In metal optics gold assumes a special status because of its practical importance in opto-electronic and nano-optical devices, and its role as a model system for the study of the elementary electronic excitations that underlie the interaction of electromagnetic fields with metals. However, largely inconsistent values for the frequency dependence of the dielectric function describing the optical response of gold are found in the literature [1][2][3]. We performed precise spectroscopic ellipsometry measurements on evaporated gold, template-stripped gold, and single-crystal gold to determine the optical dielectric function across a broad spectral range of 300 nm -25 µm (0.05 -4.14 eV) with high spectral resolution. We fit the data to the Drude free-electron model, with an electron relaxation time τD = 14 ± 3 fs and plasma energy ωp = 8.48 eV. We find that the variation in dielectric functions for the different types of samples is small compared to the range of values reported in the literature. Our values, however, are comparable to the aggregate mean of the collection of previous measurements from over the past six decades. This suggests that although some variation can be attributed to surface morphology, the past measurements using different approaches seem to have been plagued more by systematic errors than previously assumed.

Characterizing and ultimately controlling the heterogeneity underlying biomolecular functions, quantum behavior of complex matter, photonic materials, or catalysis requires large-scale spectroscopic imaging with simultaneous specificity to structure, phase, and chemical composition at nanometer spatial resolution. However, as with any ultrahigh spatial resolution microscopy technique, the associated demand for an increase in both spatial and spectral bandwidth often leads to a decrease in desired sensitivity. We overcome this limitation in infrared vibrational scattering-scanning probe near-field optical microscopy using synchrotron midinfrared radiation. Tip-enhanced localized light-matter interaction is induced by low-noise, broadband, and spatially coherent synchrotron light of high spectral irradiance, and the near-field signal is sensitively detected using heterodyne interferometric amplification. We achieve sub-40-nm spatially resolved, molecular, and phonon vibrational spectroscopic imaging, with rapid spectral acquisition, spanning the full midinfrared (700-5,000 cm) with few cm −1 spectral resolution. We demonstrate the performance of synchrotron infrared nanospectroscopy on semiconductor, biomineral, and protein nanostructures, providing vibrational chemical imaging with subzeptomole sensitivity.any properties and functions of natural or synthetic materials are defined by chemically or structurally distinct phases, domains, or interfaces on length scales of a few nanometers to micrometers. Characterizing these heterogeneities has long driven the development of advanced microscopy techniques, with notable advances in electron (1), photoemission (2), X-ray (3), and superresolution (4) microscopies. Although extremely effective, these techniques have strict sample requirements: either they operate in vacuum, are limited by electron or X-ray beam damage, or rely on labeling with exogenous fluorophores.In contrast, infrared (IR) vibrational spectroscopic imaging is minimally invasive, requires little sample preparation, is applicable in situ and under ambient conditions, and provides intrinsic chemical contrast and spectroscopic identification for a wide range of materials (5), including living cells (6) and tissues (7,8). The spatial resolution, however, is diffraction-limited to 2-10 μm, depending on wavelength. Moreover, high signal-to-noise spectra even at this low resolution are only possible with a source of high spectral irradiance (9). Subwavelength imaging has been achieved to some extent through point-spread function deconvolution (10, 11) and attenuated total reflection techniques (12). However, the micrometer-size wavelength of IR radiation, in general, has fundamentally limited its application for the characterization of essentially any mesoscopic, heterogeneous material where chemical information at the nanoscale is desired.Infrared scattering-scanning near-field microscopy (IR s-SNOM) overcomes the diffraction limit by scattering incident light with the typically metallic tip of an atomic for...

Focusing light to subwavelength dimensions has been a long-standing desire in optics but has remained challenging, even with new strategies based on near-field effects, polaritons, and metamaterials. The adiabatic propagation of surface plasmon polaritons (SPP) on a conical taper as proposed theoretically has recently emerged as particularly promising to obtain a nanoconfined light source at the tip. Employing grating-coupling of SPPs onto gold tips, we demonstrate plasmonic nanofocusing into a localized excitation of approximately 20 nm in size and investigate its near- and far-field behavior. For cone angles of approximately 10-20 degrees , the breakdown of the adiabatic propagation conditions is found to be localized at or near the apex region with approximately 10 nm radius. Despite an asymmetric side-on SPP excitation, the apex far-field emission with axial polarization characteristics representing a radially symmetric SPP mode in the nanofocus confirms that the conical tip acts as an effective mode filter with only the fundamental radially symmetric TM mode (m = 0) propagating to the apex. We demonstrate the use of these tips as a source for nearly background-free scattering-type scanning near-field optical microscopy (s-SNOM).

True nanoscale optical spectroscopy requires the efficient delivery of light for a spatially nanoconfined excitation. We utilize adiabatic plasmon focusing to concentrate an optical field into the apex of a scanning probe tip of ∼10 nm in radius. The conical tips with the ability for two-stage optical mode matching of the surface plasmon polariton (SPP) grating-coupling and the adiabatic propagating SPP conversion into a localized SPP at the tip apex represent a special optical antenna concept for far-field transduction into nanoscale excitation. The resulting high nanofocusing efficiency and the spatial separation of the plasmonic grating-coupling element on the tip shaft from the near-field apex probe region allows for true background-free nanospectroscopy. As an application, we demonstrate tip-enhanced Raman spectroscopy (TERS) of surface molecules with enhanced contrast and its extension into the near-IR with 800 nm excitation.

The spatial confinement and temporal control of an optical excitation on nanometer length scales and femtosecond time scales has been a long-standing challenge in optics. It would provide spectroscopic access to the elementary optical excitations in matter on their natural length and time scales [1] and enable applications from ultrafast nano-opto-electronics to single molecule quantum coherent control [2]. Previous approaches have largely focused on using surface plasmon polariton (SPP) resonant nanostructures [3] or SPP waveguides [4, 5] to generate nanometer localized excitations. However, these implementations generally suffer from mode mismatch [6] between the far-field propagating light and the near-field confinement. In addition, the spatial localization in itself may depend on the spectral phase and amplitude of the driving laser pulse thus limiting the degrees of freedom available to independently control the nano-optical waveform. Here we utilize femtosecond broadband SPP coupling, by laterally chirped fan gratings, onto the shaft of a monolithic noble metal tip, leading to adiabatic SPP compression and localization at the tip apex [7, 8]. In combination with spectral pulse shaping [9, 10] with feedback on the intrinsic nonlinear response of the tip apex, we demonstrate the continuous micro-to nano-scale self-similar mode matched transformation of the propagating femtosecond SPP field into a 20 nm spatially and 16 fs temporally confined light pulse at the tip apex.Furthermore, with the essentially wavelength and phase independent 3D focusing mechanism we show the generation of arbitrary optical waveforms nanofocused at the tip. This unique femtosecond nano-torch with high nano-scale power delivery in free space and full spectral and temporal control opens the door for the extension of the powerful nonlinear and ultrafast vibrational and electronic spectroscopies to the 2 nanoscale [11, 12].In order to achieve the goal of an efficient nanometer confined femtosecond light source with independent spatial localization and temporal control of the optical field, and which can freely be manipulated in 3D, the use of the unique properties of surface plasmon polaritons (SPP's) has long been discussed as a potential solution. It is well established that the strong surface field localization and size and shape dependent resonances of SPP's as electromagnetic surface waves associated with collective charge density oscillations at noble metal-dielectric interfaces allow for sub-wavelength spatial control of even broadband optical fields [13]. Elegant solutions to overcome the SPP diffraction limit [14] and achieve nano-focusing based on interference of localized SPP modes exist in the form of specially arranged cascaded, percolated, or self-similar chains of metal nanostructures as optical antennas [3,15,16]. However, the achievable optical waveforms at the nano-focus are often constrained by the phase relationship between the spectral modes already necessary to achieve the 3D nano-focusing [5]. This limits ...

The efficiency of plasmonic nanostructures as optical antennas to concentrate optical fields to the nanoscale has been limited by intrinsically short dephasing times and small absorption cross sections. We discuss a new optical antenna concept based on surface plasmon polariton (SPP) nanofocusing on conical noble metal tips to achieve efficient far- to near-field transformation of light from the micro- to the nanoscale. The spatial separation of the launching of propagating SPPs from their subsequent apex confinement with high energy concentration enables background-free near-field imaging, tip-enhanced Raman scattering, and nonlinear nanospectroscopy. The broad bandwidth and spectral tunability of the nanofocusing mechanism in combination with frequency domain pulse shaping uniquely allow for the spatial confinement of ultrashort laser pulses and few-femtosecond spatiotemporal optical control on the nanoscale. This technique not only extends powerful nonlinear and ultrafast spectroscopies to the nanoscale but can also generate fields of sufficient intensity for electron emission and higher harmonic generation.

Optical antennas can enhance the coupling between free-space propagating light and the localized excitation of nanoscopic light emitters or receivers, thus forming the basis of many nanophotonic applications. Their functionality relies on an understanding of the relationship between the geometric parameters and the resulting near-field antenna modes. Using scattering-type scanning near-field optical microscopy (s-SNOM) with interferometric homodyne detection, we investigate the resonances of linear Au wire antennas designed for the mid-IR by probing specific vector near-field components. A simple effective wavelength scaling is observed for single wires with lambda(eff) = lambda /(2.0+/- 0.2), specific to the geometric and material parameters used. The disruption of the coherent current oscillation by introducing a gap gives rise to an effective multipolar mode for the two near-field coupled segments. Using antenna theory and numerical electrodynamics simulations two distinct coupling regimes are considered that scale with gap width or reactive near-field decay length, respectively. The results emphasize the distinct antenna behavior at optical frequencies compared to impedance matched radio frequency (RF) antennas and provide experimental confirmation of theoretically predicted scaling laws at optical frequencies.

Chemically synthesized metallic nanostructures can exhibit a strong local optical field enhancement associated with their high degree of crystallinity and well-defined geometry-dependent surface plasmon resonances. The extension of the plasmon modes into the mid-IR spectral range (3-30 microm) is shown for micrometer-sized nanowires with high aspect ratios available in the form of pentagonally twinned Ag crystallites as grown by polyol synthesis. Using scattering-scanning near-field optical microscopy, the associated IR plasmon modes are identified, and their underlying spatial distribution and enhancement of the optical polarization density is measured via phase, amplitude, and polarization resolved optical vector-field mapping. The transition from dipolar to multipolar resonances is observed and described by modeling the Ag wires using a modified cylindrical waveguide theory. For 10.6 microm excitation, dipole antenna resonances are observed at a resonant length of L = lambda(eff)/2 with lambda(eff) approximately 10.6 microm/(1.8 +/- 0.5) approximately 6 +/- 2 microm. This effective wavelength scaling is the result of electronic damping, despite the high aspect ratios of the wires of order 1:10 to 1:200. With the optical cycle period tau(IR) being comparable to the Drude relaxation time of tau approximately 40 fs the mid-IR defines the low-energy limit of the coherent plasmon regime (tau(IR) less, similar tau) at the transition to purely geometric antenna resonances (tau(IR) > tau).