Abstract

We report a new approach in tip-enhanced Raman spectroscopy (TERS) in which TERS-active tips with enhancement factors of 105× can be rapidly (1–3 min) produced in situ by laser-induced synthesis of silver nanoparticles at the tip apex. The technique minimizes the risks of tip contamination and damage during handling and provides in situ feedback control, which allows the prediction of the tip performance. We show that TERS tips produced by this technique enable the measurement of spatially resolved TERS spectra of self-assembled peptide nanotubes with a spatial resolution of 20nm.

© 2012 Optical Society of America

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  1. R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
    [CrossRef]
  2. A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
    [CrossRef]
  3. B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
    [CrossRef]
  4. I. Notingher and A. Elfick, J. Phys. Chem. B 109, 15699 (2005).
    [CrossRef]
  5. E. Bailo and V. Deckert, Angew. Chem. Int. E. 47, 1658 (2008).
    [CrossRef]
  6. T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
    [CrossRef]
  7. B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
    [CrossRef]
  8. T. Deckert-Gaudig and V. Deckert, Phys. Chem. Chem. Phys. 12, 12040 (2010).
    [CrossRef]
  9. D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
    [CrossRef]
  10. M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
    [CrossRef]
  11. B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
    [CrossRef]
  12. B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
    [CrossRef]
  13. C. S. Sweetenham, M. Larraona-Puy, and I. Notingher, Appl. Spectrosc. 65, 1387 (2011).
    [CrossRef]
  14. K. G. Stamplecoskie and J. C. Scaiano, J. Am. Chem. Soc. 132, 1825 (2010).
    [CrossRef]
  15. M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
    [CrossRef]
  16. D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
    [CrossRef]
  17. B. Lekprasert, V. Sedman, C. J. Roberts, S. J. Tendler, and I. Notingher, Opt. Lett. 35, 4193 (2010).
    [CrossRef]
  18. A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
    [CrossRef]
  19. X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
    [CrossRef]

2011 (3)

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

C. S. Sweetenham, M. Larraona-Puy, and I. Notingher, Appl. Spectrosc. 65, 1387 (2011).
[CrossRef]

2010 (5)

K. G. Stamplecoskie and J. C. Scaiano, J. Am. Chem. Soc. 132, 1825 (2010).
[CrossRef]

B. Lekprasert, V. Sedman, C. J. Roberts, S. J. Tendler, and I. Notingher, Opt. Lett. 35, 4193 (2010).
[CrossRef]

T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
[CrossRef]

T. Deckert-Gaudig and V. Deckert, Phys. Chem. Chem. Phys. 12, 12040 (2010).
[CrossRef]

X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
[CrossRef]

2009 (3)

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
[CrossRef]

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

2008 (2)

E. Bailo and V. Deckert, Angew. Chem. Int. E. 47, 1658 (2008).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

2005 (2)

I. Notingher and A. Elfick, J. Phys. Chem. B 109, 15699 (2005).
[CrossRef]

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

2004 (1)

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

2003 (2)

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
[CrossRef]

2000 (1)

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Bailo, E.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

E. Bailo and V. Deckert, Angew. Chem. Int. E. 47, 1658 (2008).
[CrossRef]

Brus, L.

M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
[CrossRef]

Budich, C.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Cialla, D.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Deckert, V.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
[CrossRef]

T. Deckert-Gaudig and V. Deckert, Phys. Chem. Chem. Phys. 12, 12040 (2010).
[CrossRef]

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

E. Bailo and V. Deckert, Angew. Chem. Int. E. 47, 1658 (2008).
[CrossRef]

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Deckert, Volker

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

Deckert-Gaudig, T.

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
[CrossRef]

T. Deckert-Gaudig and V. Deckert, Phys. Chem. Chem. Phys. 12, 12040 (2010).
[CrossRef]

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Deed, S.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

Doug Suh, Y.

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Elfick, A.

I. Notingher and A. Elfick, J. Phys. Chem. B 109, 15699 (2005).
[CrossRef]

Ertl, G.

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Guo, Z.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Hartschuh, A.

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

Hedegaard, M.

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

Huang, P. R.

M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
[CrossRef]

Khiavi, M. A.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

Lampen, P.

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

Larraona-Puy, M.

Laue, M.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Leapman, R. D.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Lekprasert, B.

Li, J.

X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
[CrossRef]

Madler, S.

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

Maillard, M.

M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
[CrossRef]

Mattson, M. P.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

McNaughton, D.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

Moller, R.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Naumann, D.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Notingher, I.

Novotny, L.

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

Petkova, A. T.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Pettinger, B.

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Picardi, G.

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Popp, J.

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Rauls, E.

T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
[CrossRef]

Ren, B.

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Richter, M.

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

Roberts, C. J.

Roy, D.

D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
[CrossRef]

Sánchez, E. J.

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

Scaiano, J. C.

K. G. Stamplecoskie and J. C. Scaiano, J. Am. Chem. Soc. 132, 1825 (2010).
[CrossRef]

Schmid, T.

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

Schuster, R.

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Sedman, V.

Stadler, J.

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

Stamplecoskie, K. G.

K. G. Stamplecoskie and J. C. Scaiano, J. Am. Chem. Soc. 132, 1825 (2010).
[CrossRef]

Stöckle, R. M.

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Sweetenham, C. S.

Tendler, S. J.

Tilley, L.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

Tycko, R.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Wang, J.

D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
[CrossRef]

Williams, C.

D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
[CrossRef]

Wood, B. R.

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

Xie, X. S.

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

Yan, X.

X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
[CrossRef]

Yau, W.-M.

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Yeo, B.-S.

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

Zenobi, R.

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Zhang, W.

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

Zhu, P.

X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
[CrossRef]

Angew. Chem. Int. E. (1)

E. Bailo and V. Deckert, Angew. Chem. Int. E. 47, 1658 (2008).
[CrossRef]

Appl. Spectrosc. (1)

Chem. Phys. Lett. (2)

B.-S. Yeo, J. Stadler, T. Schmid, R. Zenobi, and W. Zhang, Chem. Phys. Lett. 472, 1 (2009).
[CrossRef]

R. M. Stöckle, Y. Doug Suh, V. Deckert, and R. Zenobi, Chem. Phys. Lett. 318, 131 (2000).
[CrossRef]

Chem. Soc. Rev. (1)

X. Yan, P. Zhu, and J. Li, Chem. Soc. Rev. 39, 1877 (2010).
[CrossRef]

J. Am. Chem. Soc. (1)

K. G. Stamplecoskie and J. C. Scaiano, J. Am. Chem. Soc. 132, 1825 (2010).
[CrossRef]

J. Appl. Phys. (1)

D. Roy, J. Wang, and C. Williams, J. Appl. Phys. 105, 013530 (2009).
[CrossRef]

J. Phys. Chem. B (1)

I. Notingher and A. Elfick, J. Phys. Chem. B 109, 15699 (2005).
[CrossRef]

J. Phys. Chem. C (2)

T. Deckert-Gaudig, E. Rauls, and V. Deckert, J. Phys. Chem. C 114, 7412 (2010).
[CrossRef]

B.-S. Yeo, S. Madler, T. Schmid, W. Zhang, and R. Zenobi, J. Phys. Chem. C 112, 4867 (2008).
[CrossRef]

J. Raman Spectrosc. (1)

D. Cialla, T. Deckert-Gaudig, C. Budich, M. Laue, R. Moller, D. Naumann, V. Deckert, and J. Popp, J. Raman Spectrosc. 40, 240 (2009).
[CrossRef]

Nano Lett. (2)

B. R. Wood, E. Bailo, M. A. Khiavi, L. Tilley, S. Deed, T. Deckert-Gaudig, D. McNaughton, and V. Deckert, Nano Lett. 11, 1868 (2011).
[CrossRef]

M. Maillard, P. R. Huang, and L. Brus, Nano Lett. 3, 1611 (2003).
[CrossRef]

Opt. Lett. (1)

Phys. Chem. Chem. Phys. (1)

T. Deckert-Gaudig and V. Deckert, Phys. Chem. Chem. Phys. 12, 12040 (2010).
[CrossRef]

Phys. Rev. Lett. (2)

A. Hartschuh, E. J. Sánchez, X. S. Xie, and L. Novotny, Phys. Rev. Lett. 90, 095503 (2003).
[CrossRef]

B. Pettinger, B. Ren, G. Picardi, R. Schuster, and G. Ertl, Phys. Rev. Lett. 92, 096101 (2004).
[CrossRef]

Science (1)

A. T. Petkova, R. D. Leapman, Z. Guo, W.-M. Yau, M. P. Mattson, and R. Tycko, Science 307, 262 (2005).
[CrossRef]

Small (1)

M. Richter, M. Hedegaard, T. Deckert-Gaudig, P. Lampen, and Volker Deckert, Small 7, 209 (2011).
[CrossRef]

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Figures (4)

Fig. 1.
Fig. 1.

Schematic description of the in situ method for fabrication of TERS-active tips.

Fig. 2.
Fig. 2.

(a) TEM and EDX images of typical TERS tips fabricated by the laser-induced synthesis (coating: APTES, scale bar 200 nm), (b) time-lapse SERS spectra of citrate during the growth of a tip, (c) intensity of the SERS during the tip growth for the three conditions.

Fig. 3.
Fig. 3.

TERS of pATP monolayer using TERS tips formed at 5 mW laser power and no precoating: effect of tip-sample distance on TERS signal intensity. Inset: TERS spectra at 10 nm tip-sample separation (top) compared to the spectrum with tip retracted (bottom). For TERS: 100 μW laser power, 20 s acquisition time.

Fig. 4.
Fig. 4.

TERS of an FF nanotube using a tip fabricated by APTES precoating and 1 mW laser power: (a), (b) topography and height profile along the white line, (c) TERS spectra across the nanotube, (d) line profile corresponding to the 1056cm1 TERS band, (e) comparison between the Raman spectrum of a 2.5 μm diameter FF tube and the spatially resolved TERS of the nanotube in (a). For TERS: 100 μW laser power, 50 s acquisition time.

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