Functionalization of three-dimensional epitaxial graphene with metal nanoparticles.

We demonstrate the first successful functionalization of epitaxial three-dimensional graphene with metal nanoparticles. The functionalization is obtained by immersing three-dimensional graphene in a nanoparticle colloidal solution. This method is versatile and demonstrated here for gold and palladium, but can be extended to other types of nanoparticles. We have measured the nanoparticle density on the top surface and in the porous layer volume by scanning electron microscopy and scanning transmission electron microscopy. The samples exhibit a wide coverage of nanoparticles with minimal clustering. We demonstrate that high-quality graphene promotes the functionalization, leading to higher nanoparticle density both on the surface and in the pores. X-ray photoelectron spectroscopy shows the absence of contamination after the functionalization process. Moreover, it confirms the thermal stability of the Au- and Pd-functionalized three-dimensional graphene up to 530 °C. Our approach opens new avenues for utilizing three-dimensional graphene as a versatile platform for catalytic applications, sensors, and energy storage and conversion.

Covalent organic functionalization of graphene nanosheets and reduced graphene oxide via 1,3-dipolar cycloaddition of azomethine ylide.

Organic functionalization of graphene is successfully performed via 1,3-dipolar cycloaddition of azomethine ylide in the liquid phase. The comparison between 1-methyl-2-pyrrolidinone and N,N-dimethylformamide as dispersant solvents, and between sonication and homogenization as dispersion techniques, proves N,N-dimethylformamide and homogenization as the most effective choice. The functionalization of graphene nanosheets and reduced graphene oxide is confirmed using different techniques. Among them, energy-dispersive X-ray spectroscopy allows to map the pyrrolidine ring of the azomethine ylide on the surface of functionalized graphene, while micro-Raman spectroscopy detects new features arising from the functionalization, which are described in agreement with the power spectrum obtained from ab initio molecular dynamics simulation. Moreover, X-ray photoemission spectroscopy of functionalized graphene allows the quantitative elemental analysis and the estimation of the surface coverage, showing a higher degree of functionalization for reduced graphene oxide. This more reactive behavior originates from the localization of partial charges on its surface due to the presence of oxygen defects, as shown by the simulation of the electrostatic features. Functionalization of graphene using 1,3-dipolar cycloaddition is shown to be a significant step towards the controlled synthesis of graphene-based complex structures and devices at the nanoscale.

Correction: Covalent organic functionalization of graphene nanosheets and reduced graphene oxide via 1,3-dipolar cycloaddition of azomethine ylide.

[This corrects the article DOI: 10.1039/D1NA00335F.].

Plasmon-induced resonant effects on the optical properties of Ag-decorated ZnSe nanowires.

In this work we show how the optical properties of ZnSe nanowires are modified by the presence of Ag nanoparticles on the sidewalls of the ZnSe nanowires. In particular, we show that the low-temperature luminescence of the ZnSe nanowires changes its shape, enhancing the phonon replicas of impurity-related recombination and affecting rise and decay times of the transient absorption bleaching at room temperatures, with an increase of the former and a decrease of the latter. In contrast, the deposition of Au nanoparticles on ZnSe nanowires does not change the optical properties of the sample. We suggest that the mechanism underlying these experimental observations is energy transfer via a resonant interaction, based on the fact that the localized surface plasmon resonance (LSPR) of Ag nanoparticles spectrally overlaps with absorption and emission of ZnSe, while the Au LSPR does not.

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.

Enhanced plasmonic properties of gold-catalysed semiconductor nanowires.

A key challenge for the development of plasmonic nanodevices is their integration into active semiconducting structures. Gold-catalysed semiconductor nanowires are promising candidates for their bottom-up growth process that aligns a single gold nanoparticle at each nanowire apex. Unfortunately these show extremely poor plasmonic properties. In this work, we propose a way to enhance their plasmonic resonance up to those of ideal and isolated gold nanoparticles. A suitable purification protocol compatible with GaAs and ZnSe molecular beam epitaxy of nanowires is used to produce plasmonic active nanowires, which were used to enhance the Raman signal of pentacene and graphene oxide. Enhancement factors up to three orders of magnitude are demonstrated.

Bundling of GaAs nanowires: a case of adhesion-induced self-assembly of nanowires.

The origin of deflections of semiconductor nanowires (NWs) induced by an electron beam in scanning electron microscopy has been subject to different interpretations. Similarly, the subsequent clumping together of NWs into bundles is frequently observed, but no interpretation has yet been advanced. Here we present results on the bundling of NWs following the intentional bending by an electron beam. Furthermore, we extend the concept of lateral collapse, usually applied to fibrillar architectures mimicking the adhesiveness of natural surfaces (the so-called Gecko effect), to analyze the mechanism of the NW bundle formation. We demonstrate how the geometry of the NW arrays and the mechanical properties of the composing materials govern bundling and how these parameters should be taken into account in the design of NW arrays both for avoiding vertical misalignment when detrimental and for achieving patterning of NW arrays into nanoarchitectures.

Tuning the growth mode of nanowires via the interaction among seeds, substrates and beam fluxes.

The growth mechanism of semiconductor nanowires is still an argument of high interest, and it is becoming clearer, investigation after investigation, that simple pictures fail to describe the complex behaviors observed under different growth conditions. We report here on the growth of semiconductor nanowires, maintaining control over the chemical composition and the physical state of the metallic seeds, and tuning the growth mechanism by varying the growth conditions. We focused on Au-assisted ZnSe nanowires grown by molecular beam epitaxy on GaAs(111)B substrates. We show that at sufficiently high temperatures, the Au seed is strongly affected by the interaction with the substrate and that nanowire growth can occur through two different mechanisms, which have a strong impact on the nanowire's morphology and crystal quality. In particular, ZnSe NWs may exhibit either a uniformly oriented, straight morphology when the nanoparticle seed is liquid, or a kinked, worm-like shape when the nanoparticle seed is switched to a solid phase. This switch, which tunes the nanowire growth mechanism, is achieved by controlling the Zn-to-Se beam pressure ratio at the Au-seed surface. Our results allow a deeper understanding of particle-assisted nanowire growth, and an accurate control of nanowire morphology via the control of the growth mechanism.

Single photons on demand from novel site-controlled GaAsN/GaAsN:H quantum dots.

We demonstrate triggered single-photon emission from a novel system of site-controlled quantum dots (QDs), fabricated by exploiting the hydrogen-assisted, spatially selective passivation of N atoms in dilute nitride semiconductors. Evidence of this nonclassical behavior is provided by the observation of strong antibunching in the autocorrelation histogram of the QD exciton emission line. This class of site-controlled quantum emitters can be exploited for the fabrication of new hybrid QD-nanocavity systems of interest for future quantum technologies.

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.

Self-catalyzed growth of GaAs nanowires on cleaved Si by molecular beam epitaxy.

Self-assembled GaAs nanowires have been grown on Si by molecular beam epitaxy without the use of any outside metal catalyst. The growth occurs on Si facets obtained by the cleavage of Si(100) substrates. The growth has been obtained with or without Ga pre-deposition. In both cases two kinds of nanowires have been obtained. The wires of the first type clearly present a Ga droplet at their free end and have a lattice structure that is wurtzite for wide regions beneath the Ga droplet. The second type, in contrast, ends with pyramidally shaped GaAs and has a crystal lattice that is mainly zincblende with only a few and small wurtzite regions, if any. The Ga-ended nanowires are longer than the others and thinner on average. The experimental findings suggest that the two types of nanowires grow after different growth processes.

Manganese-induced growth of GaAs nanowires.

GaAs nanowires have been grown on SiO2 and GaAs by molecular beam epitaxy using manganese as growth catalyst. Transmission electron microscopy shows that the wires have a wurtzite-type lattice and that alpha-Mn particles are found at the free end of the wires. X-ray absorption fine structure measurements reveal the presence of a significant fraction of Mn-As bonds, suggesting Mn diffusion and incorporation during wire growth. Transport measurements indicate that the wires are p-type, as expected from doping of GaAs with Mn.