Abstract
The presence of so-called hot spots, regions with strongly enhanced electromagnetic field, is a critical property of a substrate enabling detection of surface-enhanced Raman scattering (SERS) signals at high enhancement levels. In this work, the effect of interparticle field enhancement on SERS signals was investigated comparing SERS spectra of ethylenediaminetetraacetic-disodium salt in the chemically produced colloids with isolated and aggregated silver nanoparticles using 473 and 532-nm wavelength excitation. The presence of aggregates in the colloidal solution resulted in SERS spectra that were insensitive to wavelength excitation and much richer in structural information and of higher resolution than the corresponding SERS spectra for the colloid with isolated nanoparticles. The experimental SERS spectra were found to be consistent with the finite-difference time-domain simulation results that explored the electromagnetic response of the isolated and aggregated nanoparticles. These results provide more evidence to suggest that the aggregate formation offers favorable electromagnetic properties increasing sensitivity of Raman spectroscopy.
This is a preview of subscription content, access via your institution.





References
Kneipp K, Kneipp H, Kneipp J (2006) Surface–enhanced Raman scattering in local optical fields of silver and gold nanoaggregates from single–molecule Raman spectroscopy to ultrasensitive probing in live cells. Acc Chem Res 39(7):443–450
Lal S, Link S, Halas N (2007) Nano–optics from sensing to waveguiding. J Nat Photon 1:641–648
Brolo AG (2012) Plasmonics for future biosensors. J Nat Photon 6:709–713
Kawata S, Inouye Y, Verma P (2009) Plasmonics for near–field nano–imaging and superlensing. J Nat Photon 3:388–394
Ozbay E (2006) Plasmonics: merging photonics and electronics at nanoscale dimensions. Science 311(5758):189–193
Kelly KL, Coronado E, Zhao LL, Schatz GC (2003) The optical properties of metal nanoparticles: the influence of size, shape, and dielectric environment. J Phys Chem B 107(3):668–677
Kerker M, Wang D, Chew H (1980) Surface enhanced Raman scattering (SERS) by molecules adsorbed at spherical particles: errata. Appl Opt 19(24):4159–4174
Moskovits M (1978) Surface roughness and the enhanced intensity of Raman scattering by molecules adsorbed on metals. J Chem Phys 69:4159–4162
Fleischmann M, Hendra PJ, McQuillan A (1974) Raman spectra of pyridine adsorbed at a silver electrode. Chem Phys Lett 26(2):163–166
Jeanmaire DL, Van Duyne RP (1977) Surface Raman spectroelectrochemistry: part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode. J Electroanal Chem 84(1):1–20
Albrecht MG, Creighton JA (1977) Anomalously intense Raman spectra of pyridine at a silver electrode. J Am Chem Soc 99(15):5215–5217
Otto A, Mrozek I, Grabhorn H, Akemann W (1992) Surface–enhanced Raman scattering. J Phys: Condens Mater 4:1143–1212
Moskovits M (1985) Surface–enhanced spectroscopy. Rev Mod Phys 57(3):783–826
Schatz G (1984) Theoretical studies of surface enhanced Raman scattering. Acc Chem Res 17(10):370–376
Campion A, Kambhampati P (1998) Surface–enhanced Raman scattering. Chem Soc Rev 27:241–250
Wustholz KL, Henry A-I, McMahon JM, Freeman RG, Valley N, Piotti ME, Natan MJ, Schatz GC, Van Duyne RP (2010) Structure–activity relationships in gold nanoparticle dimers and trimers for surface–enhanced Raman spectroscopy. J Am Chem Soc 132(31):10903–10910
Yang Y, Shi JL, Tanaka T, Nogami M (2007) Self–assembled silver nanochains for surface–enhanced Raman scattering. Langmuir 23(24):12042–12047
Li W, Camargo PHC, Lu X, Xia Y (2009) Dimers of silver nanospheres: facile synthesis and their use as hot spots for surface-enhanced Raman scattering. Nano Lett 9(1):485–490
Xu HX, Aizpurua J, Käll M (2000) Electromagnetic contributions to single–molecule sensitivity in surface–enhanced Raman scattering. Phys Rev E 62(3):4318–4324
Le Ru EC, Etchegoin PG, Meyer M (2006) Enhancement factor distribution around a single surface–enhanced Raman scattering hot spot and its relation to single molecule detection. J Chem Phys 125(20):204701–204714
Nie S, Emery SR (1997) Probing single molecules and single nanoparticles by surface–enhanced Raman scattering. Science 275(5303):1102–1106
Kneipp K, Wang Y, Kneipp H, Itzkan I, Dasari RR, Feld MS Population pumping of excited vibrational states by spontaneous surface–enhanced Raman scattering. Phys ReV Lett 76(14):2444–2447
Constantino CJL, Lemma T, Antunes PA, Aroca R (2001) Single-molecule detection using surface–enhanced resonance Raman scattering and langmuir–blodgett monolayers. Anal Chem 73(15):3674–3678
Lumerical Solutions, Inc. 9 Optical and photonic design and engineering software products
Palik ED (ed) (1991) Handbook of optical constants of solids. Academic, San Diego
Krishnan K, Plane RA (1968) Raman spectra of ethylenediaminetetraacetic acid and its metal complexes. J Am Chem Soc 90(12):3195–3200
Guzonas DA, Atkinson GF, Irish DE, Adams WA (1983) SERS and normal Raman spectroscopic studies of the silver electrode/KCl + EDTA solution interface. J Electroanal Chem 150(1–2):457–468
Wetzel H, Pettinger B, Wenning U (1980) Surface–enhanced Raman scattering from ethylenediaminetetraacetic–disodium salt and nitrate ions on silver electrodes. Chem Phys Lett 75(1):173–178
Kneipp K (2007) Surface–enhanced Raman scattering. Phys Today 60(11):40–46
Knoll A (1998) Interfaces and thin films as seen by bound electromagnetic waves. Ann Rev Phys Chem 49:569–638
Otto A (2005) The ‘chemical’ (electronic) contribution to surface–enhanced Raman scattering. J Raman Spectrosc 36(6–7):497–509
Tamaru H, Kuwata H, Miyazaki HT, Miyano K (2002) Resonant light scattering from individual Ag nanoparticles and particle pairs. Appl Phys Lett 80(10):1826–1828
Su K-H, Wei Q-H, Zhang X, Mock JJ, Smith DR, Schultz S (2003) Interparticle coupling effects on plasmon resonances of nanogold particles. Nano Lett 3(8):1087–1090
Kreibig U, Vollmer M (1995) Optical properties of metal clusters. Springer, Berlin
Fang Y, Seong NH, Dlott DD (2008) Measurement of the distribution of site enhancements in surface–enhanced Raman scattering. Science 321:388–392
Chien FC, Huang WY, Shiu J, Kuo CW, Chen P (2009) Revealing the spatial distribution of the site enhancement for surface–enhanced Raman scattering on regular nanoparticle arrays. Opt Express 17(16):13974–13981
Xu H, Käll M (2003) Polarization–dependent surface–enhanced Raman spectroscopy of isolated silver nanoaggregates. ChemPhysChem 4(9):1001–1005
Emory SR, Haskins WE, Nie S (1998) Direct observation of size–dependent optical enhancement in single metal nanoparticles. J Am Chem Soc 120(31):8009–8010
Le Ru EC, Blackie E, Meyer M, Etchegoin PG (2007) Surface enhanced Raman scattering enhancement factors: a comprehensive study. J Phys Chem C 111(37):13794–13803
Acknowledgments
This work was supported by the Belarusian Scientific Research Program “Electronics and Photonics” (project 1.1.02). One author (PG) acknowledged the support of a Marie Curie Foundation within the 7th FP (project no. 298932, call reference: FP7-PEOPLE-2011-IIF).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Shautsova, V.I., Zhuravkov, V.A., Korolik, O.V. et al. Effect of Interparticle Field Enhancement in Self-Assembled Silver Aggregates on Surface-Enhanced Raman Scattering. Plasmonics 9, 993–999 (2014). https://doi.org/10.1007/s11468-014-9706-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11468-014-9706-3