In the present thesis, optical and electrical properties of Ga0.75In0.25Se layered single crystals have been studied. The optical properties of the crystals have been investigated by means of visible and infrared reflectivity and transmittance, ellipsometry, Raman spectroscopy, photoluminescence (PL) and thermoluminescence (TL) measurements. The analysis of the absorption data at room temperature revealed the existence of indirect transitions in the crystal. Moreover, the rate of change of the band gap energy with temperature was calculated from the analysis of the temperature dependence of transmission measurements. The spectroscopic ellipsometry measurements on Ga0.75In0.25Se crystals were also performed to get detailed information about the real and imaginary parts of the pseudodielectric function, pseudorefractive index and pseudoextinction coefficient. The critical point analysis of the second derivative spectra of the dielectric function was done to reveal the interband transition energies. The vibrational spectra of Ga0.75In0.25Se crystals were studied by means of infrared reflectivity and transmittance and Raman scattering. The refractive and absorption indices, the frequencies of transverse and longitudinal optical modes, high- and low-frequency dielectric constants were obtained from the analysis of the IR reflectivity spectra. PL experiments were carried out as a function of temperature and excitation laser intensity to get detailed knowledge about the recombination levels in Ga0.75In0.25Se crystals. The observed emission bands in PL spectra were interpreted as the transitions from donor levels to an acceptor level. Electrical characterization of the crystal have been performed using dark electrical conductivity, space charge limited current, photoconductivity and thermally stimulated current (TSC) measurements. The detailed information about the localized levels in the band gap has been obtained from the analysis. The photoconductivity measurements were performed to determine the dominant recombination mechanism in the crystal. Defect centers in the crystal were characterized from TSC and TL measurements accomplished in the low temperature range. The activation energies, attempt-to-escape frequencies, concentrations and capture cross sections of the traps were calculated from the analysis of the experimental data.

Cadmium sulfide (CdS) thin films are very attractive materials due to their tunable optical properties and potential applications in not only photovoltaic devices but also in electronics, bio-labeling and fluorescence imaging. Recently, there is a great interest in flexible photovoltaic devices due to their unique properties such as very low weight, mechanical durability and large area applications. Organic semiconductors and their heterojunctions with inorganic materials are the most promising candidates for flexible photovoltaic applications. Preparation of CdS and Polypyrrole (PPy) semiconducting thin films on flexible polyethyleneterephtalate (PET) substrates and investigation of their morphological, structural, optical and electrical properties are the main scopes of this thesis. In the first part of the study, CdS thin films were deposited on PET via electrodeposition method. Taking the advantages of electrodeposition methods, CdS thin films with good optical and electrical properties were produced. CdS thin films were also deposited on soda-lime glass substrates in order to observe substrate effect. Scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), X-ray diffraction (XRD) and UV-vis spectrometry have been used to determine the structural and optical properties of the films deposited at various temperatures and for different deposition time intervals. For all samples, molecularly homogenous CdS films have been observed with atomic percent ratios of the Cd to S very close to 1:1. Thin films showed (002) hexagonal crystal structure around 26 (2) with average grain size 7.0 nm. CdS films have high transmittance for the wavelength greater than 500nm. Band gap energies of the films, which range between 2.74 and 2.68 eV, decreased with increasing both deposition temperature and time. For further characterization, photoelectrochemical performances and electrochemical impedance spectroscopy (EIS) of both as deposited and CuCl2 treated CdS thin films have been investigated. Later, following to the deposition of individual CdS thin films, polypyrrole thin films were produced and then heterojunctions of polypyrrole with CdS were examined. It has been observed that cadmium sulfide enhanced the photoelectrochemical properties of the polypyrrole film. Influence of the polypyrrole thin film deposition time on the photoelectrochemical properties has been also investigated in this study. Frequency dependent measurements revealed that type of charge carrier changes as a function of polypyrrole deposition time.

This thesis aims to investigate structural, optical and photoelectrochemical behavior of CdS nanowires and their heterojunctions with CdTe and polypyrrole nanowires. In the first part, CdS nanowires have been synthesized via electrochemical template-based route. It has been observed that synthesis conditions, such as bias voltage and deposition time, affect the morphology, optical and photoelectrochemical characteristics of CdS nanowires. Depending on the deposition time, length of the CdS nanowires changed from 100-200 nm to 3-4 m. Also the diameter of the nanowires increased with increasing the deposition time. Structure of the CdS nanowires has been confirmed by X-ray diffraction spectrometry and EDX analysis. Phototelectrochemical performances of the CdS nanowires have been changed dramatically with bias voltage and deposition time.In the second part of this thesis, CdTe nanostructures have been deposited on CdS nanowires. Change in optical and photoelectrochemical behavior of CdS nanowires after CdTe deposition has been investigated. Organic semiconductors and their composites with inorganic materials have been gaining attention due to tunable optical, electrical and magnetic properties. Also, ease of fabrication techniques, and therefore, low cost made these materials attractive for lots of applications including photovoltaic devices and flexible electronics. In the last part of this thesis, heterojunctions of CdS and Polypyrrole (Ppy) nanowires have been synthesized. Like CdS/CdTe heteronanostructures, first the CdS nanowires have been electrochemically deposited in anodized alumina template and then Ppy has been successfully deposited on CdS nanowires. In order to investigate the effects of polypyrrole synthesis conditions on CdS/Ppy heteronanostructures, CdS nanowire synthesis conditions have been kept constant. It has been observed that morphology and photoelectrochemical behavior of the Ppy nanowires has been affected from Ppy synthesis conditions. The photoelectrochemical performance changes of CdS/Ppy heteronanostructures have been also investigated in this part.

Este trabalho é dividido em duas partes. Na primeira parte são estudadas moléculas isoladas, na segunda, moléculas em meio solvente. Em sua primeira parte, métodos de mecânica quântica de alto nível de correlação são utilizados para caracterizar o estado fundamental da molécula de CaC. Propriedades elétricas e óticas desta molécula, como também da molécula de MgH, são obtidas usando-se o método de campo finito. O estudo dessas moléculas é de interesse para a Astrofísica. A segunda parte deste trabalho foca o estudo teórico do solvatocromismo da molécula de 4-[(4-dimethylamino)phenyl)imino]-2, 5-cyclohexadien-1-one, ou DIA (Dimethylaminoindoaniline). Esta molécula apresenta também uma grande variação da sua primeira hiperpolarizabilidade medida em solução. Sabe-se que ela existe em solução como uma combinação de duas formas extremas: a forma com separação de cargas eno e a forma neutra ceto. Após otimizarmos teoricamente as estruturas dessas duas formas, realizamos uma simulação Monte Carlo em um número de moléculas de solventes polares e apoiares. A análise da estrutura do solvente, em torno de cada soluto, é realizada usando-se funções de distribuição radial de pares. É feita, também, a análise das pontes de hidrogênio para cada estrutura eno ou ceto. Estruturas supermoleculares, envolvendo o soluto com as moléculas mais próximas e, em separado. com as moléculas ligadas por pontes de hidrogênio, são usadas como entrada para cálculos semi-empíricos de mecânica quântica da primeira transição eletrônica de absorção e da primeira hiperpolarizabilidade. Apenas superestruturas estatisticamente descorrelacionadas foram usadas no cálculo. Os resultados são analisados e comparados com resultados experimentais em solução e com resultados teóricos em fase gasosa. Todas as interpretações sugerem que a estrutura eno é responsável pelos espectros experimentais de absorção UV-visível, tanto em solvente polares quanto em apoiares. A estrutura eno tem também uma primeira hiperpolarizabilidade calculada que concorda adequadamente com aquelas observadas em alguns solventes. Para clorofórmio a primeira hiperpolarizabilidade do DIA é dez vezes maior que em outros solventes. / This work is divided in two parts. In the first part isolated molecules are studied, in the second part the interest is in molecules in solvent media. In the first part of this work, high level quantum mechanical correlation methods are employed to characterise the ground state of the CaC molecule. Electrical and optical properlies of this molecule and also of the MgH molecule are obtained using the finite field method. The study of these molecules is of interest to Astrophysics. The second part of this work focuses on the theoretical study of the solvatochromism of the 4-[(4-dimelhylamino)phenyl)imino]-2, 5-cyclohexadien-1-one molecule, or DIA (Dimethylaminoindoaniline). This molecule also presents a large variation of its measured first hyperpolarizability in solution. It is known that in solution this molecule exists in a combination of two extreme forms, the chargeseparated eno form and the neutral kelo form. After these two structures are theoretically optimised, a Monte Carlo simulation is performed in a number of polar and non-polar solvent molecules. Analysis of1 the solvent structure around each solute is performed using radial distribution function. Hydrogen bonding analysis for each eno or keto structure is also carried out. Supermolecular structures involving the solute and the nearest solvent molecules and, separately, the hydrogen bonded molecules, are used as input to quantum mechanical semi-empirical calculations of the first electronic absorption transition and the first hyperpolarizability. Only statistically non-correlated superstructures were used in the calculation. The results are analysed and compared to experimental results in solution and theoretical results in gas-phase. All interpretations suggest that the eno structure is responsible for the experimental UV-Visible absorption spectrum, both in polar and non-polar solvents. The eno structure has also a calculated first hyperpolarizability that agrees well with that observed for some solvents. For chloroform the first hyperpolarizability of DIA is ten times greater than in other solvents.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-08-23T14:01:45Z No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-08-27T11:21:40Z (GMT) No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) / Made available in DSpace on 2018-08-27T11:37:10Z (GMT). No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) Previous issue date: 2018-08-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / This work proposes the development of a low cost protocol for the production of TCNTs based on silver nanowires (AgNWs) on rigid substrates, and the improvement of the deposition technique to obtain a higher layer homogeneous, aiming at the optimization of its optical and electrical properties. For this, silver nanowires with length and diameter control were produced, aiming to evaluate the influence of these parameters on the optical and electrical properties of TCTFs. The effects of thermal annealing on the morphology of AgNWs networks and on the electrical and optical properties of TCTFs were also investigated. Studies were carried out to improve the deposition technique to obtain more homogeneous films and, as a result of this study, a new deposition technique (VMCV - Vertical Controlled Mechanical Vibration) was developed with INPI (National Institute of Intellectual Property). Silver nanowires were synthesized through the polyol process, which uses a polymer (N-vinylpyrrolidone) (PVP) as the coating agent. The prepared solutions of AgNWs were deposited on rigid substrates (glass / silicon) for analysis of topological and chemical surfaces, resulting in a random network of nanowires. The networks of AgNWs were characterized by MEV-FEG, UV-Vis, XPS and DSC-TGA techniques. The effect of thermal annealing on the AgNWs networks was investigated by means of in situ measurements of the evolution of the electrical resistances, through the technique of two tips, on a hot plate with temperature control system. Our best results exhibit an optical transparency (~ 83% at 550 nm) equivalent to commercial metal oxide thin films (indium oxide-oxide, ITO or fluoride oxide and tin oxide, FTO) and sheet resistance of ~ 23 ? / ?. / Este trabalho tem como proposta o desenvolvimento de um protocolo de baixo custo para produ??o de TCTFs (Filmes Finos Condutores Transparentes) ? base de nanofios de prata (AgNWs) sobre substratos r?gidos, e o aperfei?oamento da t?cnica de deposi??o para a obten??o de uma camada homog?nea, visando ? otimiza??o de suas propriedades ?pticas e el?tricas. Para isto, foram produzidos nanofios de prata com controle de comprimento e di?metro, visando avaliar a influ?ncia destes par?metros sobre as propriedades ?pticas e el?tricas dos TCTFs. Tamb?m foram investigados os efeitos do recozimento t?rmico na morfologia das redes de AgNWs e sobre as propriedades el?tricas e ?pticas dos TCTFs. Foram realizados estudos para o aperfei?oamento da t?cnica de deposi??o para a obten??o de filmes homog?neos e, como resultado deste estudo, desenvolveu-se uma nova t?cnica de deposi??o (VMCV- Vibra??o Mec?nica Controlada Vertical) registrada junto ao INPI (Instituto Nacional de Propriedade Intelectual). Os nanofios de prata foram sintetizados atrav?s do processo poliol, que utiliza um pol?mero (N-vinilpirrolidona) (PVP) como o agente de cobertura. As solu??es preparadas de AgNWs foram depositadas sobre substratos r?gidos (vidro/sil?cio) para an?lises de superf?cies topol?gicas e qu?micas, resultando em uma rede aleat?ria de nanofios. As redes de AgNWs foram caracterizadas pelas t?cnicas MEV-FEG, UV-Vis, XPS e DSC-TGA. O efeito do recozimento t?rmico sobre as redes de AgNWs foi investigado por meio de medi??es in situ da evolu??o das resist?ncias el?tricas, atrav?s da t?cnica de duas pontas, sobre uma chapa quente com sistema de controle de temperatura. Nossos melhores resultados exibem uma transpar?ncia ?ptica (~ 83% a 550 nm) equivalente a das pel?culas finas de ?xido de metal comercial (?xido de ?ndio-?xido, ITO ou ?xido de fl?or e ?xido de estanho, FTO) e resist?ncia de folha de ~ 23 ?/?.

Este trabalho é dividido em duas partes. Na primeira parte são estudadas moléculas isoladas, na segunda, moléculas em meio solvente. Em sua primeira parte, métodos de mecânica quântica de alto nível de correlação são utilizados para caracterizar o estado fundamental da molécula de CaC. Propriedades elétricas e óticas desta molécula, como também da molécula de MgH, são obtidas usando-se o método de campo finito. O estudo dessas moléculas é de interesse para a Astrofísica. A segunda parte deste trabalho foca o estudo teórico do solvatocromismo da molécula de 4-[(4-dimethylamino)phenyl)imino]-2, 5-cyclohexadien-1-one, ou DIA (Dimethylaminoindoaniline). Esta molécula apresenta também uma grande variação da sua primeira hiperpolarizabilidade medida em solução. Sabe-se que ela existe em solução como uma combinação de duas formas extremas: a forma com separação de cargas eno e a forma neutra ceto. Após otimizarmos teoricamente as estruturas dessas duas formas, realizamos uma simulação Monte Carlo em um número de moléculas de solventes polares e apoiares. A análise da estrutura do solvente, em torno de cada soluto, é realizada usando-se funções de distribuição radial de pares. É feita, também, a análise das pontes de hidrogênio para cada estrutura eno ou ceto. Estruturas supermoleculares, envolvendo o soluto com as moléculas mais próximas e, em separado. com as moléculas ligadas por pontes de hidrogênio, são usadas como entrada para cálculos semi-empíricos de mecânica quântica da primeira transição eletrônica de absorção e da primeira hiperpolarizabilidade. Apenas superestruturas estatisticamente descorrelacionadas foram usadas no cálculo. Os resultados são analisados e comparados com resultados experimentais em solução e com resultados teóricos em fase gasosa. Todas as interpretações sugerem que a estrutura eno é responsável pelos espectros experimentais de absorção UV-visível, tanto em solvente polares quanto em apoiares. A estrutura eno tem também uma primeira hiperpolarizabilidade calculada que concorda adequadamente com aquelas observadas em alguns solventes. Para clorofórmio a primeira hiperpolarizabilidade do DIA é dez vezes maior que em outros solventes. / This work is divided in two parts. In the first part isolated molecules are studied, in the second part the interest is in molecules in solvent media. In the first part of this work, high level quantum mechanical correlation methods are employed to characterise the ground state of the CaC molecule. Electrical and optical properlies of this molecule and also of the MgH molecule are obtained using the finite field method. The study of these molecules is of interest to Astrophysics. The second part of this work focuses on the theoretical study of the solvatochromism of the 4-[(4-dimelhylamino)phenyl)imino]-2, 5-cyclohexadien-1-one molecule, or DIA (Dimethylaminoindoaniline). This molecule also presents a large variation of its measured first hyperpolarizability in solution. It is known that in solution this molecule exists in a combination of two extreme forms, the chargeseparated eno form and the neutral kelo form. After these two structures are theoretically optimised, a Monte Carlo simulation is performed in a number of polar and non-polar solvent molecules. Analysis of1 the solvent structure around each solute is performed using radial distribution function. Hydrogen bonding analysis for each eno or keto structure is also carried out. Supermolecular structures involving the solute and the nearest solvent molecules and, separately, the hydrogen bonded molecules, are used as input to quantum mechanical semi-empirical calculations of the first electronic absorption transition and the first hyperpolarizability. Only statistically non-correlated superstructures were used in the calculation. The results are analysed and compared to experimental results in solution and theoretical results in gas-phase. All interpretations suggest that the eno structure is responsible for the experimental UV-Visible absorption spectrum, both in polar and non-polar solvents. The eno structure has also a calculated first hyperpolarizability that agrees well with that observed for some solvents. For chloroform the first hyperpolarizability of DIA is ten times greater than in other solvents.

Scientists have recently discovered simultaneous photoconductivity and photochromism (i.e., optical switching upon light exposure) of oxygen-containing rare-earth metal hydrides (REMHO). A deep understanding of these extraordinary optical and electrical properties can open the door to advanced technological uses such as smart windows. This thesis work is to establish a correlation between the photochromism of these materials with their photoconductive response and comprehend the underlying physics behind them. The samples were grown by reactive magnetron sputtering. The dynamics of the photochromic effect were observed by recording the time-resolved relative transmittance of the films during photodarkening and bleaching using a UV-vis spectrometer. The samples were characterized electrically by employing the two-point probe resistance measurement. The depth profiles of the concentration of chemical elements were extracted from Ion Beam Analysis. A systematic study was performed to see how the photoconductive and photochromic responses of the REMHO thin films depend on the wavelength and intensity of the illuminating light as well as the chemical composition of the films. Both effects showed i) higher response for shorter wavelength, ii) a cut-off near a similar wavelength, iii) saturation near UV region, and iv) similar relaxation time but with different kinetics. Multiple measurements performed on the same sample showed that the previous measurement affects the next measurement indicating a memory effect. Finally, the photoconductive response showed an increase with increasing oxygen concentration.

Des films de nitrure de zinc et d’étain (ZnSnN2) ont été élaborés par co-pulvérisation magnétron réactive à des températures proches de l’ambiante. La composition chimique des revêtements a été optimisée en ajustant les paramètres de dépôt comme la tension appliquée aux cibles métalliques, la pression de travail et la composition du gaz plasmagène. Dans les conditions optimisées, les films sont fortement cristallisés sur les différents types de substrats testés. Une étude approfondie sur la structure des films a été entreprise par microscopie électronique en transmission. Nous avons ainsi pu montrer que nos films de ZnSnN2 cristallisent dans le système hexagonal. Toutefois, cette structure diffère de celles présentées dans la littérature pour le nitrure de zinc et d’étain. Des études sur l’environnement chimique des éléments constitutifs des revêtements ont également été menées par spectrométrie Mössbauer et par photoémission X. Elles montrent que l’étain est présent dans nos films sous forme de Sn4+ en configuration tétraédrique. Nous avons également pu montrer que l’oxygène présent dans nos films est principalement localisé dans les zones inter-colonnaires. Enfin, les propriétés optiques et électriques de nos films ont été estimées en fonction de leur composition chimique. L’ensemble des résultats obtenus durant ce travail démontre la pertinence de ZnSnN2 pour des applications futures en tant que couche absorbante dans les cellules photovoltaïques / Zinc tin nitride (ZnSnN2) thin films have been deposited by reactive magnetron co-sputtering at room temperature. The stoichiometry of the films has been controlled by optimizing the deposition conditions such as the voltage applied to the metallic targets, the deposition pressure and the composition of the gas mixture. By using the optimized parameters, the deposited films are highly crystallized on the different used substrates. A special attention has been devoted to the determination of the film structure. Among the various structures reported in the literature, we have shown by transmission electron microscopy that the films crystallised in a hexagonal structure. Nevertheless, the structure of our films does not fit with that reported in the literature for the hexagonal ZnSnN2 material. In addition to this structural study, we have performed fine characterization using conversion electron Mossbauer spectrometry and X-ray photoemission spectroscopy. Both methods show that the optimized films contain Sn4+ ions in tetrahedral configuration. Nevertheless, oxygen contamination at the column boundaries has been evidenced. The electrical and optical properties of the films have been determined has a function of the film composition. The results obtained in this PhD work clearly evidence that ZnSnN2 is a suitable material for photovoltaic applications