Un-doped, Er3+ doped (TiO2:Er3+) as well as Er3+/Yb3+ co-doped (TiO2:Er3+/Yb3+) nanocrystals with different concentrations of RE3+ (Er3+, Yb3+) were successfully synthesized using the sol-gel method. The powder X-ray diffraction (XRD) spectra revealed that all undoped and doped samples remained in anatase after annealing at 400°C. The presence of RE3+ ions in the TiO2 host lattice was confirmed by conducting elemental mapping on the samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX), which was in agreement with X-ray photoelectron spectroscopy (XPS) results. Transmission electron microscope (TEM) images approximated particle sizes of the samples to be between 1.5 – 3.5 nm in diameter and this compares well with XRD analyses. Phonon quantification in TiO2 was achieved using Fourier transform infrared (FT-IR) spectroscopy. Optical bandgap from Ultraviolet/Visible/Near-Infrared was extrapolated from Kubelka-Munk relation and the narrowing of the bandgap for the doped samples as compared to the undoped sample was observed. The photoluminescence PL study of the samples revealed two emission peaks attributed to direct band-gap and defect-related emissions. A laser beam with 980 nm wavelength was used to irradiate the samples, and the displayed emission lines of the TiO2: Er3+ in the visible region of the electromagnetic spectrum confirmed up-conversion luminescence. Enhancement of up-conversion luminescence intensity due to Yb3+ co-doping was observed, indicating an efficient energy transfer process from the sensitizer Yb3+ to the activator Er3+. / Physics / M. Sc. (Physics)

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During the last years perovskite materials have taken the photovoltaic community by storm, bringing promises of solar cells with efficiencies comparable to conventional silicon devices but at a lower price. However perovskite solar cells so far are facing two main obstacles, they are unstable in the presence of air, moisture and heat and they are usually toxic due to being based on lead-halide materials. This has spurred investigations into alternative materials with similar properties but without the mentioned drawbacks. Just next to Pb in the periodic table is bismuth (Bi) with just one more electron in its outer-shell, Bi however is less toxic. In this work the perovskite derived compounds of Ag-Bi-I and Cu-Bi-I are characterized and their properties as light absorbing material in solar cell devices are investigated. Devices are prepared by preparing Ag-Bi-I and Cu-Bi-I solutions which are then spin-coated on top of a mesoporous TiO2. A conducting polymer, P3HT, was then deposited and serve as hole transport material. For Ag-Bi-I, the molar ratios of AgI:BiI3= 1:2 and 2:1 were observed with SEM to form homogeneous crystal films with one dominating crystal phase, which by XRD could be determined to most likely have formed a cubic AgBi2I7 crystal structure for the 1:2 ratio and a hexagonal Ag2BiI5 crystal structure for the 2:1 ratio. The Cu-Bi-I materials were not successfully synthesized to form homogeneous films with a dominating crystal phase, although several molar ratios were investigated. All investigated compositions of both Cu and Ag devices showed to in principle work as light absorbing materials, the best Ag-Bi-I device showing a PCE of 1.92%, for the 2:1 ratio, while the Cu-Bi-I devices at best reached 0.32% for a ratio of 1:1. XPS measurements were carried out with a classical in-house XPS using an Al K X-ray source of 1486.7 eV as well as at the Diamond Light Source (UK) synchrotron facility using photon energies of 758 eV and 2200 eV so that a depth resolution of the composition could be observed. Because of their inhomogeneous crystal formation, XPS couldn’t give much useful quantitative information regarding the Cu devices. For Ag devices it was observed that the stoichiometry at the extreme surface deviated from that predicted by XRD, but deeper into the surface the relative ratio of elements approach the predicted ones, hinting towards a different structure at the outermost surface or a lot of surface defects. For all samples, two types of bismuth atoms were observed, metallic (Bi0) as well as a cationic (Bi+x), the later corresponding to Bi atoms which are partaking in the crystal bond. The ratio of metallic to cationic Bi was observed to decrease notably just a few nm below the extreme surface. The effect of the high presence of metallic Bi on final device performance was not concluded with certainty but not believed to be positive. By varying the annealing temperature, after spin coating the light absorber solution on the TiO2, it was observed that lower temperature resulted in a lower ratio of metallic Bi. As final conclusions, it was said that the synthesis method of Cu-Bi-I needs to be improved before those materials can be studied further. The synthesis of Ag-Bi-I is showing much more promise and one can start looking into further optimizing their final device structure to boost efficiency. Both Cu-Bi-I and Ag-Bi-I devices are relatively simple, cheap and energy efficient (with annealing temperatures around 150C) to produce, great aspects for solar cells. UVVis measurements showed they have band gaps around 1.6-1.7 eV which makes them a great potential material for use in tandem solar cells together with a semiconductor of lower band gap such as silicon.

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity. / Science, Faculty of / Chemistry, Department of / Graduate

The work of this thesis comprises extensive Noncontact Atomic Force Microscopy (NC-AFM) characterization of clean metal-oxide (YSZ(100)/(111) and MgO(100)) and graphitic (HOPG) supports as templates for the novel, photochemically induced nucleation of cobalt oxide nanostructures, particularly Cobalt (III) Oxide. The nanostructure-support surfaces were also studied by X-ray Photoelectron Spectroscopy (XPS) to verify the nature of the supported cobalt oxide and to corroborate the surface topographic and phase NC-AFM data. Heteroepitaxial growth of Co2O3 nanostructures proves to exhibit a variety of different growth modes based on the structure of the support surface. On this basis, single-crystal support surfaces ranging from nonpolar to polar and atomically flat to highly defective and reactive were chosen, again, yielding numerous substrate-nanostructure interactions that could be probed by high-performance surface science techniques.

Comprehensive investigations of the electron field emission (FE) properties of annealed single crystal and polycrystalline molybdenum plugs, which are used as substrates for actual alkali-based photocathodes were performed with a FE scanning microscope. Well-polished and dry-ice cleaned Mo samples with native oxide did not show parasitic FE up to a field level of 50 MV/m required for photoinjector cavities. In situ heat treatments (HT) above 400°C, which are usual before photocathode deposition, activated field emission at lower field strength. Oxygen loading into the Mo surface, however, partially weakened these emitters. X-ray photoelectron spectroscopy of comparable Mo samples showed the dissolution of the native oxide during such heat treatments. These results reveal the suppression of field emission by native Mo oxides. Possible improvements for the photocathode preparation will be discussed.

The direct epitaxial growth of multilayer BN by atomic layer deposition is of critical significance forfo two-dimensional device applications. X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED) demonstrate layer-by-layer BN epitaxy on two different substrates. One substrate was a monolayer of RuO2(110) formed on a Ru(0001) substrate, the other was an atomically clean Ni(111) single crystal. Growth was accomplished atomic layer deposition (ALD) cycles of BCl3/NH3 at 600 K substrate temperature and subsequent annealing in ultrahigh vacuum (UHV). This yielded stoichiometric BN layers, and an average BN film thickness linearly proportional to the number of BCl3/NH3 cycles. The BN(0001)/RuO2(110) interface had negligible charge transfer or band bending as indicated by XPS and LEED data indicate a 30° rotation between the coincident BN and oxide lattices. The atomic layer epitaxy of BN on an oxide surface suggests new routes to the direct growth and integration of graphene and BN with industrially important substrates, including Si(100). XPS and LEED indicated epitaxial deposition of h-BN(0001) on the Ni(111) single crystal by ALD, and subsequent epitaxially aligned graphene was deposited by chemical vapor deposition (CVD) of ethylene at 1000 K. Direct multilayer, in situ growth of h-BN on magnetic substrates such as Ni is important for spintronic device applications. Solid-state electrolytes (SSEs) are of significant interest for their promise as lithium-ion conducting materials but are prone to degradation due to lithium carbonate formation on the surface upon exposure to atmosphere, adversely impacting Li ion conduction. In situ XPS monitored changes in the composition of the SSE Li garnet (Li6.5La3Zr1.5Ta0.5O12, LLZTaO) upon annealing in UHV and upon Ar+ ion sputtering. Trends in core level spectra demonstrate that binding energy (BE) calibration of the Li 1s at 56.4 eV, yields a more consistent interpretation of results than the more commonly used standard of the adventitious C 1s at 284.8 eV. Annealing one ambient-exposed sample to >1000 K in UHV effectively reduced surface carbonate and oxygen, leaving significant amounts of carbon in lower oxidation states. A second ambient-exposed sample was subjected to 3 keV Ar+ ion sputtering at 500 K in UHV, which eliminated all surface carbon, and reduced the O 1s intensity and BE. These methods present alternative approaches to lithium carbonate removal than heating or polishing in inert atmospheres and are compatible with fundamental surface science studies. In particular, the data show that sputtering at mildly elevated temperatures yields facile elimination of carbonate and other forms of surface carbon. This is in contrast to annealing in either UHV or in noble gas environments, which result in carbonate reduction, but with significant remnant coverages of other forms of carbon.

The thermal stability of p-type CdTe crystals by using conductivity and Hall-effect measurements have been studied at room and slightly increased temperatures. It was observed that thermal changes often implicate an anomalous behavior of the hole density characterized by reversible decrease/increase in a heating/cooling regime. This anomaly was explained by a transfer of fast diffusing donors between Te inclusions and the bulk of the sample. Sodium and potassium were determined by the Secondary Ion Mass Spectroscopy (SIMS) as the most probable diffusing species. To verify this behavior samples were also treated in saturated NaCl solution for different time intervals in order to examine the influence of the oxide layer and sodium on the surface of the sample. To determine the structure of the surface the sample was characterized by ellipsometric and X-ray photoelectron spectroscopy (XPS) and SIMS. Very low determined diffusion coefficient of Na was explained by trapping of Na in Cd sublattice

A novel strategy for the intercalation of antimony (Sb) under the (6√3 × 6√3)R30° reconstruction, also known as buffer layer, on SiC(0001) is reported. Using X-ray photoelectron spectroscopy, low-energy electron diffraction, and angle-resolved photoelectron spectroscopy, it is demonstrated that, while the intercalation of the volatile Sb is not possible by annealing the Sb-coated buffer layer in ultrahigh vacuum, it can be achieved by annealing the sample in an atmosphere of Ar, which suppresses Sb desorption. The intercalation leads to a decoupling of the buffer layer from the SiC(0001) surface and the formation of quasi-freestanding graphene. The intercalation process paves the way for future studies of the formation of quasi-freestanding graphene by intercalation of high-vapor-pressure elements, which are not accessible by previously known intercalation techniques, and thus provides new avenues for the manipulation of epitaxial graphene on SiC.