<p>The urgent need for new, sustainable energy source intrigues scientists to provide the solution by developing new technology. Polymer solar cell appears to be the most promising candidate for its low cost, flexibility, and massive producibility. Novel polymers have been constantly synthesized and investigated, while the use of PCBM as acceptor seems to be the universal choice. Here, we studied the use of four dierent fullerene derivatives - [60]PCBM, [70]PCBM, and their bisadduct analogues - as acceptor in APFO-3 solar cells. A series of investigations were performed to study how the processing parameters - blend ratio, spin speed, and choice of solvent - influence the device performance. Using bisadduct fullerenes results in an enhanced Voc, as predicted by the up-shift of energy levels, but a strongly reduced Jsc, hence a poor PCE. Photoluminescence study indicates that all APFO-3:fullerene devices are limited by the inefficient dissociation of fullerene excitations, while it becomes more influential when bisadduct fullerenes were used as acceptor. The best device in this study was fabricated by using [70]PCBM as acceptor and chlorobenzene as solvent, exhibits a PCE of 2.9%, for the strong absorption, ne morphology, and comparatively strong driving force.</p>

Depuis leur découverte, les nanotubes de carbone ont suscité un grand interêt pour leurs propriétés électroniques et optiques. Dans ce contexte, l'objectif de la thèse a été d'étudier les propriétés optiques des nanotubes de carbone semiconducteurs pour la réalisation de composants photoniques aux longueurs d'onde des télécommunications. La première partie de la thèse a concerné l'étude de la variation de l'absorption et la photoluminescence des s-SWNTs en fonction de l'environnement des nanotubes: surfactant, matrice solide, solution. A partir d'une méthode d'extraction des s-SWNTs, développée en collaboration avec l'AIST de Tsukuba au Japon, l'influence néfaste des nanotubes métalliques et des impuretés sur les propriétés optiques des s-SWNTs a également été mise en évidence. Les différentes caractérisations effectuées sur des couches minces hautement purifiées en s-SWNTs ont révélés une amélioration du signal de luminescence des nanotubes semiconducteurs d'un facteur 6. Ces résultats ont conduit dans une seconde partie à étudier l'émission des s-SWNTs en régime non linéaire. Un fort gain optique dans les nanotubes semiconducteurs a pu être ainsi démontré expérimentalement pour la première fois. La dernière partie des travaux de thèse a porté sur l'intégration de ces nanotubes de carbone dans des structures photoniques silicium. Une étude approfondie de l'absorption et de la photoluminscence des nanotubes déposés sur des guides d'onde silicium a été effectuée. Ces travaux expérimentaux ouvrent la voie vers la réalisation de sources de lumière intégrées sur silicium à base de nanotubes de carbone et à plus long terme vers une nouvelle photonique à base de nanotubes de carbone.

Depuis le début des années 2000, une vaste classe de nanofils de nitrures d'éléments III et de ZnO peut être synthétisée avec un excellent contrôle des propriétés de dopage et de composition. La géométrie spécifique de ces nanofils permet de faire croître des hétérostructures radiales et axiales qui ont des propriétés optiques et de transport très avantageuses par rapport aux couches minces. Ces propriétés en font des candidats prometteurs pour la réalisation d'une nouvelle génération de dispositifs plus efficaces (LEDs, photodétecteurs,...). Pour cela, il est indispensable de comprendre les nouveaux effets induits par la géométrie particulière de ces nanostructures : c'est l'objet de cette thèse. Dans une première partie, je présente une étude des propriétés optiques de nanofils de semiconducteurs à grande énergie de bande interdite. J'analyse d'abord l'effet de la contrainte sur les propriétés d'émission des nanofils cœur-coquille GaN/AlGaN. En particulier, je mets en évidence le croisement des bandes de valence et son influence sur les propriétés optiques des nanofils. Ensuite, je me focalise sur l'effet du confinement quantique et les propriétés de polarisation dans les nanofils hétérostructurés de nitrures d'éléments III. Dans une seconde partie, je m'intéresse à la réalisation et à la caractérisation de dispositifs à base de nanofils de nitrures d'éléments III et de ZnO. J'expose tout d'abord la modélisation et l'étude expérimentale de photodétecteurs à ensemble de nanofils en mettant en avant l'influence des états de surface sur leur réponse. Je m'intéresse ensuite aux propriétés de transport dans des nanofils uniques de nitrures d'éléments III hétérostructurés. Je montre, en particulier, que ces hétérostructures sont le siège d'une résistance différentielle négative. Enfin, je présente la réalisation et la caractérisation de photodétecteurs et de LEDs utilisant des nanofils uniques InGaN/GaN cœur-coquille. Un modèle électrique équivalent permet de rendre compte du comportement observé.

The urgent need for new, sustainable energy source intrigues scientists to provide the solution by developing new technology. Polymer solar cell appears to be the most promising candidate for its low cost, flexibility, and massive producibility. Novel polymers have been constantly synthesized and investigated, while the use of PCBM as acceptor seems to be the universal choice. Here, we studied the use of four dierent fullerene derivatives - [60]PCBM, [70]PCBM, and their bisadduct analogues - as acceptor in APFO-3 solar cells. A series of investigations were performed to study how the processing parameters - blend ratio, spin speed, and choice of solvent - influence the device performance. Using bisadduct fullerenes results in an enhanced Voc, as predicted by the up-shift of energy levels, but a strongly reduced Jsc, hence a poor PCE. Photoluminescence study indicates that all APFO-3:fullerene devices are limited by the inefficient dissociation of fullerene excitations, while it becomes more influential when bisadduct fullerenes were used as acceptor. The best device in this study was fabricated by using [70]PCBM as acceptor and chlorobenzene as solvent, exhibits a PCE of 2.9%, for the strong absorption, ne morphology, and comparatively strong driving force.

There are three novel 2-trifluoromethyl-activated bisfluoro monomers have been successfully synthesized in this study, and the nomenclatures are shown as follows: 4,4¡¦¡¦¡¦¡¦-Difluore-3,3¡¦¡¦¡¦¡¦-bis(trifluoromethyl)-2¡¦¡¦,3¡¦¡¦,5¡¦¡¦,6¡¦¡¦-triphenyl(M4), 4,4¡¦¡¦¡¦¡¦-Difluore-3,3¡¦¡¦¡¦¡¦-bis(trifluoromethyl)-2¡¦¡¦,3¡¦¡¦,5¡¦¡¦-triphenyl(M3), 4,4¡¦¡¦¡¦¡¦-Difluore-3,3¡¦¡¦¡¦¡¦-bis(trifluoromethyl)-2¡¦¡¦,3¡¦¡¦-triphenyl(M2). Through polymerization with 1,1-dihydroxydiphenyl cyclododecane the monomers M2, M3 and M4 were accordingly converted into poly(arylene ether)s P2-1,1C, P3-1,1C and P4-1,1C, respectively. These polymers exhibit weight-average molecular weight up to 2.25¡Ñ105g/mol. The molecular weight were investigated and confirmed by MASS and GPC. The molecular structures were investigated and confirmed by NMR and FTIR. The UV-VIS absorption and photoluminescence spectra measurement of all the monomers and polymers in dilute solutions and in solid state were conducted. The results show that all monomers and polymers in dilute solutions have no absorption in the vision light region of spectrum. The absorption spectra of polymer thin films showed high optical transparency up to 90%. The photoluminescence spectra of all monomers and polymers in dilute solutions and thin film emits light with high intensity and wavelength in region of 350~380nm. Thermal analysis studies were conducted with TGA, DSC, TMA and crystal property study was performed by XRD. The results show that these polymers did not show melting but showed ultrahigh Tg values ranging from 270~330¢XC in DSC and TMA measurements, so it indicated that three polymers were not crystalline materials. Outstanding thermal stability is over then 440~ 460¢XC for 5% weight loss in TGA under nitrogen atmosphere. So it could make manufacture in higher temperature and have higher thermal stability. With optical properties of polymer thin films, we utilized Ellipsometer to measure refractive index and the results showed no birefringence for these polymers. The polymer thin films show low polarity and high hydrophobicity could be attested by the measured results of contact angle and surface energy. The HOMO and LUMO energy level of monomers are both measured by Cyclic Voltammetry and theoretical calculation. The absorption spectra of polymer thin films showed no absorption in the visible light region of the spectrum i.e., having a high optical transparency. All above stated material properties are good for doing as a plastic substrate of devices or panel display.

Photophysical, electronic, and compositional properties of single-walled carbon nanotubes (SWCNTs) and bulk nanotube samples were investigated together with graphene oxide photoluminescence. First, we studied the effect of external electric fields on SWCNT photoluminescence. Fields of up to 10 7 V/m caused dramatic, reversible decreases in emission intensity. Quenching efficiency was proportional to the projection of the field on the SWCNT axis, and showed inverse correlation with optical band gap. The magnitude of the effect was experimentally related to exciton binding energy, as consistent with a proposed field-induced exciton dissociation model. Further, the electronic composition of various SWCNT samples was studied. A new method was developed to measure the fraction of semiconducting nanotubes in as- grown or processed samples. SWCNT number densities were compared in images from near-IR photoluminescence (semiconducting species) and AFM (all species) to compute the semiconducting fraction. The results provide important information about SWCNT sample compositions that can guide controlled growth methods and help calibrate bulk characterization techniques. The nature of absorption backgrounds in SWCNT samples was also studied. A number of extrinsic perturbations such as extensive ultrasonication, sidewall functionalization, amorphous carbon impurities, and SWCNT aggregation were applied and their background contributions quantified. Spectral congestion backgrounds from overlapping absorption bands were assessed with spectral modeling. Unlike semiconducting nanotubes, metallic SWCNTs gave broad intrinsic absorption backgrounds. The shape of the metallic background component and its absorptivity coefficient were determined. These results can be used to minimize and evaluate SWCNT absorption backgrounds. Length dependence of SWCNT optical properties was investigated. Samples were dispersed by ultrasonication or shear processing, and then length-fractionated by gel electrophoresis or controlled ultrasonication shortening. Fractions from both methods showed no significant absorbance variations with SWCNT length. The photoluminescence intensity increased linearly with length, and the relative quantum yield gradually increased, approaching a limiting value. Finally, a strong pH dependence of graphene oxide photoluminescence was observed. Sharp and structured excitation/emission features resembling the spectra of molecular fluorophores were obtained in basic conditions. Based on the observed pH-dependence and quantum calculations, these spectral features were assigned to quasi-molecular fluorophores formed by the electronic coupling of oxygen-containing addends with nearby graphene carbon atoms.

Photon detectors based on single-crystalline materials are of great interest for high performance imaging applications due to their low noise and fast response. The major detector materials for sensing in the long-wavelength infrared (LWIR) band (8-14 µm) are currently HgCdTe (MCT) and AlGaAs/GaAs quantum wells (QW) used in intraband-based quantum-well infrared photodetectors (QWIPs). These either suffer from compositional variations that are detrimental to the system performance as in the case of MCT, or, have an efficient dark current generation mechanism that limits the operating temperature as for QWIPs. The need for increased on-wafer uniformity and elevated operating temperatures has resulted in the development of various alternative approaches, such as type-II strained-layer superlattice detectors (SLSs) and intraband quantum-dot infrared photodetectors (QDIPs). In this work, we mainly explore two self-assembled quantum-dot (QD) materials for use as the absorber material in photon detectors for the LWIR, with the aim to develop low-dark current devices that can allow for high operating temperatures and high manufacturability. The detection mechanism is here based on type-II interband transitions from bound hole states in the QDs to continuum states in the matrix material. Metal-organic vapor-phase epitaxy (MOVPE) was used to fabricate (Al)GaAs(Sb)/InAs and In(Ga)Sb/InAs QD structures for the development of an LWIR active material. A successive analysis of (Al)GaAs(Sb) QDs using absorption spectroscopy shows strong absorption in the range 6-12 µm interpreted to originate in intra-valence band transitions. Moreover, record-long photoluminescence (PL) wavelength up to 12 µm is demonstrated in InSb- and InGaSb QDs. Mesa-etched single-pixel photodiodes were fabricated in which photoresponse is demonstrated up to 8 µm at 230 K with 10 In0.5Ga0.5Sb QD layers as the active region. The photoresponse is observed to be strongly temperature-dependent which is explained by hole trapping in the QDs. In the current design, the photoresponse is thermally limited at typical LWIR sensor operating temperatures (60-120 K), which is detrimental to the imaging performance. This can potentially be resolved by selecting a matrix material with a smaller barrier for thermionic emission of photo-excited holes. If such an arrangement can be achieved, type-II interband InGaSb QD structures can turn out to be interesting as a high-operating-temperature sensor material for thermal imaging applications. / <p>QC 20130521</p>

Dans ce travail de thèse, nous avons étudié différentes approches qui devraient permettre d'obtenir l'effet laser dans le germanium. Nous avons pu montrer expérimentalement l'influence du dopage et de la déformation sur la structure de bande du germanium, et l'adéquation avec les modèles concluants à l'existence de gain. Nous avons exploré les possibilités offertes par l'hétéro-épitaxie sur III-V pour obtenir une déformation en tension du germanium. Nous avons évalué la déformation résultante par des mesures croisées de rayons X, de diffusion Raman et de photoluminescence, et étudié l'évolution de la qualité des couches épitaxiées en fonction de la déformation et de l'épaisseur. Une nouvelle méthode de déformation du germanium, s'appuyant sur le dépôt par plasma de couches contraintes de nitrure, a été introduite et étudiée. L'effet laser a été recherché par la conception de guides ridges et microdisques déformés par ces dépôts. Plusieurs voies d'application de la déformation dans ces cavités ont été explorées à travers des simulations par éléments finis et la conception de structures de test. Cette optimisation préalable nous a permis d'observer sur les microdisques une déformation biaxiale de 1.11%. En uniaxial, nous avons pu appliquer au germanium une déformation de 1.07% et montrer expérimentalement l'importance de la direction de la déformation dans l'augmentation de la luminescence. Nous avons pu observer et mesurer un gain optique net de 80 cm⁻¹ dans des structures déformées uniaxialement à 0.8%.

GaN quantum dots grown by molecular beam epitaxy are examined by micro-photoluminescence. The exciton and biexciton emission are identified successfully by power-dependence measurement. With two different samples, it can be deduced that the linewidth of the peaks is narrower in the thicker deposited layer of GaN. The size of the GaN quantum dots is responsible for the binding energy of biexciton (EbXX); EbXX decreases with increasing size of GaN quantum dots. Under polarization studies, polar plot shows that emission is strongly linear polarized. In particular, the orientation of polarization vector is not related to any specific crystallography orientation. The polarization splitting of fine-structure is not able to resolve due to limited resolution of the system. The emission peaks can be detected up to 80 K. The curves of transition energy with respect to temperature are S-shaped. Strain effect and screening of electric field account for  blueshift of transition energy, whereas Varshni equation stands for redshifting. Both blueshifting and redshifting are compensated at temperature ranging from 4 K to 40 K.

In this article, a multiple-responsive polymer micelles system was constructed by using ionic bond to link the hydrophobic tetraphenylthiophene (TP) fluorophores, which possess the property of aggregation-induced emission enhancement (AIEE), with the hydrophilic poly(N-isopropyl acrylamide) (PNIPAM). The susceptibility of the ionic ammonium-sulfonate (Am-Sul) bonds towards metal ions, acid and base triggered the AIEE-operative fluorescence (FL) response. To exercise the idea, PNIPAM with sulfonate terminal was primarily prepared to react with TP-derivatives functionalized with ammonium groups to generate polymer complex of TP-PNIPAM. When in water, the polymer complex TP-PNIPAM formed micelles with the aggregated TP core interconnecting the hydrophilic PNIPAM shell by the ionic Am-Sul bonds. With the operative AIEE effect, the aggregated TP core of the micelles fluoresced but upon the additions of metal ions, acid and base, the ionic bonds dissociated to result in the collapse of the micelles and the FL quenching. A novel fluorogenic sensor capable to respond to multi-stimuli was therefore constructed. Amphiphilic micelle systems with the hydrophilic poly(N-isopropyl amide) (PNIPAM) shell and the hydrophobic tetraphenylthiophene (TP), which has the novel aggregation-induced emission enhancement (AIEE) feature, core inter-connected by ionic bonds were prepared in this study to explore the AIEE-operative emission response towards critical micelle concentration (CMC) and lower critical solution temperature (LCST). To exercise the idea, TP functionalized ammonium cations and PNIPAM with terminal sulfonate group were individually prepared and mixed together to yield three amphiphilic TP-PNIPAM complexes with different hydrophobic TP to the hydrophilic PNIPAM (x/y) ratios. When in aqueous solution, TP-PNIPAMs form micelles with the aggregated TP core, which emits strongly due to the operative AIEE effect, encompassed by the PNIPAM shell. The resultant CMC and LCST of the TP-PNIPAM micelles can be varied by changing the hydrophobic to the hydrophilic x/y ratio and can be monitored by the AIEE-dominant fluorescence responses towards concentration and temperature variables.