The development of new materials with novel properties plays an important role in improving our lives and welfare. Research in Nanotechnology can provide e.g. cheaper and smarter materials in applications such as energy storage and sensors. In order for this development to proceed, we need to be able to characterize the material properties at the nano-, and even the atomic scale. The ultimate goal is to be able to tailor them according to our needs. One of the great challenges concerning the characterization of nano-sized objects is how to achieve the physical contact to them. This thesis is focused on the contacting of nanoobjects with the aim of electrically characterizing them and subsequently understanding their electrical properties. The analyzed nanoobjects are carbon nanosheets, nanotetrapods, nanoparticles and molecular systems. Two contacting strategies were employed in this thesis. The first strategy involved the development of a focused ion beam (FIB) based nanocontact platform. The platform consists of gold nanoelectrodes, having nanogaps of 10-30 nm, on top of an insulating substrate. Gold nanoparticles, double-stranded DNA and cadmium telluride nanotetrapods have been trapped in the gaps by using dielectrophoresis. In certain studies, the gold electrodes have also been coated with conducting or non-conducting molecules, prior to the trapping of gold nanoparticles, in order to form molecular junctions. These junctions were subsequently electrically characterized to evaluate the conduction properties of these molecular systems. For the purpose of better controlling the attachment of molecules to the nanoelectrodes, a novel route to synthesize alkanedithiol coated gold nanoparticles was developed. The second contacting strategy was based on the versatility of the FIB instrument as a platform for in-situ manipulation and electrical characterization of non-functionalized and functionalized carbon nanosheets, where it was found that the functionalized samples had an increased conductivity by more than one order of magnitude. Both contacting strategies proved to be valuable for building knowledge around contacting and electrical characterization of nanoobjects

In the last years, there is a rise of interest in investigation and fabrication of nanometer sized magnetic structures due to their various applications (e.g. for data storage or micro sensors). Over the last several decades ion beam implantation became an important tool for the modification of materials and in particular for the manipulation of magnetic properties. Nanopatterning and implantation can be done simultaneously using focused-ion beam (FIB) techniques. FIB implantation and standard ion implantation differ in their beam current densities by 7 orders of magnitude. This difference can strongly influence the structural and magnetic properties, e.g. due to a rise of the local temperature in the sample during ion implantation. In previous investigations both types of implantation techniques were studied separately. The aim of the current research was to compare both implantation techniques in terms of structural changes and changes in magnetic properties using the same material system. Moreover, to separate any possible annealing effects from implantation ones, the influence of temperature on the structural and magnetic properties were additionally investigated. For the current study a model material system which is widely used for industrial applications was chosen: a 50 nm thick non-ordered nano-crystalline permalloy (Ni81Fe19) film grown on a SiO2 buffer layer based onto a (100)-oriented Si substrate. The permalloy films were implanted with a 30 keV Ga+ ion beam; and also a series of as-deposited permalloy films were annealed in an ultra-high vacuum (UHV) chamber. Several investigation techniques were applied to study the film structure and composition, and were mostly based on non-destructive X-ray investigation techniques, which are the primary focus of this work. Besides X-ray diffraction (XRD), providing the long-range order crystal structural information, extended X-ray absorption fine structure (EXAFS) measurements to probe the local structure were performed. Moreover, the film thickness, surface roughness, and interface roughness were obtained from the X-ray reflectivity (XRR) measurements. Additionally cross-sectional transmission electron microscope (XTEM) imaging was used for local structural characterizations. The Ga depth distribution of the samples implanted with a standard ion implanter was measured by the use of Auger electron spectroscopy (AES) and Rutherford backscattering (RBS), and was compared with theoretical TRIDYN calculation. The magnetic properties were characterized via polar magneto-optic Kerr effect (MOKE) measurements at room temperature. It was shown that both implantation techniques lead to a further material crystallization of the partially amorphous permalloy material (i.e. to an increase of the amount of the crystalline material), to a crystallite growth and to a material texturing towards the (111) direction. For low ion fluences a strong increase of the amount of the crystalline material was observed, while for high ion fluences this rise is much weaker. At low ion fluences XTEM images show small isolated crystallites, while for high ones the crystallites start to grow through the entire film. The EXAFS analysis shows that both Ni and Ga atom surroundings have a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter for both implantation techniques increases with increasing ion fluence according to the same linear law. The lattice parameters obtained from the EXAFS measurements for both implantation types are in a good agreement with the results obtained from the XRD measurements. Grazing incidence XRD (GIXRD) measurements of the samples implanted with a standard ion implanter show an increasing value of microstrain with increasing ion fluence (i.e. the lattice parameter variation is increasing with fluence). Both types of implantation result in an increase of the surface and the interface roughness and demonstrate a decrease of the saturation polarization with increasing ion fluence. From the obtained results it follows that FIB and standard ion implantation influence structure and magnetic properties in a similar way: both lead to a material crystallization, crystallite growth, texturing and decrease of the saturation polarization with increasing ion fluence. A further crystallization of the highly defective nano-crystalline material can be simply understood as a result of exchange processes induced by the energy transferred to the system during the ion implantation. The decrease of the saturation polarization of the implanted samples is mainly attributed to the simple presence of the Ga atoms on the lattice sites of the permalloy film itself. For the annealed samples more complex results were found. The corresponding results can be separated into two temperature regimes: into low (≤400°C) and high (>400°C) temperatures. Similar to the implanted samples, annealing results in a material crystallization with large crystallites growing through the entire film and in a material texturing towards the (111) direction. The EXAFS analysis shows a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter of the annealed samples slightly decreases at low annealing temperatures, reaches its minimum at about ~400°C and slightly rises at higher ones. From the GIXRD measurements it can be observed that the permalloy material at temperatures above >400°C reaches its strain-free state. On the other hand, the film roughness increases with increasing annealing temperature and a de-wetting of the film is observed at high annealing temperatures. Regardless of the material crystallization and texturing, the samples annealed at low temperatures demonstrate no change in saturation polarization, while at high temperatures a rise by approximately ~15% at 800°C was observed. The rise of the saturation polarization at high annealing temperatures is attributed to the de-wetting effect.

WC-Co cutting tools are widely used in the machining industry. The application of diamond coatings on the surfaces of the tools would prolong the cutting lifetime and improves the manufacturing efficiency. However, direct chemical vapor deposition (CVD) of diamond coatings on WC-Co suffer from severe premature adhesion failure due to interfacial graphitization induced by the binder phase Co. In this research, a combination of hydrochloric acid (HCl) and hydrogen (H2) plasma pretreatments and a novel double interlayer of carbide forming element (CFE)/Al were developed to enhance diamond nucleation and adhesion. The results showed that both the pretreatments and interlayers were effective in forming continuous and adhesive nanocrystalline diamond coatings. The method is a promising replacement of the hazardous Murakami's regent currently used in WC-Co pretreatment with a more environmental friendly approach.<p> Apart from coatings, diamond can be fabricated into other forms of nanostructures, such as nanotips. In this work, it was demonstrated that oriented diamond nanotip arrays can be fabricated by ion beam etching of as-grown CVD diamond. The orientation of diamond nanotips can be controlled by adjusting the direction of incident ion beam. This method overcomes the limits of other techniques in producing nanotip arrays on large areas with controlled orientation. Oriented diamond nano-tip arrays have been used to produce anisotropic frictional surface, which is successfully used in ultra-precision positioning systems.<p> Diamond-like carbon (DLC) has many properties comparable to diamond. In this thesis, the preparation of á-C:H thin films by end-Hall (EH) ion source and the effects of ion energy and nitrogen doping on the microstructure and mechanical properties of the as-deposited thin films were investigated. The results have demonstrated that smooth and uniform á-C:H and á-C:H:N films with large area and reasonably high hardness and Youngs modulus can be synthesized by EH ion source with a low ion energy. The EH ion beam deposition of carbon-based thin films have potential applications such as protective coatings on high capacity magnetic memory disk, for which coating uniformity and smoothness cannot be achieved by the traditional sputtering methods.

WC-Co cutting tools are widely used in the machining industry. The application of diamond coatings on the surfaces of the tools would prolong the cutting lifetime and improves the manufacturing efficiency. However, direct chemical vapor deposition (CVD) of diamond coatings on WC-Co suffer from severe premature adhesion failure due to interfacial graphitization induced by the binder phase Co. In this research, a combination of hydrochloric acid (HCl) and hydrogen (H2) plasma pretreatments and a novel double interlayer of carbide forming element (CFE)/Al were developed to enhance diamond nucleation and adhesion. The results showed that both the pretreatments and interlayers were effective in forming continuous and adhesive nanocrystalline diamond coatings. The method is a promising replacement of the hazardous Murakami's regent currently used in WC-Co pretreatment with a more environmental friendly approach.<p> Apart from coatings, diamond can be fabricated into other forms of nanostructures, such as nanotips. In this work, it was demonstrated that oriented diamond nanotip arrays can be fabricated by ion beam etching of as-grown CVD diamond. The orientation of diamond nanotips can be controlled by adjusting the direction of incident ion beam. This method overcomes the limits of other techniques in producing nanotip arrays on large areas with controlled orientation. Oriented diamond nano-tip arrays have been used to produce anisotropic frictional surface, which is successfully used in ultra-precision positioning systems.<p> Diamond-like carbon (DLC) has many properties comparable to diamond. In this thesis, the preparation of á-C:H thin films by end-Hall (EH) ion source and the effects of ion energy and nitrogen doping on the microstructure and mechanical properties of the as-deposited thin films were investigated. The results have demonstrated that smooth and uniform á-C:H and á-C:H:N films with large area and reasonably high hardness and Youngs modulus can be synthesized by EH ion source with a low ion energy. The EH ion beam deposition of carbon-based thin films have potential applications such as protective coatings on high capacity magnetic memory disk, for which coating uniformity and smoothness cannot be achieved by the traditional sputtering methods.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO^2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and ≈1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960\'s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain \\lq magic\' angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

A challenge exists for understanding the origin of color for structurally colored, 3-dimensional bioorganic nanostructures, such as the scales of butterflies, beetles, and moths. Complex, hierarchical structures found within such scales create the overall scale appearance. The controlled alteration of color through material deposition and the addition of new optical functionalities to such structures are other areas of scientific interest. This dissertation addresses these challenges with a first-of-its-kind, systematic isolation (deconstruction) of scale component nanostructures, followed by evaluation of optical property/structure correlations. The additive deposition (constructive alteration) of emissive materials to structurally-colored templates complements this deconstructive approach towards understanding the origin of color in butterfly scales. Discoveries made through this work may help advance the bioinspired design of synthetic optical structures and subsequent color control through the addition of multilayered, emissive optical components.

The trend for designing of a titanium implant explored using different chemical compositions and crystallinity materials until people realized that the implant surface character was another important factor affecting the rate and extent of osseointegartion. Titanium received a macroporous titania surface layer by anodization, which contains open pores with average pore diameter around 5μm. An additional mesoporous titania top layer was created that followed the contour of the macropores and having 100–200 nm thickness and a pore diameter of 10 nm. Thus, a coherent laminar titania surface layer was obtained producing a hierarchical macro- and mesoporous surface. The interfacial bonding between the surface layers and the titanium matrix was characterized by a scratch test that confirmed a stable and strong bonding of the laminar titania surface layers upon titanium. The wettability to water and the effects on the osteosarcoma cell line (SaOS-2) proliferation and mineralization of the formed titania surface layers were studied systematically by cell culture and scanning electron microscopy (SEM). A synergistic role of the hierarchical macro- and mesoporosities was revealed in terms of enhancing cell adhesion, proliferation and mineralization, when compared with the titania surface with solo porosity scale topography. For the in vivo results of the evaluation of osseointegration, an argon ion beam polishing technique was applied to prepare the cross sections of implants feasible for the high resolution SEM investigation. The interfacial microstructure between newly formed bone and implants with four modified surfaces including the new hierarchical macro- and mesoporous implant surface retrieved after in vivo tests were characterized. By this approach it has become possible to directly observe early bone formation, the increase of bone density, and the evolution of bone structure. The two bone growth mechanisms, distant osteogenesis and contact osteogenesis, can also be distinguished. These direct observations give, at microscopic level, a better view of osseointegration and explain the functional mechanisms of various implant surfaces for osseointegration. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: In press. Paper 4: Manuscript.</p>

This thesis is based on a selection of six different experimental techniques used for studies in atomic and molecular physics. The techniques analysed in the thesis are compared to find similarities in strategies and ways to avoid sources of error. Paper 1 deals with collision based spectroscopy with 60 keV Xe6+ ions on sodium and argon gas targets. Information on energy of Rydberg states in Xe5+ is unveiled by optical spectroscopy in the wavelength range from vacuum ultraviolet (VUV) to visible. In paper 2, the fast ion-beam laser spectroscopy (FIBLAS) is adapted for measuring hyperfine structure of barium isotopes in an isotopically pure ion-beam. This techniques involves changing the isotope during the measurement to minimize sources of error in measurement and enhance the signal from lesser abundant isotopes. The FIBLAS technique is used in paper 3 to study samarium ions. The ions are optically pumped and the recorded optical nutation is used to measure transition probabilities. This technique eludes the difficulties inherent in relative intensity measurements of all the radiative transitions from an excited state. In Paper 4, optical emission spectroscopy is used in the VUV region to study noble gas mixture discharges. The source of the emission bands near the resonance lines of krypton and xenon are found to be heteronuclear dimers. In paper 5, radiation from a pulsed argon plasma with admixture of nitrogen is studied with time resolved spectroscopy in the VUV and ultraviolet wavelength ranges to investigate the mechanism of energy transport. A metastable state of atomic argon is found to be an important source of energy to many radiative processes. In Paper 6, photoelectron spectroscopy (PES) on thiophene, on 3-bromothiophene and on 3,4-dibromothiophene using time-of-flight photoelectron-photoelectron coincidence technique and conventional PES to investigate the onset of double ionisation compared to the onset of single ionisation in molecules.

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In 2012 the HZDR, and in consequence also the Institute of Ion Beam Physics and Materials Research (IIM) including its Ion Beam Center (IBC), has undergone a scientific evaluation. The evaluation committee composed of the Scientific Advisory Board and numerous external experts in our field of research concluded that “the overall quality of the scientific work is excellent”, that “there are an impressive number of young scientists working enthusiastically on a variety of high-level projects” and that “the choice of these projects represents a clear underlying strategy and vision”. We feel honored and are proud that the external view on our scientific achievements is that extraordinary. In view of this outstanding result we would like to express our gratitude to all our staff members for their commitment and efforts! In the past year, we continued our integration into the Helmholtz Association of German Research Centers (HGF) with our Institute mostly active in the research area “Matter”, but also involved in a number of activities in the research area “Energy”. In this respect, many consultations were held with the Helmholtz centers contributing to common research areas to precisely define the role we will play in the newly established HGF program “From Matter to Materials and Life” (see schematic below). Our IBC has been recognized as a large-scale user facility for ion beam analysis and modification of materials, i.e., specializing on materials science. In particular, the IBC plays a prominent role in the recently approved Helmholtz Energy Materials Characterization Platform (HEMCP), which mainly concentrates on the development of dedicated analytical tools for the characterization of materials required for future energy technologies. The successes achieved by the IBC allows us to invest 7200 k€ to further improve and strengthen the ion beam capabilities at the Institute. In addition to this infrastructure-related grant, we were also successful in our funding application for the establishment of the International Helmholtz Research School for Nanoelectronic Networks (IHRS NANONET), aiming at promoting the next generation of leading scientists in the field of nanoelectronics. The IHRS NANONET is coordinated by our Institute and offers a well-structured PhD program to outstanding students of all nationalities with emphasis on interdisciplinary research and comprehensive training in technical and professional skills.