Phonon response in the infrared region to thickness of oxide films formed by atomic layer deposition.

Experimental transmission infrared spectra of gamma-Al(2)O(3) and ZnO films are collected from heat-treated thin oxide films deposited with uniform thickness on Si(100) using atomic layer deposition. We show that the Berreman thickness, i.e. the upper limit for a linear relationship between oxide film thickness and phonon absorbance in the infrared region in transmission configuration, is a concept that applies to both transverse and longitudinal optical phonons. We find that for aluminum oxide films the Berreman thickness is 125 nm, and we estimate that it is around approximately 435 nm for zinc oxide films. Combining experiment and simulation, we also show that the Berreman thickness is the maximum distance allowed between interfaces for Snell's law and Fresnel's formulas to determine the optical properties in the infrared region and in transmission configuration for a layer system including an oxide film. Below the Berreman thickness, a Taylor series expansion of the absorbance coefficient determines the linear relationship between phonon absorbance and oxide film thickness t, so that as t --> 0 absorption A(p) is proportional to 4pi omega(ph)t, where omega(ph) indicates optical phonon frequency. Above the Berreman thickness, field boundary conditions at the air/oxide film interface effectively contribute with a single interface in explaining optical phonon absorbance. Preliminary infrared spectra in reflection configuration for gamma-Al(2)O(3)/Si(100) are discussed, and the obtained data support the conclusions reported for the transmission configuration.

Atomic layer deposition and abrupt wetting transitions on nonwoven polypropylene and woven cotton fabrics.

Atomic layer deposition (ALD) of aluminum oxide on nonwoven polypropylene and woven cotton fabric materials can be used to transform and control fiber surface wetting properties. Infrared analysis shows that ALD can produce a uniform coating throughout the nonwoven polypropylene fiber matrix, and the amount of coating can be controlled by the number of ALD cycles. Upon coating by ALD aluminum oxide, nonwetting hydrophobic polypropylene fibers transition to either a metastable hydrophobic or a fully wetting hydrophilic state, consistent with well-known Cassie-Baxter and Wenzel models of surface wetting of roughened surfaces. The observed nonwetting/wetting transition depends on ALD process variables such as the number of ALD coating cycles and deposition temperature. Cotton fabrics coated with ALD aluminum oxide at moderate temperatures were also observed to transition from a natural wetting state to a metastable hydrophobic state and back to wetting depending on the number of ALD cycles. The transitions on cotton appear to be less sensitive to deposition temperature. The results provide insight into the effect of ALD film growth mechanisms on hydrophobic and hydrophilic polymers and fibrous structures. The ability to adjust and control surface energy, surface reactivity, and wettability of polymer and natural fiber systems using atomic layer deposition may enable a wide range of new applications for functional fiber-based systems.

Angular behavior of the Berreman effect investigated in uniform Al2O3 layers formed by atomic layer deposition.

Experimental transmission absorbance infrared spectra of γ-Al(2)O(3) showing evidence of the angular dependence of the peaks of surface modes appearing next to the longitudinal optical phonon frequency ω(LO) (the Berreman effect) are collected from heat-treated thin oxide films deposited with thickness uniformity on Si(100) using atomic layer deposition. The peak area of the most intense surface longitudinal optical mode is plotted versus the infrared beam incidence angle θ(0). The experimental points closely follow the sin(4)(θ(0)) function in a broad thickness range. The best match occurs at a critical thickness, where a linear relationship exists between the surface longitudinal optical mode intensity and film thickness. Simulations suggest that below the critical thickness the sin(4)(θ(0)) behavior can be explained by refraction phenomena at the air/thin film and thin film/substrate interfaces. Above the critical thickness, the experimentally obtained result is derived from field boundary conditions at the air/thin film interface. The sin(4)(θ(0)) functional trend breaks down far above the critical thickness. This picture indicates that infrared radiation has a limited penetration depth into the oxide film, similarly to electromagnetic waves in conductors. Consequently, surface longitudinal optical modes are viewed as bulk phonons excited down to the penetration depth of the infrared beam. Comparison with simulated data suggests that the infrared radiation absorptance of surface longitudinal optical modes tends to approach the sin(2)(θ(0)) trend. Reflection phenomena are considered to be the origin of the deviation from the sin(4)(θ(0)) trend related to refraction.

Surface polarity shielding and hierarchical ZnO Nano-architectures produced using sequential hydrothermal crystal synthesis and thin film atomic layer deposition.

Three-dimensional nanoscale constructs are finding applications in many emerging fields, including energy generation and storage, advanced water and air purification, and filtration strategies, as well as photocatalytic and biochemical separation systems. Progress in these important technologies will benefit from improved understanding of fundamental principles underlying nanostructure integration and bottom-up growth processes. While previous work has identified hydrothermal synthesis conditions to produce nanoscale ZnO rods, sheets, and plates, strategies to systematically integrate these elements into more complex nano-architectures are not previously described. This article illustrates that amorphous nanoscale coatings formed by atomic layer deposition (ALD) are a viable means to modulate and screen the surface polarity of ZnO crystal faces and thereby regulate the growth morphology during successive hydrothermal nanocrystal synthesis. Using this new strategy, this work demonstrates direct integration and sequential assembly of nanocrystalline rods and sheets to produce complex three-dimensional geometric forms, where structure evolution is achieved by modifying the surface growth condition, keeping the hydrothermal growth chemistry unchanged. Therefore, rational planning of seed layer and feature spacing geometries may allow researchers to engineer, at the nanoscale, complex three-dimensional crystalline and semicrystalline constructs for a wide range of future applications.

Conductivity in alkylamine/gold and alkanethiol/gold molecular junctions measured in molecule/nanoparticle/molecule bridges and conducting probe structures.

Charge transport through alkane monolayers on gold is measured as a function of molecule length in a controlled ambient using a metal/molecule/nanoparticle bridge structure and compared for both thiol and amine molecular end groups. The current through molecules with an amine/gold junction is observed to be more than a factor of 10 larger than that measured in similar molecules with thiol/gold linkages. Conducting probe atomic force microscopy is also used to characterize the same monolayer systems, and the results are quantitatively consistent with those found in the nanoparticle bridge geometry. Scaling of the current with contact area is used to estimate that approximately 100 molecules are probed in the nanoparticle bridge geometry. For both molecular end groups, the room-temperature conductivity at low bias as a function of molecule length shows a reasonable fit to models of coherent nonresonant charge tunneling. The different conductivity is ascribed to differences in charge transfer and wave function mixing at the metal/molecule contact, including possible effects of amine group oxidation and molecular conformation. For the amine/Au contact, the nitrogen lone pair interaction with the gold results in a hybrid wave function directed along the molecule bond axis, whereas the thiol/Au contact leads to a more localized wave function.

Real-time conductivity analysis through single-molecule electrical junctions.

Conductance through single-molecule junctions, consisting of nanoparticle/molecule/nanoparticle units between nanoscale planar electrodes, was monitored in real time during several process sequences, including dielectrophoretic directed self-assembly and post-assembly modification. Assembly faults are directly detected in real time when non-ideal assembly conditions result in molecular junction failure and nanoparticle fusion in the junction. The real-time conductivity measured through the junction was sensitive to ambient conditions, and changes persisted over several days of exposure. Atomic layer deposition of Al(2)O(3) was used to encapsulate and isolate the molecular junctions, and the effect of the deposition process sequence on current through the junction was evaluated in real time. Results indicate that the current measured during atomic layer deposition is sensitive to the chemical oxidation and reduction reactions proceeding in the 1-2 nm confined region between assembled nanoparticles.

Conduction mechanisms and stability of single molecule nanoparticle/molecule/nanoparticle junctions.

Nanoparticle/molecule/nanoparticle dimer assemblies have been successfully trapped by dielectrophoresis across nanogap electrodes, enabling temperature dependent charge transport measurements through an oligomeric phenylene ethynylene molecule, and transition from direct tunnelling to Fowler-Nordheim tunnelling is observed at approximately 1.5 V. Samples formed by dielectrophoresis show better contact stability than those formed by receding meniscus. The junction shows stable operation over several weeks in a vacuum, but current increases with time upon exposure to air, possibly due to the adsorbed water molecules near the molecule/gold nanoparticle contacts.