A novel SERS sensor for adenine molecules is fabricated electrochemically using an ordered two-dimensional array of self-aligned silver nanoparticles encapsulated by alumina. Silver is electro-deposited on the interior surfaces at the bottom of nano-channels in a porous anodic aluminum oxide (AAO) film. After etching aluminum, the back-end alumina serves as a SERS substrate. SERS enhancement factor greater than 10⁶ is measured by 532 nm illumination. It exhibits robust chemical stability and emits reproducible Raman signals from repetitive uses for eight weeks. The inexpensive mass production process makes this reliable, durable and sensitive plasmon based optical device promising for many applications.

© 2011 OSA

1. S. Nie and S. R. Emory, “Probing single molecules and single nanoparticles by surface-enhanced Raman scattering,” Science 275(5303), 1102–1106 (1997). [CrossRef] [PubMed]
2. K. Kneipp, H. Kneipp, I. Itzkan, R. R. Dasari, and M. S. Feld, “Ultrasensitive chemical analysis by Raman spectroscopy,” Chem. Rev. 99(10), 2957–2976 (1999). [CrossRef]
3. B. Dragnea, C. Chen, E.-S. Kwak, B. Stein, and C. C. Kao, “Gold nanoparticles as spectroscopic enhancers for in vitro studies on single viruses,” J. Am. Chem. Soc. 125(21), 6374–6375 (2003). [CrossRef] [PubMed]
4. T. Qiu, J. Jiang, W. Zhang, X. Lang, X. Yu, and P. K. Chu, “High-sensitivity and stable cellular fluorescence imaging by patterned silver nanocap arrays,” ACS Appl. Mater. Interfaces 2(8), 2465–2470 (2010). [CrossRef] [PubMed]
5. H. Seki, “SERS of pyridine on Ag island films prepared on a sapphire substrate,” J. Vac. Sci. Technol. 18(2), 633–637 (1981). [CrossRef]
6. A. Campion and P. Kambhampati, “Surface-enhanced Raman scattering,” Chem. Soc. Rev. 27(4), 241–250 (1998). [CrossRef]
7. M. C. Daniel and D. Astruc, “Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology,” Chem. Rev. 104(1), 293–346 (2004). [CrossRef] [PubMed]
8. J. B. Jackson and N. J. Halas, “Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates,” Proc. Natl. Acad. Sci. U.S.A. 101(52), 17930–17935 (2004). [CrossRef] [PubMed]
9. J. Zhang, X. Li, X. Sun, and Y. Li, “Surface enhanced Raman scattering effects of silver colloids with different shapes,” J. Phys. Chem. B 109(25), 12544–12548 (2005). [CrossRef]
10. C. H. Huang, H. Y. Lin, C. H. Lin, H. C. Chui, Y. C. Lan, and S. W. Chu, “The phase-response effect of size-dependent optical enhancement in a single nanoparticle,” Opt. Express 16(13), 9580–9586 (2008). [CrossRef] [PubMed]
11. F. J. García-Vidal and J. B. Pendry, “Collective theory for surface enhanced Raman scattering,” Phys. Rev. Lett. 77(6), 1163–1166 (1996). [CrossRef] [PubMed]
12. E. C. Le Ru and P. G. Etchegoin, “Sub-wavelength localization of hot-spots in SERS,” Chem. Phys. Lett. 396(4-6), 393–397 (2004). [CrossRef]
13. H. Y. Lin, C. H. Huang, C. H. Chang, Y. C. Lan, and H. C. Chui, “Direct near-field optical imaging of plasmonic resonances in metal nanoparticle pairs,” Opt. Express 18(1), 165–172 (2010). [CrossRef] [PubMed]
14. R. Alvarez-Puebla, B. Cui, J.-P. Bravo-Vasquez, T. Veres, and H. Fenniri, “Nanoimprinted SERS-active substrates with tunable surface plasmon resonances,” J. Phys. Chem. C 111(18), 6720–6723 (2007). [CrossRef]
15. A. Tao, F. Kim, C. Hess, J. Goldberger, R. He, Y. Sun, Y. Xia, and P. Yang, “Langmuir−Blodgett silver nanowire monolayers for molecular sensing using surface-enhanced Raman spectroscopy,” Nano Lett. 3(9), 1229–1233 (2003). [CrossRef]
16. J. M. McLellan, Z.-Y. Li, A. R. Siekkinen, and Y. Xia, “The SERS activity of a supported Ag nanocube strongly depends on its orientation relative to laser polarization,” Nano Lett. 7(4), 1013–1017 (2007). [CrossRef] [PubMed]
17. G. T. Duan, W. P. Cai, Y. Y. Luo, Z. G. Li, and Y. Li, “Electrochemically induced flowerlike gold nanoarchitectures and their strong surface-enhanced Raman scattering effect,” Appl. Phys. Lett. 89(21), 211905 (2006). [CrossRef]
18. V. S. Tiwari, T. Oleg, G. K. Darbha, W. Hardy, J. P. Singh, and P. C. Ray, “Non-resonance: SERS effects of silver colloids with different shapes,” Chem. Phys. Lett. 446(1-3), 77–82 (2007). [CrossRef]
19. H. H. Wang, C. Y. Liu, S. B. Wu, N. W. Liu, C. Y. Peng, T. H. Chan, C. F. Hsu, J. K. Wang, and Y. L. Wang, “Highly Raman-enhancing substrates based on silver nanoparticle arrays with tunable sub-10 nm gaps,” Adv. Mater. (Deerfield Beach Fla.) 18(4), 491–495 (2006). [CrossRef]
20. S. M. Williams, K. R. Rodriguez, S. Teeters-Kennedy, A. D. Stafford, S. R. Bishop, U. K. Lincoln, and J. V. Coe, “Use of the extraordinary infrared transmission of metallic subwavelength arrays to study the catalyzed reaction of methanol to formaldehyde on copper oxide,” J. Phys. Chem. B 108(31), 11833–11837 (2004). [CrossRef]
21. G. H. Chan, J. Zhao, G. C. Schatz, and R. P. V. Duyne, “Localized surface plasmon resonance spectroscopy of triangular aluminum nanoparticles,” J. Phys. Chem. C 112(36), 13958–13963 (2008). [CrossRef]
22. H. W. Gao, J. Henzie, M. H. Lee, and T. W. Odom, “Screening plasmonic materials using pyramidal gratings,” Proc. Natl. Acad. Sci. U.S.A. 105(51), 20146–20151 (2008). [CrossRef] [PubMed]
23. N. C. Lindquist, W. A. Luhman, S. H. Oh, and R. J. Holmes, “Plasmonic nanocavity arrays for enhanced efficiency in organic photovoltaic cells,” Appl. Phys. Lett. 93(12), 123308 (2008). [CrossRef]
24. V. E. Ferry, L. A. Sweatlock, D. Pacifici, and H. A. Atwater, “Plasmonic nanostructure design for efficient light coupling into solar cells,” Nano Lett. 8(12), 4391–4397 (2008). [CrossRef]
25. K. Nielsch, F. Muller, A. P. Li, and U. Gosele, “Uniform nickel deposition into ordered alumina pores by pulsed electrodeposition,” Adv. Mater. (Deerfield Beach Fla.) 12(8), 582–586 (2000). [CrossRef]
26. C. H. Huang, H. Y. Lin, B. C. Lau, C. Y. Liu, H. C. Chui, and Y. Tzeng, “Plasmon-induced optical switching of electrical conductivity in porous anodic aluminum oxide films encapsulated with silver nanoparticle arrays,” Opt. Express 18(26), 27891–27899 (2010). [CrossRef]
27. A. V. Whitney, J. W. Elam, S. L. Zou, A. V. Zinovev, P. C. Stair, G. C. Schatz, and R. P. Van Duyne, “Localized surface plasmon resonance nanosensor: a high-resolution distance-dependence study using atomic layer deposition,” J. Phys. Chem. B 109(43), 20522–20528 (2005). [CrossRef]
28. B.-C. Lau, C.-Y. Liu, H.-Y. Lin, C.-H. Huang, H.-C. Chui, and Y. Tzeng, “Electrochemical fabrication of anodic aluminum oxide films with encapsulated silver nanoparticles as plasmonic photoconductors,” Electrochem. Solid-State Lett. 14(5), E15–E17 (2011). [CrossRef]
29. T. T. Xu, R. D. Piner, and R. S. Ruoff, “An improved method to strip aluminum from porous anodic alumina films,” Langmuir 19(4), 1443–1445 (2003). [CrossRef]
30. J. A. Creighton and D. G. Eadon, “Ultraviolet-visible absorption spectra of the colloidal metallic elements,” J. Chem. Soc., Faraday Trans. 87(24), 3881–3891 (1991). [CrossRef]
31. S. P. A. Fodor, R. P. Rava, T. R. Hays, and T. G. Spiro, “Ultraviolet resonance Raman spectroscopy of the nucleotides with 266-, 240-, 218-, and 200-nm pulsed laser excitation,” J. Am. Chem. Soc. 107(6), 1520–1529 (1985). [CrossRef]
32. B. Giese and D. McNaughton, “Surface-enhanced Raman spectroscopic and density functional theory study of adenine adsorption to silver surfaces,” J. Phys. Chem. B 106(1), 101–112 (2002). [CrossRef]
33. I. Mrozek and A. Otto, “Long- and short-range effects in SERS from silver,” Europhys. Lett. 11(3), 243–248 (1990). [CrossRef]
34. B. J. Kennedy, S. Spaeth, M. Dickey, and K. T. Carron, “Determination of the distance dependence and experimental effects for modified SERS substrates based on self-assembled monolayers formed using alkanethiols,” J. Phys. Chem. B 103(18), 3640–3646 (1999). [CrossRef]
35. L. Rivas, S. Sanchez-Cortes, J. V. Garcia-Ramos, and G. Morcillo, “Mixed silver/gold colloids: a study of their formation, morphology, and surface-enhanced Raman activity,” Langmuir 16(25), 9722–9728 (2000). [CrossRef]
36. X. Q. Zou and S. J. Dong, “Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution,” J. Phys. Chem. B 110(43), 21545–21550 (2006). [CrossRef] [PubMed]
37. K. G. Stamplecoskie, J. C. Scaiano, V. S. Tiwari, and H. Anis, “Optimal size of silver nanoparticles for surface-enhanced Raman spectroscopy,” J. Phys. Chem. C 115(5), 1403–1409 (2011). [CrossRef]

ACS Appl. Mater. Interfaces

• T. Qiu, J. Jiang, W. Zhang, X. Lang, X. Yu, and P. K. Chu, “High-sensitivity and stable cellular fluorescence imaging by patterned silver nanocap arrays,” ACS Appl. Mater. Interfaces 2(8), 2465–2470 (2010). [CrossRef] [PubMed]

Adv. Mater. (Deerfield Beach Fla.)

• H. H. Wang, C. Y. Liu, S. B. Wu, N. W. Liu, C. Y. Peng, T. H. Chan, C. F. Hsu, J. K. Wang, and Y. L. Wang, “Highly Raman-enhancing substrates based on silver nanoparticle arrays with tunable sub-10 nm gaps,” Adv. Mater. (Deerfield Beach Fla.) 18(4), 491–495 (2006). [CrossRef]
• K. Nielsch, F. Muller, A. P. Li, and U. Gosele, “Uniform nickel deposition into ordered alumina pores by pulsed electrodeposition,” Adv. Mater. (Deerfield Beach Fla.) 12(8), 582–586 (2000). [CrossRef]

Appl. Phys. Lett.

• N. C. Lindquist, W. A. Luhman, S. H. Oh, and R. J. Holmes, “Plasmonic nanocavity arrays for enhanced efficiency in organic photovoltaic cells,” Appl. Phys. Lett. 93(12), 123308 (2008). [CrossRef]
• G. T. Duan, W. P. Cai, Y. Y. Luo, Z. G. Li, and Y. Li, “Electrochemically induced flowerlike gold nanoarchitectures and their strong surface-enhanced Raman scattering effect,” Appl. Phys. Lett. 89(21), 211905 (2006). [CrossRef]

Chem. Phys. Lett.

• V. S. Tiwari, T. Oleg, G. K. Darbha, W. Hardy, J. P. Singh, and P. C. Ray, “Non-resonance: SERS effects of silver colloids with different shapes,” Chem. Phys. Lett. 446(1-3), 77–82 (2007). [CrossRef]
• E. C. Le Ru and P. G. Etchegoin, “Sub-wavelength localization of hot-spots in SERS,” Chem. Phys. Lett. 396(4-6), 393–397 (2004). [CrossRef]

Chem. Rev.

• K. Kneipp, H. Kneipp, I. Itzkan, R. R. Dasari, and M. S. Feld, “Ultrasensitive chemical analysis by Raman spectroscopy,” Chem. Rev. 99(10), 2957–2976 (1999). [CrossRef]
• M. C. Daniel and D. Astruc, “Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology,” Chem. Rev. 104(1), 293–346 (2004). [CrossRef] [PubMed]

Chem. Soc. Rev.

• A. Campion and P. Kambhampati, “Surface-enhanced Raman scattering,” Chem. Soc. Rev. 27(4), 241–250 (1998). [CrossRef]

Electrochem. Solid-State Lett.

• B.-C. Lau, C.-Y. Liu, H.-Y. Lin, C.-H. Huang, H.-C. Chui, and Y. Tzeng, “Electrochemical fabrication of anodic aluminum oxide films with encapsulated silver nanoparticles as plasmonic photoconductors,” Electrochem. Solid-State Lett. 14(5), E15–E17 (2011). [CrossRef]

Europhys. Lett.

• I. Mrozek and A. Otto, “Long- and short-range effects in SERS from silver,” Europhys. Lett. 11(3), 243–248 (1990). [CrossRef]

J. Am. Chem. Soc.

• S. P. A. Fodor, R. P. Rava, T. R. Hays, and T. G. Spiro, “Ultraviolet resonance Raman spectroscopy of the nucleotides with 266-, 240-, 218-, and 200-nm pulsed laser excitation,” J. Am. Chem. Soc. 107(6), 1520–1529 (1985). [CrossRef]
• B. Dragnea, C. Chen, E.-S. Kwak, B. Stein, and C. C. Kao, “Gold nanoparticles as spectroscopic enhancers for in vitro studies on single viruses,” J. Am. Chem. Soc. 125(21), 6374–6375 (2003). [CrossRef] [PubMed]

J. Chem. Soc., Faraday Trans.

• J. A. Creighton and D. G. Eadon, “Ultraviolet-visible absorption spectra of the colloidal metallic elements,” J. Chem. Soc., Faraday Trans. 87(24), 3881–3891 (1991). [CrossRef]

J. Phys. Chem. B

• A. V. Whitney, J. W. Elam, S. L. Zou, A. V. Zinovev, P. C. Stair, G. C. Schatz, and R. P. Van Duyne, “Localized surface plasmon resonance nanosensor: a high-resolution distance-dependence study using atomic layer deposition,” J. Phys. Chem. B 109(43), 20522–20528 (2005). [CrossRef]
• B. Giese and D. McNaughton, “Surface-enhanced Raman spectroscopic and density functional theory study of adenine adsorption to silver surfaces,” J. Phys. Chem. B 106(1), 101–112 (2002). [CrossRef]
• B. J. Kennedy, S. Spaeth, M. Dickey, and K. T. Carron, “Determination of the distance dependence and experimental effects for modified SERS substrates based on self-assembled monolayers formed using alkanethiols,” J. Phys. Chem. B 103(18), 3640–3646 (1999). [CrossRef]
• S. M. Williams, K. R. Rodriguez, S. Teeters-Kennedy, A. D. Stafford, S. R. Bishop, U. K. Lincoln, and J. V. Coe, “Use of the extraordinary infrared transmission of metallic subwavelength arrays to study the catalyzed reaction of methanol to formaldehyde on copper oxide,” J. Phys. Chem. B 108(31), 11833–11837 (2004). [CrossRef]
• J. Zhang, X. Li, X. Sun, and Y. Li, “Surface enhanced Raman scattering effects of silver colloids with different shapes,” J. Phys. Chem. B 109(25), 12544–12548 (2005). [CrossRef]
• X. Q. Zou and S. J. Dong, “Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution,” J. Phys. Chem. B 110(43), 21545–21550 (2006). [CrossRef] [PubMed]

J. Phys. Chem. C

• K. G. Stamplecoskie, J. C. Scaiano, V. S. Tiwari, and H. Anis, “Optimal size of silver nanoparticles for surface-enhanced Raman spectroscopy,” J. Phys. Chem. C 115(5), 1403–1409 (2011). [CrossRef]
• R. Alvarez-Puebla, B. Cui, J.-P. Bravo-Vasquez, T. Veres, and H. Fenniri, “Nanoimprinted SERS-active substrates with tunable surface plasmon resonances,” J. Phys. Chem. C 111(18), 6720–6723 (2007). [CrossRef]
• G. H. Chan, J. Zhao, G. C. Schatz, and R. P. V. Duyne, “Localized surface plasmon resonance spectroscopy of triangular aluminum nanoparticles,” J. Phys. Chem. C 112(36), 13958–13963 (2008). [CrossRef]

J. Vac. Sci. Technol.

• H. Seki, “SERS of pyridine on Ag island films prepared on a sapphire substrate,” J. Vac. Sci. Technol. 18(2), 633–637 (1981). [CrossRef]

Langmuir

• L. Rivas, S. Sanchez-Cortes, J. V. Garcia-Ramos, and G. Morcillo, “Mixed silver/gold colloids: a study of their formation, morphology, and surface-enhanced Raman activity,” Langmuir 16(25), 9722–9728 (2000). [CrossRef]
• T. T. Xu, R. D. Piner, and R. S. Ruoff, “An improved method to strip aluminum from porous anodic alumina films,” Langmuir 19(4), 1443–1445 (2003). [CrossRef]

Nano Lett.

• V. E. Ferry, L. A. Sweatlock, D. Pacifici, and H. A. Atwater, “Plasmonic nanostructure design for efficient light coupling into solar cells,” Nano Lett. 8(12), 4391–4397 (2008). [CrossRef]
• A. Tao, F. Kim, C. Hess, J. Goldberger, R. He, Y. Sun, Y. Xia, and P. Yang, “Langmuir−Blodgett silver nanowire monolayers for molecular sensing using surface-enhanced Raman spectroscopy,” Nano Lett. 3(9), 1229–1233 (2003). [CrossRef]
• J. M. McLellan, Z.-Y. Li, A. R. Siekkinen, and Y. Xia, “The SERS activity of a supported Ag nanocube strongly depends on its orientation relative to laser polarization,” Nano Lett. 7(4), 1013–1017 (2007). [CrossRef] [PubMed]

Opt. Express

• C. H. Huang, H. Y. Lin, C. H. Lin, H. C. Chui, Y. C. Lan, and S. W. Chu, “The phase-response effect of size-dependent optical enhancement in a single nanoparticle,” Opt. Express 16(13), 9580–9586 (2008). [CrossRef] [PubMed]
• H. Y. Lin, C. H. Huang, C. H. Chang, Y. C. Lan, and H. C. Chui, “Direct near-field optical imaging of plasmonic resonances in metal nanoparticle pairs,” Opt. Express 18(1), 165–172 (2010). [CrossRef] [PubMed]
• C. H. Huang, H. Y. Lin, B. C. Lau, C. Y. Liu, H. C. Chui, and Y. Tzeng, “Plasmon-induced optical switching of electrical conductivity in porous anodic aluminum oxide films encapsulated with silver nanoparticle arrays,” Opt. Express 18(26), 27891–27899 (2010). [CrossRef]

Phys. Rev. Lett.

• F. J. García-Vidal and J. B. Pendry, “Collective theory for surface enhanced Raman scattering,” Phys. Rev. Lett. 77(6), 1163–1166 (1996). [CrossRef] [PubMed]

Proc. Natl. Acad. Sci. U.S.A.

• J. B. Jackson and N. J. Halas, “Surface-enhanced Raman scattering on tunable plasmonic nanoparticle substrates,” Proc. Natl. Acad. Sci. U.S.A. 101(52), 17930–17935 (2004). [CrossRef] [PubMed]
• H. W. Gao, J. Henzie, M. H. Lee, and T. W. Odom, “Screening plasmonic materials using pyramidal gratings,” Proc. Natl. Acad. Sci. U.S.A. 105(51), 20146–20151 (2008). [CrossRef] [PubMed]

Science

• S. Nie and S. R. Emory, “Probing single molecules and single nanoparticles by surface-enhanced Raman scattering,” Science 275(5303), 1102–1106 (1997). [CrossRef] [PubMed]

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