Net-like Assembly of Au Nanoparticles
J. Phys. Chem. A, Vol. 113, No. 11, 2009 2471
References and Notes
may be overlapped with the infrared-active absorptions of the
C
C
60 precursor.25 A similar SEIRA spectrum is also obtained for
70, as shown in Figure 6B.
(
1) (a) Ebbesen, T. W.; Lezec, H. J.; Ghaemi, H. F.; Thio, T.; Wolff,
P. A. Nature 1998, 391, 667. (b) Dirix, Y.; Bastiaansen, C.; Caseri, W.;
Smith, P. AdV. Mater. 1999, 11, 223.
It should be mentioned that no reasonable SEIRA is observ-
(
2) (a) Elghanian, R.; Storhoff, J. J.; Mucic, R. C.; Letsinger, R. L.;
able from the layer-coated Au nanoparticles. As one may know,
the mechanism for SEIRA has been demonstrated with rare
similarity to SERS. It has been well-documented that SERS
Mirkin, C. A. Science 1997, 277, 1078. (b) Henglein, A.; Meisel, D. J.
Phys. Chem. B 1998, 102, 8364. (c) Haes, A. J.; Van Duyne, R. P. J. Am.
Chem. Soc. 2002, 124, 10596. (d) Zhao, J.; Zhang, X.; Yonzon, C. R.; Haes,
A. J.; Van Duyne, R. P. Nanomedicine 2006, 1, 219.
28
originates primarily from two effects: electromagnetic field
enhancement caused by LSPR associated with metallic nano-
structures and chemical enhancement caused by resonance
Raman-like interaction between the metallic nanostructure and
adsorbate. For SEIRA, it was reported that the attenuated total
reflection (ATR) geometry in infrared absorption achieves a
large effective surface area without the need for powder sample
or molecular film.28 It is likely that the adsorption of C60/C70
on Au allows the symmetry lowering, which is beneficial not
only to SERS measurement but also to the SEIRA. At the same
time, the net-assembled Au nanoparticles present remarkable
SPR, giving a strong local electric field, which can also bring
forth contributions to the vibrational modes with either Raman-
activity or infrared-activity. The synchronous observation of the
SERS and SEIRA in this system indicates that the local electric
field of SPR plays the dominant role for the physically adsorbed
(
3) Knoll, W. Annu. ReV. Phys. Chem. 1998, 49, 569. (b) Quinten,
M.; Leitner, A.; Krenn, J. R.; Aussenegg, F. R. Opt. Lett. 1998, 23, 1331.
c) Brongersma, M. L.; Hartman, J. W.; Atwater, H. A. Phys. ReV. B 2000,
62, R16356. (d) Egusa, S.; Liau, Y. H.; Scherer, N. F. Appl. Phys. Lett.
004, 84, 1257.
4) (a) Freeman, R. G.; Grabar, K. C.; Allison, K. J.; Bright, R. M.;
(
2
(
Davis, J. A.; Guthrie, A. P.; Hommer, M. B.; Jackson, M. A.; Smith, P. C.;
Walter, D. G.; Natan, M. J. Science 1995, 267, 1629. (b) Kahl, M.; Voges,
E.; Kostrewa, S.; Viets, C.; Hill, W. Sens. Actuators, B 1998, 51, 285. (c)
McFarland, A. D.; Young, M. A.; Dieringer, J. A.; Van Duyne, R. P. J.
Phys. Chem. B 2005, 109, 11279. (d) Sung, J.; Hicks, E. M.; Van Duyne,
R. P.; Spears, K. G. J. Phys. Chem. C 2008, 112, 4091–4096.
(
5) (a) Bohren, C. F.; Huffman, D. R. Absorption and Scattering of
Light by Small Particles; Wiley-VCH: Weinheim Germany, 2004. (b)
Haynes, C. L.; Van Duyne, R. P. J. Phys. Chem. B 2001, 105, 5599. (c)
Chan, G. H.; Zhao, J.; Hicks, E. M.; Schatz, G. C.; Van Duyne, R. P. Nano
Lett. 2007, 7, 1947.
(6) (a) Jensen, T. R.; Duval, M. L.; Kelly, K. L.; Lazarides, A. A.;
Schatz, G. C.; Van Duyne, R. P. J. Phys. Chem. B 1999, 103, 9846. (b)
Kelly, K. L.; Coronado, E.; Zhao, L.; Schatz, G. C. J. Phys. Chem. B 2003,
C60 or C70 molecules.
1
07, 668.
7) (a) Enders, D.; Rupp, S.; Kuller, A.; Pucci, A. Surf. Sci. 2006, 600,
L305. (b) Kosower, E. M.; Markovich, G.; Borz, G. J. Phys. Chem. B 2004,
The porous nanonet of Au nanoparticles assembly on the
AAO template shows infiltrative properties, which benefits the
decentralization of the drops of fullerene C60/C70 clusters on
(
108, 12873. (c) Bjerke, A. E.; Griffiths, P. R. Appl. Spectrosc. 2002, 56,
272A–285A. (d) Krauth, O.; Fahsold, G.; Lehmann, A. Surf. Sci. 1999,
433, 79. (e) Osawa, M.; Ikeda, M. J. Phys. Chem. 1991, 95, 9914.
2
9
the background substrates. Recently Yu et al. showed that
besides the nanodisk arrays exhibiting the SERS effect, regular
Au nanohole (100-600 nm) arrays fabricated via electron beam
lithography also exhibit a strong SERS effect attributed to the
electromagnetic coupling between the holes. Here, the fabricated
nanonet of the Au nanoparticles also shows several hundred
nanometer net-holes, which is assumed to give contributions to
the SERS and SEIRA effect.
(
8) (a) Tamaru, H.; Kuwata, H.; Miyazaki, H. T.; Miyano, K. Appl.
Phys. Lett. 2002, 80, 1826. (b) Su, K.-H.; Wei, Q.-H.; Zhang, X.; Mock,
J. J.; Smith, D. R.; Schultz, S. Nano Lett. 2003, 3, 1087. (c) Rechberger,
W.; Hohenau, A.; Leitner, A.; Krenn, J. R.; Lamprecht, B.; Aussenegg,
F. R. Opt. Commun. 2003, 220, 137. (d) Gunnarsson, L.; Rindzevicius, T.;
Prikulis, J.; Kasemo, B.; K a¨ ll, M.; Zou, S.; Schatz, G. C. J. Phys. Chem.
B 2005, 109, 1079. (e) Atay, T.; Song, J.-H.; Nurmikko, A. V. Nano Lett.
2
004, 4, 1627. (f) Jain, P. K.; Huang, W.; El-Sayed, M. A. Nano Lett. 2007,
7
, 2080.
(
9) Haynes, C. L.; McFarland, A. D.; Zhao, L.; Van Duyne, R. P.;
4
. Conclusions
Schatz, G. C.; Gunnarsson, L.; Prikulis, J.; Kasemo, B.; K a¨ ll, M. J. Phys.
Chem. B 2003, 107, 7337.
We extend the applications of AAO templates onto the
(
10) (a) Sung, J.; Hicks, E. M.; Van Duyne, R. P.; Spears, K. G. J.
filtration and assembly for Au nanoparticles. It is found that
the colloidal Au nanoparticles can be washed cleanly and
arranged into a nanonet-like array along the edge of AAO pores.
Taking fullerene C60/C70 as probe molecules and the filtrated
Au nanoparticles as substrate, we obtained high-quality SERS
spectra and SEIRA spectra. The synchronous observation of
the SERS and SEIRA indicates that the local electric field of
SPR plays the dominant role in the Raman scattering and
infrared absorption for the physically adsorbed C60 or C70
molecules. Such a work is expected to be helpful for the design
and development of highly active substrates for SERS and
SEIRA investigation.
Phys. Chem. C 2007, 111, 10368. (b) Zou, S.; Zhao, L.; Schatz, G. C. Proc.
SPIE-Int. Soc. Opt. Eng. 2003, 5221, 174. (c) Bouhelier, A.; Bachelot, R.;
Im, J. S.; Wiederrecht, G. P.; Lerondel, G.; Kostcheev, S.; Royer, P. J.
Phys. Chem. B 2005, 109, 3195. (d) Maier, S. A.; Kik, P. G.; Atwater,
H. A. Appl. Phys. Lett. 2002, 81, 1714.
(
11) Wei, Q.-H.; Su, K.-H.; Durant, S.; Zhang, X. Nano Lett. 2004, 4,
1067.
(
12) (a) Whitesides, G. M.; Grzybowski, B. Science 2002, 295, 2418–
2
421. (b) Holtz, J. H.; Asher, S. A. Nature 1997, 389, 829–832. (c)
Kobayashi, N.; Egami, C. Opt. Lett. 2005, 30, 299–301. (d) Vlasov, Y. A.;
Bo, X.-Z.; Sturm, J. C.; Norris, D. J. Nature 2001, 414, 289–293.
(
13) (a) Xia, D.; Brueck, S. R. J. Nano Lett. 2004, 4, 1295–1299. (b)
Amos, F. F.; Morin, S. A.; Streifer, J. A.; Hamers, R. J.; Jin, S. J. Am.
Chem. Soc. 2007, 129, 14296–14302. (c) Kalsin, A. M.; Fialkowski, M.;
Paszewski, M.; Smoukov, S. K.; Bishop, K. J. M.; Grzybowski, B. A.
Science 2006, 312, 420–424. (d) Yin, Y.; Lu, Y.; Gates, B.; Xia, Y. J. Am.
Chem. Soc. 2001, 123, 8718–8729.
Acknowledgment. This work was supported by the National
Natural Science Foundation of China (Nos. 50221201, 90301010,
(
14) (a) Xu, J.; Xia, J.; Lin, Z. Angew. Chem., Int. Ed. 2007, 46, 1860–
1
863. (b) Malaquin, L.; Kraus, T.; Schmid, H.; Delamarche, E.; Wolf, H.
20373077, 20471062, and 50573084) and the Chinese Academy
Langmuir 2007, 23, 11513–11521. (c) Huang, J.; Kim, F.; Tao, A. R.;
Connor, S.; Yang, P. Nat. Mater. 2005, 4, 896–900. (d) Huang, J.; Tao,
A. R.; Connor, S.; He, R.; Yang, P. Nano Lett. 2006, 6, 524–529. (e) Bigioni,
T. P.; Lin, X.-M.; Nguyen, T. T.; Corwin, E. I.; Witten, T. A.; Jaeger, H. M.
Nat. Mater. 2006, 5, 265–270. (f) Deegan, R. D.; Bakajin, O.; Dupont,
T. F.; Huber, G.; Nagel, S. R.; Witten, T. A. Nature 1997, 389, 827–829.
of Sciences.
Supporting Information Available: Figures giving a sketch
map illustration of the filtration methods; SEM images of the
as-prepared AAO templates with 20 and 20nm pores; and
Raman of only pyridine solvent media (after volatilization) on
Au nanoparticles assembled on the AAO template, Raman of
only C60 pyridine solution on the AAO template, and SERS of
(
5
g) Brinker, C. J.; Lu, Y.; Sellinger, A.; Fan, H. AdV. Mater. 1999, 11,
79–585.
(
(
15) Cai, Y.; Zhang, B. M. J. Am. Chem. Soc. 2008, 130, 6076-6077.
16) (a) Masuda, H.; Fukuda, K. Science 1995, 268, 1466. (b) Redl,
F. X.; Cho, K. S.; Murray, C. B.; O’Brien, S. Nature 2003, 423, 968–971.
c) Son, D. H.; Hughes, S. M.; Yin, Y. D.; Alivisatos, A. P. Science 2004,
06, 1009–1012. (d) Harman, T. C.; Taylor, P. J.; Walsh, M. P.; LaForge,
(
C60 from net-assembled Au nanoparticles on an AAO template.
3
This material is available free of charge via the Internet at http://
pubs.acs.org.
B. E. Science 2002, 297, 2229. (e) Venkatasubramanian, R.; Siivola, E.;
Colpitts, T.; O’Quinn, B. Nature 2001, 413, 597. (f) Prieto, A. L.; Martın-