Optical Nanoantennas for Multiband Surface-Enhanced Infrared and Raman Spectroscopy

D’Andrea, Cristiano; Bochterle, Jörg; Toma, Andréa; Huck, Christian; Neubrech, Frank; Messina, Elena; Fazio, Barbara; Maragó, Onofrio M.; Fabrizio, E. Di; Chapelle, Marc L. Lamy De La; Gucciardi, P. G.; Pucci, Annemarie

doi:10.1021/nn4004764

Cited by 212 publications

(226 citation statements)

References 82 publications

(133 reference statements)

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“…1 Au antennas have been shown to produce a strong SEIRS response. [21][22][23][24][25][26][27][28][29] For the SEIRS experiments, we used a thin, 50-nm layer of PMMA which was spincoated onto the antenna arrays. The presence of the PMMA can be observed in Fig.…”

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confidence: 99%

Surface-Enhanced Infrared Spectroscopy Using Metal Oxide Plasmonic Antenna Arrays

et al. 2013

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We successfully demonstrate surface enhanced infrared spectroscopy (SEIRS) using arrays of indium-tin oxide (ITO) plasmonic nanoantennas. The ITO antennas show a strongly reduced plasmon wavelength, which holds promise for ultracompact antenna arrays and extremely subwavelength metamaterials. The strong plasmon confinement and reduced antenna cross section allows ITO antennas to be integrated at extremely high densities with no loss in performance due to long-range transverse interactions.

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Surface-Enhanced Infrared Spectroscopy Using Metal Oxide Plasmonic Antenna Arrays

et al. 2013

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“…Molecules lying in the hot spots (located at the edges of individual nanoantennas or in the nanocavities between near-field coupled NPs [15,[25][26][27][28][29]) experience an amplified local field and an enhanced re-radiation whenever both the wavelengths of the laser pump (λ L ) and of the induced Raman dipole (λ R ) are close to the LSPR wavelength (λ LSPR ) [24]. It is well known that the enhanced local field is polarization sensitive.…”

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On the SERS depolarization ratio

et al. 2015

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According to the E 4 model, [18][19][20][21][22][23][24] in SERS the nanoantenna plays a twofold role: firstly it amplifies the local field (excitation-field enhancement) confining it to nanoscale regions (hot spots), and secondly it magnifies the Raman scattering (re-radiation enhancement). Molecules lying in the hot spots (located at the edges of individual nanoantennas or in the nanocavities between near-field coupled NPs [15,[25][26][27][28][29]) experience an amplified local field and an enhanced re-radiation whenever both the wavelengths of the laser pump (λ L ) and of the induced Raman dipole (λ R ) are close to the LSPR wavelength (λ LSPR ) [24]. It is well known that the enhanced local field is polarization sensitive. The only component of the incident field yielding the local field amplification is the one capable of exciting the LSPR of the antenna [30][31][32][33]. On the other hand, in near-field coupled nanoantennas the re-radiation effect yields a selective enhancement of the Raman dipole component parallel to the nanocavity axis at the single molecule level, linearizing the polarization of the Raman field [34][35][36][37][38].The re-radiation effect, therefore, causes a strong modification of the polarization of the SERS field, whose components will be altered with respect to what would have been measured in normal Raman spectroscopy in absence of the nanoantennas. In addition, such an alteration is dependent on the orientation of the antenna.A measurable quantity that will be strongly affected from such dependence is the depolarization ratio [39]. It is defined in Raman spectroscopy (for linear excitation polarization) as the ratio between the intensity of the Raman field polarized orthogonal to the laser field (I ⟘ ) and the intensity of the Raman field polarized parallel to the laser field (I � ). The depolarization ratio provides information on the Raman polarizability tensor (α) of the vibration considered and is therefore a very useful tool.It was recognized early on that in SERS the relationship between the depolarization ratio and the components of the Raman polarizability tensor was not straightforward [3]. One striking example is provided by Fazio and coworkers, [38] where the polarized SERS intensity is found to be at a maximum in the direction orthogonal to the excitation field, whereas in Raman spectroscopy Abstract: The Raman depolarization ratio is a quantity that can be easily measured experimentally and offers unique information on the Raman polarizability tensor of molecular vibrations. In Surface Enhanced Raman Scattering (SERS), molecules are near-field coupled with optical nanoantennas and their scattering properties are strongly affected by the radiation patterns of the nanoantenna. The polarization of the SERS photons is consequently modified, affecting, in a non trivial way, the measured value of the SERS depolarization ratio. In this article we elaborate a model that describes how the SERS depolarization ratio is influenced by the nanoantenna re-radiation properties, sugg...

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“…The transverse LSPR, associated with the short axis of the resonator, are at a smaller wavelength than the longitudinal LSPR [18]. The reflectance intensity is weaker, due to the smaller dipole moment, or higher depolarization factor, of the transverse LSPR [18,20,38].…”

Section: Optical Characterizationmentioning

confidence: 99%

“…In comparison, a typical gold nanorod antenna with resonances in the IR displays transverse resonances in another spectral range [38] due to its high aspect ratio, or the transverse resonance is below the noise level [13], so that only the longitudinal resonance can effectively be used for resonant SEIRA.…”

Section: Optical Characterizationmentioning

confidence: 99%

Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

et al. 2017

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Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surfaceenhanced infrared absorption (SEIRA) spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangularshaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR) with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR.

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Optical Nanoantennas for Multiband Surface-Enhanced Infrared and Raman Spectroscopy

Cited by 212 publications

References 82 publications

Surface-Enhanced Infrared Spectroscopy Using Metal Oxide Plasmonic Antenna Arrays

Surface-Enhanced Infrared Spectroscopy Using Metal Oxide Plasmonic Antenna Arrays

On the SERS depolarization ratio

Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

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