Control over microstructure evolution and device performance in solution processable organic field-effect transistors

Die Arbeit beschäftigt sich mit der Kontrolle von Selbstorganisation und Mikrostruktur von organischen Halbleitern und deren Einsatz in OFETs. In Kapiteln 3, 4 und 5 eine neue Lösungsmittel-basierte Verabeitungsmethode, genannt als Lösungsmitteldampfdiffusion, ist konzipiert, um die Selbstorganisation von Halbleitermolekülen auf der Oberfläche zu steuern. Diese Methode als wirkungsvolles Werkzeug erlaubt eine genaue Kontrolle über die Mikrostruktur, wie in Kapitel 3 am Beispiel einer D-A Dyad bestehend aus Hexa-peri-hexabenzocoronene (HBC) als Donor und Perylene Diimide (PDI) als Akzeptor beweisen. Die Kombination aus Oberflächenmodifikation und Lösungsmitteldampf kann die Entnetzungseffekte ausgleichen, so dass die gewüschte Mikrostruktur und molekulare Organisation auf der Oberfläche erreicht werden kann. In Kapiteln 4 und 5 wurde diese Methode eingesetzt, um die Selbstorganisation von Dithieno[2, 3-d;2’, 3’-d’] benzo[1,2-b;4,5-b’]dithiophene (DTBDT) und Cyclopentadithiophene -benzothiadiazole copolymer (CDT-BTZ) Copolymer zu steuern. Die Ergebnisse könnten weitere Studien stimulieren und werfen Licht aus andere leistungsfaähige konjugierte Polymere. rnIn Kapiteln 6 und 7 Monolagen und deren anschlieβende Mikrostruktur von zwei konjugierten Polymeren, Poly (2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) PBTTT und Poly{[N,N ′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis (dicarboximide)-2,6-diyl]-alt-5,5′- (2,2′-bithiophene)}, P(NDI2OD-T2)) wurden auf steife Oberflächen mittels Tauchbeschichtung aufgebracht. Da sist das erste Mal, dass es gelungen ist, Polymer Monolagen aus der Lösung aufzubringen. Dieser Ansatz kann weiter auf eine breite Reihe von anderen konjugierten Polymeren ausgeweitet werden.rnIn Kapitel 8 wurden PDI-CN2 Filme erfolgreich von Monolagen zu Bi- und Tri-Schichten auf Oberflächen aufgebracht, die unterschiedliche Rauigkeiten besitzen. Für das erste Mal, wurde der Einfluss der Rauigkeit auf Lösungsmittel-verarbeitete dünne Schichten klar beschrieben.rn

Fabrication of high-k dielectric thin films for spintronics

Lo scopo di questa tesi è la fabbricazione di ossidi complessi aventi struttura perovskitica, per mezzo della tecnica Channel Spark Ablation (CSA). Più precisamente sono stati depositati film sottili di manganite (LSMO), SrTiO3 (STO) e NdGaO3 (NGO). Inoltre nel laboratorio ospite è stata effettuata la caratterizzazione elettrica e dielettrica (spettroscopia di impedenza), mentre per l'analisi strutturale e chimica ci si è avvalsi di collaborazioni. Sono stati fabbricati dispositivi LSMO/STO/Co e se ne è studiato il comportamento magnetoresistivo e la bistabilità elettrica a seconda del carattere epitassiale od amorfo dell'STO. I risultati più promettenti sono stati ottenuti con STO amorfo. Sono stati costruiti diversi set di condensatori nella configurazione Metallo/Isolante/Semiconduttore (MIS), con M=Au, I=STO o NGO ed S=Nb:STO, allo scopo di indagare la dipendenza delle proprietà dielettriche ed isolanti dai parametri di crescita. In particolare ci si è concentrati sulla temperatura di deposizione e, nel caso dei film di STO, anche sulla dipendenza della costante dielettrica dallo spessore del film. Come ci si aspettava, la costante dielettrica relativa dei film di STO (65 per un film spesso 40 nm e 175 per uno di 170 nm) si è rivelata maggiore di quella dei film di NGO per i quali abbiamo ottenuto un valore di 20, che coincide con il valore del bulk. Nonostante l'elevata capacità per unità di area ottenibile con l'STO, la costante dielettrica di questo materiale risulta fortemente dipendente dallo spessore del film. Un ulteriore aspetto critico relativo all'STO è dato dal livello di ossidazione del film: le vacanze di ossigeno, infatti, possono ridurre la resistività dell'STO (nominalmente molto elevata), ed aumentarne la corrente di perdita. Al contrario l'NGO è meno sensibile ai processi tecnologici e, allo stesso tempo, ha un valore di costante dielettrica più alto rispetto ad un tipico dielettrico come l'ossido di silicio.

Biomechanical model of human cornea based on stromal microstructure

The optical characteristics of the human cornea depends on the mechanical balance between the intra-ocular pressure and intrinsic tissue stiffness. A wide range of ophthalmic surgical procedures alter corneal biomechanics to induce local or global curvature changes for the correction of visual acuity. Due to the large number of surgical interventions performed every day, a deeper understanding of corneal biomechanics is needed to improve the safety of these procedures and medical devices. The aim of this study is to propose a biomechanical model of the human cornea, based on stromal microstructure. The constitutive mechanical law includes collagen fiber distribution based on X-ray scattering analysis, collagen cross-linking, and fiber uncrimping. Our results showed that the proposed model reproduced inflation and extensiometry experimental data [Elsheikh et al., Curr. Eye Res., 2007; Elsheikh et al., Exp. Eye Res., 2008] successfully. The mechanical properties obtained for different age groups demonstrated an increase in collagen cross-linking for older specimens. In future work such a model could be used to simulate non-symmetric interventions, and provide better surgical planning.

Numerical model of the human cornea based on stromal microstructure: identification of mechanical properties for two age groups

The optical quality of the human eye mainly depends on the refractive performance of the cornea. The shape of the cornea is a mechanical balance between intraocular pressure and tissue intrinsic stiffness. Several surgical procedures in ophthalmology alter the biomechanics of the cornea to provoke local or global curvature changes for vision correction. Legitimated by the large number of surgical interventions performed every day, the demand for a deeper understanding of corneal biomechanics is rising to improve the safety of procedures and medical devices. The aim of our work is to propose a numerical model of corneal biomechanics, based on the stromal microstructure. Our novel anisotropic constitutive material law features a probabilistic weighting approach to model collagen fiber distribution as observed on human cornea by Xray scattering analysis (Aghamohammadzadeh et. al., Structure, February 2004). Furthermore, collagen cross-linking was explicitly included in the strain energy function. Results showed that the proposed model is able to successfully reproduce both inflation and extensiometry experimental data (Elsheikh et. al., Curr Eye Res, 2007; Elsheikh et. al., Exp Eye Res, May 2008). In addition, the mechanical properties calculated for patients of different age groups (Group A: 65-79 years; Group B: 80-95 years) demonstrate an increased collagen cross-linking, and a decrease in collagen fiber elasticity from younger to older specimen. These findings correspond to what is known about maturing fibrous biological tissue. Since the presented model can handle different loading situations and includes the anisotropic distribution of collagen fibers, it has the potential to simulate clinical procedures involving nonsymmetrical tissue interventions. In the future, such mechanical model can be used to improve surgical planning and the design of next generation ophthalmic devices.

A microstructure based model of the deformation mechanisms and flow stress during elevated temperature straining of a magnesium alloy

We show that the variation of flow stress with strain rate and grain size in a magnesium alloy deformed at a constant strain rate and 450 °C can be predicted by a crystal plasticity model that includes grain boundary sliding and diffusion. The model predicts the grain size dependence of the critical strain rate that will cause a transition in deformation mechanism from dislocation creep to grain boundary sliding, and yields estimates for grain boundary fluidity and diffusivity.

Efficient fabrication of polymer nanocomposites with effective exfoliation and dispersion by solid-state/melt extrusion

In this communication, solid-state/melt extrusion (SSME) is introduced as a novel technique that combines solid-state shear pulverization (SSSP) and conventional twin screw extrusion (TSE) in a single extrusion system. The morphology and property enhancements in a model linear low-density polyethylene/organically modified clay nanocomposite sample fabricated via SSME were compared to those fabricated via SSSP and TSE. The results show that SSME is capable of exfoliating and dispersing the nanofillers similarly to SSSP, while achieving a desirable output rate and producing extrudate similar in form to that from TSE.

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.

Cortico-cortical white matter motor pathway microstructure is related to psychomotor retardation in major depressive disorder

Alterations of brain structure and function have been associated with psychomotor retardation in major depressive disorder (MDD). However, the association of motor behaviour and white matter integrity of motor pathways in MDD is unclear. The aim of the present study was to first investigate structural connectivity of white matter motor pathways in MDD. Second, we explore the relation of objectively measured motor activity and white matter integrity of motor pathways in MDD. Therefore, 21 patients with MDD and 21 healthy controls matched for age, gender, education and body mass index underwent diffusion tensor imaging and 24 hour actigraphy (measure of the activity level) the same day. Applying a probabilistic fibre tracking approach we extracted connection pathways between the dorsolateral prefrontal cortex (dlPFC), the rostral anterior cingulate cortex (rACC), the pre-supplementary motor area (pre-SMA), the SMA-proper, the primary motor cortex (M1), the caudate nucleus, the putamen, the pallidum and the thalamus. Patients had lower activity levels and demonstrated increased mean diffusivity (MD) in pathways linking left pre-SMA and SMA-proper, and right SMA-proper and M1. Exploratory analyses point to a positive association of activity level and mean-fractional anisotropy in the right rACC-pre-SMA connection in MDD. Only MDD patients with low activity levels had a negative linear association of activity level and mean-MD in the left dlPFC-pre-SMA connection. Our results point to structural alterations of cortico-cortical white matter motor pathways in MDD. Altered white matter organisation of rACC-pre-SMA and dlPFC-pre-SMA pathways may contribute to movement initiation in MDD.

The Effect of Various Electrode Microstructure Parameters on the Effective Conductivity and Three-Phase Boundary Density of Infiltrated SOFC Electrodes

Solid oxide fuel cell (SOFC) technology has the potential to be a significant player in our future energy technology repertoire based on its ability to convert chemical energy into electrical energy. Infiltrated SOFCs, in particular, have demonstrated improved performance and at lower cost than traditional SOFCs. An infiltrated electrode comprises porous ceramic scaffolding (typically constructed from the oxygen ion conducting material) that is infiltrated with electron conducting and catalytic particles. Two important SOFC electrode properties are effective conductivity and three phase boundary density (TPB). Researchers study these electrode properties separately, and fail to recognize them as competing properties. This thesis aims to (1) develop a method to model the TPB density and use it to determine the effect of porosity, scaffolding particle size, and pore former size on TPB density as well as to (2) compare the effect of porosity, scaffolding particle size, and pore former size on TPB density and effective conductivity to determine a desired set of parameters for infiltrated SOFC electrode performance. A computational model was used to study the effect of microstructure parameters on the effective conductivity and TPB density of the infiltrated SOFC electrode. From this study, effective conductivity and TPB density are determined to be competing properties of SOFC electrodes. Increased porosity, scaffolding particle size, and pore former particle size increase the effective conductivity for a given infiltrate loading above percolation threshold. Increased scaffolding particle size and pore former size ratio, however, decreases the TPB density. The maximum TPB density is achievable between porosities of 45% and 60%. The effect of microstructure parameters are more prominent at low loading with scaffolding particle size being the most significant factor and pore former size ratio being the least significant factor.