Les phénomènes de non-stoehiométrie dans les ferrites du système Ba-La-Fe-O dont les structures dérivent de la perovskite, ont été étudiés au moyen de diverses techniques (diffraction X, HRTEM, spectroscopie Mössbauer...).<br />Dans le système BaFe4+O3-BaFe3+O2.50 la structure et l'ordre des lacunes des phases BaFeO3-y dépendent du taux de lacunes (y) et corrélativement du rapport Fe4+/Fe3+ (t / (1-t)) directement lié aux conditions de synthèse (PO2, T). Pour y <~ 0.35, l'empilement est un mélange des types "hexagonal compact" et "cubique compact" conduisant à des structures de type perovskite 6H ou 12H lacunaires en oxygène alors que pour des valeurs de y plus élévées (y ~> 0.35) il devient "cubique compact". Dans ce domaine de compositions, la non-stoichiométrie est accomodée grâce à la formation de structures en microdomaines soit d'une phase monoclinique (BaFeO2.50), soit d'une phase orthorombique de composition voisine de BaFe02.55.<br />En revanche pour 0.25 < y < 0.37, on observe des phénomènes d'intercroissances entre une phase de type 6H et une phase dérivée de la perovskite cubique. Pour y <= 0.25, aucun ordre des lacunes à longue distance n'apparaît.<br />Dans le système LaFeO3-BaFeO2.50, quatre phases différentes, surstructures de la perovskite cubique, apparaissent en fonction du rapport Ba/La (x/(1-x)). Leur microstructure est discutée en fonction de la composition, de l'ordre Ba-La et du taux de lacunes (y).

No description available.

<p>As energy demands for the world increase, the necessity for alternate sources of energy are critical. Just in the United States alone, 92 quadrillion British thermal units (Btu) were used in 2020. As political and geographical pressures surrounding oil increase, along with the growing concern for climate, the drive to explore alternative and renewable means for harvesting energy is on the rise. Solar cells, also known as photovoltaics (PVs), are an attractive renewable source and have been developed as an alternative energy means for over 60 years. When considering losses due to atmospheric absorption and scattering, the Earth’s surface gets about 1000 W/m2 of energy from the sun, which is why there are research efforts around the world trying to maximize the efficiency of solar cells.</p> <p>Organic-inorganic halide perovskites provide for ideal absorbing layers that feature long carrier lifetime and diffusion lengths, strong photoluminescence, and promising tunability. Furthermore, the solution-processing methods used to make these perovskites ensure that the solar cells will remain low-cost and have easy scale-up possibilities. The main problem perovskites is that they degrade in the presence of water, thus leading to decreased device performance.</p> <p>In this work two approaches are investigated to increase moisture stability. The first investigates incorporation of thiols as pseudohalides into the 2D perovskite structure. Instead of the theorized perovskite, two novel 2D compounds were created, Pb₂X(S-C₆H₅)₃ (X= I, Br, Cl) and PbI_1.524(S-C₆H₅)_0.476. While not perovskites, this study gives insight into the effect that the thiol may have on determining structure when comparing –S-C₆H₅ with –SCN groups. Future work will explore more electronegative thiols that will be used to make moisture resistant, tunable 2D perovskites.</p> <p>The second approach is to incorporate longer organic ammonium cations into the perovskite structure to produce quasi-2D perovskite films fabricate them into devices. Adding in electronically insulating ligands leads to a stricter requirement for vertically aligned 2D films and special care must be taken to have efficient charge collection. The current field has successfully incorporated short ligands such as butylammonium (BA) into PVs, however the extension to larger and more beneficially hydrophobic ligands has been very scarce. In this work, a novel solvent engineering system is developed to create vertically aligned quasi-2D perovskite absorbing layers based off of a bithiophene ligand (2T). These absorbing layers are then characterized and incorporated into efficient PV devices. Generalizations to solvent conditions related to ligand choice is discussed herein, creating deep insights into incorporating more conjugated ligands into devices.</p>

No description available.

In this work, X-ray and neutron powder diffraction experiments and complementary solid-state NMR spectroscopy are used to characterise NaNbO₃-based perovskite phases. Samples of NaNbO₃, KₓNa₁₋ₓNbO₃ and LiₓNa₁₋ₓNbO₃ are synthesised using a variety of techniques and subsequently characterised. For NaNbO₃, it is observed that at least two room temperature perovskite phases can co-exist, P and Q, and that each phase can be formed exclusively by manipulating the synthetic approach utilised. Phase Q can also be formed by the substitution of a small amount of K⁺ or Li⁺ for Na⁺. The room temperature phases of these materials are also analysed using NMR spectroscopy and X-ray diffraction. It is found that, for KₓNa₁₋ₓNbO₃, preferential A-site substitution of K⁺ for Na⁺ may occur, and this observation is supported using a range of NMR techniques and density functional theory calculations. The high-temperature phase behaviour of NaNbO₃ and KₓNa₁₋ₓNbO₃ (x = 0.03 to 0.08) is analysed using high-resolution neutron and X-ray powder diffraction to determine when phase changes occur and to characterise each phase. Characterisation of these materials is supported used complementary symmetry mode analysis. For the LiₓNa₁₋ₓNbO₃ perovskite system, complex phase behaviour is observed at room temperature. High-resolution neutron powder diffraction data shows that, over the range 0.08 < x < 0.20, phase Q may co-exist with a rhombohedral phase, with the proportions of the two highly dependent upon the synthetic conditions used. Furthermore, using X-ray diffraction and NMR spectroscopy, phase Q is shown to undergo a crystal-to-crystal transition to the rhombohedral phase. For higher values of x, two compositionally-distinct rhombohedral phases are formed, termed Na-R3c and Li-R3c, as determined from neutron powder diffraction data.

A new family of perovskite titanates with formulae La4+nSr8-nTi12-nMnnO38 and La4Sr8Ti12-nMnnO38-δ have been investigated as potential fuel electrode materials for SOFCs. The series La4+nSr8-nTi12-nMnnO38 present layered domains within their structure. As such layers appear to have a large negative effect over the electrochemical properties only a few compounds have been characterised. The series La4Sr8Ti12-nMnnO38-δ present a rhombohedral (R-3c) unit cell at room temperature which becomes cubic when increasing the temperature up to 900°C both in air and in reducing conditions. The primitive volume correlates with the oxygen content for the reduced samples. TGA and magnetic studies have revealed that the Mn present is mainly as Mn⁺³. Preliminary HRTEM investigations have revealed that some crystallographic shears distributed randomly within a perovskite matrix remain in the structure, which implies that the oxygen overstoichiometry is compatible with rhombohedral distortions in the oxygen sublattice. Mn substitution does not have a large impact on the bulk conductivity of the phases studied, which remains close to the values observed in other related titanates, although the grain boundary contributions are largely improved. Relatively low polarisation resistances were observed under both hydrogen and methane conditions for the lowest n compounds of the series. The anodic overpotential for n=1 was fairly low to those reported in the literature for other materials and especially for titanate-based anodes, i.e. a value of 55mV at 0.5A/cm2, at 950°C, under wet hydrogen was obtained. Additionally, a value 72mV was obtained in the same conditions under methane. These values indicate that the use of Mn as dopant for perovskite-related titanates enhanced electrochemical performance of these anodes, especially at high temperatures.

Abstract Methylammonium lead (II) iodide has recently attracted considerable interest which may lead to substantial developments of efficient and inexpensive industrial photovoltaics. The application of this material as a light-absorbing layer in solid-state solar cells leads to impressive efficiency of over 22% in laboratory devices. However, for industrial applications, fundamental issues regarding their thermal and moisture stability need to be addressed. MAPbI3 belongs to the perovskite family of materials with the general formula ABX3 ,where is the organic cation (methylammonium) which is reported to be a major source of instability. In this work, a variety of alkyammonium lead (II) iodide materials have been synthesized by changing the organic cation, to study the relationship between the structural and physical properties of these materials. [(A)PbI3] and (A)PbI4 series were studied. Three dimensional (3D) networks (MAPbI3,MAPbBr3), two dimensional (2D) layered systems (BdAPbI4, HdAPbI4, OdAPbI4), and one dimensional (1D) columns (EAPbI3, PAPbI3, EAPb2I6) were found for the materials. [PbI6] octahedral structural units were repeated through the material network depending on the dimensionality and connectivity of the materials. Where a bulkier cation was introduced, the crystallographic unit cell increased in size which resulted in lower symmetry crystals. The connectivity of the unit cells along the material networks was found to be based on corner-sharing and face-sharing. Lower dimensionality resulted in larger bandgaps and lower photoconductivity, and hence a lower light conversion efficiency for the related solar cells. The thermal and moisture stability was greater in the 1D and 2D materials with bulkier organic cations than with methylammonium. In total, an overview is provided of the relationship between the chemical dimensionality and physical properties of the organic-inorganic lead halide materials with focus on the solar cell application. / Svenska sammandrag: Metylammoniumbly(II)jodid har under de senaste åren genererat ett stort intresse som ett möjligt material for utveckling av effektiva och på industriell skala billiga solceller. Detta material har använts som ljusabsorberande skikt i fasta solceller med imponerande omvandlingseffektiviteter på över 22% för solceller i laboratorieskala. För att denna nya typ av solceller ska bli intressanta för produktion på industriell skala, så behöver grundläggande frågeställningar kring materialens stabilitet avseende högre temperaturer och fukt klargöras. MAPbI3 har formellt perovskitstruktur med den allmänna formel ABX3, där A utgörs av den organiska katjonen (metyammoniumjonen) och som kan kopplas till materialets instabilitet. I denna avhandling har olika alkylammoniumbly(II)jodidmaterial syntetiserats där den organiska katjonen modifierats med syftet att studera växelverkan mellan struktur och fysikaliska egenskaper hos de resulterande materialen. Material av olika dimensionalitet erhölls; tredimensionella (3D) nätverk (MAPbI3, MAPbBr3), tvådimensionella (2D) skiktade strukturer (BdAPbI4, HdAPbI4, OdAPbI4), och endimensionella (1D) kedjestrukturer (EAPbI3, PAPbI3, EAPb2I6). Flera nya lågdimensionella material (2D och 1D) tillverkats och karaktäriserats för första gången. Enkristalldiffraktometri har använts för att erhålla materialens atomära struktur. Strukturen hos material tillverkade i större mängder konfirmerades genom jämförelse mellan resultat från pulverdiffraktion och enkristalldiffraktion. Den oktaedriska strukturenheten [PbI6] utgör ett återkommande tema i materialen sammankopplade till olika dimensioner. Då större organiska katjoner används karaktäriseras i regel strukturerna av större enhetsceller och lägre symmetri. De lågdimensionella materialen ger typiskt störe elektroniskt bandgap, lägre fotoinducerad ledningsförmåga och därför sämre omvandlingseffektiviteter då de används i solceller. De lågdimensionella materialen (1D och 2D) som baseras på de större organiska katjonerna uppvisar bättre stabilitet med avseende på högre tempereratur och fukt. De tvådimensionella materialens elektroniska struktur har karaktäriserats med hjälp av röntegenfotoelektronspektroskopi, liksom röntgenabsorptions- och emissionsspektroskopi. Resultat från teoretiska beräkningar stämmer väl överens med de experimentella resultaten, och de visar att materialens valensband huvudsakligen består av bidrag från atomorbitaler hos jod, medan atomorbitaler från bly främst bidrar till edningsbandet. Sammantaget erbjuder avhandlingen en översikt av sambandet mellan kemisk dimensionalitet och fysikaliska egenskaper hos ett antal organiska/oorganiska blyhalogenidmaterial med fokus på tillämpning i solceller. / <p>QC 20170123</p>

Solid-state dye-sensitized solar cells (ssDSSCs) and recently developed perovskite solar cells (PSCs) have attracted a great attention in the scientific field of photovoltaics due to their low cost, absence of solvent, simple fabrication and promising power conversion efficiency (PCE). In these types of solar cell, the dye molecule or the perovskite can harvest the light on the basis of electron excitation. Afterwards, the electron and hole are collected at the charge transport materials. Photoelectrochemical polymerization (PEP) is employed in this thesis to synthesize conducting polymer hole transport materials (HTMs) for ssDSSCs. We have for the first time developed aqueous PEP in comparison with the conventional organic PEP with acetonitrile as solvent. This water-based PEP could potentially provide a low-cost, environmental-friendly method for efficient deposition of polymer HTM for ssDSSCs. In addition, new and simple precursors have been tested with PEP method. The effects of dye molecules on the PEP were also systematically studied, and we found that (a) the bulky structure of dye is of key importance for blocking the interfacial charge recombination; and (b) the matching of the energy levels between the dye and the precursor plays a key role in determining the kinetics of the PEP process. In PSCs, the HTM layer is crucial for efficient charge collection and its long term stability. We have studied different series of new molecular HTMs in order to understand fundamentally the influence of alkyl chains, molecular energy levels, and molecular geometry of the HTM on the photovoltaic performance. We have identified several important factors of the HTMs for efficient PSCs, including high uniformity of the HTM capping layer, perovskite-HTM energy level matching, good HTM solubility, and high conductivity. These factors affect interfacial hole injection, hole transport, and charge recombination in PSCs. By systematical optimization, a promising PCE of 19.8% has been achieved by employing a new HTM H11. We believe that this work could provide important guidance for the future development of new and efficient HTMs for PSCs.

This thesis studies parameters influencing both the performance and stability of solid state sensitized solar cells (ssSSCs). ssSSCs benefit from their low materials and manufacturing processing costs, a consequence of using solution processed materials. However, solution processed materials are often structurally and electronically disordered. By characterizing fully operational ssSSCs and their charge transport properties, this thesis elucidates the factors limiting charge transport and proposes routes towards both improved photovoltaic conversion efficiency and long-term stability. Chapter 2 provides an explanation of the operation of ssSSCs, while Chapter 3 discusses the basic methods used in this thesis. Having set this background, Chapter 4 explores the interaction between atmospheric oxygen and charge doping mechanisms in the organic semiconductors used in ssSSCs. To understand the implications of the findings presented in Chapter 4, a new technique, “transient mobility spectroscopy”, was developed to understand the evolution of balanced charge transport behaviour of disordered semiconductors at different operating conditions in ssSSCs. This technique is presented in full in Chapter 5. The understanding gained in Chapters 4 and 5 suggest that alternative light absorbers with higher extinction coefficients may be beneficial to improving the performance of ssSSCs. Chapter 6 discusses the use of an organometal trihalide perovskite, as light absorber in ssSSCs. Using time resolved techniques, the charge transport and recombination mechanisms in various device architectures are explored, allowing suggestions to be made towards future improvements. Chapter 7 uses the technique presented in Chapter 5 to understand a rapid degradation mechanism of working ssSSCs. Particular focus is placed on the titanium dioxide charge-transporting layer. Building on this newfound understanding, two methods for attaining stable photovoltaic performance are provided, a great step forward for this technology.

La plupart des processus géologiques affectant la surface de la Terre sont le reflet des mouvements de convection au sein du manteau terrestre. Ces mouvements sont essentiellement gouvernés par le fluage par dislocations des silicates du manteau et sont à l'origine d'une anisotropie des vitesses des ondes sismiques. Cependant, les mécanismes de déformation de ces minéraux sont mal connus. Les conditions dans les couches les plus profondes sont extrêmes; la température y atteint plusieurs milliers de degrés et la pression est plus d’un million de fois supérieure à la pression atmosphérique. La détermination expérimentale de la plasticité de ces minéraux nécessite des expériences de déformation sous hautes pression et température. Les mécanismes de déformation sont généralement déterminés à partir d'expériences en cellule à enclumes diamants permettant d'atteindre les conditions de pression et de température du manteau. L'objectif de cette thèse visait à développer une nouvelle technique permettant d'étudier les dislocations in situ dans les grains d’un polycristal sous haute pression, directement à partir de leur effet sur les raies de diffraction X. De ce fait, nous avons combiné la diffraction X tridimensionnelle (3D-XRD) à la méthode d'analyse des profils de pics de diffraction (XLPA, X-ray Line Profile Analysis). Les travaux de cette thèse ont été appliqués à la post-perovskite, présente dans la couche D'' à l'interface noyau-manteau et à la stishovite, présente principalement dans les plaques en subduction. Les résultats obtenus sont utiles à la compréhension et la modélisation des mouvements de convection et du développement d'anisotropie sismique dans le manteau. / The Earth mantle and inner core are submitted to large scale movements of solid materials. The physical process allowing the flow of solid materials is connected to plastic properties and, in particular, dislocations. It is the source of seismic wave velocities anisotropy. However, the deformation mechanisms of deep Earth minerals are poorly understood. Deep in the Earth’s interior, minerals are under extreme conditions; the temperature reaches several thousand degrees and the pressure is more than one million times the atmospheric pressure. The experimental study of the plasticity of those minerals requires deformation experiments under high pressure and temperature. High pressure phenomena are often determined from experiments using diamond anvil cell to reach the conditions of pressure and temperature of the mantle. The objective of this thesis was to develop a new technique for studying dislocations in situ in grains inside a polycrystal under high pressure, directly from their effect on the X ray diffraction profiles. To do so, we combine three-dimensional X-ray diffraction (3D-XRD) to X ray Line Profile Analysis method (XLPA). The development done in this thesis was applied to post-perovskite, the main constituent of the D'' layer at the core-mantle boundary and to stishovite, present mainly in subducting slabs. The results obtained are useful for understanding and modeling of convection and the development of seismic anisotropy in the mantle.