Graphitic carbon nitride (g-C3N4) heterojunction composites with the semiconducting metal oxides, CeO2, ZnO and TiO2 are prepared in situ by co-calcination of the precursor materials or by a solvothermal method. The structural, morphological and the optical properties of the prepared materials are studied using various microscopy and spectroscopy techniques. The synthesized composite materials, CeO2/g-C3N4, ZnO/g-C3N4 and TiO2/g-C3N4 are more efficient in the photocatalytic degradation of the water pollutants indigo carmine (IC) and atrazine than the pure metal oxide, g-C3N4, or their physical mixtures. The CeO2/g-C3N4 and ZnO/g-C3N4 composites also exhibit improved degradation efficiencies of atrazine as compared to the individual metal oxide or g-C3N4 materials. The improved photocatalytic activity of the composites are attributed to the effective electron-hole charge separation within composite heterojunction, resulting from the well matched energy levels of the metal oxide and g-C3N4. This strategy could be helpful for the synthesis of other metal oxide and g-C3N4 composites for photocatalytic applications.

Ce travail de thèse a pour but de comprendre l’impact des propriétés électriques du silicium cristallin sur les performances des cellules solaires Silicium à HétéroJonction (SHJ) et de déterminer des spécifications matériaux nécessaires en termes de durée de vie des porteurs de charge et de résistivité.Dans une première partie de cette thèse, le potentiel du silicium mono-like a été évalué pour la fabrication de cellules solaires SHJ. La forte productivité de cette technique permet de réduire considérablement les coûts de fabrication des plaquettes. Des rendements de conversion de 20% équivalents à ceux des matériaux du marché ont été obtenus ainsi qu’un rendement de 21.6% avec l’utilisation d’un procédé de fabrication de cellules haut rendements. Ces valeurs ont été obtenues pour des durées de vie volumiques moyennes sur les plaquettes supérieures à 1ms. Les principaux limitations de la qualité du matériau mono-like ont été identifiés. D’abord, la présence de zones multicristallines sur certaines plaquettes rend le matériau incomptable avec le procédé SHJ notamment en ce qui concerne les étapes de texturation des surfaces et ensuite l’uniformité en épaisseur des couches déposées. Ce type de défauts fait chuter en premier lieu la Jcc, puis la Vco et le FF et finalement le rendement de conversion. De plus, la présence de contamination et la génération de dislocations aux extrémités du lingot font également chuter la durée de vie volumique et les paramètres photovoltaïques des cellules. Finalement, seulement 30% de la hauteur de lingot a pu être utilisé pour des hauts rendements de conversion.La deuxième partie a été consacrée à l’étude et l’optimisation, avec la technologie SHJ, d’une technique de dopage innovante remplaçant celles utilisant des impuretés dopantes, telle que le phosphore, en générant des donneurs thermiques dans le substrat silicium cristallin. Cette méthode de dopage présente l’avantage d’utiliser l’oxygène naturellement présent dans le silicium en transformant en dopant par des recuits à 450°C. Cette technique est uniquement valable avec une procédé basse température tel que celui utilisé dans ce travail de thèse et permettrait de contrôler les propriétés électriques du silicium sur l’ensemble d’un lingot Cz afin d’augmenter le rendement matière. La compatibilité du silicium cristallin dopé par des DT a été validée pour une gamme de résistivité de 3-10Ω.cm et durées de vie volumique de 3-10ms. La limite d’utilisation des DT pour l’obtention de hauts rendements correspond à une concentration inférieure à 7x1014cm-3 (3Ω.cm, 3ms). La technique de dopage a été transférée avec succès à l’échelle du lingot et a permis d’obtenir de rendement de 20.7% avec un procédé industriel et même de 21.7% avec une métallisation « smart-wire ». Une perte de FF a été observée par rapport aux références, liées à une résistance série élevée dont l’origine n’a pas encore été confirmée mais dont la source la plus probable serait l’inhomogénéité radiale de résistivité générée par le dopage. / This study aims to understand the electrical properties impact of the crystalline Silicon on the HeteroJunction (SHJ) solar cells performances and define the required material specifications in terms of minority carrier lifetime and bulk resistivity.In the first part of this work, the potential of the mono-like silicon was evaluated for SHJ solar cells production The high productivity of the crystallization method allows to significantly reduce the material cost. 20% efficiencies comparable to reference wafers were obtained for industrial process and had reached 21.6% values have been reached with a high efficiency process. Values above 1ms bulk lifetime were mandatory to obtain these results. The main limitations of the material properties were identified. First, the presence of multicrystalline zones on the material is incompatible with the SHJ process especially regarding the texturization step and then layers thickness’ uniformity. This defects drive down, at the first order, the Jsc and then the Voc and FF. Moreover, the metallic contamination and the dislocations generation at the ingots ends induce also a bulk lifetime degradation and PV performances drop. Finally, only 30% of the ingot height was usable to obtain high solar cell efficiencies.In the second part of this work, an innovative doping method, replacing the ones which use doping impurities, such as phosphorus, by generating thermal donors (TD) was studied. The advantages of this doping method are to use the oxygen naturally content in the silicon to generate the doping after 450°C annealing. This method is only possible if low temperature solar cell process is performed such the one used in this work. It could control the electrical properties of the crystalline silicon throughout a complete Cz ingot and increase the material yield. For a resistivity range of 3-10Ω.cm and bulk lifetime between 3 and 10ms, the TD doped material is compatible with SHJ technology. The maximum TD concentration for a SHJ application was estimated to 7x1014cm-3.The doping method was successfully transferred to the ingot scale and allowed reaching 20.7% efficiency with an industrial process and 21.7% with the “smart-wire” improved metallization. A FF loss was observed compared to the references, related to high series resistances. The origin has not been confirmed yet, but the most likely source would be the radial resistivity inhomogeneity generated by doping on silicon bulk.

<p>During the last decade, AlGaN High Electron Mobility Transistors (HEMTs) have been intensively studied because their fundamental electrical properties make them attractive for highpower microwave device applications. Despite much progress, AlGaN HEMTs are far from fully understood and judged by the number of published papers the understanding of advanced structures is even poorer. This work is an exploration of the electrical and structural properties of advanced HEMT structure containing AlN exclusionlayer and double heterojunctions. These small modifications had great impact on the electrical properties.</p><p>In this work, AlGaN HEMT structures grown on SiC substrates by a hot-wall MOCVD have been characterized for their properties using optical microscopy, scanning electron microscopy, transmission electron microscopy, capacitance/voltage, eddy-current resistivity, and by homebuilt epi-thickness mapping equipment.</p><p>A high electron mobility of 1700 [cm2/Vs] was achieved in an AlN exclusion-layer HEMT. A similar electron mobility of 1650 [cm2/Vs] was achieved in a combination of a double heterojunction and exclusion-layer structure. The samples had approximately the same electron mobility but with a great difference: the exclusion-layer version gave a sheet carrier density of 1.58*1013 [electrons/cm2] while the combination of double heterojunction and exclusion-layer gave 1.07*1013 [electrons/cm2]. A second 2DEG was observed in most structures, but not all, but was not stable with time.</p><p>The structures we grew during this work were also simulated using a one-dimensional Poisson-Schrödinger solver and the simulated electron densities were in fairly good agreement with the experimentally obtained. III-nitride materials, the CVD concept, and the onedimensional solver are shortly explained.</p>

Polymer-based photovoltaics have the potential to contribute to boosting photovoltaic energy conversion overall. Besides allowing large-area inexpensive processing, polymeric materials have the added benefit of opening new market applications for photovoltaics due to their low-weight and interesting mechanical properties. The energy conversion efficiency values of polymer photovoltaics have reached new record values over the past years. It is however crucial that stability issues are addressed together with efficiency optimization. Understanding fundamental materials aspects is key in both areas. In the work presented in this thesis, the morphology of polymer:fullerene films and its influence on device performance was studied, as well as the effect of light exposure on the surface of fullerene films. Several polyfluorene copolymers were used for the morphology studies, where the effects of changing spin-coating solvent and of side chain engineering were investigated with dynamic secondary ion mass spectrometry (dSIMS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Polymer-enriched surfaces were found in all blend films, even in the cases with homogeneous distributions in the bulk. Side chain engineering of the polymer led to gradual changes in the compositional variations perpendicular to the surface, and to slight variations in the photocurrent. The electronic structure of the fullerene derivative PCBM was studied in detail and the spectroscopic fingerprint of the materials was analysed by comparison with theoretically simulated spectra. Photo-stability studies done in air showed that the surface of fullerene films underwent severe damages at the molecular level, which is evident from changes in the valence band and X-ray absorption spectra. These changes were explained by transitions from sp2-type to sp3 hybridization of the carbon atoms in the cage that resulted in the destruction of the fullerene cage.

No description available.

This thesis deals with the main aspects in chemical vapordeposition (CVD) of silicon (Si) and silicon-germanium (Si1-xGex) films for high-speed bipolar transistors.In situdoping of polycrystalline silicon (poly-Si)using phosphine (PH3) and disilane (Si2H6) in a low-pressure CVD reactor was investigated toestablish a poly-Si emitter fabrication process. The growthkinetics and P incorporation was studied for amorphous Si filmgrowth. Hydrogen (H) incorporated in the as-deposited films wasrelated to growth kinetics and the energy for H2desorption was extracted. Film properties such asresistivity, mobility, carrier concentration and grain growthwere studied after crystallization using either furnaceannealing or rapid thermal annealing (RTA). In order tointegrate an epitaxial base, non-selective epitaxial growth(NSEG) of Si and SiGe in a lamp-heated single-waferreduced-pressure CVD reactor was examined. The growth kineticsfor Si epitaxy and poly-Si deposition showed a differentdependence on the deposition conditions i.e. temperature andpressure. The growth rate difference was mainly due to growthkinetics rather than wafer surface emissivity effects. However,it was observed that the growth rate for Si epitaxy and poly-Sideposition was varying during growth and the time-dependencewas attributed to wafer surface emissivity variations. A modelto describe the emissivity effects was established, taking intoconsideration kinetics and the reactor heating mechanisms suchas heat absorption, emission andconduction. Growth ratevariations in opening of different sizes (local loading) andfor different oxide surface coverage (global loading) wereinvestigated. No local loading effects were observed, whileglobal loading effects were attributed to chemical as well astemperature effects. Finally, misfit dislocations formed in theSiGe epitaxy during NSEG were found to originate from theinterface between the epitaxial and polycrystalline regions.The dislocations tended to propagate across the activearea. <b>Keywords:</b>chemical vapor deposition (CVD), bipolarjunction transistor (BJT), heterojunction bipolar transistor(HBT), silicon-germanium (SiGe), epitaxy, poly-Si emitter,in situdoping, non-selective epitaxy (NSEG), loadingeffect, emissivity effect

Heterojunction bipolar transistors (HBT) based on SiGeC havebeen investigated. Two high-frequency architectures have beendesigned, fabricated and characterized. Different collectordesigns were applied either by using selective epitaxial growthdoped with phosphorous or by non-selective epitaxial growthdoped with arsenic. Both designs have a non-selectivelydeposited SiGeC base doped with boron and a poly-crystallineemitter doped with phosphorous. Selective epitaxial growth of the collector layer has beendeveloped by using a reduced pressure chemical vapor deposition(RPCVD) technique. The incorporation of phosphorous and defectformation during selective deposition of these layers has beenstudied. A major problem of phosphorous-doping during selectiveepitaxy is segregation. Different methods, e.g. chemical orthermal oxidation, are shown to efficiently remove thesegregated dopants. Chemical-mechanical polishing (CMP) hasalso been used as an alternative to solve this problem. The CMPstep was successfully integrated in the HBT process flow. Epitaxial growth of Si1-x-yGexCy layers for base layerapplications in bipolar transistors has been investigated indetail. The optimization of the growth parameters has beenperformed in order to incorporate carbon substitutionally inthe SiGe matrix without increasing the defect density in theepitaxial layers. The thermal stability of npn SiGe-based heterojunctionstructures has been investigated. The influence of thediffusion of dopants in SiGe or in adjacent layers on thethermal stability of the structure has also been discussed. SiGeC-based transistors with both non-selectively depositedcollector and selectively grown collector have been fabricatedand electrically characterized. The fabricated transistorsexhibit electrostatic current gain values in the range of 1000-2000. The cut-off frequency and maximum oscillation frequencyvary from 40-80 GHz and 15-30 GHz, respectively, depending onthe lateral design. The leakage current was investigated usinga selectively deposited collector design and possible causesfor leakage has been discussed. Solutions for decreasing thejunction leakage are proposed. <b>Key words:</b>Silicon-Germanium-Carbon (SiGeC),Heterojunction bipolar transistor (HBT), chemical vapordeposition (CVD), selective epitaxy, non-selective epitaxy,collector design, high-frequency measurement, dopantsegregation, thermal stability.

π-Conjugated polymers have attracted considerable attention since they are potential candidates for various opto-electronic devices such as solar cells, light emitting iodes, photodiodes, and transistors. Electronic de vices based on conjugated polymers can be easily processed at low temperature using inexpensive technologies. This leads to cost reduction, a key-deriving factor for choosing conjugated polymers for various types of applications. In particular, polymer based solar cells are of special interest due to the fact that they can play a major role in generating clean and cheap energy in the future. The investigations described in thesis are aimed mainly at understanding charge transport and the role of energy le vels in solar cells based on polymer/acceptor bulk heterojunction (BHJ) active films. Best polymer based solar cells, with efficiency 4 to 5%, rely on polymer/fullerene BHJ active films. These solar cells are in an immature state to be used for energy conversion purposes. In order to enhance their performance, it is quite important to understand the efficiency-limiting factors. Solid films of conjugated polymers compose conjugation segments that are randomly distributed in space and energy. Such distributio n gives rise to the localization of charge carriers and hence broadening of electron density of states. Consequently, electronic wave functions have quite poor overlap resulting into absence of continuous band transport. Charge transport in polymers and organic materials, in general, takes place by hopping among the localized states. This makes a bottleneck to the performance of polymer-based solar cells. In this context, the knowledge of charge transport in the solar cell materials is quite important to develop materials and device architectures that boost the efficiency of such solar cells. Most of the transport studies are based on polyfluorene copolymers and fullerene electron acceptor molecules. Fullerenes are blended with polymers to enhance the dissociation of excited state into free carriers and transport free electrons to the respective electrode. The interaction within the polymer-fullerene complex, therefore, plays a major role in the generation and transport of both electrons and holes. In this thesis, we present and discuss the effect of various polymer/fullerene compositions on hole percolation paths. We mainly focus on hole transport since its mobility is quite small as compared to electron mobility in the fullerenes, leading to creation of spa ce charges within the bulk of the solar cell composite. Changing a polymer band gap may necessitate an appropriate acceptor type in order to fulfill the need for sufficient driving force for dissociation of photogenerated electron-hole pairs. We have observed that different acceptor types give rise to completely different hole mobility in BHJ films. The change of hole transport as a function of acceptor type and concentration is mainly attributed to morphological changes. The effect of the acceptors in connection to hole transport is also discussed. The later is supported by studies of bipolar transport in pure electron acceptor layers. Moreover, the link between charge carrier mobility and photovoltaic parameters has also been studied and presented in this thesis. The efficiency of polymer/fullerene-based solar cells is also significantly limited by its open-circuit voltage (Voc), a parameter that does not obey the metal-insulator-metal principle due to its complicated characteristics. In this thesis, we address the effect of varying polymer oxidation potential on Voc of the polymer/fullerene BHJ based solar cells. Systematic investigations have been performed on solar cells that comprise several polythiophene polymers blended with a fullerene derivative electron acceptor molecule. The Voc of such solar cells was found to have a strong correlation with the oxidation potential of the polymers. The upper limit to Voc of the aforementioned solar cells is thermodynamically limited by the net internal electric filed generated by the difference in energy levels of the two materials in the blend. The cost of polymer-based solar cells can be reduced to a great extent through realization of all-plastic and flexible solar cells. This demands the replacement of the metallic components (electrodes) by highly conducting polymer films. While hole conductor polymers are available, low work function polymer electron conductors are rare. In this thesis, prototype solar cells that utilizes a highly conducting polymer, which has a work function of ~ 4.3 eV, as a cathode are demonstrated. Development of this material may eventually lead to fabrication of large area, flexible and cheap solar cells. The transparent nature of the polymer cathode may also facilitate fabrication of multi-layer and tandem solar cells. In the last chapter of this thesis, we demonstrate generation of red and near infrared polarized light by employing thermally converted thin films of polyfluorene copolymers in light emitting diodes. This study, in particular, aims at fabricating polarized infrared light emitting devices. / On the day of the defence day the status of article III was In press and article VI was Manuscript.

This thesis work aims at a better understanding of magneto-optical properties of dilute nitrides and II-VI diluted magnetic semiconductor quantum structures. The thesis is divided into two parts. The first part gives an introduction of the research fields, together with a brief summary of the scientific results included in the thesis. The second part consists of seven scientific articles that present the main findings of the thesis work. Below is a short summary of the thesis. Dilute nitrides have been of great scientific interest since their development in the early 1990s, because of their unusual fundamental physical properties as well as their potential for device applications. Incorporation of a small amount of N in conventional Ga(In)As or Ga(In)P semiconductors leads to dramatic modifications in both electronic and optical properties of the materials. This makes the dilute nitrides ideally suited for novel optoelectronic devices such as light emitting devices for fiber-optic communications, highly efficient visible light emitting devices, multi-junction solar cells, etc. In addition, diluted nitrides open a window for combining Si-based electronics with III-V compounds-based optoelectronics on Si wafers, promising for novel optoelectronic integrated circuits. Full exploration and optimization of this new material system in device applications requires a detailed understanding of their physical properties. Papers I and II report detailed studies of effects of post-growth rapid thermal annealing (RTA) and growth conditions (i.e. presence of N ions, N2 flow, growth temperature and In alloying) on the formation of grown-in defects in Ga(In)NP. High N2 flow and bombardment of impinging N ions on grown sample surface is found to facilitate formation of defects, such as Ga interstitial (Gai) related defects, revealed by optically detected magnetic resonance (ODMR). These defects act as competing carrier recombination centers, which efficiently decrease photoluminescence (PL) intensity. Incorporation of a small amount of In (e.g. 5.1%) in GaNP seems to play a minor role in the formation of the defects. In GaInNP with 45% of In, on the other hand, the defects were found to be abundant. Effect of RTA on the defects is found to depend on initial configurations of Gai related defects formed during the growth. In Paper III, the first identification of an interfacial defect at a heterojunction between two semiconductors (i.e. GaP/GaNP) is presented. The interface nature of the defect is clearly manifested by the observation of ODMR lines originating from only two out of four equivalent &lt;111&gt; orientations. Based on its resolved hyperfine interaction between an unpaired electronic spin (S=1/2) and a nuclear spin (I=1/2), the defect is concluded to involve a P atom at its core with a defect/impurity partner along a &lt;111&gt; direction. Defect formation is shown to be facilitated by N ion bombardment. In Paper IV, the effects of post-growth hydrogenation on the efficiency of the nonradiative (NR) recombination centers in GaNP are studied. Based on the ODMR results, incorporation of H is found to increase the efficiency of the NR recombination via defects such as Ga interstitials. In Paper V, we report on our results from a systematic study of layered structures containing an InGaNAs/GaAs quantum well, by the optically detected cyclotron resonance (ODCR) technique. By monitoring PL emissions from various layers, the predominant ODCR peak is shown to be related to electrons in GaAs/AlAs superlattices. This demonstrates the role of the SL as an escape route for the carriers confined within the InGaNAs/GaAs single quantum well. The last two papers are within a relatively new field of spintronics which utilizes not only the charge (as in conventional electronics) but also the quantum mechanical property of spin of the electron. Spintronics offers a pathway towards integration of information storage, processing and communications into a single technology. Spintronics also promises advantages over conventional charge-based electronics since spin can be manipulated on a much shorter time scale and at lower cost of energy. Success of semiconductor-based spintronics relies on our ability to inject spin polarized electrons or holes into semiconductors, spin transport with minimum loss and reliable spin detection. In Papers VI and VII, we study the efficiency and mechanism for carrier/exciton and spin injection from a diluted magnetic semiconductor (DMS) ZnMnSe quantum well into nonmagnetic CdSe quantum dots (QD’s) by means of spin-polarized magneto PL combined with tunable laser spectroscopy. By means of a detailed rate equation analysis presented in Paper VI, the injected spin polarization is deduced to be about 32%, decreasing from 100% before the injection. The observed spin loss is shown to occur during the spin injection process. In Paper VII, we present evidence that energy transfer is the dominant mechanism for carrier/exciton injection from the DMS to the QD’s. This is based on the fact that carrier/exciton injection efficiency is independent of the width of the ZnSe tunneling barrier inserted between the DMS and QD’s. In sharp contrast, spin injection efficiency is found to be largely suppressed in the structures with wide barriers, pointing towards increasing spin loss.

Capacitance-voltage-frequency measurements on n+-GaN/AlxGa1−xN UV/IR dual-band detectors are reported. The presence of shallow Si-donor, deep Si-donor, and C-donor/N-vacancy defect states were found to significantly alter the electrical characteristics of the detectors. The barrier Al fraction was found to change the position of the interface defect states relative to the Fermi level. The sample with Al fraction of 0.1 shows a distinct capacitance-step and hysteresis, which is attributed to C-donor/N-vacancy electron trap states located above the Fermi level (200 meV) at the heterointerface; whereas, the sample with Al fraction of 0.026 shows negative capacitance and dispersion, indicating C-donor/N-vacancy and deep Si-donor defect states located below the Fermi level (88 meV). When an i-GaN buffer layer was added to the structure, an anomalous high-frequency capacitance peak was observed and attributed to resonance scattering due to hybridization of localized Si-donor states in the band gap with conduction band states at the i-GaN/n+-GaN interface.