Highly chiral-selective growth of single-walled carbon nanotubes with a simple monometallic Co catalyst

We report on the growth of single-walled carbon nanotubes from a monometallic Co catalyst on an oxidized Si wafer support by the most simple growth recipe (vacuum annealing, growth by undiluted C 2H 2). Nevertheless, multiwavelength Raman spectroscopy and transmission electron spectroscopy show a remarkable selectivity for chiral indices and thus, e.g., high abundance with a single chirality representing 58% of all semiconducting tubes. In situ x-ray photoelectron spectroscopy monitors the catalyst chemistry during carbon nanotube growth and shows interfacial Co-Si interactions that may help to stabilize the nanoparticle/nanotube diameter. We outline a two-mechanism model explaining the selective growth. © 2012 American Physical Society.

Dye-sensitized solar cells based on a single layer deposition of TiO 2 from a new formulation paste and their photovoltaic performance

A new strategy for enhancing the efficiency and reducing the production cost of TiO 2 solar cells by design of a new formulated TiO 2 paste with tailored crystal structure and morphology is reported. The conventional three- or four-fold layer deposition process was eliminated and replaced by a single layer deposition of TiO 2 compound. Different TiO 2 pastes with various crystal structures, morphologies and crystallite sizes were prepared by an aqueous particulate sol-gel process. Based on simultaneous differential thermal (SDT) analysis the minimum annealing temperature to obtain organic-free TiO 2 paste was determined at 400°C, being one of the lowest crystallization temperatures of TiO 2 photoanode electrodes for solar cell application. Photovoltaic measurements showed that TiO 2 solar cell with pure anatase crystal structure had higher power conversion efficiency (PCE) than that made of pure rutile-TiO 2. However, the PCE of solar cells depends on the anatase to rutile weight ratio, reaching a maximum at a specific value due to the synergic effect between anatase and rutile TiO 2 nanoparticles. Moreover, it was found that the PCE of solar cells made of crystalline TiO 2 powders was much higher, increasing in the range 32-84% depending on anatase to rutile weight ratio, than that of prepared by amorphous powders. TiO 2 solar cell with the morphology of mixtures of nanoparticles and microparticles had higher PCE than the solar cell with the same phase composition containing TiO 2 nanoparticles due to the role of TiO 2 microparticles as light scattering particles. The presented strategy would open up new insight into fabrication and structural design of low-cost TiO 2 solar cells with high power conversion efficiency. © 2012 Elsevier Ltd.

The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

Three-dimensional distribution of Al in high-k metal gate: Impact on transistor voltage threshold

The three-dimensional spatial distribution of Al in the high-k metal gates of metal-oxide-semiconductor field-effect-transistors is measured by atom probe tomography. Chemical distribution is correlated with the transistor voltage threshold (VTH) shift generated by the introduction of a metallic Al layer in the metal gate. After a 1050 °C annealing, it is shown that a 2-Å thick Al layer completely diffuses into oxide layers, while a positive VTH shift is measured. On the contrary, for thicker Al layers, Al precipitation in the metal gate stack is observed and the VTH shift becomes negative. © 2012 American Institute of Physics.

End-of-range defects in germanium and their role in boron deactivation

We investigated the thermal evolution of end-of-range (EOR) defects in germanium and their impact on junction thermal stability. After solid-phase epitaxial regrowth of a preamorphized germanium layer, EOR defects exhibiting dislocation loop-like contrast behavior are present. These defects disappear during thermal annealing at 400 °C, while boron electrical deactivation occurs. After the whole defect population vanishes, boron reactivation is observed. These results indicate that germanium self-interstitials, released by EOR defects, are the cause of B deactivation. Unlike in Si, the whole deactivation/reactivation cycle in Ge is found to take place while the maximum active B concentration exceeds its solubility limit. © 2010 American Institute of Physics.

Optical properties of silicon rich oxides

Thermally treated silicon rich oxides (SRO) used as starting material for the fabrication of silicon nanodots represent the basis of tunable bandgap nanostructured materials for optoelectronic and photonic applications. The optical modelization of such materials is of great interest, as it allows the simulation of reflectance and transmittance (R&T) spectra, which is a powerful non destructive tool in the determination of phase modifications (clustering, precipitation of new phases, crystallization) upon thermal treatments. In this paper, we study the optical properties of a variety of as-deposited and furnace annealed SRO materials. The different phases are treated by means of the effective medium approximation. Upon annealing at low temperature, R&T spectra show the precipitation of amorphous silicon nanoparticles, while the crystallization occurring at temperatures higher than 1000 °C is also clearly identified, in agreement with structural results. The existing literature on the optical properties of the silicon nanocrystals is reviewed, with attention on the specificity of the compositional and structural characteristics of the involved material. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Light absorption and electrical transport in Si:O alloys for photovoltaics

Thin films (100-500 nm) of the Si:O alloy have been systematically characterized in the optical absorption and electrical transport behavior, by varying the Si content from 43 up to 100 at. %. Magnetron sputtering or plasma enhanced chemical vapor deposition have been used for the Si:O alloy deposition, followed by annealing up to 1250 °C. Boron implantation (30 keV, 3-30× 1014 B/cm2) on selected samples was performed to vary the electrical sheet resistance measured by the four-point collinear probe method. Transmittance and reflectance spectra have been extracted and combined to estimate the absorption spectra and the optical band gap, by means of the Tauc analysis. Raman spectroscopy was also employed to follow the amorphous-crystalline (a-c) transition of the Si domains contained in the Si:O films. The optical absorption and the electrical transport of Si:O films can be continuously and independently modulated by acting on different parameters. The light absorption increases (by one decade) with the Si content in the 43-100 at. % range, determining an optical band gap which can be continuously modulated into the 2.6-1.6 eV range, respectively. The a-c phase transition in Si:O films, causing a significant reduction in the absorption coefficient, occurs at increasing temperatures (from 600 to 1100 °C) as the Si content decreases. The electrical resistivity of Si:O films can be varied among five decades, being essentially dominated by the number of Si grains and by the doping. Si:O alloys with Si content in the 60-90 at. % range (named oxygen rich silicon films), are proved to join an appealing optical gap with a viable conductivity, being a good candidate for increasing the conversion efficiency of thin-film photovoltaic cell. © 2010 American Institute of Physics.

Influence of the matrix properties on the performances of Er-doped Si nanoclusters light emitting devices

We investigated the properties of light emitting devices whose active layer consists of Er-doped Si nanoclusters (nc) generated by thermal annealing of Er-doped SiOx layers prepared by magnetron cosputtering. Differently from a widely used technique such as plasma enhanced chemical vapor deposition, sputtering allows to synthesize Er-doped Si nc embedded in an almost stoichiometric oxide matrix, so as to deeply influence the electroluminescence properties of the devices. Relevant results include the need for an unexpected low Si excess for optimizing the device efficiency and, above all, the strong reduction of the influence of Auger de-excitation, which represents the main nonradiative path which limits the performances of such devices and their application in silicon nanophotonics. © 2010 American Institute of Physics.

Light absorption in silicon quantum dots embedded in silica

The photon absorption in Si quantum dots (QDs) embedded in SiO2 has been systematically investigated by varying several parameters of the QD synthesis. Plasma-enhanced chemical vapor deposition (PECVD) or magnetron cosputtering (MS) have been used to deposit, upon quartz substrates, single layer, or multilayer structures of Si-rich- SiO2 (SRO) with different Si content (43-46 at. %). SRO samples have been annealed for 1 h in the 450-1250 °C range and characterized by optical absorption measurements, photoluminescence analysis, Rutherford backscattering spectrometry and x-ray Photoelectron Spectroscopy. After annealing up to 900 °C SRO films grown by MS show a higher absorption coefficient and a lower optical bandgap (∼2.0 eV) in comparison with that of PECVD samples, due to the lower density of Si-Si bonds and to the presence of nitrogen in PECVD materials. By increasing the Si content a reduction in the optical bandgap has been recorded, pointing out the role of Si-Si bonds density in the absorption process in small amorphous Si QDs. Both the photon absorption probability and energy threshold in amorphous Si QDs are higher than in bulk amorphous Si, evidencing a quantum confinement effect. For temperatures higher than 900 °C both the materials show an increase in the optical bandgap due to the amorphous-crystalline transition of the Si QDs. Fixed the SRO stoichiometry, no difference in the optical bandgap trend of multilayer or single layer structures is evidenced. These data can be profitably used to better implement Si QDs for future PV technologies. © 2009 American Institute of Physics.

New approaches for enhancing light emission from Er-based materials and devices

In this work, we present some approaches recently developed for enhancing light emission from Er-based materials and devices. We have investigated the luminescence quenching processes limiting quantum efficiency in light-emitting devices based on Si nanoclusters (Si nc) or Er-doped Si nc. It is found that carrier injection, while needed to excite Si nc or Er ions through electron-hole recombination, at the same time produces an efficient non-radiative Auger de-excitation with trapped carriers. A strong light confinement and enhancement of Er emission at 1.54 μm in planar silicon-on-insulator waveguides containing a thin layer (slot) of SiO2 with Er-doped Si nc at the center of the Si core has been obtained. By measuring the guided photoluminescence from the cleaved edge of the sample, we have observed a more than fivefold enhancement of emission for the transverse magnetic mode over the transverse electric one at room temperature. Slot waveguides have also been integrated with a photonic crystal (PhC), consisting of a triangular lattice of holes. An enhancement by more than two orders of magnitude of the Er near-normal emission is observed when the transition is in resonance with an appropriate mode of the PhC slab. Finally, in order to increase the concentration of excitable Er ions, a completely different approach, based on Er disilicate thin films, has been explored. Under proper annealing conditions crystalline and chemically stable Er2Si2O7 films are obtained; these films exhibit a strong luminescence at 1.54 μm owing to the efficient reduction of the defect density. © 2008 Elsevier B.V. All rights reserved.

Microstructural evolution of SiOx films and its effect on the luminescence of Si nanoclusters

In this paper we demonstrate that the structural and optical properties of Si nanoclusters (Si ncs) formed by thermal annealing of SiOx films prepared by plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering are very different. In fact, at a fixed Si excess and annealing temperature, photoluminescence (PL) spectra of sputtered samples are redshifted with respect to PECVD samples, denoting a larger Si ncs size. In addition, PL intensity reaches a maximum in sputtered films at annealing temperatures much lower than those needed in PECVD films. These data are correlated with structural properties obtained by energy filtered transmission electron microscopy and electron energy loss spectroscopy. It is shown that in PECVD films only around 30% of the Si excess agglomerates in clusters while an almost complete agglomeration occurs in sputtered films. These data are explained on the basis of the different initial structural properties of the as-deposited films that become crucial for the subsequent evolution. © 2008 American Institute of Physics.

Thermal evolution of Er silicate thin films grown by rf magnetron sputtering

Stoichiometric Er silicate thin films, monosilicate (Er2SiO 5) and disilicate (Er2Si2O7), have been grown on c-Si substrates by rf magnetron sputtering. The influence of annealing temperature in the range 1000-1200 °C in oxidizing ambient (O 2) on the structural and optical properties has been studied. In spite of the known reactivity of rare earth silicates towards silicon, Rutherford backscattering spectrometry shows that undesired chemical reactions between the film and the substrate can be strongly limited by using rapid thermal treatments. Monosilicate and disilicate films crystallize at 1100 and 1200 °C, respectively, as shown by x-ray diffraction analysis; the crystalline structures have been identified in both cases. Moreover, photoluminescence (PL) measurements have demonstrated that the highest PL intensity is obtained for Er2Si2O7 film annealed at 1200 °C. In fact, this treatment allows us to reduce the defect density in the film, in particular by saturating oxygen vacancies, as also confirmed by the increase of the lifetime of the PL signal. © 2008 IOP Publishing Ltd.

The influence of stoichiometry on the structural stability and on the optical emission of erbium silicate thin films

We report the effects of thermal annealing performed in N2 or O2 ambient at 1200 °C on the structural and optical properties of Er silicate films having different compositions (Er2Si O 5,Er2 Si2 O7, and their mixture). We demonstrate that the chemical composition of the stoichiometric films is preserved after the thermal treatments. All different crystalline structures formed after the thermal annealing are identified. Thermal treatments in O 2 lead to a strong enhancement of the photoluminescence intensity, owing to the efficient reduction of defect density. In particular the highest optical efficiency is associated to Er ions in the α phase of Er 2 Si2 O7. © 2008 American Institute of Physics.

Synthesis and luminescence properties of erbium silicate thin films

We have studied the structure and the room temperature luminescence of erbium silicate thin films deposited by rf magnetron sputtering. Films deposited on silicon oxide layers are characterized by good structural properties and excellent stability. The optical properties of these films are strongly improved by rapid thermal annealing processes performed in the range of temperature 800-1250 °C. In fact through the reduction of the defect density of the material, a very efficient room temperature photoluminescence at 1535 nm is obtained. We have also investigated the influence of the annealing ambient, by finding that treatments in O2 atmosphere are significantly more efficient in improving the optical properties of the material with respect to processes in N2. Upconversion effects become effective only when erbium silicate is excited with high pump powers. The evidence that all Er atoms (about 1022 cm-3) in erbium silicate films are optically active suggests interesting perspectives for optoelectronic applications of this material. © 2007 Elsevier B.V. All rights reserved.

Erbium doped materials for a Si-based microphotonics

We have investigated the role of the Si excess on the photoluminescence properties of Er doped substoichiometric SiOx layers. We demonstrate that the Si excess has two competing roles: when agglomerated to form Si nanoclusters (Si-nc) it enhances the Er excitation efficiency but it also introduces new non-radiative decay channels. When Er is excited through an energy transfer from Si-nc, the beneficial effect on the enhanced excitation efficiency prevails and the Er emission increases with increasing Si content. Nevertheless the maximum excited Er fraction is only of the order of percent. In order to increase the concentration of excited Er ions, a different approach based on Er silicate thin film has been explored. Under proper annealing conditions, an efficient luminescence at 1535 nm is found and all of the Er ions in the material is optically active. The possibility to efficiently excite Er ions also through electron-hole mediated processes is demonstrated in nanometer-scale Er-Si-O/Si multilayers. These data are presented and discussed.