Search

Pulsed laser deposition (PLD) and in situ scanning tunneling microscopy (STM) have been employed here to investigate different deposition regimes for the synthesis of Pd nanoislands on Au(111). Atom-by-atom deposition at high kinetic energy or cluster deposition at different kinetic energies are allowed by PLD depending on experimental conditions. At variance with evaporation, which results in Pd island nucleation at the elbows of the 22 x √3 herringbone reconstruction of Au(111), PLD in vacuum leads to random island nucleation with a profound modification of surface reconstruction. In addition, deposition of preformed Pd clusters can be obtained by ablating in the presence of a background gas, and the deposits turn out to be strongly affected by both the energetic regime and by the complex anisotropic structure of the substrate surface. Low energy deposition allowed us to deposit ultrafine clusters (<2 nm), which aggregate in islands at preferential sites of the Au(111) reconstructed surface. Comparison with atom-by-atom deposition (i.e. evaporation), in which island size is strongly related with coverage and leads to lifting of the reconstruction at a coverage well below 40%, shows that low energy deposition by PLD results in a cluster arrangement nicely following the underlying surface reconstruction, in parallel rows at 40% coverage and in a zig-zag fashion for coverages up to 70%. Analysis of this deposition regime reveals that it follows a deposition diffusion aggregation (DDA) model of growth with some peculiar characteristics related to the supporting Au(111) surface reconstruction. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) hybrid sp-sp 2 carbon systems are an appealing subject for science and technology. For these materials, topology and structure significantly affect electronic and vibrational properties. We investigate here by periodic density-functional theory (DFT) calculations the Raman and IR spectra of 2D carbon crystals belonging to the family of graphdiynes (GDYs) and having different structures and topologies. By joining DFT calculations with symmetry analysis, we assign the IR and Raman modes in the spectra of all the investigated systems. On this basis, we discuss how the modulation of the Raman and IR active bands depends on the different interactions between sp and sp 2 domains. The symmetry-based classification allows identifying the marker bands sensitive to the different peculiar topologies. These results show the effectiveness of vibrational spectroscopy for the characterization of new nanostructures, deepening the knowledge of the subtle interactions that take place in these 2D materials.

Understanding the electronic structure of metal oxide semiconductors is crucial to their numerous technological applications, such as photoelectrochemical water splitting and solar cells. The needed experimental and theoretical knowledge goes beyond that of pristine bulk crystals, and must include the effects of surfaces and interfaces, as well as those due to the presence of intrinsic defects (e.g. oxygen vacancies), or dopants for band engineering. In this review, we present an account of the recent efforts in predicting and understanding the optoelectronic properties of oxides using ab initio theoretical methods. In particular, we discuss the performance of recently developed dielectric-dependent hybrid functionals, providing a comparison against the results of many-body GW calculations, including G 0 W 0 as well as more refined approaches, such as quasiparticle self-consistent GW. We summarize results in the recent literature for the band gap, the band level alignment at surfaces, and optical transition energies in defective oxides, including wide gap oxide semiconductors and transition metal oxides. Correlated transition metal oxides are also discussed. For each method, we describe successes and drawbacks, emphasizing the challenges faced by the development of improved theoretical approaches. The theoretical section is preceded by a critical overview of the main experimental techniques needed to characterize the optoelectronic properties of semiconductors, including absorption and reflection spectroscopy, photoemission, and scanning tunneling spectroscopy (STS).

Two-dimensional (2D) ZnO structures have been deposited on the Au(111) surface by means of the pulsed laser deposition technique. In situ scanning tunneling microscopy and scanning tunneling spectroscopy measurements have been performed to characterize morphological, structural and electronic properties of 2D ZnO at the nanoscale. Starting from a sub-monolayer coverage, we investigated the growth of ZnO, identifying different atomic layers (up to the fifth). At low coverage, we observed single- and bi-layer nanocrystals, characterized by a surface moiré pattern that is associated to a graphene-like ZnO structure. By increasing the coverage, we revealed a morphological change starting from the fourth layer, which was attributed to a transition toward a bulk-like structure. Investigation of the electronic properties revealed the semiconducting character of 2D ZnO. We observed a dependence of the density of states (DOS) and, in particular, of the conduction band (CB) on the ZnO thickness, with a decreasing of the CB onset energy for increasing thickness. The CB DOS of 2D ZnO shows a step-like behaviour which may be interpreted as due to a 2D quantum confinement effect in ZnO atomic layers.

The interest in the measurement of the elastic properties of thin films is witnessed by a number of new techniques being proposed. However, the precision of results is seldom assessed in detail. Brillouin spectroscopy (BS) is an established optical, contactless, non-destructive technique, which provides a full elastic characterization of bulk materials and thin films. In the present work, the whole process of measurement of the elastic moduli by BS is critically analyzed: experimental setup, data recording, calibration, and calculation of the elastic moduli. It is shown that combining BS with ellipsometry a fully optical characterization can be obtained. The key factors affecting uncertainty of the results are identified and discussed. A procedure is proposed to discriminate factors affecting the precision from those affecting the accuracy. By the characterization of a model transparent material, silica in bulk and film form, it is demonstrated that both precision and accuracy of the elastic moduli measured by BS can reach 1% range, qualifying BS as a reference technique.

We report on the reorganization and bundling of titanium oxide nanostructured layers, induced by wetting with different solvents and subsequent drying. TiO(2) layers are deposited by pulsed laser deposition and are characterized by vertically oriented, columnar-like structures resulting from assembling of nanosized particles; capillary forces acting during evaporation induce bundling of these structures and lead to a micrometer-size patterning with statistically uniform islands separated by channels. The resulting surface is characterized by a hierarchical, multiscale morphology over the nanometer-micrometer length range. The structural features of the pattern, i.e., characteristic length, island size, and channel width, are shown to depend on properties of the liquid (i.e., surface tension) and thickness and density of the TiO(2) layers. The studied phenomenon permits the controlled production of multiscale hierarchically patterned surfaces of nanostructured TiO(2) with large porosity and large surface area, characterized by superhydrophilic wetting behavior without need for UV irradiation.

Hierarchical or one-dimensional architectures are among the most exciting developments in material science these recent years. We present a nanostructured TiO(2) assembly combining these two concepts and resembling a forest composed of individual, high aspect-ratio, treelike nanostructures. We propose to use these structures for the photoanode in dye-sensitized solar cells, and we achieved 4.9% conversion efficiency in combination with C101 dye. We demonstrate this morphology beneficial to hamper the electron recombination and also mass transport control in the mesopores when solvent-free ionic liquid electrolyte is used.

A template-free process for the synthesis of nanocrystalline TiO2 hierarchical microstructures by reactive pulsed laser deposition (PLD) is here presented. By a proper choice of deposition parameters a fine control over the morphology of TiO2 microstructures is demonstrated, going from classical compact/columnar films to a dense forest of distinct hierarchical assemblies of ultrafine nanoparticles (<10 nm), up to a more disordered, aerogel-type structure. Correspondingly, the film density varies with respect to bulk TiO2 anatase, with a degree of porosity going from 48% to over 90%. These structures are stable with respect to heat treatment at 400 degrees C, which results in crystalline ordering but not in morphological changes down to the nanoscale. Both as deposited and annealed films exhibit very promising photocatalytic properties, even superior to standard Degussa-P25 powder, as demonstrated by the degradation of stearic acid as a model molecule. The observed kinetics are correlated to the peculiar morphology of the PLD grown material. We show that the 3D multiscale hierarchical morphology enhances reaction kinetics and creates an ideal environment for mass transport and photon absorption, maximizing the surface area-to-volume ratio while at the same time providing readily accessible porosity through the large inter-tree spaces that act as distributing channels. The reported strategy provides a versatile technique to fabricate high aspect ratio 3D titania microstructures through a hierarchical assembly of ultrafine nanoparticles. Beyond photocatalytic and catalytic applications, this kind of material could be of interest for those applications where high surface-to-volume and efficient mass transport are required at the same time.

Ag(4)O(4) (i.e. silver(I)-silver(III) oxide) thin films with tailored structure and morphology at the nanoscale have been grown by reactive pulsed laser deposition (PLD) in an oxygen-containing atmosphere and they are shown to exhibit a very strong antibacterial activity towards Gram-negative bacteria (E. coli) and to completely inhibit the growth of Gram-positive bacteria (S. aureus). The formation of this particular high-valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere, leading to the formation of low-stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. PLD is shown to allow control of the structure (i.e. crystallinity and grain size) and of the morphology of the films, from compact and columnar to foam-like, thus allowing the deposition of nanocrystalline films with increased porosity and surface area. The antibacterial action towards E. coli is demonstrated and is shown to be superior to that of nanostructured Ag-based medical products. This can be related to the release of Ag ions with high oxidation number, which are known to be very reactive towards bacteria, and to the peculiar morphology at the nanoscale resulting in a large effective surface area.

We report the production and characterization of a form of amorphous carbon with s p-s p(2) hybridization (atomic fraction of sp hybridized species > or =20%) where the predominant sp bonding appears to be (=C=C=)(n) cumulene. Vibrational and electronic properties have been studied by in situ Raman spectroscopy and electrical conductivity measurements. Cumulenic chains are substantially stable in high vacuum conditions for temperatures lower than 250 K and they influence the electrical transport properties of the s p-s p(2) carbon through a self-doping mechanism by pinning the Fermi level closer to one of the mobility gap edges. Upon heating above 250 K the cumulenic species decay to form graphitic nanodomains embedded in the s p(2) amorphous matrix thus reducing the activation energy of the material. This is the first example of a pure carbon system where the s p hybridization influences bulk properties.

Focused ion beam-secondary ion mass spectrometry (FIB-SIMS) with 20 nm spatial resolution has been used to analyze amorphous fluorinated carbon thin films, deposited by plasma assisted chemical vapor deposition (PACVD), at micro- to nano-scale. Mass spectra and ion imaging of film surface were acquired and the presence and distribution of contaminants were investigated. Surface images show the secondary ion distribution for F(-), CH(-), CF(-). A change in size and topology of fluorine-rich areas is correlated with film hardness and with microstructure transition from diamond-like to polymer-like, as indicated by infrared and Raman spectroscopies. Based on the surface distributions of CF(-) and CH(-) and on the vibrational spectroscopy results, a mechanism of fluorine substitution for hydrogen and an attempt to explain the film structure and microstructure is proposed.

Inelastic light scattering by acoustic phonons (Brillouin scattering) is a useful tool for probing material properties at the submicrometre scale. In media which are statistically homogeneous at this scale, it gives access to the acoustic properties and the elastic moduli. In nanostructures it probes the vibrational properties at the mesoscopic scale. Applications to carbonaceous materials are reviewed.

Nanostructured carbon films produced by supersonic cluster beam deposition have been studied by in situ Raman spectroscopy. Raman spectra show the formation of a sp2 solid with a very large fraction of sp-coordinated carbyne species with a long-term stability under ultrahigh vacuum. Distinct Raman contributions from polyyne and cumulene species have been observed, as well as different stabilities under gas exposure. Our experiments confirm theoretical predictions and demonstrate the possibility of producing a carbyne-rich pure carbon solid. The stability of the sp2-sp network has important implications for astrophysics and for the production of novel carbon-based systems.