Leonetta Baldassarre

Midinfrared Plasmon-Enhanced Spectroscopy with Germanium Antennas on Silicon Substrates

Midinfrared plasmonic sensing allows the direct targeting of unique vibrational fingerprints of molecules. While gold has been used almost exclusively so far, recent research has focused on semiconductors with the potential to revolutionize plasmonic devices. We fabricate antennas out of heavily doped Ge films epitaxially grown on Si wafers and demonstrate up to 2 orders of magnitude signal enhancement for the molecules located in the antenna hot spots compared to those located on a bare silicon substrate. Our results set a new path toward integration of plasmonic sensors with the ubiquitous CMOS platform.

Mapping the amide I absorption in single bacteria and mammalian cells with resonant infrared nanospectroscopy

Infrared (IR) nanospectroscopy performed in conjunction with atomic force microscopy (AFM) is a novel, label-free spectroscopic technique that meets the increasing request for nano-imaging tools with chemical specificity in the field of life sciences. In the novel resonant version of AFM-IR, a mid-IR wavelength-tunable quantum cascade laser illuminates the sample below an AFM tip working in contact mode, and the repetition rate of the mid-IR pulses matches the cantilever mechanical resonance frequency. The AFM-IR signal is the amplitude of the cantilever oscillations driven by the thermal expansion of the sample after absorption of mid-IR radiation. Using purposely nanofabricated polymer samples, here we demonstrate that the AFM-IR signal increases linearly with the sample thickness t for t > 50 nm, as expected from the thermal expansion model of the sample volume below the AFM tip. We then show the capability of the apparatus to derive information on the protein distribution in single cells through mapping of the AFM-IR signal related to the amide-I mid-IR absorption band at 1660 cm(-1). In Escherichia Coli bacteria we see how the topography changes, observed when the cell hosts a protein over-expression plasmid, are correlated with the amide I signal intensity. In human HeLa cells we obtain evidence that the protein distribution in the cytoplasm and in the nucleus is uneven, with a lateral resolution better than 100 nm.

Group-IV midinfrared plasmonics

Abstract. The use of heavily doped semiconductors to achieve plasma frequencies in the mid-IR has been recently proposed as a promising way to obtain high-quality and tunable plasmonic materials. We introduce a plasmonic platform based on epitaxial n-type Ge grown on standard Si wafers by means of low-energy plasma-enhanced chemical vapor deposition. Due to the large carrier concentration achieved with P dopants and to the compatibility with the existing CMOS technology, SiGe plasmonics hold promises for mid-IR applications in optoelectronics, IR detection, sensing, and light harvesting. As a representative example, we show simulations of mid-IR plasmonic waveguides based on the experimentally retrieved dielectric constants of the grown materials.

Determination of the free carrier concentration in atomic-layer doped germanium thin films by infrared spectroscopy

Novel silicon photonics applications requiring heavy n-type doping have recently driven a great deal of interest towards the phosphorous doping of germanium. In this work we report on infrared reflectance spectroscopy measurements of the electron density in heavily n-type doped germanium layers obtained by stacking multiple phosphorous δ-layers. Here, we demonstrate that the conventional Drude model of the electrodynamic response of free carriers in metals can be adapted to describe heavily doped semiconductor thin films. Consequently, the effect of the electron density on the plasma frequency, scattering rate and complex permittivity can be investigated.

Mid-infrared plasmonic platform based on heavily doped epitaxial Ge-on-Si: Retrieving the optical constants of thin Ge epilayers

The n-type Ge-on-Si epitaxial material platform enables a novel paradigm for plasmonics in the mid-infrared, prompting the future development of lab-on-a-chip and subwavelength vibrational spectroscopic sensors. In order to exploit this material, through proper electrodynamic design, it is mandatory to retrieve the dielectric constants of the thin Ge epilayers with high precision due to the difference from bulk Ge crystals. Here we discuss the procedure we have employed to extract the real and imaginary part of the dielectric constants from normal incidence reflectance measurements, by combining the standard multilayer fitting procedure based on the Drude model with Kramers-Kronig transformations of absolute reflectance data in the zero-transmission range of the thin film.

Heterogeneity of the Transmembrane Protein Conformation in Purple Membranes Identified by Infrared Nanospectroscopy

Cell membranes are intrinsically heterogeneous, as the local protein and lipid distribution is critical to physiological processes. Even in template systems embedding a single protein type, like purple membranes, there can be a different local response to external stimuli or environmental factors, resulting in heterogeneous conformational changes. Despite the dramatic advances of microspectroscopy techniques, the identification of the conformation heterogeneity is still a challenging task. Tip-enhanced infrared nanospectroscopy is here used to identify conformational changes connected to the hydration state of the transmembrane proteins contained in a 50 nm diameter cell membrane area, without the need for fluorescent labels. In dried purple membrane monolayers, areas with fully hydrated proteins are found among large numbers of molecules with randomly distributed hydration states. Infrared nanospectroscopy results are compared to the spectra obtained with diffraction-limited infrared techniques based on the use of synchrotron radiation, in which the diffraction limit still prevents the observation of nanoscale heterogeneity.

Raman Spectroscopy in Ionic Liquids Under Variable Thermodynamic and Environmental Conditions

The potentialities of the Raman spectroscopy in providing a deep insight into the microscopic anion-cation interactions in ionic liquids are discussed. We report on and discuss Raman measurements mainly collected on a particular class of ionic liquids called protic ionic liquids (PILs), based on the nitrate anion, NO3 −. Together with the spectroscopic investigation, first principle studies have been carried out for most of the measured samples. The combined experimental-theoretical approach allows us to deeply investigate the effects induced by the length of the alkyl chain on the optical properties of PILs. We also focus and report on systematic temperature (300–450 K) and pressure (0–10 GPa) dependent studies. The extended P–T region explored allows to observe liquid–solid and several solid–solid transitions and to draw general remarks on the phase diagram of PILs. Finally, exploiting the high sensitivity of the Raman spectroscopy to protein secondary and tertiary structures, the efficacy of PILs as protein refolding enhancers is also discussed.

Intrinsic linewidth of the plasmonic resonance in a micrometric metal mesh

The intrinsic linewidth and angular dispersion of Surface Plasmon Polariton resonance of a micrometric metal mesh have been measured with a collimated mid-infrared beam, provided by an External Cavity tunable Quantum Cascade Laser. We show that the use of a collimated beam yields an observed resonance linewidth γ = 12 cm(-1) at the resonance frequency ν0 = 1658 cm(-1), better by an order of magnitude than with a non-collimated beam. The extremely narrow plasmon resonance attained by our mesh is then exploited to reconstruct, by varying the QCL angle of incidence θ, the angular intensity distribution f(θ) of a globar at the focal plane of a conventional imaging setup. We thus show that f(θ) is better reproduced by a Gaussian distribution than by a uniform one, in agreement with ray-tracing simulation.

Nanospectroscopy of single purple membranes by mid-IR resonantly-enhanced mechanical photoexpansion

We present mid-infrared vibrational spectroscopy and imaging at the nanoscale of individual cell membranes deposited on ultraflat gold substrate by use of resonantly-enhanced mechanical photoexpansion technique. This platform allows one to measure the energy absorbed by the sample by monitoring its local thermal expansion with a nanometer atomic force microscope tip. The observed Amide-I and Amide-II bands of proteins in the spectrum acquired on individual purple membrane flakes, filled with bacteriorhodopsin (bR) molecules, are in good agreement with the far-field infrared spectrum collected on large numbers of membranes. Differences among the relative intensity of the two Amide bands in the near- and far-field spectra are attributed to different orientation of bR protein molecules in the two samples. Strong vibrational contrast imaging at the Amide-I of proteins with a lateral resolution of around 50 nm is reported for individual flakes of both purple membranes and artificial lipid vesicles loaded with channelrhodospin molecules.