Vertically Aligned Nanostructured Arrays of Inorganic Materials: Synthesis, Distinctive Physical Phenomena, and Device Integration
Velazquez, Jesus Manuel
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The manifestation of novel physical phenomena upon scaling materials to finite size has inspired new device concepts that take advantage of the distinctive electrical, mechanical, and optical, properties of nanostructures. The development of fabrication approaches for the preparation of their 1D nanostructured form, such as nanowires and nanotubes, has contributed greatly to advancing fundamental understanding of these systems, and has spurred the integration of these materials in novel electronics, photonic devices, power sources, and energy scavenging constructs. Significant progress has been achieved over the last decade in the preparation of ordered arrays of carbon nanotubes, II—VI and III—V semiconductors, and some binary oxides such as ZnO. In contrast, relatively less attention has been focused on layered materials with potential for electrochemical energy storage. Here, we describe the catalyzed vapor transport growth of vertical arrays of orthorhombic V 2 O 5 nanowires. In addition, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to precisely probe the alignment, uniformity in crystal growth direction, and electronic structure of single-crystalline V 2 O 5 nanowire arrays prepared by a cobalt-catalyzed vapor transport process. The dipole selection rules operational for core-level electron spectroscopy enable angle-dependant NEXAFS spectroscopy to be used as a sensitive probe of the anisotropy of these systems and provides detailed insight into bond orientation and the symmetry of the frontier orbital states. The experimental spectra are matched to previous theoretical predictions and allow experimental verification of features such as the origin of the split-off conduction band responsible for the n -type conductivity of V 2 O 5 and the strongly anisotropic nature of vanadyl-oxygen-derived (V=O) states thought to be involved in catalysis. We have also invested substantial effort in obtaining shape and size control of metal oxide materials to obtain a fundamental understanding of the influence of finite size and surface restructuring on electronic instabilities in the proximity of the Fermi level. We present here a novel synthetic approach that takes advantage of the intrinsic octahedral symmetry of rock-salt-structured VO to facilitate the growth of six-armed nanocrystallites of related, technologically more important binary vanadium oxide V 2 O 5 . The prepared nanostructures exhibit clear six-fold symmetry and most notably show remarkable retention of electronic structure. The latter has been evidenced through extensive X-ray absorption spectroscopy measurements. We have further designed a facile, generalizable, and entirely scalable approach for the fabrication of vertically aligned arrays of Fe 2 O 3 /polypyrrole core—shell nanostructures and polypyrrole nanotubes. Our "all electrochemical" approach is based on the fabrication of &agr;-Fe 2 O 3 nanowire arrays by the simple heat treatment of commodity low carbon steel substrates, followed by electropolymerization of conformal polypyrrole sheaths around the nanowires. Subsequently, electrochemical etching of the nanowires yields large-area vertically aligned polypyrrole nanotube arrays on the steel substrate. The developed methodology is generalizable to functionalized pyrrole monomers and represents a significant practical advance of relevance to the technological implementation of conjugated polymer nanostructures in electrochromics, electrochemical energy storage, and sensing. As another variation of this general synthetic route, we have extended the practice of our simple oxidative process for the fabrication of large-area ZnO nanostructures, specifically highly aligned nanowire arrays integrated onto galvanized steel substrates which via a simple device design and additive piezoelectric nanopower generation were measured across the array substrates. The nanomaterial syntheses and device fabrication approaches developed here will enable facile integration of piezoelectric nanogenerators on to structural components.