Characterization of monolayer formation on aluminum-doped zinc oxide thin films.

The optical and electronic properties of aluminum-doped zinc oxide (AZO) thin films on a glass substrate are investigated experimentally and theoretically. Optical studies with coupling in the Kretschmann configuration reveal an angle-dependent plasma frequency in the mid-IR for p-polarized radiation, suggestive of the detection of a Drude plasma frequency. These studies are complemented by oxygen depletion density functional theory studies for the calculation of the charge carrier concentration and plasma frequency for bulk AZO. In addition, we report on the optical and physical properties of thin film adlayers of n-hexadecanethiol (HDT) and n-octadecanethiol (ODT) self-assembled monolayers (SAMs) on AZO surfaces using reflectance FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), contact angle, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Our characterization of the SAM deposition onto the AZO thin film reveals a range of possible applications for this conducting metal oxide.

Measuring molecular order in poly(3-alkylthiophene) thin films with polarizing spectroscopies.

We measured the molecular order of poly(3-alkylthiophene) chains in thin films before and after melting through the combination of several polarized photon spectroscopies: infrared (IR) absorption, variable angle spectroscopic ellipsometry (SE), and near-edge X-ray absorption fine structure (NEXAFS). The data from the various techniques can be uniformly treated in the context of the dielectric constant tensor epsilon for the film. The combined spectroscopies allow determination of the orientation distribution of the main-chain axis (SE and IR), the conjugated pi system normal (NEXAFS), and the side-chain axis (IR). We find significant improvement in the backbone order of the films after recrystallization of the material at temperatures just below the melting temperature. Less aggressive thermal treatments are less effective. IR studies show that the changes in backbone structure occur without significant alteration of the structure of the alkyl side chains. The data indicate that the side chains exhibit significant disorder for all films regardless of the thermal history of the sample.

Near-edge X-ray absorption fine structure spectroscopy as a tool for investigating nanomaterials.

We have demonstrated near-edge X-ray absorption fine structure (NEXAFS) spectroscopy as a particularly useful and effective technique for simultaneously probing the surface chemistry, surface molecular orientation, degree of order, and electronic structure of carbon nanotubes and related nanomaterials. Specifically, we employ NEXAFS in the study of single-walled carbon nanotube and multi-walled carbon nanotube powders, films, and arrays, as well as of boron nitride nanotubes. We have focused on the advantages of NEXAFS as an exciting, complementary tool to conventional microscopy and spectroscopy for providing chemical and structural information about nanoscale samples.

Imperfect surface order and functionalization in vertical carbon nanotube arrays probed by near edge X-ray absorption fine structure spectroscopy (NEXAFS).

Probing surface order as well as the degree of structural modification in carbon nanotube systems is of fundamental importance for incorporation of these materials into practical functional devices. The current study pertains to the analysis of the surface order of vertically-aligned single-walled and multi-walled carbon nanotube arrays of varying length and composition by means of near-edge X-ray fine structure spectroscopy (NEXAFS). Both NEXAFS and scanning electron microscopy (SEM) studies concluded that the nanotubes in these samples were oriented vertically to the plane of the surface. However, NEXAFS polarization analysis provided a more quantitative and nuanced description of the surface structure, indicative of far less localized surface order, an observation partially attributed to misalignment and bending of the tubes. Moreover, it was demonstrated by NEXAFS that the surface order of the arrays was imperfect and relatively independent of the height of the nanotube arrays. In addition, we have shown that NEXAFS can be used to correlate the extent of chemical functionalization and oxygenation with disruption of the electronic and physical structure of nanotubes embedded in array motifs.

X-ray absorption spectroscopy to probe surface composition and surface deprotection in photoresist films.

Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is utilized to provide insight into surface chemical effects in model photoresist films. First, NEXAFS was used to examine the resist/air interface including surface segregation of a photoacid generator (PAG) and the extent of surface deprotection in the film. The concentration of PAG at the resist-air interface was higher than the bulk concentration, which led to a faster deprotection rate at that interface. Second, a NEXAFS depth profiling technique was utilized to probe for compositional gradients in model resist line edge regions. In the model line edge region, the surface composition profile for the developed line edge was dependent on the post exposure bake time.

Near-edge X-ray absorption fine structure investigations of order in carbon nanotube-based systems.

Probing order in nanotube systems is of fundamental importance in devising applications of these tubes in field emission applications as well as for components of composite materials. We use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to qualitatively and quantitatively study the degree of order and alignment in a wide range of carbon nanotube-based systems, including single-walled carbon nanotube (SWNT) powder, SWNT films, and aligned multiwalled carbon nanotubes. The results are compared to analogous data obtained from a highly ordered pyrolytic graphite (HOPG) sample.

Investigating the structure of boron nitride nanotubes by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.

Herein, we demonstrate that NEXAFS is a very effective technique at (a) identifying the phases of boron nitride nanotubes with the potential of distinguishing between hexagonal BN and cubic BN, and (b) monitoring the presence of defects and degree of crystallinity in nanoscale samples. Specifically, a prepared sample of boron nitride nanotubes was characterized by NEXAFS. Our results show that the sample consisted of hexagonal BN tubes that were highly crystalline and sp2-hybridized.

Molecular orientation of ultrahigh molecular weight polyethylene induced by various sliding motions.

Wear and wear debris of ultrahigh molecular weight polyethylene (UHMWPE) in joint replacements have been recognized as one of the major contributors to the failure of orthopedic implants. The detailed wear mechanism of polyethylene under biomechanic motions is not well understood. In simulation wear bench tests, it was found that unidirectional sliding produces the least amount of wear, reciprocating motion increases wear significantly, and cross-shear motion (similar to hip and knee joint motion in the human body) produces the highest amount of wear. Conventional wear theories are inadequate to explain this observation. This study utilizes resonant absorption of linearly polarized soft X-rays at a synchrotron radiation beam line to measure the molecular orientation of a UHMWPE surface layer subjected to different wear motions. Carbon-K-edge partial-electron-yield X-ray absorption measurements were done on the worn UHMWPE samples. X-ray absorption measurements show conclusively that the molecular chains of UHMWPE align preferentially parallel to the direction of sliding. Examination under various wear motions showed that unidirectional shear produced the maximum chain orientation, whereas cross-shear wear motions produced the least amount of orientation. When polymeric chains align, the surface layer tends to be more brittle and hard, thus resisting wear. When they do not align, loose chains may be subjected to both Mode I and Mode II fracture, hence increasing the wear rate. This molecular alignment observation may offer an explanation of why different wear motions have different wear characteristics.

A direct comparison of surface and bulk chain-relaxation in polystyrene.

Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy was used to measure simultaneously the relaxation rates of polystyrene (PS) molecules at the free surface and in the bulk. The samples were uniaxially stretched and annealed at temperatures below the bulk glass transition temperature of PS. The surface and bulk chain relaxation was monitored by measuring the partial-electron and the fluorescence NEXAFS yields, respectively, both parallel and perpendicular to the stretching direction. The decay of the optical birefringence was also measured to provide an independent measure of the bulk relaxation. Relaxation of PS chains was found to occur faster on the surface relative to the bulk. The magnitude of the surface glass transition temperature suppression over the bulk was estimated based on the information on the temperature dependence of the rates.