Spectroscopic investigations of functional bulk and thin film Heusler alloys

Functional and smart materials have gained large scientific and practical interest in current research and development. The Heusler alloys form an important class of functional materials used in spintronics, thermoelectrics, and for shape memory alloy applications. An important aspect of functional materials is the adaptability of their physical properties. In this work functional polycrystalline bulk and epitaxial thin film Heusler alloys are characterized by means of spectroscopic investigation methods, X-ray magnetic circular dichroism (XMCD) and energy dispersive X-ray analysis (EDX). With EDX the homogeneity of the samples is studied extensively. For some cases of quaternary compounds, for example Co2(MnxTi1−x)Sn and Co2(Mn0.5Dy0.5)Sn, an interesting phase separation in two nearly pure ternary Heusler phases occurs. For these samples the phase separation leads to an improvement of thermoelectric properties. XMCD as the main investigation method was used to study Co2TiZ (Z = Si, Sn, and Sb), Co2(MnxTi1−x)Si, Co2(MnxTi1−x)Ge, Co2Mn(Ga1−xGex), Co2FeAl, Mn2VAl, and Ni2MnGa Heusler compounds. The element-specific magnetic moments are calculated. Also, the spin-resolved unoccupied density of states is determined, for example giving hints for half-metallic ferromagnetism for some Co-based compounds. The systematic change of the magnetic moments and the shift of the Fermi energy is a proof that Heusler alloys are suitable for a controlled tailoring of physical properties. The comparison of the experimental results with theoretical predictions improves the understanding of complex materials needed to optimize functional Heusler alloys.

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.

Tailoring, synthesis and structure-property relationships of 2,3-thienoimide based molecular materials

Organic molecular semiconductors are subject of intense research for their crucial role as key components of new generation low cost, flexible, and large area electronic devices such as displays, thin-film transistors, solar cells, sensors and logic circuits. In particular, small molecular thienoimide (TI) based materials are emerging as novel multifunctional materials combining a good processability together to ambipolar or n-type charge transport and electroluminescence at the solid state, thus enabling the fabrication of integrated devices like organic field effect transistors (OFETs) and light emitting transistor (OLETs). Given this peculiar combination of characteristics, they also constitute the ideal substrates for fundamental studies on the structure-property relationships in multifunctional molecular systems. In this scenario, this thesis work is focused on the synthesis of new thienoimide based materials with tunable optical, packing, morphology, charge transport and electroluminescence properties by following a fine molecular tailoring, thus optimizing their performances in device as well as investigating and enabling new applications. Investigation on their structure-property relationships has been carried out and in particular, the effect of different π-conjugated cores (heterocycles, length) and alkyl end chain (shape, length) changes have been studied, obtaining materials with enhanced electron transport capability end electroluminescence suitable for the realization of OFETs and single layer OLETs. Moreover, control on the polymorphic behaviour characterizing thienoimide materials has been reached by synthetic and post-synthetic methodologies, developing multifunctional materials from a single polymorphic compound. Finally, with the aim of synthesizing highly pure materials, simplifying the purification steps and avoiding organometallic residues, procedures based on direct arylation reactions replacing conventional cross-couplings have been investigated and applied to different classes of molecules, bearing thienoimidic core or ends, as well as thiophene and anthracene derivatives, validating this approach as a clean alternative for the synthesis of several molecular materials.

Interfacial interactions, charge transport and growth phenomena in Organic Field Effect Transistors

Organic electronics is an emerging field with a vast number of applications having high potential for commercial success. Although an enormous progress has been made in this research area, many organic electronic applications such as organic opto-electronic devices, organic field effect transistors and organic bioelectronic devices still require further optimization to fulfill the requirements for successful commercialization. The main bottle neck that hinders large scale production of these devices is their performances and stability. The performance of the organic devices largely depends on the charge transport processes occurring at the interfaces of various material that it is composed of. As a result, the key ingredient needed for a successful improvement in the performance and stability of organic electronic devices is an in-depth knowledge of the interfacial interactions and the charge transport phenomena taking place at different interfaces. The aim of this thesis is to address the role of the various interfaces between different material in determining the charge transport properties of organic devices. In this framework, I chose an Organic Field Effect Transistor (OFET) as a model system to carry out this study as it An OFET offers various interfaces that can be investigated as it is made up of stacked layers of various material. In order to probe the intrinsic properties that governs the charge transport, we have to be able to carry out thorough investigation of the interactions taking place down at the accumulation layer thickness. However, since organic materials are highly instable in ambient conditions, it becomes quite impossible to investigate the intrinsic properties of the material without the influence of extrinsic factors like air, moisture and light. For this reason, I have employed a technique called the in situ real-time electrical characterization technique which enables electrical characterization of the OFET during the growth of the semiconductor.

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

Thin-Film Sparse Boundary Array Design for Passive Acoustic Mapping During Ultrasound Therapy

A new 2-D hydrophone array for ultrasound therapy monitoring is presented, along with a novel algorithm for passive acoustic mapping using a sparse weighted aperture. The array is constructed using existing polyvinylidene fluoride (PVDF) ultrasound sensor technology, and is utilized for its broadband characteristics and its high receive sensitivity. For most 2-D arrays, high-resolution imagery is desired, which requires a large aperture at the cost of a large number of elements. The proposed array's geometry is sparse, with elements only on the boundary of the rectangular aperture. The missing information from the interior is filled in using linear imaging techniques. After receiving acoustic emissions during ultrasound therapy, this algorithm applies an apodization to the sparse aperture to limit side lobes and then reconstructs acoustic activity with high spatiotemporal resolution. Experiments show verification of the theoretical point spread function, and cavitation maps in agar phantoms correspond closely to predicted areas, showing the validity of the array and methodology.

Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

Investigation into the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film gadolinium-doped ceria

The research reported in this dissertation investigates the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film Gd-doped CeO2 (GDC). Chapter 2 of this work addresses claims in the literature that submicron grain boundaries have the potential to dramatically increase the ionic conductivity of GDC films. Unambiguous testing of this claim requires directly comparing the ionic conductivity of single-crystal GDC films to films that are identical except for the presence of submicron grain boundaries. In this work techniques have been developed to grow GDC films by RF magnetron sputtering from a GDC target on single crystal r plane sapphire substrates. These techniques allow the growth of films that are single crystals or polycrystalline with 80 nm diameter grains. The ionic conductivities of these films have been measured and the data shows that the ionic conductivity of single crystal GDC is greater than that of the polycrystalline films by more than a factor of 4 over the 400-700°C temperature range. Chapter 3 of this work investigates the ionic conductivity of surface and interface regions of thin film Gd-doped CeO2. In this study, single crystal GDC films have been grown to thicknesses varying from 20 to 500 nm and their conductivities have been measured in the 500-700°C temperature range. Decreasing conductivity with decreasing film thickness was observed. Analysis of the conductivity data is consistent with the presence of an approximately 50 nm layer of less conductive material in every film. This study concludes that the surface and interface regions of thin film GDC are less conductive than the bulk single crystal regions, rather than being highly conductive paths. Chapter 4 of this work investigates the ionic conductivity of thin film Gd-doped CeO2 (GDC) as a function of crystallographic orientation. A theoretical expression has been developed for the ionic conductivity of the [100] and [110] directions in single crystal GDC. This relationship is compared to experimental data collected from a single crystal GDC film. The film was grown to a thickness of _300 nm and its conductivity measured along the [100] and [110] orientations in the 500-700°C temperature range. The experimental data shows no statistically significant difference in the conductivities of the [100] and [110] directions in single crystal GDC. This result agrees with the theoretical model which predicts no difference between the conductivities of the two directions.

HOMO Stabilisation in π-Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field-Effect Transistors

Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB-TTF) central core and a 2,1,3-chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB-TTF, have been synthesised as active materials for organic field-effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron-withdrawing 2,1,3-chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution-processed single-crystal transistors exhibit high performance with a hole mobility up to 0.04 cm2 V−1 s−1 as well as good ambient stability.

Transport properties of CuGaSe(2)-based thin-film solar cells as a function of absorber composition

The transport properties of thin-film solar cells based on wide-gap CuGaSe(2) absorbers have been investigated as a function of the bulk [Ga]/[Cu] ratio ranging from 1.01 to 1.33. We find that (i) the recombination processes in devices prepared from absorbers with a composition close to stoichiometry ([Ga]/[Cu] = 1.01) are strongly tunnelling assisted resulting in low recombination activation energies (E(a)) of approx. 0.95 eV in the dark and 1.36 eV under illumination. (ii) With an increasing [Ga]/[Cu] ratio, the transport mechanism changes to be dominated by thermally activated Shockley-Read-Hall recombination with similar E(a) values of approx. 1.52-1.57 eV for bulk [Ga]/[Cu] ratios of 1.12-1.33. The dominant recombination processes take place at the interface between CdS buffer and CuGaSe(2) absorber independently from the absorber composition. The increase of E(a) with the [Ga]/[Cu] ratio correlates with the open circuit voltage and explains the better performance of corresponding solar cells.

First principles study of Bi dopen CdTe thin film solar cells: electronic and optical properties

Nowadays, efficiency improvement of solar cells is one of the most important issues in photovoltaic systems and CdTe is one of the most promising thin film photovoltaic materials we can found. CdTe reported efficiencies in solar energy conversion have been as good as that found in polycrystalline Si thin film cell [1], besides CdTe can be easily produced at industrial scale.

Characterization of thin film PV modules under standard test conditions: Results of indoor and outdoor measurements and the effects of sunlight exposure

Photovoltaic modules based on thin film technology are gaining importance in the photovoltaic market, and module installers and plant owners have increasingly begun to request methods of performing module quality control. These modules pose additional problems for measuring power under standard test conditions (STC), beyond problems caused by the temperature of the module and the ambient variables. The main difficulty is that the modules’ power rates may vary depending both on the amount of time they have been exposed to the sun during recent hours and on their history of sunlight exposure. In order to assess the current state of the module, it is necessary to know its sunlight exposure history. Thus, an easily accomplishable testing method that ensures the repeatability of the measurements of the power generated is needed. This paper examines different tests performed on commercial thin film PV modules of CIS, a-Si and CdTe technologies in order to find the best way to obtain measurements. A method for obtaining indoor measurements of these technologies that takes into account periods of sunlight exposure is proposed. Special attention is paid to CdTe as a fast growing technology in the market.

Selective ablation with UV lasers of a-Si:H thin film solar cells in direct scribing configuration

Monolithical series connection of silicon thin-film solar cells modules performed by laser scribing plays a very important role in the entire production of these devices. In the current laser process interconnection the two last steps are developed for a configuration of modules where the glass is essential as transparent substrate. In addition, the change of wavelength in the employed laser sources is sometimes enforced due to the nature of the different materials of the multilayer structure which make up the device. The aim of this work is to characterize the laser patterning involved in the monolithic interconnection process in a different configurations of processing than the usually performed with visible laser sources. To carry out this study, we use nanosecond and picosecond laser sources working at 355nm of wavelength in order to achieve the selective ablation of the material from the film side. To assess this selective removal of material has been used EDX (energy dispersive using X-ray) analysis