Tip-enhanced Raman spectroscopic imaging of patterned thiol monolayers

Stadler, Johannes; Schmid, Thomas; Opilik, Lothar; Kuhn, Phillip; Dittrich, Petra S.; Zenobi, Renato

doi:10.3762/bjnano.2.55

Cited by 34 publications

(36 citation statements)

References 38 publications

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“…and Stadler et al 92. 94 used the ratio between two characteristic marker bands (from two different compounds) instead of their absolute values to obtain the corresponding image. In this way it was possible to achieve a uniform distribution (see Figure 7 c).…”

Section: Technical Issues To Be Considered For Ters Imagingmentioning

confidence: 99%

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Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

et al. 2013

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Methods for chemical analysis at the nanometer scale are crucial for understanding and characterizing nanostructures of modern materials and biological systems. Tip-enhanced Raman spectroscopy (TERS) combines the chemical information provided by Raman spectroscopy with the signal enhancement known from surface-enhanced Raman scattering (SERS) and the high spatial resolution of atomic force microscopy (AFM) or scanning tunneling microscopy (STM). A metallic or metallized tip is illuminated by a focused laser beam and the resulting strongly enhanced electromagnetic field at the tip apex acts as a highly confined light source for Raman spectroscopic measurements. This Review focuses on the prerequisites for the efficient coupling of light to the tip as well as the shortcomings and pitfalls that have to be considered for TERS imaging, a fascinating but still challenging way to look at the nanoworld. Finally, examples from recent publications have been selected to demonstrate the potential of this technique for chemical imaging with a spatial resolution of approximately 10 nm and sensitivity down to the single-molecule level for applications ranging from materials sciences to life sciences.

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Section: Technical Issues To Be Considered For Ters Imagingmentioning

confidence: 99%

“…In this way it was possible to achieve a uniform distribution (see Figure 7 c). 94 Another approach is to use an internal standard such as, for example, the tip material itself (Ichimura et al. used the Si peak of their tip as an internal standard)95 or an additional coating (e.g.…”

Section: Technical Issues To Be Considered For Ters Imagingmentioning

confidence: 99%

Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

et al. 2013

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“…Plasmonic excitations in metallic nanostructures are a famous example of this. It has been known for decades that the interaction of the electrons of a metal with light can lead to local enhancement of the electrical field, which is utilized in spectroscopy to achieve local sensitivity on the subwavelength scale in Raman spectroscopy and related techniques [3–4]. More recently, the interest of researchers has turned towards applications of plasmonic structures in photovoltaics (for recent reviews, see [5–6]).…”

Section: Introductionmentioning

confidence: 99%

Near-field effects and energy transfer in hybrid metal-oxide nanostructures

Herr¹,

Kuerbanjiang²,

Benel³

et al. 2013

Beilstein J. Nanotechnol.

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SummaryOne of the big challenges of the 21st century is the utilization of nanotechnology for energy technology. Nanoscale structures may provide novel functionality, which has been demonstrated most convincingly by successful applications such as dye-sensitized solar cells introduced by M. Grätzel. Applications in energy technology are based on the transfer and conversion of energy. Following the example of photosynthesis, this requires a combination of light harvesting, transfer of energy to a reaction center, and conversion to other forms of energy by charge separation and transfer. This may be achieved by utilizing hybrid nanostructures, which combine metallic and nonmetallic components. Metallic nanostructures can interact strongly with light. Plasmonic excitations of such structures can cause local enhancement of the electrical field, which has been utilized in spectroscopy for many years. On the other hand, the excited states in metallic structures decay over very short lifetimes. Longer lifetimes of excited states occur in nonmetallic nanostructures, which makes them attractive for further energy transfer before recombination or relaxation sets in. Therefore, the combination of metallic nanostructures with nonmetallic materials is of great interest. We report investigations of hybrid nanostructured model systems that consist of a combination of metallic nanoantennas (fabricated by nanosphere lithography, NSL) and oxide nanoparticles. The oxide particles were doped with rare-earth (RE) ions, which show a large shift between absorption and emission wavelengths, allowing us to investigate the energy-transfer processes in detail. The main focus is on TiO2 nanoparticles doped with Eu3+, since the material is interesting for applications such as the generation of hydrogen by photocatalytic splitting of water molecules. We use high-resolution techniques such as confocal fluorescence microscopy for the investigation of energy-transfer processes. The experiments are supported by simulations of the electromagnetic field enhancement in the vicinity of well-defined nanoantennas. The results show that the presence of the nanoparticle layer can modify the field enhancement significantly. In addition, we find that the fluorescent intensities observed in the experiments are affected by agglomeration of the nanoparticles. In order to further elucidate the possible influence of agglomeration and quenching effects in the vicinity of the nanoantennas, we have used a commercial organic pigment containing Eu, which exhibits an extremely narrow particle size distribution and no significant agglomeration. We demonstrate that quenching of the Eu fluorescence can be suppressed by covering the nanoantennas with a 10 nm thick SiOx layer.

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“…Common probe molecules include pyridines, aromatic thiols, and benzotriazole [59,[114][115][116][117][118][119]. Patterning of different molecules and imaging by TERS has been demonstrated [120]. The plasmon driven conversion of 4-nitrobenzenethiol into dimercaptoazobenzene was monitored with TERS measurements of the 1336 cm -1 band of NO 2 and 1432 cm -1 N = N stretch [121,122].…”

Section: Organic Polymers and Moleculesmentioning

confidence: 99%

Tip enhanced Raman scattering: plasmonic enhancements for nanoscale chemical analysis

2014

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Tip enhanced Raman scattering (TERS) is an emerging technique that uses a metalized scanning probe microscope tip to spatially localize electric fields that enhances Raman scattering enabling chemical imaging on nanometer dimensions. Arising from the same principles as surface enhanced Raman scattering (SERS), TERS offers unique advantages associated with controling the size, shape, and location of the enhancing nanostructure. In this article we discuss the correlations between current understanding of SERS and how this relates to TERS, as well as how TERS provides new understanding and insights. The relationship between plasmon resonances and Raman enhancements is emphasized as the key to obtaining optimal TERS results. Applications of TERS, including chemical analysis of carbon nanotubes, organic molecules, inorganic crystals, nucleic acids, proteins, cells and organisms, are used to illustrate the information that can be gained. Under ideal conditions TERS is capable of single molecule sensitivity and sub-nanometer spatial resolution. The ability to control plasmonic enhancements for chemical analysis suggests new experiments and opportunities to understand molecular composition and interactions on the nanoscale.

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Tip-enhanced Raman spectroscopic imaging of patterned thiol monolayers

Cited by 34 publications

References 38 publications

Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

Near-field effects and energy transfer in hybrid metal-oxide nanostructures

Tip enhanced Raman scattering: plasmonic enhancements for nanoscale chemical analysis

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