Unveiling Planar Defects in Hexagonal Group IV Materials.

Recently synthesized hexagonal group IV materials are a promising platform to realize efficient light emission that is closely integrated with electronics. A high crystal quality is essential to assess the intrinsic electronic and optical properties of these materials unaffected by structural defects. Here, we identify a previously unknown partial planar defect in materials with a type I3 basal stacking fault and investigate its structural and electronic properties. Electron microscopy and atomistic modeling are used to reconstruct and visualize this stacking fault and its terminating dislocations in the crystal. From band structure calculations coupled to photoluminescence measurements, we conclude that the I3 defect does not create states within the hex-Ge and hex-Si band gap. Therefore, the defect is not detrimental to the optoelectronic properties of the hex-SiGe materials family. Finally, highlighting the properties of this defect can be of great interest to the community of hex-III-Ns, where this defect is also present.

Ballistic Phonons in Ultrathin Nanowires.

According to Fourier's law, a temperature difference across a material results in a linear temperature profile and a thermal conductance that decreases inversely proportional to the system length. These are the hallmarks of diffusive heat flow. Here, we report heat flow in ultrathin (25 nm) GaP nanowires in the absence of a temperature gradient within the wire and find that the heat conductance is independent of wire length. These observations deviate from Fourier's law and are direct proof of ballistic heat flow, persisting for wire lengths up to at least 15 µm at room temperature. When doubling the wire diameter, a remarkably sudden transition to diffusive heat flow is observed. The ballistic heat flow in the ultrathin wires can be modeled within Landauer's formalism by ballistic phonons with an extraordinarily long mean free path.

Phonon Engineering in Twinning Superlattice Nanowires.

One of the current challenges in nanoscience is tailoring the phononic properties of a material. This has long been a rather elusive task because several phonons have wavelengths in the nanometer range. Thus, high quality nanostructuring at that length-scale, unavailable until recently, is necessary for engineering the phonon spectrum. Here we report on the continuous tuning of the phononic properties of a twinning superlattice GaP nanowire by controlling its periodicity. Our experimental results, based on Raman spectroscopy and rationalized by means of ab initio theoretical calculations, give insight into the relation between local crystal structure, overall lattice symmetry, and vibrational properties, demonstrating how material engineering at the nanoscale can be successfully employed in the rational design of the phonon spectrum of a material.

Crystalline, Phononic, and Electronic Properties of Heterostructured Polytypic Ge Nanowires by Raman Spectroscopy.

Semiconducting nanowires (NWs) offer the unprecedented opportunity to host different crystal phases in a nanostructure, which enables the formation of polytypic heterostructures where the material composition is unchanged. This characteristic boosts the potential of polytypic heterostructured NWs for optoelectronic and phononic applications. In this work, we investigate cubic Ge NWs where small (∼20 nm) hexagonal domains are formed due to a strain-induced phase transformation. By combining a nondestructive optical technique (Raman spectroscopy) with density-functional theory (DFT) calculations, we assess the phonon properties of hexagonal Ge, determine the crystal phase variations along the NW axis, and, quite remarkably, reconstruct the relative orientation of the two polytypes. Moreover, we provide information on the electronic band alignment of the heterostructure at points of the Brillouin zone different from the one (Γ) where the direct band gap recombination in hexagonal Ge takes place. We demonstrate the versatility of Raman spectroscopy and show that it can be used to determine the main crystalline, phononic, and electronic properties of the most challenging type of heterostructure (a polytypic, nanoscale heterostructure with constant material composition). The general procedure that we establish can be applied to several types of heterostructures.

Addressing the Fundamental Electronic Properties of Wurtzite GaAs Nanowires by High-Field Magneto-Photoluminescence Spectroscopy.

At ambient conditions, GaAs forms in the zincblende (ZB) phase with the notable exception of nanowires (NWs) where the wurtzite (WZ) lattice is also found. The WZ formation is both a complication to be dealt with and a potential feature to be exploited, for example, in NW homostructures wherein ZB and WZ phases alternate controllably and thus band gap engineering is achieved. Despite intense studies, some of the fundamental electronic properties of WZ GaAs NWs are not fully assessed yet. In this work, by using photoluminescence (PL) under high magnetic fields (B = 0-28 T), we measure the diamagnetic shift, ΔEd, and the Zeeman splitting of the band gap free exciton in WZ GaAs formed in core-shell InGaAs-GaAs NWs. The quantitative analysis of ΔEd at different temperatures (T = 4.2 and 77 K) and for different directions of B⃗ allows the determination of the exciton reduced mass, µexc, in planes perpendicular (µexc = 0.052 m0, where m0 is the electron mass in vacuum) and parallel (µexc = 0.057 m0) to the c axis of the WZ lattice. The value and anisotropy of the exciton reduced mass are compatible with the electron lowest-energy state having Γ7C instead of Γ8C symmetry. This finding answers a long discussed issue about the correct ordering of the conduction band states in WZ GaAs. As for the Zeeman splitting, it varies considerably with the field direction, resulting in an exciton gyromagnetic factor equal to 5.4 and ∼0 for B⃗//c and B⃗⊥c, respectively. This latter result provides fundamental insight into the band structure of wurtzite GaAs.

Polarized light absorption in wurtzite InP nanowire ensembles.

We investigate the absorption properties of ensembles of wurtzite (WZ) InP nanowires (NWs) by high-resolution polarization-resolved photoluminescence excitation (PLE) spectroscopy at T = 10 K. The degree of linear polarization of absorbed light, ρ(abs), resulting from the PLE spectra is governed by a competition between the dielectric mismatch effect and the WZ selection rules acting differently on different optical transitions. These two contributions are deconvoluted with the help of finite-difference time-domain simulations, thus providing information about the symmetry of the three highest valence bands (A, B, and C) of WZ InP and the extent of the spin-orbit interaction on these states. Moreover, ρ(abs) shows two characteristic dips corresponding to the two sharp A and B exciton resonances in the PLE spectra. A model developed for the dip in A provides the first experimental evidence of an enhancement in the dielectric mismatch effect originating from the Coulomb interaction between electron and hole.

GaAs/GaP superlattice nanowires: growth, vibrational and optical properties.

Nanowire geometry allows semiconductor heterostructures to be obtained that are not achievable in planar systems, as in, for example, axial superlattices made of large lattice mismatched materials. This provides a great opportunity to explore new optical transitions and vibrational properties resulting from the superstructure. Moreover, superlattice nanowires are expected to show improved thermoelectric properties, owing to the dominant role of surfaces and interfaces that can scatter phonons more effectively, reducing the lattice thermal conductivity. Here, we show the growth of long (up to 100 repetitions) GaAs/GaP superlattice nanowires with different periodicities, uniform layer thicknesses, and sharp interfaces, realized by means of Au-assisted chemical beam epitaxy. By optimizing the growth conditions, we obtained great control of the nanowire diameter, growth rate, and superlattice periodicity, offering a valuable degree of freedom for engineering photonic and phononic properties at the nanoscale. As a proof of concept, we analyzed a single type of superlattice nanowire with a well-defined periodicity and we observed room temperature optical emission and new phonon modes. Our results prove that high-quality GaAs/GaP superlattice nanowires have great potential for phononic and optoelectronic studies and applications.

Homogeneous Spatial Distribution of Deuterium Chemisorbed on Free-Standing Graphene.

Atomic deuterium (D) adsorption on free-standing nanoporous graphene obtained by ultra-high vacuum D2 molecular cracking reveals a homogeneous distribution all over the nanoporous graphene sample, as deduced by ultra-high vacuum Raman spectroscopy combined with core-level photoemission spectroscopy. Raman microscopy unveils the presence of bonding distortion, from the signal associated to the planar sp2 configuration of graphene toward the sp3 tetrahedral structure of graphane. The establishment of D-C sp3 hybrid bonds is also clearly determined by high-resolution X-ray photoelectron spectroscopy and spatially correlated to the Auger spectroscopy signal. This work shows that the low-energy molecular cracking of D2 in an ultra-high vacuum is an efficient strategy for obtaining high-quality semiconducting graphane with homogeneous uptake of deuterium atoms, as confirmed by this combined optical and electronic spectro-microscopy study wholly carried out in ultra-high vacuum conditions.

Administration of a novel high affinity PICK1 PDZ domain inhibitor attenuates cocaine seeking in rats.

Protein interacting with C kinase-1 (PICK1) regulates intra-cellular trafficking of GluA2-containing AMPA receptors, a process known to play a critical role in cocaine-seeking behavior. This suggests that PICK1 may represent a molecular target for developing novel pharmacotherapies to treat cocaine craving-induced relapse. Emerging evidence indicates that inhibition of PICK1 attenuates the reinstatement of cocaine-seeking behavior, an animal model of relapse. Here, we show that systemic administration of TAT-P4-(DATC5)2, a novel high-affinity peptide inhibitor of the PICK1 PDZ domain, dose-dependently attenuated the reinstatement of cocaine seeking in rats at doses that did not produce operant learning deficits or suppress locomotor activity. We also show that systemic TAT-P4-(DATC5)2 penetrated the brain where it was visualized in the nucleus accumbens shell. Consistent with these effects, infusions of TAT-P4-(DATC5)2 directly into the accumbens shell reduced cocaine, but not sucrose, seeking. The effects of TAT-P4-(DATC5)2 on cocaine seeking are likely due, in part, to inhibition of PICK1 in medium spiny neurons (MSNs) of the accumbens shell as TAT-P4-(DATC5)2 was shown to accumulate in striatal neurons and bind PICK1. Taken together, these findings highlight a novel role for PICK1 in the reinstatement of cocaine seeking and support future studies examining the efficacy of peptide inhibitors of PICK1 in animal and human models of cocaine relapse.

Hole and Electron Effective Masses in Single InP Nanowires with a Wurtzite-Zincblende Homojunction.

The formation of wurtzite (WZ) phase in III-V nanowires (NWs) such as GaAs and InP is a complication hindering the growth of pure-phase NWs, but it can also be exploited to form NW homostructures consisting of alternate zincblende (ZB) and WZ segments. This leads to different forms of nanostructures, such as crystal-phase superlattices and quantum dots. Here, we investigate the electronic properties of the simplest, yet challenging, of such homostructures: InP NWs with a single homojunction between pure ZB and WZ segments. Polarization-resolved microphotoluminescence (µ-PL) measurements on single NWs provide a tool to gain insights into the interplay between NW geometry and crystal phase. We also exploit this homostructure to simultaneously measure effective masses of charge carriers and excitons in ZB and WZ InP NWs, reliably. Magneto-µ-PL measurements carried out on individual NWs up to 29 T at 77 K allow us to determine the free exciton reduced masses of the ZB and WZ crystal phases, showing the heavier character of the WZ phase, and to deduce the effective mass of electrons in ZB InP NWs (me= 0.080 m0). Finally, we obtain the reduced mass of light-hole excitons in WZ InP by probing the second optically permitted transition Γ7C ↔ Γ7uV with magneto-µ-PL measurements carried out at room temperature. This information is used to extract the experimental light-hole effective mass in WZ InP, which is found to be mlh = 0.26 m0, a value much smaller than the one of the heavy hole mass. Besides being a valuable test for band structure calculations, the knowledge of carrier masses in WZ and ZB InP is important in view of the optimization of the efficiency of solar cells, which is one of the main applications of InP NWs.

Probing Lattice Dynamics and Electronic Resonances in Hexagonal Ge and SixGe1-x Alloys in Nanowires by Raman Spectroscopy.

Recent advances in nanowire synthesis have enabled the realization of crystal phases that in bulk are attainable only under extreme conditions, i.e., high temperature and/or high pressure. For group IV semiconductors this means access to hexagonal-phase SixGe1-x nanostructures (with a 2H type of symmetry), which are predicted to have a direct band gap for x up to 0.5-0.6 and would allow the realization of easily processable optoelectronic devices. Exploiting the quasi-perfect lattice matching between GaAs and Ge, we synthesized hexagonal-phase GaAs-Ge and GaAs-SixGe1-x core-shell nanowires with x up to 0.59. By combining position-, polarization-, and excitation wavelength-dependent µ-Raman spectroscopy studies with first-principles calculations, we explore the full lattice dynamics of these materials. In particular, by obtaining frequency-composition calibration curves for the phonon modes, investigating the dependence of the phononic modes on the position along the nanowire, and exploiting resonant Raman conditions to unveil the coupling between lattice vibrations and electronic transitions, we lay the grounds for a deep understanding of the phononic properties of 2H-SixGe1-x nanostructured alloys and of their relationship with crystal quality, chemical composition, and electronic band structure.

A high-affinity, bivalent PDZ domain inhibitor complexes PICK1 to alleviate neuropathic pain.

Maladaptive plasticity involving increased expression of AMPA-type glutamate receptors is involved in several pathologies, including neuropathic pain, but direct inhibition of AMPARs is associated with side effects. As an alternative, we developed a cell-permeable, high-affinity (~2 nM) peptide inhibitor, Tat-P4 -(C5)2 , of the PDZ domain protein PICK1 to interfere with increased AMPAR expression. The affinity is obtained partly from the Tat peptide and partly from the bivalency of the PDZ motif, engaging PDZ domains from two separate PICK1 dimers to form a tetrameric complex. Bivalent Tat-P4 -(C5)2 disrupts PICK1 interaction with membrane proteins on supported cell membrane sheets and reduce the interaction of AMPARs with PICK1 and AMPA-receptor surface expression in vivo. Moreover, Tat-P4 -(C5)2 administration reduces spinal cord transmission and alleviates mechanical hyperalgesia in the spared nerve injury model of neuropathic pain. Taken together, our data reveal Tat-P4 -(C5)2 as a novel promising lead for neuropathic pain treatment and expand the therapeutic potential of bivalent inhibitors to non-tandem protein-protein interaction domains.

A Universal Length-Dependent Vibrational Mode in Graphene Nanoribbons.

Graphene nanoribbons (GNRs) have attracted considerable interest, as their atomically tunable structure makes them promising candidates for future electronic devices. However, obtaining detailed information about the length of GNRs has been challenging and typically relies on low-temperature scanning tunneling microscopy. Such methods are ill-suited for practical device application and characterization. In contrast, Raman spectroscopy is a sensitive method for the characterization of GNRs, in particular for investigating their width and structure. Here, we report on a length-dependent, Raman-active low-energy vibrational mode that is present in atomically precise, bottom-up-synthesized armchair graphene nanoribbons (AGNRs). Our Raman study demonstrates that this mode is present in all families of AGNRs and provides information on their length. Our spectroscopic findings are corroborated by scanning tunneling microscopy images and supported by first-principles calculations that allow us to attribute this mode to a longitudinal acoustic phonon. Finally, we show that this mode is a sensitive probe for the overall structural integrity of the ribbons and their interaction with technologically relevant substrates.

Temperature Dependence of Interband Transitions in Wurtzite InP Nanowires.

Semiconductor nanowires (NWs) formed by non-nitride III-V compounds grow preferentially with wurtzite (WZ) lattice. This is contrary to bulk and two-dimensional layers of the same compounds, where only zincblende (ZB) is observed. The absorption spectrum of WZ materials differs largely from their ZB counterparts and shows three transitions, referred to as A, B, and C in order of increasing energy, involving the minimum of the conduction band and different critical points of the valence band. In this work, we determine the temperature dependence (T = 10-310 K) of the energy of transitions A, B, and C in ensembles of WZ InP NWs by photoluminescence (PL) and PL excitation (PLE) spectroscopy. For the whole temperature and energy ranges investigated, the PL and PLE spectra are quantitatively reproduced by a theoretical model taking into account contribution from both exciton and continuum states. WZ InP is found to behave very similarly to wide band gap III-nitrides and II-VI compounds, where the energy of A, B, and C displays the same temperature dependence. This finding unveils a general feature of the thermal properties of WZ materials that holds regardless of the bond polarity and energy gap of the crystal. Furthermore, no differences are observed in the temperature dependence of the fundamental band gap energy in WZ InP NWs and ZB InP (both NWs and bulk). This result points to a negligible role played by the WZ/ZB differences in determining the deformation potentials and the extent of the electron-phonon interaction that is a direct consequence of the similar nearest neighbor arrangement in the two lattices.

Determination of exciton reduced mass and gyromagnetic factor of wurtzite (InGa)As nanowires by photoluminescence spectroscopy under high magnetic fields.

Semiconductor nanowires (NWs) have the prospect of being employed as basic units for nanoscale devices and circuits. However, the impact of their one-dimensional geometry and peculiar crystal phase on transport and spin characteristics remains largely unknown. We determine the exciton reduced mass and gyromagnetic factor of (InGa)As NWs in the wurtzite phase by photoluminescence (PL) spectroscopy under very high magnetic fields. For B perpendicular to the NW c axis, the exciton reduced mass is 10% greater than that expected for the zincblende phase and no field-induced circular polarization of PL is observed. For B parallel to c, an exciton reduced mass 35% greater than that of the zincblende phase is derived. Moreover, a circular dichroism of 70% is found at 28 T. Finally, an analysis of the PL line shape points at two Zeeman split levels, whose separation corresponds to an exciton gyromagnetic factor |g(e) - g(h,∥)| = 5.8. These results provide a quantitative estimate of the basic electronic and spin properties of NWs and may guide a theoretical analysis of the band structure of these fascinating nanostructures.