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In this paper the optical absorption properties of n-type C60 and PTCDA, and p-type CuPc small molecule semiconductors are investigated by optical transmission and Photothermal Deflection Spectroscopy (PDS). The results show the usual absorption bands related to HOMO-LUMO transitions in the high absorption region of the transmission spectra. PDS measurements also evidences exponential absorption shoulders with different characteristic energies. In addition, broad bands in the low absorption level are observed for C60 and PTCDA thin-films. These bands have been attributed to contamination due to air exposure. In order to get deeper understanding of the degradation mechanisms single and co-evaporated thin-films have been characterized by PDS. The dependence of the optical coefficient on exposure to light and air have been studied and correlated to the structural properties of the films (as measured by X-Ray Diffraction Spectroscopy). The results show that CuPc and PTCDA are quite stable against light and air exposure, while C60 shows important changes in its absorption coefficient. The bulk heterojunctions show stability in agreement with what observed for single layers, since the absorption coefficient of CuPc:PTCDA is almost not altered after the degradation treatments, while CuPc:C60 shows changes for low energy values.
In this work, thermoelectric device was made, using a commercially available ThermoElectric Generator (TEG), in order to measure the gained power and efficiency for long-term performance. The module was subjected to sequential hot side heating at 200°C (392 0F), and cooling for 6000 cycles, in order to measure the TEG's power and EMF change. A 14% increase in the TEG’s material resistance was found, as well as a 5% reduction in the Seebeck coefficient. After the experiment, the module was disassembled and thermoelectric p- and n- legs were examined using IR spectroscopy.
We have fabricated carbon-containing nanowires by a gallium focused ion beam-induced deposition process from the precursor phenanthrene, C14H10. The electrical conductivity of the nanowires is only weakly temperature dependent below 300K, and reveals a superconducting state below Tc ˜ 7 K. We have measured the temperature dependence of the resistive upper critical field Hc2(T), and from those data, estimate the zero temperature critical field and coherence length to be 8.8 T and 6.1 nm, respectively. The Tc of this material is approximately 40% higher than that in any other FIB/direct write nanowire, such as those based on W(Ga), and thus offers the possibility of fabricating superconducting direct-write nanostructures that function at liquid helium temperature.
In the past, we have successfully designed and produced a variety of engineered spider silk-like proteins (eADF3 and eADF4) based upon the primary sequence of the natural dragline proteins ADF3 and ADF4 from the spider Araneus diadematus [1]. Genetically engineered spider silk proteins can be modified at the molecular level to optimize the biochemical and mechanical properties of the final product. Although engineered spider silk proteins can be processed into fibers using different spinning methods, our group is interested in the technical realization of a biomimetic approach.Here, we present an overview over our biomimetic fiber production process.
Large-scale two dimensional ordering of silica nanospheres on GaN substrates was fabricated using spin-coating and observed using Matlab-based Nomarski image processing, which was developed to calculate the surface coverage of 2D and 3D ordering of silica nanospheres on GaN substrates. Optimal spin coating condition and SDS concentration were investigated with Nomarski image processing and an SEM. The details on spin coating process parameters or SDS concentration vs. surface coverage of silica nanospheres on GaN substrate are discussed, along with a theoretical exploration of the effects of nanosphere patterning on photonic crystals fabricated using this method.
We have successfully investigated degradation-induced variations in electronic band-gap states in the emissive region of the Alq3-based OLEDs by a deep-level optical spectroscopy technique. Through the intrinsic degradation, both deep-level traps and near-band-edge transitions in the Alq3 emissive zone are found to be red-shifted significantly towards their corresponding bulk levels of the Alq3 single layer. These variations in the interfacial electronic states are probably induced by the intrinsic degradation and indicate that initial molecular structures characteristic of the Alq3 emissive zone are transformed into the bulk-like relaxed ones through the degradation.
Ripple formation and smoothing of pre-patterned fused silica surfaces by low-energy ion beam erosion have been investigated. As pre-pattern ripple surfaces produced by low-energy Ar+ ion beam erosion were used. In addition to the enhanced ripple formation on the pre-patterned surfaces also the smoothing characteristics of surface is changed. Due to the anisotropic surface roughness of the ripple pattern the irradiation direction with respect to the pre-pattern becomes important. It is suggested that all of these effects are related to surface gradient dependent sputtering and therefore it is an important mechanisms also in the low-energy ion beam erosion of fused silica surfaces.
In this work, results are presented regarding the characterization of nanostructured Fe matrix composites reinforced with fullerene. The fullerene is a mix of 15 wt.%C60, 5 wt.%C70 and 80 wt.% soot that is the product of the primary synthesis of C60. The composite has been produced by means of mechanical alloying and sintered by Spark Plasma Sintering (SPS). The characterization methods include XRD, SEM and TEM. The C60 and C70 withstand mechanical alloying, SPS, and thermomechanical processing and act as a control agent during mechanical alloying. The results show that the mechanically alloyed and SPS product is a nanostructured composite. A larger amount of C60 is found in the sintered composite than in the original fullerene mix, which is attributed to an in-situ synthesis of C60 during the SPS process. The synthesis of C60 is presumably assisted by the catalytic nature of Fe and the electric field generated during the SPS process. In order to study the effect of high temperature, high strain, high heating and cooling rates on C60, the composite is subjected to a thermomechanical processing; demonstrating that some of the C60 resists the above described environment and some of it partially transforms into diamond.
InGaP layers grown on non-polar and polar GaAs substrate faces are investigated by Raman spectroscopy, microphotoluminescence and cathodoluminescence. The growth on polar faces benefits disorder respect to the layers grown on non polar (001) faces. It is shown that both (111)Ga and (111)As faces result in disordered InGaP layers. However, the layers grown on (111)As faces present inhomogeneous composition. The layers grown on (111)Ga faces present homogeneous composition close to lattice matching and are almost disordered.
Atomic Layer Deposition is used to deposit HfO2 and TiO2 films on GaAs (100) native oxides and etched surfaces. For the deposition of HfO2 films two different but similar ALD chemistries are used: i) tetrakis dimethyl amido hafnium (TDMAHf) and H2O at 275°C and ii) tetrakis ethylmethyl amido hafnium (TEMAHf) and H2O at 250°C. TiO2 films are deposited from tetrakis dimethyl amido titanium (TDMATi) and H2O at 200°C. Rutherford Back Scattering shows linear film growth for all processes. The film/substrate interface is examined using x-ray Photoelectron Spectroscopy and confirms the presence of an “interfacial cleaning” mechanism.
Solution phase triangular silver nanoplate (TSNP) ensembles are herein presented as tunable, highly sensitive, LSPR sensors with excellent potential for versatile amply responsive biosensing applications. The recorded LSPR refractive index sensitivities for the highest aspect ratio TSNPs examined are amongst the highest reported to date for various other nanostructures. Calculations demonstrate that sensitivities of the TSNP sols, as high as the theoretical upper limit, are achievable by tuning the aspect ratio parameter, without any significant diminution observed due to ensemble averaging. Theoretical studies identify the aspect ratio of the nanoplates as a key parameter in controlling the LSPR sensitivity of the TSNPs.
Since 1998, Dow has been actively developing and applying high throughput research (HTR) methodologies to increase the speed to market and the probability of successful product introductions. Initially Dow implemented this approach in the area of homogeneous catalysis. Based upon the success in this area, high throughput methods have been expanded into other research areas such as waterborne coatings. Paint formulations offer an excellent opportunity to use the strengths of high throughput research to understand how complex interactions between many components affect final properties. High throughput tools enable the rapid and reproducible development of paints, preparation of coating on substrates, and evaluation of performance. Rapid formulation and testing allows the interactions between formulation variables to be investigated in much more depth and breadth than has been possible in the past. Finally, statistical anaylsis and data mining tools can be used to optimize a desired balance of properties within customer defined constraints. This paper presents an example of using Dow's HTR coatings workflow to improve properties for low VOC / low odor architectural coatings.
The wide band gap semiconductor ZnO is well known for its multifunctionality in the form of ferromagnetism (FM), piezoelectricity, and magneto optics. ZnO has been found to grow with intrinsic oxygen deficiencies which in turn are believed to give ferromagnetism and high conductivity in this material. Doping Zn2+ sites by V5+ ions creates a mixed valency as well as strain in the original ZnO hexagonal structure because of the reduced ionic size of vanadium. The mixed valency creates charge polarity between Zn-O and V-O bonds. This charge polarity and the rotation of the nonlinear V-O bonds with respect to Zn-O bonds under electric field have been shown to produce ferroelectricity. Furthermore, Mn doping of ZnO has also shown enhancement in ferromagnetic properties in ZnO. For this material to be a viable ferromagnetic material the magnetic properties should not be from segregated phases. In the present study we have grown undoped, Mn, and V doped ZnO thin films using pulsed laser deposition (PLD). ZnO target with 2% atomic Mn doping and a target with 0.5% atomic V doping were prepared by solid state reactions and sintering. Films were grown both epitaxially on sapphire substrates and in polycrystalline form on silicon substrates. Magnetization measurements by the PPMS showed M vs. H hysteresis loops with saturation for all ZnO: Mn films. V doped films showed high saturation polarization for film deposited at high pressures. We have also fabricated epitaxial bilayers of ZnO:V/ZnO:Mn on sapphire substrates. Ferroelectric and ferromagnetic properties of these heterostructures are presented.
Some crystals doped with radionuclides glow in the dark. Such materials are prospective for certain industrial scale applications. Durable self-glowing crystalline solids, which were initially suggested for development of actinide waste forms, are considered as advanced materials. Well-known durable actinide host phases, such as zircon, xenotime, and monazite are main focus of current research. Single crystal samples of these host phases doped with 239Pu, 238Pu, 241Am and 237Np have been grown by flux methods. It is demonstrated that incorporation of small amounts of non-radioactive elements such as Eu, In and Tb increases the self-glowing intensity. The optimal content of such luminescence ions supporting intensive glowing of 238Pu-doped zircon and xenotime has, at first, been identified by cathodoluminescence study of non-radioactive samples. Subsequently, the results of this study were used to grow intensively glowing crystals of zircon and xenotime doped with 0.01 wt. % and 0.1 wt.% 238Pu, respectively.
The effect of intensive electron radiation on viscous flow in silicate glasses is analysed and shown that it can result in a many orders of magnitude decrease of viscosity and stepwise decrease of activation energy of flow. Fluidisation or quasi-melting of glasses on intensive electron irradiation is caused by bond breaking via the radiation-chemical reaction ≡Si-O-Si≡ + e− Si-O + Si + (e−)′ which weakens the silicate glass network and leads tofive-fold coordination of oxygens around the silicon. An explicit equation of viscosity wasobtained for irradiated glasses as well as an equation for glass transition temperature. Theassessments of temperature increase by electron radiation show that radiation-inducedfluidisation of glasses can occur at minimal thermal effects. Radiation-induced fluidisation ofglasses can result in nanoscale patterning effects caused by surface tension forces. Changes inthe viscous flow behaviour are also important in conditions of long-term irradiation for glassesused in nuclear installations as well as for nuclear waste glasses.
A dry etch recipe was developed for porous nanostructured TiO2 thin films fabricated using glancing angle deposition (GLAD). Unlike wet chemical etches, the technique reported here preserves the vertical post nanostructure, eliminating clumping. A highly controllable and easily tailored reactive ion etching process with CF4 alone, or combined with O2, was investigated. The anisotropic etch modifies the morphology and density of standard GLAD films, which is of interest for sensing applications.
Silica nanoparticles with metallic nanoclusters are of great interest in many applications from bio imaging to optical devices. The nanometric size of metallic particles induces specific absorption properties due to surface plasmon resonance. This absorption mainly depends on the morphology of the nanoparticles. If the encapsulation of metallic nanoparticles into a silica shell is now well developed, there is a great interest on the synthesis of either silica nanoparticles covered by metallic nanoparticles or silica cores with metallic shells. Two main ways are described in the literature to bind metallic nanoparticles onto the silica nanoparticles. The first way consists on the mixing of a metallic colloidal sol with another sol containing silica nanoparticles bringing at their surface the suitable chemical functions, able to properly interact with the metal nanoparticles. The second way consists on the use of a reducing agent to reduce the metallic ions introduced successively into a suspension of silica nanoparticles. Herein is proposed an original third method based on a double surface functionalization of the silica nanoparticles. This method is actually based on an in-situ reduction of metallic ions by two chemical function (amino and thiol) previously grafted onto the surface of the silica nanoparticles. The silica nanoparticles are synthesized by a reverse micro-emulsion sol-gel process. This synthesis gives monodispersed silica nanoparticles of 40 nm diameter. The surface functionalization of the silica nanoparticles is performed by sol-gel reactions within the micro-emulsion, using two silane-coupling agents owning either a thiol function or a diamino function.The functionalized silica shell increases the chemical activity of the surface of the nanoparticles. But the capability of this functionalized surface to reduce metallic ions depends mainly on the chemical function used. Two examples are given in this study: the diamino functions, which reduce the copper ions, and the combination of the diamino and the thiol functions in a silver nitrate solutionwhich induces the growth of small silver nanoparticles (4-5 nm) on the silica nanoparticles’ surface.
We applied ab initio calculation and an object kinetic Monte Carlo modeling to the study of He-vacancy cluster nucleation under irradiation in bcc and fcc Fe, which are surrogate materials for ferritic/martensitic and austenitic steels, respectively. The ab initio calculations provided parameters for the object kinetic Monte Carlo model, such as the migration energies of point defects and the dissociation energies of He and vacancy to He-vacancy clusters. We specially focused on the simulation of high He/dpa irradiation such as He-implantation into the materials and tracked the nucleation of clusters and the fate of point defects such as SIAs, vacancies, and He atoms. We found no major difference of He-vacancy cluster nucleation between bcc and fcc Fe when we ignore the intracascade clustering even if the migration energies of point defects are significantly different between the two crystals.
Group III-V semiconductor materials are being studied as potential replacements for conventional CMOS technology due to their better electron transport properties. However, the excess scattering of carriers in MOSFET channel due to high-k gate oxide interface significantly depreciates the benefits of III-V high-mobility channel materials. We present results on Hall electron mobility of buried QW structures influenced by remote scattering due to InGaAs/HfO2 interface. Mobility in In0.77Ga0.23As QWs degraded from 12000 to 1200 cm2/V-s and the mobility vs. temperature slope changed from T-1.2 to almost T+1.0 in 77-300 K range when the barrier thickness is reduced from 50 to 0 nm. This mobility change is attributed to remote Coulomb scattering due to charges and dipoles at semiconductor/oxide interface. Elimination of the InGaAs/HfO2 interface via introduction of SiOx interface layer formed by oxidation of thin a-Si passivation layer was found to improve the channel mobility. The mobility vs. sheet carrier density shows the maximum close to 2×1012 cm-2.
The incoherent transport model based on electron-phonon interaction was introduced for calculating the current-voltage characteristics of the nanowire conductor. The current-voltage characteristics of silicon nanowire calculated based on this model was discussed.The charge transport was described by the rate equation containing the coherent (tunneling) and incoherent (energy dissipation) rates, and the incoherent rate was calculated from the Hamiltonian in which the electron-phonon interaction was incorporated. The coherent transition corresponds to the electronic transition between electrode states and channel states without any energy dissipation. On the other hand, the incoherent transition corresponds to the electronic transition between electrode states and channel states where the energy difference of those two states means a thermal dissipation. Therefore, in order to carry out the calculation by the rate equation, the density of states (DOSs) of the carriers in electrode and the channel and the DOS of the phonon in the channel are needed.The current-voltage characteristics were calculated by using the DOS of n-type semiconductor for the electrode and by using intrinsic semiconductor DOS for the channel. In addition, the calculation was performed by using the DOS of the silicon nanowire phonon.