In dieser Arbeit wurden zunächst zwei Charakterisierungsmethoden zur zerstörungsfreien Detektion von Voids in lokalen Rückseitenkontakten bei PERC Solarzellen vorgestellt, die akustische Mikroskopie und die Computertomografie. Beide Messmethoden wurden anhand von Proben mit unterschiedlichen Al-Pasten getestet und mit beiden Messmethoden können Voids sehr gut erkannt werden. Zur Vermeidung von Voidbildung konnte der positive Einfluss der Siliziumbeimischung in die Al-Paste bestätigt werden. Desweiteren konnte anhand unterschiedlicher RTP Feuerprofile gezeigt werden, dass durch eine verlangsamte Aufheizphase die Bildung von Voids deutlich reduziert werden kann, während die Abkühlphase nur einen geringen Einfluss auf die Voidbildung zeigt. Mithilfe eigens hergestellter Al-Pasten, mit unterschiedlichen Al-Partikelgrößen, wurde gezeigt, dass Al-Pasten mit einer Mischung aus kleinen und großen Al-Partikeln ebenfalls einen positiven Einfluss auf die Ausbildung von Voids haben können.

Orientador: Ana Flavia Nogueira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T14:27:05Z (GMT). No. of bitstreams: 1 Freitas_FlavioSantos_M.pdf: 1335737 bytes, checksum: 43bb80b2fab0adc9d9092583a0f45e94 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho foram investigados eletrólitos poliméricos baseados em poli(óxido de etileno-co-2-(2-metoxietoxi) etilglicidiléter) - P(EO-EM) com adição do oligômero dibenzoato de etileno-glicol (DIB)/LiI/I2 e poli(óxido de etileno-co-óxido de propileno) - P(EO-PO), com adição do líquido iônico iodeto de 1-metil-3- propilimidazólio (MPII)/I2 (com e sem a presença de LiI), visando a aplicação em células solares de TiO2/corante. Os eletrólitos foram caracterizados por Calorimetria Exploratória Diferencial (DSC), Espectroscopia de Infravermelho com Transformada de Fourier (FTIR), Ressonância Magnética Nuclear de Hidrogênio (H RMN) e Espectroscopia de Impedância Eletroquímica (EIE). Para o sistema P(EO-EM)/DIB, os estudos realizados por DSC e FTIR mostraram alta homogeneidade entre os componentes, com evidências de coordenação de sal no copolímero e no oligômero. Nas medidas de condutividade iônica, verificou-se saturação em ~10 S cm a partir de 10 % de LiI para todas as proporções de PEO-EM/DIB. Como conseqüência, a aplicação de eletrólitos com 20 % de LiI apresentou resultados bem similares, independente da proporção de DIB no sistema, indicando que os processos cinéticos relacionados ao transporte de carga são diferentes dos eletrólitos géis reportados na literatura, não sendo verificada mudança no potencial de circuito aberto (VOC) dos dispositivos. Para o sistema P(EO-PO)/MPII, as análises por DSC, FTIR e H RMN evidenciaram interações entre o oxigênio do copolímero e o hidrogênio do cátion imidazólio, possibilitando aumento na difusão do par I /I3 (estimado em 1,9x 10 cm s para o eletrólito com 70 % de MPII). A maior condutividade iônica foi obtida para o eletrólito com 70 % de MPII (2,4 x 10 S cm), possibilitando a montagem de células solares com eficiência de 5,66 %. Para todos os dispositivos, a presença de íons I3 promoveu aumento nas reações de recombinação, observando-se valores menores para o VOC com o aumento da concentração de MPII nos eletrólitos. Após a adição de LiI, não foram observadas melhores eficiências em comparação aos dispositivos montados sem a adição do sal. Esses resultados indicam que eletrólitos poliméricos baseados na combinação de polímero e líquido iônico consistem em sistemas promissores para aplicação em células solares. / Abstract: New polymer electrolytes based on poly(ethylene oxide-co-2-(2- methoxyethoxy)ethylglycidylether) - P(EO-EM) with addition of the oligomer ethyleneglycol dibenzoate (DIB)/LiI/I2, and poly(ethylene oxide-co-propylene oxide) - P(EO-PO) with addition of the ionic liquid 1-methyl-3-propylimidazolium (MPII)/I2 (with and without LiI) were investigated in this work aiming at the application in dye-sensitized solar cells. The electrolytes were characterized using Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Ressonance (H NMR) and Complex Electrochemical Impedance Spectroscopy (EIS). For the P(EO-EM)/DIB system, the DSC and FTIR measurements revealed a homogeneous mixture, with evidence of coordination of the salt with both the copolymer and the oligomer. The ionic conductivity measurements presented saturation in ~10 S cm for samples containing at least 10 % of LiI, for all P(EO-EM)/DIB concentration ratios. As consequence, the solar cells assembled with electrolytes containing 20 % of LiI presented similar performance, regardless of the DIB concentration, indicating that the kinetic processes related to the charge transport in these systems are different from those usually observed for gel electrolytes (which cause changes in the open circuit potential, VOC, of the devices). For the P(EO-PO)/MPII system, the DSC, FTIR and HNMR measurements revealed the presence of interactions between the oxygen atoms in the copolymer and the hydrogen atoms from the imidazolium cation, which increased the diffusion of the I/I3 redox couple (estimated to be 1,0 x 10 cm s for the electrolyte containing 70 % if MPII). The highest ionic conductivity was observed for the electrolyte containing 70 % of MPII (2,4 x 10 S cm), leading to the assembly of solar cells with 5,66 % of efficiency. In all the devices assembled, the presence of I3 ions leads to an increase of the recombination reactions, thus reducing the VOC values. This effect is more pronounced for higher concentrations of MPII in the electrolyte. After addition of LiI to these systems, no improvements in the device efficiency were observed. These results show that polymer electrolytes based on the mixture of polymer and ionic liquids are very promissing systems for application in solar cells. / Mestrado / Quimica Inorganica / Mestre em Química

Orientador: Ana Flavia Nogueira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T13:13:51Z (GMT). No. of bitstreams: 1 Conturbia_GiovannideLimaCabral_M.pdf: 7472586 bytes, checksum: 9ede857037431127443d2bed95bd1ccc (MD5) Previous issue date: 2009 / Resumo:Células solares orgânicas têm despertado atenções devido ao baixo custo de produção e dos materiais utilizados, bem como devido à versatilidade química e de propriedades eletrônicas e ópticas dos semicondutores orgânicos. A eficiência atual atinge 5% (100 mWcm). Nanotubos de carbono encontram suas aplicações nessas células ora como eletrodos transparentes ora como material receptor de elétrons. Nesse trabalho, foi realizada a modificação química de nanotubos de carbono de única camada com grupos tióis, visando a incorporação de nanopartículas metálicas ou semicondutoras. O material de partida, bem como os nanotubos modificados, foi caracterizado por Espectroscopia Raman, Espectroscopia de Fotoelétron por Raios-X, Análise Térmica e Microscopia Eletrônica de Transmissão de Alta Resolução. Foi necessário um pós-tratamento (térmico e lavagens com diversos solventes) para que pudéssemos obter nanotubos individuais e funcionalizados. O pós-tratamento também possibilitou um aumento na fotocorrente dos dispositivos em comparação com o dispositivo sem nanotubos de carbono. A incorporação de nanopartículas de ouro no sistema P3HT/fulereno acresceu a fotocorrente e o fator de preenchimento dos dispositivos. Estudos de caracterização através de difração de raios-X, espectroscopia UV-visível e microscopia de força atômica, indicam que esse aumento está relacionado a uma mudança na morfologia do sistema, aumentando a cristalinidade do polímero e também ao efeito plasmônico com a adição das nanopartículas. Imagens de microscopia eletrônica de transmissão revelaram que as nanopartículas de ouro estão distribuídas tanto na fase polimérica quanto na fase contendo moléculas de fulereno / Abstract: Organic solar cells have attracted attention due to their low costs of production and materials used, as well as the chemical versatility and good electronic and optical properties of organic semiconductors. The current efficiency reaches 5% (100 mWcm). Carbon nanotubes materials can be applied in these cells as both transparent electrode or as electron acceptor materials. In this work, the chemical modification of single wall carbon nanotubes was carried out attaching thiol groups, aiming the incorporation of semiconductor or metallic nanoparticles. The raw material and the modified nanotubes were characterized by Raman Spectroscopy, X-ray Photoelectron Spectroscopy, Thermal Analysis and High Resolution Transmission Electron Microscopy. A post-treatment (thermal and washing with different solvents) was necessary in order to obtain single functionalized nanotubes. The post-treatment also allowed an increase in the photocurrent of the devices compared to the device without carbon nanotubes. The incorporation of gold nanoparticles in the P3HT/fullerene system increased the photocurrent and the fill factor of the devices. X-Ray diffraction, UV-vis Spectroscopy and Atomic Force Microscopy studies reveal that such increase can be related to the plasmonic effect and also to a change in the morphology, increasing polymer crystallinity after incorporation of the gold nanoparticles. High resolution transmission microscopy images showed that the nanoparticles are distributed between both polymer and fullerene phase. / Mestrado / Físico-Química / Mestre em Química

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Wcm2) and high exchange current density (J0~2.50 mAcm-2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 – 3.1 V/μm and 4.2 – 0.4 mA, respectively.

No description available.

Dans cette thèse, deux semi-conducteurs en séléniure ayant d'excellentes propriétés ont été étudiés afin de développer des matériaux performants pour des applications photoélectriques. Tout d'abord, les nanorodes de Sb2Se3 ont été synthétisés en utilisant une méthode d'injection à chaud, et le plus grand défi associé à la faible conductivité de Sb2Se3 a été relevé en formant des hétérojonctions et/ou par un dopage. Les nanorodes de Sb2Se3 à conductivité électrique nettement améliorée ont été utilisés pour fabriquer des photo-détecteurs prototypes, qui présentent un grand potentiel d'application grâce à leur grande efficacité. Le Sb2Se3 dopés au Sn a été préparé en utilisant un procédé de fusion à haute température. Avec l'augmentation de la concentration en Sn, les cristaux (SnxSb1-x)2Se3 présentent également une grande amélioration de la conductivité et des propriétés photoconductrices. Quatre cibles à base de Sb2Se3 avec la composition chimique de Sb2Se3, Sb2Se3.3, (Sn0.1Sb0.9)2Se3 et Sb2(Se0.9I0.1)3 ont été préparées et les couches minces ont été déposées en utilisant la pulvérisation cathodique. Une étude systématique de la cristallinité, de la morphologie de surface, des propriétés optiques, du type de conduction (p ou n) et des performances photo-électro-chimique des couches minces a été réalisée. Une nouvelle cellule solaire à couches minces de Sb2Se3 avec une quasi-homojonction a été fabriquée pour la première fois et le rendement de conversion atteint déjà un taux très intéressant de 2,65%. Une méthode efficace d'injection à chaud a également été développée pour la synthèse de nano-fleurs uniformes de γ-In2Se3. Une photodiode à hétérojonction formée en déposant une couche mince de nanoflower γ-In2Se3, du type p, sur un substrat en Si de type n, a été fabriquée pour la première fois. Il a été démontré que ce photo-détecteur peut être auto-alimenté avec d'excellentes performances, notamment une réponse rapide et une sensibilité à large bande. / In this dissertation, two different selenide semiconductors with excellent properties have been studied in order to develop high performance materials and devices for photoelectric applications. Firstly, Sb2Se3 nanorods were synthesized via hot-injection method, and the biggest challenge of low conductivity of Sb2Se3 nanorods has been overcome successfully by forming heterojunction and/or doping. The Sb2Se3 nanorods with enhanced electrical conductivity were used for fabricating prototype photodetectors, which show great application potential as highly efficient photodetectors. The Sn-doped Sb2Se3 crystals were successfully prepared by using high-temperature melting process. With increasing Sn doping concentration, the (SnxSb1-x)2Se3 crystals also exhibit a great improvement of conductivity and photoconductive properties. Four Sb2Se3-based targets with the chemical composition of Sb2Se3, Sb2Se3.3, (Sn0.1Sb0.9)2Se3 and Sb2(Se0.9I0.1)3 have been successfully prepared by using high-temperature melting technique. Then thin films have been deposited by using RF magnetron-assisted sputtering. A systematic investigation of the crystallinity, surface morphology, optical properties, p/n type and photo-electro-chemical performance of the thin films has been performed. A novel quasi-homojunction Sb2Se3 thin film solar cells was fabricated for the first time and the highest conversion efficiency obtained in our work reaches already a highly interesting 2.65%. An effective hot-injection method has also been developed for synthesizing uniform γ-In2Se3 nanoflowers. An efficient heterojunction photodiode formed by n-type Si substrate and p-type γ-In2Se3 nanoflower film was fabricated for the first time. It has been demonstrated that this photodetector can be self-powered with excellent performance including fast response and broadband sensibility.

abstract: An ongoing effort in the photovoltaic (PV) industry is to reduce the major manufacturing cost components of solar cells, the great majority of which are based on crystalline silicon (c-Si). This includes the substitution of screenprinted silver (Ag) cell contacts with alternative copper (Cu)-based contacts, usually applied with plating. Plated Cu contact schemes have been under study for many years with only minor traction in industrial production. One of the more commonly-cited barriers to the adoption of Cu-based contacts for photovoltaics is long-term reliability, as Cu is a significant contaminant in c-Si, forming precipitates that degrade performance via degradation of diode character and reduction of minority carrier lifetime. Cu contamination from contacts might cause degradation during field deployment if Cu is able to ingress into c-Si. Furthermore, Cu contamination is also known to cause a form of light-induced degradation (LID) which further degrades carrier lifetime when cells are exposed to light. Prior literature on Cu-contact reliability tended to focus on accelerated testing at the cell and wafer level that may not be entirely replicative of real-world environmental stresses in PV modules. This thesis is aimed at advancing the understanding of Cu-contact reliability from the perspective of quasi-commercial modules under more realistic stresses. In this thesis, c-Si solar cells with Cu-plated contacts are fabricated, made into PV modules, and subjected to environmental stress in an attempt to induce hypothesized failure modes and understand any new vulnerabilities that Cu contacts might introduce. In particular, damp heat stress is applied to conventional, p-type c-Si modules and high efficiency, n-type c-Si heterojunction modules. I present evidence of Cu-induced diode degradation that also depends on PV module materials, as well as degradation unrelated to Cu, and in either case suggest engineering solutions to the observed degradation. In a forensic search for degradation mechanisms, I present novel evidence of Cu outdiffusion from contact layers and encapsulant-driven contact corrosion as potential key factors. Finally, outdoor exposures to light uncover peculiarities in Cu-plated samples, but do not point to especially serious vulnerabilities. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

The molecular design, synthesis and characterization of a series of ligands and the corresponding novel iridium(III) or platinum(II) complexes are discussed in this thesis. Their photophysical and electrochemical properties, the applications in organic light-emitting diodes (OLEDs), dye-sensitized solar cells (DSSCs), aggregation induced emission (AIE) and time-resolved infrared (TRIR) study are also investigated. Chapter 1 generates a brief overview of the background, principle, and development of OLEDs, DSSCs, AIE materials and the involvement of the TRIR technique. Chapter 2 describes the synthesis, spectroscopic, photophysical and electrochemical characterization of a series of cationic iridium(III) complexes. Strong electron-withdrawing carboxylic acid substituted bipyridyl was involved in the ligand system and the intra-ligand charge transfer character of diphenylamino containing ligand further shift the dominant absorption band to the lower energy region. Some of them were applied for DSSC device fabrication. Chapter 3 presents the synthesis, spectroscopic, photophysical and electrochemical characterization as well as OLED application of a group of cyclometalated iridium(III) complexes by using 2-substituted 9-benzylcarbazolyl, 9-phenylcarbazolyl or 2-methyl-7-phenylcarbazolyl groups as the ligands. They show significant bathochromatic shift from those using 3-substituted ligands. And this can be explained by the fact that more electron density is located at 2-position of carbazole moiety and make them suitable candidates for deep red OLED application. Chapter 4 delivers the synthesis, spectroscopic, photophysical and electrochemical characterization of a series of platinum(II) acetylide complexes for AIE study. All of the complexes contain [4-(1,2,2-triphenylethenyl)phenyl]ethynyl ligand, which is designed from AIE active building block tetraphenylamine (TPE). Some of these metal complexes show AIE behavior. Chapter 5 outlines the synthetic methodology and characterization of another series of cyclometalated iridium(III) and platinum(II) complexes, containing TPE or carbazole units. It is very interesting to find out that there is hardly any emission in all of the TPE-containing cyclometalated complexes, nor any signs of AIE behavior. Meanwhile, for carbazole-containing platinum(II) complexes, remarable AIE results could be generated, which is believed to be important for further organometallic AIE active material development. Chapter 6 describes the synthetic methodology and characterization of a series of symmetric or asymmetric platinum(II) acetylides. Some of them were further applied for TRIR analysis to generate detailed experimental information of the electron transitions during excitation. The results demonstrate that both localized and delocalized metal ligand orbital mixing could be generated according to the variations in electronegativity of the ligand system. Chapter 7 and 8 present the concluding remarks and summarize the experimental details of all of the previous chapters.

abstract: This dissertation focuses on the structural and optical properties of III-V semiconductor materials. Transmission electron microscopy and atomic force microscopy are used to study at the nanometer scale, the structural properties of defects, interfaces, and surfaces. A correlation with optical properties has been performed using cathodoluminescence. The dissertation consists of four parts. The first part focuses on InAs quantum dots (QDs) embedded in a GaInP matrix for applications into intermediate band solar cells. The CuPt ordering of the group-III elements in Ga0.5In0.5P has been found to vary during growth of InAs QDs capped with GaAs. The degree of ordering depends on the deposition time of the QDs and on the thickness of the capping layer. The results indicate that disordered GaInP occurs in the presence of excess indium at the growth front. The second part focuses on the effects of low-angle off-axis GaN substrate orientation and growth rates on the surface morphology of Mg-doped GaN epilayers. Mg doping produces periodic steps and a tendency to cover pinholes associated with threading dislocations. With increasing miscut angle, the steps are observed to increase in height from single to double basal planes, with the coexistence of surfaces with different inclinations. The structural properties are correlated with the electronic properties of GaN epilayers, indicating step bunching reduces the p-type doping efficiency. It is also found that the slower growth rates can enhance step-flow growth and suppress step bunching. The third part focuses on the effects of inductively-coupled plasma etching on GaN epilayers. The results show that ion energy rather than ion density plays the key role in the etching process, in terms of structural and optical properties of the GaN films. Cathodoluminescence depth-profiling indicates that the band-edge emission of etched GaN is significantly quenched. The fourth part focuses on growth of Mg-doped GaN on trench patterns. Anisotropic growth and nonuniform acceptor incorporation in p-GaN films have been observed. The results indicate that growth along the sidewall has a faster growth rate and therefore a lower acceptor incorporation efficiency, compared to the region grown on the basal plane. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

The performance of non-fullerene acceptor (NFA)- based organic solar cells (OSC) has shown continuous increase in recent years, reaching power-conversion efficiencies up to 17% through the design and synthesis of efficient acceptor materials. Recent research is directed towards achieving higher efficiency of OSC, which is limited by the open-circuit voltage (Voc) which is lower than the Voc values achieved in inorganic or perovskites solar cells with comparable bandgaps. In this work, voltage losses in NFA based OSC were calculated by investigating charge-transfer state energy (ECT) using electroluminescence spectroscopy and sensitive external quantum efficiency in three polymer:non-fullerene bulk heterojunction solar cells. PCE10:ITIC device acquired the highest ECT with a Voc of 0.82V, and a a power conversion efficiency (PCE) of 7.91%. While PCE10:O-IDTBR obtained the highest Voc of 1.03V, a PCE of 8.02% compared to PCE10:O-IDTBCN solar cell that has a lower Voc of 0.73V with a PCE of 7.98%. Both radiative and non-radiative voltage losses were calculated. In this thesis, the high open circuit voltage of PCE10:O-IDTBR is explained by the low non-radiative voltage losses compared to PCE10:O-IDTBCN and PCE10:ITIC devices.