The degradation behavior of biodegradable multiblock copolymers (PDC) containing poly(p-dioxanone) hard segments (PPDO) and crystallizable poly(epsilon-caprolactone) switching segments (PCL) synthesized via co-condensation of two oligomeric macrodiols with an aliphatic diisocyanate as junction unit was explored in in vivo and in vitro experiments. The in vitro experiments for enzymatic degradation resulted that the poly(epsilon-caprolactone) segments are degraded faster, than the poly(p-dioxanone) segments. During degradation the outer layer of the test specimen becomes porous. Finally non-soluble degradation products in form of particles were found at the surface. This observation is in good agreement with the in vivo studies, where the non-soluble degradation products in the periimplantary tissues showed a diameter of 1 – 3 micron.

The year 2009 marks 20 years since the Environmental Management program was first established in the Department of Energy. At that time, nearly 50 years of nuclear activity had left a legacy that included nuclear waste and environmental contamination at more than 100 sites across the United States. The extent of the risk to our citizens and communities was unknown, and certainly many of the processes and technologies to reduce that risk had not yet been invented. Since then, the Department of Energy has closed 86 of 108 sites originally assigned to the program nationwide. The Department of Energy has packaged and safely stored the nation’s entire excess plutonium inventory. The Department has pioneered new technologies that have allowed progress in retrieving millions of liters of tank waste and safely disposing of tens of thousands of cubic meters of transuranic waste. In Fiscal years 2006 and 2007 alone, the Department of Energy demolished approximately 500 buildings (nuclear, radioactive, and industrial) as part of our decontamination and decommissioning projects. Finally, there have been great strides in restoring groundwater contaminated with radionuclides using innovative treatment systems. In August 2005, a rigorous project management system was instituted. This Department of Energy program was built on the principle of prioritizing risk reduction supported by our four guiding tenets of safety, performance, clean-up, and closure. The mission activities at our clean-up sites are targeted at our highest risk activities. In planning its environmental clean-up efforts and developing the budget for those activities, the Department seeks to focus on work that will produce the greatest environmental benefit and the largest amount of risk reduction.

We demostrate an advanced precision cutting tool using a 349 nm nanosecond-pulsed UV laser micromachining setup. After expansion and collimation, the laser beam is directed vertically and focused with a high performance triplet lens. With an Al mirror inserted in the path of the convergent beam, the beam can be focused on a horizontal machining plane at any desired tilting angles. Microstructures of a wide range of geometries on hard materials can be formed using this custom machining method. Conventional linear and rotary machining on sapphire materials have been demonstrated.

New materials, methods, and membranes are being developed for applications in water purification. One of the model systems that can be used for fundamental studies in nanoscale transport phenomena for new membrane technologies are nanocapillary array membranes (NCAMs). Toward developing more efficient membranes for water desalination, parameters such as the concentration polarization region which are influenced by the unstirred layers, surface properties (e.g., surface charge and surface energy) of the nanocapillaries, and the electric double layer (EDL) which mediates transport across NCAMs must be better understood. In this paper, a series of parametric experiments that were conducted to better understand the relative importance of unstirred layers with respect to the transport across nanocapillaries are described. Bulk salt concentration and potential drop across the NCAMs, were varied in a systematic manner to determine the influence EDL thickness and electromigration on transport regimes for ionic permeation across NCAMs. Based on previously developed methodologies, the experiments reported here were conducted in a permeation cell with an NCAM separating two reservoirs containing potassium phosphate buffer with a concentration range from 200 μM-10 mM. Methylene blue (MB) is used as an organic marker and the transport is quantified by tracking MB concentration in each reservoir with UV/VIS spectroscopy.

In this paper we report new excitation method of surface plasmon polariton (SPP) at air/gold interface with electrospun nanofibers. Nanofibers of polyvinylpirrolidone were electrospun onto the surface of a gold film. The observations by scanning electron microscopy and optical microscopy indicated that the average diameters of the nanofibers were about 300 nm and average sizes of pores were about 30-40 μm. Optical response of the nanofibers on gold surface was investigated by polarized reflection absorption spectroscopy (RAS). The RAS spectrum with p-polarized light showed two absorption bands while the spectrum with s-polarized light only one band. One is a band at about 520 nm that also found in the spectrum with s-polarized light. Another is a broad band in the near-infrared region which found only with p-polarized light. The peak intensity of the latter band increases with increase of incident angle of the polarized light and the peak wavelength of the band shifted to longer wavelength. These responses suggested that SPP at air/gold interface was excited with the scattering light from the electrospun nanofibers. We also found that the peak wavelength of the absorption band in near-infrared region changed with the increase of the amount of the nanofibers. This may be due to the fact that the sizes of the pores on gold surface became smaller than the propagation length of SPP, which resulted in scattering and interference of SPP.

We report the synthesis and surface modification of bio-friendly ZnO based colloids, which have been used for cancer cell detection providing significant advantages on quantum confinement effects, high emission brightness in UV to blue-violate range, non-toxicity and a unique dual color imaging feature. The ZnO nanoparticles were single crystal nanoparticles having spherical shape in size of 1-2 or 4-5 nm depending on the surface capping agents. All the colloidal solutions were stable for 30-45 days. The surface capping is a more effective technique in controlling the nanoparticle size, while dopants are effective in modifying the bandgap and optical properties. Unique dual colour images with blue colour in nucleus and turquoise colour in cytoplasm were obtained using either pure ZnO or Co doped ZnO colloids on human osteosarcoma (Mg-63) cells. The dual colour function is the combined effects of quantum confinement and the bio-compatible surface capping groups. The cytotoxicity study proved no cell proliferation by the nanoparticles up to the concentration of 1000 μg/mL, which is the highest concentration reported so far. Since a dosage of only 50-100μM is enough for the in vivo detection on rate, these ZnO colloids have high potential for use as the detection media for Lab-on-a-Chip devices.

Growth orientation and type of internal structures are both observed to change abruptly as a function of growth temperature in catalyst free growth of gallium nitride nanowires. In the present work, corresponding temperature-dependent changes in the growth matrix substrate that can affect the availability of nucleation sites and influence the reactivity of constituent adatom materials in catalyst-free nanowire growth are investigated. The influence of Ga vapor pressure and an abrupt change in the availability of single versus molecular adatom constituents is identified as a possible controlling parameter.

Au nanowires (AuNWs) were produced by electroless reduction of HAuCl4 in a micellar structure formed by oleylamine and investigated by means of high-resolution transmission electron microscopy (HRTEM). Micrometer long ultra-thin flexible AuNWs with 1—2 nm diameter and AuNWs with about 12 nm diameter and a few hundred nm length were produced. Their extremities show a characteristic bulging. In contradiction with previous work, the bodies of the 12 nm nanowires are defect-free along the axial direction, their extremities, however, show the presence of twin boundaries. Ultra-thin AuNWs were often found as bundles presenting lengths of few micrometers. Although they are stable in solution for months, they were found to be quite sensitive to electron beam irradiation during HRTEM experiments, with a tendency to break up into face centered cubic (fcc) Au droplets. It is proposed that the micellar configuration of oleylamine plays a fundamental role in the atomic arrangement of nanowires. Finally, we anticipate our results to be a starting point for a more realistic experimental investigation of surface effects on the mechanical properties of ultra-thin nanowires with high aspect ratio, which have been only widely exploited theoretically.

Strong polarization effects observed in III-nitride materials can invert the surface carrier type. The corresponding band bending can be used to design InGaN solar cells. Similar surface inversion was observed in the past with silicon-based Schottky-barrier solar cells, but was limited by Fermi level pinning. The formation of two-dimensional electron gas by polarization fields in III-nitrides has been reported. Using a similar idea, the growth of a thin AlN capping layer on p-InGaN has resulted in band bending, hence depletion region, under the surface that can be used separate any generated photo-carriers. Hall measurements at different depths on these structures confirm the inversion of surface carrier type. Solar cells based on this concept have resulted in an open circuit voltage of 2.15 V and short circuit current of 21.8 μA.

This paper presents molecular dynamics simulations of shear-coupled migration of tilt boundaries pinned by triple junctions in a simple model structure of columnar grains of different sizes. Simulations are for copper at 300 K. The phenomenon is of interest as a possible explanation of the Hall-Petch relationship breakdown in nano-grained polycrystals deformed at high or moderate strain rate and low-temperature.

Interaction between nitrogen-substituted graphene-like compounds and hydrogen was investigated using ab initio molecular orbital method in the aspect of hydrogen storage. We adopted coronene as a model compound for fragmented graphene-like carbon materials and compared the interaction between hydrogen and pure or N-substituted coronenes by changing nitrogen positions. Among the assumed 19 N-substituted models, polarozabilities and HOMO–LUMO gaps were compared to evaluate physisorption and chemisorption energies. As for chemisorption, two N-substituted models were selected and closely examined to reveal the dependence on both nitrogen-substitution and hydrogen-adsorption positions. Potential energy surfaces as a function of H–H bond length and H2–coronen distance showed that the barrier height for hydrogen chemisorption strongly depends on N-substitution positions. The chemisorbed products of N-substituted coronenes are stabilized or destabilized compared with the pure carbon case depending on the sites of N-substitution and H-adsorption. These results suggest that N-substitution at certain positions possibly improve hydrogen storage properties of graphene-like materials.

Thin films of tin sulfide (SnS) were deposited on TCO-coated glass substrates by pulse electrodeposition. Cyclic voltammetry showed that SnS deposition occurs in the -0.8 V to −1 V range. The films deposited using the potential pulses of -0.95V (Von ) and +0.1V (Voff ) are of orthorhombic crystal structure with lattice parameters and grain size similar to those of the thin films of orthorhombic structure obtained by chemical deposition. The optical band gap of the films was 1.3 eV. In CdS/SnS heterojunctions an open circuit voltage110 mV, short circuit current density 0.72 mA/cm2 and fill factor of 0.32 are reported here.

A 65 m vertical shaft was sunk at Dounreay in the 1950s to build a tunnel for the offshore discharge of radioactive effluent from the various nuclear facilities then under construction. In 1959, the Shaft was licensed as a disposal facility for radioactive wastes and was routinely used for the disposal of ILW until 1970. Despite the operation of a hydraulic containment scheme, some radioactivity is known to have leaked into the surrounding rocks. Detailed logging, together with mineralogical and radiochemical analysis of drillcore has revealed four distinct bedding-parallel zones of contamination. The data show that Sr-90 dominates the bulk beta/gamma contamination signal, whereas Cs-137 and Pu-248/249 are found only to be weakly mobile, leading to very low activities and distinct clustering around the Shaft. The data also suggest that all uranium seen in the geosphere is natural in origin. At the smaller scale, contamination adjacent to fracture surfaces is present within a zone of enhanced porosity created by the dissolution of carbonate cements from the Caithness flagstones during long-term rockwater interactions. Quantitative modelling of radionuclide migration, using the multiphysics computer code QPAC shows the importance of different sorption mechanisms and different mineralogical substrates in the Caithnesss flagstones in controlling radionuclide migration.

According to recent seismic observation records, there are some cases where unexpectedly large seismic motion was observed deep underground and that was larger than at the surface. The factors influencing such phenomena are assumed to be deep geological structures with topographic irregularity, velocity structure and non-linearity of subsurface layers. These factors should be taken into account in the earthquake-resistant design of a geological repository. The influence of a deep underground geological structure with topographic irregularity on ground motion has been studied and it has been confirmed that such a structure have a significant impact on ground motion and the constructive interference of waves may result in strong earthquake ground motion in the vicinity of a structural boundary deep underground.

Real time imaging of the electric field distribution in CZT at low temperature has been carried out using the Pockels electro-optical effect. CZT detectors have been observed to show degraded spectroscopic resolution at low temperature due to so-called ‘polarization’ phenomena. By mounting a CZT device in a custom optical cryostat, we have used Pockels imaging to observe the distortion of the electric field distribution in the temperature range 240K - 300K. At 240K the electric field has a severely non-uniform depth distribution, with a high field region occupying ∼10% of the depth of the device under the cathode electrode and a low field in the remainder of the device. Using an alpha particle source positioned inside the vacuum chamber we have performed simultaneous alpha particle transient current (TCT) measurements. At low temperatures the alpha particle current pulses become significantly shorter, consistent with the reduced electron drift time due to a non-uniform electric field. These data provide useful insights into the mechanisms which limit the spectroscopic performance of CZT devices at reduced temperature.

Technology variations involving Cu and Cl impurities are among the major performance influencing factors for CdS/CdTe thin film solar cells. CuCl and CdCl2 influence on the energetic diagram of impurity levels with respect to variation of deposition parameters has been investigated. A comparative analysis has been carried out by using low temperature photoluminescence (PL) studies (17-98K) of CdTe thin films in the device configuration (from CdS/CdTe inteface and CdTe sides). To study the effect of CuCl influence, as-deposited, annealed heterojunctions, with CuCl treatment of CdS have been investigated.

Si/Ge heterostructures are one of the most promising performance boosters for next generation CMOS circuits. Lattice mismatch between Si and Ge enables us to manipulate lattice strain, that is, strain engineering is possible. The strain highly alters band structures and gives rise to band splitting and/or effective mass reduction, which brings significant mobility enhancement of the carriers in the strained channel.

High mobility channels such as strained-Si and strained-Ge can be formed on strain-relaxed SiGe buffer layers called SiGe virtual substrates (VS). Since the property of the SiGe VS directly affects that of the overgrown channel layer, creating high-quality SiGe VS is highly required to obtain high performance devices. One critical problem is a very large surface roughness arising on the SiGe VS. So-called crosshatch pattern appears on the surface, irrespective of growth methods. Since strain field coming from the underlying misfit dislocation arrays is responsible for this roughness formation, it is very difficult to create a roughness-free surface.

To overcome this problem, we employed chemical mechanical planarization (CMP) for the purpose of eliminating the roughness. Since CMP is established technology for Si wafer production, it is reasonably applicable to SiGe. Adopting the similar process as Si CMP, we demonstrated that an initial roughness of larger than 10 nm was reduced considerably down to less than 1 nm.

Post-CMP cleaning is an additional issue of great importance for regrowth of device channel structures. We found that the roughness increased during post-CMP cleaning process due to laterally nonuniform etching rate of the SiGe surface. To overcome this, we optimized the cleaning procedure, especially cleaning solution, and successfully obtained very smooth surface with RMS roughness of less than 0.4 nm, the lowest value ever obtained for SiGe surfaces.

The planarized SiGe VS was applied to strained channel structures. Strained Si modulation doped structure was fabricated on the planarized SiGe VS with a Ge concentration of 30 %. The electron Hall mobility obtained from the structure with CMP was 4 times higher than the reference structure without CMP, which is a clear evidence that the roughness-related carrier scattering can be well suppressed by the planarization. Strained Ge channel modulation doped structure was also fabricated on the SiGe VS with much higher Ge concentration (65 %). Although the roughness was much larger than 10 nm due to the high Ge concentration, the surface smoothness less than 1 nm was obtained by CMP. As a result, hole mobility enhancement factor over the reference sample without CMP was found to reach as high as 8 at low temperature and 1.8 at room temperature. These results clearly indicate that CMP is very promising technology for high performance strained Si/Ge based CMOS circuit.

Block copolymers (BCPs) consist of two or more chemically distinct and incompatible polymer chains (or blocks) covalently bonded. Due to the incompatibility and connectivity constraints between the two blocks, diblock copolymers spontaneously self-assemble into microphase-separated nanoscale domains that exhibit ordered 0, 1, 2 or 3 dimensional morphologies at equilibrium. Commonly observed microdomain morphologies in bulk samples are periodic arrangements of lamellae, cylinders, or spheres. Block copolymer lithography refers to the use of these ordered structures in the form of thin films as templates for patterning through selective etching or deposition. The self-assembly and domain orientation of block copolymers on a given substrate is critical to realize block copolymer lithography as a tool for large throughput nanolithography applications. In this work, we survey the morphology of cylinder-forming block copolymers by atomic force microscopy (AFM). Three kind of block copolymers were studied: a) poly(styrene-block-ferrocenyldimethylsilane), PS-b-PFS b) poly(styrene-block-methylmethacrylate), PS-b-PMMA and c) poly(styrene-block-dimethylsiloxane) PS-b-PDMS. Block copolymers were dissolved in a neutral solvent for both blocks (toluene) in order to obtain solutions of various concentrations (1 and 1.5 wt %). From these solutions, films were prepared by spin casting on ultrananocrystalline diamond (UNCD) thin film substrates. Results indicate that PS-b-PFS exhibits chemical and morphological compatibility to the UNCD surface in terms of wetting and domain control. A systematic comparison of self-assembly of these polymers on silicon nitride substrates demonstrates that UNCD thin films would require pre-treatment to be considered as a substrate for BCP lithography.

We investigated the reaction of HfCl4 molecules with a H2O terminated Si (001)-2×1 surface using density functional theory to understand the initial stage of atomic layer deposition (ALD) of HfO2. Half monolayer of H2O molecules were adsorbed on the buckled-down Si atoms of the Si dimers of the Si (001)-2×1 surface below the dissociation temperature of H2O and were dissociated into H and OH at room temperature. This process could make uniform and well-aligned −H and −OH’s on the Si (001) substrate. The reaction of a HfCl4 molecule was more favorable with -OH than -H. The reaction of the HfCl4 molecule with the -OH generated a HCl molecule, and the remaining HfCl3 was attached to the O atom. The first reaction of the HfCl4 molecule with −OH produced 0.21 eV energy benefit. The reaction of the second HfCl4 molecule with the most adjacent −OH of the first one produced 0.28 eV energy benefit. The third and fourth molecules showed same tendency with the first and second ones. The energy differences of the fifth and sixth HfCl4 reactions were -0.01 eV, 0.06 eV, respectively. Therefore, we found that the saturation Hf coverage was approximately 5/8 of the available −OH's, which was 2.08 × 1014 Hf/cm2. The result was well-matched with the experimental study of other group.

In this study, we explore the effects of alkyl surface terminations on ZnO for inverted, planar ZnO/poly(3-hexylthiophene) (P3HT) solar cells using two different attachment chemistries. Octadecylthiol (ODT) and octadecyltriethoxysilane (OTES) molecules were used to create 18-carbon alkyl surface molecular layers on sol gel-derived ZnO surfaces. Molecular layer formation was confirmed and characterized using water contact angle measurements, infrared (IR) transmission measurements, and X-ray photoelectron spectroscopy (XPS). The performances of the ZnO/P3HT photovoltaic cells made from ODT- and OTES-functionalized ZnO were compared. The ODT-modified devices had higher efficiencies than OTES-modified devices, suggesting that differences in the attachment scheme affect the efficiency of charge transfer through the molecular layers at the treated ZnO surface.