Nanotoxicité des points quantiques : étude in vitro chez les cellules épithéliales alvéolaires humaines A549

Les nanoparticules (NPs) sont définies comme des particules ayant au moins une dimension comprise entre 1 à 100 nanomètres. Plusieurs études in vitro et in vivo indiquent que les NPs pourraient constituer un risque potentiel pour la santé des personnes les synthétisant ou les manipulant lors de leur incorporation dans d’autres matériaux. La nanotoxicologie est un domaine de recherche émergeant. Les propriétés physico-chimiques particulières des NPs sont responsables d’interférences non spécifiques entre les nanomatériaux et certains des composants des essais in vitro pouvant mener à de faux résultats. L’inhalation a été identifiée comme une voie d’exposition présentant un risque important de toxicité. Dans le cadre de ce projet, nous avons utilisé la lignée de cellules épithéliales alvéolaires humaines, A549. Nous avons étudié chez cette lignée les conséquences de l’exposition aux points quantiques (PQs), NPs d’intérêt pour leurs applications potentielles en médecine (nanovecteur ou nanosonde). La mise au point des conditions expérimentales (interférence entre l’essai LDH et le milieu de culture) a permis de valider les essais de cytotoxicité MTS et LDH en présence des PQs. Nous avons montré que les PQs présentaient une cytotoxicité à court et long terme, et nous avons par la suite étudié un des mécanismes de toxicité potentielle, la mesure du cadmium (Cd2+) libéré des PQs. Nous avons déterminé que la mesure du Cd2+ comportait plusieurs interférences qui invalident cet essai. En conclusion, notre étude a permis d’identifier des interférences qui remettent en question plusieurs conclusions d’études publiées qui n’ont pas vérifié l’existence de telles interférences.

Growth and Characterization of ZnO based Heterojunction diodes and ZnO Nanostructuresby Pulsed Laser Ablation

Transparent conducting oxides (TCO’s) have been known and used for technologically important applications for more than 50 years. The oxide materials such as In2O3, SnO2 and impurity doped SnO2: Sb, SnO2: F and In2O3: Sn (indium tin oxide) were primarily used as TCO’s. Indium based oxides had been widely used as TCO’s for the past few decades. But the current increase in the cost of indium and scarcity of this material created the difficulty in obtaining low cost TCO’s. Hence the search for alternative TCO material has been a topic of active research for the last few decades. This resulted in the development of various binary and ternary compounds. But the advantages of using binary oxides are the easiness to control the composition and deposition parameters. ZnO has been identified as the one of the promising candidate for transparent electronic applications owing to its exciting optoelectronic properties. Some optoelectronics applications of ZnO overlap with that of GaN, another wide band gap semiconductor which is widely used for the production of green, blue-violet and white light emitting devices. However ZnO has some advantages over GaN among which are the availability of fairly high quality ZnO bulk single crystals and large excitonic binding energy. ZnO also has much simpler crystal-growth technology, resulting in a potentially lower cost for ZnO based devices. Most of the TCO’s are n-type semiconductors and are utilized as transparent electrodes in variety of commercial applications such as photovoltaics, electrochromic windows, flat panel displays. TCO’s provide a great potential for realizing diverse range of active functions, novel functions can be integrated into the materials according to the requirement. However the application of TCO’s has been restricted to transparent electrodes, ii notwithstanding the fact that TCO’s are n-type semiconductors. The basic reason is the lack of p-type TCO, many of the active functions in semiconductor originate from the nature of pn-junction. In 1997, H. Kawazoe et al reported the CuAlO2 as the first p-type TCO along with the chemical design concept for the exploration of other p-type TCO’s. This has led to the fabrication of all transparent diode and transistors. Fabrication of nanostructures of TCO has been a focus of an ever-increasing number of researchers world wide, mainly due to their unique optical and electronic properties which makes them ideal for a wide spectrum of applications ranging from flexible displays, quantum well lasers to in vivo biological imaging and therapeutic agents. ZnO is a highly multifunctional material system with highly promising application potential for UV light emitting diodes, diode lasers, sensors, etc. ZnO nanocrystals and nanorods doped with transition metal impurities have also attracted great interest, recently, for their spin-electronic applications This thesis summarizes the results on the growth and characterization of ZnO based diodes and nanostructures by pulsed laser ablation. Various ZnO based heterojunction diodes have been fabricated using pulsed laser deposition (PLD) and their electrical characteristics were interpreted using existing models. Pulsed laser ablation has been employed to fabricate ZnO quantum dots, ZnO nanorods and ZnMgO/ZnO multiple quantum well structures with the aim of studying the luminescent properties.

Synthesis and Laser induced Studies of nanosized ZnO for Photonic Applications

Over the past few years, a little word with big potential has been rapidly entering into the world's consciousness-'nano'. Nanoscience and technology is a multidisciplinary field, involving the fabrication and understanding of matter at the finest level of a few nanomters.This thesis is about the synthesis and laser induced studies of nanosized ZnO,a versatile material with a wide range of applications.After synthesizing colloids and films of nano ZnO,the samples are studied using different optical methods.Interactions of intense laser beams with nanosized particles are found to open up many interesting scenarios with possible applications in the field of photonics.

Novel Electrochemical and Fluorescence Sensors for Food Additives and Neurotransmitters

There is an enormous demand for chemical sensors in many areas and disciplines including chemistry, biology, clinical analysis, environmental science. Chemical sensing refers to the continuous monitoring of the presence of chemical species and is a rapidly developing field of science and technology. They are analytical devices which transform chemical information generating from a reaction of the analyte into an measurable signal. Due to their high selectivity, sensitivity, fast response and low cost, electrochemical and fluorescent sensors have attracted great interest among the researchers in various fields. Development of four electrochemical sensors and three fluorescent sensors for food additives and neurotransmitters are presented in the thesis. Based on the excellent properties of multi walled carbon nanotube (MWCNT), poly (L-cysteine) and gold nanoparticles (AuNP) four voltammetric sensors were developed for various food additives like propyl gallate, allura red and sunset yellow. Nanosized fluorescent probes including gold nanoclusters (AuNCs) and CdS quantum dots (QDs) were used for the fluorescent sensing of butylated hydroxyanisole, dopamine and norepinephrine. A total of seven sensors including four electrochemical sensors and three fluorescence sensors have been developed for food additives and neurotransmitters.

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

High-Speed Semiconductor Lasers based on Low-Dimensional Active Materials for Optical Telecommunication

The scope of this work is the fundamental growth, tailoring and characterization of self-organized indium arsenide quantum dots (QDs) and their exploitation as active region for diode lasers emitting in the 1.55 µm range. This wavelength regime is especially interesting for long-haul telecommunications as optical fibers made from silica glass have the lowest optical absorption. Molecular Beam Epitaxy is utilized as fabrication technique for the quantum dots and laser structures. The results presented in this thesis depict the first experimental work for which this reactor was used at the University of Kassel. Most research in the field of self-organized quantum dots has been conducted in the InAs/GaAs material system. It can be seen as the model system of self-organized quantum dots, but is not suitable for the targeted emission wavelength. Light emission from this system at 1.55 µm is hard to accomplish. To stay as close as possible to existing processing technology, the In(AlGa)As/InP (100) material system is deployed. Depending on the epitaxial growth technique and growth parameters this system has the drawback of producing a wide range of nano species besides quantum dots. Best known are the elongated quantum dashes (QDash). Such structures are preferentially formed, if InAs is deposited on InP. This is related to the low lattice-mismatch of 3.2 %, which is less than half of the value in the InAs/GaAs system. The task of creating round-shaped and uniform QDs is rendered more complex considering exchange effects of arsenic and phosphorus as well as anisotropic effects on the surface that do not need to be dealt with in the InAs/GaAs case. While QDash structures haven been studied fundamentally as well as in laser structures, they do not represent the theoretical ideal case of a zero-dimensional material. Creating round-shaped quantum dots on the InP(100) substrate remains a challenging task. Details of the self-organization process are still unknown and the formation of the QDs is not fully understood yet. In the course of the experimental work a novel growth concept was discovered and analyzed that eases the fabrication of QDs. It is based on different crystal growth and ad-atom diffusion processes under supply of different modifications of the arsenic atmosphere in the MBE reactor. The reactor is equipped with special valved cracking effusion cells for arsenic and phosphorus. It represents an all-solid source configuration that does not rely on toxic gas supply. The cracking effusion cell are able to create different species of arsenic and phosphorus. This constitutes the basis of the growth concept. With this method round-shaped QD ensembles with superior optical properties and record-low photoluminescence linewidth were achieved. By systematically varying the growth parameters and working out a detailed analysis of the experimental data a range of parameter values, for which the formation of QDs is favored, was found. A qualitative explanation of the formation characteristics based on the surface migration of In ad-atoms is developed. Such tailored QDs are finally implemented as active region in a self-designed diode laser structure. A basic characterization of the static and temperature-dependent properties was carried out. The QD lasers exceed a reference quantum well laser in terms of inversion conditions and temperature-dependent characteristics. Pulsed output powers of several hundred milli watt were measured at room temperature. In particular, the lasers feature a high modal gain that even allowed cw-emission at room temperature of a processed ridge wave guide device as short as 340 µm with output powers of 17 mW. Modulation experiments performed at the Israel Institute of Technology (Technion) showed a complex behavior of the QDs in the laser cavity. Despite the fact that the laser structure is not fully optimized for a high-speed device, data transmission capabilities of 15 Gb/s combined with low noise were achieved. To the best of the author`s knowledge, this renders the lasers the fastest QD devices operating at 1.55 µm. The thesis starts with an introductory chapter that pronounces the advantages of optical fiber communication in general. Chapter 2 will introduce the fundamental knowledge that is necessary to understand the importance of the active region`s dimensions for the performance of a diode laser. The novel growth concept and its experimental analysis are presented in chapter 3. Chapter 4 finally contains the work on diode lasers.

Molecular Beam Epitaxial Growth of III-V Semiconductor Nanostructures on Silicon Substrates

The main focus and concerns of this PhD thesis is the growth of III-V semiconductor nanostructures (Quantum dots (QDs) and quantum dashes) on silicon substrates using molecular beam epitaxy (MBE) technique. The investigation of influence of the major growth parameters on their basic properties (density, geometry, composition, size etc.) and the systematic characterization of their structural and optical properties are the core of the research work. The monolithic integration of III-V optoelectronic devices with silicon electronic circuits could bring enormous prospect for the existing semiconductor technology. Our challenging approach is to combine the superior passive optical properties of silicon with the superior optical emission properties of III-V material by reducing the amount of III-V materials to the very limit of the active region. Different heteroepitaxial integration approaches have been investigated to overcome the materials issues between III-V and Si. However, this include the self-assembled growth of InAs and InGaAs QDs in silicon and GaAx matrices directly on flat silicon substrate, sitecontrolled growth of (GaAs/In0,15Ga0,85As/GaAs) QDs on pre-patterned Si substrate and the direct growth of GaP on Si using migration enhanced epitaxy (MEE) and MBE growth modes. An efficient ex-situ-buffered HF (BHF) and in-situ surface cleaning sequence based on atomic hydrogen (AH) cleaning at 500 °C combined with thermal oxide desorption within a temperature range of 700-900 °C has been established. The removal of oxide desorption was confirmed by semicircular streaky reflection high energy electron diffraction (RHEED) patterns indicating a 2D smooth surface construction prior to the MBE growth. The evolution of size, density and shape of the QDs are ex-situ characterized by atomic-force microscopy (AFM) and transmission electron microscopy (TEM). The InAs QDs density is strongly increased from 108 to 1011 cm-2 at V/III ratios in the range of 15-35 (beam equivalent pressure values). InAs QD formations are not observed at temperatures of 500 °C and above. Growth experiments on (111) substrates show orientation dependent QD formation behaviour. A significant shape and size transition with elongated InAs quantum dots and dashes has been observed on (111) orientation and at higher Indium-growth rate of 0.3 ML/s. The 2D strain mapping derived from high-resolution TEM of InAs QDs embedded in silicon matrix confirmed semi-coherent and fully relaxed QDs embedded in defectfree silicon matrix. The strain relaxation is released by dislocation loops exclusively localized along the InAs/Si interfaces and partial dislocations with stacking faults inside the InAs clusters. The site controlled growth of GaAs/In0,15Ga0,85As/GaAs nanostructures has been demonstrated for the first time with 1 μm spacing and very low nominal deposition thicknesses, directly on pre-patterned Si without the use of SiO2 mask. Thin planar GaP layer was successfully grown through migration enhanced epitaxy (MEE) to initiate a planar GaP wetting layer at the polar/non-polar interface, which work as a virtual GaP substrate, for the GaP-MBE subsequently growth on the GaP-MEE layer with total thickness of 50 nm. The best root mean square (RMS) roughness value was as good as 1.3 nm. However, these results are highly encouraging for the realization of III-V optical devices on silicon for potential applications.

Growth of EuTe islands on SnTe by molecular beam epitaxy

Semiconductor magnetic quantum dots are very promising structures, with novel properties that find multiple applications in spintronic devices. EuTe is a wide gap semiconductor with NaCl structure, and strong magnetic moments S=7/2 at the half filled 4f(7) electronic levels. On the other hand, SnTe is a narrow gap semiconductor with the same crystal structure and 4% lattice mismatch with EuTe. In this work, we investigate the molecular beam epitaxial growth of EuTe on SnTe after the critical thickness for island formation is surpassed, as a previous step to the growth of organized magnetic quantum dots. The topology and strain state of EuTe islands were studied as a function of growth temperature and EuTe nominal layer thickness. Reflection high energy electron diffraction (RHEED) was used in-situ to monitor surface morphology and strain state. RHEED results were complemented and enriched with atomic force microscopy and grazing incidence X-ray diffraction measurements made at the XRD2 beamline of the Brazilian Synchrotron. EuTe islands of increasing height and diameter are obtained when the EuTe nominal thickness increases, with higher aspect ratio for the islands grown at lower temperatures. As the islands grow, a relaxation toward the EuTe bulk lattice parameter was observed. The relaxation process was partially reverted by the growth of the SnTe cap layer, vital to protect the EuTe islands from oxidation. A simple model is outlined to describe the distortions caused by the EuTe islands on the SnTe buffer and cap layers. The SnTe cap layers formed interesting plateau structures with easily controlled wall height, that could find applications as a template for future nanostructures growth. (C) 2010 Elsevier B.V. All rights reserved.

Magnetic-field asymmetry of nonlinear transport in a small ring

We have investigated the magnetic-field asymmetry of the conductance in the nonlinear regime in a small Aharonov-Bohm ring. We have found that the odd-in B and linear in V (the DC bias) correlation function of the differential conductance exhibits periodical oscillations with the Aharonov-Bohm flux. We have deduced the electron interaction constant and analyzed the phase rigidity of the Aharonov-Bohm oscillations in the nonlinear regime. Copyright (C) EPLA, 2009

Magnetic and optical characterization of Mn-doped PbS nanocrystals supported in oxide glass matrix

The evidence of successful growth of Mn-doped PbS (Pb(1-x)Mn(x)S) nanocrystals (NCs) in SiO(2)-Na(2)CO(3)-Al(2)O(3)-PbO(2)-B(2)O(3) template, using the fusion method, is reported on in this study. The as-grown Pb(1-x)Mn(x)S NC is characterized using optical absorption, electron paramagnetic resonance, and atomic force microscopy. The data are discussed in terms of two distinct scenarios, namely a core-doped and a shell-doped nanostructure. (C) 2008 Elsevier B.V. All rights reserved.

On the lower bound on the exchange-correlation energy in two dimensions

We study the properties of the lower bound on the exchange-correlation energy in two dimensions. First we review the derivation of the bound and show how it can be written in a simple density-functional form. This form allows an explicit determination of the prefactor of the bound and testing its tightness. Next we focus on finite two-dimensional systems and examine how their distance from the bound depends on the system geometry. The results for the high-density limit suggest that a finite system that comes as close as possible to the ultimate bound on the exchange-correlation energy has circular geometry and a weak confining potential with a negative curvature. (c) 2009 Elsevier B.V. All rights reserved.

Thermal dependence of the zero-bias conductance through a nanostructure

We show that the conductance of a quantum wire side-coupled to a quantum dot, with a gate potential favoring the formation of a dot magnetic moment, is a universal function of the temperature. Universality prevails even if the currents through the dot and the wire interfere. We apply this result to the experimental data of Sato et al. (Phys. Rev. Lett., 95 (2005) 066801). Copyright (C) EPLA, 2009

Sistemas Nanoestruturados: Heteroestruturas Quasi-Periódicas de Nitretos e Cálculos Ab initio em Polimorfos CaCO3

The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di®erent geometry optimizations have been e®ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e®ective masses and optical properties, such as dielectric constant, absorption, re°ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal

Towards coherent optical control of a single hole spin: Rabi rotation of a trion conditional on the spin state of the hole

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Coherent properties and Rabi oscillations in two-level donor systems

Coherent properties and Rabi oscillations in two-level donor systems, under terahertz excitation, are theoretically investigated. Here we are concerned with donor states in bulk GaAs and GaAs-(Ga,Al)As quantum dots. We study confinement effects, in the presence of an applied magnetic field, on the electronic and on-center donor states in GaAs- (Ga,Al)As dots, as compared to the situation in bulk GaAs, and estimate some of the associated decay rate parameters. Using the optical Bloch equations with damping, we study the time evolution of the Is and 2p(+) states in the presence of an applied magnetic field and of a terahertz laser. We also discuss the role played by the distinct dephasing rates on the photocurrent and calculate the electric dipole transition moment. Results indicate that the Rabi oscillations are more robust as the total dephasing rate diminishes, corresponding to a favorable coherence time.