Crystal Engineering of bright luminescent copper iodide clusters with phosphorus and nitrogen-based ligands

Copper(I) halide clusters are recently considered as good candidate for optoelectronic devices such as OLEDs . Although the copper halide clusters, in particular copper iodide, are very well known since the beginning of the 20th century, only in the late ‘70s the interest on these compounds grew dramatically due their particular photophysical behaviour. These complexes are characterized by a dual triplet emission bands, named Cluster Centred (3CC) and Halogen-to-Ligand charge transfer (3XLCT), the intensities of which are strictly related with the temperature. The CC transition, due to the presence of a metallophylic interactions, is prevalent at ambient temperature while the XLCT transition, located preferentially on the ligand part, became more prominent at low temperature. Since these pioneering works, it was easy to understand the photophysical properties of this compounds became more interesting in solid-state respect to solution with an improvement in emission efficiency. In this work we aim to characterize in SS organocopper(I)iodide compounds to valuate the correlation between the molecular crystal structure and the photophysical properties. It is also considered to hike new strategies to synthesize CuI complexes from the wet reactions to the more green solvent free methods. The advantages in using these strategies are evident but, obtain a single crystal suitable for SCXRD analysis from these batches is quite impossible. The structure solution still remains the key point in this research so we tackle this problem solving the structure by X-ray powder diffraction data. When the sample was fully characterized we moved to design and development of the associated OLED-device. Since copper iodide complexes are often insoluble in organic solvents, the high vacuum deposition technique is preferred. A new non-conventional deposition process have also been proposed to avoid the low complex stability in this practice with an in-situ complex formation in a layer-by layer deposition route.

Donor–acceptor systems in the quest for organic semiconductors

Die letzten Jahrzehnte brachten eine Vielzahl neuer organischen Halbleiter hervor, welche erfolgreich als aktive Materialien in Bauteilen eingesetzt wurden, wie zum Beispiel Feldeffekttransistoren (FET), organische Leuchtdioden (OLED), organischen Photovoltaikzellen (OPV) und Sensoren. Einige dieser Materialien haben, obwohl sich die Technolgie noch in der „Pubertät“ befindet, die minimalen Anforderungen für eine kommerzielle Anwendung erreicht, wobei jedoch vieles noch zu entdecken, erklären und verstehen bleibt. Diese Arbeit beschreibt das Design, die Synthese und Charakterisierung neuartiger halbleitender Polymere mit speziell eingestellten optoelektronischen Eigenschaften, welche effiziente ambipolare oder n-Leitung in OFET’s und OPV’s zeigen. Das Hauptziel wurde dadurch erreicht, dass sowohl die vorteilhaften Eigenschaften des planaren, elektronenarmen heterozyklischen Bausteines Thiadiazolo[3,4-g]quinoxalin als auch von Ethinbrücken, welche den Donor (D) und den Akzeptor (A) in einem D-A-Copolymer verbinden, durch systematische Optimierung ausgenutzt wurden. Neben synthetischen Herausforderungen werden in dieser Arbeit auch detailiiete Untersuchungen der optoelektronischen Eigenschaften der hergestellten konjugierten Polymere und Modellverbindungen dargelegt. Darüber hinaus beschreibt diese Arbeit erstmals ein Beispiel für ein Polymer, welches Dreifachbindungen im Polymerrückgrat enthält, und nahezu eine ausgeglichene ambipolare Ladungsträgerleitung in OFET’s zeigt. Zusätzlich werden gemischt-valente Phenothiazine, verbrückt mittels elektronenarmen pi-Brücken wie etwa Benzo[c][2,1,3]thiadiazol, und deren Elektronentransferprozesse, im Rahmen der Marcus-Hush-Theorie, untersucht.

Optimization of purification procedures in organic semiconductor synthesis for improving the performances of organic field-effect transistors

The aim of the research activity focused on the investigation of the correlation between the degree of purity in terms of chemical dopants in organic small molecule semiconductors and their electrical and optoelectronic performances once introduced as active material in devices. The first step of the work was addressed to the study of the electrical performances variation of two commercial organic semiconductors after being processed by means of thermal sublimation process. In particular, the p-type 2,2′′′-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DH4T) semiconductor and the n-type 2,2′′′- Perfluoro-Dihexyl-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (DFH4T) semiconductor underwent several sublimation cycles, with consequent improvement of the electrical performances in terms of charge mobility and threshold voltage, highlighting the benefits brought by this treatment to the electric properties of the discussed semiconductors in OFET devices by the removal of residual impurities. The second step consisted in the provision of a metal-free synthesis of DH4T, which was successfully prepared without organometallic reagents or catalysts in collaboration with Dr. Manuela Melucci from ISOF-CNR Institute in Bologna. Indeed the experimental work demonstrated that those compounds are responsible for the electrical degradation by intentionally doping the semiconductor obtained by metal-free method by Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) and Tributyltin chloride (Bu3SnCl), as well as with an organic impurity, like 5-hexyl-2,2':5',2''-terthiophene (HexT3) at, in different concentrations (1, 5 and 10% w/w). After completing the entire evaluation process loop, from fabricating OFET devices by vacuum sublimation with implemented intentionally-doped batches to the final electrical characterization in inherent-atmosphere conditions, commercial DH4T, metal-free DH4T and the intentionally-doped DH4T were systematically compared. Indeed, the fabrication of OFET based on doped DH4T clearly pointed out that the vacuum sublimation is still an inherent and efficient purification method for crude semiconductors, but also a reliable way to fabricate high performing devices.

A New Test Rig for In-Vitro Evaluation of the Knee Joint Behaviour

The evaluation of the knee joint behavior is fundamental in many applications, such as joint modeling, prosthesis and orthosis design. In-vitro tests are important in order to analyse knee behavior when simulating various loading conditions and studying physiology of the joint. A new test rig for in-vitro evaluation of the knee joint behavior is presented in this paper. It represents the evolution of a previously proposed rig, designed to overcome its principal limitations and to improve its performances. The design procedure and the adopted solution in order to satisfy the specifications are presented here. Thanks to its 6-6 Gough-Stewart parallel manipulator loading system, the rig replicates general loading conditions, like daily actions or clinical tests, on the specimen in a wide range of flexion angles. The restraining actions of knee muscles can be simulated when active actions are simulated. The joint motion in response to the applied loads, guided by passive articular structures and muscles, is permitted by the characteristics of the loading system which is force controlled. The new test rig guarantees visibility so that motion can be measured by an optoelectronic system. Furthermore, the control system of the new test rig allows the estimation of the contribution of the principal leg muscles in guaranteeing the equilibrium of the joint by the system for muscle simulation. Accuracy in positioning is guaranteed by the designed tibia and femur fixation systems,which allow unmounting and remounting the specimen in the same pose. The test rig presented in this paper permits the analysis of the behavior of the knee joint and comparative analysis on the same specimen before and after surgery, in a way to assess the goodness of prostheses or surgical treatments.

Characterization of integrated Bragg gratings in silicon-on-insulator

Silicon-on-insulator (SOI) is rapidly emerging as a very promising material platform for integrated photonics. As it combines the potential for optoelectronic integration with the low-cost and large volume manufacturing capabilities and they are already accumulate a huge amount of applications in areas like sensing, quantum optics, optical telecommunications and metrology. One of the main limitations of current technology is that waveguide propagation losses are still much higher than in standard glass-based platform because of many reasons such as bends, surface roughness and the very strong optical confinement provided by SOI. Such high loss prevents the fabrication of efficient optical resonators and complex devices severely limiting the current potential of the SOI platform. The project in the first part deals with the simple waveguides loss problem and trying to link that with the polarization problem and the loss based on Fabry-Perot Technique. The second part of the thesis deals with the Bragg Grating characterization from again the point of view of the polarization effect which leads to a better stop-band use filters. To a better comprehension a brief review on the basics of the SOI and the integrated Bragg grating ends up with the fabrication techniques and some of its applications will be presented in both parts, until the end of both the third and the fourth chapters to some results which hopefully make its precedent explanations easier to deal with.

Combining 3D tracking and surgical instrumentation to determine the stiffness of spinal motion segments: a validation study

The spine is a complex structure that provides motion in three directions: flexion and extension, lateral bending and axial rotation. So far, the investigation of the mechanical and kinematic behavior of the basic unit of the spine, a motion segment, is predominantly a domain of in vitro experiments on spinal loading simulators. Most existing approaches to measure spinal stiffness intraoperatively in an in vivo environment use a distractor. However, these concepts usually assume a planar loading and motion. The objective of our study was to develop and validate an apparatus, that allows to perform intraoperative in vivo measurements to determine both the applied force and the resulting motion in three dimensional space. The proposed setup combines force measurement with an instrumented distractor and motion tracking with an optoelectronic system. As the orientation of the applied force and the three dimensional motion is known, not only force-displacement, but also moment-angle relations could be determined. The validation was performed using three cadaveric lumbar ovine spines. The lateral bending stiffness of two motion segments per specimen was determined with the proposed concept and compared with the stiffness acquired on a spinal loading simulator which was considered to be gold standard. The mean values of the stiffness computed with the proposed concept were within a range of ±15% compared to data obtained with the spinal loading simulator under applied loads of less than 5 Nm.

Intraoperative determination of the load-displacement behavior of scoliotic spinal motion segments: preliminary clinical results

Introduction: Spinal fusion is a widely and successfully performed strategy for the treatment of spinal deformities and degenerative diseases. The general approach has been to stabilize the spine with implants so that a solid bony fusion between the vertebrae can develop. However, new implant designs have emerged that aim at preservation or restoration of the motion of the spinal segment. In addition to static, load sharing principles, these designs also require a profound knowledge of kinematic and dynamic properties to properly characterise the in vivo performance of the implants. Methods: To address this, an apparatus was developed that enables the intraoperative determination of the load–displacement behavior of spinal motion segments. The apparatus consists of a sensor-equipped distractor to measure the applied force between the transverse processes, and an optoelectronic camera to track the motion of vertebrae and the distractor. In this intraoperative trial, measurements from two patients with adolescent idiopathic scoliosis with right thoracic curves were made at four motion segments each. Results: At a lateral bending moment of 5 N m, the mean flexibility of all eight motion segments was 0.18 ± 0.08°/N m on the convex side and 0.24 ± 0.11°/N m on the concave side. Discussion: The results agree with published data obtained from cadaver studies with and without axial preload. Intraoperatively acquired data with this method may serve as an input for mathematical models and contribute to the development of new implants and treatment strategies.

Augmenting the effective field of view of optical tracking cameras--a way to overcome difficulties during intraoperative camera alignment

An Internet survey demonstrated the existence of problems related to intraoperative tracking camera set-up and alignment. It is hypothesized that these problems are a result of the limited field of view of today's optoelectronic camera systems, which is usually insufficiently large to keep the entire site of surgical action in view during an intervention. A method is proposed to augment a camera's field of view by actively controlling camera orientation, enabling it to track instruments as they are used intraoperatively. In an experimental study, an increase of almost 300% was found in the effective volume in which instruments could be tracked.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

The application of biomechanics to penalty corner drag-flick training: a case of Study

The penalty corner is one of the most important game situations in field hockey with one third of all goals resulting from this tactical situation. The aim of this study was to develop and apply a training method, based on previous studies, to improve the drag- flick skill on a young top-class field hockey player. A young top-class player exercised three times per week using specific drills over a four week period. A VICON optoelectronic system (Oxford Metrics, Oxford, UK) was employed to capture twenty drag-flicks, with six cameras sampling at 250 Hz, prior and after the training period. In order to analyze pre- and post-test differences a dependent t-test was carried out. Angular velocities and the kinematic sequence were similar to previous studies. The player improved (albeit not significantly) the angular velocity of the stick. The player increased front foot to the ball at T1 (p < 0.01) and the drag-flick distances. The range of motion from the front leg decreased from T1 to T6 after the training period (p < 0.01). The specific training sessions conducted with the player improved some features of this particular skill. This article shows how technical knowledge can help with the design of training programs and whether some drills are more effective than others.

Fabrication of GaN nanorods by focused ion beam

Ordered arrays of III-Nitride nanocolumns are excellent candidates for the fabrication of nano-optoelectronic devices. Different technologies such as e-beam lithography or colloidal lithography, have been used to obtain ordered arrays. All these technologies have in common several processing steps that can affect the crystalline growth of the nanocolumns. In this work, we present a single lithographic step that permits to grow ordered GaN nanocolumns with different geometries. The patterning is based in the use of a focusedionbeam with different doses. With this method has been possible to create GaN nanopillars and nanocylinders

Gas sensor based on room temperature optical properties of Surface QDs

Self-organized InGaAs QDs are intensively studied for optoelectronic applications. Several approaches are in study to reach the emission wavelengths needed for these applications. The use of antimony (Sb) in either the capping layer or into the dots is one example. However, these studies are normally focused on buried QD (BQD) where there are still different controversial theories concerning the role of Sb. Ones suggest that Sb incorporates into the dot [1], while others support the hypothesis that the Sb occupies positions surrounding the dot [2] thus helping to keep their shape during the capping growth.

Upper Limb Portable Motion Analysis System Based on Inertial Technology for Neurorehabilitation Purposes

Here an inertial sensor-based monitoring system for measuring and analyzing upper limb movements is presented. The final goal is the integration of this motion-tracking device within a portable rehabilitation system for brain injury patients. A set of four inertial sensors mounted on a special garment worn by the patient provides the quaternions representing the patient upper limb’s orientation in space. A kinematic model is built to estimate 3D upper limb motion for accurate therapeutic evaluation. The human upper limb is represented as a kinematic chain of rigid bodies with three joints and six degrees of freedom. Validation of the system has been performed by co-registration of movements with a commercial optoelectronic tracking system. Successful results are shown that exhibit a high correlation among signals provided by both devices and obtained at the Institut Guttmann Neurorehabilitation Hospital.

One-watt fiber-based power-by-light system for satellite applications

In this work, a fiber-based optical powering (or power-by-light) system capable of providing more than 1 W is developed. The prototype was used in order to power a shunt regulator for controlling the activation and deactivation of solar panels in satellites. The work involves the manufacture of a light receiver (a GaAs multiple photovoltaic converter (MPC)), a power conditioning block, and a regulator and the implementation and characterization of the whole system. The MPC, with an active area of just 3.1 mm2, was able to supply 1 W at 5 V with an efficiency of 30%. The maximum measured device efficiency was over 40% at an input power (Pin) of 0.5 W. Open circuit voltage over 7 V was measured for Pin over 0.5 W. A system optoelectronic efficiency (including the optical fiber, connectors, and MPC) of 27% was measured at an output power (Pout) of 1 W. At Pout = 0.2 W, the efficiency was as high as 36%. The power conditioning block and the regulator were successfully powered with the system. The maximum supplied power in steady state was 0.2 W, whereas in transient state, it reached 0.44 W. The paper also describes the characterization of the system within the temperature range going from -70 to +100?°C.

Effect of the oxygen isoelectronic substitution in Cu2ZnSnS4 and its photovoltaic application

The optoelectronic properties of Cu2ZnSnS4 and environmental considerations have attracted significant interest for photovoltaics. Using first-principles, we analyze the possible improvement of this material as a photovoltaic absorber via the isoelectronic substitution of S with O atoms. The evolution of the acceptor level is analyzed with respect to the atomic position of the nearest neighbors of the O atom. We estimate the maximum efficiency of this compound when used as a light absorber. The presence of the sub-band gap level below the conduction band could increases the solar-energy conversion with respect to the host.