You are on page 1of 3

ChemComm

COMMUNICATION

Silver nanoprism enhanced fluorescence in


Cite this: Chem. Commun., 2013,
YVO4:Eu3+ nanoparticles†
49, 9485
Zubair Buch,a Vineet Kumar,a Hitesh Mamgainb and Santa Chawla*a
Received 12th July 2013,
Accepted 16th August 2013

DOI: 10.1039/c3cc45267k

www.rsc.org/chemcomm

Silver nanoprisms of different sizes influence fluorescence enhance- the enhancement process.2,3 The EM field generated around
ment in YVO4:Eu3+ nanoparticles to various degrees under excitation MNPs increases the excitation of RE ions and slows down their
of green light (532 nm). The local field generated by silver nanoprisms fluorescence decay due to the increased radiative component
and their dimers is simulated through the FDTD method and a direct leading to an overall improvement of their quantum efficiency.6
correlation with fluorescence enhancement is established. In this communication, we present studies of an integrated
material system consisting of YVO4:Eu3+ nanocrystals combined
Rare-earth (RE) ion doped nanophosphors have potential applica- with Ag nanoprisms (Ag NPs). A thin (few nm) layer of polyvinyl
tions and YVO4:Eu3+ stands as a well established highly efficient alcohol (PVA) is placed between the two species to prevent direct
red emitting phosphor.1 YVO4 has proven to be a stable host for contact which otherwise can result in fluorescence quenching,
Eu3+ enabling high efficiencies at UV excitation; however, the low favoring non-radiative transitions from fluorophores in contact
response of YVO4 beyond the UV region limits its applications with MNPs.7 Ag NPs are reported to yield large EM field
especially for solar cells and nanobiotechnology due to UV induced enhancements in the visible region due to their ability to exhibit
autofluorescence and cell damage. Achieving a high fluorescence distinct dipolar and quadrupolar resonances8 with a significant
yield from YVO4:Eu3+ nanoparticles under visible light excitation is role in fluorescence enhancement of RE ions.9,10 To the best of
highly desirable for such applications and plasmon enhanced our knowledge, our study covers metal enhanced fluorescence
fluorescence can be an effective way. in YVO4:Eu3+ through green light for the first time since all
Metal enhanced fluorescence in RE doped nanophosphors previous studies involved excitation by UV light.
shows great promise with manifold enhancement.2,3 The highly YVO4:Eu3+–Ag NP integrated thin films were prepared by first
localized electromagnetic (EM) fields generated around metal spin coating a layer of YVO4:Eu3+ dispersed in ethanol on a clean
nanoparticles (MNPs) are responsible for these enhancements. microscopic cover slip followed by a spacer layer of PVA (3% PVA in
The EM fields are generated by resonant excitation of conduction water) of a few nm thickness. A colloidal solution containing Ag NPs
electrons in MNPs also known as surface plasmons, upon excita- was then spin coated on top of the PVA layer. All the parameters
tion by incident light. Another factor that contributes towards the controlling thin film formation were optimized and kept constant
enhancement process is the lightening rod effect which strictly throughout the experiment. Eu3+ (5 atomic%) doped YVO4 nano-
depends on the shape of MNPs.4a Reports5 suggest that fluores- particles were synthesized by the co-precipitation method.11 XRD
cence enhancement depends mainly on two factors (i) excitation and TEM images [ESI†] confirmed formation of monophasic, mono-
enhancement and (ii) emission enhancement for which spectral disperse, spherical and transparent YVO4:Eu3+ nanocrystals of 5 nm
overlap of the plasmon absorption band of MNPs with either the size. Two Ag NP solutions with average edge lengths of (i) 22 nm
absorption band or the emission spectra of a nanophosphor is (Ag NP 1) and (ii) 45 nm (Ag NP 2) were synthesized by adopting the
required. Scattered light by MNPs may also contribute towards method developed by V. E. Torres Heredia12 and their morphology
was studied by TEM [ESI†]. The two Ag NP solutions exhibited
a
Luminescent Materials Group, CSIR-National Physical Laboratory,
different colors upon synthesis, deep purple (22 nm edge length)
Dr K.S. Krishnan Road, New Delhi 110012, India. E-mail: santa@nplindia.org; and deep blue (45 nm edge length), as a consequence of their SPR
Fax: +91 11 45609310; Tel: +91 11 45609242 bands. The absorption spectra of the two Ag NP solutions were
b
WITec GmbH, Lise-Meitner-Str. 6, D-89081 Ulm, Germany studied using an Avantes UV-Visible spectrometer. AgNP1 solution
† Electronic supplementary information (ESI) available: Synthesis details of
revealed lmax at 540 nm and for AgNP2 the absorption spectrum
YVO4:Eu3+ nanoparticles and silver nanoprisms, instrument details, TEM, AFM
images, excitation spectra of YVO4:Eu3+ at 615 nm emission, confocal fluorescence
was centered at lmax = 632 nm. Fluorescence studies were per-
data of YVO4:Eu3+ nanoparticle clusters, decay time and fluorescence data, FDTD- formed using a confocal microscope (WITec R 300) with N.A 0.9 and
material data index and FDTD simulation parameters. See DOI: 10.1039/c3cc45267k a green DPSS laser (output wavelength 532 nm, power 44 mW) as an

This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 9485--9487 9485
Communication ChemComm

excitation source. The integrated intensity of the whole scanned


region was estimated through software (WITec Project 2.10) and
calculated by taking the total intensity divided by the number of
data points in the scanned region.
The optical and corresponding confocal fluorescence images of
YVO4:Eu3+, YVO4:Eu3+ and Ag NP1, YVO4:Eu3+ and Ag NP2, excited by
532 nm light are shown in Fig. 1(i)–(vi). TEM images of Ag NPs of
average edge lengths of 22 nm and 45 nm synthesized by a wet
chemical route are shown in Fig. 1(vii) and (viii), respectively. The Fig. 2 (a) Extinction spectra of exact Ag nanoprisms, Ag NP1 & Ag NP2 imported
from TEM in an aqueous environment (background index 1.33) using FDTD simula-
schematic arrangement of thin films prepared for confocal measure-
tions, (b) the measured UV-Visible absorption spectra of Ag NP colloidal solution.
ments is presented in Fig. 1(ix). The fluorescence spectra of samples
corresponding to the confocal scans are shown in Fig. 1(x). The
integrated spectrum taken for YVO4:Eu3+ nanocrystals reveals fluores- spectra of Eu3+ (615 nm) ruling out the possibility of emission
cence intensity only around 10 CCD counts since the YVO4 host has enhancement due to scattering by Ag NPs.
very low response to wavelengths beyond 350 nm [ESI†]. Also, the To further comprehend the optical properties and influence of
excitation energy of 532 nm is just sufficient to excite 7FJ–5D1 silver we performed three dimensional finite difference time domain
transition of the Eu3+ ion [ESI†]. For the integrated material system (FDTD) simulations of Ag NPs of exact geometry (imported from a
of YVO4:Eu3+ and Ag NPs, the fluorescence intensity increased transmission electron micrograph), one Ag NP taken from each
remarkably as shown in Fig. 1(x). The number of CCD counts reached solution on the basis of average distribution of size and geometry.
a value of 90 upon adding Ag NP1 and 160 upon addition of Ag NP2, The FDTD method has proven to be productive for simulation of
which is highly significant. The fluorescence enhancements observed plasmonic nanostructures of complex geometry, which other-
from both the samples correspond to the characteristic electric wise cannot be solved by conventional theories for spherical and
5
D0–7F2 and magnetic 5D0–7F1 dipole transition of Eu3+ ions [ESI†], ellipsoidal structures.14 In this method both electric E(t) and
which can happen only by excitation enhancement due to Ag NPs in magnetic H(t) components of the EM field are made discrete in
proximity of YVO4:Eu3+. We performed time resolved decay of 5D0–7F2 time and Maxwell’s equations are solved in both E(t) and H(t) to
emission (615 nm) at 532 nm excitation (Fig. 1(xi)) and the decay time obtain the steady state continuous wave field E(o). We used
(t) was calculated for all samples. The decay slowed down after FDTD solutions, Version 8.515 and imported TEM images of both
adding Ag NPs and similar behavior is also reported.9,13 Fluorescence Ag NP1 and Ag NP2 with appropriate simulation parameters
enhancement due to the local field generated by Ag NPs reduces non- [ESI†]. The material response for silver was taken from the study
radiative recombination leading to an increase in decay time. The performed by Palik16 and a mesh size of 0.8 nm was used.
extinction spectra of Ag NPs (Fig. 2a) do not overlap with emission Fig. 2(a) shows the extinction spectrum calculated for Ag NP1
and Ag NP2 by the FDTD method and Fig. 2(b) shows the corre-
sponding experimental UV-Visible absorption spectra of both Ag
NP solutions. The prominent peak corresponding to the localized
surface plasmon resonance (LSPR) as reflected by FDTD spectra
lies at 397 nm for single Ag NP1 and at 427 nm for Ag NP2. The
corresponding experimental UV-Visible spectra reveal a broad peak
centered at 540 nm for Ag NP1 and at 635 nm for Ag NP2, due to
inhomogeneous damping caused by different spatial positions
and random orientations of Ag NPs in colloidal solution.17
Also, due to the presence of nanoparticle clusters or closely
spaced nanoparticles, the coupling of plasmon modes leads to
red shift and broadening of the absorption spectrum.4b,18
For a quantitative understanding of the effect of Ag NPs on the
YVO4:Eu3+ complex, we calculated the EM field generated for
both Ag NP geometries by FDTD at excitation (532 nm), emission
(615 nm) and LSPR frequency. Local electric field values |E|2
calculated by FDTD are displayed in Table 1, which reveal largest
|E|2 values at LSPR frequencies for both Ag NP geometries, which
is obvious. At an excitation wavelength of 532 nm, the |E|2 value for
a single Ag NP1 reaches 23 times the incoming field, while for Ag
Fig. 1 Optical image and corresponding confocal fluorescence image of (i) & (ii) NP2 the |E|2 value becomes 65 times. However |E|2 values calcu-
YVO4:Eu, (iii) & (iv) YVO4:Eu + AgNP1 combine, (v) & (vi) YVO4:Eu + AgNP2 lated at an emission wavelength of 615 nm reduce significantly for
combine, TEM image of Ag nanoprisms of edge lengths 22 nm and 45 nm
both Ag NP sizes (Table 1). Hence it can be concluded that
(vii) & (viii), (ix) schematic of arrangements of YVO4:Eu NPs (red spheres), PVA layer
(yellow transparent layer) & Ag NPs (blue prisms) used for confocal fluorescence
excitation enhancement by Ag NPs contributes greatly towards
study, (x) confocal fluorescence spectra (integrated) under 532 nm laser excitation, the fluorescence enhancement process. To further understand the
(xi) time resolved decay of YVO4:Eu at 615 nm with and without Ag NPs. enhancement due to the Ag NP ensemble, we calculated the |E|2

9486 Chem. Commun., 2013, 49, 9485--9487 This journal is c The Royal Society of Chemistry 2013
ChemComm Communication

Table 1 EM field enhancements of Ag nanoprisms field enhancement |E|2 with the fluorescence intensity. The near
field images of the Ag NPs by FDTD are shown in Fig. 3.
E-Field enhancement |E|2 (Z-direction)
The energy corresponding to incident radiation (532 nm) could
LSPR 615 nm 532 nm
only directly excite Eu3+ ions (7FJ–5D1) and such excitation is
Sample Single Single Single Dimer validated by the emitted fluorescence observed under 532 nm
Ag NP1 260 12 23 100 excitation. Due to interaction between incident radiation and
Ag NP2 648 39 65 2074 Ag NPs, localized surface plasmon oscillations are generated
resulting in formation of electric dipoles20,21 with energy corre-
values for a dimer of both Ag NP sizes. The distance between the sponding to the plasmon energy as reflected by their extinction
two nanoprisms in a dimer was kept 5 nm and the |E|2 values rose spectrum (Fig. 2a). Under the incident radiation energy transfer
from 23 to 100 for Ag NP1 and from 65 to 2074 for Ag NP2. from Ag NP through a dipole can take place to 5D2, 5D1 and 5D0
This is a direct consequence of the ability of MNPs and their levels of Eu3+ ions resulting in enhanced excitation i.e., more Eu3+
hybrids to confine light around and in the gaps between them, ions in the excited state and hence more fluorescence output due to
resulting in large enhancements of the EM field in their near transition from the 5D0 level to lower 7FJ levels giving rise to sharp
field region,19 and thus larger enhancements are expected for emission peaks in the red spectral region, the strongest emission
bigger Ag NP ensembles. Ag NP2 causes maximum fluorescence corresponds to the 5D0–7F2 electric dipole transition (Fig. 4).
enhancement at 532 nm which can be attributed to the strong In summary, we have presented a comprehensive study involving
local electric field |E|2 generated by it, similar behaviour has also chemical synthesis of shape and size tailored metal nanoprisms and
been reported20 which shows a direct proportionality of electric a rare earth doped nanophosphor and conjugation of Ag NPs and
nanophosphors in an appropriate configuration that leads to a
twenty-three fold fluorescence enhancement. We have used confocal
fluorescence microscopy to unequivocally establish the fluorescence
enhancement due to surface plasmons under excitation of green light,
which has not been reported so far. For a comprehensive under-
standing of the experimental results, we have used the FDTD simula-
tion technique for estimating the near field generation by Ag
monomers and particle hybrids which could be correlated with the
degree of observed fluorescence enhancement thus leading to a
complete understanding through experimental results and theoretical
simulation. Plasmon enhanced red emission when excited by green
light has promising applications in solar cells and nanobiotechnology.
We thank Mithun Bhomkar of Lumerical Solutions for his
advice concerning FDTD simulation.

Notes and references


Fig. 3 Near field image of single and dimer Ag nanoprisms by FDTD simulation by
1 A. Bril and W. L. Wanmaker, Philos. Tech. Rev., 1966, 27, 22.
importing exact TEM images of Ag NP. Near field image of (i) 22 nm Ag NP, (ii) & (iii)
2 W. Feng, L. D. Sun and C. H. Yan, Chem. Commun., 2009, 4393.
22 nm Ag single and dimer with 5 nm separation, (iv) 45 nm single Ag NP, (v) & (vi)
3 J. R. Lakowicz, Anal. Biochem., 2005, 337, 171.
45 nm single and dimer with 5 nm separation. All images are shown on the log scale. 4 (a) S. A. Maier, Plasmonics: fundamentals and applications, Springer,
New York, 2007, p. 162; (b) S. A. Maier, Plasmonics: fundamentals and
applications, Springer, New York, 2007, p. 80.
5 C. D. Geddes, Metal enhanced fluorescence, John Wiley & Sons,
New Jersey, 2010, p. 91.
6 C. D. Geddes and J. R. Lakowikz, J. Fluoresc., 2002, 12, 121.
7 P. Anger, P. Bharadwaj and L. Novotny, Phys. Rev. Lett., 2006, 96, 113002.
8 E. Hao and G. C. Schatz, J. Chem. Phys., 2004, 120(1), 357.
9 F. Song, et al., Opt. Express, 2011, 19(8), 6999.
10 F. Song, et al., J. Nanopart. Res., 2011, 13, 3861.
11 A. F. Khan, D. Haranath and S. Chawla, et al., Appl. Phys. Lett., 2008,
93, 073103.
12 www.tdx.cat/bitstream/10803/52807/3/tveth1de1.pdf.
13 X. Fang, H. Song, L. Xie, Q. Liu, H. Zhang, X. Bai, B. Dong, Y. Wang
and W. Han, J. Chem. Phys., 2009, 131(5), 054506.
14 A. Taflove and S. C. Hagness, Computational Electrodynamics: the
Finite-Difference Time-Domain Method, Artech House, 2000.
15 Reference Guide for FDTD Solutions, www.lumerical.com/fdtd.
16 E. D. Palik, Handbook of optical constants of solids, Academic,
New York, 1985.
17 F. K Guedje, et al., Phys. Scr., 2012, 86, 055702.
18 S. A. Maier, P. G. Kik and H. A. Atwater, Appl. Phys. Lett., 2002, 81, 9.
Fig. 4 The scheme of the excitation and emission process involving direct 19 H. Xu, E. J. Bjerneld, M. Kall and L. Borjesson, Phys. Rev. Lett., 1999,
excitation of Eu3+ ions by incident light (green arrow) and through the EM field 83, 4357.
of Ag NPs (black dotted arrow) and subsequent energy transfer to Eu3+ (red dotted 20 T. Som and B. Karmakar, J. Appl. Phys., 2009, 105(1), 013102.
arrows) leading to red fluorescence emission. 21 E. Marega Jr., Opt. Express, 2010, 18(24), 25322.

This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 9485--9487 9487