-7028/14/6803-0297/0
Q 2014 Society for Applied Spectroscopy

APPLIED SPECTROSCOPY

297

strates.39,40 Such a type of substrate is required to have a

high level of Raman enhancement and also is expected
to demonstrate sufcient reproducibility, time stability,
and simplicity of preparation. A large number of new
SERS-active materials have appeared within the last
decade, and some of them satisfy the above requirements to a certain extent.3235,41,42
We fabricated SERS-active substrates of silvered
porous silicon (Ag-PSi) based on the method for the
formation of nanostructured silver lm on the surface of
PSi by immersion plating as rst proposed by Lin at al.43
We optimized the silver deposition procedure to obtain
maximum SERS enhancement and established the
dependence of morphological parameters of PSi on the
nanostructure of silver lms.4446 For the p-type PSibased substrates formed by the optimized procedure,
characteristics such as homogeneity, stability, and
enhancement factor were determined.44,45 For example,
the variation of the SERS signal scanned across the
sample surface appeared to be less than 10%. It was
demonstrated that the elaborated silvered PSi substrates
allow detection of the tetrapyrrole photosensitizer
chlorin e6 at a picomolar concentration level.47,48
We applied Ag-PSi substrates to antimony determination via the analysis of SERS spectra of Sb complexed
with phenyluorone (Sb-PhF). Phenyluorone and its
derivatives are widely used in photometry for heavy
metal determination.14,4951 We proposed to obtain
samples for SERS by Sb-PhF deposition on the silvered
surface of PSi from the solutions, which were prepared
in a similar way as in the photometric method. Our
results show that due to high SERS sensitivity, a very low
amount of antimony (50 pg) can be detected. This
corresponds to an equivalent volume of 50 lL of Sb-PhF
solution with Sb mass concentration of 1 ng/mL. The
method is characterized by high selectively owing to the
unique SERS ngerprint peaks and due to the resonance
character of excitation.

EXPERIMENTAL
Reagent and Chemicals. Phenyluorone (9-phenyl2,3,7-trihydroxy-6-uorone), sulphuric acid (H2SO4 98%),
and antimony oxide (Sb2O3) were analytical reagent
grade. Rhodamine 6G (98%), silver nitrate (AgNO3
99.9999%), and hydrochloric and hydrouoric acid
(38%; Sigma-Aldrich) were used without additional
purication. Samples were prepared with distilled water.
Preparation of Sb-Phenyluorone Complex. A standard Sb(III) stock solution of 1000 ng/mL was prepared in
several steps. First, we dissolved 35.914 mg of antimony
oxide (Sb 2O 3 , containing 30 mg of Sb) in 2 mL
hydrochloric acid (1.5 M HCl) water solution. Second,
100 lL of this solution was diluted to 5 mL with 1.5 M HCl.
Finally, 33.3 lL of the resulting solution was diluted with
distilled water to obtain 10 mL of 0.003 M HCl solution of
1 lg/mL Sb mass concentration.
For preparation of a phenyluorone stock solution, 5
mg of PhF powder was added into 56 mL ethyl alcohol
(96%) containing a 100 lL mixture of sulfuric acid with
water (1 : 1). The sample was heated and sonicated for
10 min to PhF full dissolution. Then the obtained

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Volume 68, Number 3, 2014

solution was diluted with ethyl alcohol to get a total

volume of 10 mL.
Formation of SERS-Active Substrates. The starting
wafers for preparation of the PSi-based substrates were
p-type, boron-doped, 0.005
cm resistivity, (100) orientation silicon crystals. Porous silicon was prepared by
electrochemical anodization in a 1 : 2 mixture of HF and
ethanol. An anodic current density and time of anodization were 10 mA/cm2 and 10 min, respectively.
Silver deposition was carried out using the immersion
plating method with the water solution of AgNO3. Before
starting deposition PSi plates were rinsed for several
seconds in an aqueous HF:ethanol mixture to remove a
layer of the oxidized silicon. Then samples were
thoroughly rinsed with ethanol and water. After these
steps PSi plates were placed into a 10 mM water solution
of AgNO3 at 4 8C for 5 min followed by rinsing with
ethanol and then dried. To eliminate carbon contaminants adsorbed on the nanostructured silver surface,
which often give rise to a rather strong SERS background, Ag-PSi substrates were immersed in a 10 mM
HCl solution for several seconds.
Scanning electron microscopy (SEM) images were
obtained using a Hitachi S4800 electron microscope with
a resolution of 1 nm. Measurements were performed
without sputtering any conductive layer at the samples.
Samples for the SERS measurements were obtained in
two ways. In the rst case Ag-PSi plates were incubated
for 2 h in Sb-PhF solutions of different concentration. The
samples of the second type were prepared by drop
casting the Sb-PhF 50 lL solution onto a silvered surface
of porous silicon and allowed to air dry.
Spectroscopic Measurements. Absorption spectra
were carried out on an UV-visible spectrophotometer
(Cary 500 Scan, Varian) in 10 3 10 mm quartz cells at
room temperature.
Both ordinary Raman and SERS spectra were recorded with a 908 scattering geometry on a MS3504i (Solar
TII) Raman spectrometer equipped with a chargecoupled device (CCD) detector SPEC10:256E (Roper
Scientic) cooled to 153 K with liquid nitrogen. Excitation
at 514.5 nm was provided by an Ar ion laser Stabilite
2017 (Spectra-Physics). In several cases the cylindrical
lens was used to stretch out the spot to 5 mm in length.
Additionally a SpectraPro 500 I spectrometer (operated
in the back-scattering geometry) equipped with CCD
detectors was used. The objective lens (NA = 0.4) was
applied to focus the laser beam on the sample and to
collect the scattered Raman signal. For 532 nm excitation, the continuous wave diode-pumped Nd:YAG laser
(GCL-025-S, CrystaLaser) was used with spot size 15
lm in diameter. Excitation laser power was monitored in
two ways: (1) before and after each experiment the
intensity of the Raman band of the silicon wafer at 521
cm1 was measured and was used as an external
standard; and (2) while studying the time evolution of
SERS spectra in the air and in a vacuum the illumination
power stability was controlled permanently using a laser
power meter. In addition, to eliminate any instrumental
errors due to possible laser power drift, alignment
variations, or reproducibility of the prepared metal
substrates, we performed all experiments in triplicate.
All measurements were made at room temperature.

FIG. 1. Structure of the complex Sb-PhF.

SERS spectra shown in the gures represent unsmoothed accumulated data followed by appropriate
background subtraction. The wavenumber peak positions accuracy is 61.0 cm1.

RESULTS AND DISCUSSION

Complex Formation Between Antimony and Phenyluorone. In a moderate acidic medium, antimony
occurs as an ionic form SbO,52 which reacts with
phenyluorone to form a complex, depicted in Fig. 1
(denoted as Sb-PhF). The most suitable acid concentration in solution for the reaction is ,0.75 M for HCl or a
range of 12.5 M in the case of H2SO4. When the solution
is insufciently acidic, precipitation of a nely dispersed
reagent occurs. Upon increase of the solution acidity the
Sb3 ions begin to dominate, which do not react with PhF.
Moreover, when the solution is too acidic, the competitive process takes place, leading to protonation of the
oxygen atom in position 4.
To determine the optimal ratio between antimony and
phenyluorone for maximal complexation at the above
mentioned acidic conditions, the titration of Sb2O3 by a
PhF solution was carried out. Figure 2 shows the
variation in absorption spectra upon successive addition
of PhF into 3 mL of Sb2O3 solution containing 2 lg/mL of
Sb. The spectrum of PhF-free 0.005 M HCl solution has a
maximum at 475 nm. This suggests that the reagent
occurs as a monocation with a proton bound to oxygen at
the O4 position.49 Addition of 10 lL of PhF to the Sb2O3
solution gives rise to the new band at 565 nm (Fig. 2,
curve 1), pointing to the formation of the Sb-PhF
complex. At the same time the band that was positioned
at 475 nm upshifts to  495 nm; this is attributed to
deprotonation of PhF. Such behavior is probably due to
the slight change in acidity of the resulting solution. On
further addition of PhF the intensity of the 565 nm band
gradually increases, reaching saturation upon addition
of 60 lL of PhF solution (Fig. 2, curve 6), which
corresponds to the maximum of complexation between
antimony and phenyluorone. The inset to Fig. 2 shows
the dependence of the 565 nm band intensity on the
added volume of PhF. It is seen that when addition of PhF
exceeds 60 lL its intensity remains nearly constant. Only
the optical density is decreased, and small red-shift for
this band was observed, which can be attributed to the
formation of Sb-PhF associates, e.g., hydrogen-bonded
dimers. At the same time the band at 475 nm, due to the
uncomplexed reagent, continues to grow because of the
presence of an excess amount of PhF. Thus the mixture
containing 60 lL of PhF was selected to be used as a
working stock solution for preparation of SERS samples
so as to get the maximum Sb-PhF complex formation.

This corresponds to addition of 10 lL/mL of PhF into our

standard Sb(III) stock solution of 1000 ng/mL.
Active Substrates for Surface-Enhanced Raman
Spectroscopy. For SERS measurements Sb-PhF was
deposited onto the nanostructured silver lm formed on
the surface of porous silicon. As previously mentioned,
we recently prepared and carefully investigated sensitive SERS-active substrates produced from silvered ntype PSi.46 It should be noted, however, that materials of
this kind were found to be unsuitable for the purpose of
the present work because they contain antimony as a
dopant to silicon wafer. Therefore, in the present study
we used the p-type boron-doped silicon for SERS-active
substrate preparation. The immersion plating of Ag onto
p-type PSi was optimized for the room-temperature
conditions in previous work.44,45 The silver deposit was
formed as densely packed particles tens of nanometers
in diameter, which displayed rather strong SERS
enhancement. Here we performed additional experiments to improve the sensitivity of Ag-PSi substrates by
preparing nanostructured silver lm at a low temperature (4 8C). Usually at these conditions the formation of
ramied silver nanostructures with many sharp protrusions and sites between particles occurs, which is known
to provide a large and spatially conned electromagnetic
enhancement effect.5355 In the case of the lowered
temperature the diffusion of adsorbed metal atoms along
the island edges is very slow, and according to the
classic theory of diffusion-limited aggregation, thin
fractal clusters are formed.56,57

FIG. 2. Absorption spectra of PhF blank solution, Sb2O3 solution with

Sb mass concentration of 2 mg/mL, and spectral variation with
successive addition of PhF from 10 to 150 lL into 3 mL of Sb2O3. Inset
shows the dependence of the 565 nm band intensity on the volume of
PhF.

APPLIED SPECTROSCOPY

299

FIG. 3. SEM images of the Ag-coated PSi plates. (a) The plan-view
image representative of the Ag lm. (b) The image of the dendritic
structure of the Ag deposit. (c) The image showing the Ag-nanoparticle
array in the area between dendrites.

Figure 3ac shows SEM images of the surface of AgPSi samples prepared by the immersion plating procedure from the silver nitrate solution at 4 8C. Unlike our
earlier reports44,45 where deposition at room temperature resulted in the formation of small Ag particles, in the

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present case the metal dendrites were randomly

scattered across the silver lm (Fig. 3a). The dendrite
dimensions are in the micrometer range, reaching up to
about 4 lm in size (Fig. 3b). Small densely packed
particles 50100 nm in size occur on the top of PSi in the
space between the dendrites (Fig. 3c). Many protruding
dendrites and the underlying corrugated surface of the
protruding silver nanoparticles obtained in this way are
expected to provide a high Raman enhancement for the
Ag-PSi samples. In our test experiments the SERS signal
of analyte rhodamine 6G adsorbed on this Ag-PSi
substrate appeared nearly twice more intense in
comparison to what was obtained from the Ag-PSi
sample formed at room temperature45 (data not shown).
Surface-Enhanced Raman Spectra Characterization: Sb-PhF versus PhF. Figure 4 shows comparison
of SERS spectra of PhF and its complex with Sb
adsorbed on the silvered surface of PSi. The excitation
at 532 nm corresponds to the resonance with Sb-PhF
absorption (see Fig. 2), which is very important for the
antimony analysis when there is a mixture of Sb-PhF and
uncomplexed PhF. In this case the Raman signal of the
Sb-PhF complex is expected to be predominantly
enhanced due to the resonance effect. Table I summarizes conventional SERS peaks of Sb-PhF and PhF and
gives their assignments as proposed recently.58,59 The
type of normal vibrations is given as natural coordinates,
ordered as their contribution decreases. Table I does not
list all coordinates but only those that undergo the
largest changes in the corresponding vibrational mode.
We have observed the following spectral changes
when going from PhF to Sb-PhF (Fig. 4). Most of the
similar peaks are present in the low-frequency region
from 300 to 1000 cm1 in SERS spectra for both samples.
The only exception was the absence of the band at 580
cm1 in the Sb-PhF spectrum as compared to that of PhF.
This band was assigned in Ref. 58 to the in-plane
bending of the double bond of C6O4. Upon Sb binding to
the O4 position of PhF this bond becomes a single bond
in character, which results in the disappearance of the
corresponding mode.
The spectrum of Sb-PhF in the high-frequency region
above 1100 cm1 differs signicantly from that of PhF.
First, it should be noted that the new intensive band
appears for Sb-PhF at 1163 cm1, which can be assigned
to the mode with the C7O5 bond contribution (Table I).
This band is a convenient marker for Sb-PhF identication due to the absence of its counterpart in the spectrum
of PhF. In addition, fortunately the adjacent band at 1190
cm1 decreases in intensity upon metal complex
formation.
The two other bands in the SERS spectrum of PhF that
can indicate the presence of a metal complex are the
very intensive peaks at 1354 and 1505 cm1. The
corresponding bands are not observed in the PhF
spectrum. According to the results of quantum-mechanical calculation, the rst band at 1354 cm1 can be almost
completely related to the vibrations of the ring IV. The
most intensive band at 1505 cm1 does not have the
denite assignment. The calculation predicts the change
of normal mode composition due to considerable
alterations in C6O4 and C7O5 bonds when going from
PhF58 to Sb-PhF.59 Thus, the characteristic peaks at 1163,

FIG. 4. SERS spectra of Sb-PhF (1) and PhF (2), deposited from the corresponding solutions on the Ag-PSi plate. Excitation wavelength was 532.0
nm. [Adapted with permission from Ref. 59. Copyright Springer. 2012.]

1354, and 1505 cm1 are unique spectral features of the

antimony complex, which permits the analysis of the
presence of metal.
Surface-Enhanced Raman Spectra Quenching in
the Air. Even though we used minimal laser excitation
power focused with the cylindrical lens, which stretched
out the excitation spot, the Raman signal decrease was
observed at a prolonged illumination of the sample.
Figure 5 depicts the representative time courses of SbPhF SERS spectra obtained for samples at ambient
conditions using 514.5 nm excitation. The data show
gradual decrease of the broad continuum background as
well as the Raman peaks dropping in intensity more than
twofold after 10 min of illumination. Such behavior could
be explained by thermal decomposition of Sb-PhF
molecules on the silver lm due to the laser irradiation.
Usually in such a case the two vibrational bands of
amorphous carbon (1350 and 1580 cm1) and other
carbon species are expected to appear in the spectra.60
However, as can be seen from Fig. 5 no additional bands
have been observed in the mentioned spectral regions
over the entire illumination.
One might assume that the background in the SERS
spectrum is related to the uorescence of the studied
complex. In such a case the loss of the spectral signal
with irradiation time can originate from a simultaneous
decrease of band intensity and uorescence quenching.
We have not found any information in the literature on the
emission of Sb-phenyluorone. Our own measurements
at rather high concentration of Sb-PhF showed that in the
resonance Raman spectrum a very weak emission with
maximum near 16 530 cm1 (605 nm) was observed,
which could be attributed to the uorescence of this
complex. However, the shape and maximum position of
the background in the SERS spectrum (17 940 cm1 or

558 nm; see Fig. 5) are completely different from that in

the ordinary Raman spectrum. In addition, it is known
that in the case of direct adsorption of the analyte
molecules on the SERS-active substrates surface their
uorescence is effectively quenched. These two facts
indicate that the photoinduced decrease of the background in SERS spectra of Sb-PhF is unlikely to be
related to uorescence quenching.
We surmise that the SERS background observed, i.e.,
a broad continuum emission on top of which the
vibrational Raman peaks are superimposed, is due to
intrinsic properties of SERS that always accompanies
this effect independently of uorescent properties of the
analyte. The mechanism of the background emission still
TABLE I. Assignments of the most characteristic SERS frequencies (cm1) observed for PhF and its antimony complex Sb-PhF.
Sb-PhF

PhF

Assignments [58,59]

580
600

(C6O4), (C2O2), (C3O1)a

I, II
II , C4C3C1, SbO4
C11O3C13, C2C1C10
C9Cph, C9C10, C9C12, C7O5, (CH, I, III)
C8C12, C13O3, C11O3, (CH, III)
C9Cph, C2O2
CC(II, I, III), C7O5, (O1H1), (O2H2)
C6C7, C6O4, C7O5, C5C6O4, C8C7O5
CC(II, I), (O1H1), C7O5, C6O4
CC(IIII), C3O1
CC(I, II), C7O5, C6O4
CC(I, III), C4C3O1, C1C2O2
CC(I, III), (O1H1)
CC(I, III), C3O1, C1C2O2

607
775
1163
1190
1218

774

1191
1222
1345

1354
1374
1504
1505
1559
1600
1621

1542
1605
1641

a
in-plane bending of bonds or ring; I, II, III: correspondence of
coordinates to a particular ring (see Fig. 1).

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301

FIG. 5. Time-dependent SERS spectra of a Sb-PhF complex adsorbed

on silvered surface of PSi from the solution. The measurements were
carried out in the presence of O2. Each subsequent spectrum was
accumulated for 2 s followed by an 8 s pause. For convenience of
analysis only 10 spectra out of 60 are depicted. The spectra are not
offset from each other. Excitation wavelength was 514.5 nm.

remains to be understood. A brief summary of the

developments in understanding the observed SERS
background as well as a new model for its origin have
been recently provided by Mahajan et al.61
The decrease of SERS intensity is often due to the
presence of molecular oxygen.60,62,63 To reduce the
possible effect of O2 we have carried out the SERS
measurements for the samples placed in the deaerated
cell. The dotted curves 1 and 2 in Fig. 6 represent the
time dependence of the 1354 cm1 Raman band intensity
for Sb-PhF (panel a) and the background signal (panel b)
obtained at ambient conditions and in a vacuum,
respectively. The background level was monitored based
on the SERS signal near 810 cm1 to the higher
frequency of the 775 cm1 peak. Clearly the intensity of
the background as well as the 1354 cm1 band rapidly
decreases in the air in the course of sample illumination.
The most essential changes occur during the rst 3 min;
after that the gradual attening is observed during the
next 10 min. It is interesting to note that the change of
the background intensity roughly follows the decrease of
the vibrational peaks intensity. The fall of the signal
level for both the background as well as for the Raman
band is nearly 2.53 and 2.50 times, respectively. When
the cell with the sample was degassed down to 5 3 104
Pa the quenching effect was signicantly diminished
(Fig. 6, curve 2). And again, like in the case of the

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experiment in the air, the level of signal degradation in a

vacuum for the background and for the SERS band was
similar; e.g., the background decreased by a factor of
1.30, while the intensity of the Raman peak at 1354 cm1
decreased by a factor of nearly 1.20.
There are several suggestions as to the mechanism of
the quenching and blinking effects in SERS spectra in the
presence of oxygen. Otto et al.62 suggested that the
decrease of Raman intensity is caused by the adsorption
of O2 and following oxidation of SERS-active sites that
are responsible for the short-range mechanism of
enhancement. A similar explanation was proposed by
Nicolai and Rubim,63 who observed that saturating an
electrolyte solution with O2 caused the irreversible loss
of SERS-active sites for Cu and Ag electrodes. The
model for the SERS blinking involved oxygen-mediated
cyclic production and destruction of photoactive silver
clusters on the thin lm.64 Our data do not exclude or
give any support to above proposed mechanisms.
Elucidation of the role of oxygen in photoinduced SERS
signal degradation is beyond the scope of our report. In
this study we used the kinetics of photobleaching to
choose the optimal regime of SERS measurement after
the start of sample illumination (marked with rectangles),
i.e., 4 min in vacuum and 7 min at ambient conditions.
Limit of Detection and Relation Between SurfaceEnhance Raman Spectroscopy Intensity and Antimony Concentration/Mass. To determine the limit of
detection (LOD) of antimony, concentration-dependent
SERS measurements were performed. The Sb-PhF
stock-solution was diluted by 0.003 M HCl in order to
keep the acidity of samples constant in concentration

FIG. 6. Quenching kinetics of the band at 1354 cm1 (a) and SERS
background at 810 cm1, (b) in the air (curves 1), and in a vacuum
(curves 2). Rectangles show optimal time intervals for SERS spectra
registration.

FIG. 7. SERS spectra of Sb-PhF adsorbed over 2 h on Ag-PSi from the

solutions with different mass concentrations. Accumulation time was
1 min. Excitation wavelength was 514.5 nm.

FIG. 8. SERS spectra of 50 lL drops of Sb-PhF deposited onto Ag-PSi

from solutions with different mass concentrations. Accumulation time
was 1 min. Excitation wavelength was 514.5 nm.

studies. We performed a dilution of Sb-PhF water-HCl

solutions to get the range of antimony content from 100
ng/mL down to 1 ng/mL. Ag-PSi substrates were
incubated in the solutions for 2 h and dried in the air.
Figure 7 shows SERS spectra of Sb-PhF deposited on
Ag-PSi for 2 h from the solutions with Sb mass
concentrations of 100, 80, 20, 10, 8, 5, 2, and 1 ng/mL.
All spectra were recorded with the samples placed in the
degassed cell. To simplify the analysis, spectra in Fig. 7
were shifted in the vertical direction. It can be seen that
the intensities of spectra are changed with the Sb-PhF
concentration. As was mentioned above, there are three
characteristic bands for identication of the Sb-PhF
complex: 1163, 1354, and 1505 cm1. The 1163 cm1
band is inconvenient for the LOD evaluation due to its
rather low relative intensity. Evidently the intensity of the
marker peaks decreases when Sb-PhF mass concentration decreases from 100 ng/mL. One can also notice that
as the antimony concentration becomes smaller and
smaller, the relative intensity of the background at 1350
and 1580 cm1, i.e., near the respective 1354 and 1505
cm1 bands, appears stronger and stronger. Nevertheless, in the spectrum of the sample with antimony mass
concentration of 1 ng/mL one can identify at least the
band at 1354 cm1. Moreover, another band at 775 cm1
is reliably observed in this spectrum. Though this peak is
not a characteristic marker band of Sb-PhF we still can
use it as an additional band for LOD evaluation because
its intensity changes simultaneously with that of the 1354
cm1 band upon variation of concentration. Thus, we

conclude that LOD of Sb by a SERS technique based on

Ag-PSi substrates is 1 ng/mL.
In order to obtain the mass value of LOD for antimony
we used another method of sample preparation, dropcoating deposition. The Sb-PhF deposits were dried at
ambient conditions. Figure 8 shows SERS spectra of SbPhF deposited on Ag-PSi plates from 50 lL drops with
the same range of concentrations as showed in Fig. 7.
Spectra were measured in a deaerated cell. It is seen
from Fig. 8 that the peaks of Sb-PhF molecules at 775,
1354, and 1505 cm1 are distinguishable from the
background in the SERS spectrum of the sample
prepared from droplets down to 1 ng/mL Sb mass
concentration. Since a 50 lL solution drop with 1 ng/mL
Sb mass concentration contains 50 pg of the metal, this
mass can be taken as the limit of detection for antimony.
It is interesting to evaluate the mass of Sb detected in the
laser spot. To do so one needs to know the droplet
spreading area and the size of the excitation laser spot.
Due to the quite good wettability of the nanostructured
silver lm, the droplet spread on the entire at surface of
the Ag-PSi sample over about 40 mm2 (5 3 8 mm). A laser
beam shaped by the cylindrical lens had a spot area of
0.8 mm2 (4 3 0.2 mm). Assuming that the Sb-PhF
molecules are uniformly spread on the Ag-PSi substrate
the minimal detectable mass of antimony in the
excitation spot can be estimated as 1 pg (50 pg/40/0.8).
The results on LOD obtained with the proposed SERS
technique were compared with those from the spectrophotometric method. Figure 9 shows absorption spectra
of the solutions that were used upon preparation of the

APPLIED SPECTROSCOPY

303

FIG. 11. The log plot of the 1354 and 775 cm1 bands intensity in SERS
spectra of droplet samples versus Sb mass concentration.

FIG. 9. Absorption spectra of 3 mL solutions of Sb-PhF at different

mass concentrations: (a) 20100 ng/mL and (b) 110 ng/mL. Spectra
were measured in a 1 3 1 cm cell. Inset shows the dependence of the
565 nm band intensity on the Sb mass concentration.

samples for SERS. It can be seen that in this case LOD of

Sb is found in the range of nearly 810 ng/mL. Thus, the
SERS technique appears to be one order of magnitude
more sensitive for antimony detection than the spectrophotometric one. Additionally, the SERS method is
characterized by high selectivity due to the set of
specic SERS features. One more advantage is the
negligible sample volume required for SERS analysis.
For the practical application of this method it is very
important to establish a quantitative relationship between the SERS spectrum intensity and the antimony
concentration. Figures 10 and 11 present the logarithmic
intensity proles of the 775 and 1354 cm1 peaks in the
SERS spectra shown in Figs. 7 and 8 as a function of the

concentration of sample solutions and Sb mass, respectively. Error bars represent the standard deviation of the
mean signal intensity of three sampled spots in two
series of samples. It can be seen that in both cases SERS
intensity increases gradually with concentration as well
as with mass. In contrast to photometric data, for which
the optical density plot is linear (as expected) over the
whole range of concentrations (inset in Fig. 9), the
increase of SERS intensity slows when reaching a high
concentration. However, it seems that the concentration
range from 1 to 10 ng/mL (or 50500 pg) can be tted
using a linear function. We performed additional measurements in the range of low concentration. The data
plotted in Fig. 12 reveal that in this region the mass
dependence for the intensity of the band at 1354 cm1 is
linear with slope k = 2.58/pg and a rather high coefcient
of determination R2 = 0.96. We did not t the band at 775
cm1 since it is not the marker of the Sb-PhF complex.
The results obtained show that by using the SERS
method on the Ag-PSi substrates, solutions with a minor
concentration of Sb can be analyzed.
It should be noted that in principle there is a way to
enhance the sensitivity of the SERS method proposed.
For example, one can downshift LOD by increasing the
duration of Ag-PSi soaking in Sb-PhF solution or by
decreasing the volume of droplets. We attempted to
deposit the single 10 lL droplet with c = 1 ng/mL onto
the silvered surface of PSi, and we managed to observe
successfully the Raman bands from Sb-PhF. However, a
strong background of unknown origin interfered with
analyte peaks, making the quantitative analysis difcult.
Nevertheless we were able to get a qualitative answer to
the question of whether or not antimony is present in
solution.

CONCLUSION

FIG. 10. The log plot of peak intensity of the 1354 and 775 cm1 bands
versus detected Sb mass concentration.

304

Volume 68, Number 3, 2014

In the present study a new method for antimony

detection based on the analysis of SERS spectra of a SbPhF complex is proposed. Highly sensitive SERS
substrates were prepared by immersion plating of silver
on a PSi surface at 4 8C. SERS spectra were obtained for
aerated and degassed samples. A signicant degradation of the SERS signal was observed during measurements in the air, while for deaerated samples the loss of

FIG. 12. The dependence of the 1354 and 775 cm1 bands intensity on
the mass of Sb.

intensity was nearly twice as low. The time evolution of

SERS spectra at ambient and degassed conditions was
investigated, and the optimal regime for SERS measurements was determined. The most essential changes
occur during the rst 3 min of irradiation; following that
the gradual attening was observed over the next 10
min. The characteristic Raman bands of Sb-PhF at 1163,
1354, and 1505 cm1 were followed in two types of
samples, as prepared (1) by soaking Ag-PSi in solutions
with varying Sb mass concentration and (2) by droplet
deposition. It was found that the limit of detection of
antimony for these two types of samples is 1 ng/mL and
50 pg, respectively. We established the quantitative
relationship between the SERS band intensities and the
concentration/mass of antimony. The dependence between the detected Sb mass and SERS intensity was
found to be linear in the mass interval from 50 to 500 pg.
Thus, we consider the proposed SERS method to be
promising for quantitative analysis. However, before we
arrive at practical applications, several issues need to
be addressed, e.g., the extension of the mass ranges for
the quantitative relationship between SERS intensity and
Sb concentration, stabilization of Sb-PhF solutions, and
purication of the samples from background molecules.
ACKNOWLEDGMENTS
This work was partly supported by the GPNI program Electronics
and Photonics task no. 2.3.03. The authors also grateful to Dr. V.P.
Bondarenko for providing porous silicon samples.
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