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The proton pump Bacteriorhodopsin (BR) undergoes repeated photocycles including reversible conformational changes upon visible light illumination. Exploiting the sensitivity of infrared (IR) spectra to the conformation, we have determined the reaction kinetic parameters of the conductive intermediate M for the wild-type protein and for its slow mutant D96N during its photocycle. Time-resolved IR micro-spectroscopy using an in-house developed confocal laser microscope operating in the mid-IR is employed to record absorption changes of 10−4 at wavelengths λ1 = 6.08 μm and λ2 = 6.35 μm, assigned to backbone and retinal structural modifications, respectively. Protein samples were embedded in dried lipid bilayers deposited on ultraflat gold supports to enhance the surface field. The signals were analyzed according to a simplified photocycle model with only two dominant states: the dark-adapted state BR* and the intermediate M. We obtained the excitation and relaxation times of the intermediate M from exponential fits to the absorption change time traces. Our results constitute a first step towards future plasmonic-assisted nanoscale time-resolved mid-IR spectrometers for the characterization of bioelectronic and light-harvesting nanodevices based on BR.

Recently, the concept of strong light-matter coupling has been demonstrated in semiconductor structures, and it is poised to revolutionize the design and implementation of components, including solid state lasers and detectors. We demonstrate an original nanospectroscopy technique that permits to study the light-matter interaction in single subwavelength-sized nano-cavities where far-field spectroscopy is not possible using conventional techniques. We inserted a thin ($\approx$ 150 nm) polymer layer with negligible absorption in the mid-IR (5 $\mu$m < $\lambda$ < 12 $\mu$m) inside a metal-insulator-metal resonant cavity, where a photonic mode and the intersubband transition of a semiconductor quantum well are strongly coupled. The intersubband transition peaks at $\lambda$ = 8.3 $\mu$m, and the nano-cavity is overall 270 nm thick. Acting as a non-perturbative transducer, the polymer layer introduces only a limited alteration of the optical response while allowing to reveal the optical power absorbed inside the concealed cavity. Spectroscopy of the cavity losses is enabled by the polymer thermal expansion due to heat dissipation in the active part of the cavity, and performed using an atomic force microscope (AFM). This innovative approach allows the typical anticrossing characteristic of the polaritonic dispersion to be identified in the cavity loss spectra at the single nano-resonator level. Results also suggest that near-field coupling of the external drive field to the top metal patch mediated by a metal-coated AFM probe tip is possible, and it enables the near-field mapping of the cavity mode symmetry including in the presence of strong light-matter interaction.

Hexagonal boron nitride (hBN) is widely used as a protective layer for few-atom-thick crystals and heterostructures (HSs), and it hosts quantum emitters working up to room temperature. In both instances, strain is expected to play an important role, either as an unavoidable presence in the HS fabrication or as a tool to tune the quantum emitter electronic properties. Addressing the role of strain and exploiting its tuning potentiality require the development of efficient methods to control it and of reliable tools to quantify it. Here we present a technique based on hydrogen irradiation to induce the formation of wrinkles and bubbles in hBN, resulting in remarkably high strains of ∼2%. By combining infrared (IR) near-field scanning optical microscopy and micro-Raman measurements with numerical calculations, we characterize the response to strain for both IR-active and Raman-active modes, revealing the potential of the vibrational properties of hBN as highly sensitive strain probes.

Localized Surface Plasmon Resonances (LSPR) based on highly doped semiconductors microstructures, such as antennas, can be engineered to exhibit resonant features at THz frequencies. In this work, we demonstrate plasmonic antennas with increased quality factor LSPRs from Fano coupling to dark modes. We also discuss the advances in the biofunctionalization of n-doped Ge antennas for specific protein immobilization and cell interfacing. Finally, albumin biolayers with a thickness of a few hundred nanometers are used to demonstrate the performance of the fano-coupled n-Ge antennas as sensors. A resonant change of over 10% in transmission, due to the presence of the biolayer, can be detected within a bandwidth of only 20 GHz.

The growing need for new and reliable surface sensing methods is arousing interest in the electromagnetic excitations of ultrathin films, i.e., to generate electromagnetic field distributions that resonantly interact with the most significant quasi-particles of condensed matter. In such a context, Bloch surface waves turned out to be a valid alternative to surface plasmon polaritons to implement high-sensitivity sensors in the visible spectral range. Only in the last few years, however, has their use been extended to infrared wavelengths, which represent a powerful tool for detecting and recognizing molecular species and crystalline structures. In this work, we demonstrate, by means of high-resolution reflectivity measurements, that a one-dimensional photonic crystal can sustain Bloch surface waves in the infrared spectral range from room temperature down to 10 K. To the best of our knowledge, this is the first demonstration of infrared Bloch surface waves at cryogenic temperatures. Furthermore, by exploiting the enhancement of the surface state and the high brilliance of infrared synchrotron radiation, we demonstrate that the proposed BSW-based sensor has a sensitivity on the order of 2.9 cm

Resonance Raman scattering, which probes electrons, phonons and their interplay in crystals, is extensively used in two-dimensional materials. Here we investigate Raman modes in MoSe$_2$ at different laser excitation energies from 2.33 eV down to the near infrared 1.16 eV. The Raman spectrum at 1.16 eV excitation energy shows that the intensity of high-order modes is strongly enhanced if compared to the first-order phonon modes intensity due to resonance effects with the MoSe$_2$ indirect band gap. By comparing the experimental results with the two-phonon density of states calculated with density functional theory, we show that the high-order modes originate mostly from two-phonon modes with opposite momenta. In particular, we identify the momenta of the phonon modes that couple strongly with the electrons to produce the resonance process at 1.16 eV, while we verify that at 2.33 eV the two-phonon modes lineshape compares well with the two-phonon density of state calculated over the entire Brillouin Zone. We also show that, by lowering the crystal temperature, we actively suppress the intensity of the resonant two-phonon modes and we interpret this as the result of the increase of the indirect band gap at low temperature that moves our excitation energy out of the resonance condition., Comment: 8 pages, 5 figures, to be published in Physical Review B

We report on the design, fabrication, and spectroscopic characterization of a 1D Photonic Cristal (1DPC) sustaining Bloch Surface Waves (BSWs) in the mid-infrared. The reported all-dielectric 1DPC structure shows potential for label-free biosensing applications to medical diagnostics.

We present n-doped germanium-on-silicon (Ge-on- Si) antennas fabricated with CMOS mainstream methods, showing resonances between 0.1 and 0.7 THz for sensing applications. After surface functionalization with α-lipoic acid, a red-shift of the antenna resonance is observed, as demonstrated by THz time domain spectroscopy. Similar results are obtained with silicon nitride (Si 3 N 4 )-coated antennas, enabling microfluidic integration. Finally, we compare antennas of bow-tie slots to antennas fabricated via maskless photolithography.

We present infrared (IR) nanospectroscopy results obtained on single hundred-nanometer-sized lipid microvesicles. The use of an IR nanospectroscopy platform allowed us to identify heterogeneities of the molecular cargo of the microvesicles that would not be possible by conventional IR spectroscopy.

We investigate Raman scattering of MoSe 2 crystals with excitation energies in the visible and in the infrared (from 1.16 eV to 2.33 eV). We show that, despite the lower scattering efficiency at longer wavelengths, it is possible to measure also MoSe 2 monolayers with photon energy of 1.16 eV, by placing the flakes on hexagonal BN slabs on Au substrates.The lineshape of the Raman modes is shown to be highly dependent on the excitation energy due to resonant processes. In particular, we observe effects of resonant Raman scattering with the indirect band gap (1.14 eV) of MoSe 2 yielding information on the electronic and phonon density of states. By the calculation of the two-phonon density of states in different position of the Brillouin zone, we are able to reproduce some experimental features of the second order Raman spectra.

Surface current patterns in single patch antennas are imaged by means of photoexpansion nanospectroscopy performed with an atomic force microscopy probe and a broadly tunable quantum cascade laser system. The local ohmic losses lead to temperature increase of a thin polymer layer positioned in the cavity, which then expands.

A thin layer of a mid-IR transparent polymer is inserted inside a metallic optical nano-resonator, where a photonic mode and an intersubband transition are strongly coupled together. Acting as a non-perturbative transducer, and without modifying the optical response, the polymer allows the detection of absorbed optical power in the form of thermal expansion due to heat dissipation. This innovative approach permits to identify - even at the single nano-resonator level - the typical anti crossing characteristic of the polaritonic system, and to perform direct imaging of the electromagnetic fields buried within the inside of an otherwise inaccessible optical nanocavity.

The strong light-matter coupling is an exotic phenomenon of interest not only for basic physics, but also because it has potential for improving optoelectronic devices. When dealing with conduction band electrons in semiconductor quantum wells (QWs), intersubband (ISB) transitions can couple to the optical resonances of plasmonic antennas. In the case of strong light-matter coupling, a characteristic anticrossing of the "light" and "matter" excitations is observed. It stems from the appearance of new eigenmodes, called cavity polaritons.

Extracellular vesicles are membrane-delimited structures, involved in several inter-cellular communication processes, both physiological and pathological, since they deliver complex biological cargo. Extracellular vesicles have been identified as possible biomarkers of several pathological diseases, thus, their characterization is fundamental in order to gain a deep understanding of their function and of the related processes. Traditional approaches for the characterization of the molecular content of the vesicles require a large quantity of sample, thereby providing an average molecular profile, while their heterogeneity is typically probed by non-optical microscopies that, however, lack the chemical sensitivity to provide information of the molecular cargo. Here, we perform a study of individual microvesicles, a subclass of extracellular vesicles generated by the outward budding of the plasma membrane, released by two cultures of glial cells under different stimuli, by applying a state-of-the-art infrared nanospectroscopy technique based on the coupling of an atomic force microscope and a pulsed laser, which combines the label-free chemical sensitivity of infrared spectroscopy with the nanometric resolution of atomic force microscopy. By correlating topographic, mechanical and spectroscopic information of individual microvesicles, we identified two main populations in both families of vesicles released by the two cell cultures. Subtle differences in terms of nucleic acid content among the two families of vesicles have been found by performing a fitting procedure of the main nucleic acid vibrational peaks in the 1000–1250 cm−1 frequency range.

Optogenetics is a revolutionary method for studying neural activity by exploiting the optical stimulation of neurons made possible by artificial genetic expression of light-sensitive transmembrane ``gate'' proteins. Evidence of functional conformational changes of the gate proteins can be obtained by difference infrared (IR) absorption spectroscopy triggered by light stimuli. Here we investigate the effect on the photocycle of the prototype optogenetic protein channelrhodopsin (ChR2) of gold surfaces placed in close proximity to the protein molecules. In order to do this, we bring difference IR spectroscopy to the nanoscale, using a platform based on the coupling of a tunable mid-IR quantum cascade laser and an atomic force microscope (AFM). Sensitivity to individual subwavelength-sized membrane patches, embedding fewer than a hundred ChR2 molecules, is achieved by taking advantage of a plasmonic field enhancement in the nanogap between the gold-coated AFM tip and an ultraflat gold surface used as a sample support. We obtain relative difference absorption variations smaller than ${10}^{\ensuremath{-}2}$ and benchmark nanospectroscopy difference spectra against those taken with the Fourier transform IR (FTIR) spectroscopic technique on the same sample. We identify distinct simultaneous processes in the ChR2 photocycle by performing singular value decomposition of the FTIR difference spectra, and use this procedure to compare IR nanospectroscopy data on individual membrane patches in contact with gold surfaces with those obtained on thick stacks of membrane patches unexposed to metal surfaces. ChR2 proteins maintain their gate function when placed in a 14-nm-wide gap between two gold surfaces, apart from minor modifications to their kinetics. Our results are relevant to optogenetic applications that require physical contact between nanoscale metallic probes and electrodes and the membrane of single neuronal cells. More generally, our work paves the way towards the spectroscopic study of transmembrane proteins at the nanoscale.

In the last decade, silicon photonics has undergone an impressive development driven by an increasing number of technological applications. Plasmonics has not yet made its way to the microelectronic industry, mostly because of the lack of compatibility of typical plasmonic materials with foundry processes. In this framework, we have developed a plasmonic platform based on heavily n-doped Ge grown on silicon substrates. We developed growth protocols to reach n-doping levels exceeding 1020 cm-3, allowing us to tune the plasma wavelength of Ge in the 3-15 μm range. The plasmonic resonances of Ge-on-Si nanoantennas have been predicted by simulations, confirmed by experimental spectra and exploited for molecular sensing. Our work represents a benchmark for group-IV mid-IR plasmonics.

High-quality n-type continuously graded Ge-rich Si1−xGex parabolic quantum wells with different doping level were grown by using ultrahigh-vacuum chemical vapor deposition on Si(001) substrates. A thorough structural characterization highlights an ideal parabolic compositional profile. THz intersubband absorption has been investigated in modulation-doped samples and samples directly doped in the wells. The comparison of experimental absorption data and theoretical calculations allowed us to quantify the impact of electron correlation effects on the absorption resonances in the different doping conditions and for electron sheet densities in the (1÷6)×1011 cm−2 range. A single optical resonance is present in modulation doped samples. Its peak energy and line-shape is independent of temperature-induced variations of the electron distribution in the subbands up to 300 K, in agreement with the generalized Kohn theorem. This achievement represents a relevant step-forward for the development of CMOS compatible optoelectronic devices in the THz spectral range, where thermal charge fluctuations play a key role.

Ge/SiGe heterostructures are promising in the view of silicon-foundry compatible THz optoelectronic applications. Here we present a structural and optical characterization of Ge/SiGe parabolic quantum wells that represent ideal systems for room-temperature THz emission and strong light-matter coupling investigation.

We apply polarized Attenuated Total Reflection Fourier Transform Infrared spectroscopy (ATR-FTIR) to study conformational changes of the prototype photosensitive protein bacteriorhodopsin (BR). The experiments are performed on hundreds-nanometer-thick films of stacked membrane patches embedding BR molecules. Moreover, we report our results on functionalization of silicon surfaces that are preliminary to further experiments involving faced-down silicon substrates on ATR crystal in order to increase the sensitivity down to very thin protein films.

The realization of a Ge/SiGe THz emitter is of great interest since it can help to reach room-temperature operation due to the peculiar electron-phonon interaction in nonpolar crystals. Here we present Ge/SiGe quantum-well building blocks epitaxially grown on silicon wafers in order to understand limitations of this material platform in the perspective of realizing a Si-based laser.

Exploiting the coupling of laser beams to atomic force microscopy probes, both scattering and absorption of mid-infrared radiation (wavelengths of 5 to $11\ \mu \mathrm{m}$ ) have been measured in the near field region of single patch-antennas, strongly coupled to the intersubband transition of an InGaAs/AlInAs quantum well.

Electron-optical phonon interaction is the dominant energy-loss mechanism in low-dimensional Ge/SiGe heterostructures and represents a key parameter for the design and realization of electronic and optoelectronic devices based on this material system compatible with the mainstream Si complementary metal-oxide semiconductor technology. Here we investigate the intersubband relaxation dynamics of $n$-type Ge/SiGe multiquantum wells with different symmetry and design by means of single-color pump-probe spectroscopy. By comparing the experimental differential transmittance data as a function of the pump-probe delay with numerical calculations based on an energy-balance rate-equation model, we could quantify an effective value for the optical phonon deformation potential describing the electron-phonon coupling in two-dimensional Ge-based systems. We found nonradiative relaxation times longer than 20 ps even in samples having intersubband energy separations larger than the optical phonon energy, evidencing the presence of a less effective electron-phonon coupling with respect to that estimated in bulk Ge.

The mid-infrared spectral region is key to several large market applications such as security, healthcare and environmental monitoring. This is due to how chemical compounds can be detected from unique vibrational modes that absorb in the molecular ‘fingerprint’ region ( $6.7-20\ \mu \mathrm{m}$ wavelength). There is significant interest in realizing cheaper and smaller spectrometers based on waveguide integrated photonics. Here we demonstrate Ge-on-Si waveguides operating up to $11\ \mu \mathrm{m}$ wavelength with low propagation loss (∼ 1 dB/cm). The performance of the waveguides is then demonstrated by measuring thin films that are used to calibrate the modal overlap for molecular sensing. Lastly, an ultra-broadband Ge-on-Si waveguide polarization rotator is presented. The fabricated polarization rotator devices demonstrate a polarization extinction ratio of ≥ 15 dB over a $2\ \mu \mathrm{m}$ bandwidth ( $9-11\ \mu \mathrm{m}$ wavelength) with an average insertion loss < 1 dB.

n-type Ge/SiGe asymmetric coupled quantum wells represent the building block of a variety of nanoscale quantum devices, including recently proposed designs for a silicon-based THz quantum cascade laser. In this paper, we combine structural and spectroscopic experiments on 20-module superstructures, each featuring two Ge wells coupled through a Ge-rich SiGe tunnel barrier, as a function of the geometry parameters of the design and the P dopant concentration. Through a comparison of THz spectroscopic data with numerical calculations of intersubband optical absorption resonances, we demonstrated that it is possible to tune, by design, the energy and the spatial overlap of quantum confined subbands in the conduction band of the heterostructures. The high structural/interface quality of the samples and the control achieved on subband hybridization are promising starting points towards a working electrically pumped light-emitting device.

n-type doped Ge quantum wells with SiGe barriers represent a promising heterostructure system for the development of radiation emitters in the terahertz range such as electrically pumped quantum cascade lasers and optically pumped quantum fountain lasers. The nonpolar lattice of Ge and SiGe provides electron&ndash, phonon scattering rates that are one order of magnitude lower than polar GaAs. We have developed a self-consistent numerical energy-balance model based on a rate equation approach which includes inelastic and elastic inter- and intra-subband scattering events and takes into account a realistic two-dimensional electron gas distribution in all the subband states of the Ge/SiGe quantum wells by considering subband-dependent electronic temperatures and chemical potentials. This full-subband model is compared here to the standard discrete-energy-level model, in which the material parameters are limited to few input values (scattering rates and radiative cross sections). To provide an experimental case study, we have epitaxially grown samples consisting of two asymmetric coupled quantum wells forming a three-level system, which we optically pump with a free electron laser. The benchmark quantity selected for model testing purposes is the saturation intensity at the 1&rarr, 3 intersubband transition. The numerical quantum model prediction is in reasonable agreement with the experiments and therefore outperforms the discrete-energy-level analytical model, of which the prediction of the saturation intensity is off by a factor 3.

We study radiative relaxation at terahertz frequencies in n-type Ge/SiGe quantum wells, optically pumped with a terahertz free electron laser. Two wells coupled through a tunneling barrier are designed to operate as a three-level laser system with non-equilibrium population generated by optical pumping around the 1→3 intersubband transition at 10 THz. The non-equilibrium subband population dynamics are studied by absorption-saturation measurements and compared to a numerical model. In the emission spectroscopy experiment, we observed a photoluminescence peak at 4 THz, which can be attributed to the 3→2 intersubband transition with possible contribution from the 2→1 intersubband transition. These results represent a step towards silicon-based integrated terahertz emitters.

The fabrication of highly doped and high quality Ge layers is a challenging and hot topic for advancements in nanoelectronics, photonics and radiation detectors. In this article, we report on a simple method for junction formation consisting in sputter depositing or evaporating a thin pure Sb layer on Ge followed by cycles of Pulsed Laser Melting (PLM). We show that PLM promotes an efficient diffusion of high Sb concentrations into the melted Ge subsurface layer, followed by a fast epitaxial regrowth. The resulting layer is perfectly pseudomorphic to the Ge substrate, preserving the high strain level induced by the Sb, having covalent radius higher than Ge. In addition, it shows extremely high active concentrations up to 3 × 1020 cm−3 and a record low resistivity of 1.4 × 10-4 Ohm cm. The carrier mobility is also in line with the extrapolation of literature data with no signs of mobility degradation. Furthermore, infrared reflectivity confirms the good optical quality of the doped layers and demonstrates, for the first time, plasma wavelengths in Ge below 3 µm. These results are highly relevant for nanolectronic and plasmonic applications.

Recent efforts in the field of surface-enhanced spectroscopies have focused on the paradigm of "superchirality", entailing the engineering of the local electromagnetic fields to boost the enantiospecific interaction between light and chiral molecules. In this framework, approaches based on both metallic and dielectric nanostructures have been proposed and have also recently been extended to vibrational circular dichroism in the mid-infrared. In this work, we design, fabricate, and characterize a lattice of chiral plasmonic slits featuring enhanced chiral fields in the mid-infrared. We exploit collective lattice resonances to further enhance the local intensity and to generate sharp features in the circular dichroism spectra of the platform. Such features are ideally suited to test the superchiral coupling with the vibrational resonances of chiral molecules.

A novel spectroscopy technique to enable the rapid characterization of discrete mid-infrared integrated photonic waveguides is demonstrated. The technique utilizes lithography patterned polymer blocks that absorb light strongly within the molecular fingerprint region. These act as integrated waveguide detectors when combined with an atomic force microscope that measures the photothermal expansion when infrared light is guided to the block. As a proof of concept, the technique is used to experimentally characterize propagation loss and grating coupler response of Ge-on-Si waveguides at wavelengths from 6 to 10 µm. In addition, when the microscope is operated in scanning mode at fixed wavelength, the guided mode exiting the output facet is imaged with a lateral resolution better than 500 nm i.e. below the diffraction limit. The characterization technique can be applied to any mid-infrared waveguide platform and can provide non-destructive in-situ testing of discrete waveguide components.

The waveguide losses from a range of surface plasmon and double metal waveguides for Ge/Si1−xGe x THz quantum cascade laser gain media are investigated at 4.79 THz (62.6 μm wavelength). Double metal waveguides demonstrate lower losses than surface plasmonic guiding with minimum losses for a 10 μm thick active gain region with silver metal of 21 cm−1 at 300 K reducing to 14.5 cm−1 at 10 K. Losses for silicon foundry compatible metals including Al and Cu are also provided for comparison and to provide a guide for gain requirements to enable lasers to be fabricated in commercial silicon foundries. To allow these losses to be calculated for a range of designs, the complex refractive index of a range of nominally undoped Si1−xGe x with x = 0.7, 0.8 and 0.9 and doped Ge heterolayers were extracted from Fourier transform infrared spectroscopy measurements between 0.1 and 10 THz and from 300 K down to 10 K. The results demonstrate losses comparable to similar designs of GaAs/AlGaAs quantum cascade laser plasmon waveguides indicating that a gain threshold of 15.1 cm−1 and 23.8 cm−1 are required to produce a 4.79 THz Ge/SiGe THz laser at 10 K and 300 K, respectively, for 2 mm long double metal waveguide quantum cascade lasers with facet coatings.

Scanning-probe-assisted mid-infrared nano-spectroscopy is employed to reveal the polaritonic dispersion of individual MIM (metal-insulator-metal) square patch antennas whose modes can be strongly coupled to a mid-infrared intersubband transition. The patch antenna side length L sets the resonances between λ = 5.5 μm and 12.5 μm. The active region consists of a highly doped AlInAs/InGaAs/AlInAs single quantum well that presents an intersubband transition at 1190 cm−1 (λ = 8.4 μm). When the patch antenna optical resonance approaches and matches the intersubband transition frequency (L ∼ 1.8 μm), a clear anticrossing behavior—evidence of strong coupling—is observed in the near-field scattering phase spectra of individual antennas. The measured Rabi splitting is 4.5 THz. The near-field scattering spectra agree with the far-field extinction spectra acquired on arrays of identical antennas.

Exploiting intersubband transitions in Ge/SiGe quantum cascade devices provides a way to integrate terahertz light emitters into silicon-based technology. With the view to realizing a Ge/SiGe Quantum Cascade Laser, we present the optical and structural properties of n-type strain-symmetrized Ge/SiGe asymmetric coupled quantum wells grown on Si(001) substrates by means of ultrahigh vacuum chemical vapor deposition. We demonstrate high material quality of strain-symmetrized structures and heterointerfaces as well as control over inter-well coupling and electron tunneling. Motivated by the promising results obtained on ACQWs, which are the basic building block of a cascade structure, we investigate, both experimentally and theoretically, a Ge/SiGe THz QCL design, optimized through a non-equilibrium Green’s function formalism

The imaging and sensing technology operating in the THz region of the electromagnetic spectrum has a number of applications, with demonstrator products already available on the market for oncology imaging, production monitoring, and non-destructive test [1]. However, the THz sources now at hand are still bulky and too expensive for expanding this technology to other proposed applications, which also include, among other, THz bandwidth photonics and security imaging. A higher level of integration with control electronics, a lower production cost, and a broader wavelength range of emission towards the far-infrared, are all desirable features to expand the fields of application of THz radiation. N-type Ge/SiGe quantum cascade structures grown on top of a Si(001) substrate are particularly promising for realizing a Si based THz source [2]. The low effective mass and long non-radiative relaxation times due to the non-polar nature of the material, are expected to i) provide gain values close to those demonstrated in III-V quantum cascade structures at 4 K, and ii) to potentially enable 300 K operation. In this presentation we will discuss the optical and structural properties of n-type s-Ge/SiGe multi-quantum wells and asymmetric coupled quantum wells grown on Si(001) substrates by means of ultrahigh vacuum chemical vapor deposition [3]. Extensive structural characterization obtained by scanning transmission electron microscopy (STEM), atomic probe tomography (APT) and X-ray diffraction shows the high material quality of strain-symmetrized structures (up to 5 micron active region thickness) and heterointerfaces (featuring interface roughness below 0.2 nm), down to the ultrathin barrier limit (about 1 nm). By performing THz absorption spectroscopy measurements combined to theoretical modeling on different asymmetric coupled quantum well systems (with varying large-well width or barrier thickness), we unambiguously demonstrated inter-well coupling and wavefunction tunneling [3]. The agreement between experimental data and simulations allowed us to characterize the tunneling barrier parameters and, in turn, achieve a highly-controlled engineering of the electronic structure in forthcoming unipolar cascade systems based on n-type Ge/SiGe multi quantum-wells. Furthermore, by pump-and-probe, and time domain spectroscopic data with a thorough theoretical modeling, we will show that this material system is indeed promising as active material in quantum cascade lasers (QCL). We found i) narrow intersubband (ISB) absorption lines; ii) relatively long non-radiative ISB relaxation times at high temperature; iii) relaxation times for different ISB transitions favorable to population inversion. Leveraging on the promising results obtained by spectroscopy experiments, we theoretically investigate an electrically-pumped Ge/SiGe THz QCL through a non-Equilibrium Green Function formalism (nextnano.QCL), using as material parameters to model the scattering processes the values estimated from the analysis of the optical experimental data [4]. As expected, due to the weaker interaction with the phonon field with respect to III-V based devices, we find a lower impact of the temperature on the gain spectrum. In addition, simulations show that the interface roughness values measured on our samples allows to achieve gain overcoming the losses of double-metal waveguides at room temperature. We believe that the present results will motivate new experimental efforts aimed at demonstrating room-temperature operation in group IV QCL THz devices. References [1] D. J. Paul, Laser Photon. Rev. 4, 610 (2010). [2] K. Driscoll, and R. Paiella, J. Appl. Phys. 102, 093103 (2007). [3] C. Ciano, M. Virgilio, M. Montanari, L. Persichetti, L. Di Gaspare, M. Ortolani, L. Baldassarre, M. H. Zollner, O. Skibitzki, G.Scalari, J. Faist, D. J. Paul, M. Scuderi, G. Nicotra, T. Grange, S. Birner, G. Capellini, and M. De Seta, Accepted in Phys. Rev. Appl., 11, 014003 (2019). [4] T. Grange, D. Stark, G. Scalari, J. Faist, L. Persichetti, L. Di Gaspare, M. De Seta, M. Ortolani, D.J. Paul, G. Capellini, S. Birner and M. Virgilio, Submitted to Applied Physics Letters. Preprint available at https://arxiv.org/pdf/1811.12879.pdf.

We explore saturable absorption and terahertz photoluminescence emission in a set of n-doped Ge/SiGe asymmetric coupled quantum wells, designed as three-level systems (i.e., quantum fountain emitter). We generate a non-equilibrium population by optical pumping at the 1→3 transition energy using picosecond pulses from a free-electron laser and characterize this effect by measuring absorption as a function of the pump intensity. In the emission experiment we observe weak emission peaks in the 14–25 meV range (3–6 THz) corresponding to the two intermediate intersubband transition energies. The results represent a step towards silicon-based integrated terahertz emitters.

The exploitation of intersubband transitions in Ge/SiGe quantum cascade devices could pave the way towards the integration of THz light emitters into the silicon-based technology. Aiming at the realization of a Ge/SiGe Quantum Cascade Laser (QCL), we investigate optical and structural properties of n-type Ge/SiGe coupled quantum well systems. The samples have been investigated by means of X-ray diffraction, scanning transmission electron microscopy, atom probe tomography and Fourier Transform Infrared absorption spectroscopy to assess the growth capability with respect to QCL design requirements, carefully identified by means of modelling based on the non-equilibrium Green function formalism.

Conformational changes of the light-sensitive membrane receptor and proton pump bacteriorhodopsin is investigated by tip-enhanced mid-infrared nanospectroscopy on individual cell membrane patches, with a dramatic increase of sensitivity (in terms of number of probed molecules) compared with standard mid-infrared spectroscopy.

Germanium-on-silicon, mid-infrared waveguides are used to demonstrate molecular fingerprint sensing of poly(methyl methacrylate) between 7.5 and 10 μm wavelength. The results are compared to Fourier transform infrared spectroscopy measurements, highlighting the potential of the platform for the identification of analytes.

Ge-on-Si waveguides with losses below 5 dB/cm across 7.5 to 11 µm wavelength are demonstrated. Sidewall etch roughness was measured using atomic force microscopy to investi- gate the waveguide loss mechanisms. Mid-infrared spectroscopy of poly(methyl methacrylate) was demonstrated using the Ge waveguides for mid-infrared sensing.

Low loss Ge-on-Si waveguides are demonstrated in the 8 – 14 μm atmospheric transmission window, a technology that will enable detection and sensing of unique molecular vibrations. Such a low cost platform would have applications in key markets such as pollution monitoring, explosives detection and point of care diagnostics. Rib-waveguides are fabricated using electron beam lithography and dry etching. The waveguides propagation losses are characterized using the Fabry-Perot technique, and are found to be below 5 dB/cm across the measurement range of 7.5 to 11 μm wavelength, reaching as low as ~ 1 dB/cm. The contribution to the losses are analyzed using the experimentally measured Si substrate losses, and the calculated scattering losses from an analytical model. The results verify the feasibility of the Ge-on-Si platform for integrated mid-infrared photonics and sensing.

Theoretical predictions indicate that the n-type Ge / Si − Ge multi-quantum-well system is the most promising material for the realization of a Si -compatible THz quantum cascade laser operating at room temperature. To advance in this direction, we study, both experimentally and theoretically, asymmetric coupled multi-quantum-well samples based on this material system, that can be considered as the basic building block of a cascade architecture. Extensive structural characterization shows the high material quality of strain-symmetrized structures grown by chemical vapor deposition, down to the ultrathin barrier limit. Moreover, THz absorption spectroscopy measurements supported by theoretical modeling unambiguously demonstrate inter-well coupling and wavefunction tunneling. The agreement between experimental data and simulations allows us to characterize the tunneling barrier parameters and, in turn, achieve highly controlled engineering of the electronic structure in forthcoming unipolar cascade systems based on n-type Ge / Si − Ge multi-quantum-wells.

Kinetic Inductance Detectors made of High-TC superconductor YBCO are designed and fabricated, in view as possible application as high sensitivity, low cost and high-manageability terahertz camera for imaging.

For the last decade, germanium has been proposed as an excellent material for passive mid-infrared (MIR) integrated photonics. This technology allows for label-free sensing in the molecular fingerprint regime (6.7–20 μm), where molecules can be uniquely identified by their absorption spectra. Such a platform has the potential to enable low cost, miniaturized mid-infrared sensors for use in crucial applications such as explosives detection, pollution monitoring and detection of breath biomarkers for point of care diagnostics. There have now been a number of demonstrations of waveguides up to 8.5 μm wavelength using Ge [1] and SiGe [2] waveguides. Previously, we have demonstrated the first low loss Ge-on-Si waveguides from 7.5 to 11 μm, with losses as low as ∼1 dB/cm [3]. Here, we demonstrate their potential for sensing applications by evanescently sensing unique vibrations in poly(methyl methacrylate) (PMMA) polymers, in the spectral region of 7.5–10 μm wavelength.

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), channel rhodopsin, 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..., Comment: published under ACS AuthorChoice license

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.