Polyacetal is a resin which has excellent property. However, polyacetal has a poor adherence property using adhesive material. Therefore, for the improvement of the adhesive strength, simultaneous surface treatments of polyacetal by irradiation of vacuum ultra-violet (VUV) light and deposition of nanometer-sized particles using laser ablation with C, Si and Ti targets were carried out. The surface treatments were carried out with different wavelengths, energies, processing times and substrate locations from normal direction of targets. The targets were irradiated with a pulsed laser from Nd-YAG laser. After surface treatments, tensile test pieces of polyacetal were bonded by epoxide-based adhesive. And, longitudinal shear strengths were measured. As a result, after surface treatment of polyacetal using C target, the highest shear bond strength which is approximately 8 times larger than that of untreated polyacetal sample was measured (5.6 MPa). It was found that increasing functional groups and increasing surface roughness are affecting improvement of the adhesive strength. The improvement of the adhesive strength is also caused by the new-creation of the dangling-bonds on the polymer surface by VUV irradiation and preservation of each dangling-bonds from re-bonding each other by a separation effect of deposited nanometer-sized particles. This method can be expected for new applications of polymers.

Resistively switching TiO2 thin films show a multitude of resistance states, which are achieved during the programming and erasing of a memory cell. These resistance states depend on the applied voltage and the allowed current. Additionally, the operation time has a relevant influence on the adjusted resistance. This parameterization points out a potential application in future multi-level cell memory systems, but also determines the persistence of the non-volatile nature and provides an additional insight into the physics of the resistance switching. Our devices consist of metal-insulator-metal stacks made of Pt/TiO2/Ti/Pt, which are built up in crosspoint junctions. The maximum programming current and the maximum erase voltage amplitude were used to tune in the low resistance and high resistance state, respectively, in combination with the operation time. The corresponding dependencies were determined by quasi-static voltage sweeps, pulse bursts and single pulses of up to 4 V and down to 10 ns.

Thermoelectric generators (TEG) are capable of transforming waste heat directly into electric power. With higher temperatures the yield of the devices rises which makes high-temperature contact materials important. The formation of titanium disilicide (TiSi2) and its properties were analyzed and optimized for the use in TEG. Depending on a direct or an indirect transformation into the C54 crystal structure the process forms a layer with a resistivity of 20-22 μΩcm. Process gases influence the resistivity and result in difference of 20 %. The growing rate of TiSi2on silicon dioxide was determined; it shows a strong dependence on the used atmosphere and temperature. A maximum overgrowing length of 30 μm was found.

The Laser induced oxidation process of bismuth was investigated using Raman spectroscopy. Upon laser irradiation (λ = 532 nm) pure Bismuth was transformed gradually into Bi2O3. Raman spectra of the samples showed the characteristics peaks for pure Bi located at 71 cm-1 and 96 cm-1. The oxidation process was monitored by Raman spectra with four additional bands located at about 127 cm-1, 241 cm-1, 313 cm-1 and 455 cm-1. Maintaining constant the exposure time of irradiation, the intensity of these bands depended on laser irradiation power. The presence of Bi2O3 in the sample was confirmed through by energy dispersion spectroscopy (EDS).

Nanopowders of cobalt iron oxide (CoFe2O4) were successfully fabricated by the co-precipitation method followed by a technique to prevent particle agglomeration. Particle sizes were in the range of 24 to 44 nm. The size of cobalt iron oxide particles decreases with increasing the concentration of the precipitation agent. The crystal structure was confirmed by X-ray diffraction (XRD), the chemical composition by energy dispersive spectroscopy (EDS), and phase changes by thermogravimetric differential thermal analysis (TGA-TDA). The particle morphology was analyzed by scanning electron microscopy (SEM). Magnetic properties were investigated by SQUID magnetometry and Mössbauer spectroscopy. Being nearly monodisperse and non-agglomerated the prepared cobalt iron oxide powders are the base for synthesizing magnetoelectric composites embedded in a ferroelectric BaTiO3 matrix.

We report the dry etch of GaSb(001) by inductively coupled plasma reactive ion etcher. Silicon Oxide, deposited by PECVD, was used as a mask. The oxide layer proved to be almost unaffected compared to the GaSb, when using chlorine compound gases as etchants (Cl2, BCl3, and SiCl4) as well as argon. This provides high selectivity for GaSb to the mask layer. The sample holder has no silicon that may contribute to the etching process. Etching using Cl2 + Ar showed increase in the etching rate as the chlorine ratio increases; however, the process led to grassy surface and chemical like reaction. The use of SiCl4+Cl2+Ar mixture with low chlorine ratio resulted in anisotropic etch with smooth sides. It has been found for this case that the increase of the chlorine ratio led to an increased etching rate as well. The repeat of previously reported result by Swaminathan et al. [Thin Solid Films 516 (2008) 8712.] yet with a sample holder not having silicon, proved the effect of Si-contribution in producing vertical profile etch with smooth surfaces.

The solid-gas phase photoassisted reduction of carbon dioxide (artificial photosynthesis) was performed using ferroelectric lithium niobate and titanium dioxide as photocatalysts. Illumination with a high pressure mercury lamp and visible sunlight showed lithium niobate achieved unexpectedly high conversion of CO2 to products despite the low levels of band gap light available and outperformed titanium dioxide under the conditions used. The high reaction efficiency of lithium niobate is explained due to its strong remnant polarization (70 μC/cm2) thought to allow longer lifetime of photo induced carriers as well as an alternative reaction pathway.

Electronic structure calculations were performed to study the effects local hydration, neighboring side chain connectivity, and protogenic group separation have in facilitating proton dissociation and transfer in fragments of 3M ionomers under conditions of low hydration. Two different types of ionomers, each consisting of a poly(tetrafluoroethylene) (PTFE) backbone, were considered: (1) perfluorosulfonic acid (PFSA) ionomeric fragments containing two pendant side chains (–O(CF2)4SO3H) of distinct separation along the PTFE backbone to model different equivalent weight ionomers and (2) single side chain fragments of three bis(sulfonyl imide)- based fragments with multiple and distinct acid groups per side chain having structural and chemical differences mediating protogenic group separation (side chains: –O(CF2)4SO2(NH)- SO2C6H4SO3H) with the sulfonic acid group located in either the meta or the ortho position on the phenyl ring and –O(CF2)4SO2(NH)SO2(CF2)3SO3H). Fully optimized structures of these fragments with and without the addition of water molecules at the B3LYP/6-311G** level revealed that both side chain connectivity and protogenic group separation, along with local hydration, are key contributors to proton dissociation and the energetics of proton transfer in these materials. Specifically, cooperative interaction between protogenic groups through hydrogen bonding and electron withdrawing –CF2– groups are critical for first proton dissociation and the state of the dissociated proton at low levels of hydration. However, the close proximity of protogenic groups in the ortho bis acid precluded second proton dissociation at low hydration as the relatively fixed protogenic group separation promoted interactions between water molecules, while the labile side chains in the PFSA ionomers allowed for greater freedom in the hydrogen bond network formed. Potential energy profiles for proton transfer were determined at the B3LYP/6-31G** level. The energetic penalty associated with proton transfer was found to be strongly dependent on the surrounding hydrogen bond network and the state of the dissociated proton(s), as well as, the separation between protogenic groups.

We describe an experiment to interface and characterize silver nanoparticle (AgNPs) aggregates that are self-assembled and plastically deformable on a thin gold (Au) film deposited on glass substrate. The electrical characterization is done using an electrical nanoprobe attached to a nano-manipulator inside a scanning electron microscope (SEM). Electrical current-voltage (I-V) measurements are made between the electrical nanoprobe in contact with the nanoparticle and the Au film. The Ag nanoparticles have diameters ranging between ~200-800nm and are self-assembled on a thiolated 100nm Au film. Application of a contact force via the nanoprobe even after substantial particle deformation reveals initially a small non-linear current. Upon current annealing through Joule heating, significant improvement in the electrical contact at the AgNP/substrate interface was observed. This is most likely based on bonding of the AgNPs to the Au film after passage of a high current. The need for such an annealing/sintering step will be critical in forming good ohmic contacts at ambient conditions during transfer printing of semiconductor micro/nanopillars.

The photoelectric properties of oxygen-deficient titanium dioxide (TiO2) nanotube arrays are investigated in this study. The TiO2 nanotube arrays are prepared by anodization, followed by annealing at 450 to 750 °C for 3 h in air to form different crystalline phase mixtures. When the annealing temperature is increased, several phenomena are observed: (1) the ratio of anatase to rutile decreases, (2) the anatase nanotubes are shortened and (3) the thickness of the dense rutile film layer underneath the anatase nanotubes increases. The efficiency of visible light absorption of the nanotube arrays is enhanced with increasing annealing temperature. This is believed to be caused by the ionic defects, especially the oxygen vacancies, generated during the annealing procedure, enabling the absorption of low-energy radiations. The X-ray photoelectron spectroscopy (XPS) depth profile analysis provides the supporting evidence on the chemical nonstoichiometry (i.e., oxygen-deficiency) of the TiO2 nanotube arrays annealed at high temperature. With increasing annealing temperature, a decrease and an increase in the photocurrent density of the nanotube arrays under UV and visible light (wavelength > 500 nm) irradiations, respectively, are detected. The decrease of the photocurrent density under UV irradiation is caused by the reduction in the specific surface area (i.e., anatase nanotubes transform into rutile film with vigorous annealing). In contrast, the increase of the photocurrent density under visible light irradiation is contributed to the oxygen vacancies in the nanostructure, providing extra electron energy levels (locating below the conduction band of TiO2) within the band structure.

Fe12%Cr was irradiated with 2MeV and 0.5MeV Fe+ ions at 320°C, to create a layer with a mean level of displacement damage of 6.18dpa to a depth of ∼800nm. Spherical indentation, with a nominal tip radius of 10μm, was used to investigate the mechanical properties of the damage layer. Indents produced with loads of 2mN, 3mN, 5mN and 10mN were cross-sectioned and fabricated into TEM foils using an in situ lift-out technique in a dual beam FIB-SEM microscope. The extent of the plastic zone beneath the indent was observed in the TEM for each indentation. The indentation results were analysed so as to give an indentation stress-strain curve, in which strain softening was found to occur beyond the yield point. At loads up to 3mN the plastic zone remained entirely within the damage layer, implying strain-softening of the damaged material. At higher indentation loads the plastic zone was observed to extend into the softer un-irradiated substrate, giving rise to a further fall in flow stress with increasing strain.

A bacteria-based healing agent for concrete is currently under development in the Microlab of TU Delft. The agent consists of organic mineral precursor compound and bacteria in a protective reservoir. Cracks in the concrete matrix may be sealed and blocked by calcium carbonate based crystals, formed by bacterial conversion of mineral precursor compound. Given the solubility of the agent components, healing agent material may be prematurely released during the wet mixing stage, potentially influencing cement hydration and functionality of other concrete additions. Several materials have been selected as potential mineral precursor compound, being organic salts and a carbohydrate. Tests on standard mortar specimens show that strength development is not compromised when calcium lactate is added to the standard mixture. Calcium lactate was added to the mortar mixture either pure or in combination with a superplasticizer, either based on sulfonated naphthalene or modified polycarboxylate ether, to determine possible interferential effects.

(1-x)K0.5Na0.5NbO3-x(0.97BiScO3-0.03BiCoO3) (KNN-xBSC) piezoelectric ceramics were prepared by the conventional solid-state method, and effects of the BSC addition on the phase structure, relaxor behavior, and electrical properties of KNN ceramics were systematically investigated. The rhombohedral to orthorhombic phase transition around room temperature was identified for the KNN-xBSC ceramics in the composition range of 0.015≤ x ≤0.0175, and improved electrical properties (d 33∼205 pC/N, k p∼0.43, ε r∼1315, and tan δ∼0.054) were observed for the ceramic with x=0.015 because of the involvement of such a phase transition at room temperature. Moreover, a relaxor ferroelectric behavior is demonstrated for these KNN-xBSC ceramics because of a more complex occupation of A and B sites in the ABO3 perovskite structure, together with a weak ferromagnetic order at room temperature.

Organic nanoparticles were deposited on LTA, ZSM5, FAU, clinoptilolite zeolites and montmorillonite clay forming a group of hybrid materials. The nanoparticles were analyzed by GC-Mass and proceed from the active phase of a plant constituted by 1.2 benzenedicarboxylic acid (66.1%), mono (2 ethilester) (66.1%), hexadecanoic acid (74.9%), and Y-isosterol (81.4%). Each of the hybrid materials was characterized by XRD, SEM and EDS. Additionally; the materials obtained were analyzed by high resolution adsorption (HRAD). The N2adsorption isotherms at 76 K obtained in the presence or absence of nanoparticles showed an Ia character for (LTA, FAU and ZSM5) synthetic zeolites, whilst (clinoptilolite) natural zeolite and clay (montmorillonite) showed a type II-IV character. The adsorption capacity of these substrates was analyzed by means of the Lagnmuir, de Boer, and Gursvitch rule approachs. The supermicropores present were measured by the NLDFT approach. The results indicated that the growth of nanoparticles in zeolites resulted in the emergence and opening of emerging pores of different geometry. However, in the case of ZSM5 and LTA zeolites their porosities were blocked by the nanoparticles.

Low dimensional structures like quantum dots (QDs) offers the the ability to tune the absorption properties of standard semiconductor materials. However, QDs are relatively weak light absorbers and hence may benefit significantly from coupling with plasmonic modes in nearby metal structures. In the case of a Si QD absorber layer for photovoltaic applications, enhanced absorption would lead to improved power conversion efficiency. Silver metal nanoparticles (MNPs) were deposited on Si QD structures using the self-assembly method of evaporation and annealing. Room temperature photoluminescence (PL) measurements were used to study the surface plasmon (SP) enhanced emission from the samples. The results were compared to conventional metal back reflectors. Enhanced surface plasmon coupled emission (SPCE) from Si QDs in the vicinity of silver metal nanoparticles (MNPs) is observed with a good correlation between the enhancement and the resonance excitation. Quenching was observed from the same emitter layers placed in close proximity to thin flat silver reflector layers, indicating the importance of the spacer layer between a metal layer and the quantum dots in optimising enhancement. The results have implications for the design of SP-enhanced QD solar cells.

In this work, we use the T-matrix method to study the tunneling of Dirac electrons through graphene multilayers. A graphene sheet is deposited on top of slabs of SiO2-SiC substrates, of which we applied a Gaussian distribution in the size width of the SiC substrate. We calculate the transmittance as a function of energy for different incident angles and different number of layers of the Gaussian distribution. We obtain different stop-band regions. These regions are wider when the width of the barrier is increased. Furthermore, it is possible to tune the width and the position of stop-band with the angle of incidence, the σ value of the Gaussian distribution, and the difference between the maximum-minimum sizes of the barrier.

To assist in the development of biomolecule-based organic semiconductors, the current project uses DFT-based computations at the B3LYP/6-31G* and 6-31G** level to screen 24 small biomolecules for desirable HOMO, LUMO, and E g energy levels. Biomolecules and their derivatives include purines, indigos, medicinal compounds, and thienyl-based molecules. Several promising compounds have been identified, including indigo and several of its derivatives.

Long wavelength photons in the red and near infrared region of the spectrum are poorly absorbed in thin film silicon cells, due to their long absorption lengths. Advanced light trapping methods are necessary to harvest these photons. The basic physical mechanisms underlying the enhanced light trapping in thin film solar cells using periodic back reflectors include strong diffraction coupled with light concentration. These will be contrasted with the scattering mechanisms involved in randomly textured back reflectors, which are commonly used for light trapping. A special class of conformal solar cells with plasmonic nano-pillar back reflectors will be described, that generates absorption beyond the classical 4n2 limit (the Lambertian limit) averaged over the entire wavelength range for nc-Si:H. The absorption beyond the classical limit exists for common 1 micron thick nc-Si:H cells, and is further enhanced for non-normal light. Predicted currents exceed 31 mA/cm2 for nc-Si:H. The nano-pillars are tapered into conical protrusions that enhance plasmonic effects. Such conformal nc-Si:H solar cells with the same device architecture were grown on periodic nano-hole, periodic nano-pillar substrates and compared with randomly textured substrates, formed by annealing Ag/ZnO or etched Ag/ZnO. The periodic back reflector solar cells with nano-pillars demonstrated higher quantum efficiency and higher photo-currents that were 1 mA/cm2higher than those for the randomly textured back reflectors. Losses within the experimental solar architectures are discussed.

Zirconia nanopowders doped with different concentrations of Eu were prepared by the solgel method followed by a thermal treatment at 500°C. Morphological and crystallographic characteristics were studied by scanning electron microscopy, X-Ray diffraction and UV spectroscopoy. Results showed a modification of the size of nanopowder particles when the concentration of Eu is increased from 0.0 to 4.0 wt%. Also, at lower concentration of Eu the tetragonal ZrO2 is the most abundant phase while high concentrations of Eu lead to the formation of the monoclinic phase. The UV spectroscopy of ZrO2 samples shows two main absorption peaks at 228 and 214 nm. The novel characteristics of the ZrO2 nanopowders doped with Eu allow us to propose them for use as solar UV radiation detectors.