Magister Scientiae - MSc / With an increase in the amount of harmful carbon emissions in the atmosphere as well as a decrease in the availability of fossil fuels, there is a relatively high demand for alternate energy devices. Solar cells have become an alternative option in aid of leading the way for clean energy; however these devices are relatively expensive and have an efficiency that is relatively low in comparison to that of fossil fuelled energy. As a result the cost of the solar cell needs to be reduced by reducing the amount of silicon used in order to compete with fossil fuelled devices; however this decrease would lead to a decrease in efficiency. In recent years silver nanoparticles have been extensively researched as a result of its extraordinary optical, electrical, catalytic, magnetic and antibacterial properties. As a result of these properties, the nanoparticles may be applied to many research areas such as photovoltaics, catalysis and medical fields. The optical properties of silver nanoparticles may thus be exploited in order to increase absorption and in turn the efficiency of the solar cell devices. This study focuses on the optimization of the polyol synthesis to possibly obtain uniformly dispersed silver nanoparticles. The silver nanoparticles would then be incorporated onto amorphous silicon thin films, deposited by hot wire chemical vapour deposition, by spraying a suspension of the silver nanoparticles onto the thin films. The silver nanoparticles were viii characterized by Ultra Violet Visible Spectroscopy (UV-VIS), High Resolution Transmission Electron Microscopy, X-ray Diffraction, and Thermogravimetric Analysis. The thin films with the incorporated silver nanoparticles were characterized by UV-VIS, and High Resolution Scanning Electron Microscopy. It was shown that silver nanoparticles with various morphologies were produced by the polyol synthesis and may be used to enhance light trapping of thin film photovoltaic devices.

Les nanomatériaux, grâce à leurs propriétés optiques et électroniques, peuvent être une opportunité pour le développement d'une nouvelle génération de cellules photovoltaïques à hauts rendements et bas coût. Les boîtes quantiques sous la forme de nanocristaux semi-conducteurs permettent de réaliser des matériaux à énergie de gap variable, propriété très recherchée pour un absorbeur solaire. Ce travail est consacré à l'élaboration et à la caractérisation de matériaux à base de nanocristaux de Ge dans différentes matrices. Une source à agrégats, procédé original de pulvérisation sous vide, a été étudiée pour synthétiser des nanoparticules de Ge. Cette technique de dépôt permet la formation de nanoparticules de Ge bien cristallisées (pour un substrat maintenu à température ambiante) et d'avoir un très bon contrôle de la taille de ces nanocristaux. Des caractérisations optiques de nanocristaux de Ge enfouis dans des matrices isolantes et semi-conductrices ont permis de démontrer la présence d’effet de confinement quantique dans ces cristaux et la possibilité de moduler leur énergie de gap sur une large gamme d'énergie entre 0,85 et 1,55 eV. Afin d’extraire et de collecter des charges photogénérées dans les nanocristaux, nous nous sommes intéressés au couple nanocristaux de Ge / matrice de ZnO:Al qui permet de séparer spatialement les photoporteurs (alignement en type II). La structure composée de nanocristaux de Ge recouverts d'une matrice de ZnO:Al sur un substrat de Si (p+), a permis de mettre en évidence un effet photovoltaïque pour lequel la génération de porteurs s'effectue uniquement dans les nanocristaux de Ge. / The particular properties of nanomaterials can be an opportunity for developing a new low cost and a high efficient generation of solar cells. Semiconducting nanocrystals can be used as quantum dots to realize band gap engineering by varying the nanocrystals size. The subject of research is to synthesize a composite material based on Ge nanocrystals embedded in various matrices and perform characterizations. A nanocluster source, under vacuum sputtering setup, was used to synthesize Ge nanoparticles. The vapor phase condensation leads to the formation of well crystallized nanoparticles, for a deposition performed at room temperature. This synthesis method allows a good control of the nanocrystals size and the nanocrystals quantity inserted in the material. Optical properties of Ge nanocrystals embedded in insulating and semiconducting matrices were studied. We have demonstrated the quantum dot behavior of Ge nanocrystals. We have also shown the ability to modulate the nanocrystals band gap from 0.85 to 1.55 eV by varying the nanocrystals size and the potential barriers. Optoelectronical characterizations were performed to estimate the ability to extract and collect the carriers photogenerated in the Ge nanocrystals by light absorption. Ge nanocrystals in ZnO:Al matrix forms type-II quantum dots. This heterostructure is very interesting because it allows the spatial separation of the carriers while keeping the quantum confinement properties. We have brought out a photovoltaic effect with the structure p+-Si wafer / Ge nanocrystals / ZnO:Al matrix. We have also demonstrated that the carrier generation only occurs in the Ge nanocrystals.

Este trabalho foi desenvolvido em duas etapas: i) síntese, caracterização e aplicação de pontos quânticos de CdS, CdSe e CdTe em células solares. ii) modificação da superfície dos pontos quânticos de CdSe através de troca de ligante, seguida de caracterização e aplicação em células solares. Os pontos quânticos foram sintetizados utilizando acetatos de cádmio, selênio, telúrio e enxofre como precursores e ácido oleico como agente de estabilização. Na segunda etapa o ácido oleico foi substituído por ligantes com maior afinidade eletrônica pelos sítios de Cd2+: ácido 3-mercaptopropiônico, 4-ácido-mercaptobenzóico e ácido 11-mercaptoundecanóico. As amostras foram caracterizadas por UV-Vis, fluorescência, microscopia eletrônica de transmissão, difratometria de raios-X e voltametria cíclica. Adicionalmente, testes de solubilidade, análises de TGA e de RMN foram realizadas para confirmar a troca de ligante. Através dos resultados, verificou-se que todos os pontos quânticos sintetizados são adequados para sensibilização de TiO2 em dispositivos fotovoltaicos. No entanto, os pontos quânticos de CdSe e CdTe apresentaram fatores que evidenciam maior confinamento quântico, sendo que a maior estabilidade do éxciton foi obtida para o CdSe. Através das análises de RMN foi possível verificar que não existe apenas uma confirguração espacial preferencial para a adsorção do ligante sobre a superfície deste ponto quântico enquanto que curvas de corrente versus potencial e de eficiência de conversão de fóton incidente mostraram que a eficiência do dispositivo é fracamente dependente do ligante. Contudo, a troca de ligantes favorece a solubilidade em solventes com diferentes polaridades, inclusive água, o que amplia as possibilidades de aplicação dos pontos quânticos sintetizados neste trabalho. / This work was developed in two stages: i) synthesis, characterization and application of CdS, CdSe and CdTe quantum dots to assemble solar cells, ii) surface modification, characterization and application of CdSe quantum dots to assemble solar cells. The quantum dots were synthesized by using cadmium acetate, Se, S or Te as precursors and oleic acid as stabilizing agent. In the second stage the oleic acid capping layer was replaced by other ligands with higher electron affinity to Cd2+: 3-mercaptopropionic acid, 4-mercaptobenzoic acid and 11-mercaptoundecanoic acid. The samples were characterized by UV-Vis, fluorescence, transmission electron microscopy, x-ray diffractometry and cyclic voltammetry. Additionally, solubility tests, TGA analysis and NMR were performed to evaluate the CdSe surface modification. The results showed that all quantum dots synthesized are adequate to sensitize TiO2 in photovoltaic devices. However, CdSe and CdTe quantum dots presented better quantum confinement and the exciton generated in CdSe presented the higher stability. NMR analysis provided information about the non-preferential orientation for adsorption of the ligands on the CdSe surface, meanwhile measurements of current vs. potential and incident photon current efficiency showed a weak dependence of photovoltaic device efficiency with the nature of the ligand. On the other side, the surface modification favors the solubility in solvents with different polarizabilities, including water, widening the range for applications of the quantum dots synthesized in this work.

Submitted by Juan Carlos Roldão null (36780115860) on 2016-04-28T18:17:40Z No. of bitstreams: 1 Dissertação-Versão-Final-Juan_Carlos_Roldao.pdf: 3885340 bytes, checksum: 0d245c89d075ddeea3f1fc7154e9c5a9 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-05-02T13:34:47Z (GMT) No. of bitstreams: 1 roldao_jc_me_bauru.pdf: 3885340 bytes, checksum: 0d245c89d075ddeea3f1fc7154e9c5a9 (MD5) / Made available in DSpace on 2016-05-02T13:34:47Z (GMT). No. of bitstreams: 1 roldao_jc_me_bauru.pdf: 3885340 bytes, checksum: 0d245c89d075ddeea3f1fc7154e9c5a9 (MD5) Previous issue date: 2016-03-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Atualmente existe uma intensa busca por novos materiais com propriedades ajustadas para utilização em células solares orgânicas de modo a obter um aumento em sua eficiência de conversão para que possam substituir os dispositivos de silício. O politieno[3,4-b]-tiofeno-co-benzoditiofeno (PTB7) é um polímero recentemente proposto na literatura e com propriedades muito interessantes em células solares orgânicas, o que o coloca como uma possível alternativa ao amplamente utilizado poli(3-hexiltiofeno) (P3HT). Tem sido relatadas modificações em diferentes posições da unidade monomérica deste copolímero, tanto na estrutura benzoditiofeno (BDT), quanto na estrutura tienotiofeno (TT), que o compõe. Estas modificações levaram a novos polímeros com propriedades diferentes e por vezes mais interessantes que aquelas do PTB7 sem substituições. O trabalho que será apresentado visou estudar as propriedades estruturais, eletrônicas e ópticas do PTB7 e possíveis alterações ocorridas devido às modificações químicas realizadas na estrutura do BDT de suas unidades monoméricas. Tal estudo utilizou ferramentas de otimização de estruturas como Mecânica Molecular, Dinâmica Molecular e o método semi-empírico Parametric Method 6 (PM6), assim como de cálculo de estrutura eletrônica de materiais, como a Teoria do Funcional da densidade (DFT) e de cálculos de propriedades ópticas como a Teoria do Funcional da Densidade Dependente do Tempo (TD-DFT). Concluímos que o PTB7 no estado sólido pode ser considerado planar. Com o nosso modelo para o PTB7, obtivemos uma diferença de energia ∆EHL entre o Último Orbital Molecular Ocupado HOMO (do inglês Highest Occupied Molecular Orbital) e o Primeiro Orbital Molecular Desocupado LUMO (do inglês Lowest Unoccupied Molecular Orbital) de aproximadamente 1,84 eV, sendo que este valor está em boa concordância com o valor experimental. Em relação às substituições químicas, estudamos teoricamente 8 derivados do PTB7 e os resultados mostraram que é possível obter compostos com uma diminuição significativa do ∆EHL e também que é possível obter compostos com valores de energia do HOMO e do LUMO mais interessantes que os do PTB7 quando na camada ativa for empregado como material doador o fenil-C61-butírico ácido metil ester (PCBM). / Currently there is an intensive search for new materials with tuned properties for use in organic solar cells to obtain an increase in its conversion efficiency and replace silicon devices. The polythieno[3,4-b]-thiophene-co-benzodithiophene (PTB7) is a polymer recently proposed in the literature and with very interesting properties in organic solar cells, which places it as a possible alternative to the widely used poli(3-hexilthiophene) (P3HT). It has been reported changes in different positions of the monomeric unit of this copolymer, both in benzodithiophene (BDT) structure, as in the thienothiophene (TT) structure that compose it. These modifications led to new polymers with different properties and sometimes more interesting than those of PTB7 without substitutions. The work to be presented aimed to study the structural, electronic and optical properties of PTB7 and possible changes due to chemical changes made in the BDT structure of its monomeric units. This study employed optimization tools like Molecular Mechanics, Molecular Dynamics and Parametric Method 6 (PM6), as well as calculations of the electronic structures with the Density Functional Theory (DFT) method, and optical properties such as the Time Dependent Density Functional Theory (TD-DFT) calculations. We conclude that the PTB7 chains in the solid state can be considered planar. With our model for PTB7, we obtained a difference ΔEHL between the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of approximately 1.84 eV, and this value is in good agreement with the experimental value. Regarding chemical substitutions, we studied theoretically 8 derivatives of PTB7 and the results showed that it is possible to obtain compounds with a significant decrease in ΔEHL and that it is possible to obtain compounds with HOMO and LUMO energy values more adjusted to the widely employed acceptor material phenylC61-butyric acid methyl ester (PCBM).

abstract: This dissertation presents my work on development of deformable electronics using microelectromechanical systems (MEMS) based fabrication technologies. In recent years, deformable electronics are coming to revolutionize the functionality of microelectronics seamlessly with their application environment, ranging from various consumer electronics to bio-medical applications. Many researchers have studied this area, and a wide variety of devices have been fabricated. One traditional way is to directly fabricate electronic devices on flexible substrate through low-temperature processes. These devices suffered from constrained functionality due to the temperature limit. Another transfer printing approach has been developed recently. The general idea is to fabricate functional devices on hard and planar substrates using standard processes then transferred by elastomeric stamps and printed on desired flexible and stretchable substrates. The main disadvantages are that the transfer printing step may limit the yield. The third method is "flexible skins" which silicon substrates are thinned down and structured into islands and sandwiched by two layers of polymer. The main advantage of this method is post CMOS compatible. Based on this technology, we successfully fabricated a 3-D flexible thermal sensor for intravascular flow monitoring. The final product of the 3-D sensor has three independent sensing elements equally distributed around the wall of catheter (1.2 mm in diameter) with 120° spacing. This structure introduces three independent information channels, and cross-comparisons among all readings were utilized to eliminate experimental error and provide better measurement results. The novel fabrication and assembly technology can also be applied to other catheter based biomedical devices. A step forward inspired by the ancient art of folding, origami, which creating three-dimensional (3-D) structures from two-dimensional (2-D) sheets through a high degree of folding along the creases. Based on this idea, we developed a novel method to enable better deformability. One example is origami-enabled silicon solar cells. The solar panel can reach up to 644% areal compactness while maintain reasonable good performance (less than 30% output power density drop) upon 40 times cyclic folding/unfolding. This approach can be readily applied to other functional devices, ranging from sensors, displays, antenna, to energy storage devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2014

abstract: This dissertation aims to demonstrate a new approach to fabricating solar cells for spectrum-splitting photovoltaic systems with the potential to reduce their cost and complexity of manufacturing, called Monolithically Integrated Laterally Arrayed Multiple Band gap (MILAMB) solar cells. Single crystal semiconductor alloy nanowire (NW) ensembles are grown with the alloy composition and band gap changing continuously across a broad range over the surface of a single substrate in a single, inexpensive growth step by the Dual-Gradient Method. The nanowire ensembles then serve as the absorbing materials in a set of solar cells for spectrum-splitting photovoltaic systems. Preliminary design and simulation studies based on Anderson's model band line-ups were undertaken for CdPbS and InGaN alloys. Systems of six subcells obtained efficiencies in the 32-38% range for CdPbS and 34-40% for InGaN at 1-240 suns, though both materials systems require significant development before these results could be achieved experimentally. For an experimental demonstration, CdSSe was selected due to its availability. Proof-of-concept CdSSe nanowire ensemble solar cells with two subcells were fabricated simultaneously on one substrate. I-V characterization under 1 sun AM1.5G conditions yielded open-circuit voltages (V_oc) up to 307 and 173 mV and short-circuit current densities (J_sc) up to 0.091 and 0.974 mA/cm<super>2</super> for the CdS- and CdSe-rich cells, respectively. Similar thin film cells were also fabricated for comparison. The nanowire cells showed substantially higher V_oc than the film cells, which was attributed to higher material quality in the CdSSe absorber. I-V measurements were also conducted with optical filters to simulate a simple form of spectrum-splitting. The CdS-rich cells showed uniformly higher V_oc and fill factor (FF) than the CdSe-rich cells, as expected due to their larger band gaps. This suggested higher power density was produced by the CdS-rich cells on the single-nanowire level, which is the principal benefit of spectrum-splitting. These results constitute a proof-of-concept experimental demonstration of the MILAMB approach to fabricating multiple cells for spectrum-splitting photovoltaics. Future systems based on this approach could help to reduce the cost and complexity of manufacturing spectrum-splitting photovoltaic systems and offer a low cost alternative to multi-junction tandems for achieving high efficiencies. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2014

abstract: In this work a newly fabricated organic solar cell based on a composite of fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) and regioregular poly (3-hexylthiophene) (P3HT) with an added interfacial layer of AgOx in between the PEDOT:PSS layer and the ITO layer is investigated. Previous equivalent circuit models are discussed and an equivalent circuit model is proposed for the fabricated device. Incorporation of the AgOx interfacial layer shows an increase in fill factor (by 33%) and power conversion efficiency (by 28%). Moreover proper correlation has been achieved between the experimental and simulated I-V plots. The simulation shows that device characteristics can be explained with accuracy by the proposed model. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

abstract: The development of high efficiency III-V solar cells is needed to meet the demands of a promising renewable energy source. Intermediate band solar cells (IBSCs) using semiconductor quantum dots (QDs) have been proposed to exceed the Shockley-Queisser efficiency limit [1]. The introduction of an IB in the forbidden gap of host material generates two additional carrier transitions for sub-bandgap photon absorption, leading to increased photocurrent of IBSCs while simultaneously allowing an open-circuit voltage of the highest band gap. To realize a high efficiency IBSC, QD structures should have high crystal quality and optimized electronic properties. This dissertation focuses on the investigation and optimization of the structural and optical properties of InAs/GaAsSb QDs and the development of InAs/GaAsSb QD-based IBSCs. In the present dissertation, the interband optical transition and carrier lifetime of InAs/GaAsSb QDs with different silicon delta-doping densities have been first studied by time-integrated and time-resolved photoluminescence (PL). It is found that an optimized silicon delta-doping density in the QDs enables to fill the QD electronic states with electrons for sub-bandgap photon absorption and to improve carrier lifetime of the QDs. After that, the crystal quality and QD morphology of single- and multi-stack InAs/GaAsSb QDs with different Sb compositions have been investigated by transmission electron microscopy (TEM) and x-ray diffraction (XRD). The TEM studies reveal that QD morphology of single-stack QDs is affected by Sb composition due to strain reducing effect of Sb incorporation. The XRD studies confirm that the increase of Sb composition increases the lattice mismatch between GaAs matrix and GaAsSb spacers, resulting in increase of the strain relaxation in GaAsSb of the multi-stack QDs. Furthermore, the increase of Sb composition causes a PL redshift and increases carrier lifetime of QDs. Finally, the spacer layer thickness of multi-stack InAs/GaAsSb QDs is optimized for the growth of InAs/GaAsSb QD solar cells (QDSCs). The InAs/GaAsSb QDSCs with GaP strain compensating layer are grown and their device performances are characterized. The increase of GaP coverage is beneficial to improve the conversion efficiency of the QDSCs. However, the conversion efficiency is reduced when using a relatively large GaP coverage. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2015

abstract: Humanity’s demand for energy is increasing exponentially and the dependence on fossil fuels is both unsustainable and detrimental to the environment. To provide a solution to the impending energy crisis, it is reasonable to look toward utilizing solar energy, which is abundant and renewable. One approach to harvesting solar irradiation for fuel purposes is through mimicking the processes of natural photosynthesis in an artificial design to use sunlight and water to store energy in chemical bonds for later use. Thus, in order to design an efficient energy conversion device, the underlying processes of the natural system must be understood. An artificial photosynthetic device has many components and each can be optimized separately. This work deals with the design, construction and study of some of those components. The first chapter provides an introduction to this work. The second chapter shows a proof of concept for a water splitting dye sensitized photoelectrochemical cell followed by the presentation of a new p-type semiconductor, the design of a modular cluster binding protein that can be used for incorporating catalysts, and a new anchoring group for semiconducting oxides with high electron injection efficiency. The third chapter investigates the role of electronic coupling and thermodynamics for photoprotection in artificial systems by triplet-triplet energy transfer from tetrapyrroles to carotenoids. The fourth chapter describes a mimic of the proton-coupled electron transfer in photosystem II and confirms that in the artificial system a concerted mechanism operates. In the fifth chapter, a microbial system is designed to work in tandem with a photovoltaic device to produce high energy fuels. A variety of quinone redox mediators have been synthesized to shuttle electrons from an electron donor to the microbial system. Lastly, the synthesis of a variety of photosensitizers is detailed for possible future use in artificial systems. The results of this work helps with the understanding of the processes of natural photosynthesis and suggests ways to design artificial photosynthetic devices that can contribute to solving the renewable energy challenge. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015

abstract: A basic theory and terminology that comprehensively applies to all different types of contacts in silicon solar cells has, thus far, been elusive. While the well established diode model has been applied to many of the complex contacts, the theory is not adequate to intuitively describe the characteristics of novel contacts. This thesis shows that the many desirable characteristics of contacts that are discussed in the literature—carrier selectivity, passivation, and low majority carrier conductance, key among them—originate from the resistance to electrons and holes in the contact. These principles are applied to describe a few popular contact technologies in order to pave the path to envisioning novel contacts. Metrics for contact performance is introduced to quantify each of the above characteristics using the two carrier resistances. The the validity of the proposed metrics is explored using extensive PC-1D simulations. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2016