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We demonstrate the use of plasmonic effects to boost the near-infrared sensitivity of metal-semiconductor-metal detectors. Plasmon-enhanced photodetection is achieved by properly optimizing Au interdigitated electrodes, micro-fabricated on Ge, a semiconductor that features a strong near IR absorption. Finite-difference time-domain simulations, photocurrent experiments and Fourier-transform IR spectroscopy are performed to validate how a relatively simple tuning of the contact geometry allows for an enhancement of the response of the device adapting it to the specific detection needs. A 2-fold gain factor in the Ge absorption characteristics is experimentally demonstrated at 1.4 µm, highlighting the potential of this approach for optoelectronic and sensing applications.

Photosensitive proteins embedded in the cell membrane (about 5 nm thickness) act as photoactivated proton pumps, ion gates, enzymes, or more generally, as initiators of stimuli for the cell activity. They are composed of a protein backbone and a covalently bound cofactor (e.g. the retinal chromophore in bacteriorhodopsin (BR), channelrhodopsin, and other opsins). The light-induced conformational changes of both the cofactor and the protein are at the basis of the physiological functions of photosensitive proteins. Despite the dramatic development of microscopy techniques, investigating conformational changes of proteins at the membrane monolayer level is still a big challenge. Techniques based on atomic force microscopy (AFM) can detect electric currents through protein monolayers and even molecular binding forces in single-protein molecules but not the conformational changes. For the latter, Fourier-transform infrared spectroscopy (FTIR) using difference-spectroscopy mode is typically employed, but it is performed on macroscopic liquid suspensions or thick films containing large amounts of purified photosensitive proteins. In this work, we develop AFM-assisted, tip-enhanced infrared difference-nanospectroscopy to investigate light-induced conformational changes of the bacteriorhodopsin mutant D96N in single submicrometric native purple membrane patches. We obtain a significant improvement compared with the signal-to-noise ratio of standard IR nanospectroscopy techniques by exploiting the field enhancement in the plasmonic nanogap that forms between a gold-coated AFM probe tip and an ultraflat gold surface, as further supported by electromagnetic and thermal simulations. IR difference-spectra in the 1450-1800 cm -1 range are recorded from individual patches as thin as 10 nm, with a diameter of less than 500 nm, well beyond the diffraction limit for FTIR microspectroscopy. We find clear spectroscopic evidence of a branching of the photocycle for BR molecules in direct contact with the gold surfaces, with equal amounts of proteins either following the standard proton-pump photocycle or being trapped in an intermediate state not directly contributing to light-induced proton transport. Our results are particularly relevant for BR-based optoelectronic and energy-harvesting devices, where BR molecular monolayers are put in contact with metal surfaces, and, more generally, for AFM-based IR spectroscopy studies of conformational changes of proteins embedded in intrinsically heterogeneous native cell membranes.

We demonstrate third harmonic generation in plasmonic antennas consisting of highly doped germanium grown on silicon substrates and designed to be resonant in the mid-infrared frequency range that is inaccessible with conventional nonlinear plasmonic materials. Owing to the near-field enhancement, the result is an ultrafast, subdiffraction, coherent light source with a wavelength tunable between 3 and 5 µm, and ideally overlapping with the fingerprint region of molecular vibrations. To observe the nonlinearity in this challenging spectral window, a high-power femtosecond laser system equipped with parametric frequency conversion in combination with an all-reflective confocal microscope setup is employed. We demonstrate spatially resolved maps of the linear scattering cross section and the nonlinear emission of single isolated antenna structures. A clear third-order power dependence as well as mid-infrared emission spectra prove the nonlinear nature of the light emission. Simulations support the observed resonance length of the double-rod antenna and demonstrate that the field enhancement inside the antenna material is responsible for the nonlinear frequency mixing., Competing Interests: The authors declare that they have no conflict of interest.

We address the oxygen-barrier properties of a nanocomposite created by layer-by-layer assembly of two biopolymers, chitosan (CS) and cellulose, in nanocrystals form (CNs), on an amorphous PET substrate. We systematically investigated the oxygen permeability, morphology, and thickness of the nanocomposite grown under two different pH combinations and with different number of deposition cycles, up to 30 bilayers. Noticeably, the thickness of each deposited bilayer can be largely tuned by the pH value of the solution, from ~7 up to ~26 nm in the tested conditions. By our analysis, it is reliably concluded that such CS/CNs nanocomposite holds promises for gas barrier applications in food and drug packaging as a clear coating on plastic films and tridimensional objects, improving performance and sustainability of the final packages., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In the presence of matter, there is no fundamental limit preventing confinement of visible light even down to atomic scales. Achieving such confinement and the corresponding resonant intensity enhancement inevitably requires simultaneous control over atomic-scale details of material structures and over the optical modes that such structures support. By means of self-assembly we have obtained side-by-side aligned gold nanorod dimers with robust atomically defined gaps reaching below 0.5 nm. The existence of atomically confined light fields in these gaps is demonstrated by observing extreme Coulomb splitting of corresponding symmetric and antisymmetric dimer eigenmodes of more than 800 meV in white-light scattering experiments. Our results open new perspectives for atomically resolved spectroscopic imaging, deeply nonlinear optics, ultrasensing, cavity optomechanics, as well as for the realization of novel quantum-optical devices.