Enhancing Electron Correlation at a 3d Ferromagnetic Surface.

Spin-resolved momentum microscopy and theoretical calculations are combined beyond the one-electron approximation to unveil the spin-dependent electronic structure of the interface formed between iron (Fe) and an ordered oxygen (O) atomic layer, and an adsorbate-induced enhancement of electronic correlations is found. It is demonstrated that this enhancement is responsible for a drastic narrowing of the Fe d-bands close to the Fermi energy (EF ) and a reduction of the exchange splitting, which is not accounted for in the Stoner picture of ferromagnetism. In addition, correlation leads to a significant spin-dependent broadening of the electronic bands at higher binding energies and their merging with satellite features, which are manifestations of a pure many-electron behavior. Overall, adatom adsorption can be used to vary the material parameters of transition metal surfaces to access different intermediate electronic correlated regimes, which will otherwise not be accessible. The results show that the concepts developed to understand the physics and chemistry of adsorbate-metal interfaces, relevant for a variety of research areas, from spintronics to catalysis, need to be reconsidered with many-particle effects being of utmost importance. These may affect chemisorption energy, spin transport, magnetic order, and even play a key role in the emergence of ferromagnetism at interfaces between non-magnetic systems.

Extremely low-energy ARPES of quantum well states in cubic-GaN/AlN and GaAs/AlGaAs heterostructures.

Quantum well (QW) heterostructures have been extensively used for the realization of a wide range of optical and electronic devices. Exploiting their potential for further improvement and development requires a fundamental understanding of their electronic structure. So far, the most commonly used experimental techniques for this purpose have been all-optical spectroscopy methods that, however, are generally averaging in momentum space. Additional information can be gained by angle-resolved photoelectron spectroscopy (ARPES), which measures the electronic structure with momentum resolution. Here we report on the use of extremely low-energy ARPES (photon energy ~ 7 eV) to increase depth sensitivity and access buried QW states, located at 3 nm and 6 nm below the surface of cubic-GaN/AlN and GaAs/AlGaAs heterostructures, respectively. We find that the QW states in cubic-GaN/AlN can indeed be observed, but not their energy dispersion, because of the high surface roughness. The GaAs/AlGaAs QW states, on the other hand, are buried too deep to be detected by extremely low-energy ARPES. Since the sample surface is much flatter, the ARPES spectra of the GaAs/AlGaAs show distinct features in momentum space, which can be reconducted to the band structure of the topmost surface layer of the QW structure. Our results provide important information about the samples' properties required to perform extremely low-energy ARPES experiments on electronic states buried in semiconductor heterostructures.

Ultrafast Carrier Relaxation Dynamics in Quantum Confined Non-Isotropic Silicon Nanostructures Synthesized by an Inductively Coupled Plasma Process.

To exploit the optoelectronic properties of silicon nanostructures (SiNS) in real devices, it is fundamental to study the ultrafast processes involving the photogenerated charges separation, migration and lifetime after the optical excitation. Ultrafast time-resolved optical measurements provide such information. In the present paper, we report on the relaxation dynamics of photogenerated charge-carriers in ultrafine SiNS synthesized by means of inductively-coupled-plasma process. The carriers' transient regime was characterized in high fluence regime by using a tunable pump photon energy and a broadband probe pulse with a photon energy ranging from 1.2 eV to 2.8 eV while varying the energy of the pump photons and their polarization. The SiNS consist of Si nanospheres and nanowires (NW) with a crystalline core embedded in a SiOx outer-shell. The NW inner core presents different typologies: long silicon nanowires (SiNW) characterized by a continuous core (with diameters between 2 nm and 15 nm and up to a few microns long), NW with disconnected fragments of SiNW (each fragment with a length down to a few nanometers), NW with a "chaplet-like" core and NW with core consisting of disconnected spherical Si nanocrystals. Most of these SiNS are asymmetric in shape. Our results reveal a photoabsorption (PA) channel for pump and probe parallel polarizations with a maximum around 2.6 eV, which can be associated to non-isotropic ultra-small SiNS and ascribed either to (i) electron absorption driven by the probe from some intermediate mid-gap states toward some empty state above the bottom of the conduction band or (ii) the Drude-like free-carrier presence induced by the direct-gap transition in the their band structure. Moreover, we pointed up the existence of a broadband and long-living photobleaching (PB) in the 1.2-2.0 eV energy range with a maximum intensity around 1.35 eV which could be associated to some oxygen related defect states present at the Si/SiOx interface. On the other hand, this wide spectral energy PB can be also due to both silicon oxide band-tail recombination and small Si nanostructure excitonic transition.

Hybridized C-O-Si Interface States at the Origin of Efficiency Improvement in CNT/Si Solar Cells.

Despite the astonishing values of the power conversion efficiency reached, in just less than a decade, by the carbon nanotube/silicon (CNT/Si) solar cells, many doubts remain on the underlying transport mechanisms across the CNT/Si heterojunction. Here, by combining transient optical spectroscopy in the femtosecond timescale, X-ray photoemission, and a systematic tracking of I-V curves across all phases of the interlayer SiOx growth at the interface, we grasp the mechanism that adequately preserves charge separation at the junction, hindering the photoexcited carrier recombination. Moreover, supported by ab initio calculations aimed to model the complex CNT-Si heterointerface, we show that oxygen-related states at the interface act as entrapping centers for the photoexcited electrons, thus preventing recombination with holes that can flow from Si to CNT across the SiOx layer.

Growth of hybrid carbon nanostructures on iron-decorated ZnO nanorods.

A novel carbon-based nanostructured material, which includes carbon nanotubes (CNTs), porous carbon, nanostructured ZnO and Fe nanoparticles, has been synthetized using catalytic chemical vapour deposition (CVD) of acetylene on vertically aligned ZnO nanorods (NRs). The deposition of Fe before the CVD process induces the presence of dense CNTs in addition to the variety of nanostructures already observed on the process done on the bare NRs, which range from amorphous graphitic carbon up to nanostructured dendritic carbon films, where the NRs are partially or completely etched. The combination of scanning electron microscopy and in situ photoemission spectroscopy indicate that Fe enhances the ZnO etching, and that the CNT synthesis is favoured by the reduced Fe mobility due to the strong interaction between Fe and the NRs, and to the presence of many defects, formed during the CVD process. Our results demonstrate that the resulting new hybrid shows a higher sensitivity to ammonia gas at ambient conditions (∼60 ppb) than the carbon nanostructures obtained without the aid of Fe, the bare ZnO NRs, or other one-dimensional carbon nanostructures, making this system of potential interest for environmental ammonia monitoring. Finally, in view of the possible application in nanoscale optoelectronics, the photoexcited carrier behaviour in these hybrid systems has been characterized by time-resolved reflectivity measurements.

Role of the Substrate Orientation in the Photoinduced Electron Dynamics at the Porphyrin/Ag Interface.

Photochemically activated reactions, despite being a powerful tool to covalently stabilize self-organized molecular structures on metallic surfaces, have struggled to take off due to several not yet well understood light-driven processes that can affect the final result. A thorough understanding of the photoinduced charge transfer mechanisms at the organic/metal interface would pave the way to controlling these processes and to developing on-surface photochemistry. Here, by time-resolved two-photon photoemission measurements, we track the relaxation processes of the first two excited molecular states at the interface between porphyrin, the essential chromophore in chlorophyll, and two different orientations of the silver surface. Due to the energy alignment of the porphyrin first excited state with the unoccupied sp-bands, an indirect charge transfer path, from the substrate to the molecule, opens in porphyrin/Ag(100) 250 fs after the laser pump excitation. The same time-resolved measurements carried out on porphyrin/Ag(111) show that in the latter case such an indirect path is not viable.