Photothermal induced resonance (PTIR) has recently attracted great interest for enabling chemical identification and imaging with nanoscale resolution. In this work, electron beam nanopatterned polymer samples are fabricated directly on 3D zinc selenide prisms and used to experimentally evaluate the PTIR lateral resolution, sensitivity and linearity. It is shown that PTIR lateral resolution for chemical imaging is comparable to the lateral resolution obtained in the atomic force microscopy height images, up to the smallest feature measured (100 nm). Spectra and chemical maps are produced from the thinnest sample analyzed (40 nm). More importantly, experiments show for the first time that the PTIR signal increases linearly with thickness for samples up to ≈ 1 μm (linearity limit); a necessary requirement towards the use of the PTIR technique for quantitative chemical analysis at the nanoscale. Finally, the analysis of thicker samples provides the first evidence that the previously developed PTIR signal generation theory is correct. It is believed that the findings of this work will foster nanotechnology development in disparate applications by proving the basis for quantitative chemical analysis with nanoscale resolution.

The collective oscillation of conduction electrons, responsible for the localized surface plasmon resonances, enables engineering nanomaterials by tuning their optical response from the visible to terahertz as a function of nanostructure size, shape, and environment. While theoretical calculations helped tremendously in understanding plasmonic nanomaterials and optimizing their light matter interaction, only a few experimental techniques are available to study these materials with high spatial resolution. In this work, the photothermal-induced resonance (PTIR) technique is applied for the first time to image the dark plasmonic resonance of gold asymmetric split ring resonators (A-SRRs) in the mid-infrared (IR) spectral region with nanoscale resolution. Additionally, the chemically specific PTIR signal is used to map the local absorption enhancement of poly(methyl methacrylate) coated on A-SRRs, revealing hot spots with local enhancement factors up to ≈30 at 100 nm lateral resolution. We argue that PTIR nanoscale characterization will facilitate the engineering and application of plasmonic nanomaterials for mid-IR applications.

Asymmetric Split Ring Resonators are known to exhibit resonant modes where the optical electric field is strongest near the ends of the arms, thereby increasing the sensitivity of spectral techniques such as surface enhanced Raman scattering (SERS). By producing asymmetry in the structures, the two arms of the ring produce distinct plasmonic resonances related to their lengths - but are also affected by the presence of the other arm. This combination leads to a steepening of the slope of the reflection spectrum between the resonances that increases the sensitivity of the resonant behavior to the addition of different molecular species. We describe experimental results, supported by simulation, on the resonances of a series of circular split ring resonators with different gap and section lengths--at wavelengths in the mid-infra red regions of the spectrum--and their utilization for highly sensitive detection of organic compounds. We have used thin films of PMMA with different thicknesses, resulting in characteristic shifts from the original resonance. We also demonstrate matching of asymmetric split ring resonators to a molecular resonance of PMMA.

No abstract

Engineering of the optical resonances in plasmonic resonators arrays is achieved by virtue of the intrinsic properties to the constituent structures such as composition, size and shape and by controlling the inter-resonator interactions by of virtue the array geometrical arrangement. The nanoscale confinement of the plasmonic field enhances light-matter interactions enabling, for instance, the surface enhanced infrared absorption (SEIRA) effect. However, the subwavelength confinement also poses an experimental challenge for discriminating the response stemming from the individual resonators and from the collective response in densely packed arrays. In this work, the photothermal induced resonance (PTIR) technique is leveraged to obtain nanoscale images and spectra of near-field SEIRA hot spots observed in isolated plasmonic resonators of different shapes and in selected resonators within closely packed plasmonic arrays informing on whether the interactions with neighboring resonators are beneficial or otherwise. Results are correlated with far-field spectra and theoretical calculations.

The photothermal induced resonance (PTIR) method measures the near‐field absorption in gold plasmonic structures. PTIR absorption images show the interference between the bright and dark modes of asymmetric split ring resonators (ASRRs). The plasmonic absorption spectra of the ASRRs individual arcs are obtained locally, confirming the collective nature of the plasmonic excitation. Scale bars are 500 nm.

In this paper, we report on a substantial shift in the response of arrays of similarly sized Split Ring Resonators (SRRs), having a rectangular U-shaped form--and made respectively of aluminium and of gold. We also demonstrate that it is possible to obtain the polarization dependent LC peak in the visible spectrum--by using SRRs based on aluminium, rather than gold. The response of metallic SRRs scales linearly with size. At optical frequencies, metals stop behaving like nearly perfect conductors and begin displaying characteristically different behaviour, in accord with the Drude model. The response at higher frequencies, such as those in the visible and near infra-red, depends both on their size and on the individual properties of the metals used. A higher frequency limit has been observed in the polarization dependent response (in particular the LC resonance peak) of gold based SRRs in the near infrared region. By using aluminium based SRRs instead of gold, the higher frequency limit of the LC resonance can be further shifted into the visible spectrum.

Surface-enhanced infrared absorption (SEIRA) spectroscopy exploits the locally enhanced field surrounding plasmonic metamaterials to increase the sensitivity of infrared spectroscopy. The light polarization and incidence angle are important factors for exciting plasmonic nanostructures; however, such angle dependence is often ignored in SEIRA experiments, typically carried out with Cassegrain objectives. Here, the photothermal induced resonance technique and numerical simulations are used to map the distribution and intensity of SEIRA hot-spots surrounding gold asymmetric split ring resonators (ASRRs) as a function of light polarization and incidence angle. The results show asymmetric near-field SEIRA enhancements as a function of the incident illumination direction which, in analogy with the symmetry-breaking occurring in asymmetric transmission, we refer to as symmetry-breaking absorption. Numerical calculations reveal that the symmetry-breaking absorption in ASRRs originates in the angle-dependent interference between the electric and magnetic excitation channels of the resonators' dark-mode. Consequently, to maximize the SEIRA intensity, ASRRs should be illuminated from the dielectric side at an angle that maximizes the constructive interference of the two excitation channels, (35° for the structures studied here), in place of the Cassegrain objectives. These results can be generalized to all structures characterized by plasmonic excitations that give rise to a surface-normal magnetic moment and that possess an electric dipole.