The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

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.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Failure and formation of axial nanowire heterostructures in vapor-liquid-solid growth

To observe the axial growth behavior of InAs on GaAs nanowires, InAs was grown for different growth durations on GaAs nanowires using Au nanoparticles. Through transmission electron microscopy, we have observed the following evolution steps for the InAs growth. (1) In the initial stages of the InAs growth, InAs clusters into a wedge shape preferentially at an edge of the Au/GaAs interface by minimizing Au/InAs interfacial area; (2) with further growth of InAs, the Au particle moves sidewards and then downwards by preserving an interface with GaAs nanowire sidewalls. The lower interfacial energy of Au/GaAs than that of Au/In As is attributed to be the reason for such Au movement. This downward movement of the Au nanoparticle later terminates when the nanoparticle encounters InAs growing radially on the GaAs nanowire sidewalls, and with further supply of In and As vapor reactants, the Au nanoparticle assists the formation of InAs branches. These observations give some insights into vapor-liquid-solid growth and the formation of kinks in nanowire heterostructures. © 2008 Materials Research Society.

Nature of heterointerfaces in GaAs/InAs and InAs/GaAs axial nanowire heterostructures

The structural and compositional characteristics of heterointerfaces of Au-catalyzed GaAs/InAs and InAs/GaAs axial nanowire heterostructures were comprehensively investigated by transmission electron microscopy. It has been found that the GaAs/InAs interface is not sharp and contains an InGaAs transition segment, and in contrast, the InAs/GaAs interface is atomically sharp. This difference in the nature of heterointerfaces can be attributed to the difference in the affinity of the group III elements with the catalyst material. © 2008 American Institute of Physics.

Understanding the kink formation in GaAs/InAs heterostructural nanowires

The kinks formation in heterostructural nanowires was observed to be dominant when InAs nanowires were grown on GaAs nanowires. Nanowires were grown through vapor-liquid-solid (VLS) mechanism in an MOCVD (metalorganic chemical vapor deposition) reactor. GaAs nanowires were grown in [1 1 1 ]B direction on a GaAs (1 1 1 )B substrate. When InAs nanowires grown on the GaAs nanowires, most of the InAs nanowires changed their growth directions from [1 1 1 ]B to other 〈111〉B directions. The kinks formation is ascribed to the large compressive misfit strain at the GaAs/InAs interface (7.2% lattice mismatch between GaAs and InAs) and the high mobility of indium species during MOCVD growth. The in-depth analysis of the kinks formation was done by growing InAs for short times on the GaAs nanowires and characterizing the samples. The hindrance to compressively strain InAs to form coherent layers with GaAs pushed the InAs/Au interfaces to the sides of the GaAs nanowires growth ends. New InAs/Au interfaces have generated at the sides of GaAs nanowires, due to lateral growth of InAs on GaAs nanowires. These new interfaces led the InAs nanowires growth in other 〈111〉B directions. The morphological and structural features of these heterostructural kinked nanowires were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. © 2006 IEEE.

Catalyst composition and impurity-dependent kinetics of nanowire heteroepitaxy.

The mechanisms and kinetics of axial Ge-Si nanowire heteroepitaxial growth based on the tailoring of the Au catalyst composition via Ga alloying are studied by environmental transmission electron microscopy combined with systematic ex situ CVD calibrations. The morphology of the Ge-Si heterojunction, in particular, the extent of a local, asymmetric increase in nanowire diameter, is found to depend on the Ga composition of the catalyst, on the TMGa precursor exposure temperature, and on the presence of dopants. To rationalize the findings, a general nucleation-based model for nanowire heteroepitaxy is established which is anticipated to be relevant to a wide range of material systems and device-enabling heterostructures.

Direct epitaxial growth of θ-Ni2Si by reaction of a thin Ni(10 at.% Pt) film with Si(1 0 0) substrate

The reaction between an 11 nm Ni(10 at.% Pt) film on a Si substrate has been examined by in situ X-ray diffraction (XRD), atom probe tomography (APT) and transmission electron microscopy (TEM). In situ XRD experiments show the unusual formation of a phase without an XRD peak through consumption of the metal. According to APT, this phase has an Si concentration gradient in accordance with the θ-Ni2Si metastable phase. TEM analysis confirms the direct formation of θ-Ni2Si in epitaxy on Si(1 0 0) with two variants of the epitaxial relationship. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.