Robert Zierold

A Practical, Self‐Catalytic, Atomic Layer Deposition of Silicon Dioxide

The outstanding chemical, electrical, and optical properties of silicon dioxide have made it ubiquitous in science and technology. The ability to create SiO2 nanostructures of well-defined geometry would broaden its range of applications even further, in particular in the chemical, electrokinetic, and biomedical realms. Atomic layer deposition (ALD) is especially suited to nanostructuring, since its kinetics are controlled by surface chemistry rather than mass transport from the gas phase. However, reports on the ALD of silica are few and far between in the open literature to date. All published reactions suffer from some weakness: a corrosive by-product or catalyst, poor reproducibility, or impurities in the deposited film. Herein, we describe a practical ALD process for SiO2 that overcomes such limitations. Based on the NH3-catalyzed hydrolysis of tetraethoxysilane (Si(OEt)4), chemical intuition dictates that a triethoxysilane bearing an aminoalkyl moiety be readily hydrolyzed without any extraneous catalyst. The basic functionality will labilize the strong Si!O bonds, a phenomenon that can be called “self-catalysis” to emphasize the fact that one chemical species is both substrate and catalyst. Subsequent oxidative cleavage of the tethered moiety should afford a silanol, amenable to further reaction with aminoalkyltriethoxysilane molecules. Accordingly, a three-step reaction sequence based on 3-aminopropyltriethoxysilane, water, and ozone (O3) can be envisioned for the ALD of SiO2 (Scheme 1).

Low temperature silicon dioxide by thermal atomic layer deposition: Investigation of material properties

SiO2 is the most widely used dielectric material but its growth or deposition involves high thermal budgets or suffers from shadowing effects. The low-temperature method presented here (150 °C) for the preparation of SiO2 by thermal atomic layer deposition (ALD) provides perfect uniformity and surface coverage even into nanoscale pores, which may well suit recent demands in nanoelectronics and nanotechnology. The ALD reaction based on 3-aminopropyltriethoxysilane, water, and ozone provides outstanding SiO2 quality and is free of catalysts or corrosive by-products. A variety of optical, structural, and electrical properties are investigated by means of infrared spectroscopy, UV-Vis spectroscopy, secondary ion mass spectrometry, capacitance-voltage and current-voltage measurements, electron spin resonance, Rutherford backscattering, elastic recoil detection analysis, atomic force microscopy, and variable angle spectroscopic ellipsometry. Many features, such as the optical constants (n, k) and optical transm...

Experimental evidence for an angular dependent transition of magnetization reversal modes in magnetic nanotubes

We report on the experimental and theoretical investigation of the magnetization reversal in magnetic nanotubes that have been synthesized by a combination of glancing angle and atomic layer deposition. Using superconducting quantum interference device magnetometry the angular dependence of the coercive fields is determined and reveals a nonmonotonic behavior. Analytical calculations predict the crossover between two magnetization reversal modes, namely, the movement of different types of domain boundaries (vortex wall and transverse wall). This transition, already known in the geometrical dependences of the magnetization reversal in various nanotubes, is found within one type of tube in the angular dependence and is experimentally confirmed in this work.

Changes in Morphology and Ionic Transport Induced by ALD SiO2 Coating of Nanoporous Alumina Membranes

Nanoporous anodic alumina membranes (NPAMs) were produced by the two-step anodization method in sulphuric, oxalic and phosphoric acidic electrolytes displaying a hexagonally ordered spatial arrangement of pores with well controlled nanopore size distribution and low porosity. Some selected NPAMs were further modified by conformal coating their surface and inner pore walls with a thin layer of SiO2 by means of atomic layer deposition (ALD), which reduces both the pore radii and porosity but it also seems to affect to the electric fixed charge on the membranes surface. A comparative study about the influence of silica modification of NPAMs surfaces on the ionic transport through the nanoporous membranes has been performed by measuring membrane potentials and electrochemical impedance spectroscopy with NaCl solutions. According to these results, a direct correlation between the membrane effective fixed charge and the NaCl diffusion coefficient can be established. The coating with a SiO2 thin layer causes a reduction of 75% in the positive effective fixed charge of the NPAMs independently of their pore radii and the increase in counterion transport (cation transport number and diffusion coefficient) even through constrained nanopores, which can be of interest in several applications (microfluidics, drug delivery, nanofilter devices, etc.). Moreover, slight changes in the membrane/solution interface due to the SiO2 cover layer are also indicated.

Magnetic characterization of nickel-rich NiFe nanowires grown by pulsed electrodeposition

Nickel-rich NiFe nanowires with well-controlled diameters and compositions are fabricated in various porous alumina templates by using a pulsed electrochemical deposition technique. The average pore diameter of the templates is tuned either by coating the pore walls with thin silica layers using an atomic layer deposition (ALD) technique or by applying a chemical pore widening process. The composition of the alloy is controlled by varying the frequency of the deposition pulse. The coercivity of the nanowire array is influenced by its texture and the amount of iron content in the alloy. The effective field and the saturation magnetization are found to be reinforced with the decrease in Ni content. A distinct enhancement of the axial coercivity and squareness of permalloy, Ni80Fe20, nanowire array are obtained by decreasing the average nanowire diameter. The processes of magnetization reversal in Ni80Fe20 nanowire array are investigated. The temperature dependence of Ni80Fe20 nanowires coercivity is interpreted in accordance with magnetization fluctuation over a single energy barrier.

Polymer-assisted self-assembly of superparamagnetic iron oxide nanoparticles into well-defined clusters: controlling the collective magnetic properties.

The combination of superstructure-forming amphiphilic block copolymers and superparamagnetic iron oxide nanoparticles produces new nano/microcomposites with unique size-dependent properties. Herein, we demonstrate the controlled clustering of superparamagnetic iron oxide nanoparticles (SPIOs) ranging from discretely encapsulated SPIOs to giant clusters, containing hundreds or even more particles, using an amphiphilic polyisoprene-block-poly(ethylene glycol) diblock copolymer. Within these clusters, the SPIOs interact with each other and show new collective properties, neither obtainable with singly encapsulated nor with the bulk material. We observed cluster-size-dependent magnetic properties, influencing the blocking temperature, the magnetoviscosity of the liquid suspension, and the r2 relaxivity for magnetic iron oxide nanoparticles. The clustering methodology can be expanded also to other nanoparticle materials [CdSe/CdS/ZnS core/shell/shell quantum dots (QDs), CdSe/CdS quantum dots/quantum rods (QDQRs), gold nanoparticles, and mixtures thereof].

Thermoelectric properties of topological insulator Bi2Te3, Sb2Te3, and Bi2Se3 thin film quantum wells

The thermoelectric (TE) figure of merit ZT of topological insulator Bi2Te3, Sb2Te3, and Bi2Se3 thin film quantum wells is calculated for thicknesses below 10 nm, for which hybridization of the surface states as well as quantum confinement in the bulk are individually predicted to enhance ZT. Here, the question is addressed what ZT can be expected from coexisting surface and bulk states in such quantum wells. It is demonstrated that the parallel contributing bulk and surface channels tend to cancel each other out. This is because the surface-to-volume ratios of the thin films prevent the domination of transport through a single channel and because the individual bulk and surface ZTs are optimized at different Fermi levels.

Impact of the Topological Surface State on the Thermoelectric Transport in Sb2Te3 Thin Films.

Ab initio electronic structure calculations based on density functional theory and tight-binding methods for the thermoelectric properties of p-type Sb2Te3 films are presented. The thickness-dependent electrical conductivity and the thermopower are computed in the diffusive limit of transport based on the Boltzmann equation. Contributions of the bulk and the surface to the transport coefficients are separated, which enables to identify a clear impact of the topological surface state on the thermoelectric properties. When the charge carrier concentration is tuned, a crossover between a surface-state-dominant and a Fuchs-Sondheimer transport regime is achieved. The calculations are corroborated by thermoelectric transport measurements on Sb2Te3 films grown by atomic layer deposition.

Thermoelectric performance of classical topological insulator nanowires

There is currently substantial effort being invested into creating efficient thermoelectric (TE) nanowires based on topological insulator (TI) chalcogenide-type materials. A key premise of these efforts is the assumption that the generally good TE properties that these materials exhibit in bulk form will translate into similarly good or even better TE performance of the same materials in nanowire form. Here, we calculate TE performance of TI nanowires based on Bi2Te3, Sb2Te3 and Bi2Se3 as a function of diameter and Fermi level. We show that the TE performance of TI nanowires does not derive from the properties of the bulk material in a straightforward way. For all investigated systems the competition between surface states and bulk channel causes a significant modification of the TE transport coefficients if the diameter is reduced into the sub 10 ?m range. Key aspects are that the surface and bulk states are optimized at different Fermi levels or have different polarity as well as the high surface to volume ratio of the nanowires. This limits the maximum TE performance of TI nanowires and thus their application in efficient TE devices.

TiO2, SiO2, and Al2O3 coated nanopores and nanotubes produced by ALD in etched ion-track membranes for transport measurements.

Low-temperature atomic layer deposition (ALD) of TiO2, SiO2, and Al2O3 was applied to modify the surface and to tailor the diameter of nanochannels in etched ion-track polycarbonate membranes. The homogeneity, conformity, and composition of the coating inside the nanochannels are investigated for different channel diameters (18-55 nm) and film thicknesses (5-22 nm). Small angle x-ray scattering before and after ALD demonstrates conformal coating along the full channel length. X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy provide evidence of nearly stoichiometric composition of the different coatings. By wet-chemical methods, the ALD-deposited film is released from the supporting polymer templates providing 30 μm long self-supporting nanotubes with walls as thin as 5 nm. Electrolytic ion-conductivity measurements provide proof-of-concept that combining ALD coating with ion-track nanotechnology offers promising perspectives for single-pore applications by controlled shrinking of an oversized pore to a preferred smaller diameter and fine-tuning of the chemical and physical nature of the inner channel surface.