Self-organized hexagonal ordering of quantum dot arrays

We report a structure of (In, Ga)As/GaAs quantum dots which are vertically correlated and laterally aligned in a hexagonal way thus forming three-dimensionally ordered arrays. The growth pathway is based on a mechanism of self-assembly by strain-mediated multilayer vertical stacking on a planar GaAs(100) substrate, rather than molecular-beam epitaxy on a prepatterned substrate. The strain energy of lateral island-island interaction is minimum for the arrangement of hexagonal ordering. However, realization of hexagonal ordering not only depends on a complicated trade-off between lateral and vertical island-island interaction but is also related to a delicate and narrow growth kinetics window.

Self-assembled GaAs quantum rings by MBE droplet epitaxy

Fabrication of semiconductor nanostructures such as quantum dots (QDs), quantum rings (QRs) has been considered as the important step for realization of solid state quantum information devices, including QDs single photon emission source, QRs single electron memory unit, etc. To fabricate GaAs quantum rings, we use Molecular Beam Epitaxy (MBE) droplet technique in this report. In this droplet technique, Gallium (Ga) molecular beams are supplied initially without Arsenic (As) ambience, forming droplet-like nano-clusters of Ga atoms on the substrate, then the Arsenic beams are supplied to crystallize the Ga droplets into GaAs crystals. Because the morphologies and dimensions of the GaAs crystal are governed by the interplay between the surface migration of Ga and As adatoms and their crystallization, the shape of the GaAs crystals can be modified into rings, and the size and density can be controlled by varying the growth temperatures and As/Ga flux beam equivalent pressures(BEPs). It has been shown by Atomic force microscope (AFM) measurements that GaAs single rings, concentric double rings and coupled double rings are grown successfully at typical growth temperatures of 200 C to 300 C under As flux (BEP) of about 1.0 x 10(-6) Torr. The diameter of GaAs rings is about 30-50 nm and thickness several nm.

Self-Assembled Monolayers (SAMs) in Organic Field-Effect Transistors

Organic printed electronics is attracting an ever-growing interest in the last decades because of its impressive breakthroughs concerning the chemical design of π-conjugated materials and their processing. This has an impact on novel applications, such as flexible-large-area displays, low- cost printable circuits, plastic solar cells and lab-on-a-chip devices. The organic field-effect transistor (OFET) relies on a thin film of organic semiconductor that bridges source and drain electrodes. Since its first discovery in the 80s, intensive research activities were deployed in order to control the chemico-physical properties of these electronic devices and consequently their charge. Self-assembled monolayers (SAMs) are a versatile tool for tuning the properties of metallic, semi-conducting, and insulating surfaces. Within this context, OFETs represent reliable instruments for measuring the electrical properties of the SAMs in a Metal/SAM/OS junction. Our experimental approach, named Charge Injection Organic-Gauge (CIOG), uses OTFT in a charge-injection controlled regime. The CIOG sensitivity has been extensively demonstrated on different homologous self-assembling molecules that differ in either chain length or in anchor/terminal group. One of the latest applications of organic electronics is the so-called “bio-electronics” that makes use of electronic devices to encompass interests of the medical science, such as biosensors, biotransducers etc… As a result, thee second part of this thesis deals with the realization of an electronic transducer based on an Organic Field-Effect Transistor operating in aqueous media. Here, the conventional bottom gate/bottom contact configuration is replaced by top gate architecture with the electrolyte that ensures electrical contact between the top gold electrode and the semiconductor layer. This configuration is named Electrolyte-Gated Field-Effect Transistor (EGOFET). The functionalization of the top electrode is the sensing core of the device allowing the detection of dopamine as well as of protein biomarkers with ultra-low sensitivity.

Atomic-scale characterization of diamond surfaces and fullerene self-assembly

In this thesis, elemental research towards the implantation of a diamond-based molecular quantum computer is presented. The approach followed requires linear alignment of endohedral fullerenes on the diamond C(100) surface in the vicinity of subsurface NV-centers. From this, four fundamental experimental challenges arise: 1) The well-controlled deposition of endohedral fullerenes on a diamond surface. 2) The creation of NV-centers in diamond close to the surface. 3) Preparation and characterization of atomically-flat diamondsurfaces. 4) Assembly of linear chains of endohedral fullerenes. First steps to overcome all these challenges were taken in the framework of this thesis. Therefore, a so-called “pulse injection” technique was implemented and tested in a UHV chamber that was custom-designed for this and further tasks. Pulse injection in principle allows for the deposition of molecules from solution onto a substrate and can therefore be used to deposit molecular species that are not stable to sublimation under UHV conditions, such as the endohedral fullerenes needed for a quantum register. Regarding the targeted creation of NV-centers, FIB experiments were carried out in cooperation with the group of Prof. Schmidt-Kaler (AG Quantum, Physics Department, Johannes Gutenberg-Universität Mainz). As an entry into this challenging task, argon cations were implanted into (111) surface-oriented CaF2 crystals. The resulting implantation spots on the surface were imaged and characterized using AFM. In this context, general relations between the impact of the ions on the surface and their valency or kinetic energy, respectively, could be established. The main part of this thesis, however, is constituted by NCAFM studies on both, bare and hydrogen-terminated diamond C(100) surfaces. In cooperation with the group of Prof. Dujardin (Molecular Nanoscience Group, ISMO, Université de Paris XI), clean and atomically-flat diamond surfaces were prepared by exposure of the substrate to a microwave hydrogen plasma. Subsequently, both surface modifications were imaged in high resolution with NC-AFM. In the process, both hydrogen atoms in the unit cell of the hydrogenated surface were resolved individually, which was not achieved in previous STM studies of this surface. The NC-AFM images also reveal, for the first time, atomic-resolution contrast on the clean, insulating diamond surface and provide real-space experimental evidence for a (2×1) surface reconstruction. With regard to the quantum computing concept, high-resolution NC-AFM imaging was also used to study the adsorption and self-assembly potential of two different kinds of fullerenes (C60 and C60F48) on aforementioned diamond surfaces. In case of the hydrogenated surface, particular attention was paid to the influence of charge transfer doping on the fullerene-substrate interaction and the morphology emerging from self-assembly. Finally, self-assembled C60 islands on the hydrogen-terminated diamond surface were subject to active manipulation by an NC-AFM tip. Two different kinds of tip-induced island growth modes have been induced and were presented. In conclusion, the results obtained provide fundamental informations mandatory for the realization of a molecular quantum computer. In the process it was shown that NC-AFM is, under proper circumstances, a very capable tool for imaging diamond surfaces with highest resolution, surpassing even what has been achieved with STM up to now. Particular attention was paid to the influence of transfer doping on the morphology of fullerenes on the hydrogenated diamond surface, revealing new possibilities for tailoring the self-assembly of molecules that have a high electron affinity.

SIRGAS reference frame realization SIR11P01

To estimate the kinematics of the SIRGAS reference frame, the Deutsches Geodätisches Forschungsinstitut (DGFI) as the IGS Regional Network Associate Analysis Centre for SIRGAS (IGS RNNAC SIR), yearly computes a cumulative (multi-year) solution containing all available weekly solutions delivered by the SIRGAS analysis centres. These cumulative solutions include those models, standards, and strategies widely applied at the time in which they were computed and cover different time spans depending on the availability of the weekly solutions. This data set corresponds to the multi-year solution SIR11P01. It is based on the combination of the weekly normal equations covering the time span from 2000-01-02 (GPS week 1043) to 2011-04-16 (GPS week 1631), when the IGS08 reference frame was introduced. It refers to ITRF2008, epoch 2005.0 and contains 230 stations with 269 occupations. Its precision was estimated to be ±1.0 mm (horizontal) and ±2.4 mm (vertical) for the station positions, and ±0.7 mm/a (horizontal) and ±1.1 mm/a (vertical) for the constant velocities. Computation strategy and results are in detail described in Sánchez and Seitz (2011). The IGS RNAAC SIR computation of the SIRGAS reference frame is possible thanks to the active participation of many Latin American and Caribbean colleagues, who not only make the measurements of the stations available, but also operate SIRGAS analysis centres processing the observational data on a routine basis (more details in http://www.sirgas.org). The achievements of SIRGAS are a consequence of a successful international geodetic cooperation not only following and meeting concrete objectives, but also becoming a permanent and self-sustaining geodetic community to guarantee quality, reliability, and long-term stability of the SIRGAS reference frame. The SIRGAS activities are strongly supported by the International Association of Geodesy (IAG) and the Pan-American Institute for Geography and History (PAIGH). The IGS RNAAC SIR highly appreciates all this support.

Temporal self-imaging effect for periodically modulated trains of pulses

In this paper, the mathematical description of the temporal selfimaging effect is studied, focusing on the situation in which the train of pulses to be dispersed has been previously periodically modulated in phase and amplitude. It is demonstrated that, for each input pulse and for some specific values of the chromatic dispersion, a subtrain of optical pulses is generated whose envelope is determined by the Discrete Fourier Transform of the modulating coefficients. The mathematical results are confirmed by simulations of various examples and some limits on the realization of the theory are commented.

Self-standing curved crystals for X and Gamma rays focusing

The efficiency of a Laue lens for X and Gamma ray focusing in the energy range 60 ÷ 600 keV is closely linked to the diffraction efficiency of the single crystals composing the lens. A powerful focusing system is crucial for applications like medical imaging and X ray astronomy where wide beams must be focused. Mosaic crystals with a high density, such as Cu or Au, and bent crystals with curved diffracting planes (CDP) are considered for the realization of a focusing system for X rays, owing to their high diffraction efficiency. In this work, a comparison of the efficiency of CDP crystals and mosaic crystals was performed on the basis of the theory of X-ray diffraction. Si, GaAs and Ge CDP crystals with optimized thicknesses and moderate radii of curvature of several tens of metres demonstrate comparable or superior performance with respect to the higher atomic number mosaic crystals generally used. A simplified approach for calculating the integrated reflectivity of the crystals is applied. A bending technique used during this work to realize CDP crystals consists in a controlled surface damaging induced by a mechanical lapping process. A compressive strained layer of few micrometres in thickness is generated and causes the convex curvature of the damaged side of the crystal. Another new bending technique is developed and the main results are shown. The process consists on a film deposition of a selected bi-component epoxy resin on one side of crystal, made uniform in thickness by mean of a spin-coater. Choosing the speed of spin-coating, so changing the thickness of the film, a control of radius of curvature can be obtained. Moreover the possibility to combine the two bending technique to obtain CDP crystal with a stronger curvature in rather thick crystals was demonstrated. Detailed characterization of Si, and GaAs CDP crystals at low and high x-ray energies are performed on flat and bent crystals obtained with the damaging and the resin deposition technique. As expected an increase of diffraction efficiency in asymmetrical diffraction geometry in CDP crystals with respect to the flat ones is observed. On the other hand an unexpected increase of the integrated intensity in symmetrical geometry, not predicted by the theory, is observed in all the measurements performed with different set up. The experimental trend of the integrated reflectivity as a function of the radius of curvature is in a good agreement with that predicted by the theory of bent perfect crystals, so it is possible to conclude that the surface damage has a limited effect on the crystal reflectivity. A study of the integrated reflectivity in the energy range of interest (100÷350 keV) in CDP crystals realized with damaging and resin deposition technique at symmetrical and asymmetrical geometries was performed at ILL Institute. Also at these energies the diffraction efficiency of bent crystals was much larger (a 12 time increase is observed for bent crystals in asymmetrical 111 geometry) than that measured in flat crystals. The diffraction efficiency of CDP crystals realized with both techniques tends to coincide with that of flat crystals at very high energies (> 200 keV). This suggesting that also real flat perfect crystals can be considered as strongly bent or mosaic crystals at very high X ray energies.

Supporting decision-making for self-adaptive systems:from goal models to dynamic decision networks

Context/Motivation - Different modeling techniques have been used to model requirements and decision-making of self-adaptive systems (SASs). Specifically, goal models have been prolific in supporting decision-making depending on partial and total fulfilment of functional (goals) and non-functional requirements (softgoals). Different goalrealization strategies can have different effects on softgoals which are specified with weighted contribution-links. The final decision about what strategy to use is based, among other reasons, on a utility function that takes into account the weighted sum of the different effects on softgoals. Questions/Problems - One of the main challenges about decisionmaking in self-adaptive systems is to deal with uncertainty during runtime. New techniques are needed to systematically revise the current model when empirical evidence becomes available from the deployment. Principal ideas/results - In this paper we enrich the decision-making supported by goal models by using Dynamic Decision Networks (DDNs). Goal realization strategies and their impact on softgoals have a correspondence with decision alternatives and conditional probabilities and expected utilities in the DDNs respectively. Our novel approach allows the specification of preferences over the softgoals and supports reasoning about partial satisfaction of softgoals using probabilities. We report results of the application of the approach on two different cases. Our early results suggest the decision-making process of SASs can be improved by using DDNs. © 2013 Springer-Verlag.

Self-organization of Functioning Process of Expert System with the Use of Subject Domain Ontology

Optimization of design, creation, functioning and accompaniment processes of expert system is the important problem of artificial intelligence theory and decisions making methods techniques. In this paper the approach to its solving with the use of technology, being based on methodology of systems analysis, ontology of subject domain, principles and methods of self-organisation, is offered. The aspects of such approach realization, being based on construction of accordance between the ontology hierarchical structure and sequence of questions in automated systems for examination, are expounded.

Use of Start Pages for Building a Mashup Personal Learning Environment to Support Self-Organized Learners

The paper explores the functionalities of eight start pages and considers their usefulness when used as a mashable platform for deployment of personal learning environments (PLE) for self-organized learners. The Web 2.0 effects and eLearning 2.0 strategies are examined from the point of view of how they influence the methods of gathering and capturing data, information and knowledge, and the learning process. Mashup technology is studied in order to see what kind of components can be used in PLE realization. A model of a PLE for self-organized learners is developed and it is used to prototype a personal learning and research environment in the start pages Netvibes, Pageflakes and iGoogle.

Advancing atomic nanolithography: cold atomic Cs beam exposure of alkanethiol self-assembled monolayers

We report the results of a study into the quality of functionalized surfaces for nanolithographic imaging. Self-assembled monolayer (SAM) coverage, subsequent post-etch pattern definition and minimum feature size all depend on the quality of the Au substrate used in atomic nanolithographic experiments. We find sputtered Au substrates yield much smoother surfaces and a higher density of {111} oriented grains than evaporated Au surfaces. A detailed study of the self-assembly mechanism using molecular resolution AFM and STM has shown that the monolayer is composed of domains with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. Exposure of the SAM to an optically-cooled atomic Cs beam traversing a two-dimensional array of submicron material masks ans also standing wave optical masks allowed determination of the minimum average Cs dose (2 Cs atoms per SAM molecule) and the realization of < 50 nm structures. The SAM monolayer contains many non-uniformities such as pin-holes, domain boundaries and monoatomic depressions which are present in the Au surface prior to SAM adsorption. These imperfections limit the use of alkanethiols as a resist in atomic nanolithography experiments. These studies have allowed us to realize an Atom Pencil suitable for deposition of precision quantities of material at the microand nanoscale to an active surface.

Self-Assembled InAs/GaAs Quantum Dot Solar Cells

Our work focuses on experimental and theoretical studies aimed at establishing a fundamental understanding of the principal electrical and optical processes governing the operation of quantum dot solar cells (QDSC) and their feasibility for the realization of intermediate band solar cell (IBSC). Uniform performance QD solar cells with high conversion efficiency have been fabricated using carefully calibrated process recipes as the basis of all reliable experimental characterization. The origin for the enhancement of the short circuit current density (Jsc) in QD solar cells was carefully investigated. External quantum efficiency (EQE) measurements were performed as a measure of the below bandgap distribution of transition states. In this work, we found that the incorporation of self-assembled quantum dots (QDs) interrupts the lattice periodicity and introduce a greatly broadened tailing density of states extending from the bandedge towards mid-gap. A below-bandgap density of states (DOS) model with an extended Urbach tail has been developed. In particular, the below-bandgap photocurrent generation has been attributed to transitions via confined energy states and background continuum tailing states. Photoluminescence measurement is used to measure the energy level of the lowest available state and the coupling effect between QD states and background tailing states because it results from a non-equilibrium process. A basic I-V measurement reveals a degradation of the open circuit voltage (Voc) of QD solar cells, which is related to a one sub-bandgap photon absorption process followed by a direct collection of the generated carriers by the external circuit. We have proposed a modified Shockley-Queisser (SQ) model that predicts the degradation of Voc compared with a reference bulk device. Whenever an energy state within the forbidden gap can facilitate additional absorption, it can facilitate recombination as well. If the recombination is non-radiative, it is detrimental to solar cell performance. We have also investigated the QD trapping effects as deep level energy states. Without an efficient carrier extraction pathway, the QDs can indeed function as mobile carriers traps. Since hole energy levels are mostly connected with hole collection under room temperature, the trapping effect is more severe for electrons. We have tried to electron-dope the QDs to exert a repulsive Coulomb force to help improve the carrier collection efficiency. We have experimentally observed a 30% improvement of Jsc for 4e/dot devices compared with 0e/dot devices. Electron-doping helps with better carrier collection efficiency, however, we have also measured a smaller transition probability from valance band to QD states as a direct manifestation of the Pauli Exclusion Principle. The non-linear performance is of particular interest. With the availability of laser with on-resonance and off-resonance excitation energy, we have explored the photocurrent enhancement by a sequential two-photon absorption (2PA) process via the intermediate states. For the first time, we are able to distinguish the nonlinearity effect by 1PA and 2PA process. The observed 2PA current under off-resonant and on-resonant excitation comes from a two-step transition via the tailing states instead of the QD states. However, given the existence of an extended Urbach tail and the small number of photons available for the intermediate states to conduction band transition, the experimental results suggest that with the current material system, the intensity requirement for an observable enhancement of photocurrent via a 2PA process is much higher than what is available from concentrated sun light. In order to realize the IBSC model, a matching transition strength needs to be achieved between valance band to QD states and QD states to conduction band. However, we have experimentally shown that only a negligible amount of signal can be observed at cryogenic temperature via the transition from QD states to conduction band under a broadband IR source excitation. Based on the understanding we have achieved, we found that the existence of the extended tailing density of states together with the large mismatch of the transition strength from VB to QD and from QD to CB, has systematically put into question the feasibility of the IBSC model with QDs.

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.