High-field cyclotron resonance and electron-phonon interaction in modulation-doped multiple quantum well structures

A systematic study of electron cyclotron resonance (CR) in two sets of GaAs/Al0.3Ga0.7As modulation-doped quantum-well samples (well widths between 12 and 24 nm) has been carried out in magnetic fields up to 30 T. Polaron CR is the dominant transition in the region of GaAs optical phonons for the set of lightly doped samples, and the results are in good agreement with calculations that include the interaction with interface optical phonons. The results from the heavily doped set are markedly different. At low magnetic fields (below the GaAs reststrahlen region), all three samples exhibit almost identical CR which shows little effect of the polaron interaction due to screening and Pauli-principle effects. Above the GaAs LO-phonon region (B > similar to 23 T), the three samples behave very differently. For the most lightly doped sample (3 x 10(11) cm(-2)) only one transition minimum is observed, which can be explained as screened polaron CR. A sample of intermediate density (6 x 10(11) cm(-2)) shows two lines above 23 T; the higher frequency branch is indistinguishable from the positions of the single line of the low density sample. For the most heavily, doped sample (1.2 x 10(12) cm(-2)) there is no evidence of high frequency resonance, and the strong, single line observed is indistinguishable from the lower branch observed from sample with intermediate doping density. We suggest that the low frequency branch in our experiment is a magnetoplasmon resonance red-shifted by disorder, and the upper branch is single-particle-like screened polaron CR. (C) 1998 Elsevier Science B.V. All rights reserved.

Resonant magnetopolaron effects in GaAs/AlGaAs multiple quantum well structures

A detailed experimental study of electron cyclotron resonance (CR) has been carried out at 4.2 K in three modulation-doped GaAs/Al0.3Ga0.7As multiple quantum well samples in fields up to 30 T. A strong avoided-level-crossing splitting of the CR energies due to resonant magnetopolaron effects is observed for all samples near the GaAs reststrahlen region. Resonant splittings in the region of AlAs-like interface phonon modes of the barriers are observed in two samples with narrower well width and smaller doping concentration. The interaction between electrons and the AlAs interface optical phonon modes has been calculated for our specific sample structures in the framework of the memory-function formalism. The calculated results are in good agreement with the experimental results, which confirms our assignment of the observed splitting near the AlAs-like phonon region is due to the resonant magnetopolaron interaction of electrons in the wells with AlAs-like interface phonons. (C) 1998 Elsevier Science B.V. All rights reserved.

Resonant magnetopolaron effects due to interface phonons in GaAs/AlGaAs multiple quantum well structures

Polaron cyclotron resonance (CR) has been studied in three modulation-doped GaAs/Al0.3Ga0.7As multiple quantum well structures in magnetic field up to 30 T. Large avoided-level-crossing splittings of the CR near the GaAs reststrahlen region, and smaller splittings in the region of the AlAs-like optical phonons of th AlGaAs barriers, are observed. Based on a comparison with a detailed theoretical calculation, the high frequency splitting, the magnitude of which increases with decreasing well width, is assigned to resonant polaron interactions with AlAs-like interface phonons.

Cyclotron-resonance mass of two-dimensional electrons in GaN/AlxGa1-xN heterostructures

The electron cyclotron-resonance (CR) mass of quasi-two-dimensional electrons in GaN/AlxGa1-xN heterostructures is studied theoretically. The correction to the CR mass due to electron-phonon interaction is investigated, taking into account band nonparabolicity, the occupation effect, and the screening of the electron-phonon coupling. The dependence of the CR mass on the electron density and on the magnetic field strength is displayed in detail, and the calculated CR mass agrees well with a recent experiment. We found that the effective electron-phonon coupling strength in GaN heterostructures is reduced below the bulk value.

High-field cyclotron resonance and electron-phonon interaction in modulation-doped multiple quantum well structures

A systematic study of electron cyclotron resonance (CR) in two sets of GaAs/Al0.3Ga0.7As modulation-doped quantum-well samples (well widths between 12 and 24 nm) has been carried out in magnetic fields up to 30 T. Polaron CR is the dominant transition in the region of GaAs optical phonons for the set of lightly doped samples, and the results are in good agreement with calculations that include the interaction with interface optical phonons. The results from the heavily doped set are markedly different. At low magnetic fields (below the GaAs reststrahlen region), all three samples exhibit almost identical CR which shows little effect of the polaron interaction due to screening and Pauli-principle effects. Above the GaAs LO-phonon region (B > similar to 23 T), the three samples behave very differently. For the most lightly doped sample (3 x 10(11) cm(-2)) only one transition minimum is observed, which can be explained as screened polaron CR. A sample of intermediate density (6 x 10(11) cm(-2)) shows two lines above 23 T; the higher frequency branch is indistinguishable from the positions of the single line of the low density sample. For the most heavily, doped sample (1.2 x 10(12) cm(-2)) there is no evidence of high frequency resonance, and the strong, single line observed is indistinguishable from the lower branch observed from sample with intermediate doping density. We suggest that the low frequency branch in our experiment is a magnetoplasmon resonance red-shifted by disorder, and the upper branch is single-particle-like screened polaron CR. (C) 1998 Elsevier Science B.V. All rights reserved.

Resonant magnetopolaron effects in GaAs/AlGaAs multiple quantum well structures

A detailed experimental study of electron cyclotron resonance (CR) has been carried out at 4.2 K in three modulation-doped GaAs/Al0.3Ga0.7As multiple quantum well samples in fields up to 30 T. A strong avoided-level-crossing splitting of the CR energies due to resonant magnetopolaron effects is observed for all samples near the GaAs reststrahlen region. Resonant splittings in the region of AlAs-like interface phonon modes of the barriers are observed in two samples with narrower well width and smaller doping concentration. The interaction between electrons and the AlAs interface optical phonon modes has been calculated for our specific sample structures in the framework of the memory-function formalism. The calculated results are in good agreement with the experimental results, which confirms our assignment of the observed splitting near the AlAs-like phonon region is due to the resonant magnetopolaron interaction of electrons in the wells with AlAs-like interface phonons. (C) 1998 Elsevier Science B.V. All rights reserved.

Synthesis, structural and electrical characterizations of Sr2Fe1-xMxNbO6 (M = Zn and Cu) with double perovskite structure

Sr2Fe1-xZnxNbO6-x/2 (0 <= x <= 0.5) and Sr2Fe1-xCuxNbO6-x/2 (0.01 <= x <= 0.05) with the double perovskite structure have been synthesized. The crystal structures at room temperature were determined from Rietveld refinements of X-ray powder diffraction data. The plots of the imaginary parts of the impedance spectrum, Z '', and the electric modulus, M '', versus log (frequency), possess maxima for both curves separated by less than a half decade in frequency with associated capacities of 2 nF. The enhancement of the overall conductivity Of Sr2Fe1-xMxNbO6-x/2 (M = Cu and Zn) is observed, as increases from 2.48 (3) x 10(-4) S/cm for Sr2FeNbO6 to 3.82 (5) x 10(-3) S/cm for Sr2Fe0.8Zn0.2NbO5.9 at 673 K. Sr2Fe0.8Zn0.2NbO5.9 is chemically stable under the oxygen partial pressure from 1 atm to 10(-22) atm at 873 K. The p and n-type electronic conductions are dominant under oxidizing and reducing conditions, respectively, suggesting a small-polaron hopping mechanism of electronic conduction.

DOPING EFFECTS ON THE POLYMER-CHAIN STRUCTURE OF POLY(3-METHYLTHIOPHENE)

The C=C stretching Raman shifts and photoluminescence (PL) for poly(3-methylthiophene) (P3MT) are measured at various doping levels by in situ electrochemical Raman and PL spectroscopic techniques. It is found that the doping for P3MT induces the nonlinear excitations (soliton, Polaron, bipolaron), but also affects the polymer-chain structure, including the conjugated length and the interchain distance.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

Dynamique des photoexcitations de nanostructures supramoléculaires d'oligothiophènes

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Effet de la microstructure sur les propriétés excitoniques des polymères semi-conducteurs semi-cristallins

Les polymères semi-conducteurs semicristallins sont utilisés au sein de diodes électroluminescentes, transistors ou dispositifs photovoltaïques organiques. Ces matériaux peuvent être traités à partir de solutions ou directement à partir de leur état solide et forment des agrégats moléculaires dont la morphologie dicte en grande partie leurs propriétés optoélectroniques. Le poly(3-hexylthiophène) est un des polymères semi-conducteurs les plus étudiés. Lorsque le poids moléculaire (Mw) des chaînes est inférieur à 50 kg/mol, la microstructure est polycristalline et composée de chaînes formant des empilements-π. Lorsque Mw>50 kg/mol, la morphologie est semicristalline et composée de domaines cristallins imbriquées dans une matrice de chaînes amorphes. À partir de techniques de spectroscopie en continu et ultrarapide et appuyé de modèles théoriques, nous démontrons que la cohérence spatiale des excitons dans ce matériau est légèrement anisotrope et dépend de Mw. Ceci nous permet d’approfondir la compréhension de la relation intime entre le couplage inter et intramoléculaire sur la forme spectrale en absorption et photoluminescence. De plus, nous démontrons que les excitations photogénérées directement aux interfaces entre les domaines cristallins et les régions amorphes génèrent des paires de polarons liés qui se recombinent par effet tunnel sur des échelles de temps supérieures à 10ns. Le taux de photoluminescence à long temps de vie provenant de ces paires de charges dépend aussi de Mw et varie entre ∼10% et ∼40% pour les faibles et hauts poids moléculaires respectivement. Nous fournissons un modèle permettant d’expliquer le processus de photogénération des paires de polarons et nous élucidons le rôle de la microstructure sur la dynamique de séparation et recombinaison de ces espèces.

Dynamique de séparation de charges à l'hétérojonction de semi-conducteurs organiques

Une compréhension profonde de la séparation de charge à l’hétérojonction de semi-con- ducteurs organiques est nécessaire pour le développement de diodes photovoltaïques organiques plus efficaces, ce qui serait une grande avancée pour répondre aux besoins mondiaux en énergie durable. L’objectif de cette thèse est de décrire les processus impliqués dans la séparation de charges à hétérojonctions de semi-conducteurs organiques, en prenant en exemple le cas particulier du PCDTBT: PCBM. Nous sondons les excitations d’interface à l’aide de méthodes spectroscopiques résolues en temps couvrant des échelles de temps de 100 femto- secondes à 1 milliseconde. Ces principales méthodes spectroscopiques sont la spectroscopie Raman stimulée femtoseconde, la fluorescence résolue en temps et l’absorption transitoire. Nos résultats montrent clairement que le transfert de charge du PCDTBT au PCBM a lieu avant que l’exciton ne soit relaxé et localisé, un fait expérimental irréconciliable avec la théorie de Marcus semi-classique. La paire de charges qui est créée se divise en deux catégories : les paires de polarons géminales non piégées et les paires profondément piégées. Les premiers se relaxent rapidement vers l’exciton à transfert de charge, qui se recombine radiativement avec une constante de temps de 1– 2 nanoseconde, alors que les seconds se relaxent sur de plus longues échelles de temps via l’effet tunnel. Notre modèle photophysique quantitatif démontre que 2 % de l’excitation créée ne peut jamais se dissocier en porteurs de charge libre, un chiffre qui est en accord avec les rendements élevés rapportés pour ce type de système.

Physical and optical properties of phthalocyanine doped inorganic glasses

Physical and optical properties of various free base and metallic phthalocyanine (Pc) doped glass matrix are reported for the first time. Absorption spectral measurements of H2Pc, MnPc, NiPc, CoPc, CuPc, MoOPc, ZnPc and FePc doped borate glass matrix have been made in the 200–1100 nm region and the spectra obtained are analyzed in the 2.1–6.2 eV region to obtain the optical band gap (Eg) and the width of the band tail (Et). Other important optical and physical parameters viz. refractive index (n), molar extinction coefficient ("), density (½), glass transition temperature (Tg), molecular concentration (N ), polaron radius (rp), intermolecular separation (R), molar refractivity (Rm) are also reported

Physical and optical properties of phthalocyanine doped inorganic glasses

Physical and optical properties of various free base and metallic phthalocyanine (Pc) doped glass matrix are reported for the first time. Absorption spectral measurements of H2Pc, MnPc, NiPc, CoPc, CuPc, MoOPc, ZnPc and FePc doped borate glass matrix have been made in the 200–1100 nm region and the spectra obtained are analyzed in the 2.1–6.2 eV region to obtain the optical band gap (Eg) and the width of the band tail (Et). Other important optical and physical parameters viz. refractive index (n), molar extinction coefficient ("), density (½), glass transition temperature (Tg), molecular concentration (N ), polaron radius (rp), intermolecular separation (R), molar refractivity (Rm) are also reported.