We describe a facile and direct method for the functionalization of single-walled carbon nanotubes with 4’-substituted phenyls and biphenyls. By means of Raman spectroscopy and thermogravimetric analysis we demonstrate that a simple protocol of a direct chemical grafting in acetonitrile solution of the corresponding diazonium salts at room temperature results in a formation of stable aryl monolayers on carbon nanotubes.

We develop Si-based nano-photonic devices for the control of light at the nano-scales. We design high quality (Q) factor photonic crystal nanobeam cavities for a variety of Si compatible materials with low index, such as silicon rich oxide and silicon nitride, all with Q > 9,000 and small mode volumes. We apply these cavity designs to active materials such as Sinanocrystal doped silicon oxide and Er doped silicon nitride. By placing emitters in these cavities, we demonstrate that the cavity enhances emission processes. We show that the free carrier absorption process is greatly enhanced in the nanobeam cavities at both room and cryogenic temperatures. In addition, we demonstrate that nanobeam cavities made of Er-doped amorphous silicon nitride have enhanced absorption and gain characteristics compared to earlier designs that included silicon in the cavity. Because of the reduced losses, we observe linewidth narrowing and material transparency at both room temperature and cryogenic temperatures.

Epitaxial ZnO layers heavily doped with Ga (GZO) were grown at 400 °C under metaland oxygen-rich conditions in terms of metal-to-reactive oxygen ratio by plasma-assisted molecular beam epitaxy (MBE). Several atomic force microscopy (AFM) techniques were used to characterize the surface morphology and electrical properties of these GZO films in ambient conditions. Local I-V spectra indicate that layers grown under both O-rich and metal-rich conditions are highly resistive until a relatively high voltage sweep (±12 V) is used. After removal of an insulating surface layer, conduction is possible at lower voltages, but eventually the film resistivity increases and it again becomes insulating. In addition to local I-V spectra, local charge injection and subsequent surface potential measurements were used to probe surface charging characteristics. For charge injection experiments, a reverse-bias voltage is applied to the sample while scanning in contact mode with a metallized tip. The resultant change in surface potential due to trapped charge is subsequently observed using scanning Kelvin probe microscopy (SKPM). The layers deposited in a metal-rich environment demonstrate the expected behavior, but the O-rich layers show anomalous negative and positive charging. Finally, surface photovoltage (SPV) measurements using above-bandgap UV illumination were performed. The GZO layers produce SPV values of 0.4 to 0.5 eV, where the films deposited in an O-rich environment have slightly higher SPV values and faster restoration.

We have recently presented a novel method for a complete thermoelectric characterization [J. de Boor, V. Schmidt. Adv. Mater. 22:4303, (2010)]. This method is based on the well-known electrical van der Pauw method and allows measurement of the electrical and thermal conductivity, the Seebeck coefficient and the thermoelectric figure of merit. After a short review of this method we will discuss the systematic measurement errors of the method. It turns out that radiative heat loss can affect the thermal conductivity measurement significantly. We will give a simple estimation for the relative error due to radiation losses and discuss error minimizing strategies.

ZnO/Au/ZnO (ZAZ) electrodes grown on flexible PEN substrates were evaluated as transparent electrodes for organic light-emitting devices (OLEDs). OLEDs fabricated with the ZAZ electrodes showed reduced leakage in contrast to control OLEDs on ITO and reduced ohmic losses at high current densities. At a luminance of 25000 cd/m2, the lum/W efficiency of the ZAZ electrode based device was 5% greater than for the device on ITO. The ZAZ electrodes also allow for a broader spectral output in the green wavelength region of peak photopic sensitivity compared to ITO. The results have implications for electrode choice in display technology.

Organic thin-film transistors (OTFTs) using cross-linked olefin polymer as a gate insulator were fabricated on a plastic film. An olefin polymer layer was formed by spin-coating and baking at temperatures below 150°C. Pentacene was used as an organic semiconductor layer. The fabricated OTFTs with a short 5-μm-long channel showed a mobility of 0.1-0.2 cm2/Vs and a current ON/OFF ratio of 107. These OTFTs also exhibited good stable performance in the atmosphere. On the basis of the results, we fabricated a 5 inches OTFT-driven flexible active-matrix organic light emitting diode (AMOLED) display. The gate insulator, some metal wirings and electrodes on the OTFT backplane were formed on the plastic film by photolithography. After fabrication of the OTFT backplane, OLED layers were formed by vacuum deposition through a shadow-mask. Clear color moving images were observed on the flexible display even when it was bent.

The results obtained by direct nano-patterning demonstrate the potential of the SPM-based techniques that include surface scratching to create 3D nanostructures. Such techniques became known as tribo-nanolithography and have prospects of being successfully implemented in the future nanofabrication industry. An important obstacle to this, however, is the effect of wear at the nanometer scale which is critical to the stability of tribo-nanolithoraphic processes. Such stability is achievable via in-depth theoretical and experimental studies of friction at the nanoscale along with the development of pioneering equipment. Our work presents the results of experimental fabrication of nanostructures formed by nanoscratching with the use of the multifunctional scanning tunneling microscopy previously developed by the authors. The authors attempted scratching the silicon surface by using a boron-doped diamond tip. This operation was undertaken in the same direction sequentially with the tip sliding a side of the groove by one of the tip’s facets and the consequent surface scanning. Although not being applicable to non-conductive surfaces, the proposed technique has significant advantages. One advantage is related to the high stiffness of the tunneling probe as compared to the stiffness of the AFM cantilever. High stiffness and perpendicularity of the tip to the surface during surface processing eliminates bending beam effects on the typical AFM and ensures machining effectiveness. Purposely synthesized boron-doped single-crystal diamonds were used as a tip material. The results of experimental fabrication of nanostructures formed by nanoscratching with the use of the multifunctional scanning probe are demonstrated and discussed.

Although Helium Ion Microscopy (HIM) was introduced only a few years ago, many new application fields are budding. The connecting factor between these novel applications is the unique interaction of the primary helium ion beam with the sample material at and just below its surface. In particular, the HIM secondary electron (SE) signal stems from an area that is very well localized around the point of incidence of the primary beam. This makes the HIM well-suited for both high-resolution imaging as well as high resolution nanofabrication. Another advantage in nanofabrication is the low ion backscattering fraction, leading to a weak proximity effect. The lack of a quantitative materials analysis mode (like EDX in Scanning Electron Microscopy, SEM) and a relatively low beam current as compared to the SEM and the Gallium Focused Ion Beam are the present drawbacks of the HIM.

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.