Electron tomography of (In,Ga)N insertions in GaN nanocolumns grown on semi-polar (11(2)over-bar2) GaN templates

We present results of scanning transmission electron tomography on GaN/(In,Ga)N/GaN nanocolumns (NCs) that grew uniformly inclined towards the patterned, semi-polar GaN( 112̄ 2 ) substrate surface by molecular beam epitaxy. For the practical realization of the tomographic experiment, the nanocolumn axis has been aligned parallel to the rotation axis of the electron microscope goniometer. The tomographic reconstruction allows for the determination of the three-dimensional indium distribution inside the nanocolumns. This distribution is strongly interrelated with the nanocolumn morphology and faceting. The (In,Ga)N layer thickness and the indium concentration differ between crystallographically equivalent and non-equivalent facets. The largest thickness and the highest indium concentration are found at the nanocolumn apex parallel to the basal planes.

Detection of explosive vapors using organic thin-film transistors

Field effect transistors (FETs) based on organic materials were investigated as sensors for detecting 2,4,6-trinitrotoluene (TNT) vapors. Several FET devices were fabricated using two types of semiconducting organic materials, solution processed polymers deposited by spin coating and, oligomers (or small molecules) deposited by vacuum sublimation. When vapors of nitroaromatic compounds bind to thin films of organic materials which form the transistor channel, the conductivity of the thin film increases and changes the transistor electrical characteristic. The use of the amplifying properties of the transistor represents a major advantage over conventional techniques based on simple changes of resistance in polymers frequently used in electronic noses.

A THEORETICAL STUDY OF INTERACTION OF NANOPARTICLES WITH BIOMOLECULE

Many types of materials at nanoscale are currently being used in everyday life. The production and use of such products based on engineered nanomaterials have raised concerns of the possible risks and hazards associated with these nanomaterials. In order to evaluate and gain a better understanding of their effects on living organisms, we have performed first-principles quantum mechanical calculations and molecular dynamics simulations. Specifically, we will investigate the interaction of nanomaterials including semiconducting quantum dots and metallic nanoparticles with various biological molecules, such as dopamine, DNA nucleobases and lipid membranes. Firstly, interactions of semiconducting CdSe/CdS quantum dots (QDs) with the dopamine and the DNA nucleobase molecules are investigated using similar quantum mechanical approach to the one used for the metallic nanoparticles. A variety of interaction sites are explored. Our results show that small-sized Cd4Se4 and Cd4S4 QDs interact strongly with the DNA nucleobase if a DNA nucleobase has the amide or hydroxyl chemical group. These results indicate that these QDs are suitable for detecting subcellular structures, as also reported by experiments. The next two chapters describe a preparation required for the simulation of nanoparticles interacting with membranes leading to accurate structure models for the membranes. We develop a method for the molecular crystalline structure prediction of 1,2-Dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC), 1,2-Dimyristoyl-sn-glycero-3-phosphorylethanolamine (DMPE) and cyclic di-amino acid peptide using first-principles methods. Since an accurate determination of the structure of an organic crystal is usually an extremely difficult task due to availability of the large number of its conformers, we propose a new computational scheme by applying knowledge of symmetry, structural chemistry and chemical bonding to reduce the sampling size of the conformation space. The interaction of metal nanoparticles with cell membranes is finally carried out by molecular dynamics simulations, and the results are reported in the last chapter. A new force field is developed which accurately describes the interaction forces between the clusters representing small-sized metal nanoparticles and the lipid bilayer molecules. The permeation of nanoparticles into the cell membrane is analyzed together with the RMSD values of the membrane modeled by a lipid bilayer. The simulation results suggest that the AgNPs could cause the same amount of deformation as the AuNPs for the dysfunction of the membrane.

Theory and optimisation of 1.3 and 1.55 μm (Al)InGaAs metamorphic quantum well lasers

The use of InGaAs metamorphic buffer layers (MBLs) to facilitate the growth of lattice-mismatched heterostructures constitutes an attractive approach to developing long-wavelength semiconductor lasers on GaAs substrates, since they offer the improved carrier and optical confinement associated with GaAs-based materials. We present a theoretical study of GaAs-based 1.3 and 1.55 μm (Al)InGaAs quantum well (QW) lasers grown on InGaAs MBLs. We demonstrate that optimised 1.3 μm metamorphic devices offer low threshold current densities and high differential gain, which compare favourably with InP-based devices. Overall, our analysis highlights and quantifies the potential of metamorphic QWs for the development of GaAs-based long-wavelength semiconductor lasers, and also provides guidelines for the design of optimised devices.

High bandwidth freestanding semipolar (11–22) InGaN/GaN light-emitting diodes

Freestanding semipolar (11–22) indium gallium nitride (InGaN) multiplequantum-well light-emitting diodes (LEDs) emitting at 445 nm have been realized by the use of laser lift-off (LLO) of the LEDs from a 50- m-thick GaN layer grown on a patterned (10–12) r -plane sapphire substrate (PSS). The GaN grooves originating from the growth on PSS were removed by chemical mechanical polishing. The 300 m × 300 m LEDs showed a turn-on voltage of 3.6 V and an output power through the smooth substrate of 0.87 mW at 20 mA. The electroluminescence spectrum of LEDs before and after LLO showed a stronger emission intensity along the [11–23]InGaN/GaN direction. The polarization anisotropy is independent of the GaN grooves, with a measured value of 0.14. The bandwidth of the LEDs is in excess of 150 MHz at 20 mA, and back-to-back transmission of 300 Mbps is demonstrated, making these devices suitable for visible light communication (VLC) applications.

Modifying the band gap and optical properties of Germanium nanowires by surface termination

Semiconductor nanowires, based on silicon (Si) or germanium (Ge) are leading candidates for many ICT applications, including next generation transistors, optoelectronics, gas and biosensing and photovoltaics. Key to these applications is the possibility to tune the band gap by changing the diameter of the nanowire. Ge nanowires of different diameter have been studied with H termination, but, using ideas from chemistry, changing the surface terminating group can be used to modulate the band gap. In this paper we apply the generalised gradient approximation of density functional theory (GGA-DFT) and hybrid DFT to study the effect of diameter and surface termination using –H, –NH2 and –OH groups on the band gap of (001), (110) and (111) oriented germanium nanowires. We show that the surface terminating group allows both the magnitude and the nature of the band gap to be changed. We further show that the absorption edge shifts to longer wavelength with the –NH2 and –OH terminations compared to the –H termination and we trace the origin of this effect to valence band modifications upon modifying the nanowire with –NH2 or –OH. These results show that it is possible to tune the band gap of small diameter Ge nanowires over a range of ca. 1.1 eV by simple surface chemistry.

Carrier momentum relaxation in highly doped polar semiconductors and semiconductor heterostructures

Highly doped polar semiconductors are essential components of today’s semiconductor industry. Most strikingly, transistors in modern electronic devices are polar semiconductor heterostructures. It is important to thoroughly understand carrier transport in such structures. In doped polar semiconductors, collective excitations of the carriers (plasmons) and the atoms (polar phonons) couple. These coupled collective excitations affect the electrical conductivity, here quantified through the carrier mobility. In scattering events, the carriers and the coupled collective modes transfer momentum between each other. Carrier momentum transferred to polar phonons can be lost to other phonons through anharmonic decay, resulting in a finite carrier mobility. The plasmons do not have a decay mechanism which transfers carrier momentum irretrievably. Hence, carrier-plasmon scattering results in infinite carrier mobility. Momentum relaxation due to either carrier–plasmon scattering or carrier–polar-phonon scattering alone are well understood. However, only this thesis manages to treat momentum relaxation due to both scattering mechanisms on an equal footing, enabling us to properly calculate the mobility limited by carrier–coupled plasmon–polar phonon scattering. We achieved this by solving the coupled Boltzmann equations for the carriers and the collective excitations, focusing on the “drag” term and on the anharmonic decay process of the collective modes. Our approach uses dielectric functions to describe both the carrier-collective mode scattering and the decay of the collective modes. We applied our method to bulk polar semiconductors and heterostructures where various polar dielectrics surround a semiconducting monolayer of MoS2, where taking plasmons into account can increase the mobility by up to a factor 15 for certain parameters. This screening effect is up to 85% higher than if calculated with previous methods. To conclude, our approach provides insight into the momentum relaxation mechanism for carrier–coupled collective mode scattering, and better tools for calculating the screened polar phonon and interface polar phonon limited mobility.

Cálculo de constantes ópticas de películas delgadas de Cu3BiS3 a través del método de Wolfe

Se calculó la obtención de las constantes ópticas usando el método de Wolfe. Dichas contantes: coeficiente de absorción (α), índice de refracción (n) y espesor de una película delgada (d ), son de importancia en el proceso de caracterización óptica del material. Se realizó una comparación del método del Wolfe con el método empleado por R. Swanepoel. Se desarrolló un modelo de programación no lineal con restricciones, de manera que fue posible estimar las constantes ópticas de películas delgadas semiconductoras, a partir únicamente, de datos de transmisión conocidos. Se presentó una solución al modelo de programación no lineal para programación cuadrática. Se demostró la confiabilidad del método propuesto, obteniendo valores de α = 10378.34 cm−1, n = 2.4595, d =989.71 nm y Eg = 1.39 Ev, a través de experimentos numéricos con datos de medidas de transmitancia espectral en películas delgadas de Cu3BiS3.

Hall Effect and transient surface photovoltage (SPV) study of Cu3BiS3 thin films

Se presentan las propiedades eléctricas del compuesto Cu3BiS3 depositado por co-evaporación. Este es un nuevo compuesto que puede tener propiedades adecuadas para ser utilizado como capa absorbente en celdas solares. Las muestras fueron caracterizadas a través de medidas de efecto Hall y fotovoltaje superficial transiente (SPV). A través de medidas de efecto Hall se encontró que la concentración de portadores de carga n es del orden de 1016 cm-3 independiente de la relación de masas de Cu/Bi. También se encontró que la movilidad de este compuesto (μ del orden de 4 cm2V -1s-1) varía de acuerdo con los mecanismos de transporte que la gobiernan en dependencia con la temperatura. A partir de las medidas de SPV se encontró alta densidad de defectos superficiales, defectos que son pasivados al superponer una capa buffer sobre el compuesto Cu3BiS3.

New functional polythiophene based materials: fine-tuning of photovoltaic or chiroptical properties

There is a remarkable level of interest in the development of π-conjugated polymers (ICPs) which have been employed, thanks to their promising optical and electronic properties, in numerous applications including photovoltaic cells, light emitting diodes and thin-film transistors. Although high power conversion efficiency can be reached using poly(3-alkylthiophenes) (P3ATs) as electron-donating materials in polymeric solar cells of the Bulk-Heterojunction type (BHJ), their relatively large band gap limits the solar spectrum fraction that can be utilized. The research work described in this dissertation thus concerns the synthesis, characterization and study of the optical and photoactivity properties of new organic semiconducting materials based on polythiophenes. In detail, various narrow band gap polymers and copolymers were developed through different approaches and were characterized by several complementary techniques, such as gel permeation chromatography (GPC), NMR spectroscopy, thermal analyses (DSC, TGA), UV-Vis/PL spectroscopy and cyclic voltammetry (CV), in order to investigate their structural and chemical/photophysical properties. Moreover, the polymeric derivatives were tested as active material in air-processed organic solar cells. The activity has also been devoted to investigate the behavior of polythiophenes with chiral side chain, that are fascinating materials capable to assume helix supramolecular structures, exhibiting optical activity in the aggregated state.

Optoelectronic investigation of defects in hybrid metal halide perovskites

The growing demand for flexible and low-cost electronics has driven research towards the study of novel semiconducting materials to replace traditional semiconductors like silicon and germanium, which are limited by mechanical rigidity and high production cost. Some of the most promising semiconductors in this sense are metal halide perovskites (MHPs), which combine low-cost fabrication and solution processability with exceptional optoelectronic properties like high absorption coefficient, long charge carrier lifetime, and high mobility. These properties, combined with an impressive effort by many research groups around the world, have enabled the fabrication of solar cells with record-breaking efficiencies, and photodetectors with better performance than commercial ones. However, MHP devices are still affected by issues that are hindering their commercialization, such as degradation under humidity and illumination, ion migration, electronic defects, and limited resistance to mechanical stress. The aim of this thesis work is the experimental characterization of these phenomena. We investigated the effects of several factors, such as X-ray irradiation, exposure to environmental gases, and atmosphere during synthesis, on the optoelectronic properties of MHP single crystals. We achieved this by means of optical spectroscopy, electrical measurements, and chemical analyses. We identified the cause of mechanical delamination in MHP/silicon tandem solar cells by atomic force microscopy measurements. We characterized electronic defects and ion migration in MHP single crystals by applying for the first time the photo-induced current transient spectroscopy technique to this class of materials. This research allowed to gain insight into both intrinsic defects, like ion migration and electron trapping, and extrinsic defects, induced by X-ray irradiation, mechanical stress, and exposure to humidity. This research paves the way to the development of methods that heal and passivate these defects, enabling improved performance and stability of MHP optoelectronic devices.

Design, synthesis and photovoltaic properties of some thiophene-based conjugated polymers for organic solar cells

The current issue of the resource of energy combined with the tendency to give a green footprint to our lifestyle have prompted the research to focus the attention on alternative sources with great strides in the optimization of polymeric photovoltaic devices. The research work described in this dissertation consists in the study of different semiconducting π-conjugated materials based on polythiophenes (Chapter I). In detail, the GRIM polymerization was deepened defining the synthetic conditions to obtain regioregular poly(3-alkylthiophene) (Chapter II). Since the use of symmetrical monomers functionalized with oxygen atom(s) allows to adopt easy synthesis leading to performing materials, disubstituted poly(3,4-dialkoxythiophene)s were successfully prepared, characterized and tested as photoactive materials in solar cells (Chapter III). A “green” resource of energy should be employed through sustainable devices and, for this purpose, the research work was continued on the synthesis of thiophene derivatives soluble in eco-friendly solvents. To make this possible, the photoactive layer was completely tailored starting from the electron-acceptor material. A fullerene derivative soluble in alcohols was successfully synthetized and adopted for the realization of the new devices (Chapter IV). New water/alcohol soluble electron-donor materials with different functional groups were prepared and their properties were compared (Chapter V). Once found the best ionic functional group, a new double-cable material was synthetized optimizing the surface area between the different materials (Chapter VI). Finally, other water/alcohol soluble materials were synthetized, characterized and used as cathode interlayers in eco-friendly devices (Chapter VII). In this work, all prepared materials were characterized by spectroscopy analyses, gel permeation chromatography and thermal analyses. Cyclic voltammetry, X-ray diffraction, atomic force microscopy and external quantum efficiency were used to investigate some peculiar aspects.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.

Fabrication by magnetron sputtering and characterization of electrodes based on CuIn0.7Ga0.3Se2 (CIGS)

This thesis work aims to produce and test multilayer electrodes for their use as photocathode in a PEC device. The electrode developed is based on CIGS, a I-III-VI2 semiconductor material composed of copper (Cu), indium (In), Gallium (Ga) and selenium (Se). It has a bandgap in the range of 1.0-2.4 eV and an absorption coefficient of about 105cm−1, which makes it a promising photocathode for PEC water splitting. The idea of our multilayer electrode is to deposit a thin layer of CdS on top of CIGS to form a solid-state p–n junction and lead to more efficient charge separation. In addition another thin layer of AZO (Aluminum doped zinc oxide) is deposit on top of CdS since it would form a better alignment between the AZO/CdS/CIGS interfaces, which would help to drive the charge transport further and minimize charge recombination. Finally, a TiO2 layer on top of the electrodes is used as protective layer during the H2 evolution. FTO (Fluorine doped tin oxide) and Molybdenum are used as back-contact. We used the technique of RF magnetron sputtering to deposit the thin layers of material. The structural characterization performed by XDR measurement confirm a polycrystalline chalcopyrite structural with a preferential orientation along the (112) direction for the CIGS. From linear fit of the Tauc plot, we get an energy gap of about 1.16 eV. In addition, from a four points measurements, we get a resistivity of 0.26 Ωcm. We performed an electrochemical characterization in cell of our electrodes. The results show that our samples have a good stability but produce a photocurrent of the order of μA, three orders of magnitude smaller than our targets. The EIS analysis confirm a significant depletion of the species in front of the electrode causing a lower conversion of the species and less current flows.