Adsorption and chemistry of tripropylphosphate (TPP) in mesoporous NaX zeolite, which was templated by cationic templated polymer (polydiallyldimethylammonium chloride, PDADMAC) with two different length chains, was investigated. The structural properties of the zeolites were characterized by X-ray diffraction (XRD) and nitrogen adsorption analysis. The chemical activities of different zeolites toward the decomposition of TPP were determined with solid state 31P NMR spectra. After exposure of zeolites to TPP was sufficient and equilibrium was reached, a stoichiometric amount of water was also adsorbed and hydrolysis was observed. The TPP decomposition yields in different NaX zeolites were compared.

We have developed a prototype spectroscopic ellipsometer for imaging/mapping purposes requiring only one measurement cycle (one rotation period of a polarizer or analyzer) for the acquisition of a two-dimensional array of data points. Our new measurement technique serves as a novel form of imaging ellipsometry, using a divergent (uncollimated, diffuse) source system and a detection system consisting of an angle-of-incidence-sensitive pinhole camera. By incorporating broad-band sources and wavelength dispersion optics, the instrument provides continuous high-resolution spectra along a line image of the sample surface. As a result, information on multilayer photovoltaics stacks can be obtained over large areas (several dm2) at high speed. The technique can be expanded to even larger areas by scaling-up the optical geometry. The spatial resolution of the line image is limited by the minimum resolved-angle as determined by the detection system. Small-aperture polarizers (25 mm diameter) are incorporated into the instrument, which reduces its cost. Demonstration mapping measurements have been performed ex situ on a multilayer sample deposited on a polymer substrate, including an intentionally graded 80-350 nm thick hydrogenated amorphous silicon (a-Si:H) layer and an intended uniform 400-500 nm thick transparent conducting ZnO:Al layer, both on opaque silver. Alternative commercial instruments for ex situ SE mapping must translate the sample in two dimensions. Even a 15 x 15 cm2 sample requires > 200 measurements with cm-resolution and at least 15 min. By collecting ex situ data in parallel along one dimension through imaging, the divergent-beam system can measure with similar spatial resolution in < 2 min. In situ measurements on both roll-to-roll polymer and rigid glass will be possible in the future.

Entrapping hydrogen molecules within the nanopores of solid adsorbents serves as a unique alternative for on-board storing of hydrogen for transportation purposes. The key advantage of the physisorption process for hydrogen storage is the higher density values achieved with the adsorbed gas, compared to that of the compressed phase, translating into higher storage capacities at lower pressures. The necessary condition for effective adsorption is the presence of narrow micropores of < 2 nm in width which provide the most suitable environment of hydrogen adsorption. Despite numerous theoretical calculations or indirect experimental estimations, there has not been a direct experimental measurement of the density of adsorbed hydrogen as a function of pressure and/or pore size. In the present study, we report on the use of in-situ small angle neutron scattering (SANS) to study the phase behavior of hydrogen confined in narrow micropores. We provide for the first time direct experimental measurements of the effect of pore size and pressure on hydrogen adsorbed on a polyfurfuryl alcohol-derived activated carbon (PFAC), at room temperature and pressures up to 207 bar. SANS studies were carried out at the General-Purpose Small-Angle Neutron Scattering spectrometer of the High Flux Isotope Reactor at Oak Ridge National Laboratory. The measurements covered the Q-range from 0.01 to 0.8 Å-1, covering the pores in the range of 9 to 34 Å of the PFAC material. Initial results suggest that the density of adsorbed hydrogen is higher than the density of bulk hydrogen gas and increases with decreasing pore size.

Molybdenum, being a strong β stabilizer, is an important alloying element in TiAl alloys, since a significant volume fraction of the disordered bcc β-phase at elevated temperatures improves the processing characteristics during hot-working. Unfortunately, the effect of Mo on the individual phases and their transition temperatures is not completely known but is necessary for designing engineering applications. In this paper, sections of the Ti-Al-Mo ternary phase diagram derived from thermodynamic calculations as well as experimental data are presented. Further, the phase transition temperatures given by the phase diagrams are compared with results from isothermal heat treatment studies, differential scanning calorimetry measurements and in-situ high-temperature diffraction experiments. Combining all of these results, a revised phase diagram is proposed.

The intrinsic channel structure and low volume work makes olivines phosphates (LiMPO4) versatile for Li uptake and release. The understanding of Li cation diffusion/transport mechanisms inside olivines are crucial aspects, which we address using advanced molecular dynamics simulations. Activation energies calculated from DFT concluded 1D diffusion within channels as also indicated by neutron diffraction direct imaging techniques. On explicitly including temperature we find that - besides main conduction paths along the easy channels - distinct, less frequent but relevant diffusion paths exist. We point out that capacity and diffusion/conduction issues must be understood in a much more detail-rich framework, under realistic simulation conditions within finite temperature simulations. For evaluating electrical conductivity, we use advanced DFT methods to correctly capture the insulating states of the charged and discharged olivine materials. Based on the Kubo formalism, reliable conductivity/resistivity curves can be calculated for comparison with experiments and for anticipating properties.

Back surface passivation is one of the major challenges in the backside illuminated sensor technology. Ion implantation followed by non-melt pulsed Laser Thermal Annealing (LTA) has been identified as a promising candidate to address this issue. In this work, a shallow B-doped layer is implanted at the backside, further activated using LTA in the non-melt regime. LTA process effectiveness in terms of crystal damage recovery as well as dopant diffusion and activation is studied through room-temperature photoluminescence, Secondary Ion Mass Spectroscopy and four-point probe sheet resistance. These studies demonstrate that non-melt LTA with multiple pulses induces high activation without visible diffusion with an effective curing of the implantation-induced crystalline defects. This is made possible thanks to a submicrosecond process timescale coupled to a reasonable number of shots as shown by thermal simulations and simple diffusion estimations.

Ultracapacitors are promising candidate for alternative energy storage applications since they can store and deliver energy at relatively high rates. In this work, we integrated large area CVD graphene with multi-walled carbon nanotubes (MWNTs) to fabricate highly conductive, large surface-area composite thin films used as electrodes in ultracapacitors. Uniform, large area graphene layers were produced by CVD on copper foils and were chemically modified. Chemically shortened MWNTs, ranging in length of 200~500 nm, were deposited by dropping on graphene layers. Graphene/MWNT composite films with different thicknesses were obtained. The surface morphology was investigated by SEM. The results demonstrated relatively dense and homogeneous net nanostructure. The measurements of cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy (EIS) are conducted to determine its performance of graphene/MWNT film structures.

Nanofluids, consisting of nanometric particles suspended in a base fluid, have become a new alternative for improving heat management technology. Silver, which is known to exhibit pretty high electrical and thermal conductivity among metals, has been selected for this research. At present, we are focused on the study of the size- and shape-controlled synthesis conditions of silver nanocrystals in polyol media. Control of crystal size and shape at the nanoscale were achieved by suitable selection of the synthesis conditions and the presence of habit-controlling agents like chloride ions. Silver nanostructures (faceted crystals, wires, rods) were remarkable monodisperse in size and their dimension could be controlled in the 30-50nm range (particles) and 24-127nm in thickness for rods or wires.

Silicon nanocrystals (Si-NCs) are of significant research interest owing to their quantum confined photoluminescent (PL) properties and biological inertness. A promising application of these NCs is as the luminescent component in multifunctional biomedical technologies. In this report, we demonstrate the encapsulation of alkyl terminated Si-NCs within a mesoporous silica shell as a multifunctional imaging and drug delivery architecture. The Si-NC concentration was found to critically impact the nanoshell morphology. The impact of the encapsulation process on the Si-NC PL was studied, showing a blue-shift and decrease in intensity attributed to the oxidation of Si-NCs under basic conditions.

The electrical characteristics of high quality single crystal boron-doped diamond are studied. Samples are synthesized in a high power-density microwave plasma-assisted chemical vapor deposition (CVD) reactor at a pressure of 160 Torr. The boron-doped diamond films are grown using diborane in the feedgas at concentrations of 0-0.25 ppm, and are compared to those grown previously with 1-10 ppm. The boron acceptor concentration is investigated using infrared absorption, and compared to the boron concentration obtained by SIMS. A four point probe is used to study the conductivity. The temperature dependent conductivity is analyzed to determine the boron dopant activation energy.

Current experimental configurations for MW PECVD diamond growth do not allow simple up-scaling towards large areas, which is essential for microelectronic industries and other applications. Another important issue is the reduction of the substrate temperature during diamond growth to enhance the compatibility with wafer processing technologies. Such advantages are provided by MW-linear antenna (LA) plasma applicators, allowing a scalable concept for diamond growing plasmas. In the present work we introduce a novel construction of LA MW applicators designed for nanodiamond growth by using plasmas ranging from continuous wave (CW) to high repetition rates pulsed modes (up to 20 kHz) which advantages are discussed in detail.

Low temperature deposited Interdigitated All Back Contact a-Si:H/c-Si Heterojunction (IBC-SHJ) devices are a promising approach for high efficiency, low cost solar cells on thin wafers. Thin intrinsic a-Si:H films (i-a-Si:H) deposited below 300°C provide excellent surface passivation and high Voc. However, the optical properties of a-Si:H layers and electronic band alignment at the heterointerface are critical to reduce optical losses and transport barriers in IBC-SHJ solar cells. At the front illumination surface, a wide band gap (Eg) i-a-Si:H layer with good passivation is desirable for high Voc and Jsc while at the rear surface a narrower Eg i-a-Si:H layer with good passivation is required for higher FF and Voc as seen in 2D numerical simulation. Various substrate temperature, H2/SiH4 dilution ratio and plasma power conditions were explored to obtain i-a-Si:H with good passivation and desired Eg. All the deposited films are characterized by Variable Angle Spectroscopic Ellipsometry (VASE) to determine Eg and thickness and by Fourier Transform Infrared spectroscopy (FTIR) to estimate hydrogen content and microstructure factor. Passivation qualities are examined by quasi-steady state photoconductance (QSS-PC) measurement. The i-layer Eg, was varied in the range from ~1.65eV to 1.91eV with lifetime >1 ms. Lowest Eg is obtained just prior to the structure transition from amorphous to epitaxial-like growth. The FF of IBC-SHJ devices improved from 20% to 70% as Eg of the a-Si:H rear passivation layer decreased from 1.78 to 1.65 eV.

In this study an electroforming free device structure based on 25nm thin TiO2 thin films is presented. The TiO2 films are deposited on CMOS compatible W plugs. The use of 5nm thick interlayers of Ti and W between the TiO2 and the Pt electrode turn out to be the key step to achieve the forming free performance. In these Pt/Ti/TiO2/W or Pt/W/TiO2/W samples the switching polarity can be repeatedly changed from “eightwise” to “counter-eightwise” in one device by a proper adjustment of the I-V measurement conditions. The most simple explanation for this observation is that the switching interface can be flipped back and forth from the bottom to the top electrode.

The reactivity of silicon nanocrystals (Si-NCs) in near-UV photochemical hydrosilylation was evaluated as a function of size. Results show that Si-NCs with photoluminescence (PL) in the visible spectral region react faster than Si-NCs with near-IR PL. Fourier-transform infrared (FTIR) spectroscopy suggests this difference in reactivity is due to quantum size effects in the exciton-mediated mechanism proposed for this reaction. We have carried out a detailed comparison of Si-NC reactivity in photochemical and thermal hydrosilylation and determined the conditions under which Si-NCs may be size-selected based on their reactivity.

In future technology nodes, 22nm and below, carbon nanotubes (CNTs) may provide a viable alternative to Cu as an interconnect material. CNTs exhibit a current carrying capacity (up to 109 A/cm2), whilst also providing a significantly higher thermal conductivity (SWCNT ~ 5000 WmK) over Copper (106 A/cm2 and ~400WmK). However, exploiting such properties of CNTs in small vias is a challenging endeavor. In reality, to outperform Cu in terms of a reduction in via resistance alone, densities in the order of 1013 CNTs/cm2 are required. At present, conventional thermal CVD of carbon nanotubes is carried out at temperatures far in excess of CMOS temperature limits (400C). Furthermore, high density CNT bundles are most commonly grown on insulating supports such as Al2O3 and SiO2 as they can effectively stabilize metallic nanoparticles at elevated temperatures but this limits their application in electronic devices. To circumvent these obstacles we employ a remote microwave plasma to grow high density CNTs at a temperature of 400C on conductive underlayers such as TiN. We identify some critical factors important for high-quality CNTs at low temperatures such as control over the catalyst to underlayer interaction and plasma growth environment while presenting a fully CMOS compatible carbon nanotube synthesis approach

A novel setup for Raman measurements under small angles of incidence during the parallel plate plasma enhanced chemical vapor deposition of μc-Si:H films is described. The possible influence of disturbances introduced by the setup on growing films is studied. The substrate heating by the probe beam is investigated and reduced as far as possible. It is shown that with optimized experimental parameters the influence of the in-situ measurements on a growing film can be neglected. With optimized settings, in-situ Raman measurements on the intrinsic layer of a microcrystalline silicon solar cell are carried out with a time resolution of about 40 s corresponding to 20 nm of deposited material during each measurement.

The kinetics of slow aggregation of monodisperse TiO2 nanocrystals in the acidic hydrosols at room temperature was studied for months by turbidimetry. The dependence of the initial rate of aggregation on the pH was calculated. The comparison of results obtained by turbidimetry and small angle X-ray scattering permits to suppose that very loose aggregates form at the low pH in HCl solution. The dependencies obtained in this work for room temperature can be taken into consideration at the tuning of TiO2 nanoparticles morphology through thermal treatment of hydrosols.

Bone fractures are one of the most common bone complications. In more severe cases, bone fixation is accomplished using titanium (Ti) implant materials. Unfortunately, the need for revision surgery often arises due to implant loosening and/or deterioration of the implant/bone interface. Rosette nanotubes (RNTs) are a class of self-assembled organic materials obtained through the self-assembly of a guanine-cytosine hybrid base (G∧C motif). These organic materials have been found to increase osteoblast (bone forming cells) adhesion and hydroxyapatite deposition (bone regeneration) on titanium implants as well as on engineered hydrogels. In order to increase the bioactivity of RNTs to enhance bone cell function on Ti implants, two RNT motifs functionalized with different bioactive deca-peptides (A, B) chosen from the knuckle region of bone morphogenic proteins-7 (BMP-7) were synthesized. Their self-assembly process was investigated in water using UV-Vis and SEM techniques.

This study reports on the structural and magnetic characterizations of free-standing bismuth ferrite, BiFeO3, nanoparticles synthesized in polyol medium. Fine tuning of the ferrite magnetic properties was achieved by adding an excess bismuth species or doping with cobalt ions, coupled with thermal annealing. Crystalline Bi1-yCoyFeO3 powders (where ‘y’ ranges from 0.00 to 0.10) were produced after annealing the precursors for one hour at 700οC. The average crystallite size was calculated to be approximately 22 nm. We found that the synthesis under stoichiometric excess of Bi species (up to 10 at.%) promoted a more complete crystallization of the material, i.e., no precursor phases remained. Furthermore, both the saturation magnetization and the coercivity of the synthesized powders were strongly influenced by the concentration of Co. They increased from 0.13 emu/g and 19 Oe to 3.5 emu/g and 1183 Oe for pure BiFeO3 and 10 at.% Co-doped BiFeO3, respectively.