Journal of Raman Spectroscopy

Cover image for Journal of Raman Spectroscopy

Special Issue: Tip-enhanced Raman Spectroscopy

October 2009

Volume 40, Issue 10

Pages 1335–1457

  1. Editorials

    1. Top of page
    2. Editorials
    3. Short Communications
    4. Research Articles
    1. Editorial (page 1335)

      W. Kiefer

      Article first published online: 12 OCT 2009 | DOI: 10.1002/jrs.2470

  2. Short Communications

    1. Top of page
    2. Editorials
    3. Short Communications
    4. Research Articles
    1. Tip-Enhanced Raman Spectroscopy (pages 1336–1337)

      V. Deckert

      Article first published online: 12 OCT 2009 | DOI: 10.1002/jrs.2452

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      Tip-enhanced Raman scattering (TERS) is a method that provides molecular information without labelling, nanometer-scale lateral resolution and low limits of detection. An overview of the current state of this technique with respect to theory, instrumentation and application is presented.

  3. Research Articles

    1. Top of page
    2. Editorials
    3. Short Communications
    4. Research Articles
    1. Local field enhancement of an infinite conical metal tip illuminated by a focused beam (pages 1338–1342)

      Weihua Zhang, Xudong Cui and Olivier J. F. Martin

      Article first published online: 1 SEP 2009 | DOI: 10.1002/jrs.2439

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      Simulated electric field intensity maps of the same conical tip under different illuminations. A focused beam which is used in experiments produces a very different optical response of the tip apex than a plane wave illumination as usually used in previous numerical studies. This brings new insights into the enhancement mechanism of tip-enhanced Raman spectroscopy (TERS).

    2. Electromagnetic field enhancement in TERS configurations (pages 1343–1348)

      Zhilin Yang, Javier Aizpurua and Hongxing Xu

      Article first published online: 1 SEP 2009 | DOI: 10.1002/jrs.2429

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      A three-dimensional finite difference time domain method was used to perform theoretical simulations of the field enhancement and spatial resolution in normal and double tip TERS configurations. The effect of the tip and substrate material, of the tip size and shape, of the tip-substrate distance, and of the configuration of the incoming light including polarization and incidence angle are presented in detail.

    3. Tip-induced heating in apertureless near-field optics (pages 1349–1354)

      A. V. Malkovskiy, V. I. Malkovsky, A. M. Kisliuk, C. A. Barrios, M. D. Foster and A. P. Sokolov

      Article first published online: 4 AUG 2009 | DOI: 10.1002/jrs.2388

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      In this paper we report on the level of an additional sample heating by the laser light in the presence of a metal-coated AFM tip (TERS experiments). The results show significant heating even at low laser power.

    4. Optimising tip-enhanced optical microscopy (pages 1355–1360)

      Andrew Downes, Rabah Mouras, Meropi Mari and Alistair Elfick

      Article first published online: 31 JUL 2009 | DOI: 10.1002/jrs.2382

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      ‘Nano-scale optical microscopy’: With measurements and simulations, we discuss which conditions are optimum for mapping Raman, fluorescence and coherent anti-Stokes Raman (CARS). We also show how thermal absorption limits the amount of laser power focussed onto the probe tip.

    5. Depolarization effects in tip-enhanced Raman spectroscopy (pages 1361–1370)

      A. Merlen, J. C. Valmalette, P. G. Gucciardi, M. Lamy de la Chapelle, A. Frigout and R. Ossikovski

      Article first published online: 21 SEP 2009 | DOI: 10.1002/jrs.2424

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      TERS is a promising technique for stress/strain mapping of silicon-based semiconductor devices on the nanometer scale. Enhancement factors of up to 104 have been reported exploiting an appropriate choice of the excitation/detection polarization states. We show that the depolarization of light due to scattering from the tip plays a key role in the selective enhancement of the one-phonon mode at 520 cm−1 with respect to the two-phonon modes. Its spatial confinement has been studied by means of approach curves, and its dependence on the excitation wavelength and power, further explored. Conclusions on the physical nature of the enhancement are presented.

    6. Parabolic mirror-assisted tip-enhanced spectroscopic imaging for non-transparent materials (pages 1371–1376)

      Dr. Dai Zhang, Xiao Wang, Kai Braun, Hans-Joachim Egelhaaf, Monika Fleischer, Laura Hennemann, Holger Hintz, Catrinel Stanciu, Christoph J. Brabec, Dieter P. Kern and Prof. Alfred J. Meixner

      Article first published online: 1 SEP 2009 | DOI: 10.1002/jrs.2411

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      Parabolic mirror-assisted tip-enhanced spectroscopic imaging of non-transparent samples is reported. Correlated topography as well as Raman and photoluminescence imaging of nanometer-sized domains composing of different chemical components in blended organic solar cell films are successfully achieved. Furthermore the plasmonic properties of Au nano cones are demonstrated using the tip-enhanced luminescence imaging technique.

    7. Optimization of tip material and shape for near-UV TERS in Si structures (pages 1377–1385)

      Vladimir Poborchii, Tetsuya Tada, Toshihiko Kanayama and Pavel Geshev

      Article first published online: 29 SEP 2009 | DOI: 10.1002/jrs.2417

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      We demonstrate both theoretically and experimentally that Al is an efficient SERS/TERS material at the 364 nm wavelength, most suitable for Raman and stress mapping of Si structures. An inclined Al-coated AFM tip was employed for TERS study of strained Si, a weak TERS signal being detected. Ways of its improvement are discussed.

    8. A tetrahedral tip as a probe for tip-enhanced Raman scattering and as a near-field Raman probe (pages 1386–1391)

      Eugene G. Bortchagovsky and Ulrich C. Fischer

      Article first published online: 14 AUG 2009 | DOI: 10.1002/jrs.2391

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      An internally illuminated metal-coated tetrahedral glass tip (T-tip) serves as a source for tip-enhanced Raman scattering (TERS). By coating the tips with thiophenol, T-tips are revealed to give rise to a TERS signal directly or only when in contact with a gold substrate. Coated tips are suggested as a near-field Raman probe to monitor the field-enhancement properties of metal nanostructures or to selectively probe surface properties which have an influence on the Raman signal of the coating.

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      Performing tip-enhanced Raman spectroscopy in liquids (pages 1392–1399)

      Thomas Schmid, Boon-Siang Yeo, Grace Leong, Johannes Stadler and Renato Zenobi

      Article first published online: 11 AUG 2009 | DOI: 10.1002/jrs.2387

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      For the first time, tip-enhanced Raman spectroscopy (TERS) performed in a liquid environment is presented. The enhancement effect has been successfully demonstrated on a self-assembled monolayer sample of thiophenol on a Au surface that was totally immersed in water. Furthermore, strategies for tip preparation and protection are discussed. These results pave the way for TERS on living biological entities in aqueous buffers.

    10. Tip-enhanced Raman spectroscopy for investigating adsorbed nonresonant molecules on single-crystal surfaces: tip regeneration, probe molecule, and enhancement effect (pages 1400–1406)

      Zheng Liu, Xiang Wang, Ke Dai, Shan Jin, Zhi-Cong Zeng, Mu-De Zhuang, Zhi-Lin Yang, De-Yin Wu, Bin Ren and Zhong-Qun Tian

      Article first published online: 25 AUG 2009 | DOI: 10.1002/jrs.2431

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      A simple method was introduced for regenerating Au tip-enhanced Raman spectroscopy (TERS) tips to ensure a good reproducibility in TERS measurements. A series of molecules adsorbed on Au(111) single crystal surface has been studied in order to choose good probe molecules for TERS. 4,4′-Bipyridine and oligo(phenylene ethynylene)s (OPE) with different molecular lengths adsorbed on were studied by TERS, and the result indicates that the OPE molecules are good TERS probes with the very stable and strong TERS signal.

    11. Tip enhanced Raman spectroscopy on azobenzene thiol self-assembled monolayers on Au(111) (pages 1407–1412)

      Gennaro Picardi, Marc Chaigneau, Razvigor Ossikovski, Christophe Licitra and Guillame Delapierre

      Article first published online: 17 JUL 2009 | DOI: 10.1002/jrs.2362

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      Tip enhanced Raman spectroscopy (TERS) and imaging experiments in tunneling mode are shown for an azobenzene thiol monolayer grafted on Au(111). The Raman intensity maps reproduce the underlying surface topography on a sub-wavelength scale.

    12. Polar phonon mode selection rules in tip-enhanced Raman scattering (pages 1413–1419)

      Samuel Berweger and Markus B. Raschke

      Article first published online: 15 SEP 2009 | DOI: 10.1002/jrs.2407

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      We describe the selection rules for tip-enhanced phonon Raman spectroscopy. These arise as a superposition of crystal symmetry, the corresponding Raman tensor, and anisotropy of the tip enhancement, enabling optical crystallography on the nanoscale. The experimental principle is demonstrated for the case of nanocrystalline LiNbO3

    13. Tip-enhanced Raman spectroscopy of carbon nanotubes (pages 1420–1426)

      Luiz Gustavo Cançado, Achim Hartschuh and Lukas Novotny

      Article first published online: 21 SEP 2009 | DOI: 10.1002/jrs.2448

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      Tip-enhanced Raman spectroscopy (TERS) provides an alternative way to go beyond the diffraction barrier by performing spectroscopic imaging with ultra-high spatial resolution. This technique can be used in order to obtain Raman images of carbon nanotubes with high spatial resolution mediated by local enhancement of the incident and scattered fields.

    14. Tip-enhanced Raman spectroscopy of 6H-SiC with graphene adlayers: selective suppression of E1 modes (pages 1427–1433)

      Katrin F. Domke and Bruno Pettinger

      Article first published online: 1 SEP 2009 | DOI: 10.1002/jrs.2434

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      We compare normal and tip-enhanced Raman spectra of SiC with few-adlayer graphene. The observed selective suppression of the E1 modes of SiC after tip approach is explained by a tip-induced symmetry change in the sample.

    15. Nano-scale analysis of graphene layers by tip-enhanced near-field Raman spectroscopy (pages 1434–1440)

      Yuika Saito, Prabhat Verma, Kyoko Masui, Yasushi Inouye and Satoshi Kawata

      Article first published online: 31 JUL 2009 | DOI: 10.1002/jrs.2366

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      We demonstrate nano-scale optical analysis of graphene layers by tip-enhanced near-field Raman spectroscopy. Besides the vibrational analysis, we successfully perform the estimation of the number of layers in two-dimensional imaging by the same experimental platform, which allows us high-throughput nondestructive identification of graphene layers critical for the evaluation of this material.

    16. Imaging of single GaN nanowires by tip-enhanced Raman spectroscopy (pages 1441–1445)

      N. Marquestaut, D. Talaga, L. Servant, P. Yang, P. Pauzauskie and F. Lagugné-Labarthet

      Article first published online: 28 AUG 2009 | DOI: 10.1002/jrs.2404

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      Tip-enhanced Raman spectroscopy (TERS) was used to image a single GaN nanowire. The topography and the Raman signal were measured along the cross section of a crystalline [110] nanowire using the combination of an AFM and a Raman microscope. A lateral spatial resolution better than 200 nm was obtained.

    17. Tip-enhanced Raman scattering studies of histidine on novel silver substrates (pages 1446–1451)

      Tanja Deckert-Gaudig and Volker Deckert

      Article first published online: 20 JUL 2009 | DOI: 10.1002/jrs.2359

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      Tip-enhanced Raman scattering (TERS) experiments of histidine immobilized on an atomically flat and transparent silver surface provide a way to investigate the structure and conformation of this molecule. The spectroscopic results strongly support homogeneous adsorption, proving the desired uniformity of the silver nanoplates.

    18. Towards a specific characterisation of components on a cell surface—combined TERS-investigations of lipids and human cells (pages 1452–1457)

      R. Böhme, M. Richter, D. Cialla, P. Rösch, V. Deckert and J. Popp

      Article first published online: 15 SEP 2009 | DOI: 10.1002/jrs.2433

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      Immobilized lipid structures and human cells were investigated using tip-enhanced Raman spectroscopy (TERS). The present results show the great capability of TERS for a detailed and fast view into the composition of the cell surface, allowing the detection of single components.

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