An Infrared Nanospectroscopy Technique for the Study of Electric-Field-Induced Molecular Dynamics.

Static electric fields play a considerable role in a variety of molecular nanosystems as diverse as single-molecule junctions, molecules supporting electrostatic catalysis, and biological cell membranes incorporating proteins. External electric fields can be applied to nanoscale samples with a conductive atomic force microscopy (AFM) probe in contact mode, but typically, no structural information is retrieved. Here we combine photothermal expansion infrared (IR) nanospectroscopy with electrostatic AFM probes to measure nanometric volumes where the IR field enhancement and the static electric field overlap spatially. We leverage the vibrational Stark effect in the polymer poly(methyl methacrylate) for calibrating the local electric field strength. In the relevant case of membrane protein bacteriorhodopsin, we observe electric-field-induced changes of the protein backbone conformation and residue protonation state. The proposed technique also has the potential to measure DC currents and IR spectra simultaneously, insofar enabling the monitoring of the possible interplay between charge transport and other effects.

Infrared Resonance Raman of Bilayer Graphene: Signatures of Massive Fermions and Band Structure on the 2D Peak.

Few-layer graphene possesses low-energy carriers that behave as massive Fermions, exhibiting intriguing properties in both transport and light scattering experiments. Lowering the excitation energy of resonance Raman spectroscopy down to 1.17 eV, we target these massive quasiparticles in the split bands close to the K point. The low excitation energy weakens some of the Raman processes that are resonant in the visible, and induces a clearer frequency-separation of the substructures of the resonance 2D peak in bi- and trilayer samples. We follow the excitation-energy dependence of the intensity of each substructure, and comparing experimental measurements on bilayer graphene with ab initio theoretical calculations, we trace back such modifications on the joint effects of probing the electronic dispersion close to the band splitting and enhancement of electron-phonon matrix elements.

Probing Enhanced Electron-Phonon Coupling in Graphene by Infrared Resonance Raman Spectroscopy.

We report on resonance Raman spectroscopy measurements with excitation photon energy down to 1.16 eV on graphene, to study how low-energy carriers interact with lattice vibrations. Thanks to the excitation energy close to the Dirac point at K, we unveil a giant increase of the intensity ratio between the double-resonant 2D and 2D^{'} peaks with respect to that measured in graphite. Comparing with fully ab initio theoretical calculations, we conclude that the observation is explained by an enhanced, momentum-dependent coupling between electrons and Brillouin zone-boundary optical phonons. This finding applies to two-dimensional Dirac systems and has important consequences for the modeling of transport in graphene devices operating at room temperature.

High electron mobility in strained GaAs nanowires.

Transistor concepts based on semiconductor nanowires promise high performance, lower energy consumption and better integrability in various platforms in nanoscale dimensions. Concerning the intrinsic transport properties of electrons in nanowires, relatively high mobility values that approach those in bulk crystals have been obtained only in core/shell heterostructures, where electrons are spatially confined inside the core. Here, it is demonstrated that the strain in lattice-mismatched core/shell nanowires can affect the effective mass of electrons in a way that boosts their mobility to distinct levels. Specifically, electrons inside the hydrostatically tensile-strained gallium arsenide core of nanowires with a thick indium aluminium arsenide shell exhibit mobility values 30-50 % higher than in equivalent unstrained nanowires or bulk crystals, as measured at room temperature. With such an enhancement of electron mobility, strained gallium arsenide nanowires emerge as a unique means for the advancement of transistor technology.

Demonstration of a Broadband Photodetector Based on a Two-Dimensional Metal-Organic Framework.

Metal-organic frameworks (MOFs) are emerging as an appealing class of highly tailorable electrically conducting materials with potential applications in optoelectronics. Yet, the realization of their proof-of-concept devices remains a daunting challenge, attributed to their poor electrical properties. Following recent work on a semiconducting Fe3 (THT)2 (NH4 )3 (THT: 2,3,6,7,10,11-triphenylenehexathiol) 2D MOF with record-high mobility and band-like charge transport, here, an Fe3 (THT)2 (NH4 )3 MOF-based photodetector operating in photoconductive mode capable of detecting a broad wavelength range from UV to NIR (400-1575 nm) is demonstrated. The narrow IR bandgap of the active layer (≈0.45 eV) constrains the performance of the photodetector at room temperature by band-to-band thermal excitation of charge carriers. At 77 K, the device performance is significantly improved; two orders of magnitude higher voltage responsivity, lower noise equivalent power, and higher specific detectivity of 7 × 108 cm Hz1/2 W-1 are achieved under 785 nm excitation. These figures of merit are retained over the analyzed spectral region (400-1575 nm) and are commensurate to those obtained with the first demonstrations of graphene- and black-phosphorus-based photodetectors. This work demonstrates the feasibility of integrating conjugated MOFs as an active element into broadband photodetectors, thus bridging the gap between materials' synthesis and technological applications.

Effective Hexagonal Boron Nitride Passivation of Few-Layered InSe and GaSe to Enhance Their Electronic and Optical Properties.

Indium selenide (InSe) and gallium selenide (GaSe), members of the III-VI chalcogenide family, are emerging two-dimensional (2D) semiconductors with appealing electronic properties. However, their devices are still lagging behind because of their sensitivity to air and device fabrication processes which induce structural damage and hamper their intrinsic properties. Thus, in order to obtain high-performance and stable devices, effective passivation of these air-sensitive materials is strongly required. Here, we demonstrate a hexagonal boron nitride (hBN)-based encapsulation technique, where 2D layers of InSe and GaSe are covered entirely between two layers of hBN. To fabricate devices out of fully encapsulated 2D layers, we employ the lithography-free via-contacting scheme. We find that hBN acts as an excellent encapsulant and a near-ideal substrate for InSe and GaSe by passivating them from the environment and isolating them from the charge disorder at the SiO2 surface. As a result, the encapsulated InSe devices are of high quality and ambient-stable for a long time and show an improved two-terminal mobility of 30-120 cm2 V-1 s-1 as compared to mere ∼1 cm2 V-1 s-1 for unencapsulated devices. On employing this technique to GaSe, we obtain a strong and reproducible photoresponse. In contrast to previous studies, where either good performance or long-term stability was achieved, we demonstrate a combination of both in our devices. This work thus provides a systematic study of fully encapsulated devices based on InSe and GaSe, which has not been reported until now. We believe that this technique can open ways for fundamental studies as well as toward the integration of these materials in technological applications.