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Enhanced luminescence from europium complex owing to

surface plasmon resonance of silver nanoparticles


Yuehui Wang
a
, Ji Zhou
b,

, Ting Wang
b
a
Department of Chemistry and Biology, University of Electronic Science and Technology of China Zhong Shan Institute,
Zhong Shan 528402, People's Republic of China
b
State Key Lab of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua University, Beijing 100084, People's Republic of China
Received 17 April 2007; accepted 22 October 2007
Available online 26 October 2007
Abstract
The effect of Ag nanoparticles on the luminescent properties of the europium complex, where the complex is ethylenediamine tetra acetate
(EDTA), was investigated in the aqueous solution system. We observed the formation of nanoparticle aggregates and the appearance of a new
absorption and enhancement of the emission intensity for the complex solution containing Ag nanoparticles when the pH of the complex solution
is 34.6. Furthermore, with increasing Ag nanoparticles concentration enhancement efficiency first increases and then decreases. The
enhancement effect was discussed in terms of the effects of nanoparticle aggregates, the local electromagnetic field enhancement effect and optical
absorption due to surface plasmon resonance.
2007 Elsevier B.V. All rights reserved.
Keywords: Ag nanoparticles; Europium complex; Luminescence; Nanomaterials; Surface plasmon resonance; Local electromagnetic field enhancement
1. Introduction
The lanthanide complexes display large Stokes shifts,
narrow emission bandwidths, and long emission lifetimes.
Due to these characteristics, lanthanide complexes are widely
used in high-sensitivity immunoassays and in DNA hybridiza-
tion assay [13]. Recently, growing attention has been paid for
the fluorescence enhancement of fluorophores, based on the
metal-enhanced fluorescence (MEF) [46]. Luminescence
spectroscopy can be enhanced when fluorophores are localized
or close to metallic islands film [7,8]. That is because metallic
nanoparticles modify a fluorophore's radiative decay rate and
increase its excitation rates by the increase of concentration the
incident light [9]. Most studies focus on the effect of the Ag
island films deposited on quartz or glass slides on luminescent
properties of lanthanide complexes [1012]. The MEL effect on
fluorescence from europium (Eu
3+
) ion doped into glass or Eu
3+
complex adsorbed onto Ag-island surface, has been reported so
far, and they observed enhanced luminescence or shortened
lifetime of Eu
3+
ion with the presence of Ag [11]. Recently,
Nakiba et al. reported enhanced luminescence from Eu
3+
complex nearby Ag colloids in N,N-dimethylformamide
[12,13]. They observed particle concentration dependences of
the luminescent intensity and regarded it as the result of a
delicate balance between an enhancing and a quenching effect
of the Ag nanoparticles.
Because of these important applications of lanthanide
complexes to biochemistry and biotechnology, and the growing
interest in the applications of MEF, we researched the effect of
Ag nanoparticles on the luminescent properties of the Eu
3+
complex in the aqueous solution system. Furthermore, we
discussed in detail the mechanisms of the MEL effect.
2. Experimental
Colloidal Ag nanoparticles were synthesized by a modified
Lee and Meisel's method [14]. The Eu
3+
complex was
synthesized by dissolving the ethylenediamine tetra acetate
(EDTA) into Eu(OH)
3
with a molar ratio of EDTA/Eu
3+
=1:1.
Thereinto, Eu(OH)
3
was prepared through the following pro-
cesses. Firstly, europium oxide (Eu
2
O
3
) was dissolved by HNO
3
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Materials Letters 62 (2008) 19371940
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Corresponding author. Tel.: +86 10 62772975; fax: +86 10 62772975.


E-mail address: zhouji@mail.tsinghua.edu.cn (J. Zhou).
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doi:10.1016/j.matlet.2007.10.045
to obtain Eu(NO
3
)
3
solution, and then a certain amount of
ammonia was dropped into the solution. Finally, Eu(OH)
3
precipitates were obtained by centrifugation to remove the free
ions. The samples for the optical measurements were prepared
by mixing the Eu
3+
complex solution and the Ag colloid with
keeping the final concentration of Eu
3+
ion at 2.0 mM.
The transmission electron microscopy (TEM) micrographs
were obtained by using a 200 kV JEOL JEM-200CX TEM.
Electrokinetic measurement of Ag nanoparticles was evaluated
with a P/ACE MDQ electrophoresis analyzer. Ag nanoparticles
were negatively charged. UVvis absorption spectra were
recorded on a ThermoSpectronic UNICAM UV-500 PC
spectrophotometer and luminescence measurements were
recorded using a Cary Eclipse spectrofluorometer.
3. Results and discussion
The UVvis absorption spectra of Eu
3+
complex solution and Eu
3+
complex solution containing Ag colloid are shown in Fig. 1A. Upon
adding Ag nanoparticles into Eu
3+
complex solution, the color of the
solution immediately changed to pinkish red, accompanying the
appearance of a new absorption around 500700 nm (curve c in
Fig. 1A). The appearance of the new band at longer wavelength region
indicates the interaction between Ag nanoparticles and Eu
3+
complex
and the formation of nanoparticles aggregates in the solution [15].
Furthermore, the peak 453 nm was broadened and decreased in
intensity, which may indicate that a wide range of particle sizes existed
[13]. It is important to note that only when the pH of the solution is 3
4.6, color and spectral change was observed. When the pH is less 3, the
color of the solution changed to pinkish red, accompanying the
appearance of precipitation. When the pH is more 4.6, no color and
spectrum changes were observed. The effect of the ambient pH of Eu
3+
complex solution on Ag nanoparticles is attributed to the results of the
intermolecular hydrogen bonding ability of carboxylic acid, namely,
EDTA. When the ambient pH of Eu
3+
complex solution is 34.6, Eu
3+
complexes are partially ionized, and carboxylic acid groups not only bind
to the surface of Ag nanoparticles but also further interaction between
Eu
3+
complexes through intermolecular hydrogen bonding to yield
nanoparticles assemblies. The representative TEM micrograph of Ag
nanoparticles added into Eu
3+
complex solution was shown in Fig. 1C.
The principal result of the present study is that the luminescence
enhances dramatically from Eu
3+
complex solution containing Ag
nanoparticles. This behavior is illustrated in Fig. 2. Most of the work in
the literature detailed the effects of either fluorescent organic molecules
or lanthanide complexes adsorbed on silver islands film/silver
nanoparticles [48]. They pointed out two possible mechanisms on
the luminescence enhanced or quenched: one is an energy transfer
between fluorescence and metal nanopartilces [4]. The other is a local
electromagnetic field enhancement around fluorophores [58].
We believe that the enhanced luminescence in our experimental
conditions is due to the local field enhancement around Eu
3+
ions. It is
known that, to a solution containing Eu
3+
, two emission peaks at
615 nm and 592 nm correspond to
5
D
0

7
F
2
(electric dipole transition)
and
5
D
0

7
F
1
(magnetic dipole transition) transitions of the Eu
3+
,
respectively. They are sensitive to change of environmental parameters.
There should be interaction between Eu
3+
ions Ag nanoparticles, and in
this process of interaction Ag nanoparticles must strongly influence
Eu
3+
ions owing to their electronic plasma resonances, causing an
intensified electromagnetic field around Eu
3+
ions [12,13,16], resulting
in an increase of the rates of excitation and ff transitions. At the same
time, nearby conducting metallic particles can modify free-space
conditions around Eu
3+
and increase the incident electric field [7],
resulting in an increasing number of densities of conduction electrons
Fig. 1. (A) Absorption spectra of Eu
3+
complex solution (a), Ag colloid (b), and Eu
3+
complex solution containing Ag nanoparticles (c); (B) TEM images of Ag
nanoparticles and (C) added into Eu
3+
complex solution when the pH of the solution is 4.6.
1938 Y. Wang et al. / Materials Letters 62 (2008) 19371940
within a very short time of electron-phonon coupling time in
picosecond order [17]. This simultaneously means quantum yields
increase and luminescence enhance.
It is noteworthy that the luminescence enhancement by metallic
nanoparticles is strongly dependent on the distance from the fluorophore
to the metallic surface, the nanoparticle size and shape and concentration
and surface, environmental parameters, and binding-state between the
fluorophore and metallic surface, and so on [12,13,17,18]. In our study,
the luminescence enhancement was observed only when the pH of the
solution is 34.6. We believe that luminescence enhancement is relative
with the aggregates formation. When several particles approach closely,
the electromagnetic fields from them are expected to be overlapped to
result in a stronger field that leads to a stronger surface enhanced
fluorescence [19]. Furthermore, we observed a new absorbance band in
the absorption spectrum in the present system. Such an absorbance could
overcome a competitive quenching to induce a luminescence enhance-
ment. As mentioned above, Eu
3+
complexes are expected to be
incorporated into nanoparticle aggregates, and thus the luminescence
was effectively enhanced in the present system. The aggregation of
particles brought up a luminescence enhancement to some extent,
indicating that the enhancement on the aggregated particle could not be
explained by an ordinary competitive mechanism of quenching and
enhancement.
The Ag nanoparticles concentration dependence on the enhancement
efficiency are illustrated in Fig. 3, in which the enhancement efficiency is
integral intensity ratio of Eu
3+
complex solution containing Ag
nanoparticles to Eu
3+
complex solution at
5
D
0

7
F
1
transition emission
wavelength. The emission intensity first increases and then decreases
with the increase of Ag nanoparitcles concentration. When Ag
nanoparticles were added into Eu
3+
complex solution, some Eu
3+
complexes were localized or close to Ag nanoparticles, so Eu
3+
complex
solution fluorescence intensity was enhanced though the local electro-
magnetic field enhancement around Eu
3+
ions owing to the induced
surface plasmon resonance of Ag nanoparticles. With increasing of Ag
Fig. 3. Enhancement efficiency of Eu
3+
complex solutions containing Ag nanoparticles at different Ag nanoparticles concentrations.
Fig. 2. Emission spectra of the Eu
3+
complex solution and the Eu
3+
complex solution containing 10 M silver nanoparticles with mean diameter 45 nm
(excitation=395 nm).
1939 Y. Wang et al. / Materials Letters 62 (2008) 19371940
nanoparticles amount, more and more Eu
3+
complexes were localized or
close to Ag nanoparticles until saturated. Further increasing of Ag
nanoparticles amount, re-absorption of surface plasmon resonance of Ag
nanoparticles was dominant, so intensity gradually decreased. Therefore,
it is deduced from concentration dependence that the observed
enhancement factor is the results from delicate balance of the local
electromagnetic field enhancement and re-absorption of surface plasmon
resonance. The effectiveness of metallic nanoparticles for enhancement
phenomenon is widely known and explained about mechanism
[12,13,1619]. However, it is very difficult to predict the effectiveness
in different system. Only in specifically experimental conditions the
effectiveness of metallic nanoparticles for enhancement phenomenon is
observed. Since the enhancement effect strongly depend on different
experimental conditions, systematic studies are required to elaborate the
relation between the local electromagnetic field enhancement and surface
plasmon resonance with respect to the condition of Ag nanoparticles for
further improvement of overall enhancement effect and is currently under
investigation in our group.
4. Conclusions
The effect of Ag nanoparticles on the luminescent properties
of the europium complex was investigated in the aqueous
solution system. We observed the formation of nanoparticle
aggregates and the appearance of a new absorption and
enhancement of the emission intensity for the complex solution
containing Ag nanoparticles when the pH of the complex
solution is 34.6. Furthermore, with increasing Ag nanoparti-
cles concentration enhancement efficiency first increases and
then decreases. The observed enhancement effect was discussed
in terms of the effects of nanoparticle aggregates, the local
electromagnetic field enhancement effect and optical absorption
due to surface plasmon resonance.
Acknowledgments
This work was supported by National Science Foundation of
China under grants 50425204, 50272032 and 90401012,
Guangdong Provincial Natural Science Foundation under
grant 07300212 and Zhongshan Institute Scientific Research
Initial Foundation of University of Electronic Science and
Technology of China.
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