Spectrochimica Acta Part A 65 (2006) 1003–1006

Spectroscopy property of Ag nanoparticles

Yan Zhao a,b , Yijian Jiang a,∗ , Yan Fang b
a National Center of Laser Technology, Beijing University of Technology, Beijing 100022, PR China
b Beijing Key Laboratory of Nano-Photonics and Nano-Structure, Capital Normal University, Beijing 100037, PR China
Received 1 August 2005; received in revised form 3 January 2006; accepted 15 January 2006

Abstract
Three silver nanoparticles of different size characterized by the UV–vis absorbance spectra and TEM images were prepared by citrate reduction
and laser ablation with excitation of 532 and 248 nm. It is proved that all of them are effective SERS-active substrates, whereas, enhancement effect
of silver colloids has not too much relation with the size and shape of the Ag nanoparticles. However, different photoluminescence spectra were
observed from these three particles, indicating that the photoluminescence property of silver nanoparticles is dependent on the size. The spectra
shift to higher energies with decreasing particle size. In addition, we also tentatively give the assignment of the luminescence bands.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Ag nanoparticles; Photoluminescence; TEM

1. Introduction
It is well known that nanoscale materials have optical prop-
erties that differ greatly from the bulk counterparts, which have
extensively studied among the researchers [1,2]. Nanoparticles,
especially some metal nanoparticles suspended in a solution, are
expected to be used as functional materials because of their spe-
cial optical properties, magnetic properties, catalytic properties
[3–5]. Nanosize metals such as gold and silver have also been
shown to exhibit novel size-dependent optical properties that
cannot be explained classically [6], for instance, gold nanopar-
ticles show photoluminescence only when their size are less than
5 nm in diameter [3].
For study of the size-dependent properties, it is necessary to
prepare the Ag nanoparticles of different size. The most com-
monly employed method in the preparation of metal nanoparti-
cles is chemical reduction, however, the size of particles cannot
be changed easily. Recently, a novel approach to prepare “chem-
ical pure” Ag colloids is laser ablation of pure Ag in aqueous in
a size-selected and size-controlled manner [7–12]. This physical
method allows us to prepare nanoparticles with ease and without
contamination by a reducing agent [13].
In this paper, three silver nanoparticles of different size were
prepared by chemical reduction and laser ablation with exci-
∗ Corresponding author. Tel.: +86 10 67392756; fax: +86 10 67391442.
E-mail addresses: zh cnu@sohu.com, yjjiang@bjut.edu.cn (Y. Jiang).
tation of 532 and 248 nm, which is shown by the TEM image
analysis and UV–vis absorbance spectra. It is shown that all of
them are effective SERS-active substrates, whereas, enhance-
ment effect of silver colloids has not too much relation with the
size and shape of the Ag nanoparticles. However, the photolu-
minescence property of nano silver particles is dependent on
the size, and the spectra shift to higher energies with decreasing
particle size.
2. Experimental section
2.1. Preparation of Ag colloids
2.1.1. Chemical reduction method
The silver colloid was prepared according to Lee and Meisel’s
method [14]. In 500 ml of deionized water, 90 mg of silver nitrate
was dissolve and the solution was heated to boiling. Then 10 ml
of a 1% trisodium citrate aqueous solution was added into the
boiling silver nitrate solution, accompanied by vigorous stirring.
The mixed solution was kept boiling for another 10 min. Finally,
a green-gray silver colloid was obtained.
2.1.2. Laser ablation method
Silver foil (99.9%, ∼1 mm thickness) first cleaned in diluted
nitric acid, and then was rinsed in ultrasonic washer with redis-
tilled deionized water for 10 min. The silver foil was immersed
in a quartz cell filled with redistilled deionized water and irradi-

1386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.01.010
1004 Y. Zhao et al. / Spectrochimica Acta Part A 65 (2006) 1003–1006

ated by a focused beam of the 532 nm line of the Nd: YAG pulsed
laser with 10 Hz repetition. The laser beam was adjusted by a
200 mm focusing lens to make the laser facula on the Ag plate to
be ∼2 mm in diameter. The irradiation by the laser of 532 nm was
continued for 20 min with an energy output 300 mJ per pulse.
For the ablation by excimer laser with 248 nm line, the focusing
lens was 100 mm, and the irradiation time was 30–40 min with
an energy output 350 mJ per pulse. The other conditions were
the same with that of laser ablation with 532 nm.

2.2. Experimental instrumentations

The transmission electron micrograph (TEM) images of the

Ag colloids were taken with a H-600 TEM. All the optical
absorption plasma spectra of the Ag colloids were measured
with a SHIMADZU Model UV-2401 PC UV–vis spectropho-
tometer. The fluorescence spectra were recorded on Fluorolog-3
spectrometer. The SERS spectra were obtained using the FT-IR
spectrometer (RFS 100/s, Bruker). All of the spectra were mea-
sured at room temperature.
3. Results and discussion
It is generally believed that the general nanoparticles are char-
acterized by the UV–vis absorption spectrum of the liquid and
with a transmission electron microscope (TEM). Fig. 1 shows
the optical surface plasmon absorption (SPA) spectra of three
kinds of Ag nanoparticles in the colloids, respectively. The char-
acteristic peak of the Ag colloid prepared by chemical reduction
centered at 440 nm as shown by band a, and for the colloids
produced by laser ablation with the beam of 532 and 248 nm,
the surface plasma peaks are both at 395 nm, shown by bands
b and c. Note the red shift of the plasmon frequency of Ag
nanoparticles in band a compared with bands b and c, which
is characteristic for increase of the size [15]. Therefore, among
these three Ag nanoparticles, the kind prepared by chemical
reduction should be the largest. However, compared with b, the
band c is more broadened and the relative intensity of the plasma
peak is reduced. The difference in the shape of the plasma band
suggested the change in particle size under different laser wave-
Fig. 1. The SPA spectra of Ag colloids produced by chemical reduction method
(a), laser ablation of 532 nm (b) and 248 nm (c).
lengths [16]. Therefore, similar to the analogy of Mafune [17],
the size of Ag nanoparticles obtained with 248 nm laser ablation
is smaller than that with 532 nm. The results accord with the
change of size distribution measured directly from the transmis-
sion electron micrograph (TEM).
Fig. 2a–c display the TEM images of Ag colloids prepared
with chemical reduction and laser ablation focused at 532 and
248 nm. The scale bar donates 50 nm. From the images, it can
be seen that the chemical reduction Ag particles are faceted
nanocrystals with high aggregation and do not have regular
shapes. Moreover, the average size is the largest (about 60 nm)
with a wide size distribution, for the growth of the particles
is a complex chemical mechanism of reactions and influenced
by many uncontrolled factors. However, despite the different
laser wavelengths, the shape of laser ablated Ag nanoparticles
is disk-like, as shown in Fig. 2b and c. The average diame-
ter of the particles prepared with 532 nm laser light (25 nm)
is larger than that prepared with 248 nm laser light (12 nm). It
has been reported the self-absorption of laser light by colloid
metal particles caused fragmentation, leading to reduce of the
metal particles [16]. It seemed that with decrease of the laser

Fig. 2. TEM images of silver colloids particles prepared with (a) chemical reduction, (b) laser ablation with 532 nm and (c) with 248 nm.
 Y. Zhao et al. / Spectrochimica Acta Part A 65 (2006) 1003–1006
Fig. 3. (a–c) Photoluminescence spectra of Ag nanoparticles prepared by citrate reduction, 532 nm laser ablation and 248 nm laser ablation, respectively.
wavelength, the self-absorption have a greater influence on the
particle size, smaller the particle is [16].
Compared with other noble metals, Ag nanoparticles, such as
Ag colloids and Ag island film have often been widely employed
as the effective active substrate for surface-enhanced Raman
scattering (SERS) that is a powerful technique revealing the
molecules’ orientation and the mechanism of interaction of the
molecules with the surface of the substrate [18–20]. Recently, we
have obtained high-quality SERS spectra of p-hydroxybenzoic
acid (PHBA) using any of these three silver nanoparticles with
different size and shape with the excitation of 1064 nm [21,22].
It is well known that the electromagnetic (EM) and the charge
transfer (CT) mechanisms are the main contributions to the
enhancement in surface-enhanced Raman scattering [23]. How-
ever, it is a difficult task to recognize the participation of each
mechanism. According to the electromagnetic mechanism, the
silver colloid with sharp edges and high aggregation of particles
should be a comparative highly SERS-active substrate, that is to
say, the nanoparticles prepared by chemical reduction should be
more suitable for the SERS-active substrate compared with that
produced by laser ablation considering this point. What’s more,
the enhancement factors have the close relationship with the
size of nanoparticles and the molecule–metal distance due to the
electromagnetic mechanism [24]. It is reported the highly active
particles fall in a narrow size range of about 90–100 nm [25].
However, from the SERS experimental results of ours, whatever
the shape and size, faceted or disk-like, 12 or 60 nm, SERS spec-
tra of p-hydroxybenzoic acid (PHBA) with high-quality were
recorded, which indicated that size and shape of the nanopar-
ticles in silver colloid did not play the important role for the
enhancement effect. We suggest that for the SERS-active sil-
ver colloid substrate, at least, for some absorbed molecules, the
electromagnetic mechanism is not the domain contributions to
the SERS enhancement factor. Well, does the charge transfer
mechanism play the first role in the enhancement effect? This
should be proved by the further experiment.
With knowledge in our mind, photoluminescence has been
used extensively in the process of inelastic scattering processes
besides the Raman scattering [26]. Renewed interest in lumines-
cence from metals came with a number of discoveries related
to noble metals with roughened surfaces [26]. It is reported
1005
that nanosize metals such as gold and silver have also been
shown to exhibit novel size-dependent optical properties [6].
In this article, photoluminescence properties of different silver
nanoparticles in colloid solutions have been studied.
Fig. 3a–c show the photoluminescence spectra of Ag
nanoparticles prepared by chemical citrate reduction, 532 nm
laser ablation and 248 nm laser ablation, respectively. The posi-
tion and shape of the photoluminescence peak is almost inde-
pendent of the excitation wavelength. From the spectra, it can
be seen that the photoluminescence spectra differ greatly from
each other, which shifts to the higher energy with decreasing the
size of Ag nanoparticles in the colloid. The relatively intense
photoluminescence peak at 340 nm is observed from 248 nm
laser ablation Ag nanoparticles of average size 12 nm. Though
the band centered at 440 nm is divided into several peaks, it is
comparatively much weak, as is shown in Fig. 3c. The lumines-
cence band from Ag nanoparticles of about 25 nm prepared by
532 nm laser ablation centered at 450 nm includes three well-
resolved peaks: 440, 450 and 466 nm. The photoluminescence
spectrum from chemical reduction Ag colloid displays obviously
red shift, and it includes the strong peak of 466 nm and the band
centered at 700 nm which includes five peaks: 668, 685, 712,
730 and 764 nm. It is notable the separation in energy between
adjacent above five peaks is 0.5 eV, and it is same as that of the
fluorescence from C60 in C60 -pyridine solution [27]. Therefore,
as for as the assignments of them are concerned, it needs the
further discussion. Besides the difference among the photolu-
minescence spectra, three peaks: 440, 450 and 466 nm can be
observed from three silver colloids of different size, though the
peaks of 440 and 450 nm are very weak in Fig. 3a. Similar to the
analogy of photoluminescence from noble metals, these three
visible PL peaks can be assigned to radiative recombination of
Fermi level electrons and sp- or d-band holes [28].
4. Conclusion
Three silver nanoparticles of different size were prepared
by chemical reduction and laser ablation with excitation of
532 and 248 nm. Together with the TEM image analysis and
UV–vis absorbance, SERS-active effect and photoluminescence
of three different size silver nanoparticles are studied. The anal-
1006 Y. Zhao et al. / Spectrochimica Acta Part A 65 (2006) 1003–1006
ysis showed that enhancement factor of silver colloids has not
too much relation with the size and shape of the nanopar-
ticles, which indicates the electromagnetic mechanism is not
the domain contributions to the SERS enhancement factor for
some absorbed molecules. However, the photoluminescence
property of nano silver particles is dependent on the size, and
the spectra shift to higher energies with decreasing particle
size.
Acknowledgments
The authors are grateful for the support of this research by
the National Natural Science Foundation of China and Natural
Science Foundation of Beijing municipality.
References
[1] M.L. Steigerwald, A.P. Alivisatos, J.M. Gibson, T.D. Harris, R. Kortan,
A.J. Muller, A.M. Thayer, T.M. Duncan, D.C. Douglass, L.E. Bruns, J.
Am. Chem. Soc. 110 (1988) 3046.
[2] L. Spanhel, M. Haase, H. Weller, A. Henglein, J. Am. Chem. Soc. 109
(1987) 5649.
[3] J.P. Wilcoxon, J.E. Martin, J. Chem. Phys. 108 (1998) 9137.
[4] P.A. Brugger, P. Cuender, M.J. Gratzel, J. Am. Chem. Soc. 103 (1981)
2923.
[5] P. Mulvaney, T. Linnert, A. Henglein, J. Phys. Chem. 95 (1991)
7843.
[6] J.P. Wilcoxon, R.L. Williamson, R.J. Baughman, J. Chem. Phys. 98 (1993)
9933.
[7] M.V. Kortennnr, Z.I. Kolar, F.D. Tichelaar, J. Phys. Chem. B 103 (1999)
2054.
[8] J.M. Petroski, Z.L. Wang, T.C. Green, M.A. El-Sayed, J. Phys. Chem. B
102 (1998) 3316.
[9] T.S. Ahmadi, Z.L. Wang, T.C. Green, A. Henglein, M.A. El-Sayed, Science
272 (1996) 1924.
[10] C.D. Bain, J. Evall, G.M. Whitesides, J. Am. Chem. Soc. 111 (1989)
7155.
[11] C. Petit, P. Lixon, M.P. Pileni, J. Phys. Chem. 97 (1993) 12974.
[12] M.P. Pileni, Langmuir 13 (1997) 3266.
[13] M. Prochazka, P. Mojzes, J. Stepanek, B. Vickova, P.Y. Turpin, Anal. Chem.
69 (1997) 5103.
[14] P.C. Lee, D. Meisel, J. Phys. Chem. 86 (1982) 3391.
[15] G.A. Shafeev, E. Freysz, F. Bozon-Verduraz, Appl. Phys. A 78 (2004)
307.
[16] T. Tsuji, K. Iryo, Y. Nishimura, M. Tsuji, J. Photochem. Photobiol. A Chem.
145 (2001) 201.
[17] F. Mafune, J.Y. Kohno, Y. Takeda, T. Kondow, J. Phys. Chem. B 104 (2000)
9111.
[18] J.S. Suh, K.H. Michaelian, J. Raman Spectrosc. 18 (1987) 409.
[19] J. Chowdhury, M. Ghosh, T.N. Misra, Spectrochim. Acta, Part A 56 (2002)
2107.
[20] I.T. Shadi, B.Z. Chowdhry, M.J. Snowden, R. Withnall, Anal. Chim. Acta
450 (2001) 115.
[21] D. Wu, Y. Fang, J. Colloid Interface Sci. 265 (2003) 234.
[22] J.B. Zhang, Y. Fang, submitted for publication.
[23] F.J. Adrian, J. Chem. Phys. 77 (1982) 5302.
[24] J. Gersten, J. Chem. Phys. 73 (1980) 3023.
[25] S.R. Emory, S.M. Nie, J. Phys. Chem. B 102 (1998) 493.
[26] G.T. Boyd, Z.H. Yu, Y.R. Shen, Phys. Rev. B 33 (1986) 7923.
[27] Y. Zhao, Y. Fang, J. Phys. Chem. B 108 (2004) 13586.
[28] A. Mooradian, Phys. Rev. Lett. 22 (1969) 185.