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This diploma thesis is about ZnO nanowires growth, their doping and analysis. High temperature and pressure oxidation of brass foil and deposition from effusion cell in oxidative atmosphere utilized for nanowires growth. The growth is affected by different temperature and pressure. It has been shown that under certain experimental conditions nanowires can be prepared by the former method. However, the growth was hindered when effusion cell was used.

This thesis deals with one-dimensional (1D) and two-dimensional nanomaterials (2D) in terms of their utilization for new types of gas sensors. Thesis focuses on study of sensing elements for gas sensors based on semiconductor metal oxide materials (MOX) and their manufacturing technology. The objective of the thesis is the design and implementation of a sensing elements formed by selected nanomaterials based on the structure of interdigital electrodes. The result of the practical part of the thesis is the characterization and comparison of materials in terms of their detection parameters in the presence of selected test gases. The first part of thesis hierarchically defines chemoresistive gas sensor, characterizes and explains its operation principle. Second part studies 1D and 2D nanomaterials of sensing elements for MOX chemoresistive gas sensors, contains a research of their properties and describes their methods of manufacturing and implementation. The last part deals with the implementation of the sensitive layer of the sensor with selected nanomaterials, characterizes and compares their detection properties.

The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and photoinduced electron transfer dynamics is required to improve the device performance of solar cells. Here, we evaluated the effects of incorporating Pt(II) on intersystem crossing and photoinduced electron transfer by comparing and analyzing the photoexcited dynamics of DPP-Pt(II)(acac) and metal-free DPP with different acceptors such as TCNE, TMPyP, and TPyP.

Le développement de nouveaux matériaux thermoélectriques disposant de bonnes performances et d’un coût contenu est un prérequis nécessaire pour permettre à cette technologie de se démocratiser et de participer activement à la transition énergétique. Les travaux présentés dans cette thèse portent ainsi sur la synthèse et la caractérisation structurale et physico-chimique de composés oxydes, oxysulfures et sulfures peu onéreux afin d’en étudier les propriétés thermoélectriques.La première étude porte sur l’influence des faibles teneurs en indium sur la structure et les propriétés de l’oxyde de zinc. La caractérisation des échantillons par microscopie électronique en transmission met en évidence que la solubilité de l’indium dans le ZnO est inférieure à 0,5 at%. Les défauts bidimensionnels formés dès les faibles concentrations d’indium diminuent fortement la résistivité électrique et la conductivité thermique du matériau. En parallèle de ce travail, notre intérêt s’est porté les performances thermoélectriques de l’oxysulfure BiCuOS au travers d’une substitution au Pb sur le site du Bi. La substitution aliovalente permet une diminution de la résistivité électrique du matériau. Cependant, celle-ci demeure trop élevée en raison d’une faible solubilité du cation divalent dans la phase BiCuOS. Les deux derniers chapitres sont dédiés à l’étude de composés sulfures. Lors de ces travaux, la phase minérale naturelle kiddcreekite (Cu6SnWS8) est synthétisée pour la toute première fois en laboratoire. Le cheminement suivi pour accroître la pureté du produit obtenu est détaillé tandis que les performances thermoélectriques du matériau sont évaluées. Enfin, notre attention s’est portée sur les composés MnBi4S7 et FeBi4S7 dont la structure cristalline semble compatible avec l’obtention d’une faible conductivité thermique de réseau. Les mesures des propriétés de transport électrique et thermique sont corrélées à la structure électronique et aux propriétés vibrationnelles calculées pour les deux phases. Le composé MnBi4S7 apparait ainsi comme un semiconducteur de type-n prometteur pour les applications thermoélectriques. / The development of new thermoelectric materials with good performance and low cost is necessary to make this technology more accessible and thus achieve a significant environmental impact. The work presented in this thesis deals with the synthesis and the structural and physicochemical characterisation of inexpensive oxides, oxysulfides and sulfides compounds in order to study their thermoelectric properties.The first study investigates the influence of low indium contents on the structure and properties of zinc oxide. The characterization of the samples by transmission electron microscopy shows that the solubility of indium in ZnO is less than 0.5 at%. The bidimensional defects formed from low concentrations of indium greatly reduce the electrical resistivity and the thermal conductivity of the material. In parallel with this work, our interest focused on the thermoelectric performances of the oxysulfide BiCuOS through a substitution of Pb at the Bi site. The aliovalent substitution allows a decrease in the electrical resistivity of the material. However, the later remains too high due to a low solubility of the divalent cation in the BiCuOS phase. The last two chapters are dedicated to the study of sulfides compounds. During this work, the natural kiddcreekite mineral phase (Cu6SnWS8) is synthesized for the first time in a laboratory. The successive steps followed to increase the purity of the product is described while the thermoelectric performance of the material is evaluated. Finally, our attention focused on the compounds MnBi4S7 and FeBi4S7 whose crystalline structure seems compatible with a low lattice thermal conductivity. The measured electrical and thermal transport properties are correlated with the electronic structure and the vibrational properties calculated for the two phases. The compound MnBi4S7 thus appears as a promising n-type semiconductor for thermoelectric applications.

1 Abstract The structure of layered zinc hydroxide intercalated with dodecyl sulfate (LZH-DS) anions was studied in detail. LZH-DS was prepared by direct precipitation in water and formed different phases. The following phases of LZH-DS were prepared - "extended" phase (ex) by direct precipitation in water, "shrunk" (s) and "super-shrunk" (ss) phases via treatment of LZH-DS(ex) phase in methanol. The studies of the thermal behavior of LZH-DS(ex) revealed interstratification of intercalated DS anions. It is the first example of interstratification in layered hydroxides that are intercalated with long aliphatic alkyl chain anions. The experimental results were used for molecular dynamic modelling of the structures. Nanometric thin films were prepared by dip-coating and inkjet printing of ZnO nanosheets on glass plates. The side-by-side alignment of the ZnO nanosheets on the substrate resulted in thin, transparent, oriented ZnO surfaces with the high-energy {001} facets exposed. The method of nanosheet deposition affected the film morphology; the dip-coated films were smooth and nonporous, while the inkjet-printed films were rough and had a surface area in the range of approximately 100-160 m2 g-1 . The first-order rate constants for the photocatalytic degradation of 4-chlorophenol on the nanosheet-based films...

The developement of a femtosecond-time-resolved spectroscopic ellipsometry setup based on a pump-probe technique is described. The characterization of the setup is presented as well as first results of experiments on a c-plane oriented ZnO thin film are shown. Indications for the study of fast charge-carrier dynamics are given.:Introduction 1 1 Theoretical framework 3 1.1 Zinc oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.1.1 Crystal and band structure . . . . . . . . . . . . . . . . . . . . . 3 1.1.2 Excitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 1.2 Dielectric function and electronic transitions . . . . . . . . . . . . . . . . 5 1.2.1 Electronic transitions . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.2.2 Dielectric function . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.3 Charge carrier dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.3.1 High excitation effects . . . . . . . . . . . . . . . . . . . . . . . . 8 1.3.2 Charge carrier density-dependent dielectric function model . . . . 9 1.4 Light polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2 Preliminary experiments 14 2.1 Methods and instrumentation . . . . . . . . . . . . . . . . . . . . . . . . 14 2.2 Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.3 Experimental challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 2.4.1 Time-integrated micro-ellipsometry . . . . . . . . . . . . . . . . . 28 2.4.2 Time-resolved ellipsometry . . . . . . . . . . . . . . . . . . . . . . 31 2.4.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 3 Conclusive experiments at ELI Beamlines 35 3.1 Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 3.2 Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 3.3 Demonstration of functionality . . . . . . . . . . . . . . . . . . . . . . . . 49 3.3.1 Time-resolved reflectometry . . . . . . . . . . . . . . . . . . . . . 49 3.3.2 Time-resolved ellipsometry . . . . . . . . . . . . . . . . . . . . . . 51 4 Results and discussion 55 4.1 Time-resolved reflectometry . . . . . . . . . . . . . . . . . . . . . . . . . 55 4.2 Time-resolved ellipsometry . . . . . . . . . . . . . . . . . . . . . . . . . . 60 5 Summary and outlook 63

Philosophiae Doctor - PhD / The commercial need to improve the performance of low-cost organic solar cells has led to the idea for this research. The study discusses the synthesis of one dimensional TiO2 and ZnO nanowire arrays synthesised using a hydrothermal autoclave method and their application in bulk heterojunction inverted organic solar cells. Previous literature has shown that the precise manipulation, positioning and assembly of 1D nanostructures remain one of the greatest challenges in the field of nanotechnology, with much of the difficulty arising primarily from the lack of size and scale of the materials as well as the inability to visualise the nanostructures. In particular, one dimensional metal-oxides such as TiO2, ZnO and Fe2O3 have emerged as attractive alternatives to traditional semiconductor structures such as Si and GaAs as they are simple and inexpensive to manufacture, with research showing that application of ZnO nano-cones yield efficiencies of 8.4%, which is very attractive given the scope that exists in optimising the metal-oxide architecture. Much is still to be learned from the precise structural features of these materials and their influence on device performance. In this regard, this work largely focuses on this aspect of metal-oxide nanowires prior their application in organic solar cells.

The present work covers investigation of the growth mechanism and growth kinetics of the ZnO nanowires and nanoneedles fabricated by using high-pressure pulsed laser deposition. The growth model based on the combination of four different flows of the interfacial particles is introduced. A variation of the free energy is given as a major reason of the change of the growth mechanism which appears by using different doped seed layers, growth temperature and the doping of the deposited material. A fabrication of the ultrathin nanowires with a diameter of d < 10 nm at CMOS compatible growth temperature of T = 400°C is demonstrated. The diameter of these nanowires is comparable with the Bohr radius. The growth of the Al and Ga doped and undoped ZnO nanoneedles with a sharp tip was shown. The doping of the nanowires and nanoneedles can be promising for their applications. By using a patterned sapphire substrate, an unidirectional growth of the nanowires and nanoneedles was achieved. These nanostructures are tilted by 58°ZnO with respect to the surface normal.:Bibliographic Record Contents 1 Introduction I Basics and Methods 2 Basic properties and growth concept 2.1 ZnO nanowires and nanoneedles 2.1.1 Applications 2.2 Nanowire and nanoneedle fabrication 2.2.1 Growth mechanisms which require a catalyst 2.2.2 Catalyst-free epitaxial growth mechanism 2.3 Free energy and the growth mechanism 2.4 NW growth techniques 2.5 Aligned tilted growth 3 Growth and characterization 3.1 Preparation of the seed layers by CVD 3.2 Preparation of the seed layers by low pressure PLD 3.3 HP PLD for the NW and NN growth 3.4 Characterization techniques 3.4.1 X-ray Diffraction 3.4.2 Atomic Force Microscopy 3.4.3 Scanning electron microscopy 3.4.4 Energy Dispersive X-ray Spectroscopy 3.4.5 Spectroscopic Ellipsometry 3.4.6 Cathodoluminescence 3.4.7 Angle-varied X-ray photoelectron spectroscopy 3.4.8 Etching of the seed layers 4 Seed layer characterization 4.1 Doping concentration 4.2 Surface morphology 4.3 Crystalline quality 4.4 Surface polarity 4.5 Summary of the Chapter II NW growth: results 5 NW growth characteristics 5.1 Material free energy and the deposited material parameters 5.2 Growth kinetics 5.3 Summary of the Chapter 6 NW growth on doped seed layers 6.1 Al doped seed layers 6.2 NW growth on Ga doped seed layers 6.3 Optical characteristics of the ZnO NWs 6.4 Summary of the Chapter 7 Growth of ZnO(Al) and ZnO(Ga) NWs 7.1 Al-doped ZnO NWs grown on ZnO(Al) seed layers 7.2 Ga-doped ZnO NWs grown on ZnO(Ga) seed layers 7.3 Summary of the Chapter 8 Growth of tilted ZnO NWs and NNs 8.1 Patterning of the substrates . 8.2 Growth of tilted NNs 8.3 Growth of tilted NWs 8.4 Optical properties of the tilted nanostructures 8.5 Summary of the Chapter 9 Summary and outloock 9.1 Summary 9.2 Outlook Acknowledgements Curriculum Vitae List of own Articles List of own Conference Talks and Posters References

Orientador: José Roberto Ribeiro Bortoleto / Resumo: O presente trabalho apresenta o estudo da interface de filmes finos de óxido de zinco (ZnO) e óxido de estanho (SnO2). Foram investigadas propriedades morfológicas e elétricas a respeito desta heterojunção. A deposição dos filmes foi realizada através da técnica de magnetron sputtering RF. A morfologia de superfície foi investigada e caracterizada através de técnicas de perfilometria e microscopia eletrônica de varredura com emissão de campo. O objetivo central desta pesquisa consiste em avaliar a interação SnO2/ZnO, uma vez que esse composto possui potencial para aplicações em células fotovoltaicas. Nessas aplicações o SnO2 atua como camada transportadora de elétrons, que apresenta como principal efeito o aumento no tempo de recombinação do par elétron-buraco, gerado quando a célula fotovoltaica é submetida à incidência luminosa. Para a investigação foram depositados filmes de SnO2 com diferentes espessuras sobre ZnO. Além disso, foram estudadas as propriedades eletrônicas do ZnO para garantir que este se comporta no trabalho como um óxido transparente condutivo (TCO do inglês Transparent Conductive Oxide), o que possibilita sua aplicação nas células fotovoltaicas. O sistema produzido apresentou características que indicam ser um material promissor para as aplicações citadas. / Abstract: This work presents the analysis of the interface between thin films of zinc oxide (ZnO) and tin oxide (SnO2). Morphological and electrical properties were investigated regarding this heterojunction. The deposition of the films was performed using the RF magnetron sputtering technique. The surface morphology was investigated and characterized by profiling and Scanning Electron Microscopy with Field Emission Gun Techniques. The main objective of this research is to evaluate the SnO2/ZnO interaction, since this compound has potential for applications in photovoltaic cells. In these applications the SnO2 acts as a electron transport layer presenting as a main effect the increase in the recombination time of the electron-hole pair, generated when the photovoltaic cell is submitted to incidence of light. For this investigation SnO2 films of different thicknesses were deposited on a reference ZnO film. In addition, the electronic properties of ZnO were evaluated to ensure that it behaves as a transparent conducting oxide (TCO), which enables its application in photovoltaic cells. The system produced presented characteristics that suggests it is a promising material for the aforementioned applications. / Doutor