We study catalyst support interactions during chemical vapor deposition of carbon nanotubes by in situ X-ray photoelectron spectroscopy over a wide range of pressures. We observe Fe 2+ and 3+ interface states for metallic Fe on Al 2 O 3 in the absence of measurable Al reduction. This support interaction is much stronger than that on SiO 2 , and it restricts Fe surface mobility. The resulting much narrower Fe catalyst particle size distribution on Al 2 O 3 leads to a higher carbon nanotube nucleation density and a vertical nanotube alignment due to proximity effects. We record the growth kinetics of carbon nanotube forests by optical imaging to understand effects that contribute to growth termination.
Self-assembled nanowires offer the prospect of accurate and scalable device engineering at an atomistic scale for applications in electronics, photonics and biology. However, deterministic nanowire growth and the control of dopant profiles and heterostructures are limited by an incomplete understanding of the role of commonly used catalysts and specifically of their interface dynamics. Although catalytic chemical vapour deposition of nanowires below the eutectic temperature has been demonstrated in many semiconductor-catalyst systems, growth from solid catalysts is still disputed and the overall mechanism is largely unresolved. Here, we present a video-rate environmental transmission electron microscopy study of Si nanowire formation from Pd silicide crystals under disilane exposure. A Si crystal nucleus forms by phase separation, as observed for the liquid Au-Si system, which we use as a comparative benchmark. The dominant coherent Pd silicide/Si growth interface subsequently advances by lateral propagation of ledges, driven by catalytic dissociation of disilane and coupled Pd and Si diffusion. Our results establish an atomistic framework for nanowire assembly from solid catalysts, relevant also to their contact formation.
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 phase evolution during realistic CNT growth recipes.
How does your graphene grow? In situ X-ray photoelectron spectroscopy and X-ray diffraction measurements during chemical vapor deposition on Ni catalyst films show that graphene forms both isothermally and by precipitation on cooling (see picture). A coherent graphene growth model is devised and sub-surface dissolved carbon is shown to play an important role
We study catalyst-support and catalyst-carbon interactions during the chemical vapor deposition of singlewalled carbon nanotubes by combining environmental transmission microscopy and in situ, time-resolved X-ray photoelectron spectroscopy. We present direct evidence of what constitutes catalyst functionality by comparing the behavior of Ni, Fe, Pd, and Au model catalyst films on SiO 2 during preannealing in O 2 and NH 3 and during C 2 H 2 decomposition. The catalyst metal surface supplies sites to dissociate the hydrocarbon precursor and then guides the formation of a carbon lattice and the liftoff of a carbon cap. The catalysts are sharply distinguished by their reactivity toward activation of the hydrocarbon precursor, following trends known from heterogeneous catalysis. For Fe and Ni, the active state of the catalyst is a crystalline metallic nanoparticle. Graphitic networks do not form on oxidized Fe. Pd forms a silicide on SiO 2 under our reducing conditions. Pd (silicides) and Au nanocrystals are catalytically less efficient in terms of precursor dissociation, while the low adhesion of C on Au surfaces impedes nanotube nucleation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.