Origin of the low frequency radiation emitted by radiative polaritons excited by infrared radiation in planar La2O3 films.

Upon excitation in thin oxide films by infrared radiation, radiative polaritons are formed with complex angular frequency ω, according to the theory of Kliewer and Fuchs (1966 Phys. Rev. 150 573). We show that radiative polaritons leak radiation with frequency ω(i) to the space surrounding the oxide film. The frequency ω(i) is the imaginary part of ω. The effects of the presence of the radiation leaked out at frequency ω(i) are observed experimentally and numerically in the infrared spectra of La(2)O(3) films on silicon upon excitation by infrared radiation of the 0TH type radiative polariton. The frequency ω(i) is found in the microwave to far infrared region, and depends on the oxide film chemistry and thickness. The presented results might aid in the interpretation of fine structures in infrared and, possibly, optical spectra, and suggest the study of other similar potential sources of electromagnetic radiation in different physical scenarios.

Effects of metallic, semiconducting, and insulating substrates on the coupling involving radiative polaritons in thin oxide films.

Through simulations, this work explores the effects of conducting, semiconducting, and insulating substrates on the absorption of infrared radiation by radiative polaritons in oxide layers with thicknesses that range from 30 nm to 9 µm. Using atomic layer deposition, oxide layers can be formed in the nanometer scale. Our results suggest that the chemistry and conductivity of the substrate determine the amount of absorption by radiative polaritons in oxide layers thinner than the skin depth. The effects of the chemistry and conductivity of the substrate are especially effective for oxide films thinner than about 250 nm, which we label as the substrate sensitive thickness of the oxide film.

Sinter-free phase conversion and scanning transmission electron microscopy of FePt nanoparticle monolayers.

Thermally robust monolayers of 4-6 nm diameter FePt nanoparticles (NPs) were fabricated by combining chemical synthesis and atomic layer deposition. Spin-cast monolayers of FePt NPs were coated with thin, 11 nm-thick layers of amorphous Al(2)O(3), followed by annealing to convert the FePt NPs from an alloy (A1) into intermetallic FePt (L1(0)) and FePt(3) (L1(2)) phases. The Al(2)O(3) layer serves as a barrier that prevents sintering between NPs during annealing at temperatures up to 730 °C. Electron and X-ray diffraction in conjunction with high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) show that as-synthesized A1 FePt NPs convert into L1(0) and L1(2) phase NPs through annealing. HAADF-STEM measurements of individual NPs reveal imperfect ordering and show that the NP composition determines which intermetallic phase is obtained. Mixed-phase NPs with L1(0) cores and FePt(3) L1(2) shells were also observed, as well as a smaller number of unconverted A1 NPs. These results highlight the need for improved control over the compositional uniformity of FePt NPs for their use in bit-patterned magnetic recording.

Atomic layer deposition of titanium dioxide on cellulose acetate for enhanced hemostasis.

TiO2 films may be used to alter the wettability and hemocompatibility of cellulose materials. In this study, pure and stoichiometric TiO2 films were grown using atomic layer deposition on both silicon and cellulose substrates. The films were grown with uniform thicknesses and with a growth rate in agreement with literature results. The TiO2 films were shown to profoundly alter the water contact angle values of cellulose in a manner dependent upon processing characteristics. Higher amounts of protein adsorption indicated by blurry areas on images generated by scanning electron microscopy were noted on TiO2 -coated cellulose acetate than on uncoated cellulose acetate. These results suggest that atomic layer deposition is an appropriate method for improving the biological properties of hemostatic agents and other blood-contacting biomaterials.

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.

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.

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.

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.

Dielectric properties of high-kappa oxides: theory and experiment for Lu2O3.

We present a combined experimental and theoretical analysis of the dielectric and vibrational properties of crystalline lutetium oxide in its ground-state bixbyite structure. The vibrational dielectric function of Lu2O3 thin films grown by atomic-layer deposition was studied by infrared transmission and reflection-absorption spectroscopies, selectively accessing transverse and longitudinal optical frequencies. The static dielectric constant is extracted analyzing the infrared response. We also present first-principles density-functional linear-response calculations, which are in close agreement with experiment, and provide insight into the microscopic nature of vibrational spectra and dielectric properties.