Eugen Panaitescu

Titania nanotubes prepared by anodization in fluorine-free acids

Recently, we reported the discovery of new high-aspect ratio titania nanotubes. These nanotubes were synthesized by means of anodization in an oxalic acid electrolyte containing chlorine ions and were found to have significant carbon content. In this article, the synthesis of similar titania nanotubes in oxalic, formic, trichloroacetic, gluconic, hydrochloric, and sulfuric acid is reported. Differences in carbon content and morphology are analyzed, which in turn provides information on the chemistry of the formation of these nanotubes. Our results suggest that the carbon content in the nanotubes can be controlled by the use of an appropriate organic acid.

Controlled attachment of gold nanoparticles on ordered titania nanotube arrays

Gold nanoparticles on titanium oxide support are known to have excellent properties suitable for photocatalytic applications such as water splitting, CO oxidation, etc. Recent advances in titania nanotube arrays synthesized by electrochemical anodization processes provide ideal supports for such applications. We report here for the first time the successful attachment of gold nanoparticles onto electrochemically-anodized titania nanotube arrays. A deposition-precipitation method has been used which is applicable for both low- and high-aspect ratio nanotubes, with lengths of the order of 0.5 µm and 5 µm respectively. Uniform coverage of gold nanoparticles both inside and outside the nanotubes has been achieved. Very good control over the gold nanoparticle diameters (in the range of 1–10 nm) and coverage percentage (up to 70%) has been demonstrated by adjusting the soaking time. With respect to immediate applications two specific results are promising: i) deposition of gold nanoparticles with diameters <5 nm, ideal for photocatalytic applications, has been achieved; ii) coalescence of nanoparticles to almost total coverage of the nanotube surfaces with a thin layer (∼10 nm) of metallic gold after very long exposure to the gold solution suggests the possibility of formation of localized Schottky barriers for current control.

Atomically thin layers of B-N-C-O with tunable composition

Atomically thin quaternary alloy of boron, nitrogen, carbon and oxygen, 2D-BNCO with tunable composition. In recent times, atomically thin alloys of boron, nitrogen, and carbon have generated significant excitement as a composition-tunable two-dimensional (2D) material that demonstrates rich physics as well as application potentials. The possibility of tunably incorporating oxygen, a group VI element, into the honeycomb sp2-type 2D-BNC lattice is an intriguing idea from both fundamental and applied perspectives. We present the first report on an atomically thin quaternary alloy of boron, nitrogen, carbon, and oxygen (2D-BNCO). Our experiments suggest, and density functional theory (DFT) calculations corroborate, stable configurations of a honeycomb 2D-BNCO lattice. We observe micrometer-scale 2D-BNCO domains within a graphene-rich 2D-BNC matrix, and are able to control the area coverage and relative composition of these domains by varying the oxygen content in the growth setup. Macroscopic samples comprising 2D-BNCO domains in a graphene-rich 2D-BNC matrix show graphene-like gate-modulated electronic transport with mobility exceeding 500 cm2 V−1 s−1, and Arrhenius-like activated temperature dependence. Spin-polarized DFT calculations for nanoscale 2D-BNCO patches predict magnetic ground states originating from the B atoms closest to the O atoms and sizable (0.6 eV < Eg < 0.8 eV) band gaps in their density of states. These results suggest that 2D-BNCO with novel electronic and magnetic properties have great potential for nanoelectronics and spintronic applications in an atomically thin platform.

The Changing Colors of a Quantum- Confined Topological Insulator

Bismuth selenide (Bi2Se3) is a 3D topological insulator, its strong spin-orbit coupling resulting in the well-known topologically protected coexistence of gapless metallic surface states and semiconducting bulk states with a band gap, Eg ≃ 300 meV. A fundamental question of considerable importance is how the electronic properties of this material evolve under nanoscale confinement. We report on catalyst-free, high-quality single-crystalline Bi2Se3 with controlled lateral sizes and layer thicknesses that could be tailored down to a few nanometers and a few quintuple layers (QLs), respectively. Energy-resolved photoabsorption spectroscopy (1.5 eV < E(photon) < 6 eV) of these samples reveals a dramatic evolution of the photon absorption spectra as a function of size, transitioning from a featureless metal-like spectrum in the bulk (corresponding to a visually gray color), to one with a remarkably large band gap (Eg ≥ 2.5 eV) and a spectral shape that correspond to orange-red colorations in the smallest samples, similar to those seen in semiconductor nanostructures. We analyze this colorful transition using ab initio density functional theory and tight-binding calculations which corroborate our experimental findings and further suggest that while purely 2D sheets of few QL-thick Bi2Se3 do exhibit small band gaps that are consistent with previous ARPES results, the presently observed large gaps of a few electronvolts can only result from a combined effect of confinement in all three directions.

Vapor–liquid–solid growth of serrated GaN nanowires: shape selection driven by kinetic frustration

Compound semiconducting nanowires are promising building blocks for several nanoelectronic devices yet the inability to reliably control their growth morphology is a major challenge. Here, we report the Au-catalyzed vapor–liquid–solid (VLS) growth of GaN nanowires with controlled growth direction, surface polarity and surface roughness. We develop a theoretical model that relates the growth form to the kinetic frustration induced by variations in the V(N)/III(Ga) ratio across the growing nanowire front. The model predictions are validated by the trends in the as-grown morphologies induced by systematic variations in the catalyst particle size and processing conditions. The principles of shape selection highlighted by our study pave the way for morphological control of technologically relevant compound semiconductor nanowires.

Effect of potassium adsorption on the photochemical properties of titania nanotube arrays

It is demonstrated that vertically-aligned titania nanotube planar arrays fabricated by electrochemical anodization using standard potassium-containing electrolytes invariably contain a significant amount of surface-adsorbed potassium ions, hitherto undetected, that affect the titania photoelectrochemical or PEC performance. Synchrotron-based near edge X-ray absorption fine structure (NEXAFS) spectroscopy reveals the strong ionic nature of surface potassium-titania bonds that alters the PEC performance over that of pure titania nanotubes through reduction of the external electrical bias needed to produce hydrogen at maximum efficiency. This result implies that the external electrical energy input required per liter of solar hydrogen produced with potassium-adsorbed titania nanotubes may be reduced. Tailoring the potassium content may thus be an alternative means to fine-tune the photoelectrochemical response of TiO2nanotube-based PEC electrodes.

Correlation of lattice defects and thermal processing in the crystallization of titania nanotube arrays

Titania nanotubes have the potential to be employed in a wide range of energy-related applications such as solar energy-harvesting devices and hydrogen production. As the functionality of titania nanostructures is critically affected by their morphology and crystallinity, it is necessary to understand and control these factors in order to engineer useful materials for green applications. In this study, electrochemically-synthesized titania nanotube arrays were thermally processed in inert and reducing environments to isolate the role of post-synthesis processing conditions on the crystallization behavior, electronic structure and morphology development in titania nanotubes, correlated with the nanotube functionality. Structural and calorimetric studies revealed that as-synthesized amorphous nanotubes crystallize to form the anatase structure in a three-stage process that is facilitated by the creation of structural defects. It is concluded that processing in a reducing gas atmosphere versus in an inert environment provides a larger unit cell volume and a higher concentration of Ti3+ associated with oxygen vacancies, thereby reducing the activation energy of crystallization. Further, post-synthesis annealing in either reducing or inert atmospheres produces pronounced morphological changes, confirming that the nanotube arrays thermally transform into a porous morphology consisting of a fragmented tubular architecture surrounded by a network of connected nanoparticles. This study links explicit data concerning morphology, crystallization and defects, and shows that the annealing gas environment determines the details of the crystal structure, the electronic structure and the morphology of titania nanotubes. These factors, in turn, impact the charge transport and consequently the functionality of these nanotubes as photocatalysts.